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Sample records for hexavalent oxidation state

  1. Groundwater contaminant by hexavalent chromium

    Energy Technology Data Exchange (ETDEWEB)

    Parsons, C. [Univ. of Texas, Austin, TX (United States)

    1995-11-01

    Oxidation of trivalent chromium to hexavalent chromium has been investigated as a function of total manganese in soils as well as various incubation conditions. Chromium and manganese contents were analyzed by atomic absorption (graphite furnace and flame emission respectively) following acid digestion. Total hexavalent chromium generation capacity was determined by addition of 0.001 M CrCL3, incubation, and analysis by s-diphenyl carbazide. Samples were then leached with CaSO{sub 4} and MgSO{sub 4} and incubated in various environments (oven, freeze-drier, field moist, ultrafreeze) to test for geogenic generation of Cr(IV). The degree of geogenic generation of hexavalent chromium was compared with total Mn and Cr content as well as hexavalent generational capacity.

  2. Application of Fe-Cu binary oxide nanoparticles for the removal of hexavalent chromium from aqueous solution.

    Science.gov (United States)

    Khan, Saif Ullah; Zaidi, Rumman; Hassan, Saeikh Z; Farooqi, I H; Azam, Ameer

    2016-01-01

    The adsorption process has been used as an effective technique for the removal of metal ions from aqueous solutions. Groundwater remediation by nanoparticles has received interest in recent years. In the present study, a binary metal oxide of Fe-Cu was prepared and used for the removal of hexavalent chromium from aqueous solution. Batch experiments were performed to investigate the effects of initial Cr (VI) concentration, dose of adsorbent, and pH of solution on the removal efficiency of Cr (VI). The prepared nanostructured Fe-Cu binary oxides were able to reduce the concentration of Cr (VI) in aqueous solution. Binary metal oxides nanoparticle exhibited an outstanding ability to remove Cr (VI) due to high surface area, low particle size, and high inherent activity. The percentage removal efficiency of Cr (VI) increased with nanoparticles doses (0.1 g L(-1)-2.5 g L(-1)), whereas it decreased with initial Cr (VI) concentration (1 mg L(-1)-25 mg L(-1)) and with pH (3-9). The Freundlich model was found to be the better fit for adsorption isotherm. The prepared nanomaterial was characterized using powder X-ray diffraction, scanning electron microscopy (SEM), and ultraviolet (UV)-visible spectroscopy. It showed that the Fe-Cu binary oxides were formed in single phase. SEM micrograph showed aggregates with many nano-sized particles. UV-visible spectroscopy showed quantum confinement effect.

  3. Mesoporous BaTiO₃@SBA-15 derived via solid state reaction and its excellent adsorption efficiency for the removal of hexavalent chromium from water.

    Science.gov (United States)

    Kumari, Vandana; Sasidharan, Manickam; Bhaumik, Asim

    2015-01-28

    We report the synthesis of a barium-titanate/mesoporous silica nanocomposite material BaTiO3@SBA-15 via aerosol assisted solid state reaction using SBA-15 as a hard template. Hexavalent chromium is one of the most harmful contaminants of industrial waste-water. We have used BaTiO3@SBA-15 nanocomposite as an adsorbent for the removal of chromium(vi)-contaminated water and it showed an adsorption capacity of 98.2 wt% within only 40 min contact time in a batch reactor. This mesoporous composite has retained this excellent adsorption efficiency of hexavalent chromium for several repetitive cycles, suggesting its future potential for the remediation of water contaminated with Cr(vi).

  4. Effective Removal of Hexavalent Chromium from Aqueous Solutions Using Ionic Liquid Modified Graphene Oxide Sorbent

    Directory of Open Access Journals (Sweden)

    A. Nasrollahpour

    2017-10-01

    Full Text Available Ionic liquid modified reduced graphene oxide (IL-rGO was prepared and examined for chromate removal. The sorbent was characterized by N2 adsorption-desorption measurement (BET, transmission electron microscopy (TEM, powder X-ray diffraction (XRD, and X-ray photoelectron spectroscopy (XPS analysis. The sorption behavior of chromate on the ionic liquid modified reduced graphene oxide sorbent from an aqueous medium was studied by varying the parameters such as contact time, initial chromate concentration, pH, and agitation speed. The results showed that sorption kinetics of chromate by IL-rGO follows the pseudo second order, which indicates that the sorption mechanism is both chemical and physical interaction. The sorption isotherm studies revealed that Langmuir model provided the best fit to all the experimental data with an adsorption capacity of 232.55 mg g–1 for IL-rGO. Thermodynamic parameters, such as Gibbs free energy (–2.85 kJ mol–1 at 298 K, enthalpy (55.41 kJ mol–1, and entropy (11.64 J mol–1 K–1 of sorption of the chromate on ionic liquid modified reduced graphene oxide was evaluated, and it was found that the reaction was spontaneous and endothermic in nature.

  5. Semi-continuous detection of toxic hexavalent chromium using a sulfur-oxidizing bacteria biosensor.

    Science.gov (United States)

    Gurung, Anup; Oh, Sang-Eun; Kim, Ki Duck; Shin, Beom-Soo

    2012-09-15

    Toxicity testing is becoming a useful tool for environmental risk assessment. A biosensor based on the metabolic properties of sulfur-oxidizing bacteria (SOB) has been applied for the detection of toxic chemicals in water. The methodology exploits the ability of SOB to oxidize elemental sulfur to sulfuric acid under aerobic conditions. The reaction results in an increase in electrical conductivity (EC) and a decrease in pH. Five hours after Cr(6+) was added to the SOB biosensor operated in semi-continuous mode (1 min rapid feeding and 29 min batch reaction), a decrease in effluent EC and an increase in pH (from 2-3 to 6) were detected due to Cr(6+) toxicity to SOB. The SOB biosensor is simple; it can detect toxic levels of Cr(6+) on the order of minutes to hours, a useful time scale for early warning detection systems designed to protect the environment from further degradation. Copyright © 2012 Elsevier Ltd. All rights reserved.

  6. Higher Americium Oxidation State Research Roadmap

    Energy Technology Data Exchange (ETDEWEB)

    Mincher, Bruce J. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Law, Jack D. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Goff, George S. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Moyer, Bruce A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Burns, Jon D. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Lumetta, Gregg J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Sinkov, Sergey I. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Shehee, Thomas C. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Hobbs, David T. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2015-12-18

    The partitioning of hexavalent Am from dissolved nuclear fuel requires the ability to efficiently oxidize Am(III) to Am(VI) and to maintain that oxidation state for a length of time sufficient to perform the separation. Several oxidants have been, or are being developed. Chemical oxidants include Ag-catalyzed ozone, Ag-catalyzed peroxydisulfate, Cu(III) periodate, and sodium bismuthate. Hexavalent americium has also now successfully been prepared by electrolysis, using functionalized electrodes. So-called auto-reduction rates of Am(VI) are sufficiently slow to allow for separations. However, for separations based on solvent extraction or ion exchange using organic resins, the high valence state must be maintained under the reducing conditions of the organic phase contact, and a holding oxidant is probably necessary. Until now, only Cu(III) periodate and sodium bismuthate oxidation have been successfully combined with solvent extraction separations. Bismuthate oxidation provided the higher DAm, since it acts as its own holding oxidant, and a successful hot test using centrifugal contactors was performed. For the other oxidants, Ag-catalyzed peroxydisulfate will not oxidize americium in nitric acid concentrations above 0.3 M, and it is not being further investigated. Peroxydisulfate in the absence of Ag catalysis is being used to prepare Am(V) in ion exchange work, discussed below. Preliminary work with Ag-catalyzed ozone has been unsuccessful for extractions of Am(VI) from 6.5 M HNO3, and only one attempt at extraction, also from 6.5 M HNO3, using the electrolytic oxidation has been attempted. However, this high acid concentration was based on the highest Am extraction efficiency using the bismuthate oxidant; which is only sparingly soluble, and thus the oxidation yield is based on bismuthate solubility. Lower acid concentrations may be sufficient with alternative oxidants and work with Ag-ozone, Cu(III) and electrolysis is on-going. Two non

  7. Natural occurrence of hexavalent chromium in a sedimentary aquifer in Urânia, State of São Paulo, Brazil

    Directory of Open Access Journals (Sweden)

    Christine Bourotte

    2009-06-01

    Full Text Available Anomalous concentrations of hexavalent chromium have been detected in ground-water of the Adamantina Aquifer inat least 54 municipalities located in the northwestern region of the State of São Paulo, southeast Brazil, occasionallyexceeding the permitted limit for human consumption (0.05 mg.L-1. An investigation was conducted in the municipality of Urânia, where the highest concentrations of chromium were detected regionally. It was defined that the originof this contamination is natural, since high concentrations of chromium were detected in aquifer sandstones (averageof 221 ppm and also in pyroxenes (6000 ppm, one of the main heavy minerals found in the sediments. Besides, noother possible diffuse or point sources of contamination were observed in the study area. Stratification of ground-waterquality was observed and the highest concentrations of Cr6+ were detected at the base of the aquifer (0.12 mg.L-1,where ground-water shows elevated values for redox potential (472.5 mV and pH (8.61. The origin of Cr6+ in water may be associated with the weathering of pyroxene (augite, followed by the oxidation of Cr3+ by manganese oxides. The highest concentrations of Cr6+ are probably related to desorption reactions, due to the anomalous alkaline pHfound in ground-water at the base of the aquifer.Concentrações anômalas de cromo hexavalente foram detectadas em águas subterrâneas do Aqüífero Adamantina em pelo menos 54 municipalidades localizadas na região noroeste do Estado de São Paulo, sudeste do Brasil, algumas vezes ultrapassando o limite máximo permitido para consumo humano (0,05 mg.L-1. Um estudo foi realizado no município de Urânia, onde as mais elevadas concentrações de cromo da região foram detectadas. A origem da contaminação foi definida como natural, pois foram detectadas concentrações de cromonos arenitos do aqüífero (média 221 ppm e em piroxênios (6000 ppm, um dos principais minerais pesados encontrados nos sedimentos

  8. Hexavalent Americium Recovery Using Copper(III) Periodate

    Energy Technology Data Exchange (ETDEWEB)

    McCann, Kevin; Brigham, Derek M.; Morrison, Samuel; Braley, Jenifer C.

    2016-11-21

    Separation of americium from the lanthanides is considered one of the most difficult separation steps in closing the nuclear fuel cycle. One approach to this separation could involve oxidizing americium to the hexavalent state to form a linear dioxo cation while the lanthanides remain as trivalent ions. This work considers aqueous soluble Cu3+ periodate as an oxidant under molar nitric acid conditions to separate hexavalent Am with diamyl amylphosphonate (DAAP) in n-dodecane. Initial studies assessed the kinetics of Cu3+ periodate auto-reduction in acidic media to aid in development of the solvent extraction system. Following characterization of the Cu3+ periodate oxidant, solvent extraction studies optimized the recovery of Am from varied nitric acid media and in the presence of other fission product, or fission product surrogate, species. Short aqueous/organic contact times encouraged successful recovery of Am (distribution values as high as 2) from nitric acid media in the absence of redox active fission products. In the presence of a post-PUREX simulant aqueous feed, precipitation of tetravalent species (Ce, Ru, Zr) occurred and the distribution values of 241Am were suppressed, suggesting some oxidizing capacity of the Cu3+ periodate is significantly consumed by other redox active metals in the simulant. The manuscript demonstrates Cu3+ periodate as a potentially viable oxidant for Am oxidation and recovery and notes the consumption of oxidizing capacity observed in the presence of the post-PUREX simulant feed will need to be addressed for any approach seeking to oxidize Am for separations relevant to the nuclear fuel cycle.

  9. Semiconductor Oxide Interface States.

    Science.gov (United States)

    1981-05-01

    0C for 30 minutes. B 9 7 and B17 curves were taken before forming gas annealing and A297 and A77 were taken after annealing in forming gas... A297 and A77’ AL .show a substantial reduction of interface states and a slight increase of positive oxide charges. The reduction of the interface...states is deduced from the voltage differences between A297 and the A77 C-V curves both above and below the cross-over point which are smaller than the

  10. Ultrafine cobalt nanoparticles supported on reduced graphene oxide: Efficient catalyst for fast reduction of hexavalent chromium at room temperature

    Science.gov (United States)

    Xu, Tingting; Xue, Jinjuan; Zhang, Xiaolei; He, Guangyu; Chen, Haiqun

    2017-04-01

    A novel composite ultrafine cobalt nanoparticles-reduced graphene oxide (Co-RGO) was firstly synthesized through a modified one-step solvothermal method with Co(OH)2 as the precursor. The prepared low-cost Co-RGO composite exhibited excellent catalytic activity for the reduction of highly toxic Cr(VI) to nontoxic Cr(III) at room temperature when formic acid (HCOOH) was employed as the reductant, and its catalytic performance was even comparable with that of noble metal-based catalysts in the same reduction reaction. Moreover, Co-RGO composite could be readily recovered under an external magnetic field and efficiently participated in recycled reaction for Cr(VI) reduction.

  11. Adsorption of hexavalent chromium onto sisal pulp/polypyrrole composites

    Science.gov (United States)

    Tan, Y. Y.; Wei, C.; Gong, Y. Y.; Du, L. L.

    2017-02-01

    Sisal pulp/polypyrrole composites(SP/PPy) utilized for the removal of hexavalent chromium [Cr(VI)] from wastewater, were prepared via in-situ chemical oxidation polymerization approach. The structure and morphology of the SP/PPy were analyzed by polarizing optical microscopy (POM), field-emission scanning electron microscopy (SEM)), Energy-dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS), the results indicated SP could be efficient dispersion of PPy. The hexavalent chromium adsorption results indicate adsorption capacity of the SP/PPy were dependent on the initial pH, with an optimum pH of 2.0. The sorption kinetic data fitted well to the pseudo-second order model and isotherm data fitted well to the Langmuir isotherm model. The maximum adsorption capacity determined from the Langmuir isotherm is 336.70 mg/g at 25° C.

  12. High-performance towards removal of toxic hexavalent chromium from aqueous solution using graphene oxide-alpha cyclodextrin-polypyrrole nanocomposites

    CSIR Research Space (South Africa)

    Chauke, VP

    2015-07-01

    Full Text Available Graphene oxide (GO) was functionalized with alpha cyclodextrin (aCD) through a covalent bond to form GO-aCD nanocomposites (NC). GO-aCD NC was further modified with polypyrrole (PPY) to afford an advanced GO-aCD-PPY NC for the removal of highly...

  13. Hexavalent-Chrome Free Coatings Project

    Data.gov (United States)

    National Aeronautics and Space Administration — The replacement of hexavalent chrome [Cr (VI)] in the processing of aluminum for high-reliability electronics applications in the aviation and aerospace sector...

  14. Reduction Rates for Higher Americium Oxidation States in Nitric Acid

    Energy Technology Data Exchange (ETDEWEB)

    Grimes, Travis Shane [Idaho National Lab. (INL), Idaho Falls, ID (United States); Mincher, Bruce Jay [Idaho National Lab. (INL), Idaho Falls, ID (United States); Schmitt, Nicholas C [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2015-09-30

    The stability of hexavalent americium was measured using multiple americium concentrations and nitric acid concentrations after contact with the strong oxidant sodium bismuthate. Contrary to our hypotheses Am(VI) was not reduced faster at higher americium concentrations, and the reduction was only zero-order at short time scales. Attempts to model the reduction kinetics using zero order kinetic models showed Am(VI) reduction in nitric acid is more complex than the autoreduction processes reported by others in perchloric acid. The classical zero-order reduction of Am(VI) was found here only for short times on the order of a few hours. We did show that the rate of Am(V) production was less than the rate of Am(VI) reduction, indicating that some Am(VI) undergoes two electron-reduction to Am(IV). We also monitored the Am(VI) reduction in contact with the organic diluent dodecane. A direct comparison of these results with those in the absence of the organic diluent showed the reduction rates for Am(VI) were not statistically different for both systems. Additional americium oxidations conducted in the presence of Ce(IV)/Ce(III) ions showed that Am(VI) is reduced without the typical growth of Am(V) observed in the systems sans Ce ion. This was an interesting result which suggests a potential new reduction/oxidation pathway for Am in the presence of Ce; however, these results were very preliminary, and will require additional experiments to understand the mechanism by which this occurs. Overall, these studies have shown that hexavalent americium is fundamentally stable enough in nitric acid to run a separations process. However, the complicated nature of the reduction pathways based on the system components is far from being rigorously understood.

  15. Zinc in a +III oxidation state

    CERN Document Server

    Samanta, Devleena

    2012-01-01

    The possibility of Group 12 elements, such as Zn, Cd, and Hg existing in an oxidation state of +III or higher and hence transforming them into transition metals has fascinated chemists for decades. It took nearly 20 years before experiment could confirm the theoretical prediction that Hg indeed can exist in an oxidation state of +IV. While this unusual property of Hg is attributed to the relativistic effects, Zn being much lighter than Hg has not been expected to have an oxidation state higher than +II. Using density functional theory we show that an oxidation state of +III for Zn can be realized by choosing specific ligands with large electron affinities. We demonstrate this by a systematic study of the interaction of Zn with F, BO2, and AuF6 ligands whose electron affinities are progressively higher, namely, 3.4 eV, 4.5 eV, and 8.6 eV, respectively. Discovery of higher oxidation states of elements can help in the formulation of new reactions and hence in the development of new chemistry.

  16. Manganese Oxidation State Assignment for Manganese Catalase.

    Science.gov (United States)

    Beal, Nathan J; O'Malley, Patrick J

    2016-04-06

    The oxidation state assignment of the manganese ions present in the superoxidized manganese (III/IV) catalase active site is determined by comparing experimental and broken symmetry density functional theory calculated (14)N, (17)O, and (1)H hyperfine couplings. Experimental results have been interpreted to indicate that the substrate water is coordinated to the Mn(III) ion. However, by calculating hyperfine couplings for both scenarios we show that water is coordinated to the Mn(IV) ion and that the assigned oxidation states of the two manganese ions present in the site are the opposite of that previously proposed based on experimental measurements alone.

  17. Solid state aspects of oxidation catalysis

    NARCIS (Netherlands)

    Gellings, Paul J.; Bouwmeester, Henny J.M.

    2000-01-01

    The main subject of this review is the consideration of catalytic oxidation reactions, which are greatly influenced by solid state effects in the catalyst material. Emphasis is laid upon the correlation between the presence of mobile ionic defects, together with the associated ionic conductivity, an

  18. Expanded Definition of the Oxidation State

    Science.gov (United States)

    Loock, Hans-Peter

    2011-01-01

    A proposal to define the oxidation state of an atom in a compound as the hypothetical charge of the corresponding atomic ion that is obtained by heterolytically cleaving its bonds such that the atom with the higher electronegativity in a bond is allocated all electrons in the bond. Bonds between like atoms are cleaved homolytically. This…

  19. Oxidation state of BZ reaction mixtures.

    Science.gov (United States)

    Sobel, Sabrina G; Hastings, Harold M; Field, Richard J

    2006-01-12

    The unstirred, ferroin (Fe(phen)(3)2+)-catalyzed Belousov-Zhabotinsky (BZ) reaction1-4 is the prototype oscillatory chemical system. After an induction period of several minutes, one sees "spontaneous" formation of "pacemaker" sites, which oscillate between a blue, oxidized state (high [Fe(phen)3(3+)]) and a red, reduced state (low [Fe(phen)(3)3+]). The reaction medium appears red (reduced) during the induction phase, and the pacemaker sites generate target patterns of concentric, outwardly moving waves of oxidation (blue). Auto-oscillatory behavior is also seen in the Oregonator model of Field, Korös, and Noyes (FKN), a robust, reduced model which captures qualitative BZ kinetics in the auto-oscillatory regime. However, the Oregonator model predicts a blue (oxidized) induction phase. Here, we show that including reaction R8 of the FKN mechanism, not incorporated in the original Oregonator, accounts for bromide release during the induction phase, thus producing the observed red oxidation state.

  20. Thermodynamic Ground States of Complex Oxide Heterointerfaces

    DEFF Research Database (Denmark)

    Gunkel, F.; Hoffmann-Eifert, S.; Heinen, R. A.

    2017-01-01

    The formation mechanism of 2-dimensional electron gases (2DEGs) at heterointerfaces between nominally insulating oxides is addressed with a thermodynamical approach. We provide a comprehensive analysis of the thermodynamic ground states of various 2DEG systems directly probed in high temperature...... equilibrium conductivity measurements. We unambiguously identify two distinct classes of oxide heterostructures: For epitaxial perovskite/perovskite heterointerfaces (LaAlO3/SrTiO3, NdGaO3/SrTiO3, and (La,Sr)(Al,Ta)O3/SrTiO3), we find the 2DEG formation being based on charge transfer into the interface...

  1. Investigation of total and hexavalent chromium in filtered and unfiltered groundwater samples at the Tucson International Airport Superfund Site

    Science.gov (United States)

    Tillman, Fred; McCleskey, R. Blaine; Hermosillo, Edyth

    2016-01-01

    Potential health effects from hexavalent chromium in groundwater have recently become a concern to regulators at the Tucson International Airport Area Superfund site. In 2016, the U.S. Geological Survey sampled 46 wells in the area to characterize the nature and extent of chromium in groundwater, to understand what proportion of total chromium is in the hexavalent state, and to determine if substantial differences are present between filtered and unfiltered chromium concentrations. Results indicate detectable chromium concentrations in all wells, over 75 % of total chromium is in the hexavalent state in a majority of wells, and filtered and unfiltered results differ substantially in only a few high-turbidity total chromium samples.

  2. Electrochemical reduction of hexavalent chromium in ground water

    Energy Technology Data Exchange (ETDEWEB)

    Bansal, S. [Lawrence Livermore National Lab., CA (United States)

    1994-12-01

    Electrochemical reduction of hexavalent chromium (Cr{sup +6}) to its trivalent state (Cr{sup +3}) is showing promising results in treating ground water at Lawrence Livermore National Laboratory`s (LLNL`s) Main Site. An electrolytic cell using stainless-steel and brass electrodes has been found to offer the most efficient reduction while yielding the least amount of precipitate. Trials have successfully lowered concentrations of Cr{sup +6} to below 11 parts per billion (micrograms/liter), the California state standard. We ran several trials to determine optimal voltage for running the cell; each trial consisted of applying a voltage between 6V and 48V for ten minutes through samples obtained at Treatment Facility C(TFC). No conclusive data has been obtained yet.

  3. Photochemical oxidants: state of the science.

    Science.gov (United States)

    Kley, D; Kleinmann, M; Sanderman, H; Krupa, S

    1999-01-01

    Atmospheric photochemical processes resulting in the production of tropospheric ozone (O(3)) and other oxidants are described. The spatial and temporal variabilities in the occurrence of surface level oxidants and their relationships to air pollution meteorology are discussed. Models of photooxidant formation are reviewed in the context of control strategies and comparisons are provided of the air concentrations of O(3) at select geographic locations around the world. This overall oxidant (O(3)) climatology is coupled to human health and ecological effects. The discussion of the effects includes both acute and chronic responses, mechanisms of action, human epidemiological and plant population studies and briefly, efforts to establish cause-effect relationships through numerical modeling. A short synopsis is provided of the interactive effects of O(3) with other abiotic and biotic factors. The overall emphasis of the paper is on identifying the current uncertainties and gaps in our understanding of the state of the science and some suggestions as to how they may be addressed.

  4. Hexavalent Chromium Reduction under Fermentative Conditions with Lactate Stimulated Native Microbial Communities

    OpenAIRE

    Somenahally, Anil C.; Mosher, Jennifer J; Tong Yuan; Mircea Podar; Phelps, Tommy J.; Brown, Steven D.; Yang, Zamin K.; Hazen, Terry C.; Arkin, Adam P.; Palumbo, Anthony V.; Joy D Van Nostrand; Jizhong Zhou; Elias, Dwayne A.

    2013-01-01

    Microbial reduction of toxic hexavalent chromium (Cr(VI)) in-situ is a plausible bioremediation strategy in electron-acceptor limited environments. However, higher [Cr(VI)] may impose stress on syntrophic communities and impact community structure and function. The study objectives were to understand the impacts of Cr(VI) concentrations on community structure and on the Cr(VI)-reduction potential of groundwater communities at Hanford, WA. Steady state continuous flow bioreactors were used to ...

  5. Origin of hexavalent chromium in groundwater

    DEFF Research Database (Denmark)

    Kazakis, N.; Kantiranis, N.; Kalaitzidou, K.

    2017-01-01

    Hexavalent chromium constitutes a serious deterioration factor for the groundwater quality of several regions around the world. High concentrations of this contaminant have been also reported in the groundwater of the Sarigkiol hydrological basin (near Kozani city, NW Greece). Specific interest....... Accordingly, detailed geochemical, mineralogical, hydro-chemical, geophysical and hydrogeological studies were performed on the rocks, soils, sediments and water resources of this basin. Cr(VI) concentrations varied in the different aquifers, with the highest concentration (up to 120 μg L− 1) recorded...

  6. Equation of state of uranium oxide

    Science.gov (United States)

    Ohse, R. W.; Babelot, J.-F.; Cercignani, C.; Hiernaut, J.-P.; Hoch, M.; Hyland, G. J.; Magill, J.

    1985-02-01

    The total and partial pressures over liquid UO 2 have been measured and calculated up to 5000K. A review of previous work is given. The equation of state of UO 2 as the main constituent of the fast breeder oxide fuel is required up to at least 5000K in order to estimate the energy release in a loss of flow (LOF) driven hypothetical core disruptive accident (HCDA) of the liquid metal fast breeder reactor (LMFBR). Two models, a macroscopic "mixture" model and a microscopic "defect" model have been developed to determine the oxygen potential of UO 200 up to 5000 K. A combination of mass spectrometric, Langmuir probe and high tension diode studies, applied for the first time to the laser vaporization process, revealed large quantities of ions emitted directly from the surface, and resolved previous discrepancies between measured and calculated vapour pressures by an enhanced rate of evaporation due to ion emission. As shown theoretically intrinsic ion emission can contribute to the net evaporation rate only if the resulting positive space charge can be neutralised. It is proposed that this can be accomplished by the presence of "hot" electrons in the plasma. The recommended equilibrium total pressure over liquid UO 2.00, valid between the melting point and 5000K, is log p (MPa) = - 2.717 - 20131/T + 1.925 log T.

  7. Chromium isotopes as indicators of hexavalent chromium reduction

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Thomas M.

    2012-03-20

    This is the final report for a university research project which advanced development of a new technology for identifying chemical reduction of hexavalent chromium contamination in groundwater systems. Reduction renders mobile and toxic hexavalent chromium immobile and less toxic. The new method uses stable isotope ratio measurements, which are made using multicollector ICP-mass spectrometry. The main objectives of this project were completed during the project period and two peer-reviewed articles were published to disseminate the information gained.

  8. Hexavalent and trivalent chromium in leather: What should be done?

    Science.gov (United States)

    Moretto, Angelo

    2015-11-01

    Trivalent chromium compounds are used for leather tanning, and chromium may be released during use of leather goods. In certain instances, small amounts of hexavalent chromium can be formed and released. Both trivalent and hexavalent chromium can elicit allergic skin reaction in chromium sensitised subjects, the latter being significantly more potent. Induction of sensitisation only occurs after exposure to hexavalent chromium. A minority of subjects are sensitised to chromium, and in a fraction of these subjects allergic skin reaction have been described after wearing leather shoes or, less frequently, other leather goods. The evidence that in all these cases the reaction is related to hexavalent chromium is not always strong. The content of hexavalent chromium in leather is regulated in European Union, but rate of release rather than content is relevant for allergic skin reaction. The role of trivalent chromium appear much less relevant if at all. Modern tanning procedure do not pose significant risk due to either hexavalent or trivalent chromium. Dismissing bad quality and worn-off leather goods is relevant in reducing or eliminating the skin reaction. It should also be pointed out that shoe components or substances other than chromium in leather may cause allergic/irritative skin reactions.

  9. Natural and induced reduction of hexavalent chromium in soil

    Science.gov (United States)

    Leita, Liviana; Margon, Alja; Sinicco, Tania; Mondini, Claudio; Valentini, Massimiliano; Cantone, Pierpaolo

    2013-04-01

    Even though naturally elevated levels of chromium can be found naturally in some soils, distressing amounts of the hexavalent form (CrVI) are largely restricted to sites contaminated by anthropogenic activities. In fact, the widespread use of chromium in various industries and the frequently associated inadequate disposal of its by-products and wastes have created serious environmental pollution problems in many parts of the world. CrVI is toxic to plants, animals and humans and exhibits also mutagenic effects. However, being a strong oxidant, CrVI can be readily reduced to the much less harmful trivalent form (CrIII) when suitable electron donors are present in the environment. CrIII is relatively insoluble, less available for biological uptake, and thus definitely less toxic for web-biota. Various electron donors in soil can be involved in CrVI reduction in soil. The efficiency of CrVI reducing abiotic agents such as ferrous iron and sulphur compounds is well documented. Furthermore, CrVI reduction is also known to be significantly enhanced by a wide variety of cell-produced monosaccharides, including glucose. In this study we evaluated the dynamics of hexavalent chromium (CrVI) reduction in contaminated soil amended or not with iron sulphate or/and glucose and assessed the effects of CrVI on native or glucose-induced soil microbial biomass size and activity. CrVI negatively affected both soil microbial activity and the size of the microbial biomass. During the incubation period, the concentration of CrVI in soil decreased over time whether iron sulphate or/and glucose was added or not, but with different reduction rates. Soil therefore displayed a natural attenuation capacity towards chromate reduction. Addition of iron sulphate or/and glucose, however, increased the reduction rate by both abiotic and biotic mechanisms. Our data suggest that glucose is likely to have exerted an indirect role in the increased rate of CrVI reduction by promoting growth of

  10. Investigation on oxidation states of rhenium in Re-HEDP

    Institute of Scientific and Technical Information of China (English)

    WANG Wen-Jin; LUO Shun-Zhong; QIAO Jian; LIU Guo-Ping; LIU Ye-Bing

    2003-01-01

    The oxidation states of rhenium in Re-HEDP (hydroxyethylidene diphosphonate) were measured bythe methods of extraction and potentiometric titration. The oxidation state of rhenium in Re-HEDP was mostly +4valence, and the Re(Ⅳ)-HEDP was oxidized to Re( Ⅴ)-HEDP when it was titrated by I3- at pH 2.0. In the reductionsystem of Vc+Sn2+ , ReO4- was only reduced by Sn2+, but Vc was oxidized earlier than Sn2+ when it was titrated by I3.

  11. On the removal of hexavalent chromium from a Class F fly ash.

    Science.gov (United States)

    Huggins, F E; Rezaee, M; Honaker, R Q; Hower, J C

    2016-05-01

    Coarse and fine samples of a Class F fly ash obtained from commercial combustion of Illinois bituminous coal have been exposed to two long-term leaching tests designed to simulate conditions in waste impoundments. ICP-AES analysis indicated that the coarse and fine fly ash samples contained 135 and 171mg/kg Cr, respectively. Measurements by XAFS spectroscopy showed that the ash samples originally contained 5 and 8% of the chromium, respectively, in the hexavalent oxidation state, Cr(VI). After exposure to water for more than four months, the percentage of chromium as Cr(VI) in the fly-ash decreased significantly for the coarse and fine fly-ash in both tests. Combining the XAFS data with ICP-AES data on the concentration of chromium in the leachates indicated that, after the nineteen-week-long, more aggressive, kinetic test on the coarse fly ash, approximately 60% of the Cr(VI) had been leached, 20% had been reduced to Cr(III) and retained in the ash, and 20% remained as Cr(VI) in the ash. In contrast, during the six-month-long baseline test, very little Cr was actually leached from either the coarse or the fine fly-ash (ash was retained in the ash in that form, while the remainder, 34% and 80%, respectively, was reduced and retained in the ash as Cr(III). The results are interpreted as indicating that Cr(VI) present in Class F fly-ash can be reduced to Cr(III) when in contact with water and that such chemical reduction can compete with physical removal of Cr(VI) from the ash by aqueous leaching.

  12. DANGER OF HEXAVALENT CHROMIUM AND STRATEGY FOR THE REMEDITATION

    Directory of Open Access Journals (Sweden)

    Aniruddha Roy

    2013-02-01

    Full Text Available Some metals as micronutrients have a major role in the life and growth process of plants and animals. However, certain forms of some metals may also act as toxic material even in relatively small quantities. Chromium is such a metal, whose concentration above a certain limit may cause a serious problem to the health of living organisms. Chromium (Cr may occur in several chemical forms in organic and inorganic systems. In biological systems only Cr (III and Cr (VI are significant. Among these two states, trivalent chromium (Cr-III is considered as an essential component, while hexavalent Chromium (Cr-VI in biological system has been detected as responsible for so many diseases, even some specific forms of cancer. This paper intends to present the adverse effect of Cr(VI on environment as well as on human beings and also try to find a way out to dissolve the problem by a newly developed efficient and cost effective technique.

  13. XPS Determination of Mn Oxidation States in Mn (Hydr)oxides

    Energy Technology Data Exchange (ETDEWEB)

    Ilton, Eugene S.; Post, Jeffrey E.; Heaney, Peter J.; Ling, Florence T.; Kerisit, Sebastien N.

    2016-03-15

    Hydrous manganese oxides are an important class of minerals that help regulate the geochemical redox cycle in near-surface environments and are also considered to be promising catalysts for energy applications such as the oxidation of water. A complete characterization of these minerals is required to better understand their catalytic activity. In this contribution an empirical methodology using X-ray photoelectron spectroscopy (XPS) is developed to quantify the oxidation state of hydrous multivalent manganese oxides with an emphasis on birnessite, a common layered structure that occurs readily in Nature but is also the oxidized endmember in biomimetic water-oxidation catalysts. The Mn2p3/2, Mn3p, and Mn3s lines of near monovalent Mn(II), Mn(III), and Mn(IV) oxides were fit with component peaks; after the best fit was obtained the relative widths, heights and binding energies of the components were fixed. Unknown multivalent samples were fit such that binding energies, intensities, and widths of each oxidation state, composed of a packet of correlated component peaks, were allowed vary. whereas widths were constrained to maintain the difference between the standards. Both average and individual mole fraction oxidation states for all three energy levels were strongly correlated with close agreement between Mn3s and Mn3p, whereas Mn2p3/2 gave systematically more reduced results. Limited stoichiometric analyses were consistent with Mn3p and Mn3s. Further, evidence indicates the shape of the Mn3p line was less sensitive to the bonding environment than Mn2p. Consequently, fitting the Mn3p and Mn3s lines yields robust quantification of oxidation states over a range of hydrous Mn oxide polytypes and compositions. In contrast, a common method for determining oxidation states that utilizes the multiplet splitting of the Mn3s line is not appropriate for birnessites.

  14. Reduction and immobilization of hexavalent chromium by microbially reduced Fe-bearing clay minerals

    Science.gov (United States)

    Bishop, Michael E.; Glasser, Paul; Dong, Hailiang; Arey, Bruce; Kovarik, Libor

    2014-05-01

    Hexavalent chromium (Cr6+) is a major contaminant in the environment. As a redox-sensitive element, the fate and toxicity of chromium is controlled by reduction-oxidation (redox) reactions. Previous research has shown the ability of structural Fe(II) in naturally present and chemically reduced clay minerals to reduce Cr6+ to Cr(III) as a way of immobilization and detoxification. However, it is still poorly known whether or not structural Fe(II) in biologically reduced clay minerals exhibits a similar reactivity and if so, what the kinetics and mechanisms of Cr6+ reduction are. The objective of this study was to determine the kinetics and possible mechanisms of Cr6+ reduction by structural Fe(II) in microbially reduced clay minerals and the nature of reduced Cr(III). Structural Fe(III) in nontronite (NAu-2), montmorillonite (SWy-2), chlorite (CCa-2), and clay-rich sediments from the Ringold Formation of the Hanford site of Washington State, USA was first bioreduced to Fe(II) by an iron-reducing bacterium Geobacter sulfurreducens with acetate as the sole electron donor and anthraquinone-2,6-disulfonate (AQDS) as electron shuttle in synthetic groundwater (pH 7). Biogenic Fe(II) was then used to reduce aqueous Cr6+ at three different temperatures, 10, 20, and 30 °C, in order to determine the temperature dependence of the redox reaction between Cr6+ and clay-Fe(II). The results showed that nontronite and montmorillonite were most effective in reducing aqueous Cr6+ at all three temperatures. In contrast, most Fe(II) in chlorite was not reactive towards Cr6+ reduction at 10 °C, though at 30 °C there was some reduction. For all the clay minerals, the ratio of total Fe(II) oxidized to Cr6+ reduced was close to the expected stoichiometric value of 3. Characterization of the Cr-clay reaction product with scanning electron microscopy with focused ion beam and transmission electron microscopy with electron energy loss spectroscopy revealed that reduced chromium was possibly

  15. Solid state tungsten oxide hydrate/tin oxide hydrate electrochromic device prepared by electrochemical reactions

    Science.gov (United States)

    Nishiyama, Kentaro; Matsuo, Ryo; Sasano, Junji; Yokoyama, Seiji; Izaki, Masanobu

    2017-03-01

    The solid state electrochromic device composed of tungsten oxide hydrate (WO3(H2O)0.33) and tin oxide hydrate (Sn(O,OH)) has been constructed by anodic deposition of WO3(H2O)0.33 and Sn(O,OH) layers and showed the color change from clear to blue by applying voltage through an Au electrode.

  16. GSDO Program Hexavalent Chrome Alternatives: Final Pretreatments Test Report

    Science.gov (United States)

    Kessel, Kurt

    2013-01-01

    Hexavalent chrome free pretreatments should be considered for use on Ground Support Equipment (OSE) and Electrical Ground Support Equipment (EOSE). Both of the hexavalent chrome free pretreatments (Metalast TCP HF and SurTec 650C) evaluated by this project met, and in some instances exceeded, the requirements ofMIL-DTL-5541 "Chemical Conversion Coatings on Aluminum and Aluminum Alloys". For DC resistance measurements, both Metalast TCP HF and SurTec (!50C met initial requirements following assembly and in many cases continued to maintain passing readings for the duration of testing.

  17. Oxidatively generated DNA/RNA damage in psychological stress states

    DEFF Research Database (Denmark)

    Jørgensen, Anders

    2013-01-01

    Both non-pathological psychological stress states and mental disorders are associated with molecular, cellular and epidemiological signs of accelerated aging. Oxidative stress on nucleic acids is a critical component of cellular and organismal aging, and a suggested pathogenic mechanism in several...... age-related somatic disorders. The overall aim of the PhD project was to investigate the relation between psychopathology, psychological stress, stress hormone secretion and oxidatively generated DNA and RNA damage, as measured by the urinary excretion of markers of whole-body DNA/RNA oxidation (8......-oxodG and 8-oxoGuo, respectively). The main hypothesis was that psychological stress states are associated with increased DNA/RNA damage from oxidation. In a study of 40 schizophrenia patients and 40 healthy controls matched for age and gender, we found that 8-oxodG/8-oxoGuo excretion was increased...

  18. Effect of microorganisms on the plutonium oxidation states

    Energy Technology Data Exchange (ETDEWEB)

    Luksiene, Benedikta, E-mail: bena@ar.fi.lt [Center for Physical Sciences and Technology, Savanoriu ave 231, LT-02300 Vilnius (Lithuania); Druteikiene, Ruta [Center for Physical Sciences and Technology, Savanoriu ave 231, LT-02300 Vilnius (Lithuania); Peciulyte, Dalia [Nature Research Centre, Akademijos street 2, LT-08412 Vilnius (Lithuania); Baltrunas, Dalis; Remeikis, Vidmantas [Center for Physical Sciences and Technology, Savanoriu ave 231, LT-02300 Vilnius (Lithuania); Paskevicius, Algimantas [Nature Research Centre, Akademijos street 2, LT-08412 Vilnius (Lithuania)

    2012-03-15

    Particular microbes from substrates at the low-level radioactive waste repository in the Ignalina NPP territory were exposed to {sup 239}Pu (IV) at low pH under aerobic conditions. Pu(III) and Pu(IV) were separated and quantitatively evaluated using the modified anion exchange method and alpha spectrometry. Tested bacteria Bacillus mycoides and Serratia marcescens were more effective in Pu reduction than Rhodococcus fascians. Fungi Paecillomyces lilacinus and Absidia spinosa var. spinosa as well as bacterium Rhodococcus fascians did not alter the plutonium oxidation state. - Highlights: Black-Right-Pointing-Pointer Particular microbes from low-level radioactive waste repository were exposed to Pu (IV). Black-Right-Pointing-Pointer Some tested bacteria induced slight Pu (IV) reduction at low pH under aerobic conditions. Black-Right-Pointing-Pointer Tested fungi did not show peculiarities to alter Pu oxidation state. Black-Right-Pointing-Pointer The modified radiochemical method was applied to differentiate Pu oxidation states.

  19. Changes in magmatic oxidation state induced by degassing

    Science.gov (United States)

    Brounce, M. N.; Stolper, E. M.; Eiler, J. M.

    2015-12-01

    Temporal variations in the oxygen fugacity (fO2) of the mantle may have been transmitted to Earth's atmosphere and oceans by volcanic degassing. However, it is unclear how redox states of volatiles relate to their source magmas because degassing and assimilation can impact fO2 before or during eruption. To explore this, we present µ-XANES measurements of the oxidation states of Fe and S and laser fluorination measurements of 18O/16O ratios in submarine glasses from two settings where degassing is recorded: 1) submarine glasses from the Reykjanes Ridge as it shoals to Iceland, including subglacial glasses from the Reykjanes Peninsula; and 2) submarine glasses from Mauna Kea recovered by the Hawaii Shield Drilling Program (HSDP). Glasses from both settings are basalts with 5.5-9.9 wt% MgO and 350-1790 ppm S. Submarine Reykjanes glasses are sulfide saturated. Subglacial Reykjanes and HSDP glasses are not sulfide saturated, and S and H2O contents are consistent with S+H2O degassing. Submarine Reykjanes glasses have 18O/16O indistinguishable from MORB and become progressively 18O-depleted as MgO decreases. Subglacial glasses have lower 18O/16O than submarine glasses at a given MgO, but both sample types project to a common 18O/16O near 10 wt% MgO, suggesting that 18O-depletion in these lavas is generated by fractional crystallization and assimilation of an 18O-depleted crustal component. The oxidation state of Fe increases only slightly as 18O/16O decrease, suggesting that the assimilant is not oxidized enough to change magmatic fO2. Fe and S do not oxidize or reduce with decreasing S or H2O, suggesting that relatively reduced magmas at depth degassed S+H2O without changing magmatic fO2, and that the fO2 of these lavas reflect the fO2of their mantle source. The oxidation states of Fe and S in HSDP glasses are broadly correlated and samples with the highest S concentrations are the most oxidized. Both Fe and S reduce with decreasing S and H2O contents. This suggests

  20. IDENTIFYING CRITICAL CYSTEINE RESIDUES IN ARSENIC (+3 OXIDATION STATE) METHYLTRANSFERASE

    Science.gov (United States)

    Arsenic (+3 oxidation state) methyltransferase (AS3MT) catalyzes methylation of inorganic arsenic to mono, di, and trimethylated arsenicals. Orthologous AS3MT genes in genomes ranging from simple echinoderm to human predict a protein with five conserved cysteine (C) residues. In ...

  1. Shifts in oxidation states of cerium oxide nanoparticles detected inside intact hydrated cells and organelles

    Energy Technology Data Exchange (ETDEWEB)

    Szymanski, Craig J.; Munusamy, Prabhakaran; Mihai, Cosmin; Xie, Yumei; Hu, Dehong; Gilles, Marry K.; Tyliszczak, T.; Thevuthasan, Suntharampillai; Baer, Donald R.; Orr, Galya

    2015-09-01

    Cerium oxide nanoparticles (CNPs) have been shown to induce diverse biological effects, ranging from toxic to beneficial. The beneficial effects have been attributed to the potential antioxidant activity of CNPs via certain redox reactions, depending on their oxidation state or Ce3+/Ce4+ ratio. However, this ratio is strongly dependent on the environment and age of the nanoparticles and it is unclear whether and how the complex intracellular environment impacts this ratio and the possible redox reactions of CNPs. To identify any changes in the oxidation state of CNPs in the intracellular environment and better understand their intracellular reactions, we directly quantified the oxidation states of CNPs outside and inside intact hydrated cells and organelles using correlated scanning transmission x-ray and super resolution fluorescence microscopies. By analyzing hundreds of small CNP aggregates, we detected a shift to a higher Ce3+/Ce4+ ratio in CNPs inside versus outside the cells, indicating a net reduction of CNPs in the intracellular environment. We further found a similar ratio in the cytoplasm and in the lysosomes, indicating that the net reduction occurs earlier in the internalization pathway. Together with oxidative stress and toxicity measurements, our observations identify a net reduction of CNPs in the intracellular environment, which is consistent with their involvement in potentially beneficial oxidation reactions, but also point to interactions that can negatively impact the health of cells.

  2. Application of modified bentonite using sulfuric acid for the removal of hexavalent chromium from aqueous solutions

    Directory of Open Access Journals (Sweden)

    Masoud Moradi

    2015-09-01

    Full Text Available Background: Environmental contamination by chromium (Cr has become an important issue due to its adverse effects on human health and environment. This study was done to evaluate the application of modified bentonite using sulfuric acid as an adsorbent in the removal of hexavalent Cr from aqueous solution. Methods: Adsorbent features were determined using x-ray diffraction (XRD, fourier transformed infrared spectroscopy (FTIR and scanning electron microscope (SEM techniques. Thereafter, the effect of pH, contact time, adsorbent dosage and different concentrations of Cr was investigated. The experimental data was fitness in terms of kinetic and equilibrium adsorption processes. Results: The maximum capacity (Qm of Cr(VI according to Langmuir model was obtained at 4.21 mg/g. The experimental data properly obeyed the Longmuir and pseudo-second-order models. The highest percentage of Cr(VI adsorption was observed at pH = 3 and the process after 60 minutes reached the equilibrium state. Conclusion: In Langmuir expression, the dimensionless constant separation term (RL values for the adsorption of Cr onto the modified bentonite was in the range of 0-1, indicating that the adsorption is a favorable process and the modified bentonite has good potential in removing hexavalent Cr using sulfuric acid.

  3. Relationship between Pd oxidation states on TiO(2) and the photocatalytic oxidation behaviors of nitric oxide.

    Science.gov (United States)

    Wu, Zhongbiao; Sheng, Zhongyi; Wang, Haiqiang; Liu, Yue

    2009-09-01

    This study has been undertaken to investigate the relationship between Pd oxidation states on TiO(2) photocatalysts and their photocatalytic oxidation behaviors of NO. Three types of Pd-modified TiO(2) with different Pd oxidation states were prepared by wet impregnation method, neutralization method and photodeposition method, respectively. And these Pd-modified photocatalysts were characterized by X-ray diffraction analysis, X-ray photoelectron spectrum analysis (XPS), UV-Vis diffuse reflectance spectra and temperature programmed desorption (TPD). It was found from XPS results that the dominant oxidation states of Pd on these Pd-modified TiO(2) catalysts were Pd(2+), PdO, and Pd(0), respectively. NO-TPD results showed that the NO adsorption capacity was improved greatly by the modification of Pd(2+) ions. The activity tests showed that Pd-modified TiO(2) by a wet impregnation method increased photocatalytic activity compared to pure TiO(2) (Degussa P25). It was concluded that Pd(2+) ions on as-prepared TiO(2) catalysts provided key contributions to the improvement of photocatalytic activity. However, Pd(0) and PdO deposits on TiO(2) almost had no positive effect on NO oxidation. The mechanism of photocatalytic oxidation of NO in gas phase over Pd-modified TiO(2) was also proposed.

  4. Oxidation Potential, Not Crystal Structure, Controls the Oxidation State of Iron in Perovskite

    Science.gov (United States)

    Panero, W. R.; Pigott, J. S.; Watson, H. C.; Scharenberg, M.; Green, H. W.; McComb, D. W.; Williams, R. E.

    2013-12-01

    The mantle's oxidation state has broad implications on the state and evolution of the earth's interior. The relatively high oxidation potential of the upper mantle is such that iron is predominantly Fe2+ with small amounts of Fe3+ . Fe3+ is more stable than Fe2+ in the dominant lower mantle mineral, perovskite, despite the fact that the effect of pressure is to reduce the oxidizing potential of a system. It is therefore suggested that iron undergoes a disproportionation reaction of 3Fe2+ =2Fe3+ +Fe0 , controlled by the crystallography instead of oxidation potential. We crystallized synthetic enstatite glass with 5% Al2O3, 14% FeO, and 3% Fe2O3 in the laser-heated diamond anvil cell at 25-63 GPa and 1700-2800 K. We find that for temperatures nm iron precipitates on grain boundaries. The precipitates have small amounts of dissolved oxygen, but are Mg- and Al- free. We interpret that the stishovite is forming due to the oxidation of the ferric iron to ferrous iron according to (Mg2+,Al3+)(Fe3+,Si4+)O3 +SiO2 + Fe0 while the lower-temperature samples crystallizing as approximately (Mg2+ Fe2+ Al3+ )(Fe3+ Al3+ Si4+ )O3. We observe 2.8(2) Å3 volume expansion of the perovskite and a 28(2) GPa decrease in compressibility of the perovskite relative to the perovskite forming at lower temperature, consistent with the proposed compositions of the perovskites. As the increased temperature increases the oxidation potential of the system, we suggest that the oxidation state of iron in perovskite is dependent on oxidation potential as opposed to perovskite's crystal structure. Transmission Electron Microscopy (TEM) coupled with Electron Energy Loss Spectroscopy (EELS) show iron precipitation on grain boundaries supporting the conclusion. We present a discussion of the results and implications for core formation and lower mantle dynamics.

  5. Mapping the Iron Oxidation State in Martian Meteorites

    Science.gov (United States)

    Martin, A. M.; Treimann, A. H.; Righter, K.

    2017-01-01

    Several types of Martian igneous meteorites have been identified: clinopyroxenites (nakhlites), basaltic shergottites, peridotitic shergottites, dunites (chassignites) and orthopyroxenites [1,2]. In order to constrain the heterogeneity of the Martian mantle and crust, and their evolution through time, numerous studies have been performed on the iron oxidation state of these meteorites [3,4,5,6,7,8,9]. The calculated fO2 values all lie within the FMQ-5 to FMQ+0.5 range (FMQ representing the Fayalite = Magnetite + Quartz buffer); however, discrepancies appear between the various studies, which are either attributed to the choice of the minerals/melts used, or to the precision of the analytical/calculation method. The redox record in volcanic samples is primarily related to the oxidation state in the mantle source(s). However, it is also influenced by several deep processes: melting, crystallization, magma mixing [10], assimilation and degassing [11]. In addition, the oxidation state in Martian meteorites is potentially affected by several surface processes: assimilation of sediment/ crust during lava flowing at Mars' surface, low temperature micro-crystallization [10], weathering at the surface of Mars and low temperature reequilibration, impact processes (i.e. high pressure phase transitions, mechanical mixing, shock degassing and melting), space weathering, and weathering on Earth (at atmospheric conditions different from Mars). Decoding the redox record of Martian meteorites, therefore, requires large-scale quantitative analysis methods, as well as a perfect understanding of oxidation processes.

  6. Biodegradation of the metallic carcinogen hexavalent chromium Cr(VI) by an indigenously isolated bacterial strain

    National Research Council Canada - National Science Library

    Das, Alok Prasad; Mishra, Susmita

    2010-01-01

    Hexavalent chromium [Cr(VI)], a potential mutagen and carcinogen, is regularly introduced into the environment through diverse anthropogenic activities, including electroplating, leather tanning, and pigment manufacturing...

  7. Oxidative Stress and Heart Failure in Altered Thyroid States

    Directory of Open Access Journals (Sweden)

    Pallavi Mishra

    2012-01-01

    Full Text Available Increased or reduced action of thyroid hormone on certain molecular pathways in the heart and vasculature causes relevant cardiovascular derangements. It is well established that hyperthyroidism induces a hyperdynamic cardiovascular state, which is associated with a faster heart rate, enhanced left ventricular systolic and diastolic function whereas hypothyroidism is characterized by the opposite changes. Hyperthyroidism and hypothyroidism represent opposite clinical conditions, albeit not mirror images. Recent experimental and clinical studies have suggested the involvement of ROS tissue damage under altered thyroid status. Altered-thyroid state-linked changes in heart modify their susceptibility to oxidants and the extent of the oxidative damage they suffer following oxidative challenge. Chronic increase in the cellular levels of ROS can lead to a catastrophic cycle of DNA damage, mitochondrial dysfunction, further ROS generation and cellular injury. Thus, these cellular events might play an important role in the development and progression of myocardial remodeling and heart failure in altered thyroid states (hypo- and hyper-thyroidism. The present review aims at elucidating the various signaling pathways mediated via ROS and their modulation under altered thyroid state and the possibility of antioxidant therapy.

  8. Oxidatively generated DNA/RNA damage in psychological stress states

    DEFF Research Database (Denmark)

    Jørgensen, Anders

    2013-01-01

    -oxodG and 8-oxoGuo, respectively). The main hypothesis was that psychological stress states are associated with increased DNA/RNA damage from oxidation. In a study of 40 schizophrenia patients and 40 healthy controls matched for age and gender, we found that 8-oxodG/8-oxoGuo excretion was increased...... correlations between 8-oxodG/8-ocoGuo excretion and 9AM plasma cortisol, but no associations to perceived stress. In an animal study of experimentally induced chronic stress performed in metabolism cages, we found no increase in urinary 8-oxodG/8-oxoGuo or cerebral (hippocampal and frontal cortex) levels...... between the 24 h urinary cortisol excretion and the excretion of 8-oxodG/8-oxoGuo, determined in the same samples. Collectively, the studies could not confirm an association between psychological stress and oxidative stress on nucleic acids. Systemic oxidatively generated DNA/RNA damage was increased...

  9. Dimensional control of cobalt spin state in oxide superlattices

    Science.gov (United States)

    Jeong, Da Woon; Choi, W. S.; Okamoto, S.; Sohn, C. H.; Park, H. J.; Kim, J.-Y.; Lee, H. N.; Kim, K. W.; Moon, S. J.; Noh, T. W.

    2013-03-01

    Perovskite cobalt oxide is a very intriguing system with various spin states owing to the delicate balance between crystal field splitting and Hund exchange energy. In this talk, we show that its spin state can be altered through dimensional control, enabled by digital synthesis of perovskite cobalt oxide superlattices. We employed a few unit cells of LaCoO3 as an active magnetic layer, separated by LaAlO3 spacer layer. High quality [(LaCoO3) n (LaAlO3) n ]8 (n = 2, 6, and 10) superlattices were fabricated using pulsed laser epitaxy. Spectroscopic tools including x-ray absorption spectroscopy and optical spectroscopy revealed clear evolution of the electronic structure and resultant spin state by changing dimensionality. Specifically, the spin state changed from a high to a low spin state with a larger optical band gap, as the dimension reduced from 3D to 2D. Dynamic mean field calculation supported the critical role of dimensionality on the spin state and electronic structure of LaCoO3.

  10. Evolution of the Oxidation State of the Earth's Mantle

    Science.gov (United States)

    Danielson, L. R.; Righter, K.; Keller, L.; Christoffersen, E.; Rahman, Z.

    2015-01-01

    The oxidation state of the Earth's mantle during formation remains an unresolved question, whether it was constant throughout planetary accretion, transitioned from reduced to oxidized, or from oxidized to reduced. We investigate the stability of Fe3(+) at depth, in order to constrain processes (water, late accretion, dissociation of FeO) which may reduce or oxidize the Earth's mantle. In our previous experiments on shergottite compositions, variable fO2, T, and P less than 4 GPa, Fe3(+)/sigma Fe decreased slightly with increasing P, similar to terrestrial basalt. For oxidizing experiments less than 7GPa, Fe3(+)/sigma Fe decreased as well, but it's unclear from previous modelling whether the deeper mantle could retain significant Fe3(+). Our current experiments expand our pressure range deeper into the Earth's mantle and focus on compositions and conditions relevant to the early Earth. Preliminary multi-anvil experiments with Knippa basalt as the starting composition were conducted at 5-7 GPa and 1800 C, using a molybdenum capsule to set the fO2 near IW, by buffering with Mo-MoO3. TEM and EELS analyses revealed the run products quenched to polycrystalline phases, with the major phase pyroxene containing approximately equal to Fe3(+)/2(+). Experiments are underway to produce glassy samples that can be measured by EELS and XANES, and are conducted at higher pressures.

  11. Bond valence parameterslinearly dependent on the molybdenum oxidation states

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Based on the available crystal data, a linear correlation between R0, the bond valence parameter for a Mo-containing chemical bond, and the Mo oxidation state n was developed for the first time. Using the "universal" value of the parameter B = 0.037 nm, the linear equations of R0-n for Mo-X (X: O, S, N, Cl and F) bonds were established. The oxidation-state independent Mo-O bond valence parameters, R0 = 0.18788 nm and B = 0.03046 nm, published recently have been shown to be a special case of the linearly correlated functions. Some bond valence sum calculations in compounds containing only Mo-O bonds using these para- meters are presented.

  12. Inhibition of CO poisoning on Pt catalyst coupled with the reduction of toxic hexavalent chromium in a dual-functional fuel cell.

    Science.gov (United States)

    Chung, Dong Young; Kim, Hyoung-il; Chung, Young-Hoon; Lee, Myeong Jae; Yoo, Sung Jong; Bokare, Alok D; Choi, Wonyong; Sung, Yung-Eun

    2014-12-12

    We propose a method to enhance the fuel cell efficiency with the simultaneous removal of toxic heavy metal ions. Carbon monoxide (CO), an intermediate of methanol oxidation that is primarily responsible for Pt catalyst deactivation, can be used as an in-situ reducing agent for hexavalent chromium (Cr (VI)) with reactivating the CO-poisoned Pt catalyst. Using electro-oxidation measurements, the oxidation of adsorbed CO molecules coupled with the concurrent conversion of Cr (VI) to Cr (III) was confirmed. This concept was also successfully applied to a methanol fuel cell to enhance its performance efficiency and to remove toxic Cr (VI) at the same time.

  13. Hexavalent Chrome Free Coatings for Electronics Applications: Joint Test Report

    Science.gov (United States)

    Kessel, Kurt

    2012-01-01

    Regardless of the corrosivity of the environment, all metals require periodic maintenance activity to guard against the insidious effects of corrosion and thus ensure that alloys meet or exceed design or performance life. The standard practice for protecting metallic substrates is the application of a coating system. Applied coating systems work via a variety of methods (barrier, galvanic, and/or inhibitor) and adhere to the substrate through a combination of chemical and physical bonds. For years hexavalent chromium has been a widely used element within applied coating systems because of its self healing and corrosion resistant properties. Occupational Safety and Health Administration (OSHA) studies have concluded that hexavalent chromium (hex chrome) is carcinogenic and poses significant risk to human health. On May 5, 2011 amendments to the Defense Federal Acquisition Regulation Supplement (DFARS) were issued in the Federal Register. Subpart 223.73 prohibits contracts from requiring hexavalent chromium in deliverables unless certain exceptions apply. These exceptions include authorization from a general or flag officer and members of the Senior Executive Service from a Program Executive Office, and unmodified legacy systems. Otherwise, Subpart 252.223-7008 provides the contract clause prohibiting contractors from using or delivering hexavalent chromium in a concentration greater than 0.1 percent by weight for all new contracts and to be included down to subcontractors for supplies, maintenance and repair services, and construction materials. National Aeronautics and Space Administration (NASA), Department of Defense (DoD), and industry stakeholders continue to search for alternatives to hex chrome in coatings applications that meet their performance requirements in corrosion protection, cost, operability, and health and safety, while typically specifying that performance must be equal to or greater than existing systems.

  14. Pentavalent Uranium Chemistry - Synthetic Pursuit Of A Rare Oxidation State

    Energy Technology Data Exchange (ETDEWEB)

    Graves, Christopher R [Los Alamos National Laboratory; Kiplinger, Jaqueline L [Los Alamos National Laboratory

    2009-01-01

    This feature article presents a comprehensive overview of pentavalent uranium systems in non-aqueous solution with a focus on the various synthetic avenues employed to access this unusual and very important oxidation state. Selected characterization data and theoretical aspects are also included. The purpose is to provide a perspective on this rapidly evolving field and identify new possibilities for future developments in pentavalent uranium chemistry.

  15. Fast and Highly Efficient Solid State Oxidation of Thiols

    Directory of Open Access Journals (Sweden)

    Nasrin Haghighat

    2007-03-01

    Full Text Available A fast and efficient solid state method for the chemoselective room temperature oxidative coupling of thiols to afford their corresponding disulfides using inexpensive and readily available moist sodiumperiodate as the reagent is described. The reaction was applicable to a variety of thiols giving high yields after short reaction times. Comparison of yield/time ratios of this method with some of those reported in the literature shows the superiority of this reagent over others under these conditions.

  16. Carbothermal synthesis of ordered mesoporous carbon-supported nano zero-valent iron with enhanced stability and activity for hexavalent chromium reduction.

    Science.gov (United States)

    Dai, Ying; Hu, Yuchen; Jiang, Baojiang; Zou, Jinlong; Tian, Guohui; Fu, Honggang

    2016-05-15

    Composites of nano zero-valent iron (nZVI) and ordered mesoporous carbon (OMC) are prepared by using simultaneous carbothermal reduction methods. The reactivity and stability of nZVI are expected to be enhanced by embedding it in the ordered pore channels. The structure characteristics of nZVI/OMC and the removal pathway for hexavalent chromium (Cr(VI)) by nZVI/OMC are investigated. Results show that nZVI/OMC with a surface area of 715.16 m(2) g(-1) is obtained at 900 °C. nZVI with particle sizes of 20-30 nm is uniformly embedded in the OMC skeleton. The stability of nZVI is enhanced by surrounding it with a broad carbon layer and a little γ-Fe is derived from the passivation of α-Fe. Detection of ferric state (Fe 2p3/2, around 711.2eV) species confirms that part of the nZVI on the outer surface is inevitably oxidized by O2, even when unused. The removal efficiency of Cr(VI) (50 mg L(-1)) by nZVI/OMC is near 99% within 10 min through reduction (dominant mechanism) and adsorption. nZVI/OMC has the advantage in removal efficiency and reusability in comparison to nZVI/C, OMC and nZVI. This study suggests that nZVI/OMC has the potential for remediation of heavy metal pollution in water.

  17. 40 CFR 749.68 - Hexavalent chromium-based water treatment chemicals in cooling systems.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Hexavalent chromium-based water treatment chemicals in cooling systems. 749.68 Section 749.68 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT WATER TREATMENT CHEMICALS Air Conditioning and Cooling Systems § 749.68 Hexavalent...

  18. Chelation and stabilization of berkelium in oxidation state +IV

    Science.gov (United States)

    Deblonde, Gauthier J.-P.; Sturzbecher-Hoehne, Manuel; Rupert, Peter B.; An, Dahlia D.; Illy, Marie-Claire; Ralston, Corie Y.; Brabec, Jiri; de Jong, Wibe A.; Strong, Roland K.; Abergel, Rebecca J.

    2017-09-01

    Berkelium (Bk) has been predicted to be the only transplutonium element able to exhibit both +III and +IV oxidation states in solution, but evidence of a stable oxidized Bk chelate has so far remained elusive. Here we describe the stabilization of the heaviest 4+ ion of the periodic table, under mild aqueous conditions, using a siderophore derivative. The resulting Bk(IV) complex exhibits luminescence via sensitization through an intramolecular antenna effect. This neutral Bk(IV) coordination compound is not sequestered by the protein siderocalin—a mammalian metal transporter—in contrast to the negatively charged species obtained with neighbouring trivalent actinides americium, curium and californium (Cf). The corresponding Cf(III)-ligand-protein ternary adduct was characterized by X-ray diffraction analysis. Combined with theoretical predictions, these data add significant insight to the field of transplutonium chemistry, and may lead to innovative Bk separation and purification processes.

  19. Americium separation from nuclear fuel dissolution using higher oxidation states.

    Energy Technology Data Exchange (ETDEWEB)

    Bruce J. Mincher

    2009-09-01

    Much of the complexity in current AFCI proposals is driven by the need to separate the minor actinides from the lanthanides. Partitioning and recycling Am, but not Cm, would allow for significant simplification because Am has redox chemistry that may be exploited while Cm does not. Here, we have explored methods based on higher oxidation states of Am (AmV and AmVI) to partition Am from the lanthanides. In a separate but related approach we have also initiated an investigation of the utility of TRUEX Am extraction from thiocyanate solution. The stripping of loaded TRUEX by Am oxidation or SCN- has not yet proved successful; however, the partitioning of inextractable AmV by TRUEX shows promise.

  20. Oxidation states of molybdenum in oxide films formed in sulphuric acid and sodium hydroxide

    Energy Technology Data Exchange (ETDEWEB)

    Okonkwo, I.A.; Doff, J.; Baron-Wiechec, A. [Corrosion and Protection Centre, School of Materials, The University of Manchester, Manchester M13 9PL (United Kingdom); Jones, G. [Waters Corporation, Floats Rd, Roundthorn Ind. Est., Manchester M23 9LZ (United Kingdom); Koroleva, E.V. [Corrosion and Protection Centre, School of Materials, The University of Manchester, Manchester M13 9PL (United Kingdom); Skeldon, P., E-mail: p.skeldon@manchester.ac.uk [Corrosion and Protection Centre, School of Materials, The University of Manchester, Manchester M13 9PL (United Kingdom); Thompson, G.E. [Corrosion and Protection Centre, School of Materials, The University of Manchester, Manchester M13 9PL (United Kingdom)

    2012-07-31

    X-ray photoelectron spectroscopy is used to investigate the oxidation states of molybdenum in thin films formed potentiostatically, over a range of potentials, in either 1 mol dm{sup -3} H{sub 2}SO{sub 4} or 10 mol dm{sup -3} NaOH at 20 Degree-Sign C. Mo 3d spectra suggested that MoO{sub 2} and Mo(OH){sub 2} were the main components of the films, with smaller amounts of MoO{sub 3} and possibly Mo{sub 2}O{sub 5}. O 1s spectra indicated the presence of oxygen as oxide and hydroxide species and as bound water. Ion beam analysis revealed the formation of thin films at all potentials, with significant losses of oxidized molybdenum to the electrolyte. - Highlights: Black-Right-Pointing-Pointer Oxides are formed on molybdenum in sulphuric acid and sodium hydroxide solutions. Black-Right-Pointing-Pointer Molybdenum IV and VI are identified by XPS, with MoO2 species dominating. Black-Right-Pointing-Pointer Thicknesses of films are determined by ion beam analysis for a range of potentials. Black-Right-Pointing-Pointer Films form at low efficiency due to loss of molybdenum species to electrolyte.

  1. Intestinal Oxidative State Can Alter Nutrient and Drug Bioavailability

    Directory of Open Access Journals (Sweden)

    Faria Ana

    2009-01-01

    Full Text Available Organic cations (OCs are substances of endogenous (e.g., dopamine, choline or exogenous (e.g., drugs like cimetidine origin that are positively charged at physiological ph. since many of these compounds can not pass the cell membrane freely, their transport in or out of cells must be mediated by specific transport systems. Transport by organic cation transporters (OCTs can be regulated rapidly by altering their trafficking and/or affinities in response to stimuli. However, for example, a specific disease could lead to modifications in the expression of OCTs. Chronic exposure to oxidative stress has been suggested to alter regulation and functional activity of proteins through several pathways. According to results from a previous work, oxidation-reduction pathways were thought to be involved in intestinal organic cation uptake modulation. The present work was performed in order to evaluate the influence of oxidative stressors, especially glutathione, on the intestinal organic cation absorption. For this purpose, the effect of compounds with different redox potential (glutathione, an endogenous antioxidant, and procyanidins, diet antioxidants was assessed on MPP+ (1-methyl-4-phenylpyridinium iodide uptake in an enterocyte cell line (Caco-2. Caco-2 cells were subcultured with two different media conditions (physiological: 5 mM glucose, referred as control cells; and high-glucose: 25 mM glucose, referred as HG cells. In HG cells, the uptake was significantly lower than in control cells. Redox changing interventions affected Mpp+ uptake, both in control and in high-glucose Caco-2 cells. Cellular glutathione levels could have an important impact on membrane transporter activity. The results indicate that modifications in the cellular oxidative state modulate MPP+ uptake by Caco-2 cells. Such modifications may reflect in changes of nutrient and drug bioavailability.

  2. An evaluation of in vivo models for toxicokinetics of hexavalent chromium in the stomach

    Energy Technology Data Exchange (ETDEWEB)

    Sasso, A.F., E-mail: sasso.alan@epa.gov; Schlosser, P.M., E-mail: schlosser.paul@epa.gov

    2015-09-15

    Hexavalent chromium (Cr6) is a drinking water contaminant that has been detected in most of the water systems throughout the United States. In 2-year drinking water bioassays, the National Toxicology Program (NTP) found clear evidence of carcinogenic activity in male and female rats and mice. Because reduction of Cr6 to trivalent chromium (Cr3) is an important detoxifying step in the gastrointestinal (GI) tract prior to systemic absorption, models have been developed to estimate the extent of reduction in humans and animals. The objective of this work was to use a revised model of ex vivo Cr6 reduction kinetics in gastric juice to analyze the potential reduction kinetics under in vivo conditions for mice, rats and humans. A published physiologically-based pharmacokinetic (PBPK) model was adapted to incorporate the new reduction model. This paper focuses on the toxicokinetics of Cr6 in the stomach compartment, where most of the extracellular Cr6 reduction is believed to occur in humans. Within the range of doses administered by the NTP bioassays, neither the original nor revised models predict saturation of stomach reducing capacity to occur in vivo if applying default parameters. However, both models still indicate that mice exhibit the lowest extent of reduction in the stomach, meaning that a higher percentage of the Cr6 dose may escape stomach reduction in that species. Similarly, both models predict that humans exhibit the highest extent of reduction at low doses. - Highlights: • We outline a new in vivo model for hexavalent chromium reduction in the stomach. • We examine in vivo reduction for mice, rats, and humans under varying conditions. • Species differences in toxicokinetics may explain susceptibility. • We show that a simplified stomach reduction model is adequate for extrapolation. • Internal dose uncertainties still exist.

  3. Composition and oxidation state of sulfur in atmospheric particulate matter

    Science.gov (United States)

    Longo, Amelia F.; Vine, David J.; King, Laura E.; Oakes, Michelle; Weber, Rodney J.; Huey, Lewis Gregory; Russell, Armistead G.; Ingall, Ellery D.

    2016-10-01

    The chemical and physical speciation of atmospheric sulfur was investigated in ambient aerosol samples using a combination of sulfur near-edge x-ray fluorescence spectroscopy (S-NEXFS) and X-ray fluorescence (XRF) microscopy. These techniques were used to determine the composition and oxidation state of sulfur in common primary emission sources and ambient particulate matter collected from the greater Atlanta area. Ambient particulate matter samples contained two oxidation states: S0 and S+VI. Ninety-five percent of the individual aerosol particles (> 1 µm) analyzed contain S0. Linear combination fitting revealed that S+VI in ambient aerosol was dominated by ammonium sulfate as well as metal sulfates. The finding of metal sulfates provides further evidence for acidic reactions that solubilize metals, such as iron, during atmospheric transport. Emission sources, including biomass burning, coal fly ash, gasoline, diesel, volcanic ash, and aerosolized Atlanta soil, and the commercially available bacterium Bacillus subtilis, contained only S+VI. A commercially available Azotobacter vinelandii sample contained approximately equal proportions of S0 and S+VI. S0 in individual aerosol particles most likely originates from primary emission sources, such as aerosolized bacteria or incomplete combustion.

  4. Proteomic indicators of oxidation and hydration state in colorectal cancer

    Directory of Open Access Journals (Sweden)

    Jeffrey M. Dick

    2016-07-01

    Full Text Available New integrative approaches are needed to harness the potential of rapidly growing datasets of protein expression and microbial community composition in colorectal cancer. Chemical and thermodynamic models offer theoretical tools to describe populations of biomacromolecules and their relative potential for formation in different microenvironmental conditions. The average oxidation state of carbon (ZC can be calculated as an elemental ratio from the chemical formulas of proteins, and water demand per residue ( ${\\overline{n}}_{{\\mathrm{H}}_{2}\\mathrm{O}}$ n ¯ H 2 O is computed by writing the overall formation reactions of proteins from basis species. Using results reported in proteomic studies of clinical samples, many datasets exhibit higher mean ZC or ${\\overline{n}}_{{\\mathrm{H}}_{2}\\mathrm{O}}$ n ¯ H 2 O of proteins in carcinoma or adenoma compared to normal tissue. In contrast, average protein compositions in bacterial genomes often have lower ZC for bacteria enriched in fecal samples from cancer patients compared to healthy donors. In thermodynamic calculations, the potential for formation of the cancer-related proteins is energetically favored by changes in the chemical activity of H2O and fugacity of O2 that reflect the compositional differences. The compositional analysis suggests that a systematic change in chemical composition is an essential feature of cancer proteomes, and the thermodynamic descriptions show that the observed proteomic transformations in host tissue could be promoted by relatively high microenvironmental oxidation and hydration states.

  5. Study on anaerobic treatment of wastewater containing hexavalent chromium*

    OpenAIRE

    Xu, Yan-Bin; Xiao, Hua-hua; Sun, Shui-yu

    2005-01-01

    A self-made anaerobic bio-filter bed which was inoculated with special sludge showed high efficiency in removing hexavalent chromium. When pump flow was 47 ml/min and CODCr of wastewater was about 140 mg/L, it took 4 h to decrease the Cr6+ concentrations from about 60 mg/L to under 0.5 mg/L, compared with 14 h without carbon source addition. Cr6+ concentrations ranged from 64.66 mg/L to 75.53 mg/L, the system efficiency was excellent. When Cr6+ concentration reached 95.47 mg/L, the treatment ...

  6. Microbial reduction of chromium from the hexavalent to divalent state

    Science.gov (United States)

    Daulton, Tyrone L.; Little, Brenda J.; Jones-Meehan, Joanne; Blom, Douglas A.; Allard, Lawrence F.

    2007-02-01

    We demonstrate that Shewanella oneidensis, a metal-reducing bacteria species with cytoplasmic-membrane-bound reductases and remarkably diverse respiratory capabilities, reduced Cr(VI) to Cr(II) in anaerobic cultures where chromate was the sole terminal electron acceptor. Individual cell microanalysis by transmission electron microscopy (TEM) using electron energy-loss spectroscopy (EELS) and energy dispersive X-ray spectroscopy (EDXS) demonstrates Cr(II) concentrated near the cytoplasmic membrane, suggesting the terminal reduction pathway is intracellularly localized. Further, estimated cellular Cr(II) concentrations are relatively high at upwards of 0.03-0.09 g Cr/g bacterium. Accumulation of Cr(II) is observed in S. oneidensis cells prior to the formation of submicron-sized precipitates of insoluble Cr(III) on their surfaces. Furthermore, under anaerobic conditions, Cr(III) precipitates that encrust cells are shown to contain Cr(II) that is likely bound in the net negatively charged extracellular biopolymers which can permeate the surfaces of the precipitates. In otherwise nearly identical incubations, Cr(III) precipitate formation was observed in cultures maintained anaerobic with bubbled nitrogen but not in three replicate cultures in an anaerobic chamber.

  7. Microbial Reduction of Chromium from the Hexavalent to Divalent State

    Science.gov (United States)

    2007-01-01

    1987, 1989) and the tendency of dissolved Cr(III) to be adsorbed by organic carbon (Fukushima et al., 1995) as well as mineral surfaces (Griffin et al...Neal et al., 2002; Kalabegishvili et al., 1987, 1989) and their soluble organo complexes et al., 2003). Electron paramagnetic resonance (EPR) mea- (Puzon... mineral chemistry has not been rigorously character- whether the Cr was concentrated as precipitates on cell sur- ized. Similar to Cr(OH) 3-nH 2 0

  8. Electrochemical removal of hexavalent chromium from wastewater using Platinum-Iron/Iron-carbon nanotubes and bipolar Electrodes

    Directory of Open Access Journals (Sweden)

    Hoshyar Hossini

    2015-01-01

    Full Text Available Background: In recent decades, electrocoagulation (EC has engrossed much attention as an environmental-friendly and effectiveness process. In addition, the EC process is a potential suitable way for treatment of wastewater with concern to costs and environment. The object of this study was electrochemical evaluation of chromium removal from industrial wastewater using Platinum and carbon nanotubes electrodes. Materials and Methods: The effect of key variables including pH (3–9, hexavalent chromium concentration (50–300 mg/l, supporting electrolyte (NaCl, KCl, Na2CO3 and KNO3 and its dosage, Oxidation-Reduction variations, sludge generation rate and current density (2–20 mA/cm2 was determined. Results: Based on experimental data, optimum conditions were determined in 20, 120 min, pH 3, NaCl 0.5% and 100 mg/L initial concentration of chromium. Conclusions: Removal of hexavalent chromium from the wastewater could be successfully performanced using Platinum-Iron/Iron-carbon nanotubes and bipolar Electrodes.

  9. Effects of hexavalent chromium on performance and microbial community of an aerobic granular sequencing batch reactor.

    Science.gov (United States)

    Wang, Zichao; Gao, Mengchun; She, Zonglian; Jin, Chunji; Zhao, Yangguo; Yang, Shiying; Guo, Liang; Wang, Sen

    2015-03-01

    The performance and microbial community of an aerobic granular sequencing batch reactor (GSBR) were investigated at different hexavalent chromium (Cr(VI)) concentrations. The COD and NH4 (+)-N removal efficiencies decreased with the increase in Cr(VI) concentration from 0 to 30 mg/L. The specific oxygen utilization rate (SOUR) decreased from 34.86 to 12.18 mg/(g mixed liquor suspended sludge (MLSS)·h) with the increase in Cr(VI) concentration from 0 to 30 mg/L. The specific ammonium oxidation rate (SAOR), specific nitrite oxidation rate (SNOR), and specific nitrate reduction rate (SNRR) decreased with the increase in Cr(VI) concentration, whereas the SNRR was always higher than the sum of SAOR and SNOR at 0-30 mg/L Cr(VI). The scanning electron micrographs (SEM) showed some undefined particles on the surface of filamentous bacteria that might be the chelation of chromium and macromolecular organics at 30 mg/L Cr(VI). The denaturing gradient gel electrophoresis (DGGE) profiles revealed that some microorganisms adapting to high Cr(VI) concentration gradually became the predominant bacteria, while others without Cr(VI)-tolerance capacity tended to deplete or weaken. Some bacteria could tolerate the toxicity of high Cr(VI) concentration in the aerobic GSBR, such as Propionibacteriaceae bacterium, Ochrobactrum anthropi, and Micropruina glycogenica.

  10. Determination of the oxidation states of metals and metalloids: An analytical review

    Science.gov (United States)

    Vodyanitskii, Yu. N.

    2013-12-01

    The hazard of many heavy metals/metalloids in the soil depends on their oxidation state. The problem of determining the oxidation state has been solved due to the use of synchrotron radiation methods with the analysis of the X-ray absorption near-edge structure (XANES). The determination of the oxidation state is of special importance for some hazardous heavy elements (arsenic, antimony, selenium, chromium, uranium, and vanadium). The mobility and hazard of each of these elements depend on its oxidation state. The mobilities are higher at lower oxidation states of As, Cr, V, and Se and at higher oxidation states of Sb and U. The determination of the oxidation state of arsenic has allowed revealing its fixation features in the rhizosphere of hydrophytes. The known oxidation states of chromium and uranium are used for the retention of these elements on geochemical barriers. Different oxidation states have been established for vanadium displacing iron in goethite. The determination of the oxidation state of manganese in the rhizosphere and the photosynthetic apparatus of plants is of special importance for agricultural chemists.

  11. Study on anaerobic treatment of wastewater containing hexavalent chromium

    Institute of Scientific and Technical Information of China (English)

    XU Yan-bin; XIAO Hua-hua; SUN Shui-yu

    2005-01-01

    A self-made anaerobic bio-filter bed which was inoculated with special sludge showed high efficiency in removing hexavalent chromium. When pump flow was 47 ml/min and CODCr ofwastewater was about 140 mg/L, it took 4 h to decrease the Cr6+ concentrations from about 60 mg/L to under 0.5 mg/L, compared with 14 h without carbon source addition. Cr6+ concentrations ranged from 64.66 mg/L to 75.53 mg/L, the system efficiency was excellent. When Cr6+ concentration reached 95.47 mg/L,the treatment time was prolonged to 7.5 h. Compared with the contrast system, the system with trace metals showed clear superiority in that the Cr6+ removal rate increased by 21.26%. Some analyses also showed that hexavalent chromium could probably be bio-reduced to trivalent chromium, and that as a result, the chrome hydroxide sediment was formed on the surface of microorganisms.

  12. Study on anaerobic treatment of wastewater containing hexavalent chromium.

    Science.gov (United States)

    Xu, Yan-bin; Xiao, Hua-hua; Sun, Shui-yu

    2005-06-01

    A self-made anaerobic bio-filter bed which was inoculated with special sludge showed high efficiency in removing hexavalent chromium. When pump flow was 47 ml/min and COD(Cr) of wastewater was about 140 mg/L, it took 4 h to decrease the Cr6+ concentrations from about 60 mg/L to under 0.5 mg/L, compared with 14 h without carbon source addition. Cr6+ concentrations ranged from 64.66 mg/L to 75.53 mg/L, the system efficiency was excellent. When Cr6+ concentration reached 95.47 mg/L, the treatment time was prolonged to 7.5 h. Compared with the contrast system, the system with trace metals showed clear superiority in that the Cr6+ removal rate increased by 21.26%. Some analyses also showed that hexavalent chromium could probably be bio-reduced to trivalent chromium, and that as a result, the chrome hydroxide sediment was formed on the surface of microorganisms.

  13. Study on anaerobic treatment of wastewater containing hexavalent chromium*

    Science.gov (United States)

    Xu, Yan-bin; Xiao, Hua-hua; Sun, Shui-yu

    2005-01-01

    A self-made anaerobic bio-filter bed which was inoculated with special sludge showed high efficiency in removing hexavalent chromium. When pump flow was 47 ml/min and CODCr of wastewater was about 140 mg/L, it took 4 h to decrease the Cr6+ concentrations from about 60 mg/L to under 0.5 mg/L, compared with 14 h without carbon source addition. Cr6+ concentrations ranged from 64.66 mg/L to 75.53 mg/L, the system efficiency was excellent. When Cr6+ concentration reached 95.47 mg/L, the treatment time was prolonged to 7.5 h. Compared with the contrast system, the system with trace metals showed clear superiority in that the Cr6+ removal rate increased by 21.26%. Some analyses also showed that hexavalent chromium could probably be bio-reduced to trivalent chromium, and that as a result, the chrome hydroxide sediment was formed on the surface of microorganisms. PMID:15909347

  14. Catalytic partial oxidation of methane to synthesis gas over a ruthenium catalyst: the role of the oxidation state.

    Science.gov (United States)

    Rabe, Stefan; Nachtegaal, Maarten; Vogel, Frédéric

    2007-03-28

    The catalytic partial oxidation of methane to synthesis gas over ruthenium catalysts was investigated by thermogravimetry coupled with infrared spectroscopy (TGA-FTIR) and in situ X-ray absorption spectroscopy (XAS). It was found that the oxidation state of the catalyst influences the product formation. On oxidized ruthenium sites, carbon dioxide was formed. The reduced catalyst yielded carbon monoxide as a product. The influence of the temperature was also investigated. At temperatures below the ignition point of the reaction, the catalyst was in an oxidized state. At temperatures above the ignition point, the catalyst was reduced. This was also confirmed by the in situ XAS spectroscopy. The results indicate that both a direct reaction mechanism as well as a combustion-reforming mechanism can occur. The importance of knowing the oxidation state of the surface is discussed and a method to determine it under reaction conditions is presented.

  15. Influence of vanadium oxidation states on the performance of V-Mg-Al mixed-oxide catalysts for the oxidative dehydrogenation of propane

    Energy Technology Data Exchange (ETDEWEB)

    Schacht, L. [IPN, Escuela Superior de Fisica y Matematicas, Departamento de Ciencia de Materiales, Av. IPN s/n, Edificio 9, Col. Lindavista, 07738 Mexico D. F. (Mexico); Navarrete, J.; Schacht, P.; Ramirez, M. A., E-mail: pschacha@imp.m [Instituto Mexicano del Petroleo, Programa de Ingenieria Molecular, Eje Central Lazaro Cardenas No. 152, 07730 Mexico D. F. (Mexico)

    2010-07-01

    V-Mg-Al mixed-oxide catalysts for oxidative dehydrogenation of propane were prepared by thermal decomposition of Mg-Al-layered double hydroxides with vanadium interlayer doping. The obtained catalysts were tested for the oxidative dehydrogenation of propane, obtaining good results in catalytic activity (conversion 16.55 % and selectivity 99.97 %) Results indicated that catalytic performance of these materials depends on how vanadium is integrated in the layered structure, which is determined by the Mg/Al ratio. Vanadium interlayer doping modifies the oxidation state of vanadium and consequently catalytic properties. Surface properties were studied by X-ray photoelectron spectroscopic and diffuse reflectance, UV-visible spectroscopy, and temperature programmed reduction. The analyses provided information about the oxidation state, before and after the reaction. From these results, it is suggested that selectivity to propylene and catalytic activity depend mainly of vanadium oxidation state. (Author)

  16. Measurement of soil carbon oxidation state and oxidative ratio by 13C nuclear magnetic resonance

    Science.gov (United States)

    Hockaday, W.C.; Masiello, C.A.; Randerson, J.T.; Smernik, R.J.; Baldock, J.A.; Chadwick, O.A.; Harden, J.W.

    2009-01-01

    The oxidative ratio (OR) of the net ecosystem carbon balance is the ratio of net O2 and CO2 fluxes resulting from photosynthesis, respiration, decomposition, and other lateral and vertical carbon flows. The OR of the terrestrial biosphere must be well characterized to accurately estimate the terrestrial CO2 sink using atmospheric measurements of changing O2 and CO2 levels. To estimate the OR of the terrestrial biosphere, measurements are needed of changes in the OR of aboveground and belowground carbon pools associated with decadal timescale disturbances (e.g., land use change and fire). The OR of aboveground pools can be measured using conventional approaches including elemental analysis. However, measuring the OR of soil carbon pools is technically challenging, and few soil OR data are available. In this paper we test three solid-state nuclear magnetic resonance (NMR) techniques for measuring soil OR, all based on measurements of the closely related parameter, organic carbon oxidation state (Cox). Two of the three techniques make use of a molecular mixing model which converts NMR spectra into concentrations of a standard suite of biological molecules of known C ox. The third technique assigns Cox values to each peak in the NMR spectrum. We assess error associated with each technique using pure chemical compounds and plant biomass standards whose Cox and OR values can be directly measured by elemental analyses. The most accurate technique, direct polarization solid-state 13C NMR with the molecular mixing model, agrees with elemental analyses to ??0.036 Cox units (??0.009 OR units). Using this technique, we show a large natural variability in soil Cox and OR values. Soil Cox values have a mean of -0.26 and a range from -0.45 to 0.30, corresponding to OR values of 1.08 ?? 0.06 and a range from 0.96 to 1.22. We also estimate the OR of the carbon flux from a boreal forest fire. Analysis of soils from nearby intact soil profiles imply that soil carbon losses associated

  17. Hexavalent chromium reduction with scrap iron in continuous-flow system. Part 2: Effect of scrap iron shape and size.

    Science.gov (United States)

    Gheju, M; Balcu, I

    2010-10-15

    Hexavalent chromium reduction with scrap iron has the advantage that two wastes are treated simultaneously. The reduction of hexavalent chromium by scrap iron was investigated in continuous system, using as reducing agent the following scrap iron shapes and sizes: (1) spiral fibers, (2) shavings, and (3) powder. The shape and size of scrap iron were found to have a significant influence on chromium and iron species concentration in column effluent, on column effluent pH and on Cr(VI) reduction mechanism. While for large scrap iron particles (spiral fibers) homogeneous reduction is the dominant Cr(VI) reduction process, for small scrap iron particles (powder) heterogeneous reduction appears to be the dominant reaction contributing to Cr(VI) reduction. All three shapes and sizes investigated in this work have both advantages and disadvantages. If found in sufficient quantities, scrap iron powder seem to be the optimum shape and size for the continuous reduction of Cr(VI), due to the following advantages: (1) the greatest reduction capacity, (2) the most important pH increase in column effluent (up to 6.3), (3) no chromium was detected in the column effluent during the first 60 h of the experiment, and (4) the lowest steady-state Cr(VI) concentration observed in column effluent (3.7 mg/L). But, despite of a lower reduction capacity in comparison with powder particles, spiral fibers and shavings have the advantage to result in large quantities from the mechanic processing of steel.

  18. Replacement for Cadmium Plating and Hexavalent Chromium on Fasteners and Electrical Connectors

    Science.gov (United States)

    2010-02-10

    radioactive materials, hexavalent chromium, (electroplating and coatings), cadmium (electroplating), mercury, or other highly toxic or carcinogenic...eliminate both UNCLASSIFIED: Dist A. Approved for public release Background - Alternative Choices • Numerous alternatives – Zinc nickel (Zn/Ni) – Tin...Plating • Aluminum Corrosion Performance –equivalent at same thickness • Heat Resistance – Trivalent Chrome protects up to about 400 F; Hexavalent

  19. Effective Management of Hexavalent Chromium (Cr+6) in DoD Organic and Inorganic Coatings Operations

    Science.gov (United States)

    2014-11-19

    Vinay V. Gadkari Battelle gadkariv@battelle.org 614-424-5751 Effective Management of Hexavalent Chromium (Cr+6) in DoD Organic and Inorganic...Coatings Operations Enhancing worker safety by minimizing health risks in hexavalent chromium environment 1 11/19/2014 John T. Stropki Battelle ...ADDRESS(ES) Battelle ,505 King Avenue,Columbus,OH,43201 8. PERFORMING ORGANIZATION REPORT NUMBER 9. SPONSORING/MONITORING AGENCY NAME(S) AND ADDRESS(ES

  20. Forest soil carbon oxidation state and oxidative ratio responses to elevated CO2

    Science.gov (United States)

    Hockaday, William C.; Gallagher, Morgan E.; Masiello, Caroline A.; Baldock, Jeffrey A.; Iversen, Colleen M.; Norby, Richard J.

    2015-09-01

    The oxidative ratio (OR) of the biosphere is the stoichiometric ratio (O2/CO2) of gas exchange by photosynthesis and respiration—a key parameter in budgeting calculations of the land and ocean carbon sinks. Carbon cycle-climate feedbacks could alter the OR of the biosphere by affecting the quantity and quality of organic matter in plant biomass and soil carbon pools. This study considers the effect of elevated atmospheric carbon dioxide concentrations ([CO2]) on the OR of a hardwood forest after nine growing seasons of Free-Air CO2 Enrichment. We measured changes in the carbon oxidation state (Cox) of biomass and soil carbon pools as a proxy for the ecosystem OR. The OR of net primary production, 1.039, was not affected by elevated [CO2]. However, the Cox of the soil carbon pool was 40% higher at elevated [CO2], and the estimated OR values for soil respiration increased from 1.006 at ambient [CO2] to 1.054 at elevated [CO2]. A biochemical inventory of the soil organic matter ascribed the increases in Cox and OR to faster turnover of reduced substrates, lignin and lipids, at elevated [CO2]. This implicates the heterotrophic soil community response to elevated [CO2] as a driver of disequilibrium in the ecosystem OR. The oxidation of soil carbon pool constitutes an unexpected terrestrial O2 sink. Carbon budgets constructed under the assumption of OR equilibrium would equate such a terrestrial O2 sink to CO2 uptake by the ocean. The potential for climate-driven disequilibriua in the cycling of O2 and CO2 warrants further investigation.

  1. Removal of chromium hexavalent of residual water from tannery using hydrotalcite; Remocion de cromo hexavalente de aguas residuales de teneria utilizando hidrotalcita

    Energy Technology Data Exchange (ETDEWEB)

    Martinez G, S.; Martinez, V.; Bulbulian, S. [Instituto nacional de Investigaciones Nucleares, A.P. 18-1027, C.P. 11801 Mexico D.F. (Mexico)

    2000-07-01

    One of the main problems of leather tanned is the treatment that must be give to the waste water polluted with chrome which stays in trivalent form, but it is easily oxidated at chromium hexavalent. This work pretends to find an elimination media for chromium (VI) from water using the original synthetic hydrotalcite and calcined as sorbent by its anion exchange and memory effect properties. The tannery water was characterized by X-ray diffraction, thermal gravimetric analysis, specific surface and infrared spectroscopy. (Author)

  2. Oxidation State of Nakhlites as inferred from Fe-Ti oxide Equilibria and Augite/Melt Europium Partitioning

    Science.gov (United States)

    Makishima, J.; McKay, G.; Le, L.; Miyamoto, M.; Mikouchi, T.

    2007-01-01

    Recent studies have shown that Martian magmas had wide range of oxygen fugacities (fO2) and that this variation is correlated with the variation of La/Yb ratio and isotopic characteristics of the Martian basalts, shergottite meteorites. The origin of this correlation must have important information about mantle sources and Martian evolution. In order to understand this correlation, it is necessary to know accurate value of oxidation state of other Martian meteorite groups. Nakhlites, cumulate clinopyroxenites, are another major group of Martian meteorites and have distinctly different trace element and isotopic characteristics from shergottites. Thus, estimates of oxidation state of nakhlites will give us important insight into the mantle source in general. Several workers have estimated oxidation state of nakhlites by using Fe-Ti oxide equilibrium. However, Fe-Ti oxides may not record the oxidation state of the parent melt of the nakhlite because it is a late-stage mineral. Furthermore, there is no comprehensive study which analyzed all nakhlite samples at the same time. Therefore, in this study (1) we reduced the uncertainty of the estimate using the same electron microprobe and the same standards under the same condition for Fe-Ti oxide in 6 nakhlites and (2) we also performed crystallization experiments to measure partition coefficients of Eu into pyroxene in the nakhlite system in order to estimate fO2 when the pyroxene core formed (i.e. Eu oxybarometer [e.g. 2,6]).

  3. Quantification of total chromium and hexavalent chromium in UHT milk by ETAAS.

    Science.gov (United States)

    Lameiras, J; Soares, M E; Bastos, M L; Ferreira, M

    1998-10-01

    Procedures for the quantification of total chromium and hexavalent chromium in UHT milk samples are presented. Total chromium was determined directly in milk with the addition of a surfactant and a mixture of Pd and Mg as a chemical modifier. For the selective separation of hexavalent chromium, the sample pre-treatment consisted in precipitation of proteins and elution of the supernatant through a Chromabond NH2 column. The metal was eluted with nitric acid. Both total chromium and hexavalent chromium were evaluated by atomic absorption spectrometry with electrothermal atomization using the same instrumental conditions. The detection limits were 0.2 and 0.15 microgram l-1 for total chromium and hexavalent chromium, respectively. The linearity ranges under the optimized conditions were 0.2-20 and 0.15-50 micrograms l-1. For total chromium the precision was 4.9 and 5.7% for the analytical and the over-all procedure, respectively, and for hexavalent chromium 4.3 and 4.9%, respectively. The validation of both procedures was performed by the standard additions method and the recoveries were higher than 93% in all cases. For total chromium, a certified reference material was also used to validate the methodology. The methods were applied to the determination of total chromium and hexavalent chromium in 60 UHT milk samples.

  4. Hexavalent Chrome Free Coatings for Electronics: Electromagnetic Interference (EMI) Shielding Effectiveness (SE)

    Science.gov (United States)

    Kessel, Kurt R.

    2016-01-01

    Determine the suitability of trivalent chromium conversion coatings that meet the requirements of MIL-DTL-5541, Type II, for use in applications where high-frequency electrical performance is important. Evaluate the ability of hexavalent chrome free pretreated aluminum to form adequate EMI seals, and maintain that seal while being subjected to harsh environmental conditions. Assess the performance of trivalent chromium pretreatments against a known control hexavalent chrome pretreatment before and after they have been exposed to a set of environmental conditions. It is known that environmental testing causes a decrease in shielding effectiveness when hexavalent chrome pretreatments are used (Alodine 1200s). Need to determine how shielding effectiveness will be affected with the use of hexavalent chrome free pretreatments. Performance will be assessed by evaluating shielding effectiveness (SE) test data from a variety of test samples comprised of different aluminum types and/or conversion coatings. The formation of corrosion will be evaluated between the mating surfaces and gasket to assess the corrosion resistant properties of the pretreatments, comparing the hexavalent control to the hexavalent chrome free pretreatments.

  5. Fabrication of Unique Magnetic Bionanocomposite for Highly Efficient Removal of Hexavalent Chromium from Water

    Science.gov (United States)

    Zhong, Yunlei; Qiu, Xun; Chen, Dongyun; Li, Najun; Xu, Qingfeng; Li, Hua; He, Jinghui; Lu, Jianmei

    2016-08-01

    Biotreatment of hexavalent chromium has attracted widespread interest due to its cost effective and environmental friendliness. However, the difficult separation of biomass from aqueous solution and the slow hexavalent chromium bioreduction rate are bottlenecks for biotechnology application. In this approach, a core-shell structured functional polymer coated magnetic nanocomposite was prepared for enriching the hexavalent chromium. Then the nanocomposite was connected to the bacteria via amines on bacterial (Bacillus subtilis ATCC-6633) surface. Under optimal conditions, a series of experiments were launched to degrade hexavalent chromium from the aqueous solution using the as-prepared bionanocomposite. Results showed that B. subtilis@Fe3O4@mSiO2@MANHE (BFSM) can degrade hexavalent chromium from the water more effectively (a respectable degradation efficiency of about 94%) when compared with pristine B. subtilis and Fe3O4@mSiO2@MANHE (FSM). Moreover, the BFSM could be separated from the wastewater by magnetic separation technology conveniently due to the Fe3O4 core of FSM. These results indicate that the application of BFSM is a promising strategy for effective treating wastewater containing hexavalent chromium.

  6. A study of the process of desorption of hexavalent chromium

    Directory of Open Access Journals (Sweden)

    W.B. Amorim

    2003-09-01

    Full Text Available In this work the process of desorption of hexavalent chromium, a toxic metal ion, from the marine algae Sargassum sp, following biosorption experiments 2³ factorial design was studied. A technique was applied to three eluents: HCl, H2SO4 and EDTA. Three factors of importance were evaluated: concentration of eluent, the ratio between mass of biosorbent and volume of eluent (S/L and process time. A statistical analysis of the experimental results showed that the three variables evaluated are significant for all three eluents. The models for chromium desorption were validated, as the results agreed well with the observed values. Through use of the response surface methodology, a factorial design based optimization technique; it was possible to identify the most suitable eluent and the interval of values for the process variables that resulted in the most significant desorption of chromium, which is relevant information for work aiming at process optimization.

  7. Adsorption of hexavalent chromium by graphite–chitosan binary composite

    Indian Academy of Sciences (India)

    RAJENDRA S DONGRE

    2016-06-01

    Graphite chitosan binary (GCB) composite was prepared for hexavalent chromium adsorption from studied water. GCB was characterized by TGA, FTIR, SEM and X-ray diffraction techniques.Wide porous sorptive surface of 3.89 m$^2$ g$^{−1}$ and absorptive functionalities of GCB was due to 20% (w/w) graphite support on chitosan evidenced from FTIR and SEM that impart maximum adsorption at pH 4, agitation with 200 rpm for 180 min. Adsorption studies revealed intraparticle diffusion models and best-fitted kinetics was pseudo 2nd order one. A wellfitted Langmuir isotherm model suggested monolayer adsorption with an adsorption capacity ($q_m$) of 105.6 mg g$^{−1}$ and $R^2 = 0.945$. Sorption mechanisms based on metal ionic interactions, intrusion/diffusion and chemisorptions onto composite. This graphite chitosan binary composite improve sorbent capacity for Cr(VI).

  8. Microbial reduction of hexavalent chromium by landfill leachate.

    Science.gov (United States)

    Li, Yarong; Low, Gary K-C; Scott, Jason A; Amal, Rose

    2007-04-02

    The reduction of hexavalent chromium (Cr(VI)) in municipal landfill leachates (MLL) and a non-putrescible landfill leachate (NPLL) was investigated. Complete Cr(VI) reduction was achieved within 17 days in a MLL when spiked with 100 mg l(-1) Cr(VI) or less. In the same period, negligible Cr(VI) reduction was observed in NPLL. In MLL, Cr(VI) reduction was demonstrated to be a function of initial Cr(VI) concentration and bacterial biomass and organic matter concentrations. The bacteria were observed to tolerate 250 mg l(-1) Cr(VI) in MLL and had an optimal growth activity at pH 7.4 in a growth medium. The MLL also possessed an ability to sequentially reduce Cr(VI) over three consecutive spiking cycles.

  9. Polyaniline coating with various substrates for hexavalent chromium removal

    Science.gov (United States)

    Qiu, Bin; Xu, Cuixia; Sun, Dezhi; Wang, Qiang; Gu, Hongbo; Zhang, Xin; Weeks, Brandon L.; Hopper, Jack; Ho, Thomas C.; Guo, Zhanhu; Wei, Suying

    2015-04-01

    Hexavalent chromium (Cr(VI)) contamination is increasingly serious in surface water and groundwater, therefore, its removal attracts increasing attention due to its highly toxic to human health. The cost effective and sustainable adsorbents are urgently needed for the remediation of Cr(VI) pollution. Polyanline (PANI), a conductive polymer, has demonstrated a great performance on Cr(VI) removal. But the recycling is the challenge for its application due to its small size. The PANI coating with various substrates is an effective approach to solve this problem. The synthesis methods and applications of the PANI coated magnetic Fe3O4, carbon fabric and cellulose composites for the Cr(VI) removal were reviewed. Finally, this review analyzed the Cr(VI) removal mechanisms by the PANI composites considering the substrate and the PANI coating.

  10. Investigation of hexavalent chromium sorption in serpentine sediments

    Science.gov (United States)

    Mpouras, Thanasis; Chrysochoou, Maria; Dermatas, Dimitris

    2017-02-01

    In this study the removal of hexavalent chromium (Cr6 +) by serpentine sediments was investigated in order to delineate Cr6 + sorption behavior in aquifers with ultramafic geologic background. Batch experiments were conducted in order to determine the influence of several parameters on Cr6 + removal, including the pH of the sediment solution, mineralogy, sediment's particle size and Cr6 + initial concentration. The results showed that Cr6 + removal was due to both adsorption and reduction phenomena. Reduction was attributed to the presence of a magnetic fraction in the sediment, mostly related to magnetite, which contributed almost 50% of the total removal in the pH range 3-7. Adsorption behavior was dominated by the finer sediment fraction (d transport modeling.

  11. Stabilization of actinides and lanthanides in unusually high oxidation states

    Energy Technology Data Exchange (ETDEWEB)

    Eller, P.G.; Penneman, R.A.

    1986-01-01

    Chemical environments can be chosen which stabilize actinides and lanthanides in unusually high or low oxidation states and in unusual coordination. In many cases, one can rationalize the observed species as resulting from strong charge/size influences provided by specific sites in host lattices (e.g., Tb(IV) in BaTbO/sub 3/ or Am(IV) in polytungstate anions). In other cases, the unusual species can be considered from an acid-base viewpoint (e.g., U(III) in AsF/sub 5//HF solution or Pu(VII) in Li/sub 5/PuO/sub 6/). In still other cases, an interplay of steric and redox effects can lead to interesting comparisons (e.g., instability of double fluoride salts of Pu(V) and Pu(VI) relative to U, Np, and Am analogues). Generalized ways to rationalize compounds containing actinides and lanthanides in unusual valences (particularly high valences), including the above and numerous other examples, will form the focus of this paper. Recently developed methods for synthesizing high valent f-element fluorides using superoxidizers and superacids at low temperatures will also be described. 65 refs., 8 figs., 9 tabs.

  12. Unusual metal-like state in HTSC and CMR oxides

    Energy Technology Data Exchange (ETDEWEB)

    Chattopadhyay, S. [Department of Physics, University of Calcutta, 92, Acharya Prafulla Chandra Road, Kolkata 700009 (India); Kumar, Ravi [Nuclear Science Centre, Aruna Asaf Ali Marg, Post Box 10502, New Delhi 110067 (India); Sarkar, A. [Department of Physics, Bangabasi Morning College, 19, Rajkumar Chakraborty Sarani, Kolkata 700009 (India)]. E-mail: sarkarcal@rediffmail.com

    2006-03-15

    Present report deals with the effect of disorder on Bi-2212 type high T {sub c} superconducting and LCMO type CMR oxide materials. Ion irradiation (50 MeV Li{sup 3+} beam) creates high level of disorder in the superconducting system and as a result increase of room temperature resistivity ({rho} {sub 30}) has been observed. Radiation induced point defects cause an increased d{rho}/dT in the metal-like regime of Bi-2212. Similar increase of d{rho}/dT in the FM (ferromagnetic and metal-like) state has also been found in LCMO system. Enhancement of metal-like behavior is unusual in the sense that a simultaneous decrease of T {sub mi} (metal-insulator transition temperature for LCMO) or T {sub c} (superconducting transition temperature for Bi-2212) due to irradiation has also been observed. Effect of the defects incorporated by other means like variation of heat treatment and ion irradiation has been investigated for a better understanding on the electrical transport in these complex materials. Results have been discussed in the light of their intrinsic granular nature.

  13. Kinetic Studies on State of the Art Solid Oxide Cells

    DEFF Research Database (Denmark)

    Njodzefon, Jean-Claude; Graves, Christopher R.; Hjelm, Johan

    2014-01-01

    Introduction The Solid Oxide Fuel Cell (SOFC), which converts hydrogen as well as hydrocarbon fuels directly into electricity, has demonstrated almost comparable performance when operated reversely as Solid Oxide Electrolyser Cell (SOEC) for electrical energy storage as fuels. In both application...

  14. Cloud droplet activation through oxidation of organic aerosol influenced by temperature and particle phase state

    Science.gov (United States)

    Slade, Jonathan H.; Shiraiwa, Manabu; Arangio, Andrea; Su, Hang; Pöschl, Ulrich; Wang, Jian; Knopf, Daniel A.

    2017-02-01

    Chemical aging of organic aerosol (OA) through multiphase oxidation reactions can alter their cloud condensation nuclei (CCN) activity and hygroscopicity. However, the oxidation kinetics and OA reactivity depend strongly on the particle phase state, potentially influencing the hydrophobic-to-hydrophilic conversion rate of carbonaceous aerosol. Here, amorphous Suwannee River fulvic acid (SRFA) aerosol particles, a surrogate humic-like substance (HULIS) that contributes substantially to global OA mass, are oxidized by OH radicals at different temperatures and phase states. When oxidized at low temperature in a glassy solid state, the hygroscopicity of SRFA particles increased by almost a factor of two, whereas oxidation of liquid-like SRFA particles at higher temperatures did not affect CCN activity. Low-temperature oxidation appears to promote the formation of highly-oxygenated particle-bound fragmentation products with lower molar mass and greater CCN activity, underscoring the importance of chemical aging in the free troposphere and its influence on the CCN activity of OA.

  15. An evaluation of in vivo models for toxicokinetics of hexavalent chromium in the stomach.

    Science.gov (United States)

    Sasso, A F; Schlosser, P M

    2015-09-15

    Hexavalent chromium (Cr6) is a drinking water contaminant that has been detected in most of the water systems throughout the United States. In 2-year drinking water bioassays, the National Toxicology Program (NTP) found clear evidence of carcinogenic activity in male and female rats and mice. Because reduction of Cr6 to trivalent chromium (Cr3) is an important detoxifying step in the gastrointestinal (GI) tract prior to systemic absorption, models have been developed to estimate the extent of reduction in humans and animals. The objective of this work was to use a revised model of ex vivo Cr6 reduction kinetics in gastric juice to analyze the potential reduction kinetics under in vivo conditions for mice, rats and humans. A published physiologically-based pharmacokinetic (PBPK) model was adapted to incorporate the new reduction model. This paper focuses on the toxicokinetics of Cr6 in the stomach compartment, where most of the extracellular Cr6 reduction is believed to occur in humans. Within the range of doses administered by the NTP bioassays, neither the original nor revised models predict saturation of stomach reducing capacity to occur in vivo if applying default parameters. However, both models still indicate that mice exhibit the lowest extent of reduction in the stomach, meaning that a higher percentage of the Cr6 dose may escape stomach reduction in that species. Similarly, both models predict that humans exhibit the highest extent of reduction at low doses.

  16. Interface Controlled Oxidation States in Layered Cobalt Oxide Nanoislands on Gold

    DEFF Research Database (Denmark)

    Walton, Alexander; Fester, Jakob; Bajdich, Michal

    2015-01-01

    Layered cobalt oxides have been shown to be highly active catalysts for the oxygen evolution reaction (OER; half of the catalytic “water splitting” reaction), particularly when promoted with gold. However, the surface chemistry of cobalt oxides and in particular the nature of the synergistic effect...... of gold contact are only understood on a rudimentary level, which at present prevents further exploration. We have synthesized a model system of flat, layered cobalt oxide nanoislands supported on a single crystal gold (111) substrate....

  17. The Effects of Decomposition on the Oxidative Ratio and Carbon Oxidation State of Organic Matter

    Science.gov (United States)

    Gallagher, M. E.; Masiello, C. A.; Clark, N.; Randerson, J. T.; Robertson, G. P.

    2006-12-01

    Ecosystem oxidative ratio (OR) and the related parameter carbon oxidation state (Cox) are critical in the apportionment of anthropogenic CO2 between the terrestrial biosphere and ocean reservoirs. OR is the ratio of O2 to CO2 in gas exchange fluxes between the biosphere and the atmosphere (Fba and Fab). Accurate measurements of OR have been challenging (Seibt et al. 2004); instead we approach the problem by measuring Cox and calculating OR from biomass reservoirs. Cox can range from -4 to +4 (CH4 to CO2) and is driven by photosynthesis, respiration, and decomposition. The net OR of the biosphere varies with ecosystem type, and this can affect the apportionment of anthropogenic CO2 between the terrestrial biosphere and ocean reservoirs (Randerson et al. 2006). This makes it essential to constrain ecosystem Cox and OR values. Although small variations in global ecosystem OR have the potential to cause shifts in atmospheric O2 concentrations, no whole ecosystem measurements of Cox yet exist. To constrain ORba and ORab, and improve our understanding of how decomposition affects Cox, we performed a litter bag experiment at the Kellogg Biological Station-Long Term Ecological Research (KBS-LTER) in Michigan at the end of the 2005 agricultural season. We placed 15 corn biomass litter bags in an agricultural field and collected 3 bags at 2, 4, 7, 26, and 29 weeks. These samples were analyzed for %C, %H, %N, and %O via elemental analysis, and these data were used to calculate Cox. Aboveground Cox was measured similarly. We anticipated that the Cox of the corn litter would become more reduced with decomposition, as the percentage of carbohydrates would decrease with time, while that of protein, lignin, and lipids would increase (Baldock et al. 2004). We report differences between the Cox of biomass fixation and biomass degradation from our experiments. Using simple assumptions about ecosystem nitrogen cycling, we convert Cox to OR and report the existence or absence of a

  18. Adsorption properties versus oxidation states of rutile TiO2(110)

    DEFF Research Database (Denmark)

    Martinez, Umberto; Hammer, Bjørk

    2011-01-01

    Using density functional theory we have studied the adsorption properties of different atoms and molecules deposited on a stoichiometric, reduced, and oxidized rutile TiO2(110) surface. Depending on the oxidation state of the surface, electrons can flow from or to the substrate and, therefore...... of the charge flow depends on the oxidation state of the rutile surface and on the adsorption site. Generally, the charging effect leads to more stable complexes. However, the increase in the binding energy of the adsorbates is highly dependent on the electronic states of the surface prior to the adsorption...

  19. Soluble and immobilized graphene oxide activates complement system differently dependent on surface oxidation state

    DEFF Research Database (Denmark)

    Wibroe, Peter Popp; Petersen, Søren Vermehren; Bovet, Nicolas Emile

    2016-01-01

    Graphene oxide (GO) is believed to become applicable in biomedical products and medicine, thereby necessitating appropriate safety evaluation dependent on their applications and the route of administration. We have examined the effect of GO form (in solution versus immobilized) and oxidation stat...

  20. Protein Cysteines Map to Functional Networks According to Steady-state Level of Oxidation

    OpenAIRE

    Go, Young-Mi; Duong, Duc M.; Peng, Junmin; Jones, Dean P

    2011-01-01

    The cysteine (Cys) proteome serves critical roles in protein structure, function and regulation, and includes key targets in oxidative mechanisms of disease. Thioredoxins maintain Cys residues in thiol forms, and previous research shows that the redox potential of thioredoxin in mitochondria and nuclei is more reduced than cytoplasm, suggesting that proteins in these compartments may have different steady-state oxidation. This study measured fractional oxidation of 641 peptidyl Cys residues f...

  1. Reduction of Hexavalent Chromium Using Sorbaria sorbifolia Aqueous Leaf Extract

    Directory of Open Access Journals (Sweden)

    Shashi Prabha Dubey

    2017-07-01

    Full Text Available Aqueous plant leaves extract (PLE of an abundant shrub, Sorbaria sorbifolia, was explored for the reduction of hexavalent chromium, Cr(VI, to trivalent chromium, Cr(III. The effect of contact time, pH, PLE quantity, ionic strength, hardness, temperature and effective initial Cr(VI ion concentration were tested; Cr(VI reduction followed the pseudo-first order rate kinetics and maximum reduction was observed at pH 2. Significantly, Cr(VI reduction efficacies varied from 97 to 66% over the pH range of 2 to 10, which bodes well for PLE to be used for the reduction of Cr(VI also at a higher pH. PLE-mediated Cr(VI reduction displays considerable efficiency at various ionic strengths; however, hardness strongly affects the reduction ability. Higher temperature significantly enhances the Cr(VI reduction. This study reveals the potential use of PLE as a green reducing agent in aqueous extract for the efficient reduction of Cr(VI to Cr(III.

  2. Carbon oxidation state as a metric for describing the chemistry of atmospheric organic aerosol.

    Science.gov (United States)

    Kroll, Jesse H; Donahue, Neil M; Jimenez, Jose L; Kessler, Sean H; Canagaratna, Manjula R; Wilson, Kevin R; Altieri, Katye E; Mazzoleni, Lynn R; Wozniak, Andrew S; Bluhm, Hendrik; Mysak, Erin R; Smith, Jared D; Kolb, Charles E; Worsnop, Douglas R

    2011-02-01

    A detailed understanding of the sources, transformations and fates of organic species in the environment is crucial because of the central roles that they play in human health, biogeochemical cycles and the Earth's climate. However, such an understanding is hindered by the immense chemical complexity of environmental mixtures of organics; for example, atmospheric organic aerosol consists of at least thousands of individual compounds, all of which likely evolve chemically over their atmospheric lifetimes. Here, we demonstrate the utility of describing organic aerosol (and other complex organic mixtures) in terms of average carbon oxidation state, a quantity that always increases with oxidation, and is readily measured using state-of-the-art analytical techniques. Field and laboratory measurements of the average carbon oxidation state, using several such techniques, constrain the chemical properties of the organics and demonstrate that the formation and evolution of organic aerosol involves simultaneous changes to both carbon oxidation state and carbon number.

  3. Oxidation Kinetics of Copper: An Experiment in Solid State Chemistry.

    Science.gov (United States)

    Ebisuzaki, Y.; Sanborn, W. B.

    1985-01-01

    Oxidation kinetics in metals and the role defects play in diffusion-controlled reactions are discussed as background for a junior/senior-level experiment in the physical or inorganic chemistry laboratory. Procedures used and typical data obtained are provided for the experiment. (JN)

  4. Towards a Predictive Thermodynamic Model of Oxidation States of Uranium Incorporated in Fe (hydr) oxides

    Energy Technology Data Exchange (ETDEWEB)

    Bagus, Paul S. [Univ. of North Texas, Denton, TX (United States)

    2013-01-01

    -Level Excited States: Consequences For X-Ray Absorption Spectroscopy”, J. Elec. Spectros. and Related Phenom., 200, 174 (2015) describes our first application of these methods. As well as applications to problems and materials of direct interest for our PNNL colleagues, we have pursued applications of fundamental theoretical significance for the analysis and interpretation of XPS and XAS spectra. These studies are important for the development of the fields of core-level spectroscopies as well as to advance our capabilities for applications of interest to our PNNL colleagues. An excellent example is our study of the surface core-level shifts, SCLS, for the surface and bulk atoms of an oxide that provides a new approach to understanding how the surface electronic of oxides differs from that in the bulk of the material. This work has the potential to lead to a new key to understanding the reactivity of oxide surfaces. Our theoretical studies use cluster models with finite numbers of atoms to describe the properties of condensed phases and crystals. This approach has allowed us to focus on the local atomistic, chemical interactions. For these clusters, we obtain orbitals and spinors through the solution of the Hartree-Fock, HF, and the fully relativistic Dirac HF equations. These orbitals are used to form configuration mixing wavefunctions which treat the many-body effects responsible for the open shell angular momentum coupling and for the satellites of the core-level spectra. Our efforts have been in two complementary directions. As well as the applications described above, we have placed major emphasis on the enhancement and extension of our theoretical and computational capabilities so that we can treat complex systems with a greater range of many-body effects. Noteworthy accomplishments in terms of method development and enhancement have included: (1) An improvement in our treatment of the large matrices that must be handled when many-body effects are treated. (2

  5. State of the Art of CHF Enhancement using Graphene Oxide

    Energy Technology Data Exchange (ETDEWEB)

    Moon, Sung Bo; Park Seong Dae; Bang, In Cheol [Ulsan National Institute of Science and Technology, Ulsan (Korea, Republic of)

    2014-05-15

    Graphene Oxide (GO) is chemically modified graphene, which is different from graphite with its structural difference and their molecular structure. Graphene oxide is a fragment of graphene with carboxyl functional group which has electrical polarity. Because of its characteristic, GO has a benefit of good solubility with water base solutions. Researchers can deposit graphene oxide on a heater surface by boiling of GO nanofluid (mixture of distilled water and graphene oxide nanoparticles) with electrically direct heating. Also, in this coating process, rough graphene structure is formed on the heater surface. A number of studies of pool boiling with graphene oxide argue that the mechanisms of CHF enhancement with GO are surface wettability, hydrodynamic instability, thermal activity, microlayer dryout model, and so on. But they cannot fully explain how GO enhances the CHF. This paper is a review of CHF enhancement mechanism using GO nanofluids. We analyze and compare CHF value, porosity, permeability ,and Scattering Electron Microscope (SEM) images to validate Liter-Kaviany CHF mechanism. It is well know that cooling a high temperature structure, nucleate boiling region has the biggest efficient in heat transfer. And the cooling limit is determined by critical heat flux. To enhance the CHF, many kinds of nanofluid were studied. Especially in GO nanofluid, it showed that the biggest CHF enhancement was obtained but the enhancement mechanism was not clear. The discrimination of GO compared to other nanoparticle is uncertainty attributed from reduction of GO. Because GO has polarity, different coating characteristics was obtained at the opposite electric sides. In this paper, the study of CHF enhancement mechanism was conducted using Liter-Kaviany models instead of surface wettability in GO nanofluid. Surface porosity, capillarity, and permeability were considered.

  6. Double shroud delivery of silica precursor for reducing hexavalent chromium in welding fume.

    Science.gov (United States)

    Wang, Jun; Kalivoda, Mark; Guan, Jianying; Theodore, Alexandros; Sharby, Jessica; Wu, Chang-Yu; Paulson, Kathleen; Es-Said, Omar

    2012-01-01

    The welding process yields a high concentration of nanoparticles loaded with hexavalent chromium (Cr(6+)), a known human carcinogen. Previous studies have demonstrated that using tetramethylsilane (TMS) as a shielding gas additive can significantly reduce the Cr(6+) concentration in welding fume particles. In this study, a novel insulated double shroud torch (IDST) was developed to further improve the reduction of airborne Cr(6+) concentration by separating the flows of the primary shielding gas and the TMS carrier gas. Welding fumes were collected from a welding chamber in the laboratory and from a fixed location near the welding arc in a welding facility. The Cr(6+) content was analyzed with ion chromatography and X-ray photoelectron spectroscopy (XPS). Results from the chamber sampling demonstrated that the addition of 3.2 ≈ 5.1% of TMS carrier gas to the primary shielding gas resulted in more than a 90% reduction of airborne Cr(6+) under all shielding gas flow rates. The XPS result confirmed complete elimination of Cr(6+) inside the amorphous silica shell. Adding 100 ≈ 1000 ppm of nitric oxide or carbon monoxide to the shielding gas could also reduce Cr(6+) concentrations up to 57% and 35%, respectively; however, these reducing agents created potential hazards from the release of unreacted agents. Results of the field test showed that the addition of 1.6% of TMS carrier gas to the primary shielding gas reduced Cr(6+) concentration to the limitation of detection (1.1 μg/m(3)). In a worst-case scenario, if TMS vapor leaked into the environment without decomposition and ventilation, the estimated TMS concentration in the condition of field sampling would be a maximum 5.7 ppm, still well below its flammability limit (1%). Based on a previously developed cost model, the use of TMS increases the general cost by 3.8%. No visual deterioration of weld quality caused by TMS was found, although further mechanical testing is necessary.

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

    Science.gov (United States)

    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. Copyright © 2016 Elsevier Ltd. All rights reserved.

  8. Generalized molybdenum oxide surface chemical state XPS determination via informed amorphous sample model

    Energy Technology Data Exchange (ETDEWEB)

    Baltrusaitis, Jonas, E-mail: job314@lehigh.edu [Department of Chemical Engineering, Lehigh University, B336 Iacocca Hall, 111 Research Drive, Bethlehem, PA 18015 (United States); PhotoCatalytic Synthesis group, MESA+ Institute for Nanotechnology, Faculty of Science and Technology, University of Twente, Meander 229, P.O. Box 217, 7500 AE Enschede (Netherlands); Mendoza-Sanchez, Beatriz [CRANN, Chemistry School, Trinity College Dublin, Dublin (Ireland); Fernandez, Vincent [Institut des Matériaux Jean Rouxel, 2 rue de la Houssinière, BP 32229, F-44322 Nantes Cedex 3 (France); Veenstra, Rick [PhotoCatalytic Synthesis group, MESA+ Institute for Nanotechnology, Faculty of Science and Technology, University of Twente, Meander 229, P.O. Box 217, 7500 AE Enschede (Netherlands); Dukstiene, Nijole [Department of Physical and Inorganic Chemistry, Kaunas University of Technology, Radvilenu pl. 19, LT-50254 Kaunas (Lithuania); Roberts, Adam [Kratos Analytical Ltd, Trafford Wharf Road, Wharfside, Manchester, M17 1GP (United Kingdom); Fairley, Neal [Casa Software Ltd, Bay House, 5 Grosvenor Terrace, Teignmouth, Devon TQ14 8NE (United Kingdom)

    2015-01-30

    Highlights: • We analyzed and modeled spectral envelopes of complex molybdenum oxides. • Molybdenum oxide films of varying valence and crystallinity were synthesized. • MoO{sub 3} and MoO{sub 2} line shapes from experimental data were created. • Informed amorphous sample model (IASM) developed. • Amorphous molybdenum oxide XPS envelopes were interpreted. - Abstract: Accurate elemental oxidation state determination for the outer surface of a complex material is of crucial importance in many science and engineering disciplines, including chemistry, fundamental and applied surface science, catalysis, semiconductors and many others. X-ray photoelectron spectroscopy (XPS) is the primary tool used for this purpose. The spectral data obtained, however, is often very complex and can be subject to incorrect interpretation. Unlike traditional XPS spectra fitting procedures using purely synthetic spectral components, here we develop and present an XPS data processing method based on vector analysis that allows creating XPS spectral components by incorporating key information, obtained experimentally. XPS spectral data, obtained from series of molybdenum oxide samples with varying oxidation states and degree of crystallinity, were processed using this method and the corresponding oxidation states present, as well as their relative distribution was elucidated. It was shown that monitoring the evolution of the chemistry and crystal structure of a molybdenum oxide sample due to an invasive X-ray probe could be used to infer solutions to complex spectral envelopes.

  9. SOLID STATE ENERGY CONVERSION ALLIANCE DELPHI SOLID OXIDE FUEL CELL

    Energy Technology Data Exchange (ETDEWEB)

    Steven Shaffer; Sean Kelly; Subhasish Mukerjee; David Schumann; Gail Geiger; Kevin Keegan; John Noetzel; Larry Chick

    2003-12-08

    The objective of Phase I under this project is to develop a 5 kW Solid Oxide Fuel Cell power system for a range of fuels and applications. During Phase I, the following will be accomplished: Develop and demonstrate technology transfer efforts on a 5 kW stationary distributed power generation system that incorporates steam reforming of natural gas with the option of piped-in water (Demonstration System A). Initiate development of a 5 kW system for later mass-market automotive auxiliary power unit application, which will incorporate Catalytic Partial Oxidation (CPO) reforming of gasoline, with anode exhaust gas injected into an ultra-lean burn internal combustion engine. This technical progress report covers work performed by Delphi from January 1, 2003 to June 30, 2003, under Department of Energy Cooperative Agreement DE-FC-02NT41246. This report highlights technical results of the work performed under the following tasks: Task 1 System Design and Integration; Task 2 Solid Oxide Fuel Cell Stack Developments; Task 3 Reformer Developments; Task 4 Development of Balance of Plant (BOP) Components; Task 5 Manufacturing Development (Privately Funded); Task 6 System Fabrication; Task 7 System Testing; Task 8 Program Management; and Task 9 Stack Testing with Coal-Based Reformate.

  10. Microbial reduction of hexavalent chromium under vadose zone conditions.

    Science.gov (United States)

    Oliver, Douglas S; Brockman, Fred J; Bowman, Robert S; Kieft, Thomas L

    2003-01-01

    Hexavalent chromium [Cr(VI)] is a common contaminant associated with nuclear reactors and fuel processing. Improper disposal at facilities in and and semiarid regions has contaminated underlying vadose zones and aquifers. The objectives of this study were to assess the potential for immobilizing Cr(VI) using a native microbial community to reduce soluble Cr(VI) to insoluble Cr(III) under conditions similar to those in the vadose zone, and to evaluate the potential for enhancing biological Cr(VI) reduction through nutrient addition. Batch microcosm and unsaturated flow column experiments were performed. Native microbial communities in subsurface sediments with no prior Cr(VI) exposure were shown to be capable of Cr(VI) reduction. In both the batch and column experiments, Cr(VI) reduction and loss from the aqueous phase were enhanced by adding high levels of both nitrate (NO3-) and organic C (molasses). Nutrient amendments resulted in up to 87% reduction of the initial 67 mg L(-1) Cr(VI) in an unsaturated batch experiment. Molasses and nitrate additions to 15 cm long unsaturated flow columns receiving 65 mg L(-1) Cr(VI) resulted in microbially mediated reduction and immobilization of 10% of the Cr during a 45-d experiment. All of the immobilized Cr was in the form of Cr(III), as shown by XANES analysis. This suggests that biostimulation of microbial Cr(VI) reduction in vadose zones by nutrient amendment is a promising strategy, and that immobilization of close to 100% of Cr contamination could be achieved in a thick vadose zone with longer flow paths and longer contact times than in this experiment.

  11. Microbial reduction of hexavalent Chromium under vadose zone conditions

    Energy Technology Data Exchange (ETDEWEB)

    Oliver, D S.(unknown); Brockman, Fred J.(BATTELLE (PACIFIC NW LAB)); Bowman, Robert (VISITORS); Kieft, Thomas L.(BATTELLE (PACIFIC NW LAB))

    2003-01-01

    Hexavalent chromium[Cr(VI)] is a common constituent of wastes associated with nuclear reactor operation and fuel processing. Improper disposal at facilities in arid and semi-arid regions has led to contamination of underlying vadose zones and aquifers. The objectives of this study were to assess the potential for immobilizing Cr(VI) contamination using a native microbial community to reduce soluble Cr(VI) to insoluble Cr(III) under conditions similar to those found in the vadose zone, and to evaluate the potential for enhancing biological reduction of Cr(VI) through the addition of nutrients. Batch microcosm and unsaturated flow column experiments were performed. Native microbial communities in subsurface sediments with no prior Cr(VI) exposure were shown to be capable of Cr(VI) reduction. In both the batch and column experiments, Cr(VI) reduction and loss from the aqueous phase were enhanced by adding high levels of both nitrate (NO3-) and organic carbon (molasses). Nutrient amendments resulted in up to 87% Cr(VI) reduction in unsaturated batch experiments. Molasses and nitrate additions to 15-cm length unsaturated flow columns receiving 65 mg L-1 Cr(VI) resulted in microbially mediated reduction and immobilization of 10% of the Cr during a 45-day experiment. All of the immobilized Cr was in the form of Cr (III), as shown by XANES analysis. This suggests that biostimulation of microbial Cr(VI) reduction in vadose zones by nutrient amendment is a promising strategy; and that immobilization of close to 100% of Cr contamination could be achieved in a thick vadose zone with longer flow paths and longer contact times than in this experiment.

  12. Exposure to particulate hexavalent chromium exacerbates allergic asthma pathology

    Energy Technology Data Exchange (ETDEWEB)

    Schneider, Brent C. [Department of Microbiology, Immunology and Tropical Medicine, The George Washington University, Washington, DC 20037 (United States); Department of Pharmacology and Physiology, The George Washington University, Washington, DC 20037 (United States); Constant, Stephanie L. [Department of Microbiology, Immunology and Tropical Medicine, The George Washington University, Washington, DC 20037 (United States); Patierno, Steven R. [Department of Pharmacology and Physiology, The George Washington University, Washington, DC 20037 (United States); GW Cancer Institute, The George Washington University, Washington, DC 20037 (United States); Jurjus, Rosalyn A. [Department of Anatomy and Regenerative Biology, The George Washington University, Washington, DC 20037 (United States); Ceryak, Susan M., E-mail: phmsmc@gwumc.edu [Department of Pharmacology and Physiology, The George Washington University, Washington, DC 20037 (United States)

    2012-02-15

    Airborne hexavalent chromate, Cr(VI), has been identified by the Environmental Protection Agency as a possible health threat in urban areas, due to the carcinogenic potential of some of its forms. Particulate chromates are produced in many different industrial settings, with high levels of aerosolized forms historically documented. Along with an increased risk of lung cancer, a high incidence of allergic asthma has been reported in workers exposed to certain inhaled particulate Cr(VI) compounds. However, a direct causal association between Cr(VI) and allergic asthma has not been established. We recently showed that inhaled particulate Cr(VI) induces an innate neutrophilic inflammatory response in BALB/c mice. In the current studies we investigated how the inflammation induced by inhaled particulate Cr(VI) might alter the pathology of an allergic asthmatic response. We used a well-established mouse model of allergic asthma. Groups of ovalbumin protein (OVA)-primed mice were challenged either with OVA alone, or with a combination of OVA and particulate zinc chromate, and various parameters associated with asthmatic responses were measured. Co-exposure to particulate Cr(VI) and OVA mediated a mixed form of asthma in which both eosinophils and neutrophils are present in airways, tissue pathology is markedly exacerbated, and airway hyperresponsiveness is significantly increased. Taken together these findings suggest that inhalation of particulate forms of Cr(VI) may augment the severity of ongoing allergic asthma, as well as alter its phenotype. Such findings may have implications for asthmatics in settings in which airborne particulate Cr(VI) compounds are present at high levels. -- Highlights: ► Allergic asthma correlated with exposure to certain inhaled particulate chromates. ► Direct causal association between Cr(VI) and allergic asthma not established. ► Cr exacerbated pathology and airway hyperresponsiveness in an OVA-challenged mouse. ► Particulate Cr

  13. SOLID STATE ENERGY CONVERSION ALLIANCE DELPHI SOLID OXIDE FUEL CELL

    Energy Technology Data Exchange (ETDEWEB)

    Steven Shaffer; Sean Kelly; Subhasish Mukerjee; David Schumann; Gail Geiger; Kevin Keegan; Larry Chick

    2004-05-07

    The objective of this project is to develop a 5 kW Solid Oxide Fuel Cell power system for a range of fuels and applications. During Phase I, the following will be accomplished: Develop and demonstrate technology transfer efforts on a 5 kW stationary distributed power generation system that incorporates steam reforming of natural gas with the option of piped-in water (Demonstration System A). Initiate development of a 5 kW system for later mass-market automotive auxiliary power unit application, which will incorporate Catalytic Partial Oxidation (CPO) reforming of gasoline, with anode exhaust gas injected into an ultra-lean burn internal combustion engine. This technical progress report covers work performed by Delphi from July 1, 2003 to December 31, 2003, under Department of Energy Cooperative Agreement DE-FC-02NT41246. This report highlights technical results of the work performed under the following tasks: Task 1 System Design and Integration; Task 2 Solid Oxide Fuel Cell Stack Developments; Task 3 Reformer Developments; Task 4 Development of Balance of Plant (BOP) Components; Task 5 Manufacturing Development (Privately Funded); Task 6 System Fabrication; Task 7 System Testing; Task 8 Program Management; Task 9 Stack Testing with Coal-Based Reformate; and Task 10 Technology Transfer from SECA CORE Technology Program. In this reporting period, unless otherwise noted Task 6--System Fabrication and Task 7--System Testing will be reported within Task 1 System Design and Integration. Task 8--Program Management, Task 9--Stack Testing with Coal Based Reformate, and Task 10--Technology Transfer from SECA CORE Technology Program will be reported on in the Executive Summary section of this report.

  14. Surface State of Carbon Fibers Modified by Electrochemical Oxidation

    Institute of Scientific and Technical Information of China (English)

    Yunxia GUO; Jie LIU; Jieying LIANG

    2005-01-01

    Surface of polyacrylonitrile (PAN)-based carbon fibers was modified by electrochemical oxidation. The modification effect on carbon fibers surface was explored using atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). Results showed that on the modified surface of carbon fibers, the carbon contents decreased by 9.7% and the oxygen and nitrogen contents increased by 53.8% and 7.5 times, respectively. The surface roughness and the hydroxyl and carbonyl contents also increased. The surface orientation index was reduced by 1.5%which decreased tensile strength of carbon fibers by 8.1%, and the microcrystalline dimension also decreased which increased the active sites of carbon fiber surface by 78%. The physical and chemical properties of carbon fibers surface were modified through the electrochemical oxidative method, which improved the cohesiveness between the fibers and resin matrix and increased the interlaminar shear strength (ILSS) of carbon fibers reinforced epoxy composite (CFRP) over 20%.

  15. Water and the Oxidation State of Subduction Zone Magmas

    Energy Technology Data Exchange (ETDEWEB)

    Kelley, K.; Cottrell, E

    2009-01-01

    Mantle oxygen fugacity exerts a primary control on mass exchange between Earth's surface and interior at subduction zones, but the major factors controlling mantle oxygen fugacity (such as volatiles and phase assemblages) and how tectonic cycles drive its secular evolution are still debated. We present integrated measurements of redox-sensitive ratios of oxidized iron to total iron (Fe{sup 3+}/{Sigma}Fe), determined with Fe K-edge micro-x-ray absorption near-edge structure spectroscopy, and pre-eruptive magmatic H{sub 2}O contents of a global sampling of primitive undegassed basaltic glasses and melt inclusions covering a range of plate tectonic settings. Magmatic Fe{sup 3+}/{Sigma}Fe ratios increase toward subduction zones (at ridges, 0.13 to 0.17; at back arcs, 0.15 to 0.19; and at arcs, 0.18 to 0.32) and correlate linearly with H{sub 2}O content and element tracers of slab-derived fluids. These observations indicate a direct link between mass transfer from the subducted plate and oxidation of the mantle wedge.

  16. Kinetic Studies on State of the Art Solid Oxide Cells

    DEFF Research Database (Denmark)

    Njodzefon, Jean-Claude; Graves, Christopher R.; Mogensen, Mogens Bjerg;

    2016-01-01

    Electrochemical reaction kinetics at the electrodes of Solid Oxide Cells (SOCs) were investigated at 700 °C for two cells with different fuel electrode microstructures as well as on a third cell with a reduced active electrode area. Three fuel mixtures were investigated – hydrogen/steam and refor......Electrochemical reaction kinetics at the electrodes of Solid Oxide Cells (SOCs) were investigated at 700 °C for two cells with different fuel electrode microstructures as well as on a third cell with a reduced active electrode area. Three fuel mixtures were investigated – hydrogen....../steam and reformate fuels hydrogen/carbon-dioxide and hydrogen/methane/steam. It was found that the kinetics at the fuel electrode were exactly the same in both reformates. The hydrogen/steam fuel displayed slightly faster kinetics than the reformate fuels. Furthermore the gas conversion impedance in the hydrogen...... into a single process as the gas conversion was reduced. The SOC with finer electrode microstructure displayed improved kinetics....

  17. On matrix stabilisation of d- and f-transition metal ions in unstable oxidation states

    Energy Technology Data Exchange (ETDEWEB)

    Kiselev, Yurii M [Department of Chemistry, M.V. Lomonosov Moscow State University, Moscow (Russian Federation)

    2009-01-31

    The state-of-the-art in matrix stabilisation of d- and f-transition metal ions in unstable oxidation states is analysed. Main aspects of this problem concerning the genealogy of appropriate matrix systems are classified. Relevant examples are given and the data that contradict the scheme proposed are discussed. The thermodynamics of the matrix stabilisation effect is considered using the concept of isomorphic miscibility. The influence of defects and non-equilibrium on the matrix stabilisation effect is discussed. The problem of identification of the oxidation states in matrix systems is examined and various types of matrix systems are considered.

  18. Approaches to Determining the Oxidation State of Nitrogen and Carbon Atoms in Organic Compounds for High School Students

    Science.gov (United States)

    Jurowski, Kamil; Krzeczkowska, Malgorzata Krystyna; Jurowska, Anna

    2015-01-01

    The concept of oxidation state (or oxidation number) and related issues have always been difficult for students. In addition, there are misunderstandings and obscurities, which can cause improper balancing of the chemical equations (mostly in organic reactions). In particular, these problems are related to determination of the oxidation state of…

  19. Approaches to Determining the Oxidation State of Nitrogen and Carbon Atoms in Organic Compounds for High School Students

    Science.gov (United States)

    Jurowski, Kamil; Krzeczkowska, Malgorzata Krystyna; Jurowska, Anna

    2015-01-01

    The concept of oxidation state (or oxidation number) and related issues have always been difficult for students. In addition, there are misunderstandings and obscurities, which can cause improper balancing of the chemical equations (mostly in organic reactions). In particular, these problems are related to determination of the oxidation state of…

  20. Adsorption properties versus oxidation states of rutile TiO2(110)

    DEFF Research Database (Denmark)

    Martinez, Umberto; Hammer, Bjørk

    2011-01-01

    Using density functional theory we have studied the adsorption properties of different atoms and molecules deposited on a stoichiometric, reduced, and oxidized rutile TiO2(110) surface. Depending on the oxidation state of the surface, electrons can flow from or to the substrate and, therefore...... of the charge flow depends on the oxidation state of the rutile surface and on the adsorption site. Generally, the charging effect leads to more stable complexes. However, the increase in the binding energy of the adsorbates is highly dependent on the electronic states of the surface prior to the adsorption...... event. In this work we have analyzed in details these mechanisms and we have also established a direct correlation between the enhanced binding energy of the adsorbates and the induced gap states...

  1. Oxidative state and oxidative metabolism in the brain of rats with adjuvant-induced arthritis.

    Science.gov (United States)

    Wendt, Mariana Marques Nogueira; de Sá-Nakanishi, Anacharis Babeto; de Castro Ghizoni, Cristiane Vizioli; Bersani Amado, Ciomar Aparecida; Peralta, Rosane Marina; Bracht, Adelar; Comar, Jurandir Fernando

    2015-06-01

    The purpose of the present study was to evaluate the oxidative status of the brain of arthritic rats, based mainly on the observation that arthritis induces a pronounced oxidative stress in the liver of arthritis rats and that morphological alterations have been reported to occur in patients with rheumatoid arthritis. Rats with adjuvant-induced arthritis were used. These animals presented higher levels of reactive oxygen species (ROS) in the total brain homogenate (25% higher) and in the mitochondria (+55%) when compared to healthy rats. The nitrite plus nitrate contents, nitric oxide (NO) markers, were also increased in both mitochondria (+27%) and cytosol (+14%). Arthritic rats also presented higher levels of protein carbonyl groups in the total homogenate (+43%), mitochondria (+69%) and cytosol (+145%). Arthritis caused a diminution of oxygen consumption in isolated brain mitochondria only when ascorbate was the electron donor. The disease diminished the mitochondrial cytochrome c oxidase activity by 55%, but increased the transmembrane potential by 16%. The pro-oxidant enzyme xanthine oxidase was 150%, 110% and 283% higher, respectively, in the brain homogenate, mitochondria and cytosol of arthritic animals. The same occurred with the calcium-independent NO-synthase activity that was higher in the brain homogenate (90%) and cytosol (122%) of arthritic rats. The catalase activity, on the other hand, was diminished by arthritis in all cellular fractions (between 30 and 40%). It is apparent that the brain of rats with adjuvant-induced arthritis presents a pronounced oxidative stress and a significant injury to lipids and proteins, a situation that possibly contributes to the brain symptoms of the arthritis disease.

  2. The normal state of high temperature oxide superconductor

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Looking back on the experiments about the normal state of thehigh temperature superconductor (HTS), the authors point out nine important experimental results. On the basis of these results, the authors have argued that the two-dimension, two-subsystem Hamiltonian is the appropriate starting point for describing the normal state of HTS. By this Hamiltonian, using the decoupling approximation of Green's function method by Kaga through numerical calculations, the authors have obtained the temperature dependent pseudogap in the density of states (DOS), which is consistent qualitatively with the experimental results by angle-resolved photoemission spectroscopy (ARPES). Theoretically, this Hamiltonian has the superconducting order parameter of d+s symmetry with d-wave as the main component, which is consistent with experiments. Further, the quantum electronic liquid in HTS is a near Fermi liquid in which there is coexistence of the delocalized states and nearly localized states, and there is finite probability for the nearly localized carriers to form the nearly localized carrier pairs at any finite temperature.

  3. Cpmmw Spectroscopy of Rydberg States of Nitric Oxide

    Science.gov (United States)

    Barnum, Timothy J.; Saladrigas, Catherine A.; Grimes, David; Coy, Stephen; Eyler, Edward E.; Field, Robert W.

    2016-06-01

    The spectroscopy of Rydberg states of NO has a long history [1], stimulating both experimental and theoretical advances in our understanding of Rydberg structure and dynamics. The closed-shell ion-core (1Σ+) and small NO+ dipole moment result in regular patterns of Rydberg series in the Hund's case (d) limit, which are well-described by long-range electrostatic models (e.g., [2]). We will present preliminary data on the core-nonpenetrating Rydberg states of NO (orbital angular momentum, ℓ ≥ 3) collected by chirped-pulse millimeter-wave (CPmmW) spectroscopy. Our technique directly detects electronic free induction decay (FID) between Rydberg states with Δn* ≈ 1 in the region of n* ˜ 40-50, providing a large quantity (12 GHz bandwidth in a single shot) of high quality (resolution ˜ 350 kHz) spectra. Transitions between high-ℓ, core-nonpenetrating Rydberg states act as reporters on the subtle details of the ion-core electric structure. * * [1] Huber KP. Die Rydberg-Serien im Absorptions-spektrum des NO-Molekuuls. Helv. Phys. Acta 3, 929 (1961). * * [2] Biernacki DT, Colson SD, Eyler EE. Rotationally resolved double resonance spectra of NO Rydberg states near the first ionization limit. J. Chem. Phys. 88, 2099 (1988).

  4. Cytotoxicity and genome-wide microarray analysis of intestinal smooth muscle cells in response to hexavalent chromium induction

    Institute of Scientific and Technical Information of China (English)

    Li-Fang JIN; Yuan-Yuan WANG; Zi-Dong ZHANG; Yi-Meng YUAN; Yi-Rui HU; Yang-Feng WEI; Jian NI

    2013-01-01

    Chronic ingestion of high concentrations of hexavalent chromium [Cr(Ⅵ)] in drinking water induces intestinal tumors in mice; however,information on its toxicity on intestinal smooth muscle cells is limited.The present study aimed to assess the in vitro and in vivo toxicological effects of Cr(Ⅵ) on intestinal smooth muscle cells.Human intestinal smooth muscle cells (HISM cells) were cultured with different concentrations of Cr(Ⅵ) to evaluate effects on cell proliferation ability,oxidative stress levels,and antioxidant system.Furthermore,tissue sections in Cr(Ⅵ) exposed rabbits were analyzed to evaluate toxicity on intestinal muscle cells in vivo.Gene chips were utilized to assess differential gene expression profiles at the genome-wide level in 1 μmol/L Cr(Ⅵ) treated cells.Intestinal tissue biopsy results showed that Cr(Ⅵ) increased the incidences of diffuse epithelial hyperplasia in intestinal jejunum but caused no obvious damage to the structure of the muscularis.Cell proliferation analysis revealed that high concentrations (≥64 μmol/L) but not low concentrations of Cr(Ⅵ) (≤16 μmol/L) significantly inhibited the growth of HISM cells.For oxidative stress levels,the expression of reactive oxygen species (ROS) and nitric oxide (NO) was elevated at high concentrations (≥64 μmol/L) but not at low concentrations of Cr(Ⅵ) (≤ 16 μmol/L).In addition,dose-dependent increases in the activity of oxidized glutathione (GSSH)/total-glutathione (T-GSH) were also observed.Gene chip screened 491 differentially expressed genes including genes associated with cell apoptosis,oxidations,and cytoskeletons.Some of these differentially expressed genes may be unique to smooth muscle cells in response to Cr(Ⅵ) induction.

  5. Isolation, identification and characterization of indigenous fungi for bioremediation of hexavalent chromium, nickel and cobalt

    Science.gov (United States)

    Hernahadini, Nelis; Suhandono, Sony; Choesin, Devi N.; Chaerun, Siti K.; Kadarusman, Ade

    2014-03-01

    Waste from nickel mining of Sorowako in South Sulawesi contains hexavalent chromium, nickel and cobalt metals in high concentration and may have a negative impact to the environment. Common waste treatment systems such as chemical treatment using a reducing reagent may still have a negative impact. Bioremediation using fungi or bacteria becomes more popular because it is an environmentally friendly alternative. The purposes of this study are to isolate and identify indigenous fungi that are resistant to heavy metals (hexavalent chromium, nickel, and cobalt) and are capable of reducing the concentration of metals in mining wastes. Ten fungal isolates were successfully isolated from the soils and pond sediments in the area of nickel mining in Sorowako. Selection of superior isolate was carried out by growing all the isolates on PDA medium, which contained all of the three metals. One superior isolate was identified to be able to grow on medium with concentrations of 6400 ppm hexavalent chromium, 200 ppm nickel and 50 ppm cobalt. Molecular identification and phylogenetic studies of the isolate using fungal PCR primers developed to amplify the ITS (internal transcribed spacer) region showed that the isolate sequence was very close to Trichoderma atroviride with 99.8% similarity. Optimum incubation time for the uptake of hexavalent chromium was 3 days, nickel and cobalt was 5 days, respectively, with an optimum pH of 4.

  6. An assessment of the environmental toxicity of hexavalent chromium in fish

    NARCIS (Netherlands)

    Putte, van der I.

    1981-01-01

    At present chromium is a common contaminant in surface waters in many countries. In water the metal may be present in the trivalent form (CrIII) or in the hexavalent form (CrVI), the latter of which is more toxic to aquatic organisms.The investigations presented in this thesis were aimed at a thorou

  7. An assessment of the environmental toxicity of hexavalent chromium in fish

    NARCIS (Netherlands)

    Putte, van der I.

    1981-01-01

    At present chromium is a common contaminant in surface waters in many countries. In water the metal may be present in the trivalent form (CrIII) or in the hexavalent form (CrVI), the latter of which is more toxic to aquatic organisms.
    The investigations presented in this thesis

  8. Hexavalent Chromium Reduction under Fermentative Conditions with Lactate Stimulated Native Microbial Communities

    Energy Technology Data Exchange (ETDEWEB)

    Somenahally, Anil C [ORNL; Mosher, Jennifer J [ORNL; Yuan, Tong [University of Oklahoma; Phelps, Tommy Joe [ORNL; Brown, Steven D [ORNL; Yang, Zamin Koo [ORNL; Hazen, Terry C [ORNL; Arkin, Adam [Lawrence Berkeley National Laboratory (LBNL); Palumbo, Anthony Vito [ORNL; Van Nostrand, Dr. Joy D. [Oklahoma University; Zhou, Jizhong [University of Oklahoma; Elias, Dwayne A [ORNL

    2013-01-01

    Microbial reduction of toxic hexavalent chromium (Cr(VI)) in-situ is a plausible bioremediation strategy in electron-acceptor limited environments. However, higher [Cr(VI)] may impose stress on syntrophic communities and impact community structure and function. The study objectives were to understand the impacts of Cr(VI) concentrations on community structure and on the Cr(VI)-reduction potential of groundwater communities at Hanford, WA. Steady state continuous flow bioreactors were used to grow native communities enriched with lactate (30 mM) and continuously amended with Cr(VI) at 0.0 (No-Cr), 0.1 (Low-Cr) and 3.0 (High-Cr) mg/L. Microbial growth, metabolites, Cr(VI), 16S rRNA gene sequences and GeoChip based functional gene composition were monitored for 15 weeks. Temporal trends and differences in growth, metabolite profiles, and community composition were observed, largely between Low-Cr and High-Cr bioreactors. In both High-Cr and Low-Cr bioreactors, Cr(VI) levels were below detection from week 1 until week 15. With lactate enrichment, native bacterial diversity substantially decreased as Pelosinus spp., and Sporotalea spp., became the dominant groups, but did not significantly differ between Cr concentrations. The Archaea diversity also substantially decreased after lactate enrichment from Methanosaeta (35%), Methanosarcina (17%) and others, to mostly Methanosarcina spp. (95%). Methane production was lower in High-Cr reactors suggesting some inhibition of methanogens. Several key functional genes were distinct in Low-Cr bioreactors compared to High-Cr. Among the Cr resistant microbes, Burkholderia vietnamiensis, Comamonas testosterone and Ralstonia pickettii proliferated in Cr amended bioreactors. In-situ fermentative conditions facilitated Cr(VI) reduction, and as a result 3.0 mg/L Cr(VI) did not impact the overall bacterial community structure.

  9. Hexavalent chromium reduction under fermentative conditions with lactate stimulated native microbial communities.

    Science.gov (United States)

    Somenahally, Anil C; Mosher, Jennifer J; Yuan, Tong; Podar, Mircea; Phelps, Tommy J; Brown, Steven D; Yang, Zamin K; Hazen, Terry C; Arkin, Adam P; Palumbo, Anthony V; Van Nostrand, Joy D; Zhou, Jizhong; Elias, Dwayne A

    2013-01-01

    Microbial reduction of toxic hexavalent chromium (Cr(VI)) in-situ is a plausible bioremediation strategy in electron-acceptor limited environments. However, higher [Cr(VI)] may impose stress on syntrophic communities and impact community structure and function. The study objectives were to understand the impacts of Cr(VI) concentrations on community structure and on the Cr(VI)-reduction potential of groundwater communities at Hanford, WA. Steady state continuous flow bioreactors were used to grow native communities enriched with lactate (30 mM) and continuously amended with Cr(VI) at 0.0 (No-Cr), 0.1 (Low-Cr) and 3.0 (High-Cr) mg/L. Microbial growth, metabolites, Cr(VI), 16S rRNA gene sequences and GeoChip based functional gene composition were monitored for 15 weeks. Temporal trends and differences in growth, metabolite profiles, and community composition were observed, largely between Low-Cr and High-Cr bioreactors. In both High-Cr and Low-Cr bioreactors, Cr(VI) levels were below detection from week 1 until week 15. With lactate enrichment, native bacterial diversity substantially decreased as Pelosinus spp., and Sporotalea spp., became the dominant groups, but did not significantly differ between Cr concentrations. The Archaea diversity also substantially decreased after lactate enrichment from Methanosaeta (35%), Methanosarcina (17%) and others, to mostly Methanosarcina spp. (95%). Methane production was lower in High-Cr reactors suggesting some inhibition of methanogens. Several key functional genes were distinct in Low-Cr bioreactors compared to High-Cr. Among the Cr resistant microbes, Burkholderia vietnamiensis, Comamonas testosterone and Ralstonia pickettii proliferated in Cr amended bioreactors. In-situ fermentative conditions facilitated Cr(VI) reduction, and as a result 3.0 mg/L Cr(VI) did not impact the overall bacterial community structure.

  10. Hexavalent chromium reduction under fermentative conditions with lactate stimulated native microbial communities.

    Directory of Open Access Journals (Sweden)

    Anil C Somenahally

    Full Text Available Microbial reduction of toxic hexavalent chromium (Cr(VI in-situ is a plausible bioremediation strategy in electron-acceptor limited environments. However, higher [Cr(VI] may impose stress on syntrophic communities and impact community structure and function. The study objectives were to understand the impacts of Cr(VI concentrations on community structure and on the Cr(VI-reduction potential of groundwater communities at Hanford, WA. Steady state continuous flow bioreactors were used to grow native communities enriched with lactate (30 mM and continuously amended with Cr(VI at 0.0 (No-Cr, 0.1 (Low-Cr and 3.0 (High-Cr mg/L. Microbial growth, metabolites, Cr(VI, 16S rRNA gene sequences and GeoChip based functional gene composition were monitored for 15 weeks. Temporal trends and differences in growth, metabolite profiles, and community composition were observed, largely between Low-Cr and High-Cr bioreactors. In both High-Cr and Low-Cr bioreactors, Cr(VI levels were below detection from week 1 until week 15. With lactate enrichment, native bacterial diversity substantially decreased as Pelosinus spp., and Sporotalea spp., became the dominant groups, but did not significantly differ between Cr concentrations. The Archaea diversity also substantially decreased after lactate enrichment from Methanosaeta (35%, Methanosarcina (17% and others, to mostly Methanosarcina spp. (95%. Methane production was lower in High-Cr reactors suggesting some inhibition of methanogens. Several key functional genes were distinct in Low-Cr bioreactors compared to High-Cr. Among the Cr resistant microbes, Burkholderia vietnamiensis, Comamonas testosterone and Ralstonia pickettii proliferated in Cr amended bioreactors. In-situ fermentative conditions facilitated Cr(VI reduction, and as a result 3.0 mg/L Cr(VI did not impact the overall bacterial community structure.

  11. Adsorption and Reduction of Hexavalent Chromium on the Surface of Vivianite at Acidic Environment

    Science.gov (United States)

    HA, S.; Hyun, S. P.; Lee, W.

    2016-12-01

    Due to the rapid increase of chemical use in industrial activities, acid spills have frequently occurred in Korea. The acid spill causes soil and water acidification and additional problems such as heavy metal leaching from the soil. Hexavalent chromium (Cr(VI)) is relatively mobile in the environment and toxic and mutagenic. Monoclinic octa-hydrated ferrous phosphate, vivianite, is one of commonly found iron-bearing soil minerals occurring in phosphorous-enriched reducing environments. We have investigated reductive sorption of Cr(VI) on the vivianite surfaces using batch experimental tests under diverse groundwater conditions. Cr(VI) (5 mg/L) was added in 6.5 g/L vivianite suspension buffered at pH 5, 7, and 9, using 0.05 M HEPES or tris buffer solution, to check the effect of pH on the reductive sorption of Cr(VI) on the vivianite surface. The aqueous Cr(VI) removal was fastest at pH 5, followed by pH 7, and pH 9. The effect of ionic strength on the removal kinetics of Cr(VI) was negligible. It could be subsequently removed via sorption and reduction on the surface of vivianite of which reactive chemical species could be aqueous Fe(II), iron oxides, and metavivianite. Adsorption test was conducted using the same amount of Cr(III) to check the selectivity of chromium species on the vivianite surface for the reductive adsorption. Through Cr extraction test, amount of strong-bound Cr to vivianite is similar for Cr(III) and Cr(VI) injection but amount of weak-bound Cr is bigger for Cr(VI) injection. Reaction mechanism for the sorption and reductive transformation of Cr(VI) to Cr(III) species at reactive sites of vivianite surface are discussed based on surface complexation modeling and K-edge Fe X-ray absorption near edge structure (XANES) results. Since vivianite is reacted with Cr(VI), two smooth peaks of absorption edge changed to one sharp peak. Pre-edge that contains 1s-3d transition information tends to show high peak when reaction time is increased and pH is

  12. Homogeneous catalytic systems for selective oxidation of methane: state of the art

    Directory of Open Access Journals (Sweden)

    Balcer Sylwia

    2015-09-01

    Full Text Available Homogeneous catalysts for methane oxidation are of a particular interest from scientific and economic points of view. The results show a great potential for activation and functionalization of CH bonds of unreactive methane. There are still gaps in the knowledge of how to rationally design catalysts for this process. In this paper state-of-the-art. in methane oxidation homogenous catalysis is presented.

  13. What Oxidation State of Iron Determines the Amethyst Colour?

    Energy Technology Data Exchange (ETDEWEB)

    Dedushenko, S. K. [Moscow State University, Department of Chemistry (Russian Federation); Makhina, I. B.; Mar' in, A. A.; Mukhanov, V. A. [Russian Research Institute for Synthesis of Materials (Russian Federation); Perfiliev, Yu. D. [Moscow State University, Department of Chemistry (Russian Federation)

    2004-12-15

    A colourless quartz crystal doped with {sup 57}Fe{sup 3+} was obtained by hydrothermal synthesis in an NH{sub 4}F solution. The crystal was transformed into violet amethyst by gamma-irradiation. The change in colour was accompanied by changes in the Moessbauer spectrum that can be interpreted as the conversion of trivalent iron into the tetravalent state: Fe{sup 3+{yields}F}e{sup 4+}.

  14. Hexavalent chromium exposure and control in welding tasks.

    Science.gov (United States)

    Meeker, John D; Susi, Pam; Flynn, Michael R

    2010-11-01

    Studies of exposure to the lung carcinogen hexavalent chromium (CrVI) from welding tasks are limited, especially within the construction industry where overexposure may be common. In addition, despite the OSHA requirement that the use of engineering controls such as local exhaust ventilation (LEV) first be considered before relying on other strategies to reduce worker exposure to CrVI, data on the effectiveness of LEV to reduce CrVI exposures from welding are lacking. The goal of the present study was to characterize breathing zone air concentrations of CrVI during welding tasks and primary contributing factors in four datasets: (1) OSHA compliance data; (2) a publicly available database from The Welding Institute (TWI); (3) field survey data of construction welders collected by the Center for Construction Research and Training (CPWR); and (4) controlled welding trials conducted by CPWR to assess the effectiveness of a portable LEV unit to reduce CrVI exposure. In the OSHA (n = 181) and TWI (n = 124) datasets, which included very few samples from the construction industry, the OSHA permissible exposure level (PEL) for CrVI (5 μg/m(3)) was exceeded in 9% and 13% of samples, respectively. CrVI concentrations measured in the CPWR field surveys (n = 43) were considerably higher, and 25% of samples exceeded the PEL. In the TWI and CPWR datasets, base metal, welding process, and LEV use were important predictors of CrVI concentrations. Only weak-to-moderate correlations were found between total particulate matter and CrVI, suggesting that total particulate matter concentrations are not a good surrogate for CrVI exposure in retrospective studies. Finally, in the controlled welding trials, LEV reduced median CrVI concentrations by 68% (p = 0.02). In conclusion, overexposure to CrVI in stainless steel welding is likely widespread, especially in certain operations such as shielded metal arc welding, which is commonly used in construction. However, exposure could be

  15. Determining the Oxidation States of Manganese in NT2 Cells and Cultured Astrocytes

    Energy Technology Data Exchange (ETDEWEB)

    Gunter,K.; Aschner, M.; Miller, L.; Eliseev, R.; Salter, J.; Andersen, K.; Gunter, T.

    2006-01-01

    Excessive brain manganese (Mn) can produce a syndrome called 'manganism', which correlates with loss of striatal dopamine and cell death in the striatum and globus pallidus. The prevalent hypothesis for the cause of this syndrome has been oxidation of cell components by the strong oxidizing agent, Mn{sup 3+}, either formed by oxidation of intracellular Mn{sup 2+} or transported into the cell as Mn{sup 3+}. We have recently used X-ray absorption near edge structure spectroscopy (XANES) to determine the oxidation states of manganese complexes in brain and liver mitochondria and in nerve growth factor (NGF)-induced and non-induced PC12 cells. No evidence was found for stabilization or accumulation of Mn{sup 3+} complexes because of oxidation of Mn{sup 2+} by reactive oxygen species in these tissues. Here we extend these studies of manganese oxidation state to cells of brain origin, human neuroteratocarcinoma (NT2) cells and primary cultures of rat astrocytes. Again we find no evidence for stabilization or accumulation of any Mn{sup 3+} complex derived from oxidation of Mn{sup 2+} under a range of conditions.

  16. Carbon oxidation state as a metric for describing the chemistry of atmospheric organic aerosol

    Energy Technology Data Exchange (ETDEWEB)

    Massachusetts Institute of Technology; Kroll, Jesse H.; Donahue, Neil M.; Jimenez, Jose L.; Kessler, Sean H.; Canagaratna, Manjula R.; Wilson, Kevin R.; Altieri, Katye E.; Mazzoleni, Lynn R.; Wozniak, Andrew S.; Bluhm, Hendrik; Mysak, Erin R.; Smith, Jared D.; Kolb, Charles E.; Worsnop, Douglas R.

    2010-11-05

    A detailed understanding of the sources, transformations, and fates of organic species in the environment is crucial because of the central roles that organics play in human health, biogeochemical cycles, and Earth's climate. However, such an understanding is hindered by the immense chemical complexity of environmental mixtures of organics; for example, atmospheric organic aerosol consists of at least thousands of individual compounds, all of which likely evolve chemically over their atmospheric lifetimes. Here we demonstrate the utility of describing organic aerosol (and other complex organic mixtures) in terms of average carbon oxidation state (OSC), a quantity that always increases with oxidation, and is readily measured using state-of-the-art analytical techniques. Field and laboratory measurements of OSC , using several such techniques, constrain the chemical properties of the organics and demonstrate that the formation and evolution of organic aerosol involves simultaneous changes to both carbon oxidation state and carbon number (nC).

  17. Simultaneously photocatalytic treatment of hexavalent chromium (Cr(VI)) and endocrine disrupting compounds (EDCs) using rotating reactor under solar irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Youngji [Korea Institute of Energy Research, New and Renewable Energy Research Division, Hydrogen Laboratory, 152 Gajeong-ro, Yuseong-gu, Daejeon 305-343 (Korea, Republic of); Yonsei University, Department of Chemical and Biomolecular Engineering, 134 Shinchon-dong, Seodaemun-gu, Seoul 120-749 (Korea, Republic of); Joo, Hyunku [Korea Institute of Energy Research, New and Renewable Energy Research Division, Hydrogen Laboratory, 152 Gajeong-ro, Yuseong-gu, Daejeon 305-343 (Korea, Republic of); Her, Namguk [Korea Army Academy at Young-Cheon, Department of Chemistry and Environmental Science, 135-1 Changhari, Kokyungmeon, Young-cheon, Gyeongbuk 770-849 (Korea, Republic of); Yoon, Yeomin [University of South Carolina, Department of Civil and Environmental Engineering, Columbia, SC 29208 (United States); Sohn, Jinsik [Kookmin University, School of Civil and Environmental Engineering, 77 Jeongneung-ro, Seongbuk-gu, Seoul 136-702 (Korea, Republic of); Kim, Sungpyo [Korea University, Department of Environmental Engineering, Sejong 339-700 (Korea, Republic of); Yoon, Jaekyung, E-mail: jyoon@kier.re.kr [Korea Institute of Energy Research, New and Renewable Energy Research Division, Hydrogen Laboratory, 152 Gajeong-ro, Yuseong-gu, Daejeon 305-343 (Korea, Republic of)

    2015-05-15

    Highlights: • Self-rotating reactor including TiO{sub 2} NTs is applied under solar irradiation. • Simultaneously photocatalysis of Cr(VI) and EDCs is observed to be up to 95%. • Photocatalytic reactions of Cr(VI) and EDCs are favorable under acidic pH. • Charge interaction and hole scavenge between TiO{sub 2} and pollutants are synergy factors. - Abstract: In this study, simultaneous treatments, reduction of hexavalent chromium (Cr(VI)) and oxidation of endocrine disrupting compounds (EDCs), such as bisphenol A (BPA), 17α-ethinyl estradiol (EE2) and 17β-estradiol (E2), were investigated with a rotating photocatalytic reactor including TiO{sub 2} nanotubes formed on titanium mesh substrates under solar UV irradiation. In the laboratory tests with a rotating type I reactor, synergy effects of the simultaneous photocatalytic reduction and oxidation of inorganic (Cr(VI)) and organic (BPA) pollutants were achieved. Particularly, the concurrent photocatalytic reduction of Cr(VI) and oxidation of BPA was higher under acidic conditions. The enhanced reaction efficiency of both pollutants was attributed to a stronger charge interaction between TiO{sub 2} nanotubes (positive charge) and the anionic form of Cr(VI) (negative charge), which are prevented recombination (electron–hole pair) by the hole scavenging effect of BPA. In the extended outdoor tests with a rotating type II reactor under solar irradiation, the experiment was extended to examine the simultaneous reduction of Cr(VI) in the presence of additional EDCs, such as EE2 and E2 as well as BPA. The findings showed that synergic effect of both photocatalytic reduction and oxidation was confirmed with single-component (Cr(VI) only), two-components (Cr(VI)/BPA, Cr(VI)/EE2, and Cr(VI)/E2), and four-components (Cr(VI)/BPA/EE2/E2) under various solar irradiation conditions.

  18. Hexavalent chromium reduction with scrap iron in continuous-flow system Part 1: effect of feed solution pH.

    Science.gov (United States)

    Gheju, M; Iovi, A; Balcu, I

    2008-05-01

    The reduction of hexavalent chromium by scrap iron was investigated in continuous system, using long-term column experiments, for aqueous Cr(VI) solutions having low buffering capacities, over the pH range of 2.00-7.30. The results showed that the initial pH of Cr(VI) solution significantly affects the reduction capacity of scrap iron. The highest reduction capacity was determined to be 19.2 mg Cr(VI)/g scrap iron, at pH 2.50, and decreased with increasing the initial pH of Cr(VI) solution. A considerable decrease in scrap iron reduction capacity (25%) was also observed at pH 2.00, as compared to pH 2.50, due to the increased contribution of H(+) ions to the corrosion of scrap iron, which leads to a rapid decrease in time of the scrap iron volume. Over the pH range of 2.50-7.30, hexavalent chromium concentration increases slowly in time after its breakthrough in column effluent, until a steady-state concentration was observed; similarly, over the same pH range, the amount of solubilized Cr(III) in treated column effluent decreases in time, until a steady-state concentration was observed. The steady-state concentration in column effluent decreased for Cr(VI) and increased for Cr(III) with decreasing the initial pH of Cr(VI) solution. No steady-state Cr(VI) or Cr(III) concentrations in column effluent were observed at pH 2.00. Over the entire studied pH range, the amount of Fe(total) in treated solution increases as the initial pH of column influent is decreased; the results show also a continuously decrease in time of Fe(total) concentration, for a constant initial pH, due to a decrease in time of iron corrosion rate. Cr(III) concentration in column effluent also continuously decreased in time, for a constant initial pH, over the pH range of 2.50-7.30. This represents an advantage, because the amount of precipitant agent used to remove Fe(total) and Cr(III) from the column effluent will also decrease in time. The optimum pH for Cr(VI) reduction with scrap iron in

  19. Effect of some non functional surfactants and electrolytes on the hexavalent chromium reduction by glycerol. A mechanistic study

    Energy Technology Data Exchange (ETDEWEB)

    Basu, A.; Ghosh, S.K.; Saha, R.; Nandi, R.; Saha, B. [Burdwan Univ., WB (India). Dept. of Chemistry; Gosh, T. [A.B.N. Seal College, Coochbehar, WB (India). Dept. of Chemistry

    2011-11-15

    Hexavalent chromium is a widespread environmental contaminant and a known human carcinogen. Kinetics of reduction of hexavalent chromium by bio-molecule glycerol in micellar media have been studied spectrophotometrically. The cytoplasmic reduction of hexavalent chromium to trivalent chromium occurs in micro-heterogeneous systems. In vitro, the micelles are considered to mimic the cellular membranes. The electron transfer processes occurring in the micellar systems is considered as model to obtain insight into the electron transport process prevailing in biological systems. Micellar media is also a probe to establish the mechanistic paths of reduction of hexavalent chromium to trivalent chromium. Effects of electrolytes common to biological system are studied to establish the proposed reaction mechanism strongly. (orig.)

  20. 99Tc and Re incorporated into metal oxide polyoxometalates: oxidation state stability elucidated by electrochemistry and theory.

    Science.gov (United States)

    McGregor, Donna; Burton-Pye, Benjamin P; Mbomekalle, Israel M; Aparicio, Pablo A; Romo, Susanna; López, Xavier; Poblet, Josep M; Francesconi, Lynn C

    2012-08-20

    The radioactive element technetium-99 ((99)Tc, half-life = 2.1 × 10(5) years, β(-) of 253 keV), is a major byproduct of (235)U fission in the nuclear fuel cycle. (99)Tc is also found in radioactive waste tanks and in the environment at National Lab sites and fuel reprocessing centers. Separation and storage of the long-lived (99)Tc in an appropriate and stable waste-form is an important issue that needs to be addressed. Considering metal oxide solid-state materials as potential storage matrixes for Tc, we are examining the redox speciation of Tc on the molecular level using polyoxometalates (POMs) as models. In this study we investigate the electrochemistry of Tc complexes of the monovacant Wells-Dawson isomers, α(1)-P(2)W(17)O(61)(10-) (α1) and α(2)-P(2)W(17)O(61)(10-) (α2) to identify features of metal oxide materials that can stabilize the immobile Tc(IV) oxidation state accessed from the synthesized Tc(V)O species and to interrogate other possible oxidation states available to Tc within these materials. The experimental results are consistent with density functional theory (DFT) calculations. Electrochemistry of K(7-n)H(n)[Tc(V)O(α(1)-P(2)W(17)O(61))] (Tc(V)O-α1), K(7-n)H(n)[Tc(V)O(α(2)-P(2)W(17)O(61))] (Tc(V)O-α2) and their rhenium analogues as a function of pH show that the Tc-containing derivatives are always more readily reduced than their Re analogues. Both Tc and Re are reduced more readily in the lacunary α1 site as compared to the α2 site. The DFT calculations elucidate that the highest oxidation state attainable for Re is VII while, under the same electrochemistry conditions, the highest oxidation state for Tc is VI. The M(V)→ M(IV) reduction processes for Tc(V)O-α1 are not pH dependent or only slightly pH dependent suggesting that protonation does not accompany reduction of this species unlike the M(V)O-α2 (M = (99)Tc, Re) and Re(V)O-α1 where M(V/IV) reduction process must occur hand in hand with protonation of the terminal M═O to

  1. Effect of environment on iodine oxidation state and reactivity with aluminum.

    Science.gov (United States)

    Smith, Dylan K; McCollum, Jena; Pantoya, Michelle L

    2016-04-28

    Iodine oxide is a highly reactive solid oxidizer and with its abundant generation of iodine gas during reaction, this oxidizer also shows great potential as a biocidal agent. A problem with using I2O5 in an energetic mixture is its highly variable reactive behavior. This study isolates the variable reactivity associated with I2O5 as a function of its chemical reaction in various environments. Specifically, aluminum fuel and iodine oxide powder are combined using a carrier fluid to aid intermixing. The carrier fluid is shown to significantly affect the oxidation state of iodine oxide, thereby affecting the reactivity of the mixture. Four carrier fluids were investigated ranging in polarity and water miscibility in increasing order from hexane X-ray photoelectric spectroscopy (XPS) and differential scanning calorimetry (DSC). Results are compared with thermal equilibrium simulations. Flame speeds increased with polarity of the fluid used to intermix the powder and ranged from 180 to 1202 m s(-1). The I2O5 processed in the polar fluids formed hydrated states of iodine oxide: HIO3 and HI3O8; and, the nonpolar and dry-mixed samples formed: I2O4 and I4O9. During combustion, the hydrated iodine oxides rapidly dehydrated from HIO3 to HI3O8 and from HI3O8 to I2O5. Both steps release 25% of their mass as vapor during combustion. Increased gas generation enhances convective energy transport and accounts for the increase in reactivity seen in the mixtures processed in polar fluids. These results explain the chemical mechanisms underlying the variable reactivity of I2O5 that are a function of the oxide's highly reactive nature with its surrounding environment. These results will significantly impact the selection of carrier fluid in the synthesis approach for iodine containing reactive mixtures.

  2. Conformational Toggling of Yeast Iso-1-Cytochrome c in the Oxidized and Reduced States

    Science.gov (United States)

    Yang, Zhongzheng; Zhu, Jing; Ying, Tianlei; Jiang, Xianwang; Zhang, Xu; Wu, Houming; Liu, Maili; Tan, Xiangshi; Cao, Chunyang; Huang, Zhong-Xian

    2011-01-01

    To convert cyt c into a peroxidase-like metalloenzyme, the P71H mutant was designed to introduce a distal histidine. Unexpectedly, its peroxidase activity was found even lower than that of the native, and that the axial ligation of heme iron was changed to His71/His18 in the oxidized state, while to Met80/His18 in the reduced state, characterized by UV-visible, circular dichroism, and resonance Raman spectroscopy. To further probe the functional importance of Pro71 in oxidation state dependent conformational changes occurred in cyt c, the solution structures of P71H mutant in both oxidation states were determined. The structures indicate that the half molecule of cyt c (aa 50–102) presents a kind of “zigzag riveting ruler” structure, residues at certain positions of this region such as Pro71, Lys73 can move a big distance by altering the tertiary structure while maintaining the secondary structures. This finding provides a molecular insight into conformational toggling in different oxidation states of cyt c that is principle significance to its biological functions in electron transfer and apoptosis. Structural analysis also reveals that Pro71 functions as a key hydrophobic patch in the folding of the polypeptide of the region (aa 50–102), to prevent heme pocket from the solvent. PMID:22087268

  3. Effect of oxidation state on Bi mineral speciation in oxidized and reduced granitoids from the Uetsu region, NE Japan

    Science.gov (United States)

    Izumino, Yuya; Maruoka, Teruyuki; Nakashima, Kazuo

    2016-06-01

    The relationship between bismuth (Bi) mineral speciation and redox state in three types of granitoids from the Uetsu region, northeast Japan is investigated. Electron microprobe analysis of Bi minerals, sphalerite, Mg-Fe-bearing carbonate minerals, and muscovite, as well as sulfur isotope analysis of sulfide minerals and microthermometric study of fluid inclusions reveal that Bi mineral speciation varies according to the redox state of the granitoids. For example, native bismuth and bismuthinite are abundant and Bi sulfosalts are rare in the lowest fS2 and fO2 mineralized zones of the reduced Iwafune granite (S-type, ilmenite-series) while Bi sulfosalts (Bi3+) are abundant and trace amounts of native bismuth (Bi0) and bismuthinite are found in the highest fS2 and fO2 mineralized zones of the oxidized Wasada granodiorite (I-type, magnetite-series). Bismuthinite is a major Bi mineral, and native bismuth and Bi sulfosalts occur in only minor amounts in the mineralized zones of the Nishitagawa granodiorite (I-type, ilmenite-series), which has intermediate fS2 and fO2 to that of the Iwafune and Wasada samples. Our study indicates that Bi mineral speciation related to granitic intrusive activity is controlled by the redox state of the magmatism, such that native bismuth is typical of reducing conditions, whereas Bi sulfosalts are typical of oxidizing conditions.

  4. The Impact of Environmental Factors in Influencing Epigenetics Related to Oxidative States in the Cardiovascular System

    Directory of Open Access Journals (Sweden)

    Francesco Angelini

    2017-01-01

    Full Text Available Oxidative states exert a significant influence on a wide range of biological and molecular processes and functions. When their balance is shifted towards enhanced amounts of free radicals, pathological phenomena can occur, as the generation of reactive oxygen species (ROS in tissue microenvironment or in the systemic circulation can be detrimental. Epidemic chronic diseases of western societies, such as cardiovascular disease, obesity, and diabetes correlate with the imbalance of redox homeostasis. Current advances in our understanding of epigenetics have revealed a parallel scenario showing the influence of oxidative stress as a major regulator of epigenetic gene regulation via modification of DNA methylation, histones, and microRNAs. This has provided both the biological link and a potential molecular explanation between oxidative stress and cardiovascular/metabolic phenomena. Accordingly, in this review, we will provide current insights on the physiological and pathological impact of changes in oxidative states on cardiovascular disorders, by specifically focusing on the influence of epigenetic regulation. A special emphasis will highlight the effect on epigenetic regulation of human’s current life habits, external and environmental factors, including food intake, tobacco, air pollution, and antioxidant-based approaches. Additionally, the strategy to quantify oxidative states in humans in order to determine which biological marker could best match a subject’s profile will be discussed.

  5. Characterization of Different on the Oxidation Behaviours Surface States and Its Effects of Alloy 690TT

    Institute of Scientific and Technical Information of China (English)

    Zhiming Zhang; Jianqiu Wang; En-Hou Han; Wei Ke

    2012-01-01

    Alloy 690TT samples with four kinds of surface states were prepared: 1) ground to 400 grit; 2) ground to 1500 grit; 3) mechanically polished (MP) and 4) electro-polished (EP). The surface morphologies and the surface skin layers' microstructures of these samples were characterized systematically using various methods and the effects of surface states on the oxidation behaviours of Alloy 690TT were also discussed. The results showed that surface roughness and micro-hardness decreased gradually from the ground to EP surfaces. The grains in the near-surface layers of the ground and MP surfaces had been refined and the residual strains were also very high. The dislocations on the ground surfaces were mainly parallel dislocation lines. The thickness of the superficial cold-worked layers decreased gradually from the ground surfaces to polished surfaces. The oxide morphologies and oxidation rate depended greatly on the surface states of samples. Cold-working by grinding treatments could benefit the outward diffusion of metallic atoms and the nucleation of surface oxides and then accelerate the growth of surface oxide films.

  6. Generalized molybdenum oxide surface chemical state XPS determination via informed amorphous sample model

    Science.gov (United States)

    Baltrusaitis, Jonas; Mendoza-Sanchez, Beatriz; Fernandez, Vincent; Veenstra, Rick; Dukstiene, Nijole; Roberts, Adam; Fairley, Neal

    2015-01-01

    Accurate elemental oxidation state determination for the outer surface of a complex material is of crucial importance in many science and engineering disciplines, including chemistry, fundamental and applied surface science, catalysis, semiconductors and many others. X-ray photoelectron spectroscopy (XPS) is the primary tool used for this purpose. The spectral data obtained, however, is often very complex and can be subject to incorrect interpretation. Unlike traditional XPS spectra fitting procedures using purely synthetic spectral components, here we develop and present an XPS data processing method based on vector analysis that allows creating XPS spectral components by incorporating key information, obtained experimentally. XPS spectral data, obtained from series of molybdenum oxide samples with varying oxidation states and degree of crystallinity, were processed using this method and the corresponding oxidation states present, as well as their relative distribution was elucidated. It was shown that monitoring the evolution of the chemistry and crystal structure of a molybdenum oxide sample due to an invasive X-ray probe could be used to infer solutions to complex spectral envelopes.

  7. Removal of hexavalent chromium from aqueous solutions using micro zero-valent iron supported by bentonite layer.

    Science.gov (United States)

    Daoud, Waseem; Ebadi, Taghi; Fahimifar, Ahmad

    2015-01-01

    Hexavalent chromium Cr(VI) is of particular environmental concern due to its toxicity, mobility, and challenging removal from industrial wastewater. It is a strong oxidizing agent that is carcinogenic and mutagenic and diffuses quickly through soil and aquatic environments. Moreover, it does not form insoluble compounds in aqueous solutions; therefore, separation by precipitation is not feasible. While Cr(VI) oxyanions are very mobile and toxic in the environment, trivalent Cr(III) cations are the opposite and, like many metal cations, Cr(III) forms insoluble precipitates. Thus, reducing Cr(VI)-Cr(III) simplifies its removal from effluent and also reduces its toxicity and mobility. Permeable reactive barriers (PRBs) with zero-valent iron (ZVI) have been used to remediate contaminated groundwater with metals, but using ZVI in remediation of contaminated groundwater or wastewater is limited due to its lack of stability, easy aggregation, and difficulty in separation of iron from the treated solution. Thus, the technology used in the present study is developed to address these problems by placing a layer of bentonite after the PRB layer to remove iron from the treated water. The removal rates of Cr(VI) under different values of pH were investigated, and the results indicated the highest adsorption capacity at low pH.

  8. On the valency state of radiogenic lead in zircon and its consequences

    DEFF Research Database (Denmark)

    Kramers, J.; Frei, Robert; Newville, M.

    2009-01-01

    at this temperature, show age effects that should have been observed in SIMS dating. Further, in zircon evaporation as well as in leaching experiments, common Pb is generally released preferentially to radiogenic Pb. After removal of less radiogenic Pb, the evaporation record generally shows pure radiogenic Pb during...... not resemble that of PbO2. The arguments why radiogenic Pb should be tetravalent are based on analogies with studies relating to the tetravalent state of 234Th and the hexavalent state of 234U, which show that a-recoil in silicates generates a strongly oxidizing environment at the site where the recoiling......-recoil damaged sites could be leached out by any electrolyte solution that reduces it to the divalent state, making it both incompatible and soluble. Thus, discordia can be generated in weathering. The curious observation that discordant Archaean zircon suites generally define trends to lower intercepts at up...

  9. How different oxidation states of crystalline myoglobin are influenced by X-rays.

    Science.gov (United States)

    Hersleth, Hans-Petter; Andersson, K Kristoffer

    2011-06-01

    X-ray induced radiation damage of protein crystals is well known to occur even at cryogenic temperatures. Redox active sites like metal sites seem especially vulnerable for these radiation-induced reductions. It is essential to know correctly the oxidation state of metal sites in protein crystal structures to be able to interpret the structure-function relation. Through previous structural studies, we have tried to characterise and understand the reactions between myoglobin and peroxides. These reaction intermediates are relevant because myoglobin is proposed to take part as scavenger of reactive oxygen species during oxidative stress, and because these intermediates are similar among the haem peroxidases and oxygenases. We have in our previous studies shown that these different myoglobin states are influenced by the X-rays used. In this study, we have in detail investigated the impact that X-rays have on these different oxidation states of myoglobin. An underlying goal has been to find a way to be able to determine mostly unreduced states. We have by using single-crystal light absorption spectroscopy found that the different oxidation states of myoglobin are to a different extent influenced by the X-rays (e.g. ferric Fe(III) myoglobin is faster reduced than ferryl Fe(IV)═O myoglobin). We observe that the higher oxidation states are not reduced to normal ferrous Fe(II) or ferric Fe(III) states, but end up in some intermediate and possibly artificial states. For ferric myoglobin, it seems that annealing of the radiation-induced/reduced state can reversibly more or less give the starting point (ferric myoglobin). Both scavengers and different dose-rates might influence to which extent the different states are affected by the X-rays. Our study shows that it is essential to do a time/dose monitoring of the influence X-rays have on each specific redox-state with spectroscopic techniques like single-crystal light absorption spectroscopy. This will determine to which

  10. Change of immune indexes and oxidative stress state of children with recurrent respiratory tract infection

    Institute of Scientific and Technical Information of China (English)

    Wei-Qing Wu; Shu-Ping Liao; Xiao-Lan Lin; Qiong-Fang Huang

    2015-01-01

    Objective:To observe and analyze the change situation of immune indexes and oxidative stress state of children with recurrent respiratory tract infection.Methods:75 children with recurrent respiratory tract infection in our hospital from January 2014 to June 2015 were selected as observation group, 75 healthy children with health examination at the same time were selected as control group, then the immune indexes and oxidative stress state related serum indexes of two groups were detected,and the detection results of observation group with boys and girls, mild, moderate and severe disease were compared.Results: The cellular immune and erythrocyte immune and oxidative stress state related serum indexes of observation group were all worse than those of control group,and the detection results of observation group with mild, moderate and severe disease had obvious differences too, allP0.05.Conclusion:The change of immune indexes and oxidative stress state of children with recurrent respiratory tract infection are obvious,and the differences of children with mild, moderate and severe disease are obvious too,while the differences of boys and girls are not obvious.

  11. Compositional and Oxidation State Zoning in Martian Pyroxene: Paradox or Process Indicator

    Science.gov (United States)

    Delaney, Jeremy S.; Dyar, M. D.

    2002-01-01

    Coordinated zoning studies of major, minor, trace elements and oxidation states in Martian minerals elucidate the magmatic evolution of QUE94201 and suggest an important role for olivine and volatile fluxing in a complex magmatic history. Additional information is contained in the original extended abstract.

  12. Theory of the electronic and structural properties of solid state oxides

    Energy Technology Data Exchange (ETDEWEB)

    Chelikowsky, J.R.

    1990-01-01

    Studies on electronic and structural properties of solid state oxides continued. This quarter, studies have concentrated on silica. Progress is discussed in the following sections: interatomic potentials and the structural properties of silica; chemical reactivity and covalent/metallic bonding on Si clusters; and surface and thermodynamic interatomic forces fields for silicon. 64 refs., 20 figs., 5 tabs. (CBS)

  13. Regulation of Ca2+ release from mitochondria by the oxidation-reduction state of pyridine nucleotides.

    Science.gov (United States)

    Lehninger, A L; Vercesi, A; Bababunmi, E A

    1978-04-01

    Mitochondria from normal rat liver and heart, and also Ehrlich tumor cells, respiring on succinate as energy source in the presence of rotenone (to prevent net electron flow to oxygen from the endogenous pyridine nucleotides), rapidly take up Ca(2+) and retain it so long as the pyridine nucleotides are kept in the reduced state. When acetoacetate is added to bring the pyridine nucleotides into a more oxidized state, Ca(2+) is released to the medium. A subsequent addition of a reductant of the pyridine nucleotides such as beta-hydroxybutyrate, glutamate, or isocitrate causes reuptake of the released Ca(2+). Successive cycles of Ca(2+) release and uptake can be induced by shifting the redox state of the pyridine nucleotides to more oxidized and more reduced states, respectively. Similar observations were made when succinate oxidation was replaced as energy source by ascorbate oxidation or by the hydrolysis of ATP. These and other observations form the basis of a hypothesis for feedback regulation of Ca(2+)-dependent substrate- or energy-mobilizing enzymatic reactions by the uptake or release of mitochondrial Ca(2+), mediated by the cytosolic phosphate potential and the ATP-dependent reduction of mitochondrial pyridine nucleotides by reversal of electron transport.

  14. Iron Oxidation States of Matrix in Carbonaceous Chondrites Acfer 094 and MIL 07687

    Science.gov (United States)

    Vaccaro, E.; King, A. J.; Schofield, P. F.; Abyaneh, M. K.; Kaulich, B.; Russell, S. S.

    2016-08-01

    STXM Fe-oxidation state study in Acfer 094 and MIL 07687 matrix revealed high Fe3+/ΣFe ratios likely to be a primordial signature. Terrestrial weathering cannot be ruled out but is unlikely to have a pervasive effect throughout entire meteorites.

  15. Influence of microorganisms on the oxidation state distribution of multivalent actinides under anoxic conditions

    Energy Technology Data Exchange (ETDEWEB)

    Reed, Donald Timothy [Los Alamos National Laboratory; Borkowski, Marian [Los Alamos National Laboratory; Lucchini, Jean - Francois [Los Alamos National Laboratory; Ams, David [Los Alamos National Laboratory; Richmann, M. K. [Los Alamos National Laboratory; Khaing, H. [Los Alamos National Laboratory; Swanson, J. S. [Los Alamos National Laboratory

    2010-12-10

    The fate and potential mobility of multivalent actinides in the subsurface is receiving increased attention as the DOE looks to cleanup the many legacy nuclear waste sites and associated subsurface contamination. Plutonium, uranium and neptunium are the near-surface multivalent contaminants of concern and are also key contaminants for the deep geologic disposal of nuclear waste. Their mobility is highly dependent on their redox distribution at their contamination source as well as along their potential migration pathways. This redox distribution is often controlled, especially in the near-surface where organic/inorganic contaminants often coexist, by the direct and indirect effects of microbial activity. Under anoxic conditions, indirect and direct bioreduction mechanisms exist that promote the prevalence of lower-valent species for multivalent actinides. Oxidation-state-specific biosorption is also an important consideration for long-term migration and can influence oxidation state distribution. Results of ongoing studies to explore and establish the oxidation-state specific interactions of soil bacteria (metal reducers and sulfate reducers) as well as halo-tolerant bacteria and Archaea for uranium, neptunium and plutonium will be presented. Enzymatic reduction is a key process in the bioreduction of plutonium and uranium, but co-enzymatic processes predominate in neptunium systems. Strong sorptive interactions can occur for most actinide oxidation states but are likely a factor in the stabilization of lower-valent species when more than one oxidation state can persist under anaerobic microbiologically-active conditions. These results for microbiologically active systems are interpreted in the context of their overall importance in defining the potential migration of multivalent actinides in the subsurface.

  16. Structural oxidation state studies of the manganese cluster in the oxygen evolving complex of photosystem II

    Energy Technology Data Exchange (ETDEWEB)

    Liang, Wenchuan [Univ. of California, Berkeley, CA (United States)

    1994-11-01

    X-ray absorption spectroscopy (XAS) was performed on Photosystem II (PSII)-enriched membranes prepared from spinach to explore: (1) the correlation between structure and magnetic spin state of the Mn cluster in the oxygen evolving complex (OEC) in the S2 state; and (2) the oxidation state changes of the Mn cluster in the flash-induced S-states. The structure of the Mn cluster in the S2 state with the g~4 electron paramagnetic resonance (EPR) signal (S2-g4 state) was compared with that in the S2 state with multiline signal (S2-MLS state) and the S1 state. The S2-g4 state has a higher XAS inflection point energy than that of the S1 state, indicating the oxidation of Mn in the advance from the S1 to the S2-g4 state. Differences in the edge shape and in the extended X-ray absorption fine structure (EXAFS) show that the structure of the Mn cluster in the S2-g4 state is different from that in the S2-MLS or the S1 state. In the S2-g4 state, the second shell of backscatterers from the Mn absorber contains two Mn-Mn distances of 2.73 Å and 2.85 Å. Very little distance disorder exists in the second shell of the S1 or S2-MLS states. The third shell of the S2-g4 state at about 3.3 Å also contains increased heterogeneity relative to that of the S2-MLS or the S1 state. Various S-states were prepared at room-temperature by saturating, single-turnover flashes. The flash-dependent oscillation in the amplitude of the MLS was used to characterize the S-state composition and to construct "pure" S-state Mn K-edge spectra. The edge position shifts to higher energy by 1.8 eV upon the S1 → S2 transition.

  17. Heterogeneous Oxidation of Atmospheric Organic Aerosol: Kinetics of Changes to the Amount and Oxidation State of Particle-Phase Organic Carbon.

    Science.gov (United States)

    Kroll, Jesse H; Lim, Christopher Y; Kessler, Sean H; Wilson, Kevin R

    2015-11-01

    Atmospheric oxidation reactions are known to affect the chemical composition of organic aerosol (OA) particles over timescales of several days, but the details of such oxidative aging reactions are poorly understood. In this study we examine the rates and products of a key class of aging reaction, the heterogeneous oxidation of particle-phase organic species by the gas-phase hydroxyl radical (OH). We compile and reanalyze a number of previous studies from our laboratories involving the oxidation of single-component organic particles. All kinetic and product data are described on a common basis, enabling a straightforward comparison among different chemical systems and experimental conditions. Oxidation chemistry is described in terms of changes to key ensemble properties of the OA, rather than to its detailed molecular composition, focusing on two quantities in particular, the amount and the oxidation state of the particle-phase carbon. Heterogeneous oxidation increases the oxidation state of particulate carbon, with the rate of increase determined by the detailed chemical mechanism. At the same time, the amount of particle-phase carbon decreases with oxidation, due to fragmentation (C-C scission) reactions that form small, volatile products that escape to the gas phase. In contrast to the oxidation state increase, the rate of carbon loss is nearly uniform among most systems studied. Extrapolation of these results to atmospheric conditions indicates that heterogeneous oxidation can have a substantial effect on the amount and composition of atmospheric OA over timescales of several days, a prediction that is broadly in line with available measurements of OA evolution over such long timescales. In particular, 3-13% of particle-phase carbon is lost to the gas phase after one week of heterogeneous oxidation. Our results indicate that oxidative aging represents an important sink for particulate organic carbon, and more generally that fragmentation reactions play a major

  18. Electronic Structure and Oxidation State Changes in the Mn (4) Ca Cluster of Photosystem II

    Energy Technology Data Exchange (ETDEWEB)

    Yano, J.; Pushkar, Y.; Messinger, J.; Bergmann, U.; Glatzel, P.; Yachandra, V.K.; /SLAC

    2012-08-17

    Oxygen-evolving complex (Mn{sub 4}Ca cluster) of Photosystem II cycles through five intermediate states (S{sub i}-states, i = 0-4) before a molecule of dioxygen is released. During the S-state transitions, electrons are extracted from the OEC, either from Mn or alternatively from a Mn ligand. The oxidation state of Mn is widely accepted as Mn{sub 4}(III{sub 2},IV{sub 2}) and Mn{sub 4}(III,IV{sub 3}) for S{sub 1} and S{sub 2} states, while it is still controversial for the S{sub 0} and S{sub 3} states. We used resonant inelastic X-ray scattering (RIXS) to study the electronic structure of Mn{sub 4}Ca complex in the OEC. The RIXS data yield two-dimensional plots that provide a significant advantage by obtaining both K-edge pre-edge and L-edge-like spectra (metal spin state) simultaneously. We have collected data from PSII samples in the each of the S-states and compared them with data from various inorganic Mn complexes. The spectral changes in the Mn 1s2p{sub 3/2} RIXS spectra between the S-states were compared to those of the oxides of Mn and coordination complexes. The results indicate strong covalency for the electronic configuration in the OEC, and we conclude that the electron is transferred from a strongly delocalized orbital, compared to those in Mn oxides or coordination complexes. The magnitude for the S{sub 0} to S{sub 1}, and S{sub 1} to S{sub 2} transitions is twice as large as that during the S{sub 2} to S{sub 3} transition, indicating that the electron for this transition is extracted from a highly delocalized orbital with little change in charge density at the Mn atoms.

  19. Control of lipid oxidation during exercise: role of energy state and mitochondrial factors

    DEFF Research Database (Denmark)

    Sahlin, K; Harris, R C

    2008-01-01

    to an exercise intensity of about 50-60% of VO(2max) after which the contribution of lipid decreases. The switch from lipid to carbohydrate (CHO) is of energetic advantage due to the increased ATP/O(2) yield. In the low-intensity domain (VO(2max)) a moderate reduction in energy state will stimulate both LOx...... and CHO oxidation and relative fuel utilization is mainly controlled by substrate availability and the capacity of the metabolic pathways. In the high-intensity domain (>60%VO(2max)) there is a pronounced decrease in energy state, which will stimulate glycolysis in excess of the substrate requirements......Despite considerable progress during recent years our understanding of how lipid oxidation (LOx) is controlled during exercise remains incomplete. This review focuses on the role of mitochondria and energy state in the control of LOx. LOx increases in parallel with increased energy demand up...

  20. Exploring Bioelectrochemical Systems for Removal and Recovery of Hexavalent Chromium or Nutrients

    OpenAIRE

    2016-01-01

    Bioelectrochemical systems (BES) is a platform technology that is able to realize versatile engineering functions and recover valuable resources in an energy-efficient manner. One of the potential applications of BES is to remove and recover nutrients simultaneously from nutrient-rich wastewater, such as digested manure from livestock. A four-chamber BES was developed and used in this study to explore the potential to remove and recover hexavalent Chromium from synthetic wastewater, and ammon...

  1. Radiation hardness of indium oxide films in the Cooper-pair insulator state

    Directory of Open Access Journals (Sweden)

    Lazarević Đorđe R.

    2012-01-01

    Full Text Available This paper investigates possible radiation effects in the Cooper-pair insulator state of indium oxide films. Radiation effects are predicted on the basis of Monte Carlo simulations. Results of a combined theoretical and numerical analysis suggest that radiation-induced changes in the investigated films could significantly affect their current-voltage characteristics, and that a transition to a metallic state is possible, due to radiation-induced disruption of the fine-tuned granular structure. Dissociation of Cooper pairs, caused by both the incident radiation and the ions displaced within InOx films, can also destroy the conditions for this specific insulating state to subsist.

  2. Oxidation state, bioavailability & biochemical pathway define the fate of carbon in soil

    Science.gov (United States)

    Kuzyakov, Yakov; Apostel, Carolin; Gunina, Anna; Herrmann, Anke M.; Dippold, Michaela

    2015-04-01

    Numerous experiments under laboratory and field conditions analyzed microbial utilization and mean residence time (MRT) of carbon (C) from plant and microbial residues as well as root exudates in soil. Most of these studies tested the effects of various environmental factors, such as temperature, soil moisture, texture etc. on these parameters. However, only a few studies compared the properties of the substances themselves and there is no conceptual framework based on biochemical pathways. We hypothesize that the fate of C from organic substances in soil strongly depends on the first step of their microbial utilization, specifically, on biochemical pathway and initial C oxidation state, as well as its bioavailability in soils, defined by its hydrophobicity and molecular weight. Here we introduce and evaluate a new conceptual framework based on the following parameters: 1) C oxidation state, 2) molecular weight and hydrophobicity, 3) initial biochemical pathway of a substance class in microbial cells. To assess these parameters, two databases were prepared based on the literature and own studies. The first database included only the studies with 14C or 13C position specific labeled sugars, amino acids, carboxylic acids, phenols and lipids in soil. This database allowed us to analyze microbial utilization and mineralization of organics to CO2 depending on their C oxidation state (OS) and on functional groups. Additionally, we calculated data on the bond electronegativity of all compounds investigated in these studies. The second data base included the results of 14C and 13C studies with uniformly labeled substances of various classes. This database considered the free enthalpie (Delta H) per C unit from a variety of substrates differing in their aromaticity, hydrophobicity/electronegativity and location of the substance on the van Krevelen diagram. In addition, we calculated the hydrophobicity from the electronegativity of the individual bonds and recorded their

  3. Optimization and Modeling of Hexavalent Chromium Removal from Aqueous Solution Via Adsorption on Multiwalled Carbon Nanotubes

    Directory of Open Access Journals (Sweden)

    Mina Gholipour

    2011-09-01

    Full Text Available Hexavalent chromium and its derivatives are potential pollutant due to their mortal affects. Therefore, It is essential to remove these components from wastewaters before disposal. Adsorption can be effective and versatile method for removing of hexavalent chromium. In this article, removal of hexavalent chromium via adsorption on multiwalled carbon nanotubes was investigated as a function of adsorbent dosage, initial solution pH, initial Cr(VI concentrations, contact time and temperature. The batch experiments were conducted at 3 different temperatures (17, 27 and 37ºC and shows that Cr (VI removal obeys pseudo-second order rate equation. Rate constant (K values in 3 temperatures, pre-exponential factor and adsorption activation energy (E was also obtained. The sorption data fitted well with Freundlich isotherm adsorption model. Thermodynamic parameters such as Gibbs free energy (ΔGº, enthalpy (ΔHº and entropy (ΔSº for Cr(VI adsorption were estimated and Results suggest that the adsorption process is a spontaneous and endothermic.

  4. Biodegradation of hexavalent chromium (Cr+6) in wastewater using Pseudomonas sp. and Bacillus sp. bacterial strains

    Energy Technology Data Exchange (ETDEWEB)

    Qasim, Muhammad [Department of Chemical Engineering, American University of Sharjah (United Arab Emirates)

    2013-07-01

    The recovery of toxic metal compounds is a deep concern in all industries. Hexavalent chromium is particularly worrying because of its toxic influence on human health. In this paper, biodegradation of hexavalent chromium (Cr+6) present in wastewater has been studied using two different bacterial strains; Pseudomonas sp. and Bacillus sp. A chemostat (with and without recycle of cells) with 10 L liquid culture volume was used to study the substrate and the biomass cell concentrations with time. Also, the degree of substrate conversion was studied by the varying the dilution rate as an independent parameter. The dilution rate (ratio of feed flow rate to the culture volume) was varied by varying the feed volumetric rate from 110-170 mL/h for inlet hexavalent chromium concentrations of 70 mg/dm3. The results show that a chemostat with recycle gives a better performance in terms of substrate conversion than a chemostat without a recycle. Moreover, the degree of substrate conversion decreases as the dilution rate is increased. Also, Bacillus sp. was found to give higher conversions compared to pseudomonas sp.

  5. HEXAVALENT CHROMIUM REMOVAL FROM AQUEOUS SOLUTIONS BY PLEUROTUS OSTREATUS SPENT BIOMASS.

    Directory of Open Access Journals (Sweden)

    D.CAROL

    2012-01-01

    Full Text Available The Pleurotus ostreatus spent biomass after the harvest, is a waste which was used as a potential sorbent after coating it with chitosan an deacetylated derivative from chitin the most abundant carbohydratesecond to cellulose .The study is an attempt to elaborate and justify the optional utility of Spent Pleurotus ostreatus biomass for hexavalent chromium removal from aqueous industrial effluents. The effect of experimental parameters such as pH, biosorbent dosage, biosorbent dosage, initial metal concentration, temperature and sorption time is very striking from the obtained results .The Freundlich isotherm and Langmuir isotherm fitted well to the data of Cr (VI sorption capacity of Spent Pleurotus biomass. The intraparticle diffusion plot suggest that the sorption process proceeds by surface adsorption alone in case of activated spentbiomass but when coated with chitosan the process is sorption along with intra particle diffusion or pore diffusion. The overall adsorption process was endothermic and spontaneous innature.EDX analysis indicated the presence of hexavalent chromium ions on the surface of chitosan coated spent Pleurotus biomass. The resultssuggest that the enhanced spent biomass could be employed as an efficient adsorbent for the removal of hexavalent chromium from industrial effluents as well as from contaminated water sources.

  6. Synthesis, structure, and reactivity of high oxidation state silver fluorides and related compounds

    Energy Technology Data Exchange (ETDEWEB)

    Lucier, George Michael [Univ. of California, Berkeley, CA (United States)

    1995-05-01

    This thesis has been largely concerned with defining the oxidizing power of Ag(III) and Ag(II) in anhydrous hydrogen fluoride (aHF) solution. Emphasis was on cationic species, since in a cation the electronegativity of a given oxidation state is greatest. Cationic Ag(III) solv has a short half life at ordinary temperatures, oxidizing the solvent to elemental fluorine with formation of Ag(II). Salts of such a cation have not yet been preparable, but solutions which must contain such a species have proved to be effective and powerful oxidizers. In presence of PtF6-, RuF6-, or RhF6-, Ag(III) solv effectively oxidizes the anions to release the neutral hexafluorides. Such reactivity ranks cationic Ag(III) as the most powerfully oxidizing chemical agent known as far. Unlike its trivalent relative Ag (II) solv is thermodynamically stable in acid aHF. Nevertheless, it oxidizes IrF6- to IrF6 at room temperature, placing its oxidizing potential not more than 2 eV below that of cationic Ag(III). Range of Ag2+ (MF6-2 salts attainable in aHF has been explored. An anion must be stable with respect to electron loss to Ag2+. The anion must also be a poor F- donor; otherwise, either AgF+ salts or AgF2 are generated.

  7. Development of Surface Complexation Models of Cr(VI) Adsorption on Soils, Sediments and Model Mixtures of Kaolinite, Montmorillonite, γ-Alumina, Hydrous Manganese and Ferric Oxides and Goethite

    Energy Technology Data Exchange (ETDEWEB)

    Koretsky, Carla [Western Michigan University

    2013-11-29

    Hexavalent chromium is a highly toxic contaminant that has been introduced into aquifers and shallow sediments and soils via many anthropogenic activities. Hexavalent chromium contamination is a problem or potential problem in the shallow subsurface at several DOE sites, including Hanford, Idaho National Laboratory, Los Alamos National Laboratory and the Oak Ridge Reservation (DOE, 2008). To accurately quantify the fate and transport of hexavalent chromium at DOE and other contaminated sites, robust geochemical models, capable of correctly predicting changes in chromium chemical form resulting from chemical reactions occurring in subsurface environments are needed. One important chemical reaction that may greatly impact the bioavailability and mobility of hexavalent chromium in the subsurface is chemical binding to the surfaces of particulates, termed adsorption or surface complexation. Quantitative thermodynamic surface complexation models have been derived that can correctly calculate hexavalent chromium adsorption on well-characterized materials over ranges in subsurface conditions, such pH and salinity. However, models have not yet been developed for hexavalent chromium adsorption on many important constituents of natural soils and sediments, such as clay minerals. Furthermore, most of the existing thermodynamic models have been developed for relatively simple, single solid systems and have rarely been tested for the complex mixtures of solids present in real sediments and soils. In this study, the adsorption of hexavalent chromium was measured as a function of pH (3-10), salinity (0.001 to 0.1 M NaNO3), and partial pressure of carbon dioxide(0-5%) on a suite of naturally-occurring solids including goethite (FeOOH), hydrous manganese oxide (MnOOH), hydrous ferric oxide (Fe(OH)3), γ-alumina (Al2O3), kaolinite (Al2Si2O5(OH)4), and montmorillonite (Na3(Al, Mg)2Si4O10(OH)2-nH2O). The results show that all of these materials can bind substantial quantities of

  8. The Influence of Base Metal (M Oxidation State in Au-M-O/TiO2 Systems on Their Catalytic Activity in Carbon Monoxide Oxidation

    Directory of Open Access Journals (Sweden)

    Katarzyna Samson

    2011-12-01

    Full Text Available Base metal promoted gold/titania catalysts were synthesized, characterized and tested in CO oxidation reaction. Catalysts containing dopant metals in higher oxidation states exhibited higher activity than catalysts containing dopants in reduced states. The activity of fresh catalysts promoted by Cu, Fe and Ni was similar to the unpromoted one, but treatment in reducing and oxidizing atmospheres revealed the supremacy of the copper promoted catalyst. The sequential deposition method proved to be better than the co-deposition—precipitation method. An attempt to explain these differences using XPS, FTIR and H2 TPR was performed.

  9. Coupled interactions between volatile activity and Fe oxidation state during arc crustal processes

    Science.gov (United States)

    Humphreys, Madeleine C.S.; Brooker, R; Fraser, D.C.; Burgisser, A; Mangan, Margaret T.; McCammon, C

    2015-01-01

    Arc magmas erupted at the Earth’s surface are commonly more oxidized than those produced at mid-ocean ridges. Possible explanations for this high oxidation state are that the transfer of fluids during the subduction process results in direct oxidation of the sub-arc mantle wedge, or that oxidation is caused by the effect of later crustal processes, including protracted fractionation and degassing of volatile-rich magmas. This study sets out to investigate the effect of disequilibrium crustal processes that may involve coupled changes in H2O content and Fe oxidation state, by examining the degassing and hydration of sulphur-free rhyolites. We show that experimentally hydrated melts record strong increases in Fe3+/∑Fe with increasing H2O concentration as a result of changes in water activity. This is relevant for the passage of H2O-undersaturated melts from the deep crust towards shallow crustal storage regions, and raises the possibility that vertical variations in fO2 might develop within arc crust. Conversely, degassing experiments produce an increase in Fe3+/∑Fe with decreasing H2O concentration. In this case the oxidation is explained by loss of H2 as well as H2O into bubbles during decompression, consistent with thermodynamic modelling, and is relevant for magmas undergoing shallow degassing en route to the surface. We discuss these results in the context of the possible controls on fO2 during the generation, storage and ascent of magmas in arc settings, in particular considering the timescales of equilibration relative to observation as this affects the quality of the petrological record of magmatic fO2.

  10. Constraints on the oxidation state of chondrule precursors from titanium XANES analysis of Semarkona Chondrules

    Energy Technology Data Exchange (ETDEWEB)

    Simon, S.B.; Sutton, S.R.; Grossman, L. (UofC)

    2008-04-28

    The valence of Ti is not easily reset during chondrule formation. To investigate the oxidation state of chondrule precursors, we measured the valence of Ti in olivine, pyroxene and mesostasis in a type I and a type II chondrule in Semarkona. Chondrules are very important because they formed in the solar nebula and are a major component of chondrites, the most common type of meteorite. In unequilibrated chondrites, the ferromagnesian silicates in chondrules exhibit wide ranges of fe (Fe/(Mg + Fe)). On this basis, chondrules can be divided into type I (fe < 0.1) and type II (fe > 0.1). Because a metal must be oxidized to enter a silicate, mafic silicates with low fe's are inferred to have formed in environments where little oxidized iron was available, implying reducing conditions. Therefore, type I and type II chondrules record different oxidation states. A fundamental question in the study of chondrules is whether this difference was established during chondrule formation, or if it reflects differences in their precursors. Last year, we reported the presence of trivalent Ti in refractory forsterite found in the dense fraction of the Tagish Lake CM chondrite. In addition, in the corresponding oral presentation, we reported high Ti{sup 3+}/Ti{sup 4+} in refractory forsterite containing 0.4-0.7 wt% FeO, present in a type I chondrule. Even these low FeO contents reflect a much higher fO{sub 2} than that at which pyroxene with equivalent Ti{sup 3+}/Ti{sup 4+} would be stable. This suggests that either: the equilibrium Ti{sup 3+}/Ti{sup 4+} is higher in olivine than in pyroxene for a given fO{sub 2}; or the grains formed under highly reducing conditions and the valence of Ti in chondrule olivine is a robust recorder of the oxidation state of chondrule precursors, not easily reset during chondrule formation. To improve our understanding of the origin of chondrules we have used XANES (X-ray absorption near edge structure) spectroscopy to measure the valence state of

  11. Microbial utilization of low molecular weight organic substrates in soil depends on their carbon oxidation state

    Science.gov (United States)

    Gunina, Anna; Smith, Andrew; Jones, Davey; Kuzyakov, Yakov

    2017-04-01

    Removal of low molecular weight organic substances (LMWOS), originating from plants and microorganisms, from soil solution is regulated by microbial uptake. In addition to the concentration of LMWOS in soil solution, the chemical properties of each substance (e.g. C oxidation state, number of C atoms, number of -COOH groups) can affect their uptake and subsequent partitioning of C within the soil microbial community. The aim of this study was to trace the initial fate of three dominant classes of LMWOS in soil (sugars, carboxylic and amino acids), including their removal from solution and utilization by microorganisms, and to reveal the effect of substance chemical properties on these processes. Soil solution, spiked at natural abundance levels with 14C-labelled glucose, fructose, malate, succinate, formate, alanine or glycine, was added to the soil and 14C was traced in the dissolved organic carbon (DOC), CO2, cytosol and soil organic carbon (SOC) over 24 hours. The half-life time of all LMWOS in the DOC (T1 /2-solution) varied between 0.6-5.0 min showing extremely fast initial uptake of LMWOS. The T1 /2-solution of substances was dependent on C oxidation state, indicating that less oxidized organic substances (with C oxidation state "0") were retained longer in soil solution than oxidized substances. The LMWOS-C T1 /2-fast, characterizing the half-life time of 14C in the fast mineralization pool, ranged between 30 and 80 min, with the T1 /2-fast of carboxylic acids (malic acid) being the fastest and the T1 /2-fast of amino acids (glycine) being the slowest. An absence of correlation between T1 /2-fast and either C oxidation state, number of C atoms, or number of -COOH groups suggests that intercellular metabolic pathways are more important for LMWOS transformation in soil than their basic chemical properties. The CO2 release during LMWOS mineralization accounted for 20-90% of 14C applied. Mineralization of LMWOS was the least for sugars and the greatest for

  12. Characterization of Interface State in Silicon Carbide Metal Oxide Semiconductor Capacitors

    Science.gov (United States)

    Kao, Wei-Chieh

    Silicon carbide (SiC) has always been considered as an excellent material for high temperature and high power devices. Since SiC is the only compound semiconductor whose native oxide is silicon dioxide (SiO2), it puts SiC in a unique position. Although SiC metal oxide semiconductor (MOS) technology has made significant progress in recent years, there are still a number of issues to be overcome before more commercial SiC devices can enter the market. The prevailing issues surrounding SiC MOSFET devices are the low channel mobility, the low quality of the oxide layer and the high interface state density at the SiC/SiO2 interface. Consequently, there is a need for research to be performed in order to have a better understanding of the factors causing the poor SiC/SiO2 interface properties. In this work, we investigated the generation lifetime in SiC materials by using the pulsed metal oxide semiconductor (MOS) capacitor method and measured the interface state density distribution at the SiC/SiO2 interface by using the conductance measurement and the high-low frequency capacitance technique. These measurement techniques have been performed on n-type and p-type SiC MOS capacitors. In the course of our investigation, we observed fast interface states at semiconductor-dielectric interfaces in SiC MOS capacitors that underwent three different interface passivation processes, such states were detected in the nitrided samples but not observed in PSG-passivated samples. This result indicate that the lack of fast states at PSG-passivated interface is one of the main reasons for higher channel mobility in PSG MOSFETs. In addition, the effect of mobile ions in the oxide on the response time of interface states has been investigated. In the last chapter we propose additional methods of investigation that can help elucidate the origin of the particular interface states, enabling a more complete understanding of the SiC/SiO2 material system.

  13. Study on All-Solid-State Chloride Sensor Based on Tin Oxide/Indium Tin Oxide Glass

    Science.gov (United States)

    Cheng, Jui-Fu; Chou, Jung-Chuan; Sun, Tai-Ping; Hsiung, Shen-Kan; Kao, Hui-Ling

    2011-03-01

    An all-solid-state chloride electrode based on a tin oxide (SnO2)/indium tin oxide (ITO) glass was developed in this study. The sensing membrane of the electrode was prepared by mixing poly(vinyl chloride) (PVC), bis(2-ethylhexyl) sebacate (DOS), [4,5-dimethy-l-3,6-bis(dodecyloxy)-1,2-phenylene] bis(mercury chloride) (ETH9033), and tridodecylmethyl ammonium chloride (TDDMACl). The mixed solution was mixed with tetrahydrofuran (THF), and then dropped on the sensing window of SnO2/ITO glass. According to the experimental results, the optimal weight ratio were PVC:DOS:ETH9033:TDDMACl=33:66:2:5. At this optimum weight ratio, the sensitivity was 54 mV/dec while the range of linear concentrations of NaCl solutions was between 10-4 and 1 M. The lower detection limit of the sensor reached 8×10-5 M and the response time was less than 1 s. The selectivity coefficient was consistent with the theory of Hofmeister lipophilicity. The lifetime was over 60 days and the repeatability was over 50 times. Moreover, the chloride ion sensor was successfully applied to detecting chloride ions in rinsing solutions for contact lenses, and the experimental results revealed that the correlation coefficient was 0.99.

  14. Size- and support-dependent evolution of the oxidation state and structure by oxidation of subnanometer cobalt clusters.

    Science.gov (United States)

    Yin, Chunrong; Zheng, Fan; Lee, Sungsik; Guo, Jinghua; Wang, Wei-Cheng; Kwon, Gihan; Vajda, Viktor; Wang, Hsien-Hau; Lee, Byeongdu; DeBartolo, Janae; Seifert, Sönke; Winans, Randall E; Vajda, Stefan

    2014-09-18

    Size-selected subnanometer cobalt clusters with 4, 7, and 27 cobalt atoms supported on amorphous alumina and ultrananocrystalline diamond (UNCD) surfaces were oxidized after exposure to ambient air. Grazing incidence X-ray absorption near-edge spectroscopy (GIXANES) and near-edge X-ray absorption fine structure (NEXAFS) were used to characterize the clusters revealed a strong dependency of the oxidation state and structure of the clusters on the surface. A dominant Co(2+) phase was identified in all samples. However, XANES analysis of cobalt clusters on UNCD showed that ∼10% fraction of a Co(0) phase was identified for all three cluster sizes and about 30 and 12% fraction of a Co(3+) phase in 4, 7, and 27 atom clusters, respectively. In the alumina-supported clusters, the dominating Co(2+) component was attributed to a cobalt aluminate, indicative of a very strong binding to the support. NEXAFS showed that in addition to strong binding of the clusters to alumina, their structure to a great extent follows the tetrahedral morphology of the support. All supported clusters were found to be resistant to agglomeration when exposed to reactive gases at elevated temperatures and atmospheric pressure.

  15. Ab initio quantum Monte Carlo calculations of ground-state properties of manganese's oxides

    Science.gov (United States)

    Sharma, Vinit; Krogel, Jaron T.; Kent, P. R. C.; Reboredo, Fernando A.

    One of the critical scientific challenges of contemporary research is to obtain an accurate theoretical description of the electronic properties of strongly correlated systems such as transition metal oxides and rare-earth compounds, since state-of-art ab-initio methods based on approximate density functionals are not always sufficiently accurate. Quantum Monte Carlo (QMC) methods, which use statistical sampling to evaluate many-body wave functions, have the potential to answer this challenge. Owing to the few fundamental approximations made and the direct treatment of electron correlation, QMC methods are among the most accurate electronic structure methods available to date. We assess the accuracy of the diffusion Monte Carlo method in the case of rocksalt manganese oxide (MnO). We study the electronic properties of this strongly-correlated oxide, which has been identified as a suitable candidate for many applications ranging from catalysts to electronic devices. ``This work was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division.'' Ab initio quantum Monte Carlo calculations of ground-state properties of manganese's oxides.

  16. Engineering the defect state and reducibility of ceria based nanoparticles for improved anti-oxidation performance

    Science.gov (United States)

    Wang, Yan-Jie; Dong, Hao; Lyu, Guang-Ming; Zhang, Huai-Yuan; Ke, Jun; Kang, Li-Qun; Teng, Jia-Li; Sun, Ling-Dong; Si, Rui; Zhang, Jing; Liu, Yan-Jun; Zhang, Ya-Wen; Huang, Yun-Hui; Yan, Chun-Hua

    2015-08-01

    Due to their excellent anti-oxidation performance, CeO2 nanoparticles receive wide attention in pharmacological application. Deep understanding of the anti-oxidation mechanism of CeO2 nanoparticles is extremely important to develop potent CeO2 nanomaterials for anti-oxidation application. Here, we report a detailed study on the anti-oxidation process of CeO2 nanoparticles. The valence state and coordination structure of Ce are characterized before and after the addition of H2O2 to understand the anti-oxidation mechanism of CeO2 nanoparticles. Adsorbed peroxide species are detected during the anti-oxidation process, which are responsible for the red-shifted UV-vis absorption spectra of CeO2 nanoparticles. Furthermore, the coordination number of Ce in the first coordination shell slightly increased after the addition of H2O2. On the basis of these experimental results, the reactivity of coordination sites for peroxide species is considered to play a key role in the anti-oxidation performance of CeO2 nanoparticles. Furthermore, we present a robust method to engineer the anti-oxidation performance of CeO2 nanoparticles through the modification of the defect state and reducibility by doping with Gd3+. Improved anti-oxidation performance is also observed in cell culture, where the biocompatible CeO2-based nanoparticles can protect INS-1 cells from oxidative stress induced by H2O2, suggesting the potential application of CeO2 nanoparticles in the treatment of diabetes.Due to their excellent anti-oxidation performance, CeO2 nanoparticles receive wide attention in pharmacological application. Deep understanding of the anti-oxidation mechanism of CeO2 nanoparticles is extremely important to develop potent CeO2 nanomaterials for anti-oxidation application. Here, we report a detailed study on the anti-oxidation process of CeO2 nanoparticles. The valence state and coordination structure of Ce are characterized before and after the addition of H2O2 to understand the anti-oxidation

  17. A magnetic route to measure the average oxidation state of mixed-valent manganese in manganese oxide octahedral molecular sieves (OMS).

    Science.gov (United States)

    Shen, Xiong-Fei; Ding, Yun-Shuang; Liu, Jia; Han, Zhao-Hui; Budnick, Joseph I; Hines, William A; Suib, Steven L

    2005-05-04

    A magnetic route has been applied for measurement of the average oxidation state (AOS) of mixed-valent manganese in manganese oxide octahedral molecular sieves (OMS). The method gives AOS measurement results in good agreement with titration methods. A maximum analysis deviation error of +/-7% is obtained from 10 sample measurements. The magnetic method is able to (1) confirm the presence of mixed-valent manganese and (2) evaluate AOS and the spin states of d electrons of both single oxidation state and mixed-valent state Mn in manganese oxides. In addition, the magnetic method may be extended to (1) determine AOS of Mn in manganese oxide OMS with dopant "diamagnetic" ions, such as reducible V5+ (3d0) ions, which is inappropriate for the titration method due to interference of redox reactions between these dopant ions and titration reagents, such as KMnO4, (2) evaluate the dopant "paramagnetic" ions that are present as clusters or in the OMS framework, and (3) determine AOS of other mixed-valent/single oxidation state ion systems, such as Mo3+(3d3)-Mo4+(3d2) systems and Fe3+ in FeCl3.

  18. Arsenic (+ 3 Oxidation State) Methyltransferase and the Methylation of Arsenicals in the Invertebrate Chordate Ciona intestinalis

    OpenAIRE

    Thomas, David J; Nava, Gerardo M.; Cai, Shi-Ying; Boyer, James L.; Hernández-Zavala, Araceli; Gaskins, H. Rex

    2009-01-01

    Biotransformation of inorganic arsenic (iAs) involves methylation catalyzed by arsenic (+ 3 oxidation state) methyltransferase (As3mt) yielding mono-, di-, and trimethylated arsenicals. To investigate the evolution of molecular mechanisms that mediate arsenic biotransformation, a comparative genomic approach focusing on the invertebrate chordate Ciona intestinalis was used. Bioinformatic analyses identified an As3mt gene in the C. intestinalis genome. Constitutive As3mt RNA expression was obs...

  19. Tailoring the oxidation state of cobalt through halide functionality in sol-gel silica

    OpenAIRE

    Gianni Olguin; Christelle Yacou; Simon Smart; Diniz da Costa, João C.

    2013-01-01

    The functionality or oxidation state of cobalt within a silica matrix can be tailored through the use of cationic surfactants and their halide counter ions during the sol-gel synthesis. Simply by adding surfactant we could significantly increase the amount of cobalt existing as Co3O4 within the silica from 44% to 77%, without varying the cobalt precursor concentration. However, once the surfactant to cobalt ratio exceeded 1, further addition resulted in an inhibitory mechanism whereby the alt...

  20. Unsupervised learning in probabilistic neural networks with multi-state metal-oxide memristive synapses

    OpenAIRE

    Serb, Alexander; Bill, Johannes; Khiat, Ali; Berdan, Radu; Legenstein, Robert; Prodromakis, Themis

    2016-01-01

    In an increasingly data-rich world the need for developing computing systems that cannot only process, but ideally also interpret big data is becoming continuously more pressing. Brain-inspired concepts have shown great promise towards addressing this need. Here we demonstrate unsupervised learning in a probabilistic neural network that utilizes metal-oxide memristive devices as multi-state synapses. Our approach can be exploited for processing unlabelled data and can adapt to time-varying cl...

  1. The oxidation state, and sulfur and Cu contents of arc magmas: implications for metallogeny

    Science.gov (United States)

    Richards, Jeremy P.

    2015-09-01

    Global data for measured Fe2O3/FeO ratios and Cu contents in unaltered volcanic and intrusive arc rocks indicate that, on average, they are slightly more oxidized than other magmas derived from depleted upper mantle (such as MORB), but contain similar Cu contents across their compositional ranges. Although Cu scatters to elevated values in some intermediate composition samples, the bulk of the data show a steady but gentle trend to lower concentrations with differentiation, reaching modal values of 50-100 ppm in andesitic rocks. These data suggest that Cu is mildly compatible during partial melting and fractionation processes, likely reflecting minor degrees of sulfide saturation throughout the magmatic cycle. However, the volume of sulfides must be small such that significant proportions of the metal content remain in the magma during fractionation to intermediate compositions. Previous studies have shown that andesitic magmas containing 50 ppm Cu can readily form large porphyry-type Cu deposits upon emplacement in the upper crust. A review of the literature suggests that the elevated oxidation state in the asthenospheric mantle wedge source of arc magmas (ΔFMQ ≈ + 1 ± 1) derives from the subduction of seawater-altered and oxidized oceanic crust, and is transmitted into the mantle wedge via prograde metamorphic dehydration fluids carrying sulfate and other oxidizing components. Progressive hydration and oxidation of the mantle wedge may take up to 10 m.y. to reach a steady state from the onset of subduction, explaining the rarity of porphyry deposits in primitive island arcs, and the late formation of porphyries in continental arc magmatic cycles. Magmas generated from this metasomatized and moderately oxidized mantle source will be hydrous basalts containing high concentrations of sulfur, mainly dissolved as sulfate or sulfite. Some condensed sulfides (melt or minerals) may be present due to the high overall fS2, despite the moderately high oxidation state

  2. On the origin of interface states at oxide/III-nitride heterojunction interfaces

    Science.gov (United States)

    Matys, M.; Adamowicz, B.; Domanowska, A.; Michalewicz, A.; Stoklas, R.; Akazawa, M.; Yatabe, Z.; Hashizume, T.

    2016-12-01

    The energy spectrum of interface state density, Dit(E), was determined at oxide/III-N heterojunction interfaces in the entire band gap, using two complementary photo-electric methods: (i) photo-assisted capacitance-voltage technique for the states distributed near the midgap and the conduction band (CB) and (ii) light intensity dependent photo-capacitance method for the states close to the valence band (VB). In addition, the Auger electron spectroscopy profiling was applied for the characterization of chemical composition of the interface region with the emphasis on carbon impurities, which can be responsible for the interface state creation. The studies were performed for the AlGaN/GaN metal-insulator-semiconductor heterostructures (MISH) with Al2O3 and SiO2 dielectric films and AlxGa1-x layers with x varying from 0.15 to 0.4 as well as for an Al2O3/InAlN/GaN MISH structure. For all structures, it was found that: (i) Dit(E) is an U-shaped continuum increasing from the midgap towards the CB and VB edges and (ii) interface states near the VB exhibit donor-like character. Furthermore, Dit(E) for SiO2/AlxGa1-x/GaN structures increased with rising x. It was also revealed that carbon impurities are not present in the oxide/III-N interface region, which indicates that probably the interface states are not related to carbon, as previously reported. Finally, it was proven that the obtained Dit(E) spectrum can be well fitted using a formula predicted by the disorder induced gap state model. This is an indication that the interface states at oxide/III-N interfaces can originate from the structural disorder of the interfacial region. Furthermore, at the oxide/barrier interface we revealed the presence of the positive fixed charge (QF) which is not related to Dit(E) and which almost compensates the negative polarization charge ( Qp o l - ).

  3. Spin-Orbit Coupling Controlled J =3 /2 Electronic Ground State in 5 d3 Oxides

    Science.gov (United States)

    Taylor, A. E.; Calder, S.; Morrow, R.; Feng, H. L.; Upton, M. H.; Lumsden, M. D.; Yamaura, K.; Woodward, P. M.; Christianson, A. D.

    2017-05-01

    Entanglement of spin and orbital degrees of freedom drives the formation of novel quantum and topological physical states. Here we report resonant inelastic x-ray scattering measurements of the transition metal oxides Ca3 LiOsO6 and Ba2 YOsO6 , which reveals a dramatic spitting of the t2 g manifold. We invoke an intermediate coupling approach that incorporates both spin-orbit coupling and electron-electron interactions on an even footing and reveal that the ground state of 5 d3-based compounds, which has remained elusive in previously applied models, is a novel spin-orbit entangled J =3 /2 electronic ground state. This work reveals the hidden diversity of spin-orbit controlled ground states in 5 d systems and introduces a new arena in the search for spin-orbit controlled phases of matter.

  4. The charge percolation mechanism and simulation of Ziegler–Natta polymerizations Part III. Oxidation states of transition metals

    Directory of Open Access Journals (Sweden)

    BRANKA PILIC

    2006-04-01

    Full Text Available The oxidation state of the transition metal (Mt active centre is the most disputable question in the polymerization of olefins by Ziegler–Natta (ZN and metallocene complexes. In this paper the importance and the changes of the Mt active centres are presented and discussed on the basis of a charge percolation mechanism (CPM of olefin polymerization. Mt atoms can exist in different oxidation states and can be easily transformed from one to another state during activation. In all cases, the Mt atoms are present in several oxidation states, i.e., Mt+(n-1, Mt+(n to Mt+(n+1, producing an irregular charge distribution over the support surface. There is a tendency to equalize the oxidation states by a charge transfer from Mt+(n–1 (donor toMt+(n+1 (acceptor. This cannot occur since the different oxidation states are highly separated on the support. However, monomer molecules are adsorbed on the support producing clusters with stacked p-bonds, making a p-bond bridge between a donor and an acceptor. Once a bridge is formed (percolation moment, charge transfer occurs. The donor and acceptor equalize their oxidation states simultaneously with the polymerization of the monomer. The polymer chain is desorbed from the support, freeing the surface for subsequent monomer adsorption. The whole process is repeated with the oxidation-reduction of other donor-acceptor ensembles.

  5. Effect of surface state on the oxidation behavior of welded 308L in simulated nominal primary water of PWR

    Energy Technology Data Exchange (ETDEWEB)

    Ming, Hongliang; Zhang, Zhiming; Wang, Jiazhen; Zhu, Ruolin; Ding, Jie; Wang, Jianqiu, E-mail: wangjianqiu@imr.ac.cn; Han, En-Hou; Ke, Wei

    2015-05-15

    Highlights: • A duplex oxide film can be formed on the Welded 308L. • Surface state has no influence on the phase composition of the oxide film. • Surface state can affect the thickness of the oxide film. • Surface state can affect the morphology of the oxide film. - Abstract: The oxidation behavior of 308L weld metal (WM) with different surface state in the simulated nominal primary water of pressurized water reactor (PWR) was studied by scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD) analyzer and X-ray photoelectron spectroscopy (XPS). After 480 h immersion, a duplex oxide film composed of a Fe-rich outer layer (Fe{sub 3}O{sub 4}, Fe{sub 2}O{sub 3} and a small amount of NiFe{sub 2}O{sub 4}, Ni(OH){sub 2}, Cr(OH){sub 3} and (Ni, Fe)Cr{sub 2}O{sub 4}) and a Cr-rich inner layer (FeCr{sub 2}O{sub 4} and NiCr{sub 2}O{sub 4}) can be formed on the 308L WM samples with different surface state. The surface state has no influence on the phase composition of the oxide films but obviously affects the thickness of the oxide films and the morphology of the oxides (number & size). With increasing the density of dislocations and subgrain boundaries in the cold-worked superficial layer, the thickness of the oxide film, the number and size of the oxides decrease.

  6. Synchrotron Micro-XANES Measurements of Vanadium Oxidation State in Glasses as a Function of Oxygen Fugacity: Experimental Calibration of Data Relevant to Partition Coefficient Determination

    Science.gov (United States)

    Delaney, J. S.; Sutton, S. R.; Newville, M.; Jones, J. H.; Hanson, B.; Dyar, M. D.; Schreiber, H.

    2000-01-01

    Oxidation state microanalyses for V in glass have been made by calibrating XANES spectral features with optical spectroscopic measurements. The oxidation state change with fugacity of O2 will strongly influence partitioning results.

  7. The Oxidation State of Terrestrial Basalts and its Link with the Mantle

    Science.gov (United States)

    Mallmann, G.; O'Neill, H. S.; Berry, A. J.; Norman, M. D.; Eggins, S. M.; Kamenetsky, V.; Turner, S.; Smith, I. E.; Ballhaus, C.

    2011-12-01

    The prevailing paradigm is that the Earth's mantle is both laterally and vertically heterogeneous in regards to its oxidation state. This view has been motivated by the observation that, on average, primitive island arc basalts (IAB) preserve Fe3+/Fe2+ higher than ocean island (OIB) and, particularly, mid-ocean ridge basalts (MORB), and reinforced by the higher oxygen fugacities (fO2) determined in lithospheric (mantle wedge) arc peridotites. fO2 measurements in peridotites equilibrated over a range of pressures have also led to the notion that the mantle becomes more reduced with depth. V and Sc behave very similarly during partial melting of the mantle, but while V is redox-sensitive Sc is not. Their ratio in basalts has therefore a memory of the redox conditions during partial melting. Within the many assumptions involved in forward trace-element modeling, the bulk-rock V/Sc of MORBs, OIBs and IABs indicate that the partial melting events responsible for their genesis occurred at a relatively narrow range of fO2s between QFM and QFM-1. V olivine-liquid partition coefficients are also sensitive to oxidation state (normalization to Sc is useful to minimize the effect of variables other than fO2), and the values determined between olivine phenocrysts (Fo76-90) and quenched basaltic melts suggest that, at the time of olivine crystallization, terrestrial basalts have already oxidized about 1 log fO2 unit (IABs even more so, approximately 2 log fO2 units). The results reveal no statistically significant distinction between the oxidation states of MORBs and OIBs. This has been confirmed by Fe3+/Fe2+ determined by XANES.

  8. Oxidative stress markers in hypertensive states of pregnancy: preterm and term disease.

    Science.gov (United States)

    Kurlak, Lesia O; Green, Amanda; Loughna, Pamela; Broughton Pipkin, Fiona

    2014-01-01

    Discussion continues as to whether de novo hypertension in pregnancy with significant proteinuria (pre-eclampsia; PE) and non-proteinuric new hypertension (gestational hypertension; GH) are parts of the same disease spectrum or represent different conditions. Non-pregnant hypertension, pregnancy and PE are all associated with oxidative stress. We have established a 6 weeks postpartum clinic for women who experienced a hypertensive pregnancy. We hypothesized that PE and GH could be distinguished by markers of oxidative stress; thiobarbituric acid reactive substances (TBARS) and antioxidants (ferric ion reducing ability of plasma; FRAP). Since the severity of PE and GH is greater pre-term, we also compared pre-term and term disease. Fifty-eight women had term PE, 23 pre-term PE, 60 had term GH and 6 pre-term GH, 11 pre-existing (essential) hypertension (EH) without PE. Limited data were available from normotensive pregnancies (n = 7) and non-pregnant controls (n = 14). There were no differences in postpartum TBARS or FRAP between hypertensive states; TBARS (P = 0.001) and FRAP (P = 0.009) were lower in plasma of non-pregnant controls compared to recently-pregnant women. Interestingly FRAP was higher in preterm than term GH (P = 0.013). In PE and GH, TBARS correlated with low density lipoprotein (LDL)-cholesterol (P = 0.036); this association strengthened with inclusion of EH (P = 0.011). The 10 year Framingham index for cardiovascular risk was positively associated with TBARS (P = 0.003). Oxidative stress profiles do not differ between hypertensive states but appear to distinguish between recently-pregnant and non-pregnant states. This suggests that pregnancy may alter vascular integrity with changes remaining 6 weeks postpartum. LDL-cholesterol is a known determinant of oxidative stress in cardiovascular disease and we have shown this association to be present in hypertensive pregnancy further emphasizing that such a pregnancy may be revealing a pre

  9. Anticlastogenic Effect of Redistilled Cow's Urine Distillate in Human Peripheral Lymphocytes Challenged With Manganese Dioxide and Hexavalent Chromium

    Institute of Scientific and Technical Information of China (English)

    DIPANWITA DUTTA; S.SARAVANA DEVI; K. KRISHNAMURTHI; T. CHAKRABARTI

    2006-01-01

    Objective To study the anticlastogenic effect of redistilled cow's urine distillate (RCUD) in human peripheral lymphocytes (HLC) challenged with manganese dioxide and hexavalent chromium. Methods The anticlastogenic activity of redistilled cow's urine distillate was studied in human polymorphonuclear leukocytes (HPNLs) and human peripheral lymphocytes in vitro challenged with manganese dioxide and hexavalent chromium as established genotoxicants and clastogens which could cause induction of DNA strand break, chromosomal aberration and micronucleus. Three different levels of RCUD: 1 μL/mL, 50 μL/mL and 100μL/mL, were used in the study. Results Manganese dioxide and hexavalent chromium caused statistically significant DNA strand break, chromosomal aberration and micronucleus formation, which could be protected by redistilled cow's urine distillate. Conclusion The redistilled cow's urine distillate posseses strong antigenotoxic and anticlastogenic properties against HPNLs and HLC treated with Cr+6 and MnO2. This property is mainly due to the antioxidants present in RCUD.

  10. Chronic wound state exacerbated by oxidative stress in Pax6+/- aniridia-related keratopathy.

    Science.gov (United States)

    Ou, J; Walczysko, P; Kucerova, R; Rajnicek, A M; McCaig, C D; Zhao, M; Collinson, J M

    2008-08-01

    Heterozygosity for the transcription factor PAX6 causes eye disease in humans, characterized by corneal opacity. The molecular aetiology of such disease was investigated using a Pax6+/- mouse model. We found that the barrier function of uninjured Pax6+/- corneas was compromised and that Ca2+-PKC/PLC-ERK/p38 signalling pathways were abnormally activated, mimicking a 'wounded' epithelial state. Using proteomic analysis and direct assay for oxidized proteins, Pax6+/- corneas were found to be susceptible to oxidative stress and they exhibited a wound-healing delay which could be rescued by providing reducing agents such as glutathione. Pax6 protein was oxidized and excluded from the nucleus of stressed corneal epithelial cells, with concomitant loss of corneal epithelial markers and expression of fibroblast/myofibroblast markers. We suggest a chronic wound model for Pax6-related corneal diseases, in which oxidative stress underlies a positive feedback mechanism by depleting nuclear Pax6, delaying wound healing, and activating cell signalling pathways that lead to metaplasia of the corneal epithelium. The study mechanistically links a relatively minor dosage deficiency of a transcription factor with potentially catastrophic degenerative corneal disease.

  11. Diversity of Chemical Bonding and Oxidation States in MS4 Molecules of Group 8 Elements.

    Science.gov (United States)

    Huang, Wei; Jiang, Ning; Schwarz, W H Eugen; Yang, Ping; Li, Jun

    2017-08-04

    The geometric and electronic ground-state structures of 30 isomers of six MS4 molecules (M=Group 8 metals Fe, Ru, Os, Hs, Sm, and Pu) have been studied by using quantum-chemical density functional theory and correlated wavefunction approaches. The MS4 species were compared to analogous MO4 species recently investigated (W. Huang, W.-H. Xu, W. H. E. Schwarz, J. Li, Inorg. Chem. 2016, 55, 4616). A metal oxidation state (MOS) with a high value of eight appeared in the low-spin singlet Td geometric species (Os,Hs)S4 and (Ru,Os,Hs)O4 , whereas a low MOS of two appeared in the high-spin septet D2d species Fe(S2 )2 and (slightly excited) metastable Fe(O2 )2 . The ground states of all other molecules had intermediate MOS values, with S(2-) , S2(2-) , S2(1-) (and O(2-) , O(1-) , O2(2-) , O2(1-) ) ligands bonded by ionic, covalent, and correlative contributions. The known tendencies toward lower MOS on going from oxides to sulfides, from Hs to Os to Ru, and from Pu to Sm, and the specific behavior of Fe, were found to arise from the different atomic orbital energies and radii of the (n-1)p core and (n-1)d and (n-2)f valence shells of the metal atoms in row n of the periodic table. The comparative results of the electronic and geometric structures of the MO4 and MS4 species provides insight into the periodicity of oxidation states and bonding. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. The influence of iridium chemical oxidation state on the performance and durability of oxygen evolution catalysts in PEM electrolysis

    Science.gov (United States)

    Siracusano, S.; Baglio, V.; Grigoriev, S. A.; Merlo, L.; Fateev, V. N.; Aricò, A. S.

    2017-10-01

    Nanosized Ir-black (3 nm) and Ir-oxide (5 nm) oxygen evolution electrocatalysts showing high performance in polymer electrolyte membrane (PEM) water electrolysis based on Aquivion® short-side chain ionomer membrane are investigated to understand the role of the Ir oxidation state on the electrocatalytic activity and stability. Despite the smaller mean crystallite size, the Ir-black electrocatalyst shows significantly lower initial performance than the Ir-oxide. During operation at high current density, the Ir-black shows a decrease of cell potential with time whereas the Ir-oxide catalyst shows increasing cell potential resulting in a degradation rate of about 10 μV/h, approaching 1000 h. The unusual behaviour of the Ir-black results from the oxidation of metallic Ir to IrOx. The Ir-oxide catalyst shows instead a hydrated structure on the surface and a negative shift of about 0.5 eV for the Ir 4f binding energy after 1000 h electrolysis operation. This corresponds to the formation of a sub-stoichiometric Ir-oxide on the surface. These results indicate that a hydrated IrO2 with high oxidation state on the surface is favourable in decreasing the oxygen evolution overpotential. Modifications of the Ir chemical oxidation state during operation can affect significantly the catalytic activity and durability of the electrolysis system.

  13. Surface State Capture Cross-Section at the Interface between Silicon and Hafnium Oxide

    Directory of Open Access Journals (Sweden)

    Fu-Chien Chiu

    2013-01-01

    Full Text Available The interfacial properties between silicon and hafnium oxide (HfO2 are explored by the gated-diode method and the subthreshold measurement. The density of interface-trapped charges, the current induced by surface defect centers, the surface recombination velocity, and the surface state capture cross-section are obtained in this work. Among the interfacial properties, the surface state capture cross-section is approximately constant even if the postdeposition annealing condition is changed. This effective capture cross-section of surface states is about 2.4 × 10−15 cm2, which may be an inherent nature in the HfO2/Si interface.

  14. MODELING THE RATE-CONTROLLED SORPTION OF HEXAVALENT CHROMIUM.

    Science.gov (United States)

    Grove, D.B.; Stollenwerk, K.G.

    1985-01-01

    Sorption of chromium VI on the iron-oxide- and hydroxide-coated surface of alluvial material was numerically simulated with rate-controlled reactions. Reaction kinetics and diffusional processes, in the form of film, pore, and particle diffusion, were simulated and compared with experimental results. The use of empirically calculated rate coefficients for diffusion through the reacting surface was found to simulate experimental data; pore or particle diffusion is believed to be a possible rate-controlling mechanism. The use of rate equations to predict conservative transport and rate- and local-equilibrium-controlled reactions was shown to be feasible.

  15. SOLID STATE ENERGY CONVERSION ALLIANCE (SECA) SOLID OXIDE FUEL CELL PROGRAM

    Energy Technology Data Exchange (ETDEWEB)

    Unknown

    2003-06-01

    This report summarizes the progress made during the September 2001-March 2002 reporting period under Cooperative Agreement DE-FC26-01NT41245 for the U. S. Department of Energy, National Energy Technology Laboratory (DOE/NETL) entitled ''Solid State Energy Conversion Alliance (SECA) Solid Oxide Fuel Cell Program''. The program focuses on the development of a low-cost, high-performance 3-to-10-kW solid oxide fuel cell (SOFC) system suitable for a broad spectrum of power-generation applications. The overall objective of the program is to demonstrate a modular SOFC system that can be configured to create highly efficient, cost-competitive, and environmentally benign power plants tailored to specific markets. When fully developed, the system will meet the efficiency, performance, life, and cost goals for future commercial power plants.

  16. Influence of the Sn oxidation state in ferromagnetic Sn-doped In2O3 nanowires

    Science.gov (United States)

    Maloney, Francis Scott; Wang, Wenyong

    2016-12-01

    Sn-doped indium oxide nanowires were grown using a vapor-liquid-solid technique (VLS). The Sn content of the nanowires was tunable based on the source powder ratios used in the VLS process. The oxidation state of the Sn ions was examined using x-ray photoelectron spectroscopy. It was found that Sn2+ was the dominant ionic species in samples over 6% (atomic percentage) Sn. The nanowires were found to be ferromagnetic at room temperature, and their saturation magnetization increased with increasing Sn concentration, which could be associated with the spin-splitting of a defect band that was encouraged by the imbalance of Sn2+ to Sn4+ species at high Sn concentrations.

  17. SOLID STATE ENERGY CONVERSION ALLIANCE (SECA) SOLID OXIDE FUEL CELL PROGRAM

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen Minh; Jim Powers

    2003-10-01

    This report summarizes the work performed for April 2003--September 2003 reporting period under Cooperative Agreement DE-FC26-01NT41245 for the U.S. Department of Energy, National Energy Technology Laboratory (DOE/NETL) entitled ''Solid State Energy Conversion Alliance (SECA) Solid oxide Fuel Cell Program''. During this reporting period, the conceptual system design activity was completed. The system design, including strategies for startup, normal operation and shutdown, was defined. Sealant and stack materials for the solid oxide fuel cell (SOFC) stack were identified which are capable of meeting the thermal cycling and degradation requirements. A cell module was tested which achieved a stable performance of 0.238 W/cm{sup 2} at 95% fuel utilization. The external fuel processor design was completed and fabrication begun. Several other advances were made on various aspects of the SOFC system, which are detailed in this report.

  18. Genesis and transport of hexavalent chromium in the system ophiolitic rocks - groundwater

    Science.gov (United States)

    Shchegolikhina, Anastasia; Guadagnini, Laura; Guadagnini, Alberto

    2015-04-01

    Our study aims at contributing to the quantification and characterization of chromium transport processes from host rocks and soil matrices to groundwater. We focus on dissolved hexavalent chromium detected in groundwaters of geological regions with ophiolitic rocks (ophiolites and serpentinites) inclusions due to its critical ecological impact. (Oze et al., 2004). Despite the large number of analyses on the occurrence of high concentrations of hazardous hexavalent chromium ions in natural waters, only few studies were performed with the objective of identifying and investigating the geochemical reactions which could occur in the natural system rock - groundwater - dissolved chromium (Fantoni et al., 2002, Stephen and James, 2004, Lelli et al., 2013). In this context, there is a need for integration of results obtained from diverse studies in various regions and settings to improve our knowledge repository. Our theoretical analyses are grounded and driven by practical scenarios detected in subsurface reservoirs exploited for civil and industrial use located in the Emilia-Romagna region (Italy). Available experimental datasets are complemented with data from other international regional-scale settings (Altay mountains region, Russia). Modeling of chromium transformation and migration particularly includes characterization of the multispecies geochemical system. A key aspect of our study is the analysis of the complex competitive sorption processes governing heavy metal evolution in groundwater. The results of the research allow assessing the critical qualitative features of the mechanisms of hexavalent chromium ion mobilization from host rocks and soils and the ensuing transformation and migration to groundwater under the influence of diverse environmental factors. The study is then complemented by the quantification of the main sources of uncertainty associated with prediction of heavy metal contamination levels in the groundwater system explored. Fantoni, D

  19. Detection of hexavalent uranium with inline and field-portable immunosensors

    Energy Technology Data Exchange (ETDEWEB)

    Melton, Scott J.; Yu, Haini; Ali, Mehnaaz F.; Williams, Kenneth H; Wilkins, Michael J.; Long, Philip E.; Blake, Diane A.

    2008-10-02

    An antibody that recognizes a chelated form of hexavalent uranium was used in the development of two different immunosensors for uranium detection. Specifically, these sensors were utilized for the analysis of groundwater samples collected during a 2007 field study of in situ bioremediation in a aquifer located at Rifle, CO. The antibody-based sensors provided data comparable to that obtained using Kinetic Phosphorescence Analysis (KPA). Thus, these novel instruments and associated reagents should provide field researchers and resource managers with valuable new tools for on-site data acquisition.

  20. Determination of Model Kinetics for Forced Unsteady State Operation of Catalytic CH4 Oxidation

    Directory of Open Access Journals (Sweden)

    Effendy Mohammad

    2016-01-01

    Full Text Available The catalytic oxidation of methane for abating the emission vented from coal mine or natural gas transportation has been known as most reliable method. A reverse flow reactor operation has been widely used to oxidize this methane emission due to its capability for autothermal operation and heat production. The design of the reverse flow reactor requires a proper kinetic rate expression, which should be developed based on the operating condition. The kinetic rate obtained in the steady state condition cannot be applied for designing the reactor operated under unsteady state condition. Therefore, new approach to develop the dynamic kinetic rate expression becomes indispensable, particularly for periodic operation such as reverse flow reactor. This paper presents a novel method to develop the kinetic rate expression applied for unsteady state operation. The model reaction of the catalytic methane oxidation over Pt/-Al2O3 catalyst was used with kinetic parameter determined from laboratory experiments. The reactor used was a fixed bed, once-through operation, with a composition modulation in the feed gas. The switching time was set at 3 min by varying the feed concentration, feed flow rate, and reaction temperature. The concentrations of methane in the feed and product were measured and analysed using gas chromatography. The steady state condition for obtaining the kinetic rate expression was taken as a base case and as a way to judge its appropriateness to be applied for dynamic system. A Langmuir-Hinshelwood reaction rate model was developed. The time period during one cycle was divided into some segments, depending on the ratio of CH4/O2. The experimental result shows that there were kinetic regimes occur during one cycle: kinetic regime controlled by intrinsic surface reaction and kinetic regime controlled by external diffusion. The kinetic rate obtained in the steady state operation was not appropriate when applied for unsteady state operation

  1. Evolution of the Oxidation State of the Earth's Mantle: Challenges of High Pressure Quenching

    Science.gov (United States)

    Danielson, L. R.; Righter, K.; Keller, L.; Christoffersen, R.; Rahman, Z.

    2015-01-01

    The oxidation state of the Earth's mantle during formation remains an unresolved question, whether it was constant throughout planetary accretion, transitioned from reduced to oxidized, or from oxidized to reduced. We investigate the stability of Fe3+ at depth, in order to constrain processes (water, late accretion, dissociation of FeO) which may reduce or oxidize the Earth's mantle. Experiments of more mafic compositions and at higher pressures commonly form a polyphase quench intergrowth composed primarily of pyroxenes, with interstitial glass which hosts nearly all of the more volatile minor elements. In our previous experiments on shergottite compositions, variable fO2, T, and P is less than 4 GPa, Fe3+/TotFe decreased slightly with increasing P, similar to terrestrial basalt. For oxidizing experiments less than 7GPa, Fe3+/TotFe decreased as well, but it's unclear from previous modelling whether the deeper mantle could retain significant Fe3+. Our current experiments expand our pressure range deeper into the Earth's mantle and focus on compositions and conditions relevant to the early Earth. Experiments with Knippa basalt as the starting composition were conducted at 1-8 GPa and 1800 C, using a molybdenum capsule to set the fO2 near IW, by buffering with Mo-MoO3. TEM and EELS analyses revealed the run products from 7-8 GPa quenched to polycrystalline phases, with the major phase pyroxene containing approximately equal Fe3+/2+. A number of different approaches have been employed to produce glassy samples that can be measured by EELS and XANES. A more intermediate andesite was used in one experiment, and decompression during quenching was attempted after, but both resulted in a finer grained polyphase texture. Experiments are currently underway to test different capsule materials may affect quench texture. A preliminary experiment using liquid nitrogen to greatly enhance the rate of cooling of the assembly has also been attempted and this technique will be

  2. The impact of degassing on the oxidation state of basaltic magmas: A case study of Kīlauea volcano

    Science.gov (United States)

    Moussallam, Yves; Edmonds, Marie; Scaillet, Bruno; Peters, Nial; Gennaro, Emanuela; Sides, Issy; Oppenheimer, Clive

    2016-09-01

    Volcanic emissions link the oxidation state of the Earth's mantle to the composition of the atmosphere. Whether the oxidation state of an ascending magma follows a redox buffer - hence preserving mantle conditions - or deviates as a consequence of degassing remains under debate. Thus, further progress is required before erupted basalts can be used to infer the redox state of the upper mantle or the composition of their co-emitted gases to the atmosphere. Here we present the results of X-ray absorption near-edge structure (XANES) spectroscopy at the iron K-edge carried out for a series of melt inclusions and matrix glasses from ejecta associated with three eruptions of Kīlauea volcano (Hawai'i). We show that the oxidation state of these melts is strongly correlated with their volatile content, particularly in respect of water and sulfur contents. We argue that sulfur degassing has played a major role in the observed reduction of iron in the melt, while the degassing of H2O and CO2 appears to have had a negligible effect on the melt oxidation state under the conditions investigated. Using gas-melt equilibrium degassing models, we relate the oxidation state of the melt to the composition of the gases emitted at Kīlauea. Our measurements and modelling yield a lower constraint on the oxygen fugacity of the mantle source beneath Kīlauea volcano, which we infer to be near the nickel nickel-oxide (NNO) buffer. Our findings should be widely applicable to other basaltic systems and we predict that the oxidation state of the mantle underneath most hotspot volcanoes is more oxidised than that of the associated lavas. We also suggest that whether the oxidation states of a basalt (in particular MORB) reflects that of its source, is primarily determined by the extent of sulfur degassing.

  3. Arsenic in hydrothermal apatite: Oxidation state, mechanism of uptake, and comparison between experiments and nature

    Science.gov (United States)

    Liu, Weihua; Mei, Yuan; Etschmann, Barbara; Brugger, Joël; Pearce, Mark; Ryan, Chris G.; Borg, Stacey; Wykes, Jeremey; Kappen, Peter; Paterson, David; Boesenberg, Ulrike; Garrevoet, Jan; Moorhead, Gareth; Falkenberg, Gerald

    2017-01-01

    Element substitution that occurs during fluid-rock interaction permits assessment of fluid composition and interaction conditions in ancient geological systems, and provides a way to fix contaminants from aqueous solutions. We conducted a series of hydrothermal mineral replacement experiments to determine whether a relationship can be established between arsenic (As) distribution in apatite and fluid chemistry. Calcite crystals were reacted with phosphate solutions spiked with As(V), As(III), and mixed As(III)/As(V) species at 250 °C and water-saturated pressure. Arsenic-bearing apatite rims formed in several hours, and within 48 h the calcite grains were fully replaced. X-ray Absorption Near-edge Spectroscopy (XANES) data show that As retained the trivalent oxidation state in the fully-reacted apatite grown from solutions containing only As(III). Extended X-ray Fine Spectroscopy (EXAFS) data reveal that these As(III) ions are surrounded by about three oxygen atoms at an Assbnd O bond length close to that of an arsenate group (AsO43-), indicating that they occupy tetrahedral phosphate sites. The three-coordinated As(III)-O3 structure, with three oxygen atoms and one lone electron pair around As(III), was confirmed by geometry optimization using ab initio molecular simulations. The micro-XANES imaging data show that apatite formed from solutions spiked with mixed As(III) and As(V) retained only As(V) after completion of the replacement reaction; in contrast, partially reacted samples revealed a complex distribution of As(V)/As(III) ratios, with As(V) concentrated in the center of the grain and As(III) towards the rim. Most natural apatites from the Ernest Henry iron oxide copper gold deposit, Australia, show predominantly As(V), but two grains retained some As(III) in their core. The As-anomalous amphibolite-facies gneiss from Binntal, Switzerland, only revealed As(V), despite the fact that these apatites in both cases formed under conditions where As(III) is

  4. Synthesis, Characterization, and Electrochemistry of sigma-Bonded Cobalt Corroles in High Oxidation States.

    Science.gov (United States)

    Will, Stefan; Lex, Johann; Vogel, Emanuel; Adamian, Victor A.; Van Caemelbecke, Eric; Kadish, Karl M.

    1996-09-11

    The synthesis, electrochemistry, spectroscopy, and structural characterization of two high-valent phenyl sigma-bonded cobalt corroles containing a central cobalt ion in formal +IV and +V oxidation states is presented. The characterized compounds are represented as phenyl sigma-bonded cobalt corroles, (OEC)Co(C(6)H(5)) and [(OEC)Co(C(6)H(5))]ClO(4), where OEC is the trianion of 2,3,7,8,12,13,17,18-octaethylcorrole. The electronic distribution in both molecules is discussed in terms of their NMR and EPR spectroscopic data, magnetic susceptibility, and electrochemistry.

  5. Energy state distributions at oxide-semiconductor interfaces investigated by Laplace DLTS

    Energy Technology Data Exchange (ETDEWEB)

    Dobaczewski, L., E-mail: dobacz@ifpan.edu.p [Institute of Physics Polish Academy of Science, al. Lotnikow 32/46, 02-668 Warsaw (Poland); School of Electrical and Electronic Engineering, University of Manchester, M60 1QD Manchester (United Kingdom); Markevich, V.P. [School of Electrical and Electronic Engineering, University of Manchester, M60 1QD Manchester (United Kingdom); Kruszewski, P. [Institute of Physics Polish Academy of Science, al. Lotnikow 32/46, 02-668 Warsaw (Poland); Hawkins, I.D.; Peaker, A.R. [School of Electrical and Electronic Engineering, University of Manchester, M60 1QD Manchester (United Kingdom)

    2009-12-15

    At disordered Si/SiO{sub 2} interfaces the lattice mismatching results in dangling bond P{sub b} centres forming a rather broad distribution of energy states. In this study these energy distributions have been determined using isothermal current Laplace deep level transient spectroscopy (DLTS) for the (1 0 0) and (1 1 1) interface orientations. The (1 1 1) distribution is 0.08 eV broad and centred at 0.38 eV below the silicon conduction band. This is consistent with only P{sub b0} states being present. While for the (1 0 0) orientation this distribution is broader (0.1 eV) and deeper (0.43 eV) on the energy scale. Detailed studies revealed two types of the interface states in this broad distribution: one similar to the (1 1 1) orientation while the other has a negative-U character in which the emission rate versus surface potential dependence is qualitatively different from that observed for P{sub b0} and is presumed to be P{sub b1}. Discrepancies between P{sub b} states energy distributions obtained with a use of the isothermal Laplace and conventional DLTS measurements are discussed. The presented experimental procedure can be used for analysis of interface states observed at interfaces of other semiconductor-oxide/dielectric systems.

  6. Energy state distributions at oxide-semiconductor interfaces investigated by Laplace DLTS

    Science.gov (United States)

    Dobaczewski, L.; Markevich, V. P.; Kruszewski, P.; Hawkins, I. D.; Peaker, A. R.

    2009-12-01

    At disordered Si/SiO2 interfaces the lattice mismatching results in dangling bond Pb centres forming a rather broad distribution of energy states. In this study these energy distributions have been determined using isothermal current Laplace deep level transient spectroscopy (DLTS) for the (1 0 0) and (1 1 1) interface orientations. The (1 1 1) distribution is 0.08 eV broad and centred at 0.38 eV below the silicon conduction band. This is consistent with only Pb0 states being present. While for the (1 0 0) orientation this distribution is broader (0.1 eV) and deeper (0.43 eV) on the energy scale. Detailed studies revealed two types of the interface states in this broad distribution: one similar to the (1 1 1) orientation while the other has a negative-U character in which the emission rate versus surface potential dependence is qualitatively different from that observed for Pb0 and is presumed to be Pb1. Discrepancies between Pb states energy distributions obtained with a use of the isothermal Laplace and conventional DLTS measurements are discussed. The presented experimental procedure can be used for analysis of interface states observed at interfaces of other semiconductor-oxide/dielectric systems.

  7. Evaluating chemical extraction techniques for the determination of uranium oxidation state in reduced aquifer sediments

    Science.gov (United States)

    Stoliker, Deborah L.; Campbell, Kate M.; Fox, Patricia M.; Singer, David M.; Kaviani, Nazila; Carey, Minna; Peck, Nicole E.; Barger, John R.; Kent, Douglas B.; Davis, James A.

    2013-01-01

    Extraction techniques utilizing high pH and (bi)carbonate concentrations were evaluated for their efficacy in determining the oxidation state of uranium (U) in reduced sediments collected from Rifle, CO. Differences in dissolved concentrations between oxic and anoxic extractions have been proposed as a means to quantify the U(VI) and U(IV) content of sediments. An additional step was added to anoxic extractions using a strong anion exchange resin to separate dissolved U(IV) and U(VI). X-ray spectroscopy showed that U(IV) in the sediments was present as polymerized precipitates similar to uraninite and/or less ordered U(IV), referred to as non-uraninite U(IV) species associated with biomass (NUSAB). Extractions of sediment containing both uraninite and NUSAB displayed higher dissolved uranium concentrations under oxic than anoxic conditions while extractions of sediment dominated by NUSAB resulted in identical dissolved U concentrations. Dissolved U(IV) was rapidly oxidized under anoxic conditions in all experiments. Uraninite reacted minimally under anoxic conditions but thermodynamic calculations show that its propensity to oxidize is sensitive to solution chemistry and sediment mineralogy. A universal method for quantification of U(IV) and U(VI) in sediments has not yet been developed but the chemical extractions, when combined with solid-phase characterization, have a narrow range of applicability for sediments without U(VI).

  8. Evaluating chemical extraction techniques for the determination of uranium oxidation state in reduced aquifer sediments.

    Science.gov (United States)

    Stoliker, Deborah L; Campbell, Kate M; Fox, Patricia M; Singer, David M; Kaviani, Nazila; Carey, Minna; Peck, Nicole E; Bargar, John R; Kent, Douglas B; Davis, James A

    2013-08-20

    Extraction techniques utilizing high pH and (bi)carbonate concentrations were evaluated for their efficacy in determining the oxidation state of uranium (U) in reduced sediments collected from Rifle, CO. Differences in dissolved concentrations between oxic and anoxic extractions have been proposed as a means to quantify the U(VI) and U(IV) content of sediments. An additional step was added to anoxic extractions using a strong anion exchange resin to separate dissolved U(IV) and U(VI). X-ray spectroscopy showed that U(IV) in the sediments was present as polymerized precipitates similar to uraninite and/or less ordered U(IV), referred to as non-uraninite U(IV) species associated with biomass (NUSAB). Extractions of sediment containing both uraninite and NUSAB displayed higher dissolved uranium concentrations under oxic than anoxic conditions while extractions of sediment dominated by NUSAB resulted in identical dissolved U concentrations. Dissolved U(IV) was rapidly oxidized under anoxic conditions in all experiments. Uraninite reacted minimally under anoxic conditions but thermodynamic calculations show that its propensity to oxidize is sensitive to solution chemistry and sediment mineralogy. A universal method for quantification of U(IV) and U(VI) in sediments has not yet been developed but the chemical extractions, when combined with solid-phase characterization, have a narrow range of applicability for sediments without U(VI).

  9. Real-time plasmon spectroscopy study of the solid-state oxidation and Kirkendall void formation in copper nanoparticles.

    Science.gov (United States)

    Susman, Mariano D; Feldman, Yishai; Bendikov, Tatyana A; Vaskevich, Alexander; Rubinstein, Israel

    2017-08-31

    Oxidation and corrosion reactions have a major effect on the application of non-noble metals. Kinetic information and simple theoretical models are often insufficient for describing such processes in metals at the nanoscale, particularly in cases involving formation of internal voids (nano Kirkendall effect, NKE) during oxidation. Here we study the kinetics of solid-state oxidation of chemically-grown copper nanoparticles (NPs) by in situ localized surface plasmon resonance (LSPR) spectroscopy during isothermal annealing in the range 110-170 °C. We show that LSPR spectroscopy is highly effective in kinetic studies of such systems, enabling convenient in situ real-time measurements during oxidation. Change of the LSPR spectra throughout the oxidation follows a common pattern, observed for different temperatures, NP sizes and substrates. The well-defined initial Cu NP surface plasmon (SP) band red-shifts continuously with oxidation, while the extinction intensity initially increases to reach a maximum value at a characteristic oxidation time τ, after which the SP intensity continuously drops. The characteristic time τ is used as a scaling parameter for the kinetic analysis. Evolution of the SP wavelength and extinction intensity during oxidation at different temperatures follows the same kinetics when the oxidation time is normalized to τ, thus pointing to a general oxidation mechanism. The characteristic time τ is used to estimate the activation energy of the process, determined to be 144 ± 6 kJ mol(-1), similar to previously reported values for high-temperature Cu thermal oxidation. The central role of the NKE in the solid-state oxidation process is revealed by electron microscopy, while formation of Cu2O as the major oxidation product is established by X-ray diffraction, XPS, and electrochemical measurements. The results indicate a transition of the oxidation mechanism from a Valensi-Carter (VC) to NKE mechanism with the degree of oxidation. To interpret the

  10. Pomegranate juice sugar fraction reduces macrophage oxidative state, whereas white grape juice sugar fraction increases it.

    Science.gov (United States)

    Rozenberg, Orit; Howell, Amy; Aviram, Michael

    2006-09-01

    The antiatherogenic properties of pomegranate juice (PJ) were attributed to its antioxidant potency and to its capacity to decrease macrophage oxidative stress, the hallmark of early atherogeneis. PJ polyphenols and sugar-containing polyphenolic anthocyanins were shown to confer PJ its antioxidant capacity. In the present study, we questioned whether PJ simple or complex sugars contribute to the antioxidative properties of PJ in comparison to white grape juice (WGJ) sugars. Whole PJ decreased cellular peroxide levels in J774A.1 macrophage cell-line by 23% more than PJ polyphenol fraction alone. Thus, we next determined the contribution of the PJ sugar fraction to the decrease in macrophage oxidative state. Increasing concentrations of the PJ sugar fraction resulted in a dose-dependent decrement in macrophage peroxide levels, up to 72%, compared to control cells. On the contrary, incubation of the cells with WGJ sugar fraction at the same concentrations resulted in a dose-dependent increment in peroxide levels by up to 37%. The two sugar fractions from PJ and from WGJ showed opposite effects (antioxidant for PJ and pro-oxidant for WGJ) also in mouse peritoneal macrophages (MPM) from control as well as from streptozotocin-induced diabetic Balb/C mice. PJ sugar consumption by diabetic mice for 10 days resulted in a small but significant decrement in their peritoneal macrophage total peroxide levels and an increment in cellular glutathione content, compared to MPM harvested from control diabetic mice administrated with water. In contrast, WGJ sugar consumption by diabetic mice resulted in a 22% increment in macrophage total peroxide levels and a 45% decrement in cellular glutathione content. Paraoxonase 2 activity in macrophages increases under oxidative stress conditions. Indeed, macrophage paraoxonase 2 activity was decreased after PJ sugars supplementation, but increased after WGJ sugars supplementation. We conclude that PJ sugar fraction, unlike WGJ sugar fraction

  11. Probing the transition state region in catalytic CO oxidation on Ru

    Energy Technology Data Exchange (ETDEWEB)

    Ostrom, H. [Stockholm Univ. (Sweden); Oberg, H. [Stockholm Univ. (Sweden); Xin, H. [SLAC National Accelerator Lab., Menlo Park, CA (United States); LaRue, J. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States); Beye, M. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Helmholtz Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Dell' Angela, M. [Univ. of Hamburg and Center for Free Electron Laser Science, Hamburg (Germany); Gladh, J. [Stockholm Univ. (Sweden); Ng, M. L. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Sellberg, J. A. [Stockholm Univ. (Sweden); SLAC National Accelerator Lab., Menlo Park, CA (United States); Kaya, S. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Mercurio, G. [Univ. of Hamburg and Center for Free Electron Laser Science, Hamburg (Germany); Nordlund, D. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Hantschmann, M. [Helmholtz Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Hieke, F. [Univ. of Hamburg and Center for Free Electron Laser Science, Hamburg (Germany); Kuhn, D. [Helmholtz Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Schlotter, W. F. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Dakovski, G. L. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Turner, J. J. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Minitti, M. P. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Mitra, A. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Moeller, S. P. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Fohlisch, A. [Helmholtz Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany); Univ. Potsdam, Potsdam (Germany); Wolf, M. [Fritz-Haber Institute of the Max-Planck-Society, Berlin (Germany); Wurth, W. [Univ. of Hamburg and Center for Free Electron Laser Science, Hamburg (Germany); DESY Photon Science, Hamburg (Germany); Persson, M. [The Univ. of Liverpool, Liverpool (United Kingdom); Norskov, J. K. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States); Abild-Pedersen, F. [Stanford Univ., Stanford, CA (United States); Ogasawara, H. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Pettersson, L. G. M. [Stockholm Univ. (Sweden); Nilsson, A. [Stockholm Univ. (Sweden); SLAC National Accelerator Lab., Menlo Park, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)

    2015-02-12

    Femtosecond x-ray laser pulses are used to probe the CO oxidation reaction on ruthenium (Ru) initiated by an optical laser pulse. On a time scale of a few hundred femtoseconds, the optical laser pulse excites motions of CO and O on the surface, allowing the reactants to collide, and, with a transient close to a picosecond (ps), new electronic states appear in the O K-edge x-ray absorption spectrum. Density functional theory calculations indicate that these result from changes in the adsorption site and bond formation between CO and O with a distribution of OC–O bond lengths close to the transition state (TS). After 1 ps, 10% of the CO populate the TS region, which is consistent with predictions based on a quantum oscillator model.

  12. Origin of major donor states in In–Ga–Zn oxide

    Energy Technology Data Exchange (ETDEWEB)

    Nakashima, Motoki; Oota, Masashi; Ishihara, Noritaka; Nonaka, Yusuke; Hirohashi, Takuya; Takahashi, Masahiro; Yamazaki, Shunpei [Semiconductor Energy Laboratory Co., Ltd., 398 Hase, Atsugi, Kanagawa 243-0036 (Japan); Obonai, Toshimitsu; Hosaka, Yasuharu; Koezuka, Junichi [Advanced Film Device Inc., 161-2 Masuzuka, Tsuga-machi, Tochigi, Tochigi 328-0114 (Japan)

    2014-12-07

    To clarify the origin of the major donor states in indium gallium zinc oxide (IGZO), we report measurement results and an analysis of several physical properties of IGZO thin films. Specifically, the concentration of H atoms and O vacancies (V{sub O}), carrier concentration, and conductivity are investigated by hard X-ray photoelectron spectroscopy, secondary ion mass spectroscopy, thermal desorption spectroscopy, and Hall effect measurements. The results of these experiments suggest that the origin of major donor states is H occupancy of V{sub O} sites. Furthermore, we use first-principles calculations to investigate the influence of the coexistence of V{sub O} and H in crystalline InGaO{sub 3}(ZnO){sub m} (m = 1). The results indicate that when H is trapped in V{sub O}, a stable complex is created that serves as a shallow-level donor.

  13. On the chemical state of Co oxide electrocatalysts during alkaline water splitting.

    Science.gov (United States)

    Friebel, Daniel; Bajdich, Michal; Yeo, Boon Siang; Louie, Mary W; Miller, Daniel J; Sanchez Casalongue, Hernan; Mbuga, Felix; Weng, Tsu-Chien; Nordlund, Dennis; Sokaras, Dimosthenis; Alonso-Mori, Roberto; Bell, Alexis T; Nilsson, Anders

    2013-10-28

    Resonant inelastic X-ray scattering and high-resolution X-ray absorption spectroscopy were used to identify the chemical state of a Co electrocatalyst in situ during the oxygen evolution reaction. After anodic electrodeposition onto Au(111) from a Co(2+)-containing electrolyte, the chemical environment of Co can be identified to be almost identical to CoOOH. With increasing potentials, a subtle increase of the Co oxidation state is observed, indicating a non-stoichiometric composition of the working OER catalyst containing a small fraction of Co(4+) sites. In order to confirm this interpretation, we used density functional theory with a Hubbard-U correction approach to compute X-ray absorption spectra of model compounds, which agree well with the experimental spectra. In situ monitoring of catalyst local structure and bonding is essential in the development of structure-activity relationships that can guide the discovery of efficient and earth abundant water splitting catalysts.

  14. Solid-State Thermal Reaction of a Molecular Material and Solventless Synthesis of Iron Oxide

    Science.gov (United States)

    Roy, Debasis; Roy, Madhusudan; Zubko, Maciej; Kusz, Joachim; Bhattacharjee, Ashis

    2016-09-01

    Solid-state thermal decomposition reaction of a molecular material {As}({C}6{H}5)4[{Fe}^{II}{Fe}^{III} ({C}2{O}4)3]}n has been studied using non-isothermal thermogravimetry (TG) in an inert atmosphere. By analyzing the TG data collected at multiple heating rates in 300 K-1300 K range, the kinetic parameters (activation energy, most probable reaction mechanism function and frequency factor) are determined using different multi-heating rate analysis programs. Activation energy and the frequency factor are found to be strongly dependent on the extent of decomposition. The decomposed material has been characterized to be hematite using physical techniques (FT-IR and powder XRD). Particle morphology has been checked by TEM. A solid-state reaction pathway leading the molecular precursor to hematite has been proposed illustrating an example of solventless synthesis of iron oxides utilizing thermal decomposition as a technique using innocuous materials.

  15. Localized and itinerant states in lanthanide oxides united by GW @ LDA+U.

    Science.gov (United States)

    Jiang, Hong; Gomez-Abal, Ricardo I; Rinke, Patrick; Scheffler, Matthias

    2009-03-27

    Many-body perturbation theory in the GW approach is applied to lanthanide oxides, using the local-density approximation plus a Hubbard U correction (LDA+U) as the starting point. Good agreement between the G0W0 density of states and experimental spectra is observed for CeO2 and Ce2O3. Unlike the LDA+U method G0W0 exhibits only a weak dependence on U in a physically meaningful range of U values. For the whole lanthanide sesquioxide (Ln2O3) series G0W0 @ LDA+U reproduces the main features found for the optical experimental band gaps. The relative positions of the occupied and unoccupied f states predicted by G0W0 confirm the experimental conjecture derived from phenomenological arguments.

  16. Hexavalent chromium affects sperm motility by influencing protein tyrosine phosphorylation in the midpiece of boar spermatozoa.

    Science.gov (United States)

    Zhen, Linqing; Wang, Lirui; Fu, Jieli; Li, Yuhua; Zhao, Na; Li, Xinhong

    2016-01-01

    Hexavalent chromium reportedly induces reproductive toxicity and further inhibits male fertility in mammals. In this study, we investigated the molecular mechanism by which hexavalent chromium affects motility signaling in boar spermatozoa in vitro. The results indicated that Cr(VI) decreased sperm motility, protein phosphorylation, mitochondrial membrane potential (ΔΨm) and metabolic enzyme activity starting at 4μmol/mL following incubation for 1.5h. Notably, all parameters were potently inhibited by 10μmol/mL Cr, while supplementation with the dibutyryl-cAMP (dbcAMP) and the 3-isobutyl-1-methylxanthine (IBMX) prevented the inhibition of protein phosphorylation. Interestingly, high concentrations of Cr (>10μmol/mL) increased the tyrosine phosphorylation of some high-molecular-weight proteins in the principle piece but decreased that in the middle piece associated with an extreme reduction of sperm motility. These results suggest that chromium affects boar sperm motility by impairing tyrosine phosphorylation in the midpiece of sperm by blocking the cAMP/PKA pathway in boar sperm in vitro.

  17. Biological groundwater treatment for chromium removal at low hexavalent chromium concentrations.

    Science.gov (United States)

    Mamais, Daniel; Noutsopoulos, Constantinos; Kavallari, Ioanna; Nyktari, Eleni; Kaldis, Apostolos; Panousi, Eleni; Nikitopoulos, George; Antoniou, Kornilia; Nasioka, Maria

    2016-06-01

    The objective of this work is to develop and evaluate biological groundwater treatment systems that will achieve hexavalent chromium reduction and total chromium removal from groundwater at hexavalent chromium (Cr(VI)) groundwater concentrations in the 0-200 μg/L range. Three lab-scale units operated, as sequencing batch reactors (SBR) under aerobic, anaerobic and anaerobic-aerobic conditions. All systems received groundwater with a Cr(VI) content of 200 μg/L. In order to support biological growth, groundwater was supplemented with milk, liquid cheese whey or a mixture of sugar and milk to achieve a COD concentration of 200 mg/L. The results demonstrate that a fully anaerobic system or an anaerobic-aerobic system dosed with simple or complex external organic carbon sources can lead to practically complete Cr(VI) reduction to Cr(III). The temperature dependency of maximum Cr(VI) removal rates can be described by the Arrhenius relationship. Total chromium removal in the biological treatment systems was not complete because a significant portion of Cr(III) remained in solution. An integrated system comprising of an anaerobic SBR followed by a sand filter achieved more than 95% total chromium removal thus resulting in average effluent total and dissolved chromium concentrations of 7 μg/L and 3 μg/L, respectively.

  18. Treatment of Wastewater Containing Hexavalent Chromium Using Zeolite Ceramic Adsorbent in Adsorption Column

    Directory of Open Access Journals (Sweden)

    Tuty Emilia Agustina

    2017-04-01

    Full Text Available Natural Zeolites in powdered form have commonly used as adsorbent and one of the most crucial compound in water treatment plant, in filter system of petrochemicals or other processes under environmentally, physically and chemically conditions.  But in the form of powder, zeolites are easily washed out in liquid or gas stream. Therefore, a modification would be necessary to solve this problem. Zeolites and clay were modified into ceramic adsorbent to adsorb heavy metal pollutant that is hexavalent chromium Cr (VI contained in electroplating industrial effluents. Zeolite and clay were mixed evenly and molded into small balls with 5-6 mm diameter and dried at 1000oC for 48 hrs. This adsorbent was activated with HCl 32% solution for 1 hr to enhance its adsorption potential. Ten samples with various ratios of zeolite:clay (3:37-12:28 with the total adsorbent mass of 1000 g was examined.  Cr (VI uptake in liquid wastewater was studied by varying contact time and the ratio of zeolite and clay. The effect of activation treatment with HCl 32% solution on adsorption performance of zeolite ceramic adsorbent was also investigated. Analysis of wastewater output indicates a reduction of hexavalent chromium concentration reaches 99.45% at contact time 10 h with 12:28 ratio of activated adsorbent. This shown that the process of adsorption had greatly reduced the contamination of Cr (VI and may have been a solution for environment problem regarding wastewater containing Cr (VI. 

  19. Hexavalent chromium removal from aqueous solutions by a novel powder prepared from Colocasia esculenta leaves.

    Science.gov (United States)

    Nakkeeran, E; Saranya, N; Giri Nandagopal, M S; Santhiagu, A; Selvaraju, N

    2016-08-01

    In this study, batch removal of hexavalent chromium from aqueous solutions by powdered Colocasia esculenta leaves was investigated. Batch experiments were conducted to study the effects of adsorption of Cr(VI) at different pH values, initial concentrations, agitation speeds, temperatures, and contact times. The biosorbent was characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and Fourier transform infrared spectrometer analysis. The biosorptive capacity of the adsorbent was dependent on the pH of the chromium solution in which maximum removal was observed at pH 2. The adsorption equilibrium data were evaluated for various adsorption isotherm models, kinetic models, and thermodynamics. The equilibrium data fitted well with Freundlich and Halsey models. The adsorption capacity calculated was 47.62 mg/g at pH 2. The adsorption kinetic data were best described by pseudo-second-order kinetic model. Thus, Colocasia esculenta leaves can be considered as one of the efficient and cheap biosorbents for hexavalent chromium removal from aqueous solutions.

  20. Toxic hexavalent chromium reduction by Bacillus pumilis, Cellulosimicrobium cellulans and Exiguobacterium

    Science.gov (United States)

    Rehman, Fatima; Faisal, Muhammad

    2015-05-01

    Three bacterial strains Bacillus pumilis, Cellulosimicrobium cellulans and Exiguobacterium were investigated when grown in Luria-Bertani (LB) medium at 500 μg/mL Cr(VI). The hexavalent chromium reduction was measured by growing the strains in DeLeo and Ehrlich (1994) medium at 200 and 400 μg/mL K2CrO4. The optimal Cr (VI) reduction by strains B. pumilis, Exigubacterium and C. cellulans was 51%, 39%, and 41%, respectively, at an initial K2CrO4 concentration of 200 μg/mL at pH 3 and temperature 37°C. At an initial chromate concentration of 400 μg/mL, the Cr(VI) reduction by strains B. pumilis, Exigubacterium and C. cellulans was 24%, 19%, and 18%, respectively at pH 3 at 37°C after 24 h. These strains have ability to reduce toxic hexavalent chromium to the less mobile trivalent chromium at a wide range of different environmental conditions and can be useful for the treatment of contaminated wastewater and soils.

  1. Removal of hexavalent chromium from aqueous solution using Cassava peel (Manihot Esculenta: column experiments

    Directory of Open Access Journals (Sweden)

    Alberto Ricardo Albis Arrieta

    2017-01-01

    Full Text Available Introduction: Hexavalent chromium is a highly toxic metal and it is considered one of the contaminants with the highest environmental impact. Bioadsorbents have been considered as a viable option for chromium removal, leading to the necessity to study the behavior of these adsorbents in unit operations similar to the ones employed in the industry. Objective: To study the potential of cassava peels as bio-sorbent in the adsorption of hexavalent chromium in a semi-continuous process in fixed bed columns. Methodology: The effect of parameters such as feed flow rate, initial concentration and bed column height on the response variables rupture time and removal capacity was analyzed using a laboratory scale experimental set-up. Results: Low feed flow rates, low initial concentrations, and higher bed height produce the best conditions for chromium removal. Additionally, three classical models for removal on the packed column were used to fit the dynamic behavior of this process and to obtain significantly physical parameters. However, the best fitting was obtained using the model of the response surface. Conclusions: The concentration of chromium in the feed stream is the experimental factor that has the most influence on removal capacity and rupture time in fixed bed columns packed with cassava peel.

  2. Fully delocalized (ethynyl)(vinyl)phenylene bridged triruthenium complexes in up to five different oxidation states.

    Science.gov (United States)

    Wuttke, Evelyn; Pevny, Florian; Hervault, Yves-Marie; Norel, Lucie; Drescher, Malte; Winter, Rainer F; Rigaut, Stéphane

    2012-02-01

    Triruthenium [(dppe)(2)Ru{-C≡C-1,4-C(6)H(2)-2,5-R(2)-CH═CH-RuCl(CO)(P(i)Pr(3))(2)}(2)](n+) (4a, R = H; 4b, R = OMe) containing unsymmetrical (ethynyl)(vinyl)phenylene bridging ligands and displaying five well-separated redox states (n = 0-4) are compared to their bis(alkynyl)ruthenium precursors (dppe)(2)Ru{-C≡C-1,4-C(6)H(2)-2,5-R(2)-C≡CR'} (2a,b: R' = TMS; 3a,b: R' = H) and their symmetrically substituted bimetallic congeners, complexes {Cl(dppe)(2)Ru}(2){μ-C≡C-1,4-C(6)H(2)-2,5-R(2)-C≡C} (A(a), R = H; A(b), R = OMe) and {RuCl(CO)(P(i)Pr(3))(2)}(2){μ-CH═CH-1,4-C(6)H(2)-2,5-R(2)-CH═CH} (V(a), R = H; V(b), R = OMe) as well as the mixed (ethynyl)(vinyl)phenylene bridged [Cl(dppe)(2)Ru-C≡C-1,4-C(6)H(4)-CH═CH-RuCl(CO)(P(i)Pr(3))(2)] (M(a)). Successive one-electron transfer steps were studied by means of cyclic voltammetry, EPR and UV-vis-NIR-IR spectroelectrochemistry. These studies show that the first oxidation mainly involves the central bis(alkynyl) ruthenium moiety with only limited effects on the appended vinyl ruthenium moieties. The second to fourth oxidations (n = 2, 3, 4) involve the entire carbon-rich conjugated path of the molecule with an increased charge uniformly distributed between the two arms of the molecules, including the terminal vinyl ruthenium sites. In order to assess the charge distribution, we judiciously use (13)CO labeled analogues to distinguish stretching vibrations due to the acetylide triple bonds and the intense and charge-sensitive Ru(CO) IR probe in different oxidation states. The comparison between complex pairs 4a,b(n+) (n = 0-3), A(a,b)(n+) and V(a,b)(n+) (n = 0-2) serves to elucidate the effect of the methoxy donor substituents on the redox and spectroscopic properties of these systems in their various oxidation states and on the metal/ligand contributions to their frontier orbitals.

  3. Oxidative stress markers in hypertensive states of pregnancy: preterm and term disease.

    Directory of Open Access Journals (Sweden)

    Lesia Olha Kurlak

    2014-08-01

    Full Text Available Discussion continues as to whether de novo hypertension in pregnancy with significant proteinuria (pre-eclampsia; PE and non-proteinuric new hypertension (gestational hypertension; GH are parts of the same disease spectrum or represent different conditions. Non-pregnant hypertension, pregnancy and PE are all associated with oxidative stress. We have established a 6 weeks post-partum clinic for women who experienced a hypertensive pregnancy. We hypothesized that PE and GH could be distinguished by markers of oxidative stress; thiobarbituric acid reactive substances (TBARS and antioxidants (ferric ion reducing ability of plasma; FRAP. Since the severity of PE and GH is greater pre-term, we also compared pre-term and term disease. Fifty-eight women had term PE, 23 pre-term PE, 60 had term GH and 6 pre-term GH, 11 pre-existing (essential hypertension (EH without PE. Limited data were available from normotensive pregnancies (n=7 and non-pregnant controls (n=14. There were no differences in postpartum TBARS or FRAP between hypertensive states; TBARS (P=0.001 and FRAP (P=0.009 were lower in plasma of non-pregnant controls compared to recently-pregnant women. Interestingly FRAP was higher in preterm than term GH (P=0.013. In PE and GH, TBARS correlated with low density lipoprotein (LDL-cholesterol (P=0.036; this association strengthened with inclusion of EH ((P=0.011. The 10 year Framingham index for cardiovascular risk was positively associated with TBARS (P=0.003.Oxidative stress profiles do not differ between hypertensive states but appear to distinguish between recently-pregnant and non-pregnant states. This suggests that pregnancy may alter vascular integrity with changes remaining 6 weeks postpartum. LDL-cholesterol is a known determinant of oxidative stress in cardiovascular disease and we have shown this association to be present in hypertensive pregnancy further emphasizing that such a pregnancy may be revealing a pre-existing cardiovascular

  4. The Survey of Melia Azaderach L. ash in Removal of Hexavalent Chromium from Synthetic Electroplating Industry Wastewater

    Directory of Open Access Journals (Sweden)

    MT Ghaneian

    2014-11-01

    Conclusion: Melia azedarach ash is an effective adsorbent in removal of hexavalent chromium from synthetic electroplating industries wastewater. In addition, the use of this biosorbent in preparation and application aspects is simple and cheap compared to many other natural and man-made adsorbent.

  5. Photodeposition of platinum nanoparticles on well-defined Tungsten oxide: controlling oxidation state, particle size and geometrical distribution

    NARCIS (Netherlands)

    Wenderich, Kasper

    2016-01-01

    In this thesis, structure-directed photodeposition of the cocatalyst platinum (Pt) on monoclinic tungsten oxide (WO3) nanoplates is described, both considering fundamental aspects, as well as usefulness for applications in photocatalytic propane oxidation. Before such studies are described, the conc

  6. Obesity-associated oxidative stress: strategies finalized to improve redox state.

    Science.gov (United States)

    Savini, Isabella; Catani, Maria Valeria; Evangelista, Daniela; Gasperi, Valeria; Avigliano, Luciana

    2013-05-21

    Obesity represents a major risk factor for a plethora of severe diseases, including diabetes, cardiovascular disease, non-alcoholic fatty liver disease, and cancer. It is often accompanied by an increased risk of mortality and, in the case of non-fatal health problems, the quality of life is impaired because of associated conditions, including sleep apnea, respiratory problems, osteoarthritis, and infertility. Recent evidence suggests that oxidative stress may be the mechanistic link between obesity and related complications. In obese patients, antioxidant defenses are lower than normal weight counterparts and their levels inversely correlate with central adiposity; obesity is also characterized by enhanced levels of reactive oxygen or nitrogen species. Inadequacy of antioxidant defenses probably relies on different factors: obese individuals may have a lower intake of antioxidant- and phytochemical-rich foods, such as fruits, vegetables, and legumes; otherwise, consumption of antioxidant nutrients is normal, but obese individuals may have an increased utilization of these molecules, likewise to that reported in diabetic patients and smokers. Also inadequate physical activity may account for a decreased antioxidant state. In this review, we describe current concepts in the meaning of obesity as a state of chronic oxidative stress and the potential interventions to improve redox balance.

  7. Caesium in high oxidation states and as a p-block element.

    Science.gov (United States)

    Miao, Mao-sheng

    2013-10-01

    The periodicity of the elements and the non-reactivity of the inner-shell electrons are two related principles of chemistry, rooted in the atomic shell structure. Within compounds, Group I elements, for example, invariably assume the +1 oxidation state, and their chemical properties differ completely from those of the p-block elements. These general rules govern our understanding of chemical structures and reactions. Here, first-principles calculations show that, under pressure, caesium atoms can share their 5p electrons to become formally oxidized beyond the +1 state. In the presence of fluorine and under pressure, the formation of CsF(n) (n > 1) compounds containing neutral or ionic molecules is predicted. Their geometry and bonding resemble that of isoelectronic XeF(n) molecules, showing a caesium atom that behaves chemically like a p-block element under these conditions. The calculated stability of the CsF(n) compounds shows that the inner-shell electrons can become the main components of chemical bonds.

  8. Role of the oxidation state of cerium on the ceria surfaces for silicate adsorption

    Science.gov (United States)

    Seo, Jihoon; Moon, Jinok; Kim, Joo Hyun; Lee, Kangchun; Hwang, Junha; Yoon, Heesung; Yi, Dong Kee; Paik, Ungyu

    2016-12-01

    In this study, we have investigated the role of the Ce oxidation state (Ce3+/Ce4+) on the CeO2 surfaces for silicate adsorption. In aqueous medium, the Ce3+ sites lead to the formation of -OH groups at the CeO2 surface through H2O dissociation. Silicate ions can adsorb onto the CeO2 surface through interaction with the -OH groups (-Ce-OH- + -Si-O- ↔ -Ce-O-Si- + OH-). As the Ce3+ concentration increased from 19.3 to 27.6%, the surface density of -OH group increased from 0.34 to 0.72 OH/nm2. To evaluate the adsorption behaviors of silicate ions onto CeO2 NPs, we carried out an adsorption isothermal analysis, and the adsorption isotherm data followed the Freundlich model. The Freundlich constant for the relative adsorption capacity (KF) and adsorption intensity (1/n) indicated that CeO2 NPs with high Ce3+ concentration show higher adsorption affinity with silicate ions. As a result, we have demonstrated that the Ce oxidation state (Ce3+/Ce4+) on the CeO2 surface can have a significant influence on the silicate adsorption.

  9. Ferrous sulphate mono and heptahydrate reduction of hexavalent chromium in cement: effectiveness and storability

    Directory of Open Access Journals (Sweden)

    Valverde, J. L.

    2005-09-01

    Full Text Available In Community legislation, substances containing hexavalent chromium are classified as carcinogenic, mutagenic and sensitizing. In cement, hexavalent chromium intensifies sensitization and may set off severe allergic reactions in workers in routine contact with the product, whether in the factory or on construction sites. The allergic or contact dermatitis causes is a very painful disease that may lead to permanent worker disability. According to Directive 2003/53/EC of the European Parliament and the Council, Governments of all member countries will be required to prohibit the marketing and use, as of 17 January 2005, of any cement or cement preparation containing more than 2 ppm of chromium (VI. Hexavalent chromium can be reduced with ferrous sulphate to trivalent chromium, which is water-insoluble and therefore innocuous to the skin. The present paper reports the effects of adding ferrous sulphate mono- or heptahydrate to a commercial cement and the storage time of the mix on the concentration of hexavalent chromium. The salts studied were found to effectively reduce hexavalent chromium in cement for at least three months.

    Las sustancias que contienen cromo hexavalente están clasificadas en la legislación comunitaria como sustancias carcinogénicas, mutagénicas y sensibilizantes. El cromo hexavalente del cemento potencia la sensibilización y provoca graves reacciones alérgicas que sufren bastante a menudo los trabajadores que lo manipulan habitualmente, ya sea en fábrica o en el sector de la construcción. La dermatitis alérgica o de contacto que produce es muy dolorosa y puede dejar a los trabajadores en estado de discapacidad. La Directiva 2003/53/CE del Parlamento Europeo y del Consejo, exige a los Gobiernos de los países miembros, que a partir del 17 de enero de 2005, prohiban el uso y la comercialización de todos aquellos cementos y preparados que contengan cemento, cuyo contenido en cromo (VI soluble, una vez hidratados

  10. Effect of high doses of L-ascorbic acid on the antioxidative/oxidative state in the rats

    DEFF Research Database (Denmark)

    Niemiec, T.; Sawosz, E.; Chwalibog, André

    2005-01-01

    The objective of this study was to determine the effects of mega-doses of vitamin C (0.3, 0.6 and 0.9% of diet) as a dietary supplement for rats on selected indices of the antioxidative/oxidative state in 40 growing Wistar rats (4x10). It was found that L-ascorbic acid and Total Antioxidative State...

  11. Cellulose nanofibril/reduced graphene oxide/carbon nanotube hybrid aerogels for highly flexible and all-solid-state supercapacitors

    Science.gov (United States)

    Qifeng Zheng; Zhiyong Cai; Zhenqiang Ma; Shaoqin Gong

    2015-01-01

    A novel type of highly flexible and all-solid-state supercapacitor that uses cellulose nanofibril (CNF)/reduced graphene oxide (RGO)/carbon nanotube (CNT) hybrid aerogels as electrodes and H2SO4 poly (vinyl alcohol) PVA gel as the electrolyte was developed and is reported here. These flexible solid-state supercapacitors...

  12. Normal-state nodal electronic structure in underdoped high-Tc copper oxides.

    Science.gov (United States)

    Sebastian, Suchitra E; Harrison, N; Balakirev, F F; Altarawneh, M M; Goddard, P A; Liang, Ruixing; Bonn, D A; Hardy, W N; Lonzarich, G G

    2014-07-03

    An outstanding problem in the field of high-transition-temperature (high-Tc) superconductivity is the identification of the normal state out of which superconductivity emerges in the mysterious underdoped regime. The normal state uncomplicated by thermal fluctuations can be studied using applied magnetic fields that are sufficiently strong to suppress long-range superconductivity at low temperatures. Proposals in which the normal ground state is characterized by small Fermi surface pockets that exist in the absence of symmetry breaking have been superseded by models based on the existence of a superlattice that breaks the translational symmetry of the underlying lattice. Recently, a charge superlattice model that positions a small electron-like Fermi pocket in the vicinity of the nodes (where the superconducting gap is minimum) has been proposed as a replacement for the prevalent superlattice models that position the Fermi pocket in the vicinity of the pseudogap at the antinodes (where the superconducting gap is maximum). Although some ingredients of symmetry breaking have been recently revealed by crystallographic studies, their relevance to the electronic structure remains unresolved. Here we report angle-resolved quantum oscillation measurements in the underdoped copper oxide YBa2Cu3O6 + x. These measurements reveal a normal ground state comprising electron-like Fermi surface pockets located in the vicinity of the nodes, and also point to an underlying superlattice structure of low frequency and long wavelength with features in common with the charge order identified recently by complementary spectroscopic techniques.

  13. Evolution of electronic states in n-type copper oxide superconductor via electric double layer gating.

    Science.gov (United States)

    Jin, Kui; Hu, Wei; Zhu, Beiyi; Kim, Dohun; Yuan, Jie; Sun, Yujie; Xiang, Tao; Fuhrer, Michael S; Takeuchi, Ichiro; Greene, Richard L

    2016-01-01

    The occurrence of electrons and holes in n-type copper oxides has been achieved by chemical doping, pressure, and/or deoxygenation. However, the observed electronic properties are blurred by the concomitant effects such as change of lattice structure, disorder, etc. Here, we report on successful tuning the electronic band structure of n-type Pr2-xCexCuO4 (x = 0.15) ultrathin films, via the electric double layer transistor technique. Abnormal transport properties, such as multiple sign reversals of Hall resistivity in normal and mixed states, have been revealed within an electrostatic field in range of -2 V to + 2 V, as well as varying the temperature and magnetic field. In the mixed state, the intrinsic anomalous Hall conductivity invokes the contribution of both electron and hole-bands as well as the energy dependent density of states near the Fermi level. The two-band model can also describe the normal state transport properties well, whereas the carrier concentrations of electrons and holes are always enhanced or depressed simultaneously in electric fields. This is in contrast to the scenario of Fermi surface reconstruction by antiferromagnetism, where an anti-correlation is commonly expected.

  14. Evolution of electronic states in n-type copper oxide superconductor via electric double layer gating

    Science.gov (United States)

    Jin, Kui; Hu, Wei; Zhu, Beiyi; Kim, Dohun; Yuan, Jie; Sun, Yujie; Xiang, Tao; Fuhrer, Michael S.; Takeuchi, Ichiro; Greene, Richard. L.

    2016-01-01

    The occurrence of electrons and holes in n-type copper oxides has been achieved by chemical doping, pressure, and/or deoxygenation. However, the observed electronic properties are blurred by the concomitant effects such as change of lattice structure, disorder, etc. Here, we report on successful tuning the electronic band structure of n-type Pr2−xCexCuO4 (x = 0.15) ultrathin films, via the electric double layer transistor technique. Abnormal transport properties, such as multiple sign reversals of Hall resistivity in normal and mixed states, have been revealed within an electrostatic field in range of −2 V to + 2 V, as well as varying the temperature and magnetic field. In the mixed state, the intrinsic anomalous Hall conductivity invokes the contribution of both electron and hole-bands as well as the energy dependent density of states near the Fermi level. The two-band model can also describe the normal state transport properties well, whereas the carrier concentrations of electrons and holes are always enhanced or depressed simultaneously in electric fields. This is in contrast to the scenario of Fermi surface reconstruction by antiferromagnetism, where an anti-correlation is commonly expected. PMID:27221198

  15. Theoretical spectroscopic constants for the low-lying states of the oxides and sulfides of Mo and Tc

    Science.gov (United States)

    Langhoff, Stephen R.; Bauschlicher, Charles W., Jr.; Pettersson, Lars G. M.; Siegbahn, Per E. M.

    1989-01-01

    Spectroscopic results were determined for the ground and low-lying states of the oxides and sulfides of Mo and Tc, using the single-reference-based modified coupled pair functional method of Ahlrichs et al. (1985) and Chong et al. (1986) and the multireference-based state-averaged CASSCF/MRCI method. Spectroscopic constants, dipole moments, Mulliken populations, and radiative lifetimes were calculated for selected low-lying states of these molecular systems. The spectroscopy of the MoS and TcS molecules was found to be quite analogous to the corresponding oxides.

  16. Electronic state of ruthenium deposited onto oxide supports: An XPS study taking into account the final state effects

    Science.gov (United States)

    Larichev, Yurii V.; Moroz, Boris L.; Bukhtiyarov, Valerii I.

    2011-12-01

    The electronic state of ruthenium in the supported Ru/EOx (EOx = MgO, Al2O3 or SiO2) catalysts prepared by with the use of Ru(OH)Cl3 or Ru(acac)3 (acac = acetylacetonate) and reduced with H2 at 723 K is characterized by X-ray photoelectron spectroscopy (XPS) in the Ru 3d, Cl 2p and O 1s regions. The influence of the final state effects (the differential charging and variation of the relaxation energy) on the binding energy (BE) of Ru 3d5/2 core level measured for supported Ru nanoparticles is estimated by comparison of the Fermi levels and the modified Auger parameters determined for the Ru/EOx samples with the corresponding characteristics of the bulk Ru metal. It is found that the negative shift of the Ru 3d5/2 peak which is observed in the spectrum of ruthenium deposited onto MgO (BE = 279.5-279.7 eV) with respect to that of Ru black (BE = 280.2 eV) or ruthenium supported on γ-Al2O3 and SiO2 (BE = 280.4 eV) is caused not by the transfer of electron density from basic sites of MgO, as considered earlier, but by the differential charging of the supported Ru particles compared with the support surface. Correction for the differential charging value reveals that the initial state energies of ruthenium in the Ru/EOx systems are almost identical (BE = 280.5 ± 0.1 eV) irrespectively of acid-base properties of the support, the mean size of supported Ru crystallites (within the range of 2-10 nm) and the surface Cl content. The results obtained suggest that the difference in ammonia synthesis activity between the Ru catalysts supported on MgO and on the acidic supports is accounted for by not different electronic state of ruthenium on the surface of these oxides but by some other reasons.

  17. Evolution of the Oxidation State of the Earth's Mantle: Challenges of High Pressure Quenching

    Science.gov (United States)

    Danielson, L. R.; Righter, K.; Keller, L. P.; Rahman, Z.

    2015-12-01

    The oxidation state of the Earth's mantle during formation remains an unresolved question, whether it was constant throughout planetary accretion [1], transitioned from reduced to oxidized [2,3,4], or from oxidized to reduced [1,5]. We investigate the stability of Fe3+ at depth, in order to constrain processes (water, late accretion, dissociation of FeO) which may reduce or oxidize the Earth's mantle. Experiments of more mafic compositions and at higher pressures commonly form a polyphase quench intergrowth composed primarily of pyroxenes, with interstitial glass which hosts nearly all of the more volatile minor elements. In our previous experiments on shergottite compositions, variable fO2, T, and P <4 GPa, Fe3+/ΣFe decreased slightly with increasing P, similar to terrestrial basalt [6,7,8]. For oxidizing experiments < 7GPa, Fe3+/ΣFe decreased as well [9], but it's unclear from previous modelling whether the deeper mantle could retain significant Fe3+ [1,10]. Our current experiments expand our pressure range deeper into the Earth's mantle and focus on compositions and conditions relevant to the early Earth. Experiments with Knippa basalt as the starting composition were conducted at 1-8 GPa and 1800 °C, using a molybdenum capsule to set the fO2 near IW, by buffering with Mo-MoO3. TEM and EELS analyses revealed the run products from 7-8 GPa quenched to polycrystalline phases, with the major phase pyroxene containing approximately equal Fe3+/2+. A number of different approaches have been employed to produce glassy samples that can be measured by EELS and XANES. A more intermediate andesite was used in one experiment, and decompression during quenching was attempted after [11], but both resulted in a finer grained polyphase texture. Experiments are currently underway to test how different capsule materials may affect quench texture. A preliminary experiment using liquid nitrogen to greatly enhance the rate of cooling of the assembly has also been attempted and

  18. Chromium III histidinate exposure modulates antioxidant gene expression in HaCaT human keratinocytes exposed to oxidative stress

    Science.gov (United States)

    While the toxicity of hexavalent chromium is well established, trivalent Cr (Cr(III)) is an essential nutrient involved in insulin and glucose homeostasis. Recently, antioxidant effects of chromium (III) histidinate (Cr(III)His) were reported in HaCaT human keratinocytes exposed to oxidative stress...

  19. Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries

    Science.gov (United States)

    Yabuuchi, Naoaki; Nakayama, Masanobu; Takeuchi, Mitsue; Komaba, Shinichi; Hashimoto, Yu; Mukai, Takahiro; Shiiba, Hiromasa; Sato, Kei; Kobayashi, Yuki; Nakao, Aiko; Yonemura, Masao; Yamanaka, Keisuke; Mitsuhara, Kei; Ohta, Toshiaki

    2016-12-01

    Further increase in energy density of lithium batteries is needed for zero emission vehicles. However, energy density is restricted by unavoidable theoretical limits for positive electrodes used in commercial applications. One possibility towards energy densities exceeding these limits is to utilize anion (oxide ion) redox, instead of classical transition metal redox. Nevertheless, origin of activation of the oxide ion and its stabilization mechanism are not fully understood. Here we demonstrate that the suppression of formation of superoxide-like species on lithium extraction results in reversible redox for oxide ions, which is stabilized by the presence of relatively less covalent character of Mn4+ with oxide ions without the sacrifice of electronic conductivity. On the basis of these findings, we report an electrode material, whose metallic constituents consist only of 3d transition metal elements. The material delivers a reversible capacity of 300 mAh g-1 based on solid-state redox reaction of oxide ions.

  20. 3D Imaging of Nickel Oxidation States using Full Field X-ray Absorption Near Edge Structure Nanotomography

    Energy Technology Data Exchange (ETDEWEB)

    Nelson, George; Harris, William; Izzo, John; Grew, Kyle N. (Connecticut); (USARL)

    2012-01-20

    Reduction-oxidation (redox) cycling of the nickel electrocatalyst phase in the solid oxide fuel cell (SOFC) anode can lead to performance degradation and cell failure. A greater understanding of nickel redox mechanisms at the microstructural level is vital to future SOFC development. Transmission x-ray microscopy (TXM) provides several key techniques for exploring oxidation states within SOFC electrode microstructure. Specifically, x-ray nanotomography and x-ray absorption near edge structure (XANES) spectroscopy have been applied to study samples of varying nickel (Ni) and nickel oxide (NiO) compositions. The imaged samples are treated as mock SOFC anodes containing distinct regions of the materials in question. XANES spectra presented for the individual materials provide a basis for the further processing and analysis of mixed samples. Images of composite samples obtained are segmented, and the distinct nickel and nickel oxide phases are uniquely identified using full field XANES spectroscopy. Applications to SOFC analysis are discussed.

  1. AN IN-SITU PERMEABLE REACTIVE BARRIER FOR THE TREATMENT OF HEXAVALENT CHROMIUM AND TRICHLOROETHYLENE IN GROUNDWATER: VOLUME 3 MULTICOMPONENT REACTIVE TRANSPORT MODELING

    Science.gov (United States)

    Reactive transport modeling has been conducted to describe the performance of the permeable reactive barrier at the Coast Guard Support Center near Elizabeth City, NC. The reactive barrier was installed to treat groundwater contaminated by hexavalent chromium and chlorinated org...

  2. Determination of oxidation state of iron in normal and pathologically altered human aortic valves

    Energy Technology Data Exchange (ETDEWEB)

    Czapla-Masztafiak, J. [Institute of Nuclear Physics PAN, Radzikowskiego 152, 31-342 Kraków (Poland); Lis, G.J.; Gajda, M.; Jasek, E. [Department of Histology, Jagiellonian University Medical College, Kopernika 7, 31-034 Kraków (Poland); Czubek, U. [Department of Coronary Disease, Jagiellonian University Medical College, John Paul II Hospital, Prądnicka 80, 31-202 Kraków (Poland); Bolechała, F. [Department of Forensic Medicine, Jagiellonian University Medical College, Grzegórzecka 16, 31-531 Kraków (Poland); Borca, C. [Swiss Light Source, Paul Scherrer Institute, 5232 Villigen PSI (Switzerland); Kwiatek, W.M. [Institute of Nuclear Physics PAN, Radzikowskiego 152, 31-342 Kraków (Poland)

    2015-12-01

    In order to investigate changes in chemical state of iron in normal and pathologically altered human aortic valves X-ray absorption spectroscopy was applied. Since Fe is suspected to play detrimental role in aortic valve stenosis pathogenesis the oxidation state of this element has been determined. The experimental material consisted of 10 μm sections of valves excised during routine surgery and from autopsies. The experiment was performed at the MicroXAS beamline of the SLS synchrotron facility in Villigen (Switzerland). The Fe K-edge XANES spectra obtained from tissue samples were carefully analyzed and compared with the spectra of reference compounds containing iron in various chemical structures. The analysis of absorption edge position and shape of the spectra revealed that both chemical forms of iron are presented in valve tissue but Fe{sup 3+} is the predominant form. Small shift of the absorption edge toward higher energy in the spectra from stenotic valve samples indicates higher content of the Fe{sup 3+} form in pathological tissue. Such a phenomenon suggests the role of Fenton reaction and reactive oxygen species in the etiology of aortic valve stenosis. The comparison of pre-edge regions of XANES spectra for control and stenotic valve tissue confirmed no differences in local symmetry or spin state of iron in analyzed samples.

  3. The effect of cerium valence states at cerium oxide nanoparticle surfaces on cell proliferation

    KAUST Repository

    Naganuma, Tamaki

    2014-05-01

    Understanding and controlling cell proliferation on biomaterial surfaces is critical for scaffold/artificial-niche design in tissue engineering. The mechanism by which underlying integrin ligates with functionalized biomaterials to induce cell proliferation is still not completely understood. In this study, poly-l-lactide (PL) scaffold surfaces were functionalized using layers of cerium oxide nanoparticles (CNPs), which have recently attracted attention for use in therapeutic application due to their catalytic ability of Ce4+ and Ce3+ sites. To isolate the influence of Ce valance states of CNPs on cell proliferation, human mesenchymal stem cells (hMSCs) and osteoblast-like cells (MG63) were cultured on the PL/CNP surfaces with dominant Ce4+ and Ce3+ regions. Despite cell type (hMSCs and MG63 cells), different surface features of Ce4+ and Ce3+ regions clearly promoted and inhibited cell spreading, migration and adhesion behavior, resulting in rapid and slow cell proliferation, respectively. Cell proliferation results of various modified CNPs with different surface charge and hydrophobicity/hydrophilicity, indicate that Ce valence states closely correlated with the specific cell morphologies and cell-material interactions that trigger cell proliferation. This finding suggests that the cell-material interactions, which influence cell proliferation, may be controlled by introduction of metal elements with different valence states onto the biomaterial surface. © 2014 Elsevier Ltd.

  4. Change in metallothionein phosphorylation state in Mya arenaria clams: implication in metal metabolism and oxidative stress

    Directory of Open Access Journals (Sweden)

    F Gagné

    2010-01-01

    Full Text Available The contamination of the benthic environment poses a threat to long-lived sessile organisms such as clams. The purpose of this study was to investigate metal contamination in tissues and changes in metallothioneins (MT in respect to its redox status in Mya arenaria clams collected at three polluted sites. The phosphorylation state of MT was also investigated to determine whether this state is changed in clams collected at heavy-metal contaminated site and its involvement in cytoprotective signaling during stress contamination. The results show that clams collected at least one of the three polluted sites presented significantly higher concentrations of silver (Ag, arsenic (As, cobalt (Co, copper (Cu, mercury (Hg, nickel (Ni, tin (Sn and lead (Pb in tissues. In the visceral tissue, total MT levels and the reduced, metal-binding form of the protein were significantly induced at the sites. The phosphorylation of MT and mitochondrial activity, as determined by electron transport and cytochrome c oxidase activities, were also significantly reduced at the contaminated sites. Reduced phosphate levels in MT were negatively correlated with total MT levels, suggesting that decreased phosphorylation was involved in kinase-mediated signaling during cellular stress and could possibly alter the protein’s affinity to confer cytoprotection against heavy metal contamination. These preliminary investigations revealed that the phosphorylation state could change in polluted environment and provide some clues on the modulation of binding affinities during heavy-metal and oxidative stress in clams.

  5. Solid State Energy Conversion Alliance (SECA) Solid Oxide Fuel Cell Program

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen Minh

    2006-07-31

    This report summarizes the work performed for Phase I (October 2001 - August 2006) under Cooperative Agreement DE-FC26-01NT41245 for the U. S. Department of Energy, National Energy Technology Laboratory (DOE/NETL) entitled 'Solid State Energy Conversion Alliance (SECA) Solid Oxide Fuel Cell Program'. The program focuses on the development of a low-cost, high-performance 3-to-10-kW solid oxide fuel cell (SOFC) system suitable for a broad spectrum of power-generation applications. During Phase I of the program significant progress has been made in the area of SOFC technology. A high-efficiency low-cost system was designed and supporting technology developed such as fuel processing, controls, thermal management, and power electronics. Phase I culminated in the successful demonstration of a prototype system that achieved a peak efficiency of 41%, a high-volume cost of $724/kW, a peak power of 5.4 kW, and a degradation rate of 1.8% per 500 hours. . An improved prototype system was designed, assembled, and delivered to DOE/NETL at the end of the program. This prototype achieved an extraordinary peak efficiency of 49.6%.

  6. Solid state chemistry of nitrogen oxides--part II: surface consumption of NO2.

    Science.gov (United States)

    Ioppolo, S; Fedoseev, G; Minissale, M; Congiu, E; Dulieu, F; Linnartz, H

    2014-05-14

    Nitrogen oxides are considered to be important astrochemical precursors of complex species and prebiotics. However, apart from the hydrogenation of solid NO that leads to the surface formation of hydroxylamine, little is known about the full solid state reaction network involving both nitrogen and oxygen. Our study is divided into two papers, hereby called Part I and Part II. In the accompanying paper, we investigate the surface reactions NO + O/O2/O3 and NO + N with a focus on the formation of NO2 ice. Here, we complement this study by measurements of the surface destruction of solid NO2, e.g., NO2 + H/O/N. Experiments are performed in two separate ultra-high vacuum setups and therefore under different experimental conditions to better constrain the experimental results. Surface reaction products are monitored by means of Fourier Transform Reflection Absorption Infrared Spectroscopy (FT-RAIRS) and Temperature Programmed Desorption (TPD) techniques using mass spectrometry. The surface destruction of solid NO2 leads to the formation of a series of nitrogen oxides such as NO, N2O, N2O3, and N2O4 as well as HNO, NH2OH, and H2O. When NO2 is mixed with an interstellar more relevant apolar (i.e., CO) ice, solid CO2 and HCOOH are also formed due to interactions between different reaction routes. The astrophysical implications of the full nitrogen and oxygen reaction network derived from Parts I and II are discussed.

  7. Probing local coordination and oxidation state of uranium in ThO2: U nanostructured

    Science.gov (United States)

    Gupta, Santosh K.; Pathak, N.; Kadam, R. M.

    2015-12-01

    Uranium doped thorium oxide nanoparticle (UDT) was synthesized using citric acid assisted combustion method. The concentration of uranium was varied from 0.5 to 5.0 mol % to investigate the effect of doping concentration on its optical properties. The synthesised UDT powder were characterized systematically using X-ray diffraction (XRD), transmission electron microscopy (TEM) and selected area electron diffraction (SAED) respectively for phase purity, morphology and crystallinity. Pertaining to nuclear industry, UDT is an important material and investigating the local structure of uranium in UDT is interesting as well as challenging because of complexity involved in synthesis of such ceramic powder. We have used time resolved photoluminescence spectroscopy (TRPLS) to probe the local coordination and oxidation state of uranium in UDT. Based on PL emission spectroscopy it was confirmed that uranium stabilizes as UO22+ ion in UDT. Lifetime spectroscopy shows that uranyl ion is not homogenously distributed in UDT lattice; rather it has two different chemical environments. Effect of concentration on PL behaviour shows that, concentration quenching takes place beyond 2.0 mol %; and based on critical distance calculation multipolar interaction was found to be responsible for such non-radiative quenching. As far as application in luminescence industry is concerned PL measurement shows that UDT gives intense green emission under UV excitation.

  8. New strain states and radical property tuning of metal oxides using a nanocomposite thin film approach

    Directory of Open Access Journals (Sweden)

    Judith MacManus-Driscoll

    2015-06-01

    Full Text Available Auxetic-like strain states were generated in self-assembled nanocomposite thin films of (Ba0.6Sr0.4TiO31−x − (Sm2O3x(BSTO − SmO. A switch from auxetic-like to elastic-like strain behavior was observed for x > 0.50, when the SmO switched from being nanopillars in the BSTO matrix to being the matrix with BSTO nanopillars embedded in it. A simple model was adopted to explain how in-plane strain varies with x. At high x (0.75, strongly enhanced ferroelectric properties were obtained compared to pure BSTO films. The nanocomposite method represents a powerful new way to tune the properties of a wide range of strongly correlated metal oxides whose properties are very sensitive to strain.

  9. Oxidation-state distribution of plutonium in surface and subsurface waters at Thule, northwest Greenland

    DEFF Research Database (Denmark)

    McMahon, C.A.; Vintró, L.L.; Mitchell, P.I.

    2000-01-01

    chemical form) is present as fully dissolved species. Most of this plutonium would seem to be of weapons fallout origin, as the mean Pu-238/Pu-239,Pu-240 activity ratio in the water column (dissolved phase) at Thule (0.06 +/- 0.02; n = 10) is similar to the global fallout ratio at this latitude......The speciation of plutonium in Arctic waters sampled on the northwest Greenland shelf in August 1997 is discussed in this paper. Specifically, we report the results of analyses carried out on seawater sampled (a) close to the Thule air base where, in 1968, a US military aircraft carrying four......(V, VI) (mean, 68 +/- 6%; n = 6), with little if any distinction apparent between surface and bottom waters. Further, the oxidation state distribution at stations close to the accident site is similar to that measured at Upernavik, remote from this site. It is also similar to the distribution observed...

  10. Unsupervised learning in probabilistic neural networks with multi-state metal-oxide memristive synapses

    Science.gov (United States)

    Serb, Alexander; Bill, Johannes; Khiat, Ali; Berdan, Radu; Legenstein, Robert; Prodromakis, Themis

    2016-09-01

    In an increasingly data-rich world the need for developing computing systems that cannot only process, but ideally also interpret big data is becoming continuously more pressing. Brain-inspired concepts have shown great promise towards addressing this need. Here we demonstrate unsupervised learning in a probabilistic neural network that utilizes metal-oxide memristive devices as multi-state synapses. Our approach can be exploited for processing unlabelled data and can adapt to time-varying clusters that underlie incoming data by supporting the capability of reversible unsupervised learning. The potential of this work is showcased through the demonstration of successful learning in the presence of corrupted input data and probabilistic neurons, thus paving the way towards robust big-data processors.

  11. On the Oxidation State of Manganese Ions in Li-Ion Battery Electrolyte Solutions.

    Science.gov (United States)

    Banerjee, Anjan; Shilina, Yuliya; Ziv, Baruch; Ziegelbauer, Joseph M; Luski, Shalom; Aurbach, Doron; Halalay, Ion C

    2017-02-08

    We demonstrate herein that Mn(3+) and not Mn(2+), as commonly accepted, is the dominant dissolved manganese cation in LiPF6-based electrolyte solutions of Li-ion batteries with lithium manganate spinel positive and graphite negative electrodes chemistry. The Mn(3+) fractions in solution, derived from a combined analysis of electron paramagnetic resonance and inductively coupled plasma spectroscopy data, are ∼80% for either fully discharged (3.0 V hold) or fully charged (4.2 V hold) cells, and ∼60% for galvanostatically cycled cells. These findings agree with the average oxidation state of dissolved Mn ions determined from X-ray absorption near-edge spectroscopy data, as verified through a speciation diagram analysis. We also show that the fractions of Mn(3+) in the aprotic nonaqueous electrolyte solution are constant over the duration of our experiments and that disproportionation of Mn(3+) occurs at a very slow rate.

  12. Tailoring the oxidation state of cobalt through halide functionality in sol-gel silica

    Science.gov (United States)

    Olguin, Gianni; Yacou, Christelle; Smart, Simon; Diniz da Costa, João C.

    2013-01-01

    The functionality or oxidation state of cobalt within a silica matrix can be tailored through the use of cationic surfactants and their halide counter ions during the sol-gel synthesis. Simply by adding surfactant we could significantly increase the amount of cobalt existing as Co3O4 within the silica from 44% to 77%, without varying the cobalt precursor concentration. However, once the surfactant to cobalt ratio exceeded 1, further addition resulted in an inhibitory mechanism whereby the altered pyrolysis of the surfactant decreased Co3O4 production. These findings have significant implications for the production of cobalt/silica composites where maximizing the functional Co3O4 phase remains the goal for a broad range of catalytic, sensing and materials applications. PMID:24022785

  13. Unsupervised learning in probabilistic neural networks with multi-state metal-oxide memristive synapses

    Science.gov (United States)

    Serb, Alexander; Bill, Johannes; Khiat, Ali; Berdan, Radu; Legenstein, Robert; Prodromakis, Themis

    2016-01-01

    In an increasingly data-rich world the need for developing computing systems that cannot only process, but ideally also interpret big data is becoming continuously more pressing. Brain-inspired concepts have shown great promise towards addressing this need. Here we demonstrate unsupervised learning in a probabilistic neural network that utilizes metal-oxide memristive devices as multi-state synapses. Our approach can be exploited for processing unlabelled data and can adapt to time-varying clusters that underlie incoming data by supporting the capability of reversible unsupervised learning. The potential of this work is showcased through the demonstration of successful learning in the presence of corrupted input data and probabilistic neurons, thus paving the way towards robust big-data processors. PMID:27681181

  14. Influence of Copper Oxidation State on the Bonding and Electronic Structure of Cobalt-Copper Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Eisenhart, Reed J.; Carlson, Rebecca K.; Clouston, Laura J.; Young, Jr., Victor G.; Chen, Yu-Sheng; Bill, Eckhard; Gagliardi, Laura; Lu, Connie C. (UC); (UMM); (MXPL)

    2016-03-04

    Heterobimetallic complexes that pair cobalt and copper were synthesized and characterized by a suite of physical methods, including X-ray diffraction, X-ray anomalous scattering, cyclic voltammetry, magnetometry, electronic absorption spectroscopy, electron paramagnetic resonance, and quantum chemical methods. Both Cu(II) and Cu(I) reagents were independently added to a Co(II) metalloligand to provide (py3tren)CoCuCl (1-Cl) and (py3tren)CoCu(CH3CN) (2-CH3CN), respectively, where py3tren is the triply deprotonated form of N,N,N-tris(2-(2-pyridylamino)ethyl)amine. Complex 2-CH3CN can lose the acetonitrile ligand to generate a coordination polymer consistent with the formula “(py3tren)CoCu” (2). One-electron chemical oxidation of 2-CH3CN with AgOTf generated (py3tren)CoCuOTf (1-OTf). The Cu(II)/Cu(I) redox couple for 1-OTf and 2-CH3CN is reversible at -0.56 and -0.33 V vs Fc+/Fc, respectively. The copper oxidation state impacts the electronic structure of the heterobimetallic core, as well as the nature of the Co–Cu interaction. Quantum chemical calculations showed modest electron delocalization in the (CoCu)+4 state via a Co–Cu σ bond that is weakened by partial population of the Co–Cu σ antibonding orbital. By contrast, no covalent Co–Cu bonding is predicted for the (CoCu)+3 analogue, and the d-electrons are fully localized at individual metals.

  15. Effect of MgO/Fe Interface Oxidation State on Electric-Field Modulation of Interfacial Magnetic Anisotropy

    Science.gov (United States)

    Guan, X. W.; Cheng, X. M.; Wang, S.; Huang, T.; Xue, K. H.; Miao, X. S.

    2016-06-01

    The impact of the MgO/Fe interface oxidation state on the electric-field-modified magnetic anisotropy in MgO/Fe has been revealed by density functional calculations. It is shown that the influence of the interface oxidation is strong enough to dominate the effect of the electric field on the magnetic anisotropy of MgO/Fe-based films. The magnetoelectric coefficients are calculated to be positive for the ideal and overoxidized MgO/Fe interface, but an abnormal negative value emerges in the underoxidized case. By analyzing the interface states based on density of states and band structures, we demonstrate that the considerably different electronic structures of the three oxidized MgO/Fe interfaces lead to the strong discrepancy in the electric-field modulation of the interfacial magnetic anisotropy. These results are of considerable interest in the area of electric-field-controlled magnetic anisotropy and switching.

  16. Accessibility of myofilament cysteines and effects on ATPase depend on the activation state during exposure to oxidants.

    Directory of Open Access Journals (Sweden)

    Sean M Gross

    Full Text Available Signaling by reactive oxygen species has emerged as a major physiological process. Due to its high metabolic rate, striated muscle is especially subject to oxidative stress, and there are multiple examples in cardiac and skeletal muscle where oxidative stress modulates contractile function. Here we assessed the potential of cysteine oxidation as a mechanism for modulating contractile function in skeletal and cardiac muscle. Analyzing the cysteine content of the myofilament proteins in striated muscle, we found that cysteine residues are relatively rare, but are very similar between different muscle types and different vertebrate species. To refine this list of cysteines to those that may modulate function, we estimated the accessibility of oxidants to cysteine residues using protein crystal structures, and then sharpened these estimates using fluorescent labeling of cysteines in cardiac and skeletal myofibrils. We demonstrate that cysteine accessibility to oxidants and ATPase rates depend on the contractile state in which preparations are exposed. Oxidant exposure of skeletal and cardiac myofibrils in relaxing solution exposes myosin cysteines not accessible in rigor solution, and these modifications correspond to a decrease in maximum ATPase. Oxidant exposure under rigor conditions produces modifications that increase basal ATPase and calcium sensitivity in ventricular myofibrils, but these effects were muted in fast twitch muscle. These experiments reveal how structural and sequence variations can lead to divergent effects from oxidants in different muscle types.

  17. The effect of Rhδ+ dopant in SrTiO3 on the active oxidation state of co-catalytic Pt nanoparticles in overall water splitting

    NARCIS (Netherlands)

    Zoontjes, M.G.C.; Han, K.; Huijben, M.; Wiel, van der W.G.; Mul, G.

    2016-01-01

    We report on the oxidation state of Pt nanoparticles when deposited on SrTiO3 or Rh-doped SrTiO3 under realistic solar water-splitting conditions. The oxidation state was investigated using state-of-the-art analysis of the reaction in a continuously stirred tank reactor (CSTR) connected to a micro g

  18. Assessment of Hexavalent Chromium Natural Attenuation for the Hanford Site 100 Area

    Energy Technology Data Exchange (ETDEWEB)

    Truex, Michael J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Szecsody, James E. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Qafoku, Nikolla P. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Sahajpal, Rahul [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Zhong, Lirong [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Lawter, Amanda R. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Lee, Brady D. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2015-09-01

    Hexavalent chromium (Cr(VI)) plumes are present in the 100 Area at the Hanford Site. Remediation efforts are under way with objectives of restoring the groundwater to meet the drinking-water standard (48 µg/L) and protecting the Columbia River by ensuring that discharge of groundwater to the river is below the surface-water quality standard (10 µg/L). Current remedies include application of Pump-and-Treat (P&T) at the 100-D, 100-H, and 100-K Areas and Monitored Natural Attenuation (MNA) at the 100-F/IU Area. Remedy selection is still under way at the other 100 Areas. Additional information about the natural attenuation processes for Cr(VI) is important in all of these cases. In this study, laboratory experiments were conducted to demonstrate and quantify natural attenuation mechanisms using 100 Area sediments and groundwater conditions.

  19. Effect of acclimatization on hexavalent chromium reduction in a biocathode microbial fuel cell.

    Science.gov (United States)

    Wu, Xiayuan; Zhu, Xujun; Song, Tianshun; Zhang, Lixiong; Jia, Honghua; Wei, Ping

    2015-03-01

    A simple acclimatization method for the reduction of hexavalent chromium (Cr(VI)) at a biocathode by first enriching an exoelectrogenic biofilm on a microbial fuel cell (MFC) anode, followed by direct inversion of the anode to function as the biocathode, has been established. This novel method significantly enhanced the Cr(VI) reduction efficiency of the MFC, which was mainly attributed to the higher microbial density and less resistive Cr(III) precipitates on the cathode when compared with a common biocathode acclimatization method (control). The biocathode acclimatization period was shortened by 19days and the Cr(VI) reduction rate was increased by a factor of 2.9. Microbial community analyses of biocathodes acclimatized using different methods further verified the feasibility of this electrode inversion method, indicating similar dominant bacteria species in biofilms, which mainly consist of Gamma-proteobacteria and Bacteria.

  20. Hexavalent Chrome Free Coatings for Electronics; Electromagnetic Interference (EMI) Shielding Effectiveness (SE)

    Science.gov (United States)

    Kessel, Kurt R.

    2014-01-01

    The purpose of this testing is to determine the suitability of trivalent chromium conversion coatings that meet the requirements of MIL-DTL-5541, Type II, for use in applications where high-frequency electrical performance is important. This project will evaluate the ability of coated aluminum to form adequate EMI seals. Testing will assess performance of the trivalent chromium coatings against the known control hexavalent chromium MIL-DTL-5541 Type I Class 3 before and after they have been exposed to a set of environmental conditions. Performance will be assessed by evaluating shielding effectiveness (SE) test data from a variety of test samples comprised of different aluminum types and/or conversion coatings.

  1. Synthesis, physical properties and application of the zero-valent iron/titanium dioxide heterocomposite having high activity for the sustainable photocatalytic removal of hexavalent chromium in water.

    Science.gov (United States)

    Petala, Eleni; Baikousi, Maria; Karakassides, Michael A; Zoppellaro, Giorgio; Filip, Jan; Tuček, Jiří; Vasilopoulos, Konstantinos C; Pechoušek, Jiří; Zbořil, Radek

    2016-04-21

    A magnetic photocatalytic material composed of nanoscale zero-valent iron (nZVI) homogeneously distributed over a mesoporous nanocrystalline TiO2 matrix has been prepared by a multistage chemical process, including sol-gel technique, wet impregnation, and chemical reduction. X-ray powder diffraction and Raman spectroscopy were used for the structural and chemical characterization of the magnetic photocatalyst, while bulk magnetization measurements and scanning/transmission electron microscopy were employed to determine the physical and textural properties of the photocatalyst. The synthesized nZVI@TiO2 photocatalyst shows very high efficiency in the removal of hexavalent chromium, Cr(vi), from water. The degradation rate follows a pseudo-first-order kinetic model. Most importantly, the remarkable efficiency of the photocatalyst is found to be due to the synergistic contributions of both counterparts, nZVI and TiO2, as validated by comparative experiments with neat TiO2 and nZVI@TiO2 under UV-C irradiation and without irradiation. New insights into the mechanism of synergistic degradation of chromium(vi) and suppressed oxidation of nZVI particles in the composite material are proposed and therein discussed.

  2. Survey of Nano filtration Performance for Hexavalent Chromium Removal fromWater Containing Sulfate

    Directory of Open Access Journals (Sweden)

    Gh.R Moussavi

    2010-10-01

    Full Text Available "n "n "nBackgrounds and Objectives: Geological situation and/or anthropogenic contamination contain an increased concentration of ions such as hexavalent chromium as well as some other dissolved components such as sulfate in the upper of the establishedMCLs (50µg/L. In this paper, simultaneous removal of Cr (VI and sulfate from water was investigated using nanofiltration as a promising method for reaching drinking water standards."nMaterials and Methods: For varying pressure, pH , anion and cation solution effect, Sulfate and Cr (VI concentration which have chosen were levels found in drinking water sources (Cr=0.1- 0.5mg/L and (SO4-2= 100-800mg/L.Experiments were performed using NaCl, Na2SO4,K2 Cr2O7and anhydrous CrCl3. 6H2O which prepared with de mineralized water on procedure detailed in standard methods. All salts were purchased from Merck Corporation with purity over 99'."nResults: The results for hexavalent chromium experiments showed that when the concentration decreases, the chromate anions were given a better retention to 4 bars (96'. But when the concentration increases, concentration polarization led to increased removal of Cr (VI (98'. For Cr (III the influences of the ionic strength as well as the concentrations were strongly dependant on rejection but operating pressure were found weak. In addition, with increasing total dissolved solids, perfect rejection of chromium was seen. The effect of pH showed that better retention was obtained at natural and basic pH."nConclusion: This study indicates that the nature of anions and cations, driven pressure and pH have significant effect on nano filtration operation. Research findings show that it seems nano filtration is a very good promising method of simultaneous removal of Cr (VI and sulfate from water.

  3. Inactivation of nitric oxide by cytochrome c oxidase under steady-state oxygen conditions.

    Science.gov (United States)

    Unitt, David C; Hollis, Veronica S; Palacios-Callender, Miriam; Frakich, Nanci; Moncada, Salvador

    2010-03-01

    We have developed a respiration chamber that allows intact cells to be studied under controlled oxygen (O(2)) conditions. The system measures the concentrations of O(2) and nitric oxide (NO) in the cell suspension, while the redox state of cytochrome c oxidase is continuously monitored optically. Using human embryonic kidney cells transfected with a tetracycline-inducible NO synthase we show that the inactivation of NO by cytochrome c oxidase is dependent on both O(2) concentration and electron turnover of the enzyme. At a high O(2) concentration (70 microM), and while the enzyme is in turnover, NO generated by the NO synthase upon addition of a given concentration of l-arginine is partially inactivated by cytochrome c oxidase and does not affect the redox state of the enzyme or consumption of O(2). At low O(2) (15 microM), when the cytochrome c oxidase is more reduced, inactivation of NO is decreased. In addition, the NO that is not inactivated inhibits the cytochrome c oxidase, further reducing the enzyme and lowering O(2) consumption. At both high and low O(2) concentrations the inactivation of NO is decreased when sodium azide is used to inhibit cytochrome c oxidase and decrease electron turnover.

  4. Electronic State of Fe in Double Perovskite Oxide Sr 2FeWO 6

    Science.gov (United States)

    Kawanaka, Hirofumi; Hase, Izumi; Toyama, Shunichiro; Nishihara, Yoshikazu

    1999-09-01

    The magnetic properties of double perovskite oxide Sr2FeWO6 have been reported. The magnetic susceptibility and Mössbauer effect of 57Fe show that this compound is an antiferromagnet with T N=37 K. The Mössbauer parameters below ˜20 K are the center shift of +1.2 mm/s relative to metallic iron, the quadrupole splitting of 1.9 mm/s and the hyperfine field of ˜110 kOe. The quadrupole splitting has a strong temperature dependence. From these data, we conclude that Fe in Sr2FeWO6 is in the Fe2+ high-spin state, while the hyperfine field seems to be quite small. The cell volume shows a large increase compared to other Sr2FeTO6 ( T= Mo, Re, etc.), which is in the Fe3+ high-spin state. These results suggest that these compounds have a strongly coupled charge and lattice systems.

  5. In vivo reduction-oxidation state of protein disulfide isomerase: the two active sites independently occur in the reduced and oxidized forms

    DEFF Research Database (Denmark)

    Appenzeller-Herzog, Christian; Ellgaard, Lars

    2008-01-01

    by the redox state of active-site cysteines found in a Cys-Xaa-Xaa-Cys motif. Progress in understanding redox regulation of the mammalian enzymes is currently hampered by the lack of reliable methods to determine quantitatively their redox state in living cells. We developed such a method based......Thiol-disulfide oxidoreductases of the human protein disulfide isomerase (PDI) family promote protein folding in the endoplasmic reticulum (ER), while also assisting the retrotranslocation of toxins and misfolded ER proteins to the cytosol. The redox activity of PDI-like proteins is determined...... on the alkylation of cysteines by methoxy polyethylene glycol 5000 maleimide. With this method, we showed for the first time that in vivo PDI is present in two semi-oxidized forms in which either the first active site (in the a domain) or the second active site (in the a' domain) is oxidized. We report a steady...

  6. Reactivity of biogenic manganese oxide for metal sequestration and photochemistry: Computational solid state physics study

    Energy Technology Data Exchange (ETDEWEB)

    Kwon, K.D.; Sposito, G.

    2010-02-01

    Many microbes, including both bacteria and fungi, produce manganese (Mn) oxides by oxidizing soluble Mn(II) to form insoluble Mn(IV) oxide minerals, a kinetically much faster process than abiotic oxidation. These biogenic Mn oxides drive the Mn cycle, coupling it with diverse biogeochemical cycles and determining the bioavailability of environmental contaminants, mainly through strong adsorption and redox reactions. This mini review introduces recent findings based on quantum mechanical density functional theory that reveal the detailed mechanisms of toxic metal adsorption at Mn oxide surfaces and the remarkable role of Mn vacancies in the photochemistry of these minerals.

  7. Environmental Factors Affecting Chromium-Manganese Oxidation-Reduction Reactions in Soil

    Institute of Scientific and Technical Information of China (English)

    D.O.P.TREBIEN; L.BORTOLON; M.J.TEDESCO; C.A.BISSANI; F.A.O.CAMARGO

    2011-01-01

    Disposal of chromium (Cr) hexavalent form, Cr(Ⅵ), in soils as additions in organic fertilizers, liming materials or plant nutrient sources can be dangerous since Cr(Ⅵ) can be highly toxic to plants, animals, and humans. In order to explore soil conditions that lead to Cr(Ⅵ) generation, this study were performed using a Paleudult (Dystic Nitosol) from a region that has a high concentration of tannery operations in the Rio Grande do Sul State, southern Brazil. Three laboratory incubation experiments were carried out to examine the influences of soil moisture content and concentration of cobalt and organic matter additions on soil Cr(Ⅵ) formation and release and manganese (Mn) oxide reduction with a salt of chromium chloride (CrCl3) and tannery sludge as inorganic and organic sources of Cr(Ⅲ), respectively. The amount of Cr(Ⅲ) oxidation depended on the concentration of easily reducible Mn oxides and the oxidation was more intense at the soil water contents in which Mn(Ⅲ/Ⅳ) oxides were more stable. Soluble organic compounds in soil decreased Cr(Ⅵ) formation due to Cr(Ⅲ) complexation. This mechanism also resulted in the decrease in the oxidation of Cr(Ⅲ) due to the tannery sludge additions. Chromium(Ⅲ) oxidation to Cr(Ⅵ) at the solid/solution interface involved the following mechanisms:the formation of a precursor complex on manganese (Mn) oxide surfaces, followed by electron transfer from Cr(Ⅲ) to Mn(Ⅲ or Ⅳ),the formation of a successor complex with Mn(Ⅱ) and Cr(Ⅵ), and the breakdown of the successor complex and release of Mn(Ⅱ) and Cr(Ⅵ) into the soil solution.

  8. Hydrophobic matrix-free graphene-oxide composites with isotropic and nematic states

    Science.gov (United States)

    Wåhlander, Martin; Nilsson, Fritjof; Carlmark, Anna; Gedde, Ulf W.; Edmondson, Steve; Malmström, Eva

    2016-08-01

    We demonstrate a novel route to synthesise hydrophobic matrix-free composites of polymer-grafted graphene oxide (GO) showing isotropic or nematic alignment and shape-memory effects. For the first time, a cationic macroinitiator (MI) has been immobilised on anionic GO and subsequently grafted with hydrophobic polymer grafts. Dense grafts of PBA, PBMA and PMMA with a wide range of average graft lengths (MW: 1-440 kDa) were polymerised by surface-initiated controlled radical precipitation polymerisation from the statistical MI. The surface modification is designed similarly to bimodal graft systems, where the cationic MI generates nanoparticle repulsion, similar to dense short grafts, while the long grafts offer miscibility in non-polar environments and cohesion. The state-of-the-art dispersions of grafted GO were in the isotropic state. Transparent and translucent matrix-free GO-composites could be melt-processed directly using only grafted GO. After processing, birefringence due to nematic alignment of grafted GO was observed as a single giant Maltese cross, 3.4 cm across. Permeability models for composites containing aligned 2D-fillers were developed, which were compared with the experimental oxygen permeability data and found to be consistent with isotropic or nematic states. The storage modulus of the matrix-free GO-composites increased with GO content (50% increase at 0.67 wt%), while the significant increases in the thermal stability (up to 130 °C) and the glass transition temperature (up to 17 °C) were dependent on graft length. The tuneable matrix-free GO-composites with rapid thermo-responsive shape-memory effects are promising candidates for a vast range of applications, especially selective membranes and sensors.We demonstrate a novel route to synthesise hydrophobic matrix-free composites of polymer-grafted graphene oxide (GO) showing isotropic or nematic alignment and shape-memory effects. For the first time, a cationic macroinitiator (MI) has been

  9. Oxidation States of Grim Glasses in EET79001 Based on Vanadium Valence

    Science.gov (United States)

    Sutton, S. R.; Rao, M. N.; Nyquist, L. E.

    2010-01-01

    Gas-rich impact-melt (GRIM) glasses in SNC meteorites are very rich in Martian atmospheric noble gases and sulfur suggesting a possible occurrence of regolith-derived secondary mineral assemblages in these samples. Previously, we have studied two GRIM glasses, 506 and 507, from EET79001 Lith A and Lith B, respectively, for elemental abundances and spatial distribution of sulfur using EMPA (WDS) and FE-SEM (EDS) techniques and for sulfur-speciation using K-edge XANES techniques. These elemental and FE-SEM micro-graph data at several locations in the GRIM glasses from Shergotty (DBS), Zagami 994 and EET79001, Lith B showed that FeO and SO3 are positively correlated (SO3 represents a mixture of sulfide and sulfate). FE-SEM (EDS) study revealed that the sulfur-rich pockets in these glasses contain numerous micron-sized iron-sulfide (Fe-S) globules sequestered throughout the volume. However, in some areas (though less frequently), we detected significant Fe-S-O signals suggesting the occurrence of iron sulfate. These GRIM glasses were studied by K-edge microXANES techniques for sulfur speciation in association with iron in sulfur-rich areas. In both samples, we found the sulfur speciation dominated by sulfide with minor oxidized sulfur mixed in with various proportions. The abundance of oxidized sulfur was greater in 506 than in 507. Based on these results, we hypothesize that sulfur initially existed as sulfate in the glass precursor materials and, on shock-impact melting of the precursor materials producing these glasses, the oxidized sulfur was reduced to predominately sulfide. In order to further test this hypothesis, we have used microXANES to measure the valence states of vanadium in GRIM glasses from Lith A and Lith B to complement and compare with previous analogous measurements on Lith C (note: 506 and 507 contain the largest amounts of martian atmospheric gases but the gas-contents in Lith C measured by are unknown). Vanadium is ideal for addressing this re

  10. Solid state oxidation of phenols to quinones with sodium perborate on wet montmorillonite K10

    Energy Technology Data Exchange (ETDEWEB)

    Hashemi, Mohammed M.; Eftekhari-Sis, Bagher; Khalili, Behzad; Karimi-Jaberi, Zahed [Sharif University of Technology, Tehran (Iran, Islamic Republic of). Dept. of Chemistry]. E-mail: mhashemi@sharif.edu

    2005-09-15

    Phenols were oxidized to quinones using sodium perborate (SPB) on wet montmorillonite as oxidant. The reaction was carried out at ambient temperature on the solid phase under solvent free conditions. (author)

  11. The electrochemical aspect of the corrosion of austenitic stainless steels, in nitric acid and in the presence of hexavalent chromium (1961); Aspect electrochimique de la corrosion d'aciers inoxydables austenitiques en milieu nitrique et en presence de chrome hexavalent (1961)

    Energy Technology Data Exchange (ETDEWEB)

    Coriou, H.; Hure, J.; Plante, G. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1961-07-01

    The corrosion of austenitic stainless steels in boiling nitric acid markedly increases when the medium contains hexavalent chromium ions. Because of several redox phenomena, the potential of the steel generally changes in course of time. Measurements show a relation between the weight loss and the potential of specimens. Additions of Mn(VII) and Ce(IV) are compared with that of Cr(VI), and show that the relation is a general one. The attack cf the metal in oxidizing media is largely intergranular, leading to exfoliation of the grains, although the steel studied is not sensitive to the classical Huey and Strauss tests. Also even in the absence of any other oxidizing reaction, the current density observed when the steel is anodically polarized under potentiostatic conditions does not correspond to the actual weight loss of the metal. (authors) [French] La corrosion d'aciers inoxydables austenitiques en milieu nitrique bouillant augmente notablement quand le milieu contient des ions chrome a l'etat hexavalent. Par suite de divers phenomenes d'oxydo-reduction, le potentiel de l'acier evolue generalement au cours du temps. Les mesures effectuees permettent d'etablir une relation entre les pertes de poids et le potentiel des echantillons. L'addition de Mn(VI) et Ce(IV) est compare a celle de Cr(VI) et montre que la relation precedente s'applique de facon generale. L'attaque du metal en milieu oxydant est en grande, partie due a une corrosion intergranulaire conduisant a un dechaussement des grains bien que l'acier etudie ne soit pas sensible aux tests classiques de Huey et de Strauss. Aussi, meme en l'absence de toute autre reaction d'oxydation l'intensite qu l'on observerait en soumettant l'acier a un potentiel anodique dans un montage potentiostatique ne correspondrait pas a la perte de poids reelle du metal. (auteurs)

  12. The Effect of Precursor Ligands and Oxidation State in the Synthesis of Bimetallic Nano-Alloys

    KAUST Repository

    LaGrow, Alec P.

    2015-05-12

    The characteristics of bimetallic nanomaterials are dictated by their size, shape and elemental distribution. Solution synthesis is widely utilized to form nanomaterials, such as nanoparticles, with controlled size and shape. However, the effects of variables on the characteristics of bimetallic nanomaterials are not completely understood. In this study, we used a continuous-flow synthetic strategy to explore the effects of the ligands and the oxidation state of a metal precursor in a shape-controlled synthesis on the final shape of the nanomaterials and the elemental distribution within the alloy. We demonstrate that this strategy can tune the size of monodisperse PtM (M=Ni or Cu) alloy nanocrystals ranging from 3 to 16 nm with an octahedral shape using acetylacetonate or halide precursors of Pt(II), Pt(IV) and Ni or Cu (II). The nanoparticles formed from halide precursors showed an enrichment of platinum on their surfaces, and the bromides could oxidatively etch the nanoparticles during synthesis with the O2/Br- pair. The two nanocrystal precursors can be uti-lized independently and can control the size with a trend of Pt(acac)2

  13. Redox-State Dependent Ligand Exchange in Manganese-Based Oxidation Catalysis

    NARCIS (Netherlands)

    Abdolahzadeh, Shaghayegh; de Boer, Johannes W.; Browne, Wesley R.

    Manganese-based oxidation catalysis plays a central role both in nature, in the oxidation of water in photosystem II (PSII) and the control of reactive oxygen species, as well as in chemical processes, in the oxidation of organic substrates and bleaching applications. The focus of this review is on

  14. Geochemical Constraints on the Oxidation States of the Europan Ocean and Mantle

    Science.gov (United States)

    Zolotov, M. Yu.; Shock, E. L.

    2001-01-01

    We present observational, meteoritic, and physical-chemical arguments for an oxidized Fe-metal free mantle and an oxidized sulfate-carbonate rich ocean on Europa. The ocean should be out of equilibrium even with oxidized igneous rocks at the oceanic floor. Additional information is contained in the original extended abstract.

  15. Redox-State Dependent Ligand Exchange in Manganese-Based Oxidation Catalysis

    NARCIS (Netherlands)

    Abdolahzadeh, Shaghayegh; de Boer, Johannes W.; Browne, Wesley R.

    2015-01-01

    Manganese-based oxidation catalysis plays a central role both in nature, in the oxidation of water in photosystem II (PSII) and the control of reactive oxygen species, as well as in chemical processes, in the oxidation of organic substrates and bleaching applications. The focus of this review is on

  16. Pu oxidation state distributions in suspensions of the Mont Terri Opalinus Clay isolate Sporomusa sp. MT-2.99

    Energy Technology Data Exchange (ETDEWEB)

    Moll, Henry [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Biogeochemistry; Cherkouk, Andrea [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). HZDR Young Investigator Group; Bok, Frank [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Surface Processes

    2017-06-01

    The time-dependent {sup 242}Pu oxidation state distribution in the presence of Sporomusa sp. cells as a function of pH with or without Na-pyruvate was analyzed. In all cases, the presence of bacterial cells enhanced removal of Pu from solution and accelerated Pu interaction reactions, e.g. biosorption and bioreduction.

  17. Ultrathin reduced graphene oxide films as transparent top-contacts for light switchable solid-state molecular junctions

    DEFF Research Database (Denmark)

    Li, Tao; Jevric, Martyn; Hauptmann, Jonas Rahlf

    2013-01-01

    A new type of solid-state molecular junction is introduced, which employs reduced graphene oxide as a transparent top contact that permits a self-assembled molecular monolayer to be photoswitched in situ, while simultaneously enabling charge-transport measurements across the molecules...

  18. Assessing the influence of the carbon oxidation-reduction state on organic pollutant biodegradation in algal-bacterial photobioreactors

    NARCIS (Netherlands)

    Bahr, M.; Stams, A.J.M.; Rosa, de la F.; Garcia-Encina, P.; Munoz, R.

    2011-01-01

    The influence of the carbon oxidation-reduction state (CORS) of organic pollutants on their biodegradation in enclosed algal-bacterial photobioreactors was evaluated using a consortium of enriched wild-type methanotrophic bacteria and microalgae. Methane, methanol and glucose (with CORS -4, -2 and 0

  19. Chemical reactivity of graphene oxide towards amines elucidated by solid-state NMR

    Science.gov (United States)

    Vacchi, Isabella A.; Spinato, Cinzia; Raya, Jésus; Bianco, Alberto; Ménard-Moyon, Cécilia

    2016-07-01

    Graphene oxide (GO) is an attractive nanomaterial for many applications. Controlling the functionalization of GO is essential for the design of graphene-based conjugates with novel properties. But, the chemical composition of GO has not been fully elucidated yet. Due to the high reactivity of the oxygenated moieties, mainly epoxy, hydroxyl and carboxyl groups, several derivatization reactions may occur concomitantly. The reactivity of GO with amine derivatives has been exploited in the literature to design graphene-based conjugates, mainly through amidation. However, in this study we undoubtedly demonstrate using magic angle spinning (MAS) solid-state NMR that the reaction between GO and amine functions occurs via ring opening of the epoxides, and not by amidation. We also prove that there is a negligible amount of carboxylic acid groups in two GO samples obtained by a different synthesis process, hence eliminating the possibility of amidation reactions with amine derivatives. This work brings additional insights into the chemical reactivity of GO, which is fundamental to control its functionalization, and highlights the major role of MAS NMR spectroscopy for a comprehensive characterization of derivatized GO.Graphene oxide (GO) is an attractive nanomaterial for many applications. Controlling the functionalization of GO is essential for the design of graphene-based conjugates with novel properties. But, the chemical composition of GO has not been fully elucidated yet. Due to the high reactivity of the oxygenated moieties, mainly epoxy, hydroxyl and carboxyl groups, several derivatization reactions may occur concomitantly. The reactivity of GO with amine derivatives has been exploited in the literature to design graphene-based conjugates, mainly through amidation. However, in this study we undoubtedly demonstrate using magic angle spinning (MAS) solid-state NMR that the reaction between GO and amine functions occurs via ring opening of the epoxides, and not by

  20. Utility of Ochrobactrum anthropi YC152 in a Microbial Fuel Cell as an Early Warning Device for Hexavalent Chromium Determination

    OpenAIRE

    Guey-Horng Wang; Chiu-Yu Cheng; Man-Hai Liu; Tzu-Yu Chen; Min-Chi Hsieh; Ying-Chien Chung

    2016-01-01

    Fast hexavalent chromium (Cr(VI)) determination is important for environmental risk and health-related considerations. We used a microbial fuel cell-based biosensor inoculated with a facultatively anaerobic, Cr(VI)-reducing, and exoelectrogenic Ochrobactrum anthropi YC152 to determine the Cr(VI) concentration in water. The results indicated that O. anthropi YC152 exhibited high adaptability to pH, temperature, salinity, and water quality under anaerobic conditions. The stable performance of t...

  1. Microcalorimetric study the toxic effect of hexavalent chromium on microbial activity of Wuhan brown sandy soil: an in vitro approach.

    Science.gov (United States)

    Yao, Jun; Tian, Lin; Wang, Yanxin; Djah, Atakora; Wang, Fei; Chen, Huilun; Su, Chunli; Zhuang, Rensheng; Zhou, Yong; Choi, Martin M F; Bramanti, Emilia

    2008-02-01

    A multi-channel thermal activity monitor was applied to study soil microbial activity in Wuhan brown sandy soil in the presence of different concentrations of hexavalent chromium (K(2)Cr(2)O(7)). In order to stimulate the soil microbial activity, 5.0mg of glucose and 5.0mg of ammonium sulfate were added to a 1.20-g soil sample under a controlled humidity of 35%. The results show that the poisonous species of K(2)Cr(2)O(7) at an half inhibitory concentration (IC(50)) value of 4.27 microg mL(-1) against soil microbe, and an increase of the amount of hexavalent chromium is associated to a decrease in the microbial activity of the soil, probably due to an increase in the toxicity of hexavalent chromium, affecting strongly the life in this soil microbial environment. Our work also suggests that microcalorimetry is a fast, simple and more sensitive method that can be easily performed to study the toxicity of different species of heavy metals on microorganism compared to other biological methods.

  2. All-Graphene Oxide Flexible Solid-State Supercapacitors with Enhanced Electrochemical Performance.

    Science.gov (United States)

    Ogata, Chikako; Kurogi, Ruriko; Awaya, Keisuke; Hatakeyama, Kazuto; Taniguchi, Takaaki; Koinuma, Michio; Matsumoto, Yasumichi

    2017-08-09

    The rapid development of flexible and wearable electronics has led to an increase in the demand for flexible supercapacitors with enhanced electrochemical performance. Graphene oxide (GO) and reduced GO (rGO) exhibit several key properties required for supercapacitor components. Although solid-state rGO/GO/rGO supercapacitors with unique structures are promising, their moderate capacitance is inadequate for practical applications. Herein, we report a flexible solid-state rGO/GO/rGO supercapacitor comprising H2SO4-intercalated GO electrolyte/separator and pseudocapacitive rGO electrodes, which demonstrate excellent electrochemical performance. The resulting supercapacitor delivered an areal capacitance of 14.5 mF cm(-2), which is among the highest values achieved for any rGO/GO/rGO supercapacitor. High ionic concentration and fast ion conduction in the H2SO4-intercalated GO electrolyte/separator and abundant CH defects, which serve as pseudocapacitive sites on the rGO electrode, were responsible for the high capacitance of this device. The rGO electrode, well separated by the H2SO4 molecular spacer, supplied highly efficient ion transport channels, leading to excellent rate capability. The highly packed rGO electrode and high specific capacitance resulted in a high volumetric energy density (1.24 mWh cm(-3)) observed in this supercapacitor. The structure, without a clear interface between GO and rGO, provides extremely low resistance and flexibility for devices. Our device operated in air (25 °C 40%) without the use of external electrolytes, conductive additives, and binders. Furthermore, we demonstrate a simple and versatile technique for supercapacitor fabrication by combining photoreduction and electrochemical treatment. These advantages are attractive for developing novel carbon-based energy devices with high device performance and low fabrication costs.

  3. Quasi-solid state rechargeable Na-CO2 batteries with reduced graphene oxide Na anodes.

    Science.gov (United States)

    Hu, Xiaofei; Li, Zifan; Zhao, Yaran; Sun, Jianchao; Zhao, Qing; Wang, Jianbin; Tao, Zhanliang; Chen, Jun

    2017-02-01

    Na-CO2 batteries using earth-abundant Na and greenhouse gas CO2 are promising tools for mobile and stationary energy storage, but they still pose safety risks from leakage of liquid electrolyte and instability of the Na metal anode. These issues result in extremely harsh operating conditions of Na-CO2 batteries and increase the difficulty of scaling up this technology. We report the development of quasi-solid state Na-CO2 batteries with high safety using composite polymer electrolyte (CPE) and reduced graphene oxide (rGO) Na anodes. The CPE of PVDF-HFP [poly(vinylidene fluoride-co-hexafluoropropylene)]-4% SiO2/NaClO4-TEGDME (tetraethylene glycol dimethyl ether) has high ion conductivity (1.0 mS cm(-1)), robust toughness, a nonflammable matrix, and strong electrolyte-locking ability. In addition, the rGO-Na anode presents fast and nondendritic Na(+) plating/stripping (5.7 to 16.5 mA cm(-2)). The improved kinetics and safety enable the constructed rGO-Na/CPE/CO2 batteries to successfully cycle in wide CO2 partial pressure window (5 to 100%, simulated car exhaust) and especially to run for 400 cycles at 500 mA g(-1) with a fixed capacity of 1000 mA·hour g(-1) in pure CO2. Furthermore, we scaled up the reversible capacity to 1.1 A·hour in pouch-type batteries (20 × 20 cm, 10 g, 232 Wh kg(-1)). This study makes quasi-solid state Na-CO2 batteries an attractive prospect.

  4. Quasi–solid state rechargeable Na-CO2 batteries with reduced graphene oxide Na anodes

    Science.gov (United States)

    Hu, Xiaofei; Li, Zifan; Zhao, Yaran; Sun, Jianchao; Zhao, Qing; Wang, Jianbin; Tao, Zhanliang; Chen, Jun

    2017-01-01

    Na-CO2 batteries using earth-abundant Na and greenhouse gas CO2 are promising tools for mobile and stationary energy storage, but they still pose safety risks from leakage of liquid electrolyte and instability of the Na metal anode. These issues result in extremely harsh operating conditions of Na-CO2 batteries and increase the difficulty of scaling up this technology. We report the development of quasi–solid state Na-CO2 batteries with high safety using composite polymer electrolyte (CPE) and reduced graphene oxide (rGO) Na anodes. The CPE of PVDF-HFP [poly(vinylidene fluoride-co-hexafluoropropylene)]–4% SiO2/NaClO4–TEGDME (tetraethylene glycol dimethyl ether) has high ion conductivity (1.0 mS cm−1), robust toughness, a nonflammable matrix, and strong electrolyte-locking ability. In addition, the rGO-Na anode presents fast and nondendritic Na+ plating/stripping (5.7 to 16.5 mA cm−2). The improved kinetics and safety enable the constructed rGO-Na/CPE/CO2 batteries to successfully cycle in wide CO2 partial pressure window (5 to 100%, simulated car exhaust) and especially to run for 400 cycles at 500 mA g−1 with a fixed capacity of 1000 mA·hour g−1 in pure CO2. Furthermore, we scaled up the reversible capacity to 1.1 A·hour in pouch-type batteries (20 × 20 cm, 10 g, 232 Wh kg−1). This study makes quasi–solid state Na-CO2 batteries an attractive prospect. PMID:28164158

  5. Atomic scale imaging of competing polar states in a Ruddlesden-Popper layered oxide

    Science.gov (United States)

    Stone, Greg; Ophus, Colin; Birol, Turan; Ciston, Jim; Lee, Che-Hui; Wang, Ke; Fennie, Craig J.; Schlom, Darrell G.; Alem, Nasim; Gopalan, Venkatraman

    2016-08-01

    Layered complex oxides offer an unusually rich materials platform for emergent phenomena through many built-in design knobs such as varied topologies, chemical ordering schemes and geometric tuning of the structure. A multitude of polar phases are predicted to compete in Ruddlesden-Popper (RP), An+1BnO3n+1, thin films by tuning layer dimension (n) and strain; however, direct atomic-scale evidence for such competing states is currently absent. Using aberration-corrected scanning transmission electron microscopy with sub-Ångstrom resolution in Srn+1TinO3n+1 thin films, we demonstrate the coexistence of antiferroelectric, ferroelectric and new ordered and low-symmetry phases. We also directly image the atomic rumpling of the rock salt layer, a critical feature in RP structures that is responsible for the competing phases; exceptional quantitative agreement between electron microscopy and density functional theory is demonstrated. The study shows that layered topologies can enable multifunctionality through highly competitive phases exhibiting diverse phenomena in a single structure.

  6. Atomic scale imaging of competing polar states in a Ruddlesden–Popper layered oxide

    Science.gov (United States)

    Stone, Greg; Ophus, Colin; Birol, Turan; Ciston, Jim; Lee, Che-Hui; Wang, Ke; Fennie, Craig J.; Schlom, Darrell G.; Alem, Nasim; Gopalan, Venkatraman

    2016-01-01

    Layered complex oxides offer an unusually rich materials platform for emergent phenomena through many built-in design knobs such as varied topologies, chemical ordering schemes and geometric tuning of the structure. A multitude of polar phases are predicted to compete in Ruddlesden–Popper (RP), An+1BnO3n+1, thin films by tuning layer dimension (n) and strain; however, direct atomic-scale evidence for such competing states is currently absent. Using aberration-corrected scanning transmission electron microscopy with sub-Ångstrom resolution in Srn+1TinO3n+1 thin films, we demonstrate the coexistence of antiferroelectric, ferroelectric and new ordered and low-symmetry phases. We also directly image the atomic rumpling of the rock salt layer, a critical feature in RP structures that is responsible for the competing phases; exceptional quantitative agreement between electron microscopy and density functional theory is demonstrated. The study shows that layered topologies can enable multifunctionality through highly competitive phases exhibiting diverse phenomena in a single structure. PMID:27578622

  7. Synthesis and spectroscopic analysis of polydiphenylamine via oxidation with bentonite clay in the solid state.

    Science.gov (United States)

    Kubota, Mayara Masae; Sacco, Bruno Luis; Bento, Danielly Cristina; de Santana, Henrique

    2015-12-05

    In this study, solids of polydiphenylamine (PDPA) synthesized mechanochemically by reaction with bentonite (PDPAOB) were studied using Raman spectroscopy. It was possible to identify the chemical species in the PDPA-bentonite compound. The spectra obtained were compared to the spectra of PDPA prepared chemically by oxidation of DPA with K2S2O8 in the solid state, and PDPA produced electrochemically, with the aim of studying the characteristic frequencies of the aromatic segments (DPB), radical cation (DPB(+)) and dication (DPB(2+)) of N,N-diphenylbenzidine (DPB) in the polymer structure of the PDPA. To analyze the segments present, the band characteristic of CC asymmetric stretching of the aromatic ring in the Raman spectra was deconvoluted because of the widening of the band and shifts observed by irradiation at wavelengths of 532 and 785 nm. This procedure showed that there are three distinct contributions in the spectra which facilitate the monitoring of changes in the contributions of the segments in the materials doped with HCl (PDPAOBD) and de-doped with NH4OH, (PDPAOBR). Copyright © 2015 Elsevier B.V. All rights reserved.

  8. Analysis of the complete detonation state of solutions of TNT in advanced oxidizers

    Energy Technology Data Exchange (ETDEWEB)

    Austing, J.L.; Tulis, A.J. [IIT Research Institute, Chicago, Illinois (United States); Patel, D.L.; Heberlein, D.C. [U.S. Army, Cecom, RD et E Center, NVESD, Virginia (United States)

    1996-12-31

    Solutions of TNT in liquid oxidizers such as dinitrogen tetroxide and chlorine trifluoride are different in chemical composition from that of TNT alone, which is an organic high explosive. The experimentally-measured detonation state of such solutions was mathematically analyzed in accordance with published correlations for conventional explosives. The computations verified that the Chapman-Jouguet density and adiabatic exponent were independent of the chemical composition and were functions only of the initial density. The detonation velocity of a TNT/Dinitrogen Tetroxide change was calculated from the Hugoniot data for the constituent elements by recourse to the method developed by Walker. The calculated velocity was 6.637 km/s, which differed from the experimental value by only 1.6 percent. Detonations of 50/50 by weight TNT/Chlorine Trifluoride solutions confined in glass tubes were conducted at diameters of 131 mm, 77 mm, and 43 mm, for purposes of assessing the diameter effect. The analysis was conducted according to the correlations of Eyring et al. Extrapolation of the detonation velocity-reciprocal diameter curve to infinite diameter established that the ideal detonation velocity was 7.732 km/s. The detonation at the three finite diameters propagated at the near-ideal velocity. The critical diameter was less than 43 mm. (authors) 11 refs.

  9. Arsenic (+3 oxidation state methyltransferase is a specific but replaceable factor against arsenic toxicity

    Directory of Open Access Journals (Sweden)

    Maki Tokumoto

    2014-01-01

    Full Text Available Inorganic metalloids, such as arsenic (As, antimony (Sb, selenium (Se, and tellurium (Te, are methylated in biota. In particular, As, Se, and Te are methylated and excreted in urine. The biomethylation is thought to be a means to detoxify the metalloids. The methylation of As is catalyzed by arsenic (+3 oxidation state methyltransferase (AS3MT. However, it is still unclear whether AS3MT catalyzes the methylation of the other metalloids. It is also unclear whether other factors catalyze the As methylation instead of AS3MT. Recombinant human AS3MT (rhAS3MT was prepared and used in the in vitro methylation of As, Se, and Te. As, but not Se and Te, was specifically methylated in the presence of rhAS3MT. Then, siRNA targeting AS3MT was introduced into human hepatocarcinoma (HepG2 cells. Although AS3MT protein expression was completely silenced by the gene knockdown, no increase in As toxicity was found in the HepG2 cells transfected with AS3MT-targeting siRNA. We conclude that AS3MT catalyzes the methylation of As and not other biomethylatable metalloids, such as Se and Te. We speculate that other methylation enzyme(s also catalyze the methylation of As in HepG2 cells.

  10. FTIR assessment of poly(ethylene oxide) irradiated in solid state, melt and aqeuous solution

    Science.gov (United States)

    Pucić, Irina; Jurkin, Tanja

    2012-09-01

    FTIR spectroscopy was used to study poly(ethylene oxide), PEO, irradiated in solid and molten aggregate states and as aqueous solutions of various concentrations. The changes in shape and width of -C-O-C- complex absorption intensities at around 1112 cm-1 were the most prominent. On irradiation of solid samples in contact with air shrinking of -C-O-C- complex and increase in its absorption intensities indicated predominant degradation. Crosslinking prevailed on irradiation of molten PEO and of its aqueous solutions in nitrogen atmosphere and manifested itself as widening of -C-O-C- absorption and decrease of corresponding intensities. Partial or complete merging of CH2 wagging vibrations at 1342 cm-1 and 1360 cm-1 that are characteristic of crystalline PEO into a single absorption at around 1350 cm-1 indicated amorphization what was observed for samples that had reduced degree of crystallinity determined by differential scanning calorimetry. DSC could not discriminate between degradation and crosslinking while the changes in width and shape of -C-O-C- complex were independent of the changes in crystallinity. Comparison of FTIR spectra of the same PEO samples obtained as thin film and as KBr pellets revealed that pellet preparation results in a number of spectral artefacts.

  11. Chemical reactivity of graphene oxide towards amines elucidated by solid-state NMR.

    Science.gov (United States)

    Vacchi, Isabella A; Spinato, Cinzia; Raya, Jésus; Bianco, Alberto; Ménard-Moyon, Cécilia

    2016-07-14

    Graphene oxide (GO) is an attractive nanomaterial for many applications. Controlling the functionalization of GO is essential for the design of graphene-based conjugates with novel properties. But, the chemical composition of GO has not been fully elucidated yet. Due to the high reactivity of the oxygenated moieties, mainly epoxy, hydroxyl and carboxyl groups, several derivatization reactions may occur concomitantly. The reactivity of GO with amine derivatives has been exploited in the literature to design graphene-based conjugates, mainly through amidation. However, in this study we undoubtedly demonstrate using magic angle spinning (MAS) solid-state NMR that the reaction between GO and amine functions occurs via ring opening of the epoxides, and not by amidation. We also prove that there is a negligible amount of carboxylic acid groups in two GO samples obtained by a different synthesis process, hence eliminating the possibility of amidation reactions with amine derivatives. This work brings additional insights into the chemical reactivity of GO, which is fundamental to control its functionalization, and highlights the major role of MAS NMR spectroscopy for a comprehensive characterization of derivatized GO.

  12. Oxygen Fugacity at High Pressure: Equations of State of Metal-Oxide Pairs

    Science.gov (United States)

    Campbell A. J.; Danielson, L.; Righter, K.; Wang, Y.; Davidson, G.; Wang, Y.

    2006-01-01

    Oxygen fugacity (fO2) varies by orders of magnitude in nature, and can induce profound changes in the chemical state of a substance, and also in the chemical equilibrium of multicomponent systems. One prominent area in high pressure geochemistry, in which fO2 is widely recognized as a principal controlling factor, is that of metal-silicate partitioning of siderophile trace elements (e.g., [1]). Numerous experiments have shown that high pressures and temperatures can significantly affect metal/silicate partitioning of siderophile and moderately siderophile elements. Parameterization of these experimental results over P, T, X, and fO2 can allow the observed siderophile element composition of the mantle to be associated with particular thermodynamic conditions [2]. However, this is best done only if quantitative control exists over each thermodynamic variable relevant to the experiments. The fO2 values for many of these partitioning experiments were determined relative to a particular metal-oxide buffer (e.g., Fe-FeO (IW), Ni-NiO (NNO), Co-CoO, Re-ReO2 (RRO)), but the parameterization of all experimental results is weakened by the fact that the pressure-induced relative changes between these buffer systems are imprecisely known.

  13. Oxidative Stress State Is Associated with Left Ventricular Mechanics Changes, Measured by Speckle Tracking in Essential Hypertensive Patients

    Directory of Open Access Journals (Sweden)

    Luis Antonio Moreno-Ruíz

    2015-01-01

    Full Text Available The oxidative stress state is characterized by an increase in oxygen reactive species that overwhelms the antioxidant defense; we do not know if these pathological changes are correlated with alterations in left ventricular mechanics. The aim was correlating the oxidative stress state with the left ventricular global longitudinal strain (GLS and the left ventricular end diastolic pressure (LVEDP. Twenty-five patients with essential hypertension and 25 controls paired by age and gender were studied. All of the participants were subjected to echocardiography and biochemical determination of oxidative stress markers. The hypertensive patients, compared with control subjects, had significantly (p<0.05 higher levels of oxidized proteins (5.03±1.05 versus 4.06±0.63 nmol/mg, lower levels of extracellular superoxide dismutase (EC-SOD activity (0.045±0.02 versus 0.082±0.02 U/mg, higher LVEDP (16.2±4.5 versus 11.3±1.6 mm Hg, and lower GLS (−12% versus −16%. Both groups had preserved ejection fraction and the results showed a positive correlation of oxidized proteins with GLS (r=0.386, p=0.006 and LVEDP (r=0.389, p=0.005; we also found a negative correlation of EC-SOD activity with GLS (r=-0.404, p=0.004 and LVEDP (r=-0.347, p=0.014.

  14. Oxidative Stress State Is Associated with Left Ventricular Mechanics Changes, Measured by Speckle Tracking in Essential Hypertensive Patients

    Science.gov (United States)

    Moreno-Ruíz, Luis Antonio; Ibarra-Quevedo, David; Rodríguez-Martínez, Erika; Maldonado, Perla D.; Sarabia-Ortega, Benito; Hernández-Martínez, José Gustavo; Espinosa-Caleti, Beda; Mendoza-Pérez, Beatriz; Rivas-Arancibia, Selva

    2015-01-01

    The oxidative stress state is characterized by an increase in oxygen reactive species that overwhelms the antioxidant defense; we do not know if these pathological changes are correlated with alterations in left ventricular mechanics. The aim was correlating the oxidative stress state with the left ventricular global longitudinal strain (GLS) and the left ventricular end diastolic pressure (LVEDP). Twenty-five patients with essential hypertension and 25 controls paired by age and gender were studied. All of the participants were subjected to echocardiography and biochemical determination of oxidative stress markers. The hypertensive patients, compared with control subjects, had significantly (p < 0.05) higher levels of oxidized proteins (5.03 ± 1.05 versus 4.06 ± 0.63 nmol/mg), lower levels of extracellular superoxide dismutase (EC-SOD) activity (0.045 ± 0.02 versus 0.082 ± 0.02 U/mg), higher LVEDP (16.2 ± 4.5 versus 11.3 ± 1.6 mm Hg), and lower GLS (−12% versus −16%). Both groups had preserved ejection fraction and the results showed a positive correlation of oxidized proteins with GLS (r = 0.386, p = 0.006) and LVEDP (r = 0.389, p = 0.005); we also found a negative correlation of EC-SOD activity with GLS (r = −0.404, p = 0.004) and LVEDP (r = −0.347, p = 0.014). PMID:26504504

  15. Titanium dioxide-gold nanocomposite materials embedded in silicate sol-gel film catalyst for simultaneous photodegradation of hexavalent chromium and methylene blue

    Energy Technology Data Exchange (ETDEWEB)

    Pandikumar, Alagarsamy [Centre for Photoelectrochemistry, School of Chemistry, Madurai Kamaraj University, Madurai 625021 (India); Ramaraj, Ramasamy, E-mail: ramarajr@yahoo.com [Centre for Photoelectrochemistry, School of Chemistry, Madurai Kamaraj University, Madurai 625021 (India)

    2012-02-15

    Graphical abstract: Aminosilicate sol-gel supported TiO{sub 2}-Au nanocomposite material photocatalyst was prepared by deposition-precipitation method and used for the simultaneous oxidation and reduction of methyelene blue dye and Cr(VI) ions. Highlights: Black-Right-Pointing-Pointer The EDAS/(TiO{sub 2}-Au){sub nps} is used to design the solid-phase thin film photocatalyst. Black-Right-Pointing-Pointer Au promotes the interfacial electron transfer from TiO{sub 2} to Cr(VI) to form Cr(III). Black-Right-Pointing-Pointer The holes produced at the TiO{sub 2} oxidize the MB dye. Black-Right-Pointing-Pointer The EDAS/(TiO{sub 2}-Au){sub nps} film was used for the simultaneous oxidation and reduction of toxic molecules. Black-Right-Pointing-Pointer The photoinduced simultaneous redox process provides dual benefit for the environment remediation. - Abstract: Aminosilicate sol-gel supported titanium dioxide-gold (EDAS/(TiO{sub 2}-Au){sub nps}) nanocomposite materials were synthesized by simple deposition-precipitation method and characterized. The photocatalytic oxidation and reduction activity of the EDAS/(TiO{sub 2}-Au){sub nps} film was evaluated using hexavalent chromium (Cr(VI)) and methylene blue (MB) dye under irradiation. The photocatalytic reduction of Cr(VI) to Cr(III) was studied in the presence of hole scavengers such as oxalic acid (OA) and methylene blue (MB). The photocatalytic degradation of MB was investigated in the presence and absence of Cr(VI). Presence of Au{sub nps} on the (TiO{sub 2}){sub nps} surface and its dispersion in the silicate sol-gel film (EDAS/(TiO{sub 2}-Au){sub nps}) improved the photocatalytic reduction of Cr(VI) and oxidation of MB due to the effective interfacial electron transfer from the conduction band of the TiO{sub 2} to Au{sub nps} by minimizing the charge recombination process when compared to the TiO{sub 2} and (TiO{sub 2}-Au){sub nps} in the absence of EDAS. The EDAS/(TiO{sub 2}-Au){sub nps} nanocomposite materials provided

  16. Exploratory Characterization of Phenolic Compounds with Demonstrated Anti-Diabetic Activity in Guava Leaves at Different Oxidation States

    Science.gov (United States)

    Díaz-de-Cerio, Elixabet; Verardo, Vito; Gómez-Caravaca, Ana María; Fernández-Gutiérrez, Alberto; Segura-Carretero, Antonio

    2016-01-01

    Psidium guajava L. is widely used like food and in folk medicine all around the world. Many studies have demonstrated that guava leaves have anti-hyperglycemic and anti-hyperlipidemic activities, among others, and that these activities belong mainly to phenolic compounds, although it is known that phenolic composition in guava tree varies throughout seasonal changes. Andalusia is one of the regions in Europe where guava is grown, thus, the aim of this work was to study the phenolic compounds present in Andalusian guava leaves at different oxidation states (low, medium, and high). The phenolic compounds in guava leaves were determined by HPLC-DAD-ESI-QTOF-MS. The results obtained by chromatographic analysis reported that guava leaves with low degree of oxidation had a higher content of flavonols, gallic, and ellagic derivatives compared to the other two guava leaf samples. Contrary, high oxidation state guava leaves reported the highest content of cyanidin-glucoside that was 2.6 and 15 times higher than guava leaves with medium and low oxidation state, respectively. The QTOF platform permitted the determination of several phenolic compounds with anti-diabetic properties and provided new information about guava leaf phenolic composition that could be useful for nutraceutical production. PMID:27187352

  17. Exploratory Characterization of Phenolic Compounds with Demonstrated Anti-Diabetic Activity in Guava Leaves at Different Oxidation States.

    Science.gov (United States)

    Díaz-de-Cerio, Elixabet; Verardo, Vito; Gómez-Caravaca, Ana María; Fernández-Gutiérrez, Alberto; Segura-Carretero, Antonio

    2016-05-11

    Psidium guajava L. is widely used like food and in folk medicine all around the world. Many studies have demonstrated that guava leaves have anti-hyperglycemic and anti-hyperlipidemic activities, among others, and that these activities belong mainly to phenolic compounds, although it is known that phenolic composition in guava tree varies throughout seasonal changes. Andalusia is one of the regions in Europe where guava is grown, thus, the aim of this work was to study the phenolic compounds present in Andalusian guava leaves at different oxidation states (low, medium, and high). The phenolic compounds in guava leaves were determined by HPLC-DAD-ESI-QTOF-MS. The results obtained by chromatographic analysis reported that guava leaves with low degree of oxidation had a higher content of flavonols, gallic, and ellagic derivatives compared to the other two guava leaf samples. Contrary, high oxidation state guava leaves reported the highest content of cyanidin-glucoside that was 2.6 and 15 times higher than guava leaves with medium and low oxidation state, respectively. The QTOF platform permitted the determination of several phenolic compounds with anti-diabetic properties and provided new information about guava leaf phenolic composition that could be useful for nutraceutical production.

  18. Exploratory Characterization of Phenolic Compounds with Demonstrated Anti-Diabetic Activity in Guava Leaves at Different Oxidation States

    Directory of Open Access Journals (Sweden)

    Elixabet Díaz-de-Cerio

    2016-05-01

    Full Text Available Psidium guajava L. is widely used like food and in folk medicine all around the world. Many studies have demonstrated that guava leaves have anti-hyperglycemic and anti-hyperlipidemic activities, among others, and that these activities belong mainly to phenolic compounds, although it is known that phenolic composition in guava tree varies throughout seasonal changes. Andalusia is one of the regions in Europe where guava is grown, thus, the aim of this work was to study the phenolic compounds present in Andalusian guava leaves at different oxidation states (low, medium, and high. The phenolic compounds in guava leaves were determined by HPLC-DAD-ESI-QTOF-MS. The results obtained by chromatographic analysis reported that guava leaves with low degree of oxidation had a higher content of flavonols, gallic, and ellagic derivatives compared to the other two guava leaf samples. Contrary, high oxidation state guava leaves reported the highest content of cyanidin-glucoside that was 2.6 and 15 times higher than guava leaves with medium and low oxidation state, respectively. The QTOF platform permitted the determination of several phenolic compounds with anti-diabetic properties and provided new information about guava leaf phenolic composition that could be useful for nutraceutical production.

  19. Assigning Oxidation States to Organic Compounds via Predictions from X-Ray Photoelectron Spectroscopy: A Discussion of Approaches and Recommended Improvements

    Science.gov (United States)

    Gupta, Vipul; Ganegoda, Hasitha; Engelhard, Mark H.; Terry, Jeff; Linford, Matthew R.

    2014-01-01

    The traditional assignment of oxidation states to organic molecules is problematic. Accordingly, in 1999, Calzaferri proposed a simple and elegant solution that is based on the similar electronegativities of carbon and hydrogen: hydrogen would be assigned an oxidation state of zero when bonded to carbon. Here, we show that X-ray photoelectron…

  20. Assigning Oxidation States to Organic Compounds via Predictions from X-Ray Photoelectron Spectroscopy: A Discussion of Approaches and Recommended Improvements

    Science.gov (United States)

    Gupta, Vipul; Ganegoda, Hasitha; Engelhard, Mark H.; Terry, Jeff; Linford, Matthew R.

    2014-01-01

    The traditional assignment of oxidation states to organic molecules is problematic. Accordingly, in 1999, Calzaferri proposed a simple and elegant solution that is based on the similar electronegativities of carbon and hydrogen: hydrogen would be assigned an oxidation state of zero when bonded to carbon. Here, we show that X-ray photoelectron…

  1. Rapid loss of adiponectin-stimulated fatty acid oxidation in skeletal muscle of rats fed a high fat diet is not due to altered muscle redox state.

    Science.gov (United States)

    Ritchie, Ian R W; Dyck, David J

    2012-01-01

    A high fat (HF) diet rapidly impairs the ability of adiponectin (Ad) to stimulate fatty acid (FA) oxidation in oxidative soleus muscle, but the underlying mechanism remains elusive. Mere days of HF feeding also increase the muscle's production and accumulation of reactive oxygen species (ROS) and shift cellular redox to a more oxidized state. It seems plausible that this shift towards a more oxidized state might act as negative feedback to suppress the ability of Ad to stimulate FA oxidation and generate more ROS. Therefore, we sought to determine whether i) a shift towards a more oxidized redox state (reduction in GSH/2GSSG) coincided with impaired Ad-stimulated palmitate oxidation in oxidative and glycolytic rodent muscle after 5 days of HF feeding (60% kCal), and ii) if supplementation with the antioxidant, N-acetylcysteine (NAC) could prevent the HF-diet induced impairment in Ad-response. Globular Ad (gAd) increased palmitate oxidation in isolated soleus and EDL muscles by 42% and 34%, respectively (pmuscles. HF feeding decreased total GSH (-26%, pmuscle. Furthermore, direct incubations with H(2)O(2) did not impair Ad-stimulated FA oxidation in either muscle. In conclusion, our data indicates that skeletal muscle Ad resistance is rapidly induced in both oxidative and glycolytic muscle, independently of altered cellular redox state.

  2. Rapid Synthesis of Lead Oxide Nanorods by One-step Solid-state Chemical Reaction at Room Temperature

    Institute of Scientific and Technical Information of China (English)

    CAO, Ya-Li(曹亚丽); JIA, Dian-Zeng(贾殿赠); LIU, Lang(刘浪); LUO, Jian-Min(骆建敏)

    2004-01-01

    A simple and facile method was reported to synthesize lead oxide nanorods. Nanorods of lead oxide were obtained directly from grinding solid metal salt and sodium hydroxide in agate mortar with the assistance of a suitable nonionic surfactant in only one step, which is different from the result of hydroxide in solution. The product has been characterized by XRD, TEM and SEM. The formation mechanism of rod-like morphology is discussed and the surfactant plays an important soft-template role in modifying the interface of solid-state reaction and according process of rod-formation.

  3. Seasonal variations of nitric oxide flux from agricultural soils in the Southeast United States

    Science.gov (United States)

    Aneja, Viney P.; Robarge, Wayne P.; Sullivan, Lee J.; Moore, Thomas C.; Pierce, Thomas E.; Geron, Chris; Gay, Bruce

    1996-11-01

    Fluxes of nitric oxide (NO) were measured from the summer of 1994 to the spring of 1995 from an intensively managed agricultural soil using a dynamic flow through chamber technique in order to study the seasonal variability in the emissions of NO. The measurements were made on a Norfolk sandy loam (Fine-Loamy, Siliceous, Thermic Typic Paleudult) soil located at an agricultural research station in the Upper Coastal Plain region of North Carolina. Soil nitric oxide fluxes from 3 crops, representing 3 levels of fertilizer application (corn, 168kgNha1; cotton, 68kgNha1; and soybean, 0kgNha1), were measured in each season (summer, fall, winter, and spring). Additional measured soil parameters included soil temperature, soil water content (expressed as percent water filled pore space,%WFPS), and extractable nitrogen. The greatest NO flux observed in each crop occurred during the summer (June to August) measurement period (corn, 21.9±18.6ngNm2 s1; cotton, 4.3±3.7ngNm2 s1; and soybean, 2.1±0.9ngNm2 s1). NO flux decreased in each crop through the fall months to a minimum flux in the winter. Application of fertilizer during the spring months once again produced substantial NO flux, but not as high as during the summer months. Over 80% of NO flux from the three crops measured occurred in the summer months with an estimated 5% of the nitrogen applied as fertilizer emitted as NO in a year's time. The corn crop, which had the highest amount of applied fertilizer, had the highest average yearly NO flux (7.0±4.8ngNm2 s1) followed by cotton and soybean in order (1.7±1.2ngNm2 s1 and 1.0±0.3ngNm2 s-1, respectively). NO flux from soil tracked soil temperature very closely throughout the year, especially through the summer and spring months. However, NO flux measured under a cotton canopy decreased when soil temperature was>25°C and soil moisture content wasassumption that in the Southeast United States, which has naturally emitted VOC's and large acreages of fertilized

  4. Mitigation of Hexavalent Chromium in Storm Water Resulting from Demolition of Large Concrete Structure at the East Tennessee Technology Park - 12286

    Energy Technology Data Exchange (ETDEWEB)

    Britto, Ronnie; Brown, Bridget; Hale, Timothy B.; Hensley, Janice L.; Johnson, Robert T.; Patel, Madhu [Tetra Tech, Inc. (United States); Emery, Jerry A. [Energy Solutions, Inc. (United States); Gaston, Clyde [LATA-SHARP Remediation Services - LSRS (United States); Queen, David C. [U.S. DOE-ORO (United States)

    2012-07-01

    American Recovery and Reinvestment Act (ARRA) funding was provided to supplement the environmental management program at several DOE sites, including the East Tennessee Technology Park (ETTP) in Oak Ridge, Tennessee. Demolition of the ETTP K-33 Building, the largest building to be demolished to date in Oak Ridge, was awarded to LSRS in FY-2010 under the ARRA program. The K-33 building was an 82 foot tall 2-story structure covering approximately 32 acres. Once this massive building was brought down to the ground, the debris was segregated and consolidated into piles of concrete rubble and steel across the remaining pad. The process of demolishing the building, tracking across concrete debris with heavy equipment, and stockpiling the concrete rubble caused it to become pulverized. During and after storm events, hexavalent chromium leached from the residual cement present in the large quantities of concrete. Storm water control measures were present to preclude migration of contaminants off-site, but these control measures were not designed to control hexavalent chromium dissolved in storm water from reaching nearby receiving water. The following was implemented to mitigate hexavalent chromium in storm water: - Steel wool was distributed around K-33 site catch basins and in water pools as an initial step in addressing hexavalent chromium. - Since the piles of concrete were too massive and unsafe to tarp, they were placed into windrows in an effort to reduce total surface area. - A Hach colorimetric field meter was acquired by the K-33 project to provide realtime results of hexavalent chromium in site surface water. - Three hexavalent chromium treatment systems were installed at three separate catch basins that receive integrated storm water flow from the K-33 site. Sodium bisulfite is being used as a reducing agent for the immobilization of hexavalent chromium while also assisting in lowering pH. Concentrations initially were 310 - 474 ppb of hexavalent chromium in

  5. Evaluation of extraction methods for hexavalent chromium determination in dusts, ashes, and soils

    Science.gov (United States)

    Wolf, Ruth E.; Wilson, Stephen A.

    2010-01-01

    One of the difficulties in performing speciation analyses on solid samples is finding a suitable extraction method. Traditional methods for extraction of hexavalent chromium, Cr(VI), in soils, such as SW846 Method 3060A, can be tedious and are not always compatible with some determination methods. For example, the phosphate and high levels of carbonate and magnesium present in the U.S. Environmental Protection Agency (USEPA) Method 3060A digestion for Cr(VI) were found to be incompatible with the High Performance Liquid Chromatography-Inductively Coupled Plasma-Mass Spectrometry (HPLC-ICP-MS) detection method used by our laboratory. Modification of Method 3060A by eliminating the use of the phosphate buffer provided improved performance with the detection method, however dilutions are still necessary to achieve good chromatographic separation and detection of Cr(VI). An ultrasonic extraction method using a 1 mM Na2CO3 - 9 mM NaHCO3 buffer solution, adapted from Occupational Safety and Health Administration (OSHA) Method ID215, has been used with good results for the determination of Cr(VI) in air filters. The average recovery obtained for BCR-545 - Welding Dust Loaded on Filter (IRMM, Belgium) using this method was 99 percent (1.2 percent relative standard deviation) with no conversion of Cr(VI) to Cr(III) during the extraction process. This ultrasonic method has the potential for use with other sample matrices, such as ashes and soils. Preliminary investigations using NIST 2701 (Hexavalent Chromium in Contaminated Soil) loaded onto quartz filters showed promising results with approximately 90 percent recovery of the certified Cr(VI) value. Additional testing has been done using NIST 2701 and NIST 2700 using different presentation methods. Extraction efficiency of bulk presentation, where small portions of the sample are added to the bottom of the extraction vessel, will be compared with supported presentation, where small portions of the sample are loaded onto a

  6. L-Edge Xanes Measurements of the Oxidation State of Tungsten in Iron Bearing and Iron Free Silicate Glasses

    Science.gov (United States)

    Danielson, L. R.; Righter, K.; Sutton, S.; Newville, M.

    2008-01-01

    Tungsten is important in constraining core formation of the Earth because this element is a moderately siderophile element (depleted 10 relative to chondrites) and, as a member of the Hf-W isotopic system, it is useful in constraining the timing of core formation. A number of previous experimental studies have been carried out to determine the silicate solubility and metal-silicate partitioning behavior of W, including its concomitant oxidation state. However, results of previous studies are inconsistent on whether W occurs as W(4+) or W(6+). It is assumed that W(4+) is the cation valence relevant to core formation. Given the sensitivity to silicate composition of high valence cations, knowledge of the oxidation state of W over a wide range of fO2 is critical to understanding the oxidation state of the mantle and core formation processes. This study seeks to measure the W valence and change in valence state over the range of fO2 most relevant to core formation, around IW-2.

  7. Fortification of CdSe quantum dots with graphene oxide. Excited state interactions and light energy conversion.

    Science.gov (United States)

    Lightcap, Ian V; Kamat, Prashant V

    2012-04-25

    Graphene based 2-D carbon nanostructures provide new opportunities to fortify semiconductor based light harvesting assemblies. Electron and energy transfer rates from photoexcited CdSe colloidal quantum dots (QDs) to graphene oxide (GO) and reduced graphene oxide (RGO) were isolated by analysis of excited state deactivation lifetimes as a function of degree of oxidation and charging in (R)GO. Apparent rate constants for energy and electron transfer determined for CdSe-GO composites were 5.5 × 10(8) and 6.7 × 10(8) s(-1), respectively. Additionally, incorporation of GO in colloidal CdSe QD films deposited on conducting glass electrodes was found to enhance the charge separation and electron conduction through the QD film, thus allowing three-dimensional sensitization. Photoanodes assembled from CdSe-graphene composites in quantum dot sensitized solar cells display improved photocurrent response (~150%) over those prepared without GO.

  8. Enhancement of photovoltage of dye-sensitized solid-state solar cells by introducing high-band-gap oxide layers

    Energy Technology Data Exchange (ETDEWEB)

    Bandara, J.; Weerasinghe, H.C. [Institute of Fundamental Studies, Department of Photochemistry, Hantana Road, Kandy (Sri Lanka)

    2005-09-15

    Electrodes constructed using nanocrystalline TiO{sub 2} particulates for dye-sensitized solid-state solar cells (SS-DSSCs) showed open-circuit voltage (V{sub oc}) in the 500-600mV range, which is less than the theoretical expected value. Incorporation of high-band-gap semiconducting oxides with a flatband potential higher than TiO{sub 2}, such as SrTiO{sub 3} or ZnO, results in a dramatic increase in V{sub oc} of SS-DSSC as compared to porous TiO{sub 2} nanocrystalline films. The observed photovoltage difference could be correlated to the difference in the flatband potential values of the respective oxides and shift of the flatband potentials of the oxide films. Hence, this method could be used to enhance the V{sub oc} and overall cell performance of SS-DSSC.

  9. Forming mechanism of nitrogen doped graphene prepared by thermal solid-state reaction of graphite oxide and urea

    Energy Technology Data Exchange (ETDEWEB)

    Mou Zhigang [College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123 (China); Chen Xiaoye [Jiangsu Key Laboratory for Carbon-Based Functional Materials and Devices, Institute of Functional Nano and Soft Materials (FUNSOM), Soochow University, Suzhou 215123 (China); Du Yukou; Wang Xiaomei [College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123 (China); Yang Ping, E-mail: pyang@suda.edu.cn [College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123 (China); Wang Suidong, E-mail: wangsd@suda.edu.cn [Jiangsu Key Laboratory for Carbon-Based Functional Materials and Devices, Institute of Functional Nano and Soft Materials (FUNSOM), Soochow University, Suzhou 215123 (China)

    2011-12-15

    Nitrogen doped graphene was synthesized from graphite oxide and urea by thermal solid-state reaction. The samples were characterized by transmission electron microscopy, atomic force microscopy, scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectra, element analysis, and electrical conductivity measurement. The results reveal that there is a gradual thermal transformation of nitrogen bonding configurations from amide form nitrogen to pyrrolic, then to pyridinic, and finally to 'graphitic' nitrogen in graphene sheets with increasing annealing temperature from 200 to 700 Degree-Sign C. The products prepared at 600 Degree-Sign C and 700 Degree-Sign C show that the quantity of nitrogen incorporated into graphene lattice is {approx}10 at.% with simultaneous reduction of graphite oxide. Oxygen-containing functional groups in graphite oxide are responsible for the doping reaction to produce nitrogen doped graphene.

  10. Understanding the Chemistry of Uncommon Americium Oxidation States for Application to Actinide/Lanthanide Separations

    Energy Technology Data Exchange (ETDEWEB)

    Leigh Martin; Bruce J. Mincher; Nicholas C. Schmitt

    2007-09-01

    A spectroscopic study of the stability of Am(V) and Am(VI) produced by oxidizing Am(III) with sodium bismuthate is presented, varying the initial americium concentration, temperature and length of the oxidation was seen to have profound effects on the resultant solutions.

  11. The changing face of lower tropospheric sulfur oxides in the United States

    Directory of Open Access Journals (Sweden)

    G. M. Hidy

    2016-12-01

    Full Text Available Abstract Sulfur oxides, sulfur dioxide and airborne sulfate, SOx, are short-lived species in the troposphere whose concentrations in air and precipitation have changed dramatically in association with fossil fuel combustion. The historic rise in concentration is coincident with the era of the so-called “Anthropocene.” Unlike concentrations of long-lived species such as carbon dioxide, atmospheric SOx in the United States (US peaked between 1970 and 2005 then declined. The rise and fall of SOx is traced by comparing national data on emission changes, ambient concentrations, and precipitation sulfate from prior to World War II to the present. Surface SOx concentrations and precipitation sulfate have decreased with emissions in most parts of the US after the late 1970s. Continued reduction toward a natural “background” condition has depended on aggressive management of anthropogenic emission sources. Annual average ambient concentrations of SO2 and SO4 have become more uniform across the US at levels of 1–3 ppbv and 0.3–3 µg/m3, respectively. Precipitation SO4 has a nominal concentration generally less than 0.5 mg/L. The effective lifetime of SOx in the troposphere is a few days. This duration limits the spatial extent of emission source influence of SOx to regional scales, wherein spatial gradients in species concentrations lead to variations in human exposure and impacts on vulnerable terrestrial and aquatic ecosystems. The effects of domestic emission reductions on SOx levels are moderated by intra- and intercontinental transport of SOx from Canada, Mexico, Asia and elsewhere. The trends in tropospheric SOx concentrations illustrate the results of more than a century of rising public awareness and action to progressively reduce a US environmental risk, accomplished with advances in energy production technology that have maintained economic well-being.

  12. Metabolomic profiles of arsenic (+3 oxidation state) methyltransferase knockout mice: effect of sex and arsenic exposure.

    Science.gov (United States)

    Huang, Madelyn C; Douillet, Christelle; Su, Mingming; Zhou, Kejun; Wu, Tao; Chen, Wenlian; Galanko, Joseph A; Drobná, Zuzana; Saunders, R Jesse; Martin, Elizabeth; Fry, Rebecca C; Jia, Wei; Stýblo, Miroslav

    2017-01-01

    Arsenic (+3 oxidation state) methyltransferase (As3mt) is the key enzyme in the pathway for methylation of inorganic arsenic (iAs). Altered As3mt expression and AS3MT polymorphism have been linked to changes in iAs metabolism and in susceptibility to iAs toxicity in laboratory models and in humans. As3mt-knockout mice have been used to study the association between iAs metabolism and adverse effects of iAs exposure. However, little is known about systemic changes in metabolism of these mice and how these changes lead to their increased susceptibility to iAs toxicity. Here, we compared plasma and urinary metabolomes of male and female wild-type (WT) and As3mt-KO (KO) C57BL/6 mice and examined metabolomic shifts associated with iAs exposure in drinking water. Surprisingly, exposure to 1 ppm As elicited only small changes in the metabolite profiles of either WT or KO mice. In contrast, comparisons of KO mice with WT mice revealed significant differences in plasma and urinary metabolites associated with lipid (phosphatidylcholines, cytidine, acyl-carnitine), amino acid (hippuric acid, acetylglycine, urea), and carbohydrate (L-sorbose, galactonic acid, gluconic acid) metabolism. Notably, most of these differences were sex specific. Sex-specific differences were also found between WT and KO mice in plasma triglyceride and lipoprotein cholesterol levels. Some of the differentially changed metabolites (phosphatidylcholines, carnosine, and sarcosine) are substrates or products of reactions catalyzed by other methyltransferases. These results suggest that As3mt KO alters major metabolic pathways in a sex-specific manner, independent of iAs treatment, and that As3mt may be involved in other cellular processes beyond iAs methylation.

  13. DAYCENT national-scale simulations of nitrous oxide emissions from cropped soils in the United States.

    Science.gov (United States)

    Del Grosso, S J; Parton, W J; Mosier, A R; Walsh, M K; Ojima, D S; Thornton, P E

    2006-01-01

    Until recently, Intergovernmental Panel on Climate Change (IPCC) emission factor methodology, based on simple empirical relationships, has been used to estimate carbon (C) and nitrogen (N) fluxes for regional and national inventories. However, the 2005 USEPA greenhouse gas inventory includes estimates of N2O emissions from cultivated soils derived from simulations using DAYCENT, a process-based biogeochemical model. DAYCENT simulated major U.S. crops at county-level resolution and IPCC emission factor methodology was used to estimate emissions for the approximately 14% of cropped land not simulated by DAYCENT. The methodology used to combine DAYCENT simulations and IPCC methodology to estimate direct and indirect N2O emissions is described in detail. Nitrous oxide emissions from simulations of presettlement native vegetation were subtracted from cropped soil N2O to isolate anthropogenic emissions. Meteorological data required to drive DAYCENT were acquired from DAYMET, an algorithm that uses weather station data and accounts for topography to predict daily temperature and precipitation at 1-km2 resolution. Soils data were acquired from the State Soil Geographic Database (STATSGO). Weather data and dominant soil texture class that lie closest to the geographical center of the largest cluster of cropped land in each county were used to drive DAYCENT. Land management information was implemented at the agricultural-economic region level, as defined by the Agricultural Sector Model. Maps of model-simulated county-level crop yields were compared with yields estimated by the USDA for quality control. Combining results from DAYCENT simulations of major crops and IPCC methodology for remaining cropland yielded estimates of approximately 109 and approximately 70 Tg CO2 equivalents for direct and indirect, respectively, mean annual anthropogenic N2O emissions for 1990-2003.

  14. Oxidation state of Paleozoic subcontinental lithospheric mantle below the Pali Aike volcanic field in southernmost Patagonia

    Science.gov (United States)

    Wang, Jian; Hattori, Keiko H.; Li, Jianping; Stern, Charles R.

    2008-09-01

    Mantle xenoliths in the Quaternary Pali Aike alkaline basalts of southernmost Patagonia include lherzolites and harzburgites with and without garnet. The values of fO 2 for all xenoliths range from 0.33 logarithmic unit below the fayalite-magnetite-quartz buffer (FMQ - 0.33) to FMQ + 0.75, which overlap those for abyssal peridotites. The fO 2 data, together with the bulk rock and mineral compositions, suggest that the subcontinental lithospheric mantle (SCLM) below Pali Aike formed through the accretion of oceanic lithosphere. The oceanic accretion likely occurred in mid to late Paleozoic time when the southern Patagonian terrane formed along the southwest margin of Gondwana. Relict spinel inclusions in garnet suggest that garnet-facies peridotites formed from spinel-facies peridotites most likely in response to pressure increase during the accretion. Comparable fO 2 for garnet- and spinel-facies peridotites suggests that this spinel-garnet transformation was not accompanied by changes in fO 2. Metasomatism by asthenosphere-derived melt through a slab window resulted in the formation of Ti-bearing minerals, and lowering of Mg and enrichment of Ti in bulk rocks and minerals. The replacement of olivine by orthopyroxene formed orthopyroxenites in extreme cases. No significant change in fO 2 is associated with this metasomatism since similar oxidation state is observed between un-metasomatized (FMQ - 0.23 to + 0.48) and metasomatized (FMQ - 0.33 to + 0.75) samples. This is explained by the fO 2 of the asthenospheric melt (~ FMQ - 0.50) similar to the SCLM prior to the metasomatism.

  15. The synthesis, characterization and reactivity of high oxidation state nickel fluorides

    Energy Technology Data Exchange (ETDEWEB)

    Chacon, L.C. [Univ. of Berkeley, CA (United States). Dept. of Chemistry]|[Lawrence Berkeley National Lab., CA (United States). Chemical Sciences Div.

    1997-12-01

    The research described in this thesis has mainly addressed the challenge of the synthesis of thermodynamically unstable nickel fluorides, which cannot be made by traditional thermal methods. A low-temperature approach towards the synthesis of such transition metal fluorides exploits the greater thermodynamic stability of high oxidation states in anions and involves the use of anhydrous hydrogen fluoride (aHF) as a solvent. The general method consists of combining an aHF soluble starting material (e.g., K{sub 2}NiF{sub 6}) with a Lewis fluoroacid (e.g., BF{sub 3}), which precipitates a neutral polymeric solid state fluoride: 2 K{sup +} + NiF{sub 6}{sup 2{minus}} + BF{sub 3} {r_arrow} NiF{sub 4} + 2 BF{sub 4}{sup {minus}} + 2 K{sup +}. At room temperature, this reaction yields a different structural phase, with composition K{sub x}NiF{sub 3} (x {approx} 0.18). This material has a pseudo-hexagonal tungsten bronze structure (H{sub 0}-K{sub x}NiF{sub 3}), and is an ionic conductor, probably due to K{sup +} ions hosted in the lattice channels. R-NiF{sub 3} is capable of fluorinating a wide range of inorganic and organic substrates. These reactions have probably shed light on the mechanism of the Simons Electrochemical Fluorination (ECF) Process, an important industrial method of fluorinating organic compounds. It has long been speculated that NiF{sub 3} plays a role in the ECF process, which uses nickel electrodes in aHF solvent. K{sub 2}NiF{sub 6} also fluorinates organic compounds in aHF, but interestingly, yields different fluorinated products. The reduction of R-NiF{sub 3} and K{sub 2}NiF{sub 6} during fluorination reactions yields NiF{sub 2}. A method has been developed to regenerate NiF{sub 6}{sup 2{minus}} from NiF{sub 2}.

  16. The synthesis, characterization and reactivity of high oxidation state nickel fluorides

    Energy Technology Data Exchange (ETDEWEB)

    Chacon, L.C. [Univ. of Berkeley, CA (United States). Dept. of Chemistry]|[Lawrence Berkeley National Lab., CA (United States). Chemical Sciences Div.

    1997-12-01

    The research described in this thesis has mainly addressed the challenge of the synthesis of thermodynamically unstable nickel fluorides, which cannot be made by traditional thermal methods. A low-temperature approach towards the synthesis of such transition metal fluorides exploits the greater thermodynamic stability of high oxidation states in anions and involves the use of anhydrous hydrogen fluoride (aHF) as a solvent. The general method consists of combining an aHF soluble starting material (e.g., K{sub 2}NiF{sub 6}) with a Lewis fluoroacid (e.g., BF{sub 3}), which precipitates a neutral polymeric solid state fluoride: 2 K{sup +} + NiF{sub 6}{sup 2{minus}} + BF{sub 3} {r_arrow} NiF{sub 4} + 2 BF{sub 4}{sup {minus}} + 2 K{sup +}. At room temperature, this reaction yields a different structural phase, with composition K{sub x}NiF{sub 3} (x {approx} 0.18). This material has a pseudo-hexagonal tungsten bronze structure (H{sub 0}-K{sub x}NiF{sub 3}), and is an ionic conductor, probably due to K{sup +} ions hosted in the lattice channels. R-NiF{sub 3} is capable of fluorinating a wide range of inorganic and organic substrates. These reactions have probably shed light on the mechanism of the Simons Electrochemical Fluorination (ECF) Process, an important industrial method of fluorinating organic compounds. It has long been speculated that NiF{sub 3} plays a role in the ECF process, which uses nickel electrodes in aHF solvent. K{sub 2}NiF{sub 6} also fluorinates organic compounds in aHF, but interestingly, yields different fluorinated products. The reduction of R-NiF{sub 3} and K{sub 2}NiF{sub 6} during fluorination reactions yields NiF{sub 2}. A method has been developed to regenerate NiF{sub 6}{sup 2{minus}} from NiF{sub 2}.

  17. TRLFS Studies on luminescence enhancement of U(VI) using oxidants for quencher species in samples

    Energy Technology Data Exchange (ETDEWEB)

    Cha, Wansik; Jung, Euo Chang; Cho, Hye Ryun [Nuclear Chemistry Research Division, Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2012-10-15

    The pulse laser-based method detects photo luminescent emission of U(VI) so that it is highly sensitive for non-isotopic al determination of total uranium concentration. Thus, this method has been used for detection of trace quantity of uranium in the environmental, geological, and bioassay samples. One of widely-used pulse laser-based methods is kinetic phosphorescence analysis (KPA), of which instrument is commercially available. The intensity and lifetime of characteristic phosphorescence at 515-520 nm of hexavalent uranium are measured with an excitation wavelength of 425 nm. Particularly in KPA the use of phosphate-based luminescence enhancing agent (LEA) leading to the formation of uranyl-phosphate complexes extends the luminescence (LM) lifetime of uranium (> {approx} 200 {mu}s) and subsequently the overall luminescence intensity. In KPA, however, an extensive sample pretreatment procedure is required to reduce the luminescence quenching effects of ions and molecules present in samples. During such procedures the uranium species in low oxidation states are also oxidized to hexavalent uranium so that the measurement of the total uranium concentration can be achieved. In general, a series of high temperature dry and wet ashing procedures is implemented prior to the addition of LEA to decompose the interfering substances. The aim of this study is to examine the characteristics of the interfering species exhibiting significant quenching effects and to develop a way of minimizing the time required for the sample pretreatment step particularly for certain oxidizable quencher species. In fact, in a previous study we reported that significant LM quenching effects are observed from those possessing chemical reduction capability such as Fe(II) and cysteine. Under such sample conditions it is shown that the conventional KPA is not applicable due to the short lifetime (< {approx} 1 {mu}s), therefore a time-resolved laser-induced fluorescence spectroscopy (TRLFS) capable

  18. Were ancient granitoid compositions influenced by contemporaneous atmospheric and hydrosphere oxidation states?Were ancient granitoid compositions influenced by contemporaneous atmospheric and hydrosphere oxidation states?

    Science.gov (United States)

    Jagoutz, Oliver

    2014-05-01

    A fundamental shift in the nature of granitoids occurs at approximately the Archean-Proterozoic boundary. Archean crust is dominated Na-rich tonalite-trondhjemite-granodiorites (TTGs), whereas post-Archean granitoids are characterized by K-rich granodiorite-granite (GG). Due to the HREE depletion commonly found in TTGs indicating the presence of residual garnet, many researchers have proposed that the difference in Na/K is related to the deeper melting depth of the TTG parental liquids. Here I present a compilation of the relevant experimental data, documenting that no correlation exists between the Na/K of derivative felsic liquids and the pressure of partial melting/fractional crystallization. Instead, the Na/K ratio of the felsic liquid best correlates with the Na/K ratio of the source. This implies that in Archean time the source material of TTG rocks must have been Na/K enriched relative to the modern. Modern granitoids are dominantly formed in a supra subduction zone environment, where a feedback loop exists between subducted materials (oceanic crust and sediments) and arc magmatism. Sea-floor weathering and the Na/K of the altered oceanic crust strongly depends on f(O2) conditions during alteration, which likely changed with earth history. During alteration under oxidized condition K2O is fixated due to the formation of celadonite (K-Mica), wheres during anoxic condition saponite (Na-Smectite) is the stable alteration mineral. I propose that the rise of oxygen at 2600-2400 Ma triggered associated changes in f(O2) seafloor alteration conditions. The change in the dominant seafloor alteration mineral from reduced to oxidized causes a change in the nature of the arc magma source and provides a possible explanation for the observed transition from TTGrocks in the Archean to the GG-granitoids in post-Archean times.

  19. Biosorption of hexavalent chromium from aqueous solutions by Macadamia nutshell powder

    Science.gov (United States)

    Pakade, Vusumzi Emmanuel; Ntuli, Themba Dominic; Ofomaja, Augustine Enakpodia

    2016-04-01

    Macadamia nutshell biosorbents treated in three different activating agents [raw Macadamia nutshell powder (RMN), acid-treated Macadamia nutshell (ATMN) and base-treated Macadamia nutshell (BTMN)] were investigated for the adsorption of hexavalent chromium [Cr(VI)] from aqueous solutions. Fourier transform infrared spectroscopy spectra of free and Cr(VI)-loaded sorbents as well as thermogravimetric analysis revealed that the acid and base treatments modified the surface properties of the sorbent. Surface characteristics were also evaluated by the scanning electron microscopy and surface area analyzer. The optimum conditions for the adsorption of Cr(VI) by sorbents were pH 2, contact time 10 h, adsorbent mass 0.2 g and concentration 100 mg L-1. The equilibrium data were fitted into the Langmuir, Freundlich, Redlich-Peterson and Sips isotherms, and no single model could clearly explain the sorption mechanism. Maximum binding capacities of 45.23, 44.83 and 42.44 mg g-1 for RMN, ATMN and BTMN, respectively, were obtained. The kinetic data were analyzed using the pseudo-first, pseudo-second and Elovich kinetic models, and it was observed that the pseudo-second-order model produced the best fit for the experimental data. Macadamia nutshell sorbents showed potential as low-cost adsorbent for the removal of Cr(VI) from aqueous solution.

  20. Equilibrium and dynamic study on hexavalent chromium adsorption onto activated carbon.

    Science.gov (United States)

    Di Natale, F; Erto, A; Lancia, A; Musmarra, D

    2015-01-08

    In this work, the results of equilibrium and dynamic adsorption tests of hexavalent chromium, Cr (VI), on activated carbon are presented. Adsorption isotherms were determined at different levels of pH and temperature. Dynamic tests were carried out in terms of breakthrough curves of lab-scale fixed bed column at different pH, inlet concentration and flow rate. Both the adsorption isotherms and the breakthrough curves showed non-linear and unconventional trends. The experimental results revealed that chromium speciation played a key role in the adsorption process, also for the occurrence of Cr(VI)-to-Cr(III) reduction reactions. Equilibrium tests were interpreted in light of a multi-component Langmuir model supported by ion speciation analysis. For the interpretation of the adsorption dynamic tests, a mass transfer model was proposed. Dynamic tests at pH 11 were well described considering the external mass transfer as the rate controlling step. Differently, for dynamic tests at pH 6 the same model provided a satisfying description of the experimental breakthrough curves only until a sorbent coverage around 1.6mgg(-1). Above this level, a marked reduction of the breakthrough curve slope was observed in response to a transition to an inter-particle adsorption mechanism.

  1. The Growth of Gypsum in the Presence of Hexavalent Chromium: A Multiscale Study

    Directory of Open Access Journals (Sweden)

    Juan Morales

    2016-03-01

    Full Text Available The sorption of dissolved inorganic pollutants into the structure of minerals is an important process that controls the mobility and fate of these pollutants in the Earth’s crust. It also modifies the surface structure and composition of the host mineral, affecting its crystallization kinetics. Here, we investigate the effect of hexavalent chromium, Cr(VI, on the nucleation and growth of gypsum by conducting two types of experiments: (i in situ atomic force microscopy (AFM observations of the growth of gypsum {010} surfaces in the presence of Cr(VI and (ii gypsum precipitation experiments by mixing aqueous solutions containing variable amounts of Cr(VI. Gypsum precipitation is progressively delayed when occurring from solutions bearing increasing Cr(VI concentrations. Chemical analyses of gypsum precipitates show that gypsum incorporates small Cr(VI amounts that correlate with the content of this ion in the aqueous solution. Gypsum cell parameters variation reflects this incorporation. At the molecular scale, Cr(VI induces a slowdown of step advance rates on gypsum {010} surfaces accompanied by the roughening of nanostep edges and the so-called “template effect”. This effect involves the reproduction of the original nanotopography after the completion of individual advancing monolayers and appears as a general nanoscale phenomenon occurring during growth of solid solutions from aqueous solutions even in the case of compositionally-restricted solid solutions.

  2. Hexavalent Chromium Removal by a Paecilomyces sp. Fungal Strain Isolated from Environment

    Directory of Open Access Journals (Sweden)

    Juan F. Cárdenas-González

    2010-01-01

    Full Text Available A resistant and capable fungal strain in removing hexavalent chromium was isolated from an environment near of Chemical Science Faculty, located in the city of San Luis Potosí, Mexico. The strain was identified as Paecilomyces sp., by macro- and microscopic characteristics. Strain resistance of the strain to high Cr (VI concentrations and its ability to reduce chromium were studied. When it was incubated in minimal medium with glucose, another inexpensive commercial carbon source like unrefined and brown sugar or glycerol, in the presence of 50 mg/L of Cr (VI, the strain caused complete disappearance of Cr (VI, with the concomitant production of Cr (III in the growth medium after 7 days of incubation, at 28∘C, pH 4.0, 100 rpm, and an inoculum of 38 mg of dry weight. Decrease of Cr (VI levels from industrial wastes was also induced by Paecilomyces biomass. These results indicate that reducing capacity of chromate resistant filamentous fungus Cr (VI could be useful for the removal of Cr (VI pollution.

  3. Biodegradation of the metallic carcinogen hexavalent chromium Cr(VI by an indigenously isolated bacterial strain

    Directory of Open Access Journals (Sweden)

    Das Alok

    2010-01-01

    Full Text Available Background : Hexavalent chromium [Cr(VI], a potential mutagen and carcinogen, is regularly introduced into the environment through diverse anthropogenic activities, including electroplating, leather tanning, and pigment manufacturing. Human exposure to this toxic metal ion not only causes potential human health hazards but also affects other life forms. The World Health Organization, the International Agency for Research on Cancer, and the Environmental Protection Agency have determined that Cr(VI compounds are known human carcinogens. The Sukinda valley in Jajpur District, Orissa, is known for its deposit of chromite ore, producing nearly 98% of the chromite ore in India and one of the prime open cast chromite ore mines in the world (CES, Orissa Newsletter. Materials and Methods: Our investigation involved microbial remediation of Cr(VI without producing any byproduct. Bacterial cultures tolerating high concentrations of Cr were isolated from the soil sample collected from the chromite-contaminated sites of Sukinda, and their bioaccumulation properties were investigated. Strains capable of growing at 250 mg/L Cr(VI were considered as Cr resistant. Results: The experimental investigation showed the maximum specific Cr uptake at pH 7 and temperature 30oC. At about 50 mg/L initial Cr(VI concentrations, uptake of the selected potential strain exceeded 98% within 12 h of incubation. The bacterial isolate was identified by 16S rRNA sequencing as Brevebacterium casei. Conclusion: Results indicated promising approach for microbial remediation of effluents containing elevated levels of Cr(VI.

  4. Reduction of Hexavalent Chromium Using L-Cysteine Capped Nickel Nanocatalysts

    Directory of Open Access Journals (Sweden)

    Razium Ali Soomro

    2013-06-01

    Full Text Available The aim of this study was to reduce the highly toxic hexavalent chromium Cr(VI into less toxic chromium Cr(III species by using nickel nanoparticles (Ni NPs as catalysts in order to provide safety to the aqueous environment. In the first phase Ni NPs were synthesized in ethylene glycol and capped with l-cysteine by a modified microwave irradiation method using NaOH as the accelerator. The formed Ni NPs were characterized by various techniques such as UV-Visible spectroscopy, Fourier Transform Infra-red (FTIR spectroscopy and Scanning Electron Microscopy (SEM. In the second phase the formed Ni NPs were immobilized on glass surfaces and employed as catalyst for the reduction of Cr(VI ions. According to observations, 99% reduction of Cr(VI ions was achieved in the presence of 0.5 mg of Ni NPs catalyst in just five minutes as compared to nickel powder that showed only 16% reduction in 15 minutes. The study has a great impact on the aqueous pollution control of Cr(VI especially caused by the discharge of waste water from several industries utilizing Cr(VI containing salt as one of the essential gradients.

  5. Soil microbial community response to hexavalent chromium in planted and unplanted soil.

    Science.gov (United States)

    Ipsilantis, Ioannis; Coyne, Mark S

    2007-01-01

    Theories suggest that rapid microbial growth rates lead to quicker development of metal resistance. We tested these theories by adding hexavalent chromium [Cr(VI)] to soil, sowing Indian mustard (Brassica juncea), and comparing rhizosphere and bulk soil microbial community responses. Four weeks after the initial Cr(VI) application we measured Cr concentration, microbial biomass by fumigation extraction and soil extract ATP, tolerance to Cr and growth rates with tritiated thymidine incorporation, and performed community substrate use analysis with BIOLOG GN plates. Exchangeable Cr(VI) levels were very low, and therefore we assumed the Cr(VI) impact was transient. Microbial biomass was reduced by Cr(VI) addition. Microbial tolerance to Cr(VI) tended to be higher in the Cr-treated rhizosphere soil relative to the non-treated systems, while microorganisms in the Cr-treated bulk soil were less sensitive to Cr(VI) than microorganisms in the non-treated bulk soil. Microbial diversity as measured by population evenness increased with Cr(VI) addition based on a Gini coefficient derived from BIOLOG substrate use patterns. Principal component analysis revealed separation between Cr(VI) treatments, and between rhizosphere and bulk soil treatments. We hypothesize that because of Cr(VI) addition there was indirect selection for fast-growing organisms, alleviation of competition among microbial communities, and increase in Cr tolerance in the rhizosphere due to the faster turnover rates in that environment.

  6. Reduction of hexavalent chromium by a novel Ochrobactrum sp. - microbial characteristics and reduction kinetics.

    Science.gov (United States)

    Narayani, M; Vidya Shetty, K

    2014-04-01

    A Gram negative hexavalent chromium (Cr(VI)) reducing bacteria, Ochrobactrum sp. Cr-B4 (genbank accession number: JF824998) was isolated from the aerator water of an activated sludge process of a wastewater treatment facility of a dye and pigment based specialty chemical industry. It showed a resistance for 1000 mg L(-1) Cr(VI). It exhibited resistance against other heavy metal ions like Ni(2+) (900 mg L(-1) ), Cu(2+) (500 mg L(-1) ), Pb(2+) (800 mg L(-1) ), and Cd(2+) (250 mg L(-1) ), Zn(2+) (700 mg L(-1) ), Fe(3+) (800 mg L(-1) ), and against selected antibiotics. Cr-B4 could efficiently reduce 200 mg L(-1) Cr(VI) completely in nutrient and LB media and could convert Cr(VI) to Cr(III) efficiently. Cr(VI) reduction in nutrient media followed allosteric enzyme kinetics with Km values of 59.39 mg L(-1) and Vmax values of 47.03 mg L(-1)  h(-1) . The reduction in LB media followed Michaelis-Menten kinetics with Km values of 99.52 mg L(-1) and Vmax of 77.63 mg L(-1)  h(-1) . Scanning electron micrograms revealed the presence of extracellular polymeric secretions.

  7. Hexavalent chromium reduction and energy recovery by using dual-chambered microbial fuel cell.

    Science.gov (United States)

    Gangadharan, Praveena; Nambi, Indumathi M

    2015-01-01

    Microbial fuel cell (MFC) technology is utilized to treat hexavalent chromium (Cr(VI)) from wastewater and to generate electricity simultaneously. The Cr(VI) is bioelectrochemically reduced to non-toxic Cr(III) form in the presence of an organic electron donor in a dual-chambered MFC. The Cr(VI) as catholyte and artificial wastewater inoculated with anaerobic sludge as anolyte, Cr(VI) at 100 mg/L was completely removed within 48 h (initial pH value 2.0). The total amount of Cr recovered was 99.87% by the precipitation of Cr(III) on the surface of the cathode. In addition to that 78.4% of total organic carbon reduction was achieved at the anode chamber within 13 days of operation. Furthermore, the maximum power density of 767.01 mW/m² (2.08 mA/m²) was achieved by MFCs at ambient conditions. The present work has successfully demonstrated the feasibility of using MFCs for simultaneous energy production from wastewater and reduction of toxic Cr(VI) to non-toxic Cr(III).

  8. Investigation of Hexavalent Chromium Flux to Groundwater at the 100-C-7:1 Excavation Site

    Energy Technology Data Exchange (ETDEWEB)

    Truex, Michael J.; Vermeul, Vincent R.; Fritz, Brad G.; Mackley, Rob D.; Horner, Jacob A.; Johnson, Christian D.; Newcomer, Darrell R.

    2012-11-16

    Deep excavation of soil has been conducted at the 100-C-7 and 100-C-7:1 waste sites within the 100-BC Operable Unit at the Department of Energy (DOE) Hanford Site to remove hexavalent chromium (Cr(VI)) contamination with the excavations reaching to near the water table. Soil sampling showed that Cr(VI) contamination was still present at the bottom of the 100-C-7:1 excavation. In addition, Cr(VI) concentrations in a downgradient monitoring well have shown a transient spike of increased Cr(VI) concentration following initiation of excavation. Potentially, the increased Cr(VI) concentrations in the downgradient monitoring well are due to Cr(VI) from the excavation site. However, data were needed to evaluate this possibility and to quantify the overall impact of the 100-C-7:1 excavation site on groundwater. Data collected from a network of aquifer tubes installed across the floor of the 100-C-7:1 excavation and from temporary wells installed at the bottom of the entrance ramp to the excavation were used to evaluate Cr(VI) releases into the aquifer and to estimate local-scale hydraulic properties and groundwater flow velocity.

  9. The Photocatalytic Reduction of Hexavalent Chromium by Controllable Mesoporous Anatase TiO2 Nanoparticles

    Directory of Open Access Journals (Sweden)

    Vorrada Loryuenyong

    2014-01-01

    Full Text Available Titania (TiO2 nanoparticles with periodical mesopore size (up to 150 Å have successfully been synthesized by sol-gel template method, using titanium(IV tetraisopropoxide as a starting precursor and isopropanol as a solvent. Different quantities of activated carbon (0%, 5%, and 10% by weight were used as templates to control the porosity and particle size of titania nanoparticles. The templates were completely removed during the calcination in air at 500°C for 3 hr. The results showed that the specific surface area of titania is increased with increasing activated carbon content. The optical bandgap of synthesized titania exhibits a blue shift by 0.3–0.6 eV when compared to the reported value for the bulk anatase and rutile phases. The photocatalytic activity of porous titania is determined with its reduction efficiency of hexavalent chromium (Cr6+. The reduction efficiency is optimized under ultraviolet illumination.

  10. Hexavalent chromium removal from wastewater using aniline formaldehyde condensate coated silica gel.

    Science.gov (United States)

    Kumar, P Albino; Ray, Manabendra; Chakraborty, Saswati

    2007-05-08

    A resinous polymer, aniline formaldehyde condensate (AFC) coated on silica gel was used as an adsorbent in batch system for removal of hexavalent chromium from aqueous solution by considering the effects of various parameters like reaction pH, dose of AFC coated silica gel, initial Cr(VI) concentration and aniline to formaldehyde ratio in AFC synthesis. The optimum pH for total chromium [Cr(VI) and Cr(III)] adsorption was observed as 3. Total chromium adsorption was second order and equilibrium was achieved within 90-120 min. Aniline to formaldehyde ratio of 1.6:1 during AFC synthesis was ideal for chromium removal. Total chromium adsorption followed Freundlich's isotherm with adsorption capacity of 65 mg/g at initial Cr(VI) 200mg/L. Total chromium removal was explained as combinations of electrostatic attraction of acid chromate ion by protonated AFC, reduction of Cr(VI) to Cr(III) and bond formation of Cr(III) with nitrogen atom of AFC. Almost 40-84% of adsorbed chromium was recovered during desorption by NaOH, EDTA and mineral acids. AFC coated silica gel can be effectively used for treatment of chromium containing wastewaters as an alternative.

  11. Hexavalent chromium removal in contaminated water using reticulated chitosan micro/nanoparticles from seafood processing wastes.

    Science.gov (United States)

    Dima, Jimena Bernadette; Sequeiros, Cynthia; Zaritzky, Noemi E

    2015-12-01

    Chitosan particles (CH) were obtained from seafood processing wastes (shrimp shells) and physicochemically characterized; deacetylation degree of CH was measured by Infrared Spectroscopy (FTIR) and potentiometric titration; polymer molecular weight was determined by intrinsic viscosity measurements. Reticulated micro/nanoparticles of chitosan (MCH) with an average diameter close to 100nm were synthesized by ionic gelation of chitosan using tripolyphosphate (TPP), and characterized by SEM, size distribution and Zeta-potential. Detoxification capacities of CH and MCH were tested analyzing the removal of hexavalent chromium Cr(VI) from contaminated water, at different initial chromium concentrations. The effect of pH on adsorption capacity of CH and MCH was experimentally determined and analyzed considering the Cr(VI) stable complexes (anions) formed, the presence of protonated groups in chitosan particles and the addition of the reticulating agent (TPP). Chitosan crosslinking was necessary to adsorb Cr(VI) at pHremoved from the solution was reduced and bound to the MCH as Cr(III). The reduction of toxic Cr(VI) to the less or nontoxic Cr(III) by the reticulated chitosan micro/nanoparticles can be considered a very efficient detoxification technique for the treatment of Cr(VI) contaminated water. Copyright © 2015 Elsevier Ltd. All rights reserved.

  12. Removal of hexavalent chromium by using red mud activated with cetyltrimethylammonium bromide.

    Science.gov (United States)

    Li, Deliang; Ding, Ying; Li, Lingling; Chang, Zhixian; Rao, Zhengyong; Lu, Ling

    2015-01-01

    The removal of hexavalent chromium [Cr(VI)] from aqueous solution by using red mud activated with cetyltrimethylammonium bromide (CTAB) was studied. The optimum operation parameters, such as CTAB concentration, pH values, contact time, and initial Cr(VI) concentration, were investigated. The best concentration of CTAB for modifying red mud was found to be 0.50% (mCTAB/VHCl,0.6 mol/L). The lower pH (Red mud activated with CTAB can greatly improve the removal ratio of Cr(VI) as high as four times than that of original red mud. Adsorption equilibrium was reached within 30 min under the initial Cr(VI) concentration of 100 mg L(-1). The isotherm data were analysed using Langmuir and Freundlich models. The adsorption of Cr(VI) on activated red mud fitted well to the Langmuir isotherm model, and the maximum adsorption capacity was estimated as 22.20 mg g(-1) (Cr/red mud). The adsorption process could be well described using the pseudo-second-order model. The result shows that activated red mud is a promising agent for low-cost water treatment.

  13. INFLUENCE OF HEXAVALENT CHROMIUM INITIAL CONCENTRATION ON RETARDATION FACTOR AND CONTAMINANT VELOCITY IN A SOIL MEDIA

    Directory of Open Access Journals (Sweden)

    K. SHIVA PRASHANTH KUMAR

    2016-02-01

    Full Text Available Sources of soil and ground water contamination are many and include many folds of accidental spills and leaks of toxic and hazardous chemicals. Preparation of ground water contamination model needs good understanding of the behavior of contaminant transport through soil media for predicting the level of contamination of ground water in the near future at the intended site conditions. Sorption is a natural process; due to its presence, the contaminant can move slowly as compared to the ground water and hence the effects of sorption must be taken into consideration while predicting the travel time of the contaminant to reach the ground water sources. This paper discusses the results of column test studies carried out in the laboratory under controlled conditions about the spreading of contaminant (Hexavalent chromium, Cr (VI through the clay mixed red soil at two different initial concentrations (800 mg/L and 4200 mg/L. The variations of the contaminant flow velocity and retardation factor for two different initial concentrations of contaminant were brought out and discussed. The contaminant flow velocity drastically coming down for a relative concentration of 0 to 0.2 and beyond this range, the contaminant flow velocity value is decreasing in a slow rate for both the lower and higher initial contaminant concentrations tested. At the lower relative concentration, the higher retardation factor was observed and it may be due to slowly filling the available sorption sites in the soil column.

  14. Investigations of adsorption sites on oxide surfaces using solid-state NMR and TPD-IGC

    Science.gov (United States)

    Golombeck, Rebecca A.

    diameters and thermal histories. The bulk structural features in both compositions of glass fibers were identified using high-resolution 29Si, 27Al, and 11B magic-angle spinning (MAS) NMR spectroscopic measurements. In multi-component glasses, the determination of silicon, aluminum, and boron distributions becomes difficult due to the competitive nature of the network-modifying oxides among the network-forming oxides. In pure silicates, 29Si MAS NMR can often resolve resonances arising from silicate tetrahedron having varying numbers of bridging oxygens. In aluminoborosilicate glasses, aluminum is present in four-, five-, and six- coordination with oxygen as neighbors. The speciation of the aluminum can be determined using 27Al MAS NMR. The fraction of tetrahedral boron species in the glass fibers were measured using 11B MAS NMR, which is typically used to study the short-range structure of borate containing glasses such as alkali borate, borosilicate, and aluminoborosilicate glasses. While solid-state NMR is a powerful tool for elucidating bonding environments and coordination changes in the glass structure, it cannot quantitatively probe low to moderate surface area samples due to insufficient spins. Chemical probes either physisorbed or chemisorbed to the fiber's surface can increase the surface selectivity of NMR for analysis of samples with low surface areas and provide information about the local molecular structure of the reactive surface site. Common chemical probe molecules contain NMR active nuclei such as 19F or may be enriched with 13C. A silyating agent, (3,3,3-trifluoropropyl)dimethylchlorosilane (TFS), reacts with reactive surface hydroxyls, which can be quantified by utilizing the NMR active nucleus (19F) contained in the probe molecule. The observed 19F MAS NMR peak area is integrated and compared against a standard of known fluorine spins (concentration), allowing the number of reactive hydroxyl sites to be quantified. IGC is a method used to study the

  15. Changes in dry state hemoglobin over time do not increase the potential for oxidative DNA damage in dried blood.

    Directory of Open Access Journals (Sweden)

    April Marrone

    Full Text Available BACKGROUND: Hemoglobin (Hb is the iron-containing oxygen transport protein present in the red blood cells of vertebrates. Ancient DNA and forensic scientists are particularly interested in Hb reactions in the dry state because both regularly encounter aged, dried bloodstains. The DNA in such stains may be oxidatively damaged and, in theory, may be deteriorated by the presence of Hb. To understand the nature of the oxidative systems potentially available to degrade DNA in the presence of dried Hb, we need to determine what molecular species Hb forms over time. These species will determine what type of iron (i.e. Fe(2+/Fe(3+/Fe(4+ is available to participate in further chemical reactions. The availability of "free" iron will affect the ability of the system to undergo Fenton-type reactions which generate the highly reactive hydroxyl radical (OH*. The OH* can directly damage DNA. METHODOLOGY/PRINCIPAL FINDINGS: Oxygenated Hb (oxyHb converts over time to oxidized Hb (metHb, but this happens more quickly in the dry state than in the hydrated state, as shown by monitoring stabilized oxyHb. In addition, dry state oxyHb converts into at least one other unknown species other than metHb. Although "free" iron was detectable as both Fe(2+ and Fe(3+ in dry and hydrated oxyHb and metHb, the amount of ions detected did not increase over time. There was no evidence that Hb becomes more prone to generating OH* as it ages in either the hydrated or dry states. CONCLUSIONS: The Hb molecule in the dried state undergoes oxidative changes and releases reactive Fe(II cations. These changes, however, do not appear to increase the ability of Hb to act as a more aggressive Fenton reagent over time. Nevertheless, the presence of Hb in the vicinity of DNA in dried bloodstains creates the opportunity for OH*-induced oxidative damage to the deoxyribose sugar and the DNA nucleobases.

  16. Homoleptic Ce(III) and Ce(IV) Nitroxide Complexes: Significant Stabilization of the 4+ Oxidation State

    Energy Technology Data Exchange (ETDEWEB)

    Bogart, Justin A.; Lewis, Andrew J.; Medling, Scott A.; Piro, Nicholas A.; Carroll, Patrick J.; Booth, Corwin H.; Schelter, Eric J.

    2014-06-25

    Electrochemical experiments performed on the complex Ce-IV[2-((BuNO)-Bu-t)py](4), where [2-((BuNO)-Bu-t)py](-) = N-tert-butyl-N-2-pyridylnitroxide, indicate a 2.51 V stabilization of the 4+ oxidation state of Ce compared to [(Bu4N)-Bu-n](2)[Ce(NO3)(6)] in acetonitrile and a 2.95 V stabilization compared to the standard potential for the ion under aqueous conditions. Density functional theory calculations suggest that this preference for the higher oxidation state is a result of the tetrakis(nitroxide) ligand framework at the Ce cation, which allows for effective electron donation into, and partial covalent overlap with, vacant 4f orbitals with delta symmetry. The results speak to the behavior of CeO2 and related solid solutions in oxygen uptake and transport applications, in particular an inherent local character of bonding that stabilizes the 4+ oxidation state. The results indicate a cerium(IV) complex that has been stabilized to an unprecedented degree through tuning of its ligand-field environment.

  17. Homoleptic cerium(III) and cerium(IV) nitroxide complexes: significant stabilization of the 4+ oxidation state.

    Science.gov (United States)

    Bogart, Justin A; Lewis, Andrew J; Medling, Scott A; Piro, Nicholas A; Carroll, Patrick J; Booth, Corwin H; Schelter, Eric J

    2013-10-07

    Electrochemical experiments performed on the complex Ce(IV)[2-((t)BuNO)py]4, where [2-((t)BuNO)py](-) = N-tert-butyl-N-2-pyridylnitroxide, indicate a 2.51 V stabilization of the 4+ oxidation state of Ce compared to [(n)Bu4N]2[Ce(NO3)6] in acetonitrile and a 2.95 V stabilization compared to the standard potential for the ion under aqueous conditions. Density functional theory calculations suggest that this preference for the higher oxidation state is a result of the tetrakis(nitroxide) ligand framework at the Ce cation, which allows for effective electron donation into, and partial covalent overlap with, vacant 4f orbitals with δ symmetry. The results speak to the behavior of CeO2 and related solid solutions in oxygen uptake and transport applications, in particular an inherent local character of bonding that stabilizes the 4+ oxidation state. The results indicate a cerium(IV) complex that has been stabilized to an unprecedented degree through tuning of its ligand-field environment.

  18. Vitamin C combined with atorvastatin calcium state of micro oxidative stress and inflammation in patients with hemodialysis

    Institute of Scientific and Technical Information of China (English)

    En-Hao Bao; Ai-Guo Zhu; Zhi-Hong Wang

    2016-01-01

    Objective:To discuss Vitamin C combined with statins atorvastatin calcium affect oxidative stress in hemodialysis patients with micro-inflammatory state.Methods:92 hemodialysis patients admitted to hospital were randomly divided into atorvastatin calcium group (A) and vitamin C combined with atorvastatin calcium group (group B), select the same period and 30 healthy volunteers as group C, compare three groups before and after treatment with the micro-inflammatory state of oxidative stress indexes, including malondialdehyde (MDA), superoxide dismutase (SOD), C-reactive protein (CRP), interleukin-6 (IL-6), tumor necrosis factor (TNF-α) levels in the case.Results:Group A Group B and MDA levels before treatment were significantly higher than group C, after treatment indicators were significantly lower than before treatment, and group B index level change is more significant, the difference was statistically significant (P<0.05); two SOD levels before treatment were significantly higher than group C, the target level after treatment was significantly lower than before treatment, and the B group index change is more obvious, the difference was statistically significant (P<0.05);A group and group B before treatment were significantly higher than the index of water group C, were significantly decreased after treatment than before treatment groups level, and group B decreased more significantly, the difference was statistically significant (P<0.05).Conclusions:Vitamin C combined with atorvastatin calcium can improve hemodialysis patients oxidative stress and micro-inflammatory state, fewer adverse reactions, is worthy of clinical application.

  19. Plutonium uptake by the green alga Scenedesmus obliquus (Turp) Kutz, as a function of isotope and oxidation state

    Energy Technology Data Exchange (ETDEWEB)

    Tkacik, M.F.

    1977-01-01

    This study was designed to determine the effect of plutonium chemical valence state on the availability of small concentrations of /sup 238/Pu and /sup 239/Pu to algae. The uptake experiments involved the green alga Scenedesmus obliquus, grown in batch cultures. Plutonium concentrations accumulated by this alga were linearly related to plutonium concentrations. There was no significant difference (rho = 0.05) in algal plutonium accumulations, on a mass basis, of either /sup 238/Pu or /sup 239/Pu in either Pu/sup +4/ or Pu/sup +6/ oxidation state at the concentrations studied.

  20. Current emission trends for nitrogen oxides, sulfur dioxide, and volatile organic compounds by month and state: Methodology and results

    Energy Technology Data Exchange (ETDEWEB)

    Kohout, E.J.; Miller, D.J.; Nieves, L.A.; Rothman, D.S.; Saricks, C.L.; Stodolsky, F.; Hanson, D.A.

    1990-08-01

    This report presents estimates of monthly sulfur dioxide (SO{sub 2}), nitrogen oxides (NO{sub x}), and nonmethane voltatile organic compound (VOC) emissions by sector, region, and state in the contiguous United States for the years 1975 through 1988. This work has been funded as part of the National Acid Precipitation Assessment Program`s Emissions and Controls Task Group by the US Department of Energy (DOE) Office of Fossil Energy (FE). The DOE project officer is Edward C. Trexler, DOE/FE Office of Planning and Environment.

  1. Current emission trends for nitrogen oxides, sulfur dioxide, and volatile organic compounds by month and state: Methodology and results

    Energy Technology Data Exchange (ETDEWEB)

    Kohout, E.J.; Miller, D.J.; Nieves, L.A.; Rothman, D.S.; Saricks, C.L.; Stodolsky, F.; Hanson, D.A.

    1990-08-01

    This report presents estimates of monthly sulfur dioxide (SO{sub 2}), nitrogen oxides (NO{sub x}), and nonmethane voltatile organic compound (VOC) emissions by sector, region, and state in the contiguous United States for the years 1975 through 1988. This work has been funded as part of the National Acid Precipitation Assessment Program's Emissions and Controls Task Group by the US Department of Energy (DOE) Office of Fossil Energy (FE). The DOE project officer is Edward C. Trexler, DOE/FE Office of Planning and Environment.

  2. The Oxidation State of Fe in Glasses from the Galapagos Archipelago: Variable Oxygen Fugacity as a Function of Mantle Source

    Science.gov (United States)

    Peterson, M. E.; Kelley, K. A.; Cottrell, E.; Saal, A. E.; Kurz, M. D.

    2015-12-01

    The oxidation state of the mantle plays an intrinsic role in the magmatic evolution of the Earth. Here we present new μ-XANES measurements of Fe3+/ΣFe ratios (a proxy for ƒO2) in a suite of submarine glasses from the Galapagos Archipelago. Using previously presented major, trace, and volatile elements and isotopic data for 4 groups of glass that come from distinct mantle sources (depleted upper mantle, 2 recycled, and a primitive mantle source) we show that Fe3+/ΣFe ratios vary both with the influence of shallow level processes and with variations in mantle source. Fe3+/ΣFe ratios increase with differentiation (i.e. decreasing MgO), but show a large variation at a given MgO. Progressive degassing of sulfur accompanies decreasing Fe3+/ΣFe ratios, while assimilation of hydrothermally altered crust (as indicated by increasing Sr/Sr*) is shown to increase Fe3+/ΣFe ratios. After taking these processes into account, there is still variability in the Fe3+/ΣFe ratios of the isotopically distinct sample suites studied, yielding a magmatic ƒO2 that ranges from ΔQFM = +0.16 to +0.74 (error < 0.5 log units) and showing that oxidation state varies as a function of mantle source composition in the Galapagos hotspot system. After correcting back to a common MgO content = 8.0 wt%, the trace element depleted group similar to MORB (ITD), and the group similar to Pinta (WD = high Th/La, Δ7/4, Δ8/4 ratios) show Fe3+/ΣFe ratios within the range of MORB (average ITD = 0.162 ± 0.003 and WD = 0.164 ± 0.006). Another trace element enriched group similar to Sierra Negra and Cerro Azul (ITE = enriched Sr and Pb isotopes) shows evidence of mixing between oxidized and reduced sources (ITE oxidized end-member = 0.177). This suggests that mantle sources in the Galapagos that are thought to contain recycled components (i.e., WD and ITE groups) have distinct oxidation states. The high 3He/4He Fernandina samples (HHe group) are shown to be the most oxidized (ave. 0.175 ± 0

  3. Nanoporous zeolite and solid-state electrochemical devices for nitrogen-oxide sensing

    Science.gov (United States)

    Yang, Jiun-Chan

    Solid-state electrochemical gas sensing devices composed of stabilized-zirconia electrolyte have used extensively in the automobile and chemical industry. Two types of electrochemical devices, potentiometric and amperometric, were developed in this thesis for total NOx (NO + NO2) detection in harsh environments. In potentiometric devices, Pt covered with Pt containing zeolite Y (PtY) and WO3 were examined as the two electrode materials. Significant reactivity differences toward NOx between PtY and WO 3 led to the difference in non-electrochemical reactions and resulted in a electrode potential. With gases passing through a PtY filter, it was possible to remove interferences from 2000 ppm CO, 800 ppm propane, 10 ppm NH3, as well as to minimize effects of 1˜13% O2, CO2, and H2O. Total NOx concentration was measured by maintaining a temperature difference between the filter and the sensor. The sensitivity was significantly improved by connecting sensors in series. Amperometic devices were also developed to detect NOx passing through the PtY filter. By applying a low anodic potential of 80 mV, NO in the NOx equilibrated mixture can be oxidized at a Pt working electrode on the YSZ electrolyte at 500°C. The PtY can be held separate from the YSZ or coated onto the YSZ as a film. This design was demonstrated to exhibit total-NOx detection capability, a low NOx detection limit (selectivity relative to CO and oxygen, and linear dependence on NOx concentration. The non-electrochemical reactions around the triple-phase boundary were studied to understand the origin of the superior performance of WO3 on potentiometric NOx sensing. From TPD, DRIFTS, XRD, Raman, and catalytic activity measurements, the interfacial reactions between WO 3 and YSZ were found to dramatically reduce the NOx catalytic activity of YSZ. WO3 reacted with surface Y2O3 on YSZ and formed less catalytically active yttrium tungsten oxides and monoclinic ZrO2, which suppressed the non

  4. Total atmospheric deposition of oxidized nitrogen in the United States Pacific Northwest for 2002

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — This spatial data set was created by the U.S. Geological Survey (USGS) to represent the amount of wet and dry deposition of oxidized nitrogen in the Pacific...

  5. Total atmospheric deposition of oxidized and reduced nitrogen in the United States Pacific Northwest for 2002

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — This spatial data set was created by the U.S. Geological Survey (USGS) to represent the amount of wet and dry deposition of oxidized and reduced nitrogen in the...

  6. Wet deposition of oxidized nitrogen in the United States Pacific Northwest for 2002

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — This spatial data set was created by the U.S. Geological Survey (USGS) to represent the amount of wet deposition of oxidized nitrogen in the Pacific Northwest region...

  7. Dark current reduction of small molecule organic photodetectors by controlling gap states of molybdenum oxide buffer layers

    Science.gov (United States)

    Kim, Seong Heon; Heo, Sung; Yun, Dong-Jin; Satoh, Ryu-ichi; Park, Gyeongsu; Kim, Kyu-Sik

    2016-09-01

    The gap states of the molybdenum-oxide (MoO x ) hole-extraction layer (HEL) in an organic photodetector (OPD) device, which originate from oxygen-vacancy defects, are controlled by appropriate plasma treatments on the MoO x layer. The density of MoO x gap states, investigated using X-ray photoelectron spectroscopy (XPS), is enhanced and depressed with Ar- and O2-plasma treatments, respectively. The dark current of an OPD with a MoO x HEL is considerably reduced by controlling the MoO x gap states using the plasma-treatment method. The mechanism of dark-current reduction may be interpreted by reduced gap states and by a suitable energy level bending and alignment.

  8. Hexavalent Chromium: Analysis of the Mechanism of Groundwater Contamination in a Former Industrial Site in the Province of Vicenza (Northern Italy

    Directory of Open Access Journals (Sweden)

    Valentina Accoto

    2017-01-01

    Full Text Available The study consisted in the analysis of the mobilization mechanisms of hexavalent chromium (Cr(VI into groundwater from a decommissioned contaminated factory. The site is located in the Province of Vicenza and formerly was a chrome-plating plant. The subsoil consists predominantly of gravelly deposits with a thickness of at least one hundred meters. An unconfined aquifer is present with water table at about 23 m depth bgl. During the seven years of monitoring (2008-2014, the fluctuation of groundwater level was more than 6 m; hydraulic conductivity is about 1.0E-03 m/s and groundwater seepage velocity about 12 m/day. At the area of the source of contamination, the unsaturated soil is contaminated by hexavalent chromium throughout the thickness: concentrations range from 200 to 500 mg/kg. At the bottom of zone of groundwater level fluctuation, the hexavalent chromium concentration decreases to below the detection limit. The available data (e.g. hexavalent chromium concentrations in groundwater, groundwater level, local rainfall give the opportunity to assess the effects, on the magnitude of groundwater contamination, of the effective infiltration versus the fluctuation of groundwater level. The main analysis was performed on a statistical basis, in order to find out which of the two factors was most likely related to the periodic peaks of hexavalent chromium concentration in groundwater. Statistical analysis results were verified by a mass balance. Data show that at the site both the effective infiltration through the unsaturated zone and the leaching of soil contaminated by groundwater, when it exceeds a certain piezometric level, lead to peak concentrations of hexavalent chromium, even if with characteristics and effects different.

  9. The protective and toxic effects of rhubarb tannins and anthraquinones in treating hexavalent chromium-injured rats: the Yin/Yang actions of rhubarb.

    Science.gov (United States)

    Zeng, Ling-na; Ma, Zhi-jie; Zhao, Yan-ling; Zhang, Lin-dong; Li, Rui-sheng; Wang, Jia-bo; Zhang, Ping; Yan, Dan; Li, Qi; Jiang, Bing-qian; Pu, Shi-biao; Lü, Yang; Xiao, Xiao-he

    2013-02-15

    Chromium nephrotoxicity (CrNT) is thought to occur through the oxidant lesion mechanism. There is still a lack of specific remedies against CrNT. We primarily screened Chinese herbal medicines with a potential protective effect against CrNT, e.g., rhubarb (Rheum palmatum L.). However, the active constituents in rhubarb and its mechanisms remain unclear. In this study, the total rhubarb extract (TR) was successively separated into three parts: total anthraquinone extract (TA), total tannin extract (TT) and remaining component extract (RC). The effects of each extract on the potassium dichromate (K(2)Cr(2)O(7))-induced nephrotoxicity in rats were comparatively assessed. The results showed that only the administration of TT protected the kidney function in K(2)Cr(2)O(7)-injured rats. Besides, TT showed significant activity to scavenge hydroxyl radicals, which is considered to be the dominant lesion product generated by hexavalent chromium. TT also showed a reduced ability to transform toxic high valence chromium ions into non-toxic low valence ions. And TT was able to further precipitate chromium ions. These results suggested that rhubarb tannins treat CrNT as a free radical scavenger, reductant, and metal precipitant. The multiple protective routes of the plant tannins reveal a superior option for development into a promising natural remedy against CrNT. In addition, the opposite effects of rhubarb anthraquinones in treating CrNT were observed compared to rhubarb tannins, which suggested the duo-directional effects (Yin and Yang) of herbal medicines should be addressed.

  10. Oxidation-reduction signalling components in regulatory pathways of state transitions and photosystem stoichiometry adjustment in chloroplasts.

    Science.gov (United States)

    Puthiyaveetil, Sujith; Ibrahim, Iskander M; Allen, John F

    2012-02-01

    State transitions and photosystem stoichiometry adjustment are two oxidation-reduction (redox)-regulated acclimatory responses in photosynthesis. State transitions are short-term adaptations that, in chloroplasts, involve reversible post-translational modification by phosphorylation of light-harvesting complex II (LHC II). Photosystem stoichiometry adjustments are long-term responses involving transcriptional regulation of reaction centre genes. Both responses are initiated by changes in light quality and are regulated by the redox state of plastoquinone (PQ). The LHC II kinase involved in the state 2 transition is a serine/threonine kinase known as STT7 in Chlamydomonas, and as STN7 in Arabidopsis. The phospho-LHC II phosphatase that produces the state 1 transition is a PP2C-type protein phosphatase currently termed both TAP38 and PPH1. In plants and algae, photosystem stoichiometry adjustment is governed by a modified two-component sensor kinase of cyanobacterial origin - chloroplast sensor kinase (CSK). CSK is a sensor of the PQ redox state. Chloroplast sigma factor 1 (SIG1) and plastid transcription kinase (PTK) are the functional partners of CSK in chloroplast gene regulation. We suggest a signalling pathway for photosystem stoichiometry adjustment. The signalling pathways of state transitions and photosystem stoichiometry adjustments are proposed to be distinct, with the two pathways sensing PQ redox state independently of each other.

  11. Methane Conversion to C2 Hydrocarbons in Solid State Oxide Electrolyte Membrane Reactor

    Institute of Scientific and Technical Information of China (English)

    LI Jun; ZHAO Ling; ZHU Zhong-nan; XI Dan-li

    2005-01-01

    Provskite-type catalysts, Ln0.6 Sr0.4 FexCo1-x O3 (Ln = Nd,Pr, Gd, Sm, La, 0<x<1) and Ln0.8Na0.2CoO3(Ln= La,Gd, Sm) were synthesized, their catalytic properties in the oxidative coupling of methane (OCM) were examined in a fixed-bed reactor. The former group presented higher activity in the OCM, but the main product was carbon dioxide. While the later group showed lower activity but much higher selectivity to C2 hydrocarbons compared with the former. Electrochemical measurements were conducted in a solid oxide membrane reactor with La0.8 Na0.2CoO3 as catalyst. The results showed that methane was oxidized to carbon dioxide and ethane by two parallel reactions. Ethane was oxidized to ethene and carbon dioxide. A fraction of ethene was oxidized deeply to carbon dioxide. The total selectivity to C2 hydrocarbons exceeded 70%. Based on the experimental results, a kinetic model was suggested to describe the reaction results.

  12. SNC Oxygen Fugacity Recorded in Pyroxenes and its Implications for the Oxidation State of the Martian Interior: An Experimental and Analytical Study

    Science.gov (United States)

    McCanta, M. C.; Rutherford, M. J.

    2003-01-01

    Knowledge of the oxidation state of a magma is critical as it is one of the parameters which controls the nature and composition of the resulting crystals. In terrestrial magmatic systems, oxygen fugacity (fo2) is known to vary by over nine orders of magnitude. With variations of this magnitude, understanding the compositional differences, phase changes, and crystallization sequence variations, caused by the magma fo2, is essential in deciphering the origin of all igneous rocks. Magmatic oxidation state is of great importance in that it reflects the degree of oxidation of the source region and can provide insight into magmatic processes, such as metasomatism, degassing, and assimilation, which may have changed them. Carmichael [1991] argues that most magmas are unlikely to have their redox states altered from those of their source region. This assumption allows for estimation of the oxidation state of planetary interiors. Conversely, it is known that the fo2 of the magma can be affected by other processes, which occur outside of the source region and therefore, the oxidation state may record those too. Processes which could overprint source region fugacities include melt dehydrogenation or other volatile loss, water or melt infiltration, or assimilation of oxidized or reduced wallrock. Understanding which of these processes is responsible for the redox state of a magma can provide crucial information regarding igneous processes and other forces active in the region. The composition of the SNC basalts and their widely varying proposed oxidation states raise some interesting questions. Do the SNC meteorites have an oxidized or reduced signature? What was the oxygen fugacity of the SNC source region at the time of melt generation? Is the fugacity calculated for the various SNC samples the fugacity of the magma source region or was it overprinted by later events? Are there different oxidation states in the Martian interior or a single one? This proposal seeks to

  13. Oxidation states of Fe in LaNi{sub 1-x}Fe{sub x}O{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Goeta, A.E. [La Plata Univ. Nacional (Argentina). Dept. de Fisica; Goya, G.F. [La Plata Univ. Nacional (Argentina). Dept. de Fisica; Mercader, R.C. [La Plata Univ. Nacional (Argentina). Dept. de Fisica; Punte, G. [La Plata Univ. Nacional (Argentina). Dept. de Fisica]|[Facultad de Ingenieria, UNLP, La Plata (Argentina); Falcon, H. [INFIQC, Dept. de Fisic-Quimica, Univ. Nacional de Cordoba (Argentina); Carbonio, R. [INFIQC, Dept. de Fisic-Quimica, Univ. Nacional de Cordoba (Argentina)

    1994-11-01

    The distribution of oxidation states in perovskites of the type LaA{sub 1-x}B{sub x}O{sub 3} (A and B transition metal ions) can be ``tailored`` by x variation. In particular, in LaNiO{sub 3} it has been shown that Fe substitution for Ni foces some Ni{sup 3+} into Ni{sup 2+}, while some Fe{sup 3+} changes into the unusual Fe{sup 4+} state. In addition, the existence of mixed oxidation states of Fe and/or Ni in LaNi{sub 1-x}Fe{sub x}O{sub 3} has been related to its catalytic activity in hydrogen peroxide decomposition. The Fe{sup 4+} population, obtained using Moessbauer spectroscopy, was found to be constant for all the analyzed annealing temperatures for x = 0.25 concentration, where the isomer shift difference for both states is the highest and the catalytic activity is maximum. (orig.)

  14. Low temperature reduction of hexavalent chromium by a microbial enrichment consortium and a novel strain of Arthrobacter aurescens

    OpenAIRE

    Thompson Vicki S; Apel William A; Horton Rene' N; Sheridan Peter P

    2006-01-01

    Abstract Background Chromium is a transition metal most commonly found in the environment in its trivalent [Cr(III)] and hexavalent [Cr(VI)] forms. The EPA maximum total chromium contaminant level for drinking water is 0.1 mg/l (0.1 ppm). Many water sources, especially underground sources, are at low temperatures (less than or equal to 15 Centigrade) year round. It is important to evaluate the possibility of microbial remediation of Cr(VI) contamination using microorganisms adapted to these l...

  15. [Nicolau syndrome induced by intramuscular injection of a hexavalent vaccine in a 6-month-old girl].

    Science.gov (United States)

    Stefano, Paola C; Garello, Mónica; Nolte, María F; Lamy, Patricia; Giglio, Norberto; Castellano, Vanesa; Gentile, Ángela

    2017-02-01

    Nicolau syndrome, also known as embolia cutis medicamentosa or livedo-like dermatitis, is a sudden tissue necrosis, a rare complication of intramuscular injection of some drugs. We report a case of a 6-month-old girl who received intramuscularly the third dose of hexavalent vaccine (DTaP- HVB-IPV/HIb), and immediately presented a livedoid lesion around the injection site, progressing to necrosis. We reinforce the importance of early diagnosis to perform a suitable treatment and clinical follow-up to avoid ischemic secondary complications.

  16. Density of states-based design of metal oxide thin-film transistors for high mobility and superior photostability.

    Science.gov (United States)

    Kim, Hyun-Suk; Park, Joon Seok; Jeong, Hyun-Kwang; Son, Kyoung Seok; Kim, Tae Sang; Seon, Jong-Baek; Lee, Eunha; Chung, Jae Gwan; Kim, Dae Hwan; Ryu, Myungkwan; Lee, Sang Yoon

    2012-10-24

    A novel method to design metal oxide thin-film transistor (TFT) devices with high performance and high photostability for next-generation flat-panel displays is reported. Here, we developed bilayer metal oxide TFTs, where the front channel consists of indium-zinc-oxide (IZO) and the back channel material on top of it is hafnium-indium-zinc-oxide (HIZO). Density-of-states (DOS)-based modeling and device simulation were performed in order to determine the optimum thickness ratio within the IZO/HIZO stack that results in the best balance between device performance and stability. As a result, respective values of 5 and 40 nm for the IZO and HIZO layers were determined. The TFT devices that were fabricated accordingly exhibited mobility values up to 48 cm(2)/(V s), which is much elevated compared to pure HIZO TFTs (∼13 cm(2)/(V s)) but comparable to pure IZO TFTs (∼59 cm(2)/(V s)). Also, the stability of the bilayer device (-1.18 V) was significantly enhanced compared to the pure IZO device (-9.08 V). Our methodology based on the subgap DOS model and simulation provides an effective way to enhance the device stability while retaining a relatively high mobility, which makes the corresponding devices suitable for ultradefinition, large-area, and high-frame-rate display applications.

  17. Signatures of Quantized Energy States in Solution-Processed Ultrathin Layers of Metal-Oxide Semiconductors and Their Devices

    KAUST Repository

    Labram, John G.

    2015-02-13

    Physical phenomena such as energy quantization have to-date been overlooked in solution-processed inorganic semiconducting layers, owing to heterogeneity in layer thickness uniformity unlike some of their vacuum-deposited counterparts. Recent reports of the growth of uniform, ultrathin (<5 nm) metal-oxide semiconductors from solution, however, have potentially opened the door to such phenomena manifesting themselves. Here, a theoretical framework is developed for energy quantization in inorganic semiconductor layers with appreciable surface roughness, as compared to the mean layer thickness, and present experimental evidence of the existence of quantized energy states in spin-cast layers of zinc oxide (ZnO). As-grown ZnO layers are found to be remarkably continuous and uniform with controllable thicknesses in the range 2-24 nm and exhibit a characteristic widening of the energy bandgap with reducing thickness in agreement with theoretical predictions. Using sequentially spin-cast layers of ZnO as the bulk semiconductor and quantum well materials, and gallium oxide or organic self-assembled monolayers as the barrier materials, two terminal electronic devices are demonstrated, the current-voltage characteristics of which resemble closely those of double-barrier resonant-tunneling diodes. As-fabricated all-oxide/hybrid devices exhibit a characteristic negative-differential conductance region with peak-to-valley ratios in the range 2-7.

  18. Reduction of interface states by hydrogen treatment at the aluminum oxide/4H-SiC Si-face interface

    Directory of Open Access Journals (Sweden)

    Hironori Yoshioka

    2016-10-01

    Full Text Available Processes to form aluminum oxide as a gate insulator on the 4H-SiC Si-face are investigated to eliminate the interface state density (DIT and improve the mobility. Processes that do not involve the insertion or formation of SiO2 at the interface are preferential to eliminate traps that may be present in SiO2. Aluminum oxide was formed by atomic layer deposition with hydrogen plasma pretreatment followed by annealing in forming gas. Hydrogen treatment was effective to reduce DIT at the interface of aluminum oxide and SiC without a SiO2 interlayer. Optimization of the process conditions resulted in DIT for the metal oxide semiconductor (MOS capacitor of 1.7×1012 cm−2eV−1 at 0.2 eV, and the peak field-effect mobility of the MOS field-effect transistor (MOSFET was approximately 57 cm2V−1s−1.

  19. RNA oxidation

    DEFF Research Database (Denmark)

    Kjaer, L. K.; Cejvanovic, V.; Henriken, T.

    2015-01-01

    in diabetes resulting from the diabetic state, a dysfunction that includes increased production of hydrogen peroxide. We suggest that the intracellular RNA oxidation is compartmentalized from the traditional biomarkers in the extracellular compartment, and therefore provides independent prognostic value...... diabetes. In agreement with our previous finding, DNA oxidation did not show any prognostic value. RNA oxidation represents oxidative stress intracellularly, presumably predominantly in the cytosol. The mechanism of RNA oxidation is not clear, but hypothesized to result from mitochondrial dysfunction...

  20. Solid-state synthesis of Ti2Nb10O29/reduced graphene oxide composites with enhanced lithium storage capability

    Science.gov (United States)

    Wang, Wan Lin; Oh, Byeong-Yun; Park, Ju-Young; Ki, Hangil; Jang, Jaewon; Lee, Gab-Yong; Gu, Hal-Bon; Ham, Moon-Ho

    2015-12-01

    Owing to their multiple redox couples, titanium-niobium-based oxides are still considered promising candidates for use as anodes for safe, rechargeable lithium ion batteries with high energy and power densities. Titanium-niobium-based oxide electrodes have, however, exhibited relatively poor cycling performance as a result of pulverization. In this study, we report on a simple two-step solid-state reaction route for producing hybrid composites of Ti2Nb10O29 (TNO) anchored on reduced graphene oxide (RGO), and the electrochemical performance of the resulting TNO/RGO composites. Solid-state reactions enable both the formation of TNO and the uniform distribution of RGO in the TNO/RGO composites. The TNO/RGO composites exhibited discharge and charge capacities of 261 and 256 mAh g-1, respectively, with much better cycling performance (182 mAh g-1 after the 50th cycles) and rate capability (165 mAh g-1 at a current density of 500 mA g-1) compared to the pure TNO.

  1. Stable Copper-Nitrosyl Formation By Nitrite Reductase in Either Oxidation State

    Energy Technology Data Exchange (ETDEWEB)

    Tocheva, E.I.; Rosell, F.I.; Mauk, A.G.; Murphy, M.E.P.

    2009-06-04

    Nitrite reductase (NiR) is an enzyme that uses type 1 and type 2 copper sites to reduce nitrite to nitric oxide during bacterial denitrification. A copper-nitrosyl intermediate is a proposed, yet poorly characterized feature of the NiR catalytic cycle. This intermediate is formally described as Cu(I)-NO{sup +} and is proposed to be formed at the type 2 copper site after nitrite binding and electron transfer from the type 1 copper site. In this study, copper-nitrosyl complexes were formed by prolonged exposure of exogenous NO to crystals of wild-type and two variant forms of NiR from Alcaligenes faecalis (AfNiR), and the structures were determined to 1.8 {angstrom} or better resolution. Exposing oxidized wild-type crystals to NO results in the reverse reaction and formation of nitrite that remains bound at the active site. In a type 1 copper site mutant (H145A) that is incapable of electron transfer to the type 2 site, the reverse reaction is not observed. Instead, in both oxidized and reduced H145A crystals, NO is observed bound in a side-on manner to the type 2 copper. In AfNiR, Asp98 forms hydrogen bonds to both substrate and product bound to the type 2 Cu. In the D98N variant, NO is bound side-on but is more disordered when observed for the wild-type enzyme. The solution EPR spectra of the crystallographically characterized NiR-NO complexes indicate the presence of an oxidized type 2 copper site and thus are interpreted as resulting from stable copper-nitrosyls and formally assigned as Cu(II)-NO{sup -}. A reaction scheme in which a second NO molecule is oxidized to nitrite can account for the formation of a CuD-NO{sup -} species after exposure of the oxidized H145A variant to NO gas.

  2. Fully printable transparent monolithic solid-state dye-sensitized solar cell with mesoscopic indium tin oxide counter electrode.

    Science.gov (United States)

    Yang, Ying; Ri, Kwangho; Rong, Yaoguang; Liu, Linfeng; Liu, Tongfa; Hu, Min; Li, Xiong; Han, Hongwei

    2014-09-07

    We present a new transparent monolithic mesoscopic solid-state dye-sensitized solar cell based on trilamellar films of mesoscopic TiO2 nanocrystalline photoanode, a ZrO2 insulating layer and an indium tin oxide counter electrode (ITO-CE), which were screen-printed layer by layer on a single substrate. When the thickness of the ITO-CE was optimized to 2.1 μm, this very simple and fully printable solid-state DSSC with D102 dye and spiro-OMeTAD hole transport materials presents efficiencies of 1.73% when irradiated from the front side and 1.06% when irradiated from the rear side under a standard simulated sunlight condition (AM 1.5 Global, 100 mW cm(-2)). Higher parameters could be expected with a better transparent mesoscopic counter electrode and hole conductor for the printable monolithic mesoscopic solid-state DSSC.

  3. Removal of hexavalent chromium upon interaction with biochar under acidic conditions: mechanistic insights and application.

    Science.gov (United States)

    Choudhary, Bharat; Paul, Debajyoti; Singh, Abhas; Gupta, Tarun

    2017-07-01

    Chromium pollution of soil and water is a serious environmental concern due to potential carcinogenicity of hexavalent chromium [Cr(VI)] when ingested. Eucalyptus bark biochar (EBB), a carbonaceous black porous material obtained by pyrolysis of biomass at 500 °C under oxygen-free atmosphere, was used to investigate the removal of aqueous Cr(VI) upon interaction with the EBB, the dominant Cr(VI) removal mechanism(s), and the applicability to treat Cr(VI)-contaminated wastewater. Batch experiments showed complete removal of aqueous Cr(VI) at pH 1-2; sorption was negligible at pH 1, but ~55% of total Cr was sorbed onto the EBB surface at pH 2. Detailed investigations on unreacted and reacted EBB through Fourier transform infrared spectroscopy and X-ray photoelectron spectrometry (XPS) indicate that the carboxylic groups in biochar played a dominant role in Cr(VI) sorption, whereas the phenolic groups were responsible for Cr(VI) reduction. The predominance of sorption-reduction mechanism was confirmed by XPS studies that indicated ~82% as Cr(III) and ~18% as Cr(VI) sorbed on the EBB surface. Significantly, Cr(VI) reduction was also facilitated by dissolved organic matter (DOM) extracted from biochar. This reduction was enhanced by the presence of biochar. Overall, the removal of Cr(VI) in the presence of biochar was affected by sorption due to electrostatic attraction, sorption-reduction mediated by surface organic complexes, and aqueous reduction by DOM. Relative dominance of the aqueous reduction mechanism depended on a critical biochar dosage for a given electrolyte pH and initial Cr(VI) concentration. The low-cost EBB developed here successfully removed all Cr(VI) in chrome tanning acidic wastewater and Cr(VI)-contaminated groundwater after pH adjustment, highlighting its potential applicability in effective Cr(VI) remediation.

  4. Recovery of hexavalent chromium from water using photoactive TiO2-montmorillonite under sunlight

    Directory of Open Access Journals (Sweden)

    Ridha Djellabi

    2016-04-01

    Full Text Available Hexavalent chromium was removed from water under sunlight using a synthesized TiO2-montmorillonite (TiO2-M employing tartaric acid as a hole scavenger. Cr(VI species was then reduced to Cr(III species by electrons arising from TiO2 particles. After that, the produced Cr(III species  was transferred to montmorillonite  due to electrostatic attractions leading to  set free TiO2 particles for a further Cr(VI species reduction. Furthermore, produced Cr(III, after Cr(VI reduction, does not  penetrate into the solution. The results indicate that no dark adsorption of Cr(VI species on TiO2-M is present, however, the reduction of Cr(VI species under sunlight increased strongly as a function of tartaric acid concentration up to 60 ppm, for which the extent of reduction is maximum within 3 h. On the other hand, the reduction extent of Cr(VI species is maximum with an initial concentration of Cr(VI species lower than 30 ppm by the use of 0.2 g/L of TiO2-M. Nevertheless, the increase of the Cr(VI initial concentration led to increase the amount of Cr(VI species reduced (capacity of reduction until a Cr(VI concentration of 75 and 100 ppm, for which  it remained constant at around 221 mg/g. For comparison, the increase of Cr(VI species concentration in the case of the commercial TiO2 P25 under the same conditions exhibited its deactivation when the reduced amount decreased from 198.1 to 157.6 mg/g as the concentration increased from 75 to 100 ppm.

  5. Differential uptake and transport of trivalent and hexavalent chromium by tumbleweed (Salsola kali).

    Science.gov (United States)

    Gardea-Torresdey, J L; de la Rosa, G; Peralta-Videa, J R; Montes, M; Cruz-Jimenez, G; Cano-Aguilera, I

    2005-02-01

    Experiments were conducted to determine the differential absorption of Cr species by tumbleweed (Salsola kali) as well as the effect of this heavy metal on plant growth and nutrient uptake. Tumbleweed seeds were grown in an agar-based media containing different concentrations of either Cr(III) or Cr(VI). The results demonstrated that the uptake of Cr was influenced by the Cr concentration in the growth medium and the speciation of this heavy metal. When supplied in the hexavalent form, the concentration of Cr in the different plant parts (2900, 790, and 600 mg kg(-1) for roots, stems, and leaves, respectively) was between 10 and 20 times higher than the amounts found when Cr was supplied in the trivalent form. In addition, it was found that in most of the experiments, Cr(III) exhibited more toxic effects on tumbleweed plants than Cr(VI). The size of roots of plants grown in 20 mg L(-1) Cr(III) were significantly smaller (p < 0.05) than those grown in 20 mg L(-1) Cr(VI). Plants exposed to 20 mg L(-1) Cr(III) produced shoots significantly shorter (p < 0.05) compared with the size of control plants and with those grown in 20 mg L(-1) Cr(VI). In addition, the absorption of macronutrients and microelements was in general lower when the plants were grown in the medium containing Cr(III). The amounts of Cr concentrated in the aerial plant parts under experimental conditions may indicate tumbleweed as a new option for the phytoremediation of Cr-contaminated soil.

  6. Hexavalent chromium is cytotoxic and genotoxic to hawksbill sea turtle cells

    Energy Technology Data Exchange (ETDEWEB)

    Wise, Sandra S., E-mail: sandra.wise@maine.edu [Wise Laboratory of Environmental and Genetic Toxicology, University of Southern Maine, Science Building, 96 Falmouth Street, Portland, ME 04103 (United States); Maine Center for Toxicology and Environmental Health, University of Southern Maine, Science Building, 96 Falmouth Street, Portland, ME 04103 (United States); Department of Applied Medical Science, University of Southern Maine, Science Building, 96 Falmouth Street, Portland, ME 04103 (United States); Xie, Hong, E-mail: hongxie@usm.maine.edu [Wise Laboratory of Environmental and Genetic Toxicology, University of Southern Maine, Science Building, 96 Falmouth Street, Portland, ME 04103 (United States); Maine Center for Toxicology and Environmental Health, University of Southern Maine, Science Building, 96 Falmouth Street, Portland, ME 04103 (United States); Department of Applied Medical Science, University of Southern Maine, Science Building, 96 Falmouth Street, Portland, ME 04103 (United States); Fukuda, Tomokazu, E-mail: tomofukuda009@gmail.com [Graduate School of Agricultural Sciences, Tohoku University, Laboratory of Animal Breeding and Genetics, Second Research Building, Rm 112, 1-1 Amamiyamachi, Aoba-ku, Sendai 981-8555 (Japan); Douglas Thompson, W., E-mail: dougt@usm.maine.edu [Maine Center for Toxicology and Environmental Health, University of Southern Maine, Science Building, 96 Falmouth Street, Portland, ME 04103 (United States); Department of Applied Medical Science, University of Southern Maine, Science Building, 96 Falmouth Street, Portland, ME 04103 (United States); and others

    2014-09-01

    Sea turtles are a charismatic and ancient ocean species and can serve as key indicators for ocean ecosystems, including coral reefs and sea grass beds as well as coastal beaches. Genotoxicity studies in the species are absent, limiting our understanding of the impact of environmental toxicants on sea turtles. Hexavalent chromium (Cr(VI)) is a ubiquitous environmental problem worldwide, and recent studies show it is a global marine pollutant of concern. Thus, we evaluated the cytotoxicity and genotoxicity of soluble and particulate Cr(VI) in hawksbill sea turtle cells. Particulate Cr(VI) was both cytotoxic and genotoxic to sea turtle cells. Concentrations of 0.1, 0.5, 1, and 5 μg/cm{sup 2} lead chromate induced 108, 79, 54, and 7% relative survival, respectively. Additionally, concentrations of 0, 0.1, 0.5, 1, and 5 μg/cm{sup 2} lead chromate induced damage in 4, 10, 15, 26, and 36% of cells and caused 4, 11, 17, 30, and 56 chromosome aberrations in 100 metaphases, respectively. For soluble Cr, concentrations of 0.25, 0.5, 1, 2.5, and 5 μM sodium chromate induced 84, 69, 46, 25, and 3% relative survival, respectively. Sodium chromate induced 3, 9, 9, 14, 21, and 29% of metaphases with damage, and caused 3, 10, 10, 16, 26, and 39 damaged chromosomes in 100 metaphases at concentrations of 0, 0.25, 0.5, 1, 2.5, and 5 μM sodium chromate, respectively. These data suggest that Cr(VI) may be a concern for hawksbill sea turtles and sea turtles in general. - Highlights: • Particulate Cr(VI) is cytotoxic and clastogenic to hawksbill sea turtle cells. • Soluble Cr(VI) is cytotoxic and clastogenic to hawksbill sea turtle cells. • Cr(VI) may be a risk factor for hawksbill sea turtle health.

  7. A Comparative Survey on Parameters Influencing on Hexavalent Chromium Measurement as an Occupational Carcinogen

    Directory of Open Access Journals (Sweden)

    A. Tirgar

    2008-07-01

    Full Text Available Introduction & Objective: Hexavalent chromium, Cr+6, is a very harmful pollutant and a relatively unstable compound that is present in many industries. It is a known human respiratory carcinogen and occupational exposure to this chemical is associated with different health hazards. The purpose of this study was to evaluate the effects of four parameters including: type of sampling head, sampling height from the surface of electroplating solution, sampling duration, and sample storage duration on Cr+6 mist monitoring.Materials & Methods: To evaluate the influence of the main parameters as an experimental study, the 24 factorial design was applied at constant electroplating condition. A chromium electroplating bath with the ability to produce homogenous mist was used to create Cr+6 mist in laboratory setting. The National Institute for Occupational Safety and Health (NIOSH method 7600 was used to determine the Cr+6 concentration. Results: The results of 48 Cr+6 mist samples showed that Cr+6 concentration was higher: (1 for sampling by closed-face filter cassettes than for sampling by open-face filter cassettes (P<0.001; (2 for samples collected at 35 cm above the electroplating solution surface than for samples collected at 50 cm (P <0.001; (3 for sampling duration of 30 minutes than for sampling duration of 180 minutes (P <0.001; and, (4 for samples extracted immediately after sampling than for samples with delayed extraction (24 hours after sampling (P <0.001. Conclusion: It is concluded that the accuracy of Cr+6 mist sampling in electroplating shops will be enhanced when: (1 a closed-face filter cassette is used to prevent liquid splash contamination; (2 the sampling height is suitable as determined by further research; (3 the sampling duration is short (approximately 30 minutes; and, (4 the extraction of the Cr+6 sample is performed as soon as the sampling is completed.

  8. A cohort study to evaluate persistence of hepatitis B immunogenicity after administration of hexavalent vaccines

    Directory of Open Access Journals (Sweden)

    Chionne Paola

    2008-07-01

    Full Text Available Abstract Background In 2001, two hexavalent vaccines were licensed in Italy (Hexavac®, Infanrix Hexa®, and since 2002 were extensively used for primary immunization in the first year of life (at 3, 5, 11/12 months of age. In 2005, the market authorization of Hexavac® was precautionary suspended by EMEA, because of doubts on long-term protection against hepatitis B virus. The objectives of this study were to evaluate the persistence of antibodies to anti-HBs, in children in the third year of life, and to investigate the response to a booster dose of hepatitis B vaccine. Methods Participant children were enrolled concomitantly with the offering of anti-polio booster dose, in the third year of life. Anti-HBs titers were determined on capillary blood samples. A booster dose of hepatitis B vaccine was administered to children with anti-HBs titers Results Sera from 113 children previously vaccinated with Hexavac®, and from 124 vaccinated with Infanrix Hexa® were tested for anti-HBs. Titers were ≥ 10 mIU/ml in 69% and 96% (p Post-booster, 93% of children achieved titers ≥ 10 mIU/ml, with no significant difference by vaccine group. Discussion Fifteen months after third dose administration, a significant difference in anti-HBs titers was noted in the two vaccine groups considered. Monovalent hepatitis B vaccine administration in 3-year old children induced a proper booster response, confirming that immunologic memory persists in children with anti-HBs titers

  9. Hexavalent chromium is cytotoxic and genotoxic to hawksbill sea turtle cells.

    Science.gov (United States)

    Wise, Sandra S; Xie, Hong; Fukuda, Tomokazu; Douglas Thompson, W; Wise, John Pierce

    2014-09-01

    Sea turtles are a charismatic and ancient ocean species and can serve as key indicators for ocean ecosystems, including coral reefs and sea grass beds as well as coastal beaches. Genotoxicity studies in the species are absent, limiting our understanding of the impact of environmental toxicants on sea turtles. Hexavalent chromium (Cr(VI)) is a ubiquitous environmental problem worldwide, and recent studies show it is a global marine pollutant of concern. Thus, we evaluated the cytotoxicity and genotoxicity of soluble and particulate Cr(VI) in hawksbill sea turtle cells. Particulate Cr(VI) was both cytotoxic and genotoxic to sea turtle cells. Concentrations of 0.1, 0.5, 1, and 5μg/cm(2) lead chromate induced 108, 79, 54, and 7% relative survival, respectively. Additionally, concentrations of 0, 0.1, 0.5, 1, and 5μg/cm(2) lead chromate induced damage in 4, 10, 15, 26, and 36% of cells and caused 4, 11, 17, 30, and 56 chromosome aberrations in 100 metaphases, respectively. For soluble Cr, concentrations of 0.25, 0.5, 1, 2.5, and 5μM sodium chromate induced 84, 69, 46, 25, and 3% relative survival, respectively. Sodium chromate induced 3, 9, 9, 14, 21, and 29% of metaphases with damage, and caused 3, 10, 10, 16, 26, and 39 damaged chromosomes in 100 metaphases at concentrations of 0, 0.25, 0.5, 1, 2.5, and 5μM sodium chromate, respectively. These data suggest that Cr(VI) may be a concern for hawksbill sea turtles and sea turtles in general.

  10. About the performance of Sphaerotilus natans to reduce hexavalent chromium in batch and continuous reactors

    Energy Technology Data Exchange (ETDEWEB)

    Caravelli, Alejandro H., E-mail: alejandrocaravelli@hotmail.com [Centro de Investigacion y Desarrollo en Criotecnologia de Alimentos (CIDCA), CCT - CONICET - La Plata. Fac., Ciencias Exactas, Universidad Nacional de La Plata, 47 y 116 La Plata (1900) (Argentina); Zaritzky, Noemi E., E-mail: zaritzky@ing.unlp.edu.ar [Centro de Investigacion y Desarrollo en Criotecnologia de Alimentos (CIDCA), CCT - CONICET - La Plata. Fac., Ciencias Exactas, Universidad Nacional de La Plata, 47 y 116 La Plata (1900) (Argentina); Fac. de Ingenieria, Universidad Nacional de La Plata, 48 y 115 La Plata (1900) (Argentina)

    2009-09-15

    The hexavalent chromium biological reduction constitutes a safe and economical detoxification procedure of wastewaters containing Cr(VI). However, little research has been done to evaluate Cr(VI) tolerance and reduction capacity of microbial cultures under different growth conditions. The aims of this work were (a) to evaluate the capacity of Sphaerotilus natans to reduce Cr(VI) to Cr(III) in a continuous system limited in carbon and energy source or in nitrogen source, (b) to evaluate the toxic effect of Cr(VI) on this microorganism, (c) to carry out a complete analysis of Cr(VI) reduction by S. natans not only in continuous regime but also in batch system, and (d) to model the obtained results mathematically. S. natans exhibited great resistance to Cr(VI) (19-78 mg l{sup -1}) and optimal growth in continuous and batch systems using a mineral medium supplemented only with citric acid as organic substrate. In carbon- and energy-limited continuous systems, a maximum percentual decrease in Cr(VI) by 13% was reached for low influent Cr(VI) concentration (4.3-5.32 mgCr(VI) l{sup -1}); the efficiency of the process did not notoriously increase as the length of cellular residence time was increased from 4.16 to 50 h. A nitrogen-limited continuous operation with a cellular residence time of 28.5 h resulted in a Cr(VI) decrease of approximately 26-32%. In batch system, a mathematical model allowed to predict the Cr(VI) concentration as a function of time and the ratio between the initial Cr(VI) concentration and that of the biomass. High concentrations of initial Cr(VI) and biomass produced the highest performance of the process of Cr(VI) reduction reached in batch system, aspects which should be considered in detoxification strategies of wastewaters.

  11. Electrode-Impregnable and Cross-Linkable Poly(ethylene oxide)-Poly(propylene oxide)-Poly(ethylene oxide) Triblock Polymer Electrolytes with High Ionic Conductivity and a Large Voltage Window for Flexible Solid-State Supercapacitors.

    Science.gov (United States)

    Han, Jae Hee; Lee, Jang Yong; Suh, Dong Hack; Hong, Young Taik; Kim, Tae-Ho

    2017-10-04

    We present cross-linkable precursor-type gel polymer electrolytes (GPEs) that have large ionic liquid uptake capability, can easily penetrate electrodes, have high ion conductivity, and are mechanically strong as high-performance, flexible all-solid-state supercapacitors (SC). Our polymer precursors feature a hydrophilic-hydrophobic poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock main-chain structure and trifunctional silane end groups that can be multi-cross-linked with each other through a sol-gel process. The cross-linked solid-state electrolyte film with moderate IL content (200 wt %) shows a well-balanced combination of excellent ionic conductivity (5.0 × 10(-3) S cm(-1)) and good mechanical stability (maximum strain = 194%). Moreover, our polymer electrolytes have various advantages including high thermal stability (decomposition temperature > 330 °C) and the capability to impregnate electrodes to form an excellent electrode-electrolyte interface due to the very low viscosity of the precursors. By assembling our GPE-impregnated electrodes and solid-state GPE film, we demonstrate an all-solid-state SC that can operate at 3 V and provides an improved specific capacitance (112.3 F g(-1) at 0.1 A g(-1)), better rate capability (64% capacity retention until 20 A g(-1)), and excellent cycle stability (95% capacitance decay over 10 000 charge/discharge cycles) compared with those of a reference SC using a conventional PEO electrolyte. Finally, flexible SCs with a high energy density (22.6 W h kg(-1) at 1 A g(-1)) and an excellent flexibility (>93% capacitance retention after 5000 bending cycles) can successfully be obtained.

  12. Synthesis and applications of SnO nanosheets: parallel control of oxidation state and nanostructure through an aqueous solution route.

    Science.gov (United States)

    Sakaushi, Ken; Oaki, Yuya; Uchiyama, Hiroaki; Hosono, Eiji; Zhou, Haoshen; Imai, Hiroaki

    2010-03-22

    Tin monoxide (SnO) nanosheets 5 nm in thickness are generated on substrates through an aqueous solution process under mild conditions. Parallel control of the oxidation state and morphology is achieved by a urea-mediated approach in aqueous solution. The SnO nanosheets form a porous thin film on substrates such as indium tin oxide and carbon nanofiber (CNF). The porous thin film of SnO nanosheets shows cathodic photocurrent generation upon irradiation by UV and visible light. In contrast, the photocurrent is not observed in the bulk SnO microcrystals. Composites of the SnO nanosheets and CNF perform as the anode material of lithium-ion batteries with improved charge-discharge reversible stability.

  13. Analytical Expressions for Steady-State Concentrations of Substrate and Oxidized and Reduced Mediator in an Amperometric Biosensor

    Directory of Open Access Journals (Sweden)

    Loghambal Shunmugham

    2013-01-01

    Full Text Available A mathematical model of modified enzyme-membrane electrode for steady-state condition is discussed. This model contains a nonlinear term related to enzyme kinetics reaction mechanism. The thickness dependence of an amperometric biosensor is presented both analytically and numerically where the biological layer is immobilized between a solid substrate and permeable electrode. The analytical expressions pertaining to the concentration of species and normalized current are obtained using the Adomian decomposition method (ADM. Simple and approximate polynomial expressions of concentrations of an oxidized mediator, substrate, and reduced mediator are derived for all possible values of parameters ϕO2 (Thiele modulus, BO (normalized surface concentration of oxidized mediator, and BS (normalized surface concentration of substrate. A comparison of the analytical approximation and numerical simulation is also presented. A good agreement between theoretical predictions and numerical results is observed.

  14. A study of relaxation mechanisms in the A{sup 2}{Sigma}{sup +} state of nitric oxide by time resolved double resonant polarization spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Stampanoni-Panariello, A.; Bombach, R.; Hemmerling, B.; Hubschmid, W. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1997-06-01

    Double resonant polarization labeling spectroscopy is applied to detect nitric oxide in flames and to characterize rotational energy transfer and orientation changing collisions in its first excited electronic state. (author) 4 figs., 3 refs.

  15. Valence State of Active Copper in CuOx/CeO2 Catalysts for CO Oxidation

    Institute of Scientific and Technical Information of China (English)

    Zeng Shanghong; Bai Xue; Wang Xiaoyan; Yu Wenguo; Liu Yuan

    2006-01-01

    CuOx/CeO2 catalysts were prepared by adsorption-impregnation method.CO conversion was tested over the catalysts pretreated under different conditions for preferential CO oxidation in H2, and the catalysts were characterized with X-ray photoelectron spectroscopy and temperature programmed reduction.Experimental results show that there are two kinds of copper, which are Cu+ and Cu2+ in calcined CuOx/CeO2.Among them, the Cu+ is the key active component for CO oxidation.The main reason is as follows: CO is activated by copper for CO oxidation over CuOx/CeO2, while CO can not be activated by Cu2+.Only when Cu2+ is reduced to Cu+ or Cu0, the copper may be active for CO oxidation, moreover, the experimental results show that the reduction of Cu2+ does not lead to an increase of catalytic activity.So the active species is Cu+ in CuOx/CeO2 catalysts.

  16. Mossbauer investigations of corrosion environment influence on Fe valence states in oxide films of zirconium alloys

    NARCIS (Netherlands)

    Filippov, V. P.; Petrov, V. I.; Shikanova, Yu. A.

    2006-01-01

    Mossbauer investigations about iron atom redistribution in oxide films of zirconium alloys subjected to corrosion at 500 degrees C in pure oxygen and water pair have been analysed. The alloys were also subjected to autoclave conditions at a pressure of 10.0 MPa and autoclave conditions at 350 degree

  17. Nitric oxide in plants: an assessment of the current state of knowledge

    DEFF Research Database (Denmark)

    Mur, Luis A J; Mandon, Julien; Persijn, Stefan

    2013-01-01

    Background and aims After a series of seminal works during the last decade of the 20th century nitric oxide (NO) is now firmly placed in the pantheon of plant signals. NO acts in plant-microbe interactions, responses to abiotic stress, stomatal regulation and a range of developmental processes...

  18. Mossbauer investigations of corrosion environment influence on Fe valence states in oxide films of zirconium alloys

    NARCIS (Netherlands)

    Filippov, V. P.; Petrov, V. I.; Shikanova, Yu. A.

    2006-01-01

    Mossbauer investigations about iron atom redistribution in oxide films of zirconium alloys subjected to corrosion at 500 degrees C in pure oxygen and water pair have been analysed. The alloys were also subjected to autoclave conditions at a pressure of 10.0 MPa and autoclave conditions at 350

  19. Unimolecular decomposition of tetrazine-N-oxide based high nitrogen content energetic materials from excited electronic states

    Science.gov (United States)

    Bhattacharya, A.; Guo, Y. Q.; Bernstein, E. R.

    2009-11-01

    Unimolecular excited electronic state decomposition of novel high nitrogen content energetic molecules, such as 3,3'-azobis(6-amino-1,2,4,5-tetrazine)-mixed N-oxides (DAATO3.5), 3-amino-6-chloro-1,2,4,5-tetrazine-2,4-dioxide (ACTO), and 3,6-diamino-1,2,4,5-tetrazine-1,4-dioxde (DATO), is investigated. Although these molecules are based on N-oxides of a tetrazine aromatic heterocyclic ring, their decomposition behavior distinctly differs from that of bare tetrazine, in which N2 and HCN are produced as decomposition products through a concerted dissociation mechanism. NO is observed to be an initial decomposition product from all tetrazine-N-oxide based molecules from their low lying excited electronic states. The NO product from DAATO3.5 and ACTO is rotationally cold (20 K) and vibrationally hot (1200 K), while the NO product from DATO is rotationally hot (50 K) and vibrationally cold [only the (0-0) vibronic transition of NO is observed]. DAATO3.5 and ACTO primarily differ from DATO with regard to molecular structure, by the relative position of oxygen atom attachment to the tetrazine ring. Therefore, the relative position of oxygen in tetrazine-N-oxides is proposed to play an important role in their energetic behavior. N2O is ruled out as an intermediate precursor of the NO product observed from all three molecules. Theoretical calculations at CASMP2/CASSCF level of theory predict a ring contraction mechanism for generation of the initial NO product from these molecules. The ring contraction occurs through an (S1/S0)CI conical intersection.

  20. Anisotropy and oxidative resistance of highly crosslinked UHMWPE after deformation processing by solid-state ram extrusion.

    Science.gov (United States)

    Kurtz, Steven M; Mazzucco, Dan; Rimnac, Clare M; Schroeder, Dave

    2006-01-01

    Solid-state deformation processing is a promising technique for modifying the physical and mechanical properties of highly crosslinked ultra-high molecular weight polyethylene (UHMWPE) beyond simple thermal treatment cycles that have been employed previously. This study evaluates anisotropy and oxidative resistance in a novel, radiation crosslinked (50 kGy) UHMWPE material (ArComXL: Biomet, Inc., Warsaw, IN), incorporating solid-state, deformation processing by extrusion below the melt transition for application in total hip arthroplasty. Tensile, compression, and small punch tests were conducted to evaluate the material properties in the three principal axes of the resulting material. Furthermore, short-term oxidative resistance was evaluated using Fourier transform infrared spectroscopy and the small punch test in conjunction with accelerated shelf aging protocols. The results of this testing indicate that the material is anisotropic, with significantly enhanced strength oriented along the long axis of the rod. For certain other properties, the magnitude of the anisotropy was relatively slight, especially in the elastic regime, in which only a 20% difference was noted between the long axis of the rod and the orthogonal, radial direction. The highly crosslinked material contains detectable free radicals, at a concentration that is 90% less than control, gamma inert sterilized UHMWPE. An unexpected finding of this study was evidence of oxidative stability of the deformation-processed material, even after 4 weeks of accelerated aging in a pressure vessel containing five atmospheres of oxygen (ASTM F2003), which resulted in macroscopic embrittlement of the control material. The oxidative stability observed in ArComXL suggests that the deformation-processed material may be suitable for air-permeable packaging and gas sterilization, which has thus far been reserved for remelted highly crosslinked UHMWPE.

  1. Climatic, tectonic, and biological factors affecting the oxidation state of the atmosphere and oceans: Implications for Phanerozoic O2 evolution

    Science.gov (United States)

    Ozaki, K.; Tajika, E.

    2015-12-01

    The Earth's atmosphere and oceans have seen fundamental changes in its oxidation state in response to the climatic, tectonic and geochemical variations. Over the past decade, several geochemical proxies have led to significant progress in understanding the paleredox states of ancient oceans. However, a quantitative interpretation of these data for atmospheric O2 levels remain unclear because the relationship between atmospheric O2 levels (pO2) and oceanic redox state depends on several environmental factors, such as terrestrial weathering rate, sea-level stands, and sinking rate of particulate organic matter (POM) in the water column and so on. It is widely thought that the redox-dependent P cycling also plays a crucial role in regulating pO2 because it acts as a negative feedback on a geological timescale. It is important that strength of this feedback for a given pO2 is also modulated by environmental factors, affecting not only O2 levels at steady state but also its susceptibility to environmental changes. In this study, a quantitative role of environmental factors in the oxidation state of Earth's surface environment is evaluated with an oceanic biogeochemical cycle model (CANOPS) coupled with global C cycle model, which enables us to understand the ancient CO2 and O2 evolution. Our results demonstrate that atmospheric O2 level at steady state is affected by CO2 input flux from Earth's interior via changes in biogeochemical cycles, but its response is modulated by several internal factors such as shelf area and POM sinking rate. We also found that early Paleozoic atmospheric O2 levels before the advent of land plant would be determined so that oceans may locate at the "edge of anoxia (EoA)" where the redox-dependency of marine P cycle plays a crucial role in regulating O2 cycle, and that POM sinking rate has a great impact on the EoA. Our findings provide insights into the O2 cycle over the Phanerozoic in response to the climatic and tectonic variations and

  2. Physically-based simulation of zinc oxide thin-film transistors: Contact resistance contribution on density of states

    Science.gov (United States)

    Dominguez, Miguel A.; Alcantara, Salvador; Soto, Susana

    2016-06-01

    In this work, using a physically-based simulator, the density of states DOS is modeled to reproduce the experimental electrical characteristics of ZnO TFTs fabricated by Ultrasonic Spray Pyrolysis at 200 °C. The contact resistance was experimentally extracted from the ZnO TFTs and included into the simulation, in order to separate the metal-semiconductor interface contribution from the DOS. A comparison between the modeled DOS considering the contact resistance and disregarding it is also presented. It is proposed to consider the acceptor-like states and the tail-donor states, where the deep-acceptor states have approximately an exponential form and the distribution of tail-acceptor states are sharper than the distribution of tail-donor states. The simulated electrical characteristics reproduce very well the experimental data at different channel lengths. The use of physically-based simulation can be useful to model the DOS of Oxide semiconductor films in TFTs by reproducing the experimental data.

  3. Hemoglobin redux: combining neutron and X-ray diffraction with mass spectrometry to analyse the quaternary state of oxidized hemoglobins

    Energy Technology Data Exchange (ETDEWEB)

    Mueser, Timothy C., E-mail: timothy.mueser@utoledo.edu; Griffith, Wendell P. [Department of Chemistry, University of Toledo, Toledo, OH 43606 (United States); Kovalevsky, Andrey Y. [Bioscience Division, MS M888, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Guo, Jingshu; Seaver, Sean [Department of Chemistry, University of Toledo, Toledo, OH 43606 (United States); Langan, Paul [Department of Chemistry, University of Toledo, Toledo, OH 43606 (United States); Bioscience Division, MS M888, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Hanson, B. Leif [Department of Chemistry, University of Toledo, Toledo, OH 43606 (United States)

    2010-11-01

    X-ray and neutron diffraction studies of cyanomethemoglobin are being used to evaluate the structural waters within the dimer–dimer interface involved in quaternary-state transitions. Improvements in neutron diffraction instrumentation are affording the opportunity to re-examine the structures of vertebrate hemoglobins and to interrogate proton and solvent position changes between the different quaternary states of the protein. For hemoglobins of unknown primary sequence, structural studies of cyanomethemoglobin (CNmetHb) are being used to help to resolve sequence ambiguity in the mass spectra. These studies have also provided additional structural evidence for the involvement of oxidized hemoglobin in the process of erythrocyte senescence. X-ray crystal studies of Tibetan snow leopard CNmetHb have shown that this protein crystallizes in the B state, a structure with a more open dyad, which possibly has relevance to RBC band 3 protein binding and erythrocyte senescence. R-state equine CNmetHb crystal studies elaborate the solvent differences in the switch and hinge region compared with a human deoxyhemoglobin T-state neutron structure. Lastly, comparison of histidine protonation between the T and R state should enumerate the Bohr-effect protons.

  4. Temperature and field-dependent transport measurements in continuously tunable tantalum oxide memristors expose the dominant state variable

    Science.gov (United States)

    Graves, Catherine E.; Dávila, Noraica; Merced-Grafals, Emmanuelle J.; Lam, Si-Ty; Strachan, John Paul; Williams, R. Stanley

    2017-03-01

    Applications of memristor devices are quickly moving beyond computer memory to areas of analog and neuromorphic computation. These applications require the design of devices with different characteristics from binary memory, such as a large tunable range of conductance. A complete understanding of the conduction mechanisms and their corresponding state variable(s) is crucial for optimizing performance and designs in these applications. Here we present measurements of low bias I-V characteristics of 6 states in a Ta/ tantalum-oxide (TaOx)/Pt memristor spanning over 2 orders of magnitude in conductance and temperatures from 100 K to 500 K. Our measurements show that the 300 K device conduction is dominated by a temperature-insensitive current that varies with non-volatile memristor state, with an additional leakage contribution from a thermally-activated current channel that is nearly independent of the memristor state. We interpret these results with a parallel conduction model of Mott hopping and Schottky emission channels, fitting the voltage and temperature dependent experimental data for all memristor states with only two free parameters. The memristor conductance is linearly correlated with N, the density of electrons near EF participating in the Mott hopping conduction, revealing N to be the dominant state variable for low bias conduction in this system. Finally, we show that the Mott hopping sites can be ascribed to oxygen vacancies, where the local oxygen vacancy density responsible for critical hopping pathways controls the memristor conductance.

  5. Electronic Structure, Oxidation State of Sn, and Chemical Stability of Photovoltaic Perovskite Variant Cs2SnI6

    CERN Document Server

    Xiao, Zewen; Zhang, Xiao; Zhou, Yuanyuan; Hosono, Hideo; Kamiya, Toshio

    2015-01-01

    Cs2SnI6, a variant of perovskite CsSnI3, is expected for a photovoltaic material. Based on a simple ionic model, it is expected that Cs2SnI6 is composed of Cs+, I-, and Sn4+ ions and that the band gap is primarily made of occupied I- 5p6 valence band maximum (VBM) and unoccupied Sn4+ 5s conduction band minimum (CBM) similar to SnO2. In this work, we performed density functional theory (DFT) calculations and revealed that the real charge state of the Sn ion in this compound is +2 similar to CsSnI3. This is due to strong covalent nature between the I ion and the Sn ion, the VBM consists of I 5p - I 5p antibonding states, and the CBM of I 5p - Sn 5s antibonding states. The +2 oxidation state of Sn is realized by the apparent charge state of I-2/3, because the I 5p - Sn 5s antibonding states form the unoccupied CBM and apparently 1/18 of the I 5p orbitals are unoccupied. These results are further supported by comparing chemical bonding analyses with those of related compounds. The chemical stability of the Cs2SnI...

  6. Oxidation states, geometries, and electronic structures of plutonium tetroxide PuO4 isomers: is octavalent Pu viable?

    Science.gov (United States)

    Huang, Wei; Xu, Wen-Hua; Su, Jing; Schwarz, W H E; Li, Jun

    2013-12-16

    In neutral chemical compounds, the highest known oxidation state of all elements in the Periodic Table is +VIII. While PuO4 is viewed as an exotic Pu(+VIII) complex, we have shown here that no stable electronic homologue of octavalent RuO4 and OsO4 exists for PuO4, even though Pu has the same number of eight valence electrons as Ru and Os. Using quantum chemical approaches at the levels of quasi-relativistic DFT, MP2, CCSD(T), and CASPT2, we find the ground state of PuO4 as a quintet (5)C2v-(PuO2)(+)(O2)(-) complex with the leading valence configuration of an (f(3))plutonyl(V) unit, loosely coupled to a superoxido (π*(3))O2(-) ligand. This stable isomer is likely detectable as a transient species, while the previously suggested planar (1)D4h-Pu(VIII)O4 isomer is only metastable. Through electronic structure analyses, the bonding and the oxidation states are explained and rationalized. We have predicted the characteristics of the electronic and vibrational spectra to assist future experimental identification of (PuO2)(+)(O2)(-) by IR, UV-vis, and ionization spectroscopy.

  7. Variation in the Markers of Nutritional and Oxidative State in a Long-Lived Seabird: Associations with Age and Longevity.

    Science.gov (United States)

    Urvik, Janek; Meitern, Richard; Rattiste, Kalev; Saks, Lauri; Hõrak, Peeter; Sepp, Tuul

    2016-01-01

    Age-related declines in life-history traits have been widely observed in free-living animals. Several theories link senescence to oxidative stress. The aim of this study was to measure several widely used markers of oxidative and nutritional state in a long-lived seabird, the common gull (Larus canus), in order to assess the suitability of these markers for describing deterioration in physiological condition associated with chronological age and survival. Associations with longevity and individual consistency of these parameters over the years (repeatability) were also assessed. Senescence in fitness parameters was observed during the study period: in females, laying date and clutch mass were related to bird age in a curvilinear manner, with middle-aged birds breeding earlier and laying heavier eggs. The only parameter associated with aging processes was glutathione concentration in erythrocytes, which was lower in female birds with longer life spans. Of indexes of nutritional state, plasma triglyceride concentration showed a between-individual increase with age, suggesting selective mortality of birds with low levels. Additionally, total plasma protein levels of individual males increased with age. The mostly negative results of this study hint that the commonly used parameters of physiological condition and oxidative state used in this study do not adequately reflect an individual's long-term health condition. Alternatively, it is possible that in common gulls, senescence occurs in reproductive mechanisms but not in mechanisms responsible for maintaining an organism's redox balance, consistent with the idea that different aspects of an organism's physiological condition age at different rates. Significant interannual repeatability was detected in three plasma constituents-carotenoids, uric acid, and total protein-all of which can possibly be linked to variation in dietary habits.

  8. Chronic exposure to sublethal hexavalent chromium affects organ histopathology and serum cortisol profile of a teleost, Channa punctatus (Bloch)

    Energy Technology Data Exchange (ETDEWEB)

    Mishra, Ashish K. [Department of Zoology, University of Allahabad, Allahabad-211002 (India); Mohanty, Banalata, E-mail: drbana_mohanty@rediffmail.com [Department of Zoology, University of Allahabad, Allahabad-211002 (India)

    2009-09-01

    Effects of chronic exposures (one and two months) to sublethal doses of hexavalent chromium (2 and 4 mg/L potassium dichromate) on organ histopathology and serum cortisol profile were investigated and their overall impact on growth and behavior of a teleost fish, Channa punctatus was elucidated. Histopathological lesions were distinct in the vital organs gill, kidney and liver. The gill lamellae became lifted, fused, and showed oedema. Hyperplasia and hypertrophy of lamellar epithelial cells were distinct with desquamation. Hypertrophy of epithelial cells of renal tubules and reduction in tubular lumens were observed in the trunk kidney. The atrophy of the head kidney interrenal cells and decreased serum cortisol level indicated exhaustion of interrenal activity. Hepatocyte vacuolization and shrinkage, nuclear pyknosis and increase of sinusoidal spaces were observed in the liver. Abnormal behavioral patterns and reduced growth rate were also noticed in the exposed fish. The chronic hexavalent chromium exposure thus by affecting histopathology of gill, kidney (including interrenal tissue) and liver could impair the vital functions of respiration, excretion, metabolic regulation and maintenance of stress homeostasis which in the long-run may pose serious threat to fish health and affect their population.

  9. Chronic exposure to sublethal hexavalent chromium affects organ histopathology and serum cortisol profile of a teleost, Channa punctatus (Bloch).

    Science.gov (United States)

    Mishra, Ashish K; Mohanty, Banalata

    2009-09-01

    Effects of chronic exposures (one and two months) to sublethal doses of hexavalent chromium (2 and 4 mg/L potassium dichromate) on organ histopathology and serum cortisol profile were investigated and their overall impact on growth and behavior of a teleost fish, Channa punctatus was elucidated. Histopathological lesions were distinct in the vital organs gill, kidney and liver. The gill lamellae became lifted, fused, and showed oedema. Hyperplasia and hypertrophy of lamellar epithelial cells were distinct with desquamation. Hypertrophy of epithelial cells of renal tubules and reduction in tubular lumens were observed in the trunk kidney. The atrophy of the head kidney interrenal cells and decreased serum cortisol level indicated exhaustion of interrenal activity. Hepatocyte vacuolization and shrinkage, nuclear pyknosis and increase of sinusoidal spaces were observed in the liver. Abnormal behavioral patterns and reduced growth rate were also noticed in the exposed fish. The chronic hexavalent chromium exposure thus by affecting histopathology of gill, kidney (including interrenal tissue) and liver could impair the vital functions of respiration, excretion, metabolic regulation and maintenance of stress homeostasis which in the long-run may pose serious threat to fish health and affect their population.

  10. X-ray diffraction and high-resolution TEM observations of biopolymer nanoskin-covered metallic copper fine particles: preparative conditions and surface oxidation states.

    Science.gov (United States)

    Yonezawa, Tetsu; Uchida, Yoshiki; Tsukamoto, Hiroki

    2015-12-28

    Metallic copper fine particles used for electro conductive pastes were prepared by the chemical reduction of cupric oxide microparticles in the presence of gelatin. After reduction, the fine particles were collected by decantation with pH control and washing, followed by drying at a moderate temperature. The surface oxidation state of the obtained copper fine particles could be considerably varied by altering the pH of the particle dispersion, as shown by X-ray diffraction and high-resolution transmission electron microscopy. Our results strongly indicate that decantation under a nitrogen atmosphere can prevent the oxidation of copper fine particles but a slight oxidation was found.

  11. Steady state creep of Ni-8YSZ substrates for application in solid oxide fuel and electrolysis cells

    Science.gov (United States)

    Wei, J.; Malzbender, J.

    2017-08-01

    Steady state creep was characterized for Ni-8YSZ solid oxide fuel/electrolysis cell (SOFC/SOEC) substrate material. Intrinsic and extrinsic factors affecting creep behavior were assessed, such as compositional ratio, porosity and mechanical loading configuration. Mechanical tests were supported by analytical and numerical calculations. The results indicated a diffusion-dominated creep mechanism under both compressive and tensile creep conditions. Creep appeared to be dominated by the ceramic phase. Porosity significantly reduced creep resistance. The activation energy was discussed based on loading configuration, temperature and porosity.

  12. Knockout of arsenic (+3 oxidation state) methyltransferase results in sex-dependent changes in phosphatidylcholine metabolism in mice.

    Science.gov (United States)

    Huang, Madelyn C; Douillet, Christelle C; Stýblo, Miroslav

    2016-12-01

    Arsenic (+3 oxidation state) methyltransferase is the key enzyme in the methylation pathway for inorganic arsenic. We have recently shown that As3mt knockout (KO) has a profound effect on metabolomic profiles in mice. Phosphatidylcholine species (PCs) were the largest group of metabolites altered in both plasma and urine. The present study used targeted analysis to investigate the KO-associated changes in PC profiles in the liver, the site of PC synthesis. Results show that As3mt KO has a systemic effect on PC metabolism and that this effect is sex dependent.

  13. Health economics of a hexavalent meningococcal outer-membrane vesicle vaccine in children : potential impact of introduction in the Dutch vaccination program

    NARCIS (Netherlands)

    Bos, JM; Rumke, HC; Welte, R; Postma, MJ; Jager, JC

    2001-01-01

    The cost-effectiveness of universal vaccination of infants with a new hexavalent meningococcal B outer-membrane vesicle vaccine is projected for The Netherlands by applying decision analysis. The societal perspective is taken and direct and productivity costs (friction costs method) are considered.

  14. Immunogenicity and safety of monovalent RIVM meningococcal B OMP vesicle F91 vaccine administered to children that received hexavalent meningococcal B vaccine 2.5 years ago

    NARCIS (Netherlands)

    Lafeber AB; Limpt CJP van; Berbers GAM; Labadie J; Kleijn ED de; Groot R de; Rumke HC; Alphen AJW van; Sophia Kinderziekenhuis /; LVO

    2000-01-01

    This report describes the results with respect to immunogenicity as well as reactogenicity of a monovalent P1.7h,4 OMV vaccine (MonoMen) used as booster vaccination in children previously vaccinated with a hexavalent MenB vaccine. The participants in this study were immunised in 1995-1996 with hexav

  15. TREATMENT OF HEXAVALENT CHROMIUM IN CHROMITE ORE PROCESSING SOLID WASTE USING A MIXED REDUCTANT SOLUTION OF FERROUS SULFATE AND SODIUM DITHIONITE

    Science.gov (United States)

    We developed a method for disseminating ferrous iron in the subsurface to enhance chemical reduction of hexavalent chromium (Cr(VI)) in a chromite ore processing solid waste derived from the production of ferrochrome alloy. The method utilizes ferrous sulfate (FeSO4) in combinati...

  16. Immunogenicity and safety of monovalent RIVM meningococcal B OMP vesicle F91 vaccine administered to children that received hexavalent meningococcal B vaccine 2.5 years ago

    NARCIS (Netherlands)

    Lafeber AB; van Limpt CJP; Berbers GAM; Labadie J; de Kleijn ED; de Groot R; Rumke HC; van Alphen AJW; LVO

    2000-01-01

    Dit rapport beschrijft een follow-up studie naar veiligheid en immunogeniciteit van monovalent P1.7h,4 OMV vaccin (MonoMen) gebruikt als boostervaccinatie in kinderen eerder gevaccineerd met hexavalent MenB vaccin. De deelnemers aan deze studie zijn in het kader van een eerdere studie gevaccineerd

  17. Health economics of a hexavalent meningococcal outer-membrane vesicle vaccine in children : potential impact of introduction in the Dutch vaccination program

    NARCIS (Netherlands)

    Bos, JM; Rumke, HC; Welte, R; Postma, MJ; Jager, JC

    2001-01-01

    The cost-effectiveness of universal vaccination of infants with a new hexavalent meningococcal B outer-membrane vesicle vaccine is projected for The Netherlands by applying decision analysis. The societal perspective is taken and direct and productivity costs (friction costs method) are considered.

  18. AN IN SITU PERMEABLE REACTIVE BARRIER FOR THE TREATMENT OF HEXAVALENT CHROMIUM AND TRICHLOROETHYLENE IN GROUNDWATER:VOLUME 2 PERFORMANCE MONITORING

    Science.gov (United States)

    A 46 m long, 7.3 m deep, and 0.6 m wide permeable subsurface reactive wall was installed at the U.S. Coast Guard (USCG) Support Center, near Elizabeth City, North Carolina, in June 1996. The reactive wall was designed to remediate hexavalent chromium [Cr(VI)] contaminated ground ...

  19. AN IN-SITU PERMEABLE REACTIVE BARRIER FOR THE TREATMENT OF HEXAVALENT CHROMIUM AND TRICHLOROETHYLENE IN GROUND WATER: VOLUME 1 DESIGN AND INSTALLATION

    Science.gov (United States)

    A 46 m long, 7.3 m deep, and 0.6 m wide permeable subsurface reactive wall was installed at the U.S. Coast Guard (USCG) Support Center, near Elizabeth City, North Carolina, in June 1996. The reactive wall was designed to remediate hexavalent chromium [Cr(VI)] contaminated ground ...

  20. Thiol switches in redox regulation of chloroplasts: balancing redox state, metabolism and oxidative stress.

    Science.gov (United States)

    Dietz, Karl-Josef; Hell, Rüdiger

    2015-05-01

    In photosynthesizing chloroplasts, rapidly changing energy input, intermediate generation of strong reductants as well as oxidants and multiple participating physicochemical processes and pathways, call for efficient regulation. Coupling redox information to protein function via thiol modifications offers a powerful mechanism to activate, down-regulate and coordinate interdependent processes. Efficient thiol switching of target proteins involves the thiol-disulfide redox regulatory network, which is highly elaborated in chloroplasts. This review addresses the features of this network. Its conditional function depends on specificity of reduction and oxidation reactions and pathways, thiol redox buffering, but also formation of heterogeneous milieus by microdomains, metabolite gradients and macromolecular assemblies. One major player is glutathione. Its synthesis and function is under feedback redox control. The number of thiol-controlled processes and involved thiol switched proteins is steadily increasing, e.g., in tetrapyrrole biosynthesis, plastid transcription and plastid translation. Thus chloroplasts utilize an intricate and versatile redox regulatory network for intraorganellar and retrograde communication.

  1. The influence of magmatic differentiation on the oxidation state of Fe in a basaltic arc magma

    Energy Technology Data Exchange (ETDEWEB)

    Kelley, Katherine A.; Cottrell, Elizabeth (Rhode Island); (Smithsonian)

    2012-05-09

    Subduction zone basalts are more oxidized than basalts from other tectonic settings (e.g., higher Fe{sup 3+}/{Sigma}Fe), and this contrast may play a central role in the unique geochemical processes that generate arc and continental crust. The processes generating oxidized arc magmas, however, are poorly constrained, although they appear inherently linked to subduction. Near-surface differentiation processes unique to arc settings might drive oxidation of magmas that originate in equilibrium with a relatively reduced mantle source. Alternatively, arc magmas could record the oxidation conditions of a relatively oxidized mantle source. Here, we present new measurements of olivine-hosted melt inclusions from a single eruption of Agrigan volcano, Marianas, in order to test the influence of differentiation processes vs. source conditions on the Fe{sup 3+}/{Sigma}Fe ratio, a proxy for system oxygen fugacity (fO{sub 2}). We determined Fe{sup 3+}/{Sigma}Fe ratios in glass inclusions using {mu}-XANES and couple these data with major elements, dissolved volatiles, and trace elements. After correcting for post-entrapment crystallization, Fe{sup 3+}/{Sigma}Fe ratios in the Agrigan melt inclusions (0.219 to 0.282), and their modeled fO{sub 2}s ({Delta}QFM + 1.0 to + 1.8), are uniformly more oxidized than MORB, and preserve a portion of the evolution of this magma from 5.7 to 3.2 wt.% MgO. Fractionation of olivine {+-} clinopyroxene {+-} plagioclase should increase Fe{sup 3+}/{Sigma}Fe as MgO decreases in the melt, but the data show Fe{sup 3+}/{Sigma}Fe ratios decreasing as MgO decreases below 5 wt.% MgO. The major element trajectories, taken in combination with this strong reduction trend, are inconsistent with crystallization of common ferromagnesian phases found in the bulk Agrigan sample, including magnetite. Rather, decreasing Fe{sup 3+}/{Sigma}Fe ratios correlate with decreasing S concentrations, suggesting that electronic exchanges associated with SO{sub 2} degassing may

  2. Determination of plutonium oxidation states in dilute nitric acid by complementary tristimulus colorimetry.

    Science.gov (United States)

    Silver, G L

    1967-06-01

    The preparation of reference standards for use in complementary tristimulus colorimetry for plutonium is described. Plutonium(III) and (VI) are prepared by hydrazine reduction and silver(II) oxidation, respectively, of plutonium(IV). Plutonium(V) is prepared by reduction of plutonium(VI) with ascorbic or sulphurous acid. A method for computerizing tristimulus colorimetry is presented, and the technique is extended to three dimensions ("quadristimulus colorimetry").

  3. Investigation of the solid-state reaction between nickel oxide and alumina by Rutherford backscattering (RBS)

    NARCIS (Netherlands)

    Roos, G. de; Geus, John W.; Fluit, J.M.; Wit, J.H. de

    1980-01-01

    The reaction of NiO and Al2O3 to form NiAl2O4 was investigated by means of Rutherford backscattering of 3 MeV He+-ions. The NiO was obtained by oxidation at 900°C of a nickel film vapour-deposited onto alumina substrates. The reaction of NiO and Al2O3 did not proceed markedly at 900°C. The reaction

  4. Implementation of Inverse Photoelectron Spectroscopy for Measuring the Empty Electronic States of Metal Oxide Surfaces

    Science.gov (United States)

    2014-11-05

    turbomolecular pump were also purchased from the DURIP funds. This equipment was installed in an existing photoelectron spectrometer in the Whitten group...auxiliary equipment, including a mass spectrometer for thermal desorption and a Kelvin probe. Figure 1: Photograph of the photoelectron spectrometer at...hydroxides and oxides and how this is affected by adsorption of hazardous gases. Ultimately, we are interested in correlating adsorbate-induced changes in

  5. Oxidation state of chromium associated with cell surfaces of Shewanella oneidensis during chromate reduction

    Energy Technology Data Exchange (ETDEWEB)

    Neal, Andrew L.; Lowe, Kristine; Daulton, Tyrone L.; Jones-Meehan, Joanne; Little, Brenda J

    2002-12-30

    Employing electron energy loss spectroscopy (EELS) and X-ray photoelectron spectroscopy (XPS), we demonstrate that in both aerobic and anaerobic culture Shewanella oneidensis cells are capable of chromate reduction. No Cr(VI) or Cr(V) species were identified at the cell surfaces in Cr 2p{sub 3/}ore photoelectron spectra. More chromium was associated with cell surfaces recovered from anaerobic medium than aerobic. Multiplet-splitting models derived for Cr(III) and Cr(IV) were employed to determine contributions from each ion to Cr 2p{sub 3/2} photopeaks collected from the various cell treatments. Whilst in all cases Cr(III) was the major ion associated with cell surfaces, a significant contribution was identified due to Cr(IV) in anaerobically grown cells. The Cr(IV) contribution was far less when cells were grown aerobically. Moreover, when anaerobically grown cells were exposed to oxygen very little re-oxidation of Cr-precipitates occurred, the precipitates were again identified as a mixture of Cr(III) and Cr(IV). A positive relationship was observed between amounts of chromium and phosphorous associated with cell surfaces resulting from the various treatments, suggesting the precipitates included Cr(III)-phosphate. The fact that Cr(IV) remained associated with precipitates following re-oxidation suggests that under anaerobic conditions the intermediate ion is afforded sufficient stability to be incorporated within the precipitate matrix and thus conferred a degree of protection from oxidation.

  6. Hemoglobin redux: combining neutron and X-ray diffraction with mass spectrometry to analyse the quaternary state of oxidized hemoglobins.

    Science.gov (United States)

    Mueser, Timothy C; Griffith, Wendell P; Kovalevsky, Andrey Y; Guo, Jingshu; Seaver, Sean; Langan, Paul; Hanson, B Leif

    2010-11-01

    Improvements in neutron diffraction instrumentation are affording the opportunity to re-examine the structures of vertebrate hemoglobins and to interrogate proton and solvent position changes between the different quaternary states of the protein. For hemoglobins of unknown primary sequence, structural studies of cyanomethemoglobin (CNmetHb) are being used to help to resolve sequence ambiguity in the mass spectra. These studies have also provided additional structural evidence for the involvement of oxidized hemoglobin in the process of erythrocyte senescence. X-ray crystal studies of Tibetan snow leopard CNmetHb have shown that this protein crystallizes in the B state, a structure with a more open dyad, which possibly has relevance to RBC band 3 protein binding and erythrocyte senescence. R-state equine CNmetHb crystal studies elaborate the solvent differences in the switch and hinge region compared with a human deoxyhemoglobin T-state neutron structure. Lastly, comparison of histidine protonation between the T and R state should enumerate the Bohr-effect protons.

  7. All-solid-state reduced graphene oxide supercapacitor with large volumetric capacitance and ultralong stability prepared by electrophoretic deposition method.

    Science.gov (United States)

    Wang, Mei; Duong, Le Dai; Mai, Nguyen Thi; Kim, Sanghoon; Kim, Youngjun; Seo, Heewon; Kim, Ye Chan; Jang, Woojin; Lee, Youngkwan; Suhr, Jonghwan; Nam, Jae-Do

    2015-01-21

    Portable energy storage devices have gained special attention due to the growing demand for portable electronics. Herein, an all-solid-state supercapacitor is successfully fabricated based on a poly(vinyl alcohol)-H3PO4 (PVA-H3PO4) polymer electrolyte and a reduced graphene oxide (RGO) membrane electrode prepared by electrophoretic deposition (EPD). The RGO electrode fabricated by EPD contains an in-plane layer-by-layer alignment and a moderate porosity that accommodate the electrolyte ions. The all-solid-state RGO supercapacitor is thoroughly tested to give high specific volumetric capacitance (108 F cm(-3)) and excellent energy and power densities (7.5 Wh cm(-3) and 2.9 W cm(-3), respectively). In addition, the all-solid-state RGO supercapacitor exhibits an ultralong lifetime for as long as 180 days (335 000 cycles), which is an ultrahigh cycling capability for a solid-state supercapacitor. The RGO is also tested for being used as a transparent supercapacitor electrode demonstrating its possible use in various transparent optoelectronic devices. Due to the facile scale-up capability of the EPD process and RGO dispersion, the developed all-solid-state supercapacitor is highly applicable to large-area portable energy storage devices.

  8. Iron oxides as pedoenvironmental indicators: state of the art, answers and questions (Philippe Duchaufour Medal Lecture)

    Science.gov (United States)

    Torrent, J.

    2012-04-01

    The colour and magnetic properties of soils largely reflect the content and mineralogy of their iron oxides, which in turn relate to the physical, chemical and biological characteristics of the soil environment. For more than 50 years, soil mineralogists and chemists have collected data for iron oxides in soils formed in widely different environments and tried to understand the complex nature of the different suites and formation pathways for these minerals via laboratory experiments. The discovery of ferrihydrite —the poorly crystalline precursor of most Fe oxides— in 1971, and the recognition of its common presence in soils, raised interest in deciphering the environmental factors that affect its transformation into goethite and hematite, the two most abundant crystalline iron oxides in soil. Field observations were consistent with laboratory experiments in which temperature, water activity, pH, foreign ions and organic matter were found to play a key role in the crystallization of ferrihydrite. Thus, the hematite/(hematite + goethite) ratio increased with increasing temperature and also with the likelihood of seasonal soil drying. Exploiting this ratio as a (pedo)environment indicator is, however, not devoid of problems derived from insufficient knowledge of the interactions between the influential chemical variables, difficulties in quantifying the two minerals and changes brought about by reductive dissolution. Soil formation usually leads to magnetic enhancement as a result of the production of magnetite and/or maghemite, which are ferrimagnetic iron oxides, and, possibly, an ordered ferrimagnetic ferrihydrite, as suggested by recent laboratory experiments. The concentration of pedogenic ferrimagnets as estimated via proxies such as magnetic susceptibility or frequency-dependent magnetic susceptibility has been found to relate to climate variables [particularly (paleo)rainfall] in many studies reported over the last 30 years. However, extracting accurate

  9. Hexavalent chromium induces energy metabolism disturbance and p53-dependent cell cycle arrest via reactive oxygen species in L-02 hepatocytes.

    Science.gov (United States)

    Xiao, Fang; Feng, Xiaotao; Zeng, Ming; Guan, Lan; Hu, Qingqing; Zhong, Caigao

    2012-12-01

    Hexavalent chromium [Cr(VI)] has become a non-negligible pollutant in the world. Cr(VI) exposure leads to severe damage to the liver, but the mechanisms involved in Cr(VI)-mediated toxicity in the liver are unclear. The present study aimed to explore whether Cr(VI) induces energy metabolism disturbance and cell cycle arrest in human L-02 hepatocytes. We showed that Cr(VI) inhibited state 3 respiration, respiratory control rate (RCR), and subsequently induced energy metabolism disturbance with decreased ATP production. Interestingly, cell cycle analysis by flow cytometry and protein expression analysis by western blotting revealed that low dose of Cr(VI) (4 uM) exposure induced S phase cell cycle arrest with decreased mediator of replication checkpoint 1 (Mrc1) and cyclin-dependent kinase 2 (CDK2), while higher doses of Cr(VI) (16, 32 uM) exposure resulted in G2/M phase arrest with decreased budding uninhibited by benzimidazoles-related 1 (BubR1) and cell division cycle 25 (CDC25). Mechanism study revealed that Cr(VI) decreased the activities of mitochondrial respiratory chain complex (MRCC) I and II, thus leading to ROS accumulation. Moreover, inhibiting ROS production by antioxidant N-acetyl-L-cysteine (NAC) rescued Cr(VI)-induced ATP depletion and cell cycle arrest. ROS-mediated p53 activation was found to involve in Cr(VI)-induced cell cycle arrest, and p53 inhibitor Pifithrin-α (PFT-α) rescued Cr(VI)-induced reduction of check point proteins Mrc1 and BubR1, thus inhibiting cell cycle arrest. In summary, the present study provides experimental evidence that Cr(VI) leads to energy metabolism disturbance and p53-dependent cell cycle arrest via ROS in L-02 hepatocytes.

  10. Analyzer for measurement of nitrogen oxide concentration by ozone content reduction in gas using solid state chemiluminescent sensor

    Science.gov (United States)

    Chelibanov, V. P.; Ishanin, G. G.; Isaev, L. N.

    2014-05-01

    Role of nitrogen oxide in ambient air is described and analyzed. New method of nitrogen oxide concentration measurement in gas phase is suggested based on ozone concentration measurement with titration by nitrogen oxide. Research of chemiluminescent sensor composition is carried out on experimental stand. The sensor produced on the base of solid state non-activated chemiluminescent composition is applied as ozone sensor. Composition is put on the surface of polymer matrix with developed surface. Sensor compositions includes gallic acid with addition of rodamine-6G. Model of interaction process between sensor composition and ozone has been developed, main products appeared during reaction are identified. The product determining the speed of luminescense appearance is found. This product belongs to quinone class. Then new structure of chemiluminescent composition was suggested, with absence of activation period and with high stability of operation. Experimental model of gas analyzer was constructed and operation algorithm was developed. It was demonstrated that developed NO measuring instrument would be applied for monitoring purposes of ambient air. This work was partially financially supported by Government of Russian Federation, Grant 074-U01

  11. Correlation of Mn charge state with the electrical resistivity of Mn doped indium tin oxide thin films

    KAUST Repository

    Kumar, S. R. Sarath

    2010-09-15

    Correlation of charge state of Mn with the increase in resistivity with Mn concentration is demonstrated in Mn-doped indium tin oxide films. Bonding analysis shows that Mn 2p3/2 core level can be deconvoluted into three components corresponding to Mn2+ and Mn4+ with binding energies 640.8 eV and 642.7 eV, respectively, and a Mn2+ satellite at ∼5.4 eV away from the Mn2+ peak. The presence of the satellite peak unambiguously proves that Mn exists in the +2 charge state. The ratio of concentration of Mn2+ to Mn4+ of ∼4:1 suggests that charge compensation occurs in the n-type films causing the resistivity increase.

  12. On the Highest Oxidation States of Metal Elements in MO4 Molecules (M = Fe, Ru, Os, Hs, Sm, and Pu).

    Science.gov (United States)

    Huang, Wei; Xu, Wen-Hua; Schwarz, W H E; Li, Jun

    2016-05-02

    Metal tetraoxygen molecules (MO4, M = Fe, Ru, Os, Hs, Sm, Pu) of all metal atoms M with eight valence electrons are theoretically studied using density functional and correlated wave function approaches. The heavier d-block elements Ru, Os, Hs are confirmed to form stable tetraoxides of Td symmetry in (1)A1 electronic states with empty metal d(0) valence shell and closed-shell O(2-) ligands, while the 3d-, 4f-, and 5f-elements Fe, Sm, and Pu prefer partial occupation of their valence shells and peroxide or superoxide ligands at lower symmetry structures with various spin couplings. The different geometric and electronic structures and chemical bonding types of the six iso-stoichiometric species are explained in terms of atomic orbital energies and orbital radii. The variations found here contribute to our general understanding of the periodic trends of oxidation states across the periodic table.

  13. Toxicity of iron-based nanoparticles to green algae: Effects of particle size, crystal phase, oxidation state and environmental aging.

    Science.gov (United States)

    Lei, Cheng; Zhang, Luqing; Yang, Kun; Zhu, Lizhong; Lin, Daohui

    2016-11-01

    With the increasing environmental application and discharge of iron-based nanoparticles (NPs), a comprehensive understanding of their fate and ecotoxicological effect in the aquatic environment is very urgent. In this study, toxicities of 4 zero-valent iron NPs (nZVI) of different sizes, 2 Fe2O3 NPs of different crystal phases, and 1 type of Fe3O4 NPs to a green alga (Chlorella pyrenoidosa) were investigated, with a focus on the effects of particle size, crystal phase, oxidation state, and environmental aging. Results show that the algal growth inhibition of nZVI increased significantly with decreasing particle size; with similar particle sizes (20-30 nm), the algal growth inhibition decreased with oxidation of the NPs with an order of nZVI > Fe3O4 NPs > Fe2O3 NPs, and α-Fe2O3 NPs presented significantly higher toxicity than γ-Fe2O3 NPs. The NP-induced oxidative stress was the main toxic mechanism, which could explain the difference in algal toxicity of the NPs. The NP-cell heteroagglomeration and physical interactions also contributed to the nanotoxicity, whereas the effect of NP dissolution was negligible. The aging in distilled water and 3 surface water samples for 3 months increased surface oxidation of the iron-based NPs especially nZVI, which decreased the toxicity to algae. These findings will be helpful for the understanding of the fate and toxicity of iron-based NPs in the aquatic environment.

  14. State-of-the-art Sn2+-based ternary oxides as photocatalysts for water splitting: electronic structures and optoelectronic properties

    KAUST Repository

    Noureldine, Dalal

    2016-09-19

    Developing visible light responsive metal oxide photocatalysts is a challenge that must be conquered to achieve high efficiency for water splitting or hydrogen evolution reactions. Valence band engineering is possible by forming ternary oxides using the combination of a metal cation with an s2d10 electronic configuration and a transition metal oxide with a d0 configuration. Many (Sn2+, Bi3+, Pb2+)-based ternary metal oxide photocatalysts have been reported for hydrogen and/or oxygen evolution under visible irradiation. Sn2+-based materials have attracted particular attention because tin is inexpensive, abundant and more environmentally friendly than lead or bismuth. In this review, we provide a fruitful library for Sn2+-based photocatalysts that have been reported to evolve hydrogen using sacrificial reagents, including SnNb2O6, Sn2Nb2O7, SnTaxNb2−xO6, SnTa2O6, Sn2Ta2O7, SnWO4 (α and β phases), SnSb2O6·nH2O, and Sn2TiO4. The synthesis method used in the literature and the resultant morphology and crystal structure of each compound are discussed. The density functional theory (DFT) calculations of the electronic structure and density of states are provided, and the consequent optoelectronic properties such as band gap, nature of the bandgap, dielectric constant, and effective masses are summarized. This review will help highlight the main challenges for Sn2+-based materials.

  15. Chromium Oxidation State in Planetary Basalts: Oxygen Fugacity Indicator and Critical Variable for Cr-Spinel Stability

    Science.gov (United States)

    Bell, A. S.; Burger, P. V.; Le, Loan; Papike, J. J.; Jone, J.; Shearer, C. K.

    2014-01-01

    Cr is a ubiquitous and relatively abundant minor element in basaltic, planetary magmas. At the reduced oxidation states (basalts Cr is present in melts as both divalent and trivalent forms. The ratio of trivalent to divalent Cr present in the melt has many consequences for the stability and Cr concentration of magmatic phases such as spinel, clinopyroxene, and olivine. However, understanding the Cr valence in quenched melts has historically been plagued with analytical issues, and only recently has reliable methodology for quantifying Cr valence in quenched melts been developed. Despite this substantial difficulty, the pioneering works of Hanson and Jones and Berry and O'Neill provided important insights into the oxidation state of Cr in in silicate melts. Here we present a series of 1-bar gas mixing experiments performed with a Fe-rich basaltic melt in which have determined the Cr redox ratio of the melt at over a range of fO2 values by measuring this quantity in olivine with X-ray Absorption Near Edge Spectroscopy (XANES). The measured Cr redox ratio of the olivine phenocrysts can be readily converted to the ratio present in the conjugate melt via the ratio of crystal-liquid partition coefficients for Cr3+ and Cr2+. We have applied these results to modeling Cr spinel stability and Cr redox ratios in a primitive, iron-rich martian basalt.

  16. Solid-state voltammetry-based electrochemical immunosensor for Escherichia coli using graphene oxide-Ag nanoparticle composites as labels.

    Science.gov (United States)

    Jiang, Xiaochun; Chen, Kun; Wang, Jing; Shao, Kang; Fu, Tao; Shao, Feng; Lu, Donglian; Liang, Jiangong; Foda, M Frahat; Han, Heyou

    2013-06-21

    A new electrochemical immunosensor based on solid-state voltammetry was fabricated for the detection of Escherichia coli (E. coli) by using graphene oxide-Ag nanoparticle composites (P-GO-Ag) as labels. To construct the platform, Au nanoparticles (AuNPs) were first self-assembled on an Au electrode surface through cysteamine and served as an effective matrix for antibody (Ab) attachment. Under a sandwich-type immunoassay format, the analyte and the probe (P-GO-Ag-Ab) were successively captured onto the immunosensor. Finally, the bonded AgNPs were detected through a solid-state redox process in 0.2 M of KCl solution. Combining the advantages of the high-loading capability of graphene oxide with promoted electron-transfer rate of AuNPs, this immunosensor produced a 26.92-fold signal enhancement compared with the unamplified protocol. Under the optimal conditions, the immunosensor exhibited a wide linear dependence on the logarithm of the concentration of E. coli ranging from 50 to 1.0 × 10(6) cfu mL(-1) with a detection limit of 10 cfu mL(-1). Moreover, as a practical application, the proposed immunosensor was used to monitor E. coli in lake water with satisfactory results.

  17. Kinetics deformation of current-voltage characteristics of the varistor oxide structures due to overcharging of the localized states

    Directory of Open Access Journals (Sweden)

    Tonkoshkur A. S.

    2014-12-01

    Full Text Available Prolonged exposure of zinc oxide varistors to the electrical load leads to current-voltage characteristics (CVC deformation, which is associated with a change in the height and width of the intergranular barriers, which are main structural element of the varistors. Polarization phenomena in zinc oxide ceramics are studied in a number of works, but those are mainly limited to the study of the physics of the CVC deformation process and to determining the parameters of localized electronic states involved in this process. This paper presents the results on the simulation of the deformation of pulse CVC of a separate intergranular potential barrier at transient polarization/depolarization, associated with recharging of surface electronic states (SES, which cause this barrier. It is found that at high density of SES their degree of electron filling is small and the effect of DC voltage leads to a shift of pulse current-voltage characteristics into the region of small currents. Conversely, the low density SES are almost completely filled with electrons, and after crystallite polarization CVC is shifted to high currents. Experimental studies have confirmed the possibility of applying the discovered laws to ceramic varistor structures. The proposed model allows interpreting the «anomalous» effects (such as increase in the classification voltage and reduction of active losses power observed during the varistors accelerated aging test.

  18. Assessing the influence of the carbon oxidation-reduction state on organic pollutant biodegradation in algal-bacterial photobioreactors.

    Science.gov (United States)

    Bahr, Melanie; Stams, Alfons J M; De la Rosa, Francisco; García-Encina, Pedro A; Muñoz, Raul

    2011-05-01

    The influence of the carbon oxidation-reduction state (CORS) of organic pollutants on their biodegradation in enclosed algal-bacterial photobioreactors was evaluated using a consortium of enriched wild-type methanotrophic bacteria and microalgae. Methane, methanol and glucose (with CORS -4, -2 and 0, respectively) were chosen as model organic pollutants. In the absence of external oxygen supply, microalgal photosynthesis was not capable of supporting a significant methane and methanol biodegradation due to their high oxygen demands per carbon unit, while glucose was fully oxidized by photosynthetic oxygenation. When bicarbonate was added, removal efficiencies of 37 ± 4% (20 days), 65 ± 4% (11 days) and 100% (2 days) were recorded for CH(4,) CH(3)OH and C(6)H(12)O(6), respectively due to the additional oxygen generated from photosynthetic bicarbonate assimilation. The use of NO(3)(-) instead of NH(4)(+) as nitrogen source (N oxidation-reduction state of +5 vs. -3) resulted in an increase in CH(4) degradation from 0 to 33 ± 3% in the absence of bicarbonate and from 37 ± 4% to 100% in the presence of bicarbonate, likely due to a decrease in the stoichiometric oxygen requirements and the higher photosynthetic oxygen production. Hypothetically, the CORS of the substrates might affect the CORS of the microalgal biomass composition (higher lipid content). However, the total lipid content of the algal-bacterial biomass was 19 ± 7% in the absence and 16 ± 2% in the presence of bicarbonate.

  19. Assessing the influence of the carbon oxidation-reduction state on organic pollutant biodegradation in algal-bacterial photobioreactors

    Energy Technology Data Exchange (ETDEWEB)

    Bahr, Melanie; Garcia-Encina, Pedro A.; Munoz, Raul [Valladolid Univ. (Spain). Dept. of Chemical Engineering and Environmental Technology; Stams, Alfons J.M. [Valladolid Univ. (Spain). Dept. of Chemical Engineering and Environmental Technology; Wageningen Univ. (Netherlands). Lab. of Microbiology; Rosa, Francisco de la [Valladolid Univ. (Spain). Dept. of Analytical Chemistry

    2011-05-15

    The influence of the carbon oxidation-reduction state (CORS) of organic pollutants on their biodegradation in enclosed algal-bacterial photobioreactors was evaluated using a consortium of enriched wild-type methanotrophic bacteria and microalgae. Methane, methanol and glucose (with CORS -4, -2 and 0, respectively) were chosen as model organic pollutants. In the absence of external oxygen supply, microalgal photosynthesis was not capable of supporting a significant methane and methanol biodegradation due to their high oxygen demands per carbon unit, while glucose was fully oxidized by photosynthetic oxygenation. When bicarbonate was added, removal efficiencies of 37 {+-} 4% (20 days), 65 {+-} 4% (11 days) and 100% (2 days) were recorded for CH{sub 4}, CH{sub 3}OH and C{sub 6}H{sub 12}O{sub 6}, respectively due to the additional oxygen generated from photosynthetic bicarbonate assimilation. The use of NO{sub 3}{sup -} instead of NH{sub 4}{sup +} as nitrogen source (N oxidation-reduction state of +5 vs. -3) resulted in an increase in CH4 degradation from 0 to 33 {+-} 3% in the absence of bicarbonate and from 37 {+-} 4% to 100% in the presence of bicarbonate, likely due to a decrease in the stoichiometric oxygen requirements and the higher photosynthetic oxygen production. Hypothetically, the CORS of the substrates might affect the CORS of the microalgal biomass composition (higher lipid content). However, the total lipid content of the algal-bacterial biomass was 19 {+-} 7% in the absence and 16 {+-} 2% in the presence of bicarbonate. (orig.)

  20. Efficient Deep-Blue Electroluminescence Based on Phenanthroimidazole-Dibenzothiophene Derivatives with Different Oxidation States of the Sulfur Atom.

    Science.gov (United States)

    Tang, Xiangyang; Shan, Tong; Bai, Qing; Ma, Hongwei; He, Xin; Lu, Ping

    2017-03-02

    Developing efficient deep-blue materials is a long-term research focus in the field of organic light-emitting diodes (OLEDs). In this paper, we report two deep-blue molecules, PITO and PISF, which share similar chemical structures but exhibit different photophysical and device properties. These two molecules consist of phenanthroimidazole and dibenzothiophene analogs. The distinction of their chemical structures lies in the different oxidation states of the S atom. For PITO, the S atom is oxidized and the resulting structure dibenzothiophene S,S-dioxide becomes electron deficient. Therefore, PITO displays remarkable solvatochromism, implying a charge-transfer (CT) excited state formed between the donor (D) phenanthroimidazole and acceptor (A) dibenzothiophene S,S-dioxide. For PISF, it is constituted of phenanthroimidazole and dibenzothiophene in which the S atom is not oxidized. PISF displays locally excited (LE) emission with little solvatochromism. Compared with PISF, the D-A molecule PITO with an electron-deficient group shows a much lower LUMO energy level, which is in favor of electron injection in device. In addition, PITO exhibits more balanced carrier transport. However, PISF is capable of emitting in the shorter wavelength region, which is beneficial to obtain better color purity. The doped electroluminescence (EL) device of the D-A molecule PITO manifests deep-blue emission with CIE coordinates of (0.15, 0.08) and maximum external quantum efficiency (EQE) of 4.67 %. The doped EL device of the LE molecule PISF, however, reveals an even bluer emission with CIE coordinates of (0.15, 0.06) and a maximum EQE of 4.08 %.

  1. Adsorption characteristics of hexavalent chromium on HCB/TiO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Li; Zhang, Yonggang, E-mail: 13502182420@163.com

    2014-10-15

    Graphical abstract: - Highlights: • Sol–gel method was adopted to prepare HCB/TiO{sub 2}. • Its adsorption performance of Cr(VI) was investigated. • The maximum adsorption capacity for Cr(VI) was at 27.33 mg g{sup −1} in an acidic medium. • The value is worth comparable with other low-cost adsorbents. - Abstract: Sol–gel method was adopted to prepare HCB/TiO{sub 2} and its adsorption ability of hexavalent chromium, Cr(VI), and removal from aqueous solution were investigated. The samples were characterized by Power X-ray diffraction (XRD) and a transmission electron microscope (TEM) which showed that the TiO{sub 2} was deposited on the surface of HCB. FTIR was used to identify the changes of the surface functional groups before and after adsorption. Potentiometric titration method was used to characterize the zero charge (pH{sub pzc}) characteristics of the surface of HCB/TiO{sub 2} which showed more acidic functional groups containing. Batch experiments showed that initial pH, absorbent dosage, contact time and initial concentration of Cr(VI) were important parameters for the Cr(VI) adsorption studies. The Freundlich isotherm model better reflected the experimental data better. Cr(VI) adsorption process followed the pseudo-second order kinetic model, which illustrated chemical adsorption. The thermodynamic parameters, such as Gibbs free energy (ΔG), changes in enthalpy change (ΔH) and changes in entropy change (ΔS) were also evaluated. Negative value of free energy occurred at temperature range of 25–45 °C, so Cr(VI) adsorption by HCB/TiO{sub 2} is spontaneous. Desorption results showed that the adsorption capacity could maintain 80% after five cycles. The maximum adsorption capacity for Cr(VI) was at 27.33 mg g{sup −1} in an acidic medium, of which the value is worth comparable with other low-cost adsorbents.

  2. The role of EDTA in phytoextraction of hexavalent and trivalent chromium by two willow trees.

    Science.gov (United States)

    Yu, Xiao-Zhang; Gu, Ji-Dong

    2008-04-01

    Effects of the synthetic chelator ethylenediamine tetraacetate (EDTA) on uptake and internal translocation of hexavalent and trivalent chromium by plants were investigated. Two different concentrations of EDTA were studied for enhancing the uptake and translocation of Cr from the hydroponic solution spiked with K(2)CrO(4) or CrCl(3) maintained at 24.0 +/- 1 degrees C. Faster removal of Cr(3+) than Cr(6+) by hybrid willows (Salix matsudana Koidz x Salix alba L.) from the plant growth media was observed. Negligible effect of EDTA on the uptake of Cr(6+) was found, but significant decrease of the Cr concentration in roots was measured. Although the translocation of Cr(6+) within plant materials was detected in response to EDTA concentration, the amount of Cr(6+) translocated to the lower stems was considerably small. EDTA in the nutrient media showed a negative effect on the uptake of Cr(3+ )by hybrid willows; the removal rates of Cr(3+ )were significantly decreased. Translocation of Cr(3+) into the stems and leaves was undetectable, but roots were the exclusive sink for Cr(3+) accumulation. Weeping willows (Salix babylonica L.) showed lower removal rates for both chemical forms of Cr than hybrid willows. Although EDTA had a minor effect on Cr(6+ )uptake by weeping willows, positive effect on Cr(6+ )translocation within plant materials was observed. It was also determined that EDTA in plant growth media significantly decreased the amount of Cr(3+) taken up by plants, but significantly increased Cr(3+) mobilization from roots to stems. Results indicated that EDTA was unable to increase the uptake of Cr(6+) by both plant species, but translocation of Cr(6+)-EDTA within plant materials was possible. Addition of EDTA in the nutrient media showed a strong influence on the uptake and translocation of Cr(3+) in both willows. Cr(3+)-EDTA in tissues of weeping willows was more mobile than that in hybrid willows. The information has important implications for the use of metal

  3. Cancer mortality in a Chinese population exposed to hexavalent chromium in drinking water

    Science.gov (United States)

    Beaumont, J.J.; Sedman, R.M.; Reynolds, S.D.; Sherman, C.D.; Li, L.-H.; Howd, R.A.; Sandy, M.S.; Zeise, L.; Alexeeff, G.V.

    2008-01-01

    BACKGROUND: In 1987, investigators in Liaoning Province, China, reported that mortality rates for all cancer, stomach cancer, and lung cancer in 1970-1978 were higher in villages with hexavalent chromium (Cr)-contaminated drinking water than in the general population. The investigators reported rates, but did not report statistical measures of association or precision. METHODS: Using reports and other communications from investigators at the local Jinzhou Health and Anti-Epidemic Station, we obtained data on Cr contamination of groundwater and cancer mortality in 9 study regions near a ferrochromium factory. We estimated:(1) person-years at risk in the study regions, based on census and population growth rate data, (2) mortality counts, based on estimated person-years at risk and previously reported mortality rates, and (3) rate ratios and 95% confidence intervals. RESULTS: The all-cancer mortality rate in the combined 5 study regions with Cr-contaminated water was negligibly elevated in comparison with the rate in the 4 combined study regions without contaminated water (rate ratio = 1.13; 95% confidence interval = 0.86-1.46), but was somewhat more elevated in comparison with the whole province (1.23; 0.97-1.53). Stomach cancer mortality in the regions with contaminated water was more substantially elevated in comparison with the regions without contaminated water (1.82; 1.11-2.91) and the whole province (1.69; 1.12-2.44). Lung cancer mortality was slightly elevated in comparison with the unexposed study regions (1.15; 0.62-2.07), and more strongly elevated in comparison with the whole province (1.78; 1.03-2.87). Mortality from other cancers combined was not elevated in comparison with either the unexposed study regions (0.86; 0.53-1.36) or the whole province (0.92; 0.58-1.38). CONCLUSIONS: While these data are limited, they are consistent with increased stomach cancer risk in a population exposed to Cr in drinking water. ?? 2008 Lippincott Williams & Wilkins, Inc.

  4. Equilibrium and kinetics study on hexavalent chromium adsorption onto diethylene triamine grafted glycidyl methacrylate based copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Maksin, Danijela D., E-mail: dmaksin@vinca.rs [University of Belgrade, Vinca Institute of Nuclear Sciences, P.O. Box 522, Belgrade (Serbia); Nastasovic, Aleksandra B., E-mail: anastaso@chem.bg.ac.rs [University of Belgrade, Institute of Chemistry, Technology and Metallurgy, Njegoseva 12, Belgrade (Serbia); Milutinovic-Nikolic, Aleksandra D., E-mail: snikolic@nanosys.ihtm.bg.ac.rs [University of Belgrade, Institute of Chemistry, Technology and Metallurgy, Njegoseva 12, Belgrade (Serbia); Surucic, Ljiljana T., E-mail: ljilja_m@yahoo.com [University of Belgrade, Faculty of Forestry, Kneza Viseslava 1, Belgrade (Serbia); Sandic, Zvjezdana P., E-mail: zvjezdana.sandic@gmail.com [Faculty of Science, Mladena Stojanovica 2, Banja Luka, Bosnia and Herzegovina (Bosnia and Herzegowina); Hercigonja, Radmila V., E-mail: radah@ffh.bg.ac.rs [University of Belgrade, Faculty of Physical Chemistry, Studentski trg 12-16, 11001 Belgrade (Serbia); Onjia, Antonije E., E-mail: onjia@vinca.rs [University of Belgrade, Vinca Institute of Nuclear Sciences, P.O. Box 522, Belgrade (Serbia)

    2012-03-30

    Highlights: Black-Right-Pointing-Pointer Methacrylate based copolymers grafted with diethylene triamine as Cr(VI) sorbents. Black-Right-Pointing-Pointer Chemisorption and pore diffusion are characteristics of this sorption system. Black-Right-Pointing-Pointer Langmuir isotherm provided best fit and maximum adsorption capacity was 143 mg g{sup -1}. Black-Right-Pointing-Pointer Cr(VI) sorption onto amino-functionalized copolymer was endothermic and spontaneous. Black-Right-Pointing-Pointer A simple, efficient and cost-effective hexavalent chromium removal method. - Abstract: Two porous and one non-porous crosslinked poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) [abbreviated PGME] were prepared by suspension copolymerization and functionalized with diethylene triamine [abbreviated PGME-deta]. Samples were characterized by elemental analysis, mercury porosimetry, scanning electron microscopy with energy-dispersive X-ray spectroscopy, and transmission electron microscopy. Kinetics of Cr(VI) sorption by PGME-deta were investigated in batch static experiments, in the temperature range 25-70 Degree-Sign C. Sorption was rapid, with the uptake capacity higher than 80% after 30 min. Sorption behavior and rate-controlling mechanisms were analyzed using five kinetic models (pseudo-first order, pseudo-second order, Elovich, intraparticle diffusion and Bangham model). Kinetic studies showed that Cr(VI) adsorption adhered to the pseudo-second-order model, with definite influence of pore diffusion. Equilibrium data was tested with Langmuir, Freundlich and Tempkin adsorption isotherm models. Langmuir model was the most suitable indicating homogeneous distribution of active sites on PGME-deta and monolayer sorption. The maximum adsorption capacity from the Langmuir model, Q{sub max}, at pH 1.8 and 25 Degree-Sign C was 143 mg g{sup -1} for PGME2-deta (sample with the highest amino group concentration) while at 70 Degree-Sign C Q{sub max} reached the high value of 198

  5. Modeling hexavalent chromium reduction in groundwater in field-scale transport and laboratory batch experiments

    Science.gov (United States)

    Friedly, J.C.; Davis, J.A.; Kent, D.B.

    1995-01-01

    A plausible and consistent model is developed to obtain a quantitative description of the gradual disappearance of hexavalent chromium (Cr(VI)) from groundwater in a small-scale field tracer test and in batch kinetic experiments using aquifer sediments under similar chemical conditions. The data exhibit three distinct timescales. Fast reduction occurs in well-stirred batch reactors in times much less than 1 hour and is followed by slow reduction over a timescale of the order of 2 days. In the field, reduction occurs on a timescale of the order of 8 days. The model is based on the following hypotheses. The chemical reduction reaction occurs very fast, and the longer timescales are caused by diffusion resistance. Diffusion into the secondary porosity of grains causes the apparent slow reduction rate in batch experiments. In the model of the field experiments, the reducing agent, heavy Fe(II)-bearing minerals, is heterogeneously distributed in thin strata located between larger nonreducing sand lenses that comprise the bulk of the aquifer solids. It is found that reducing strata of the order of centimeters thick are sufficient to contribute enough diffusion resistance to cause the observed longest timescale in the field. A one-dimensional advection/dispersion model is formulated that describes the major experimental trends. Diffusion rates are estimated in terms of an elementary physical picture of flow through a stratified medium containing identically sized spherical grains. Both reduction and sorption reactions are included. Batch simulation results are sensitive to the fraction of reductant located at or near the surface of grains, which controls the amount of rapid reduction, and the secondary porosity, which controls the rate of slow reduction observed in batch experiments. Results of Cr(VI) transport simulations are sensitive to the thickness and relative size of the reducing stratum. Transport simulation results suggest that nearly all of the reductant must be

  6. Epoxide hydrolase-catalyzed enantioselective conversion of trans-stilbene oxide: Insights into the reaction mechanism from steady-state and pre-steady-state enzyme kinetics.

    Science.gov (United States)

    Archelas, Alain; Zhao, Wei; Faure, Bruno; Iacazio, Gilles; Kotik, Michael

    2016-02-01

    A detailed kinetic study based on steady-state and pre-steady-state measurements is described for the highly enantioselective epoxide hydrolase Kau2. The enzyme, which is a member of the α/β-hydrolase fold family, preferentially reacts with the (S,S)-enantiomer of trans-stilbene oxide (TSO) with an E value of ∼200. The enzyme follows a classical two-step catalytic mechanism with formation of an alkyl-enzyme intermediate in the first step and hydrolysis of this intermediate in a rate-limiting second step. Tryptophan fluorescence quenching during TSO conversion appears to correlate with alkylation of the enzyme. The steady-state data are consistent with (S,S) and (R,R)-TSO being two competing substrates with marked differences in k(cat) and K(M) values. The high enantiopreference of the epoxide hydrolase is best explained by pronounced differences in the second-order alkylation rate constant (k2/K(S)) and the alkyl-enzyme hydrolysis rate k3 between the (S,S) and (R,R)-enantiomers of TSO. Our data suggest that during conversion of (S,S)-TSO the two active site tyrosines, Tyr(157) and Tyr(259), serve mainly as electrophilic catalysts in the alkylation half-reaction, polarizing the oxirane oxygen of the bound epoxide through hydrogen bond formation, however, without fully donating their hydrogens to the forming alkyl-enzyme intermediate.

  7. Breakdown of Clays by Ectomycorrhizal Fungi Through Changes in Oxidation State of Iron

    Science.gov (United States)

    Arocena, J. M.; Velde, B.

    2012-04-01

    Organisms are known to play a significant role in the transformation of clay minerals in soils. In our earlier work on canola, barley and alfalfa, we reported that Glomus, an arbuscular mycorrhizae, selectively transformed biotite into 2:1 expanding clays through the oxidation of Fe (II) in biotite to Fe(III). In this presentation, we will share similar results on clay transformations mediated by ectomycorrhizal fungi colonizing the roots of coniferous trees. Clay samples were isolated from rhizosphere soils of sub-alpine fir (Abies lasiocarpa (Hook.) Nutt.) in northern British Columbia (Canada). Chemical and mineralogical properties of these soils had been reported in our earlier paper. In this study, we subjected the clay samples to iron X-ray Absorption Near Edge Spectroscopy (Fe-XANES) at the Canadian Light Source synchrotron facility in Saskatoon (Canada). Our initial results showed relatively higher amounts of Fe (III) than Fe(II) in clays collected from rhizosphere of Piloderma (an ectomycorrhizal fungus) compared to soils influenced by non-Piloderma species and Control (non-rhizosphere soil). Coupled with the results of X-ray diffraction (XRD) analysis, there seems to be a positive relationship between the relative amounts of Fe(III) and the 2:1 expanding clays. This relationship is consistent with our results on agricultural plants in laboratory experiments on biotites where we suggested that oxidation of Fe(II) to Fe(III) results in the formation of 2:1 expanding clays. In a related data set on chlorite alteration we observed that after dithionite-citrate-bicarbonate (DCB) treatment, the d-spacing of a slight portion of chloritic expanding clays shifted to higher angles indicating decreased d-spacing towards micaceous clays. The reductive process initiated through the action of the DCB treatment seems to indicate the collapsed of expandable clays upon the reduction of Fe(III) to Fe(II). Initial results from the Fe-XANES and XRD analysis of DCB

  8. Microwave-assisted solid-state synthesis of oxide ion conducting stabilized bismuth vanadate phases

    Energy Technology Data Exchange (ETDEWEB)

    Vaidhyanathan, B.; Balaji, K.; Rao, K.J. [Indian Inst. of Science, Bangalore (India). Solid State and Structural Chemistry Unit

    1998-11-01

    A microwave-assisted method for the preparation of substituted bismuth vanadates has been described. The method consists of starting with the respective oxides mixed in stoichiometric proportions and exposing the mixture to microwaves. Substitution takes place at the vanadium sites and it has been possible to prepare Ag{sup +}-, Mn{sup 4+}-, Ga{sup 3+}-, Y{sup 3+}-, and Ce{sup 4+}-substituted compounds with up to 10% substitution. Mn{sup 4+}- and Ag{sup +}-substituted compounds are found to exhibit better oxygen ion conductivities than any reported so far in the literature.

  9. Amnion-Epithelial-Cell-Derived Exosomes Demonstrate Physiologic State of Cell under Oxidative Stress.

    Directory of Open Access Journals (Sweden)

    Samantha Sheller

    Full Text Available At term, the signals of fetal maturity and feto-placental tissue aging prompt uterine readiness for delivery by transitioning quiescent myometrium to an active stage. It is still unclear how the signals reach the distant myometrium. Exosomes are a specific type of extracellular vesicle (EVs that transport molecular signals between cells, and are released from a wide range of cells, including the maternal and fetal cells. In this study, we hypothesize that i exosomes act as carriers of signals in utero-placental compartments and ii exosomes reflect the physiologic status of the origin cells. The primary aims of this study were to determine exosomal contents in exosomes derived from primary amnion epithelial cells (AEC. We also determined the effect of oxidative stress on AEC derived exosomal cargo contents. AEC were isolated from amniotic membrane obtained from normal, term, not in labor placentae at delivery, and culture under standard conditions. Oxidative stress was induced using cigarette smoke extract for 48 hours. AEC-conditioned media were collected and exosomes isolated by differential centrifugations. Both growth conditions (normal and oxidative stress induced produced cup shaped exosomes of around 50 nm, expressed exosomes enriched markers, such as CD9, CD63, CD81 and HSC70, embryonic stem cell marker Nanog, and contained similar amounts of cell free AEC DNA. Using confocal microscopy, the colocalization of histone (H 3, heat shock protein (HSP 70 and activated form of pro-senescence and term parturition associated marker p38 mitogen activated protein kinase (MAPK (P-p38 MAPK co-localized with exosome enrich marker CD9. HSP70 and P-p38 MAPK were significantly higher in exosomes from AEC grown under oxidative stress conditions than standard conditions (p<0.05. Finally, mass spectrometry and bioinformatics analysis identified 221 different proteins involved in immunomodulatory response and cell-to-cell communication. This study determined

  10. Change in metallothionein phosphorylation state in Mya arenaria clams: implication in metal metabolism and oxidative stress

    OpenAIRE

    Gagné, F.; M Gélinas; Gagnon, C.; André, C.; C Blaise

    2010-01-01

    The contamination of the benthic environment poses a threat to long-lived sessile organisms such as clams. The purpose of this study was to investigate metal contamination in tissues and changes in metallothioneins (MT) in respect to its redox status in Mya arenaria clams collected at three polluted sites. The phosphorylation state of MT was also investigated to determine whether this state is changed in clams collected at heavy-metal contaminated site and its involvement in cytoprotective si...

  11. Incoherent vs. coherent behavior in the normal state of copper oxide superconductors

    Science.gov (United States)

    Tesanovic, Zlatko

    1991-01-01

    The self-consistent quantum fluctuations around the mean-field Hartree-Fock state of the Hubbard model provide a very good description of the ground state and low temperature properties of a 2-D itinerant antiferromagnet. Very good agreement with numerical calculations and experimental data is obtained by including the one- and two-loop spin wave corrections to various physical quantities. In particular, the destruction of the long-range order above the Neel temperature can be understood as a spontaneous generation of a length-scale epsilon(T), which should be identified as the spin correlation length. For finite doping, the question of the Hartree-Fock starting point becomes a more complex one since an extra hole tends to self-trap in antiferromagnetic background. Such quantum defects in an underlying antiferromagnetic state can be spin-bags or vortex-like structures and tend to suppress the long-range order. If motion of the holes occurs on a time-scale shorter than the one associated with the motion of these quantum defects of a spin background, one obtains several important empirical features of the normal state of CuO superconductors like linear T-dependence of resistivity, the cusp in the tunneling density of states, etc. As opposed to a familiar Fermi-liquid behavior, the phenomenology of the above system is dominated by a large incoherent piece of a single hole propagator, resulting in many unusual normal state properties.

  12. Shifting redox states of the iron center partitions CDO between crosslink formation or cysteine oxidation.

    Science.gov (United States)

    Njeri, Catherine W; Ellis, Holly R

    2014-09-15

    Cysteine dioxygenase (CDO) is a mononuclear iron-dependent enzyme that catalyzes the oxidation of L-cysteine to L-cysteine sulfinic acid. The mammalian CDO enzymes contain a thioether crosslink between Cys93 and Tyr157, and purified recombinant CDO exists as a mixture of the crosslinked and non crosslinked isoforms. The current study presents a method of expressing homogenously non crosslinked CDO using a cell permeative metal chelator in order to provide a comprehensive investigation of the non crosslinked and crosslinked isoforms. Electron paramagnetic resonance analysis of purified non crosslinked CDO revealed that the iron was in the EPR silent Fe(II) form. Activity of non crosslinked CDO monitoring dioxygen utilization showed a distinct lag phase, which correlated with crosslink formation. Generation of homogenously crosslinked CDO resulted in an ∼5-fold higher kcat/Km value compared to the enzyme with a heterogenous mixture of crosslinked and non crosslinked CDO isoforms. EPR analysis of homogenously crosslinked CDO revealed that this isoform exists in the Fe(III) form. These studies present a new perspective on the redox properties of the active site iron and demonstrate that a redox switch commits CDO towards either formation of the Cys93-Tyr157 crosslink or oxidation of the cysteine substrate.

  13. Setting the stage for electron transfer: Molecular basis of ABTS-binding to four laccases from Trametes versicolor at variable pH and protein oxidation state

    DEFF Research Database (Denmark)

    Christensen, Niels Johan; Kepp, Kasper Planeta

    2014-01-01

    functional theory calculations, homology modeling, and multiple induced-fit docking protocols at variable pH-dependent protonation states and T1-copper oxidation state. Clustering analysis provided a systematic overview of laccases across Trametes and revealed distinct isoenzyme classes (A–J) with the four T...... docking to reduce inactive false positives....

  14. Near-exact enthalpy-entropy compensation governs the thermal unfolding of protonation states of oxidized cytochrome c.

    Science.gov (United States)

    Soffer, Jonathan B; Schweitzer-Stenner, Reinhard

    2014-10-01

    This paper reports the first quantitative analysis of the thermal transitions of all protonation states of oxidized horse heart cytochrome c at low anion concentration. Changes of secondary and tertiary structure were probed by ultraviolet (UV) as well as visible circular dichroism and absorption spectroscopy, respectively. The temperature dependence of spectra were recorded at pH values assignable to a set of different protonation states which encompass the canonical Theorell-Åkesson states and the recently discovered III* state. Our experimental data suggest a two-step process of thermal unfolding for all protonation states. The respective thermodynamic parameters were obtained from a global analysis of the temperature dependence of corresponding visible circular dichroism (CD) and absorption spectra. The results of this analysis revealed a statistically significant enthalpy-entropy compensation with different apparent compensation temperatures for the two consecutive thermal transitions (319 and 357 K). This reflects the narrow distribution of the respective folding temperatures. UVCD spectra suggest that even the thermal transitions of protonation states occupied at acidic and alkaline pH cause only a very modest unfolding of the protein's helical structure. Our data indicate the protonation-induced unfolding at room temperatures predominantly affects the Ω-loops of the protein. The two thermal transitions involve changes of two foldons, i.e. the unfolding of two short β-strand segments (associated with the yellow foldon) followed by the unfolding of the 60' helix (green foldon) that connects the two Ω-loops of the protein. Apparently, intra-backbone hydrogen bonding is strong enough to mostly protect the terminal N- and C-helices from unfolding even at rather extreme conditions.

  15. Bradykinin inhibits oxidative stress-induced cardiomyocytes senescence via regulating redox state.

    Directory of Open Access Journals (Sweden)

    Ruolan Dong

    Full Text Available BACKGROUND: Cell senescence is central to a large body of age related pathology, and accordingly, cardiomyocytes senescence is involved in many age related cardiovascular diseases. In consideration of that, delaying cardiomyocytes senescence is of great importance to control clinical cardiovascular diseases. Previous study indicated that bradykinin (BK protected endothelial cells from senescence induced by oxidative stress. However, the effects of bradykinin on cardiomyocytes senescence remain to be elucidated. In this study, we investigated the effect of bradykinin on H2O2-induced H9C2 cells senescence. METHODS AND RESULTS: Bradykinin pretreatment decreased the senescence induced by H2O2 in cultured H9C2 cells in a dose dependent manner. Interestingly, 1 nmol/L of BK almost completely inhibited the increase in senescent cell number and p21 expression induced by H2O2. Since H2O2 induces senescence through superoxide-induced DNA damage, we also observed the DNA damage by comet assay, and BK markedly reduced DNA damage induced by H2O2, and moreover, BK treatment significantly prevented reactive oxygen species (ROS production in H9C2 cells treated with H2O2. Importantly, when co-incubated with bradykinin B2 receptor antagonist HOE-140 or eNOS inhibitor N-methyl-L-arginine acetate salt (L-NAME, the protective effects of bradykinin on H9C2 senescence were totally blocked. Furthermore, BK administration significantly prevented the increase in nicotinamide adenine dinucleotide phosphate (NADPH oxidase activity characterized by increased ROS generation and gp91 expression and increased translocation of p47 and p67 to the membrane and the decrease in superoxide dismutase (SOD activity and expression induced by H2O2 in H9C2 cells, which was dependent on BK B2 receptor mediated nitric oxide (NO release. CONCLUSIONS: Bradykinin, acting through BK B2 receptor induced NO release, upregulated antioxidant Cu/Zn-SOD and Mn-SOD activity and expression while

  16. Low-temperature solid-state microwave reduction of graphene oxide for transparent electrically conductive coatings on flexible polydimethylsiloxane (PDMS).

    Science.gov (United States)

    Liang, Qizhen; Hsie, Sinsar Alec; Wong, Ching Ping

    2012-11-12

    Microwaves (MWs) are applied to initialize deoxygenation of graphene oxide (GO) in the solid state and at low temperatures (∼165 °C). The Fourier-transform infrared (FTIR) spectra of MW-reduced graphene oxide (rGO) show a significantly reduced concentration of oxygen-containing functional groups, such as carboxyl, hydroxyl and carbonyl. X-ray photoelectron spectra confirm that microwaves can promote deoxygenation of GO at relatively low temperatures. Raman spectra and TGA measurements indicate that the defect level of GO significantly decreases during the isothermal solid-state MW-reduction process at low temperatures, corresponding to an efficient recovery of the fine graphene lattice structure. Based on both deoxygenation and defect-level reduction, the resurgence of interconnected graphene-like domains contributes to a low sheet resistance (∼7.9×10(4) Ω per square) of the MW-reduced GO on SiO(2) -coated Si substrates with an optical transparency of 92.7 % at ∼547 nm after MW reduction, indicating the ultrahigh efficiency of MW in GO reduction. Moreover, the low-temperature solid-state MW reduction is also applied in preparing flexible transparent conductive coatings on polydimethylsiloxane (PDMS) substrates. UV/Vis measurements indicate that the transparency of the thus-prepared MW-reduced GO coatings on PDMS substrates ranges from 34 to 96 %. Correspondingly, the sheet resistance of the coating ranges from 10(5) to 10(9) Ω per square, indicating that MW reduction of GO is promising for the convenient low-temperature preparation of transparent conductors on flexible polymeric substrates.

  17. Anomalous spin state of Fe in double perovskite oxide Sr 2FeWO 6

    Science.gov (United States)

    Kawanaka, H.; Hase, I.; Toyama, S.; Nishihara, Y.

    2000-07-01

    In the series of Sr 2FeTO 6 (T=4d or 5d), the valence of Fe is 3+ in most of the compounds. However, recently we have found that the Sr 2FeWO 6 has Fe 2+ state. Sr 2FeWO 6 is an insulator with an antiferromagnetic transition temperature of 37 K. From the Mössbauer experiment, below ∼20 K, a center shift of +1.2 mm/ s relative to metallic iron and a quadrupole splitting of 1.9 mm/ s are obtained. The quadrupole splitting has strong temperature dependence. The hyperfine field is ∼110 kOe which seems to be quite small. We concluded that the iron ground state of Sr 2FeWO 6 is Fe 2+ high-spin ( S=2) state.

  18. A novel solid-state thermal rectifier based on reduced graphene oxide.

    Science.gov (United States)

    Tian, He; Xie, Dan; Yang, Yi; Ren, Tian-Ling; Zhang, Gang; Wang, Yu-Feng; Zhou, Chang-Jian; Peng, Ping-Gang; Wang, Li-Gang; Liu, Li-Tian

    2012-01-01

    Recently, manipulating heat transport by phononic devices has received significant attention, in which phonon--a heat pulse through lattice, is used to carry energy. In addition to heat control, the thermal devices might also have broad applications in the renewable energy engineering, such as thermoelectric energy harvesting. Elementary phononic devices such as diode, transistor and logic devices have been theoretically proposed. In this work, we experimentally create a macroscopic scale thermal rectifier based on reduced graphene oxide. Obvious thermal rectification ratio up to 1.21 under 12 K temperature bias has been observed. Moreover, this ratio can be enhanced further by increasing the asymmetric ratio. Collectively, our results raise the exciting prospect that the realization of macroscopic phononic device with large-area graphene based materials is technologically feasible, which may open up important applications in thermal circuits and thermal management.

  19. Early single cell bifurcation of pro- and antiapoptotic states during oxidative stress.

    Science.gov (United States)

    Nair, Venugopalan D; Yuen, Tony; Olanow, C Warren; Sealfon, Stuart C

    2004-06-25

    In a population of cells undergoing oxidative stress, an individual cell either succumbs to apoptotic cell death or maintains homeostasis and survives. Exposure of PC-12-D(2)R cells to 200 microm hydrogen peroxide (H(2)O(2)) induces apoptosis in about half of cells after 24 h. After 1-h exposure to 200 microm H(2)O(2), both antiapoptotic extracellular regulated kinase (ERK) phosphorylation and pro-apoptotic Ser-15-p53 phosphorylation are observed. Microarray and real-time PCR assays of gene expression after H(2)O(2) exposure identified several transcripts, including egr1, that are rapidly induced downstream of ERK. Single cell analysis of egr1 induction and of phospho-ERK and phospho-p53 formation revealed the presence of two distinct cellular programs. Whereas the proportion of cells activating ERK versus p53 at 1 h depended on H(2)O(2) concentration, individual cells showed exclusively either phospho-p53 formation or activation of ERK and egr1 induction. Exposure to H(2)O(2) for 1 h also elicited these two non-overlapping cellular responses in both dopaminergic SN4741 cells and differentiated postmitotic PC-12-D(2)R cells. Repressing p53 with pifithrin-alpha or small interfering RNA increased ERK phosphorylation by H(2)O(2), indicating that p53-dependent suppression of ERK activity may contribute to the bi-stable single cell responses observed. By 24 h, the subset of cells in which ERK activity was suppressed exhibit caspase 3 activation and the nuclear condensation characteristic of apoptosis. These studies suggest that the individual cell rapidly and stochastically processes the oxidative stress stimulus, leading to an all-or-none cytoprotective or pro-apoptotic signaling response.

  20. Were ancient granitoid compositions influenced by contemporaneous atmospheric and hydrosphere oxidation states?

    Science.gov (United States)

    Jagoutz, O. E.

    2013-12-01

    A fundamental shift in the nature of granitoids occurs at approximately the Archean-Proterozoic boundary. Archean crust is dominated Na-rich tonalite-trondhjemite-granodiorites (TTGs), whereas post-Archean granitoids are characterized by K-rich granodiorite-granite (GG). Due to the HREE depletion commonly found in TTGs indicating the presence of residual garnet, many researchers have proposed that the difference in Na/K is related to the deeper melting depth of the TTG parental liquids. Here I present a compilation of the relevant experimental data, documenting that no correlation exists between the Na/K of derivative felsic liquids and the pressure of partial melting/fractional crystallization. Instead, the Na/K ratio of the felsic liquid best correlates with the Na/K ratio of the source. This implies that in Archean time the source material of TTG rocks must have been Na/K enriched relative to the modern. Modern granitoids are dominantly formed in a supra subduction zone environment, where a feedback loop exists between subducted materials (oceanic crust and sediments) and arc magmatism. Sea-floor weathering and the Na/K of the altered oceanic crust strongly depends on f(O2) conditions during alteration, which likely changed with earth history. During alteration under oxidized condition K2O is fixated due to the formation of celadonite (K-Mica), wheres during anoxic condition saponite (Na-Smectite) is the stable alteration mineral. I propose that the rise of oxygen at 2600-2400 Ma triggered associated changes in f(O2) seafloor alteration conditions. The change in the dominant seafloor alteration mineral from reduced to oxidized causes a change in the nature of the arc magma source and provides a possible explanation for the observed transition from TTGrocks in the Archean to the GG-granitoids in post-Archean times.

  1. Spiral spin state in high-temperature copper-oxide superconductors: Evidence from neutron scattering measurements

    DEFF Research Database (Denmark)

    Lindgård, Per-Anker

    2005-01-01

    An effective spiral spin phase ground state provides a new paradigm for the high-temperature superconducting cuprates. It accounts for the recent neutron scattering observations of spin excitations regarding both the energy dispersion and the intensities, including the "universal" rotation by 45...

  2. Manipulation of oxidative protein folding and PDI redox state in mammalian cells

    NARCIS (Netherlands)

    Braakman, L.J.; Mezghrani, A.; Fassio, A.; Benham, A.; Simmen, T.; Sitia, R.

    2001-01-01

    In the endoplasmic reticulum (ER), disulfide bonds are simultaneously formed in nascent proteins and removed from incorrectly folded or assembled molecules. In this compartment, the redox state must be, therefore, precisely regulated. Here we show that both human Ero1-L and Ero1-L (hEROs) facilitate

  3. SURFACE AND LIGHTNING SOURCES OF NITROGEN OXIDES OVER THE UNITED STATES: MAGNITUDES, CHEMICAL EVOLUTION, AND OUTFLOW

    Science.gov (United States)

    We use observations from two aircraft during the ICARTT campaign over the eastern United States and North Atlantic during summer 2004, interpreted with a global 3-D model of tropospheric chemistry (GEOS-Chem) to test current understanding of regional sources, chemical evolution...

  4. Fat oxidation before and after a high fat load in the obese insulin-resistant state

    NARCIS (Netherlands)

    Blaak, E.E.; Hul, G.; Verdich, C.; Stich, V.; Martinez, A.; Petersen, M.; Feskens, E.J.M.; Patel, K.; Oppert, J.M.; Barbe, P.; Toubro, S.; Anderson, I.; Polak, J.; Astrup, A.; Macdonald, I.A.; Holst, C.; Sørensen, T.I.; Saris, W.H.

    2006-01-01

    Background: Obesity may be associated with a lowered use of fat as a fuel, which may contribute to the enlarged adipose tissue stores. Aim: The aim of the present study was to study fatty acid use in the fasting state and in response to a high fat load in a large cohort of obese subjects (n = 701) a

  5. SURFACE AND LIGHTNING SOURCES OF NITROGEN OXIDES OVER THE UNITED STATES: MAGNITUDES, CHEMICAL EVOLUTION, AND OUTFLOW

    Science.gov (United States)

    We use observations from two aircraft during the ICARTT campaign over the eastern United States and North Atlantic during summer 2004, interpreted with a global 3-D model of tropospheric chemistry (GEOS-Chem) to test current understanding of regional sources, chemical evolution...

  6. Fat oxidation before and after a high fat load in the obese insulin-resistant state

    NARCIS (Netherlands)

    Blaak, E.E.; Hul, G.; Verdich, C.; Stich, V.; Martinez, A.; Petersen, M.; Feskens, E.J.M.; Patel, K.; Oppert, J.M.; Barbe, P.; Toubro, S.; Anderson, I.; Polak, J.; Astrup, A.; Macdonald, I.A.; Holst, C.; Sørensen, T.I.; Saris, W.H.

    2006-01-01

    Background: Obesity may be associated with a lowered use of fat as a fuel, which may contribute to the enlarged adipose tissue stores. Aim: The aim of the present study was to study fatty acid use in the fasting state and in response to a high fat load in a large cohort of obese subjects (n = 701)

  7. Oxidation state of the Earth's upper mantle during the last 3800 million years: Implications for the origin of life

    Science.gov (United States)

    Delano, J. W.

    1993-01-01

    A popular, as well as scientifically rigorous, scenario for the origin of life on Earth involves the production of organic molecules by interaction of lightning (or other forms of energy) with a chemically reducing atmosphere in the early history of Earth. Experiments since the 1950's have convincingly demonstrated that the yield of organic molecules is high when the atmosphere contains molecular hydrogen, methane, ammonia, and water vapor. Additional work has also shown that such a highly reducing atmosphere might not, however, have been sufficiently long-lived in the presence of intense solar ultraviolet radiation for life to have formed from it. One way of maintaining such an atmosphere would be to have a continual replenishment of the reduced gases by prolonged volcanic outgassing from a reducing of Earth's interior. The length of time that this replenishment might need to continue is in part constrained by the flux of asteroids onto the Earth's surface containing sufficient energy to destroy most, if not all, life that had developed up to that point in time. If a reducing atmosphere is a key ingredient for the origin of life on Earth, the time of the last environmental sterilization due to large impacts would be an important constraint. In a deep marine setting (e.g., hydrothermal vent), the last global sterilization might have occurred at 4200-4000 Ma. On the Earth's surface, the last global sterilization event might have occurred at 4000-3700 Ma. If these are meaningful constraints, how likely is it that a reducing atmosphere could have survived on the Earth until about 3800 Ma ago? Due to the importance of replenishing this atmosphere with reducing components by volcanic outgassing from the mantle, geochemical information on the history of the mantle's oxidation state would be useful for addressing this question. Geochemical and experimental data discussed in this abstract suggest that extrusive mafic volcanics derived from the upper mantle have had

  8. Mixed-valent metals bridged by a radical ligand: fact or fiction based on structure-oxidation state correlations.

    Science.gov (United States)

    Sarkar, Biprajit; Patra, Srikanta; Fiedler, Jan; Sunoj, Raghavan B; Janardanan, Deepa; Lahiri, Goutam Kumar; Kaim, Wolfgang

    2008-03-19

    Electron-rich Ru(acac)2 (acac- = 2,4-pentanedionato) binds to the pi electron-deficient bis-chelate ligands L, L = 2,2'-azobispyridine (abpy) or azobis(5-chloropyrimidine) (abcp), with considerable transfer of negative charge. The compounds studied, (abpy)Ru(acac)2 (1), meso-(mu-abpy)[Ru(acac)2]2 (2), rac-(mu-abpy)[Ru(acac)2]2 (3), and (mu-abcp)[Ru(acac)2]2 (4), were calculated by DFT to assess the degree of this metal-to-ligand electron shift. The calculated and experimental structures of 2 and 3 both yield about 1.35 A for the length of the central N-N bond which suggests a monoanion character of the bridging ligand. The NBO analysis confirms this interpretation, and TD-DFT calculations reproduce the observed intense long-wavelength absorptions. While mononuclear 1 is calculated with a lower net ruthenium-to-abpy charge shift as illustrated by the computed 1.30 A for d(N-N), compound 4 with the stronger pi accepting abcp bridge is calculated with a slightly lengthened N-N distance relative to that of 2. The formulation of the dinuclear systems with monoanionic bridging ligands implies an obviously valence-averaged Ru(III)Ru(II) mixed-valent state for the neutral molecules. Mixed valency in conjunction with an anion radical bridging ligand had been discussed before in the discussion of MLCT excited states of symmetrically dinuclear coordination compounds. Whereas 1 still exhibits a conventional electrochemical and spectroelectrochemical behavior with metal centered oxidation and two ligand-based one-electron reduction waves, the two one-electron oxidation and two one-electron reduction processes for each of the dinuclear compounds Ru2.5(L*-)Ru2.5 reveal more unusual features via EPR and UV-vis-NIR spectroelectrochemistry. In spite of intense near-infrared absorptions, the EPR results show that the first reduction leads to Ru(II)(L*-)Ru(II) species, with an increased metal contribution for system 4*-. The second reduction to Ru(II)(L2-)Ru(II) causes the

  9. Diversity of Chemical Bonding and Oxidation States in MS 4 Molecules of Group 8 Elements

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Wei [Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Tsinghua University, Beijing 100084 P.R. China; Jiang, Ning [Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Tsinghua University, Beijing 100084 P.R. China; Schwarz, W. H. Eugen [Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Tsinghua University, Beijing 100084 P.R. China; Physical and Theoretical Chemistry, University of Siegen, Siegen 57068 Germany; Yang, Ping [Theoretical Division, Los Alamos National Laboratory, Los Alamos New Mexico 87545 USA; Environmental Molecular Science Laboratory, Pacific Northwest National Laboratory, Richland Washington 953002 USA; Li, Jun [Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Tsinghua University, Beijing 100084 P.R. China; Environmental Molecular Science Laboratory, Pacific Northwest National Laboratory, Richland Washington 953002 USA

    2017-07-11

    The geometric and electronic ground-state structures of six MS4 molecules (M = group-8 metals Fe, Ru, Os, Hs, Sm, and Pu) have been studied by using quantum-chemical density-functional and correlated wave-function approaches. The MS4 species are compared to analogous MO4 species recently investi-gated (Inorg. Chem. 2016, 55: 4616). Metal oxidation state (MOS) of high value VIII appears in low- spin singlet Td geometric species (Os,Hs)S4 and (Ru,Os,Hs)O4, whereas low MOS=II appears in high- spin septet D2d species Fe(S2)2 and (slightly excited) metastable Fe(O2)2. The ground states of all other molecules have intermediate MOS values, containing S2-, S22-, S21- (and resp. O2--, O1-, O22-, O21-) ligands, bonded by ionic, covalent and correlative contributions.

  10. Electronic Structure and Excited-State Dynamics of an Arduengo-Type Carbene and its Imidazolone Oxidation Product.

    Science.gov (United States)

    Schmitt, Hans-Christian; Flock, Marco; Welz, Eileen; Engels, Bernd; Schneider, Heidi; Radius, Udo; Fischer, Ingo

    2017-03-02

    We describe an investigation of the excited-state dynamics of isolated 1,3-di-tert-butyl-imidazoline-2-ylidene (tBu2 Im, C11 H20 N2 , m/z=180), an Arduengo-type carbene, by time- and frequency-resolved photoionization using a picosecond laser system. The energies of several singlet and triplet excited states were calculated by time-dependent density functional theory (TD-DFT). The S1 state of the carbene deactivates on a 100 ps time scale possibly by intersystem crossing. In the experiments we observed an additional signal at m/z=196, that was assigned to the oxidation product 1,3-di-tert-butyl-imidazolone, tBu2 ImO. It shows a well-resolved resonance-enhanced multiphoton ionization (REMPI) spectrum with an origin located at 36951 cm(-1) . Several low-lying vibrational bands could be assigned, with a lifetime that depends strongly on the excitation energy. At the origin the lifetime is longer than 3 ns, but drops to 49 ps at higher excess energies. To confirm formation of the imidazolone we also performed experiments on benzimidazolone (BzImO) for comparison. Apart from a redshift for BzImO the spectra of the two compounds are very similar. The TD-DFT values display a very good agreement with the experimental data.

  11. Solid-state charge-based device for control of catalytic carbon monoxide oxidation on platinum nanofilms using external bias and light.

    Science.gov (United States)

    Baker, L Robert; Hervier, Antoine; Kennedy, Griffin; Somorjai, Gabor A

    2012-05-09

    Using a Pt/Si catalytic nanodiode, we externally control the rate of CO oxidation on a Pt nanofilm. The catalytic reaction can be turned on and off by alternating between bias states of the device. Additionally, the reaction rate is sensitive to photocurrent induced by visible light. The effects of both bias and light show that negative charge on the Pt increases catalytic activity, while positive charge on the Pt decreases catalytic activity for CO oxidation.

  12. Synthesis, spectral characterization, structures, and oxidation state distributions in [(corrolato)Fe(III)(NO)](n) (n = 0, +1, -1) complexes.

    Science.gov (United States)

    Sinha, Woormileela; Deibel, Naina; Agarwala, Hemlata; Garai, Antara; Schweinfurth, David; Purohit, Chandra Shekhar; Lahiri, Goutam Kumar; Sarkar, Biprajit; Kar, Sanjib

    2014-02-03

    Two novel trans-A2B-corroles and three [(corrolato){FeNO}(6)] complexes have been prepared and characterized by various spectroscopic techniques. In the native state, all these [(corrolato){FeNO}(6)] species are diamagnetic and display "normal" chemical shifts in the (1)H NMR spectra. For two of the structurally characterized [(corrolato){FeNO}(6)] derivatives, the Fe-N-O bond angles are 175.0(4)° and 171.70(3)° (DFT: 179.94°), respectively, and are designated as linear nitrosyls. The Fe-N (NO) bond distances are 1.656(4) Å and 1.650(3) Å (DFT: 1.597 Å), which point toward a significant Fe(III) → NO back bonding. The NO bond lengths are 1.159(5) Å and 1.162(3) Å (DFT: 1.162 Å) and depict their elongated character. These structural data are typical for low-spin Fe(III). Electrochemical measurements show the presence of a one-electron oxidation and a one-electron reduction process for all the complexes. The one-electron oxidized species of a representative [(corrolato){FeNO}(6)] complex exhibits ligand to ligand charge transfer (LLCT) transitions (cor(π) → cor(π*)) at 399 and 637 nm, and the one-electron reduced species shows metal to ligand charge transfer (MLCT) transition (Fe(dπ) → cor(π*)) in the UV region at 330 nm. The shift of the νNO stretching frequency of a representative [(corrolato){FeNO}(6)] complex on one-electron oxidation occurs from 1782 cm(-1) to 1820 cm(-1), which corresponds to 38 cm(-1), and on one-electron reduction occurs from 1782 cm(-1) to 1605 cm(-1), which corresponds to 177 cm(-1). The X-band electron paramagnetic resonance (EPR) spectrum of one-electron oxidation at 295 K in CH2Cl2/0.1 M Bu4NPF6 displays an isotropic signal centered at g = 2.005 with a peak-to-peak separation of about 15 G. The in situ generated one-electron reduced species in CH2Cl2/0.1 M Bu4NPF6 at 295 K shows an isotropic signal centered at g = 2.029. The 99% contribution of corrole to the HOMO of native species indicates that oxidation occurs from

  13. Equation of state of aluminum-iron oxide-epoxy composite

    Science.gov (United States)

    Jordan, Jennifer L.; Ferranti, Louis; Austin, Ryan A.; Dick, Richard D.; Foley, Jason R.; Thadhani, Naresh N.; McDowell, David L.; Benson, David J.

    2007-05-01

    We report on the measurements of the shock equation of state (Hugoniot) of an Al/Fe2O3/epoxy composite, prepared by epoxy cast curing of powder mixtures. Explosive loading, with Baratol, trinitrotoluene (TNT), and Octol, was used for performing experiments at higher pressures, in which case shock velocities were measured in the samples and aluminum, copper, or polymethyl methacrylate (PMMA) donor material, using piezoelectric pins. The explosive loading of the metal donors (aluminum and copper) will be discussed. Gas gun experiments provide complementary lower pressure data in which piezoelectric polyvinylidene fluoride (PVDF) stress gauges were used to measure the input and propagated stress wave profiles in the sample and the corresponding shock propagation velocity. The results of the Hugoniot equation of state are compared with mesoscale finite-element simulations, which show good agreement.

  14. Ground-state diagrams for lattice-gas models of catalytic CO oxidation

    Directory of Open Access Journals (Sweden)

    I.S.Bzovska

    2007-01-01

    Full Text Available Based on simple lattice models of catalytic carbon dioxide synthesis from oxygen and carbon monoxide, phase diagrams are investigated at temperature T=0 by incorporating the nearest-neighbor interactions on a catalyst surface. The main types of ground-state phase diagrams of two lattice models are classified describing the cases of clean surface and surface containing impurities. Nonuniform phases are obtained and the conditions of their existence dependent on the interaction parameters are established.

  15. Pre-steady-state Kinetics Reveal the Substrate Specificity and Mechanism of Halide Oxidation of Truncated Human Peroxidasin 1*

    Science.gov (United States)

    Paumann-Page, Martina; Katz, Romy-Sophie; Bellei, Marzia; Schwartz, Irene; Edenhofer, Eva; Sevcnikar, Benjamin; Soudi, Monika

    2017-01-01

    Human peroxidasin 1 is a homotrimeric multidomain peroxidase that is secreted to the extracellular matrix. The heme enzyme was shown to release hypobromous acid that mediates the formation of specific covalent sulfilimine bonds to reinforce collagen IV in basement membranes. Maturation by proteolytic cleavage is known to activate the enzyme. Here, we present the first multimixing stopped-flow study on a fully functional truncated variant of human peroxidasin 1 comprising four immunoglobulin-like domains and the catalytically active peroxidase domain. The kinetic data unravel the so far unknown substrate specificity and mechanism of halide oxidation of human peroxidasin 1. The heme enzyme is shown to follow the halogenation cycle that is induced by the rapid H2O2-mediated oxidation of the ferric enzyme to the redox intermediate compound I. We demonstrate that chloride cannot act as a two-electron donor of compound I, whereas thiocyanate, iodide, and bromide efficiently restore the ferric resting state. We present all relevant apparent bimolecular rate constants, the spectral signatures of the redox intermediates, and the standard reduction potential of the Fe(III)/Fe(II) couple, and we demonstrate that the prosthetic heme group is post-translationally modified and cross-linked with the protein. These structural features provide the basis of human peroxidasin 1 to act as an effective generator of hypobromous acid, which mediates the formation of covalent cross-links in collagen IV. PMID:28154175

  16. Spectral changes of Atlantic salmon ( Salmo salar L.) muscle during cold storage as affected by the oxidation state of heme.

    Science.gov (United States)

    Sone, Izumi; Olsen, Ragnar L; Heia, Karsten

    2012-09-26

    The spectra of fresh salmon fillets change due to storage and packaging atmospheres. The aim of this study was to demonstrate the effects of heme oxidation states on spectral development in salmon fillets and to investigate the origin of a shoulder peak representing important spectral variations during storage. Hyperspectral images of fresh salmon fillets and mince with various water contents were collected during storage under different atmospheres. In addition, the absorption spectra of extracted salmon hemoglobin and its derivatives (methemoglobin and deoxyhemoglobin) were obtained. Air storage resulted in an increased similarity between spectra of methemoglobin and salmon fillets in principal component analysis. Results from the mince storage demonstrated that absorption features at the shoulder peak could be related to water content in the salmon muscle. This study established that the formation of oxidized heme is the primary source of spectral variations that occur during air storage of fresh salmon. Changes in the status of heme due to storage and packaging can influence the appearance of the underlying water absorption at the shoulder peak and create variations in the salmon spectra.

  17. Steady-state oxidation of cholesterol catalyzed by cholesterol oxidase in lipid bilayer membranes on platinum electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Bokoch, Michael P.; Devadoss, Anando; Palencsar, Mariela S.; Burgess, James D

    2004-08-09

    Cholesterol oxidase is immobilized in electrode-supported lipid bilayer membranes. Platinum electrodes are initially modified with a self-assembled monolayer of thiolipid. A vesicle fusion method is used to deposit an outer leaflet of phospholipids onto the thiolipid monolayer forming a thiolipid/lipid bilayer membrane on the electrode surface. Cholesterol oxidase spontaneously inserts into the electrode-supported lipid bilayer membrane from solution and is consequently immobilized to the electrode surface. Cholesterol partitions into the membrane from buffer solutions containing cyclodextrin. Cholesterol oxidase catalyzes the oxidation of cholesterol by molecular oxygen, forming hydrogen peroxide as a product. Amperometric detection of hydrogen peroxide for continuous solution flow experiments are presented, where flow was alternated between cholesterol solution and buffer containing no cholesterol. Steady-state anodic currents were observed during exposures of cholesterol solutions ranging in concentration from 10 to 1000 {mu}M. These data are consistent with the Michaelis-Menten kinetic model for oxidation of cholesterol as catalyzed by cholesterol oxidase immobilized in the lipid bilayer membrane. The cholesterol detection limit is below 1 {mu}M for cholesterol solution prepared in buffered cyclodextrin. The response of the electrodes to low density lipoprotein solutions is increased upon addition of cyclodextrin. Evidence for adsorption of low density lipoprotein to the electrode surface is presented.

  18. Electroencephalogram, cognitive state, psychological disorders, clinical symptom, and oxidative stress in horticulture farmers exposed to organophosphate pesticides.

    Science.gov (United States)

    Bayrami, Mansour; Hashemi, Touraj; Malekirad, Ali Akbar; Ashayeri, Hassan; Faraji, Fardin; Abdollahi, Mohammad

    2012-02-01

    The aim of this paper was to study the toxicity of organophosphate (OP) pesticides in exposed farmers for electroencephalography, cognitive state, psychological disorders, clinical symptom, oxidative stress, acetylcholinesterase, and DNA damage. A comparative cross-sectional analysis was carried out in 40 horticulture farmers who were exposed to OPs in comparison to a control group containing 40 healthy subjects with the same age and sex and education level. Lipid peroxidation (LPO), superoxide dismutase (SOD), catalase, glutathione peroxidase, DNA damage, total antioxidant capacity (TAC), total thiol molecules, and acetylcholinesterase (AChE) activity were measured in the blood of subjects. Clinical examination and complete blood test were undertaken in order to record any abnormal sign or symptoms. Cognitive function, psychological symptoms, and psychological distress were examined and recorded. Comparing with controls, the farmers showed higher blood levels of SOD and LPO while their TAC decreased. Farmers showed clinical symptoms such as eczema, breathing muscle weakness, nausea, and saliva secretion. Regarding cognitive function, the orientation, registration, attention and calculation, recall, and language were not significantly different in farmers and controls. Among examinations for psychological distress, only labeled somatization was significantly higher in farmers. The present findings indicate that oxidative stress and inhibition of AChE can be seen in chronically OP-exposed people but incidence of neuropsychological disorders seems a complex multivariate phenomenon that might be seen in long-term high-dose exposure situations. Use of supplementary antioxidants would be useful in the treatment of farmers.

  19. In situ and nonvolatile photoluminescence tuning and nanodomain writing demonstrated by all-solid-state devices based on graphene oxide.

    Science.gov (United States)

    Tsuchiya, Takashi; Tsuruoka, Tohru; Terabe, Kazuya; Aono, Masakazu

    2015-02-24

    In situ and nonvolatile tuning of photoluminescence (PL) has been achieved based on graphene oxide (GO), the PL of which is receiving much attention because of various potential applications of the oxide (e.g., display, lighting, and nano-biosensor). The technique is based on in situ and nonvolatile tuning of the sp(2) domain fraction to the sp(3) domain fraction (sp(2)/sp(3) fraction) in GO through an electrochemical redox reaction achieved by solid electrolyte thin films. The all-solid-state variable PL device was fabricated by GO and proton-conducting mesoporous SiO2 thin films, which showed an extremely low PL background. The device successfully tuned the PL peak wavelength in a very wide range from 393 to 712 nm, covering that for chemically tuned GO, by adjusting the applied DC voltage within several hundred seconds. We also demonstrate the sp(2)/sp(3) fraction tuning using a conductive atomic force microscope. The device achieved not only writing, but also erasing of the sp(2)/sp(3)-fraction-tuned nanodomain (both directions operation). The combination of these techniques is applicable to a wide range of nano-optoelectronic devices including nonvolatile PL memory devices and on-demand rewritable biosensors that can be integrated into nano- and microtips which are transparent, ultrathin, flexible, and inexpensive.

  20. Support- dependent evolution of oxidation state and nanoassembly formation of subnanometer copper clusters under carbon dioxide conversion conditions

    Science.gov (United States)

    Halder, Avik; Yang, Bing; Kolipaka, Karthika L.; Pellin, Michael; Seifert, Soenke; Vajda, Stefan; Materials Science Division Team

    Size- and support- dependence of the properties of copper clusters have been investigated during carbon dioxide conversion with hydrogen at high reactant concentrations and atmospheric pressure. The model catalyst systems were prepared by depositing size-selected Cun clusters (n = 3, 4, 12 and 20) on various amorphous metal oxide (Al2O3, ZnO, and ZrO2) , and carbon-based (UNCD = ultrananocrystaline diamond) supports. During the temperature ramp, the evolution of the chemical state and size of the particles were characterized by in situ grazing incidence X-ray absorption near edge structure (GIXANES), and grazing incidence small angle X-ray scattering (GISAXS) respectively. Under reaction conditions the initially oxidized Cu clusters reduced at various temperatures depending on cluster size and support. Clusters supported on ZnO and UNCD were found to be sinter-resistant under reactive gases at elevated temperatures and atmospheric pressures, whereas on ZrO2 support the clusters formed stable aggregates. Clusters on Al2O3 support demonstrated unique properties, where a formation of a nanostructure was observed during heating, which then disintegrated during the cool down. Under applied conditions, Cu4 clusters on Al2O3 were found to be the most efficient in methanol formation.

  1. A revised model of ex-vivo reduction of hexavalent chromium in human and rodent gastric juices

    Energy Technology Data Exchange (ETDEWEB)

    Schlosser, Paul M., E-mail: schlosser.paul@epa.gov; Sasso, Alan F.

    2014-10-15

    Chronic oral exposure to hexavalent chromium (Cr-VI) in drinking water has been shown to induce tumors in the mouse gastrointestinal (GI) tract and rat oral cavity. The same is not true for trivalent chromium (Cr-III). Thus reduction of Cr-VI to Cr-III in gastric juices is considered a protective mechanism, and it has been suggested that the difference between the rate of reduction among mice, rats, and humans could explain or predict differences in sensitivity to Cr-VI. We evaluated previously published models of gastric reduction and believe that they do not fully describe the data on reduction as a function of Cr-VI concentration, time, and (in humans) pH. The previous models are parsimonious in assuming only a single reducing agent in rodents and describing pH-dependence using a simple function. We present a revised model that assumes three pools of reducing agents in rats and mice with pH-dependence based on known speciation chemistry. While the revised model uses more fitted parameters than the original model, they are adequately identifiable given the available data, and the fit of the revised model to the full range of data is shown to be significantly improved. Hence the revised model should provide better predictions of Cr-VI reduction when integrated into a corresponding PBPK model. - Highlights: • Hexavalent chromium (Cr-VI) reduction in gastric juices is a key detoxifying step. • pH-dependent Cr-VI reduction rates are explained using known chemical speciation. • Reduction in rodents appears to involve multiple pools of electron donors. • Reduction appears to continue after 60 min, although more slowly than initial rates.

  2. Probing the density of states of two-level tunneling systems in silicon oxide films using superconducting lumped element resonators

    Energy Technology Data Exchange (ETDEWEB)

    Skacel, S. T. [Physikalisches Institut, Karlsruher Institut für Technologie, Wolfgang-Gaede-Straße 1, D-76131 Karlsruhe (Germany); Institut für Mikro- und Nanoelektronische Systeme, Karlsruher Institut für Technologie, Hertzstraße 16, D-76187 Karlsruhe (Germany); Kaiser, Ch.; Wuensch, S.; Siegel, M. [Institut für Mikro- und Nanoelektronische Systeme, Karlsruher Institut für Technologie, Hertzstraße 16, D-76187 Karlsruhe (Germany); Rotzinger, H.; Lukashenko, A.; Jerger, M.; Weiss, G. [Physikalisches Institut, Karlsruher Institut für Technologie, Wolfgang-Gaede-Straße 1, D-76131 Karlsruhe (Germany); Ustinov, A. V. [Physikalisches Institut, Karlsruher Institut für Technologie, Wolfgang-Gaede-Straße 1, D-76131 Karlsruhe (Germany); Russian Quantum Center, 100 Novaya St., Skolkovo, Moscow Region 143025 (Russian Federation)

    2015-01-12

    We have investigated dielectric losses in amorphous silicon oxide (a-SiO) thin films under operating conditions of superconducting qubits (mK temperatures and low microwave powers). For this purpose, we have developed a broadband measurement setup employing multiplexed lumped element resonators using a broadband power combiner and a low-noise amplifier. The measured temperature and power dependences of the dielectric losses are in good agreement with those predicted for atomic two-level tunneling systems (TLS). By measuring the losses at different frequencies, we found that the TLS density of states is energy dependent. This had not been seen previously in loss measurements. These results contribute to a better understanding of decoherence effects in superconducting qubits and suggest a possibility to minimize TLS-related decoherence by reducing the qubit operation frequency.

  3. Structural and optical properties of zinc oxide doped by V2O5 synthesized by solid-state reaction

    Science.gov (United States)

    Abaira, R.; Dammak, T.; Matoussi, A.; Younes, A.

    2016-03-01

    Vanadium doped zinc oxide with different vanadium concentration were synthesized by conventional solid state reaction. The structural and optical properties of ZnO: V2O5 pellets were studied by using a panalytic diffraktometer (X'pert) with Cu-K radiation, the UV-visible spectrophotometer and photoluminescence (PL). X-ray diffraction (XRD) show that all the samples have a wurtzite structure and grow mainly in the (101) orientation, we show also the presence of dominated phase Zn3 (VO4)2, Optical studied indicate a decrease in optical band gap energy, and photoluminescence (PL) spectra showed a strong visible emission band, energy position and intensity of this emission depends on the temperature measurement. The activate energy Ea has been fitted and studied using Arunis equation.

  4. Simulation of the steady-state behaviour of a new design of a single planar Solid Oxide Fuel Cell

    Directory of Open Access Journals (Sweden)

    Pianko-Oprych Paulina

    2016-03-01

    Full Text Available The aim of the work was to develop a mathematical model for computing the steady-state voltage – current characteristics of a planar Solid Oxide Fuel Cell and to determine the performance of a new SOFC design. The design involves cross-flow bipolar plates. Each of the bipolar plates has an air channel system on one side and a fuel channel system on the other side. The proposed model was developed using the ANSYS-Fluent commercial Computational Fluid Dynamics (CFD software supported by additional Fuel Cell module. The results confirm that the model can well simulate the diagonal current path. The effects of temperature and gas flow through the channels and a Membrane Electrode Assembly (MEA structure were taken into account. It was shown that a significant increase of the MEA temperature at high current density can lead to hot spots formation and hence electrode damage.

  5. Studies on Oxidation States of Cobalt Extracted from Soils with EDTA·HOAc·NH4OAc

    Institute of Scientific and Technical Information of China (English)

    CAIZU-CONG; LIUZHENG

    1991-01-01

    A method determining di-and tri-valent cobalt extracted from soils with EDTA·HOAc·NH4OAc solution (pH4.65) was developed based on the difference of the stability constants of Co(II) EDTA and Co(III) EDTA.Analytical results indicated that soil cobalt existed in both two oxidation states,i.e.,di-and tri-valent cobalt.Extractable di-valent cobalt in 60 soil samples collected from various soils in China ranged from 0.02 ppm to 3.54ppm,with the mean of 0.62ppm,and extractable tri-valent cobalt from 0.04 ppm to 27.65ppm,with the mean of 2.93ppm.

  6. Eco-friendly wood-based solid-state flexible supercapacitors from wood transverse section slice and reduced graphene oxide

    Science.gov (United States)

    Lv, Shaoyi; Fu, Feng; Wang, Siqun; Huang, Jingda; Hu, La

    2015-07-01

    An interesting wood-based all-solid-state supercapacitor is produced using reduced graphene oxide (RGO) coated on wood transverse section slice (WTSS) as electrode material by means of a low-cost, eco-friendly, and simple method for the first time. The RGO-coated WTSS electrode has a porous 3D honeycomb framework due to the hierarchical cellular structure of the WTSS substrate and can function as an electrolyte reservoir. This special construction endows this novel electrode with good areal capacitance (102 mF cm-2) and excellent cyclic stability (capacitance retention of 98.9% after 5000 cycles). In addition, the supercapacitors exhibit good mechanical flexibility and preserve almost constant capacitive behavior under different bending conditions. Our study introduces a new and eco-friendly material design for electrodes in future flexible energy storage devices that closely resemble natural materials. [Figure not available: see fulltext.

  7. Pseudonegative thermal expansion and the state of water in graphene oxide layered assemblies.

    Science.gov (United States)

    Zhu, Jian; Andres, Christine M; Xu, Jiadi; Ramamoorthy, Ayyalusamy; Tsotsis, Thomas; Kotov, Nicholas A

    2012-09-25

    Unraveling the complex interplay between thermal properties and hydration is a part of understanding the fundamental properties of many soft materials and very essential for many applications. Here we show that graphene oxide (GO) demonstrates a highly negative thermal expansion (NTE) coefficient owing to unique thermohydration processes related with fast transport of water between the GO sheets, the amphiphilic nature of nanochannels, and close-to-zero intrinsic thermal expansion of GO. The humidity-dependent NTE of GO layered assemblies, or "pseudonegative thermal expansion" (PNTE), differs from that of other hygroscopic materials due to its relatively fast and highly reversible expansion/contraction cycles and occurrence at low humidity levels while bearing similarities to classic NTE. Thermal expansion of polyvinyl alcohol/GO composites is easily tunable with additional intricacy of thermohydration effects. PNTE combined with isotropy, nontoxicity, and mechanical robustness is an asset for applications of actuators, sensors, MEMS devices, and memory materials and crucial for developing methods of thermal/photopatterning of GO devices.

  8. A GdAlO3 Perovskite Oxide Electrolyte-Based NOx Solid-State Sensor

    Science.gov (United States)

    Xiao, Yihong; Wang, Dongmei; Cai, Guohui; Zheng, Yong; Zhong, Fulan

    2016-11-01

    NOx is a notorious emission from motor vehicles and chemical factories as the precursor of acid rain and photochemical smog. Although zirconia-based NOx sensors have been developed and showed high sensitivity and selectivity at a high temperature of above 800 °C, they fail to show good performance, and even don’t work at the typical work temperature window of the automotive engine (type oxide Gd1‑xCaxAlO3‑δ(GCA) as the electrolyte and NiO as the sensing electrode. NOx sensing properties of the device were investigated at the temperature region of 400–500 °C. The response current value at ‑300 mV was almost linearly proportional to the NOx concentration between 300 and 500 ppm at 500 °C. At such a temperature, the optimal sensor gave the highest NO2 sensitivity of 20.15 nA/ppm, and the maximum response current value reached 5.57 μA. Furthermore, a 90% response and 90% recover time to 500 ppm NO2 were about 119 and 92 s, respectively. The excellent selectivity and stability towards NOx sensing showed the potential application of the sensor in motor vehicles.

  9. High efficiency solid state dye sensitized solar cells with graphene-polyethylene oxide composite electrolytes.

    Science.gov (United States)

    Akhtar, M Shaheer; Kwon, Soonji; Stadler, Florian J; Yang, O Bong

    2013-06-21

    Novel and highly effective composite electrolytes were prepared by combining the two dimensional graphene (Gra) and polyethylene oxide (PEO) for the solid electrolyte of dye sensitized solar cells (DSSCs). Gra sheets were uniformly coated by the polymer layer through the ester carboxylate bonding between oxygenated species on Gra sheets and PEO. The Gra-PEO composite electrolyte showed the large scale generation of iodide ions in a redox couple. From rheological analysis, the decrease in viscosity after the addition of LiI and I2 in the Gra-PEO electrolyte might be explained by the dipolar interactions being severely disrupted by the ionic interactions of Li(+), I(-), and I3(-) ions. A composite electrolyte with 0.5 wt% Gra presented a higher ionic conductivity (3.32 mS cm(-1)) than those of PEO and other composite electrolytes at room temperature. A high overall conversion efficiency (∼5.23%) with a very high short circuit current (JSC) of 18.32 mA cm(-2), open circuit voltage (VOC) of 0.592 V and fill factor (FF) of 0.48 was achieved in DSSCs fabricated with the 0.5 wt% Gra-PEO composite electrolyte. This enhanced photovoltaic performance might be attributed to the large scale formation of iodide ions in the redox electrolyte and the relatively high ionic conductivity.

  10. Fluorosulfates of graphite and boron nitride and other high oxidation state studies

    Energy Technology Data Exchange (ETDEWEB)

    Biagioni, R.N.

    1980-10-01

    The adduct XeF/sub 2/.AsF/sub 5/ was re-examined and assessed to be intermediate between the salt formulation (FXe)/sup +/AsF/sub 6//sup -/ and the fluorine bridged molecular adduct. A series of graphite fluorosulfates were prepared, using as the oxidizing agent S/sub 2/O/sub 6/F/sub 2/, and the effects of incorporating varying amounts of fluorosulfonic acid were studied. Physical data indicated that the S/sub 2/O/sub 6/F/sub 2/ was incorported as SO/sub 3/F/sup -/, and the HSO/sub 3/F was bound tightly, probably due to hydrogen bonding. The c-spacings of HSO/sub 3/F containing materials were larger than those of acid free materials, and the influences of charging, guest size and guest orientation were examined. X-ray diffractometer studies of graphite slabs intercalated with SO/sub 3/F/HSO/sub 3/F and IrF/sub 6/ indicated structures consistent with the characterization of these materials as containing tetrahedral SO/sub 3/F and octahedral IrF/sub 6/. Boron nitride reacted with S/sub 2/O/sub 6/F/sub 2/ to yield a deep blue, conducting intercalation compound. This material was in many respects similar to its graphite analog, but chemically more labile.

  11. Dynamics, stability, and adsorption states of water on oxidized RuO2(110)

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen, Manh Thuong; Mu, Rentao; Cantu Cantu, David; Lyubinetsky, Igor V.; Glezakou, Vassiliki-Alexandra; Dohnalek, Zdenek; Rousseau, Roger J.

    2017-08-31

    Identifying and understanding how excess oxygen atoms affect the adsorption of water on metal oxides is crucial for their use in water splitting. Here, by means of high-resolution scanning tunneling microscopy and density-functional calculations, we show that excess oxygen atoms on the stoichiometric RuO2(110) significantly change the clustering, conformation, and deprotonation equilibrium of adsorbed water. We considered two reactive scenarios during which the stoichiometric surface was exposed to: (i) first to oxygen followed by water, and (ii) first to water followed by oxygen. In both cases the [OH-OH] complex on Ru rows is the dominant species, showing a significant difference from water-only adsorption on the stoichiometric surface in which the [OH-H2O] species is found to be prevalent. Surface reactivity at almost full O coverage is also addressed; there we show that site selectivity of the surface for H adsorption and dissociation of H2O is hindered, notwithstanding the increase of the dynamical motion of both species. We found that the work function of RuO2 can serve as a descriptor for the reactivity of this surface to water and its constituents.

  12. Timing and characterization of the change in the redox state of uranium in Precambrian surface environments: A proxy for the oxidation state of the atmosphere

    Science.gov (United States)

    Pollack, Gerald D.

    The redox-sensitive geochemical behavior of uranium permits the use of Th/U ratios as a geochemical proxy for the oxidation state of the atmosphere and oceans during sedimentary processes. Due to the effects of post-depositional uranium mobility on Th/U ratios during events involving oxygenated fluids, direct measurements of Th/U ratios are often misleading, but the whole rock Pb isotope composition may be used to determine a sample's apparent time-integrated Th/U ratio (kappaa) and the timing associated with the onset of the U-Th-Pb geochemistry. Rare earth element (REE) concentrations were determined by isotope dilution mass spectrometry to evaluate the influence of multiple provenance components and potential mobility of Th, U, and Pb during post-depositional processes on the Th/U ratio. The Pb isotope compositions and REE concentrations were determined for six Paleoproterozoic sedimentary sequences, which were the focus of previous studies involving the timing of the rise of atmospheric oxygen. The Mount McRae Shale, Huronian Supergroup, and Zaonezhskaya Formation have been interpreted as experiencing post-depositional alteration (perhaps associated with orogenic events) due to Pb-Pb ages that are younger than the likely depositional age and observed fractionation of REE in chondrite normalized REE patterns and interelement REE ratios (e.g. La/Nd, La/Yb, Eu/Eu*). Similar geochemical proxies have been interpreted as sedimentary geochemical features of the Timeball Hill Formation, Hotazel Formation, and Sengoma Argillite Formation. This study of Paleoproterozoic sedimentary units constrains the onset of U-Th decoupling, most likely due to the onset of oxidative weathering conditions, began by 2.32 Ga, the latest. Index words. Pb isotopes, Rare earth elements, Th/U ratios, Time-integrated, Atmospheric evolution, Oxygen content of the atmosphere, U-Th decoupling

  13. Comparison of potentiality of Zinc oxide nanoparticles and hydrogen peroxide in removal of hexavalent chromium from polluted water

    Directory of Open Access Journals (Sweden)

    Anvar Asadi

    2012-12-01

    Conclusion: The results of this study indicated that H2O2 as a cheap and available agent and also UV/ZnO, as a friendly and without residual environmental treatment process, can be used for effective reduction of Cr(VI to yield Cr(III.

  14. IN-VIVO EVALUATION OF HEXAVALENT CHROMIUM INDUCED DNA DAMAGE BY ALKALINE COMET ASSAY AND OXIDATIVE STRESS IN CATLA CATLA

    Directory of Open Access Journals (Sweden)

    Kantha Deivi Arunachalam

    2013-01-01

    Full Text Available In the present study, the acute toxicity of Chromium in fingerlings of Catla catla, an Indian major carp, was evaluated with renewal bioassay method. In vivo studies were designed to assess the extent of Micronucleus Assay, Comet Assay under the exposure of common heavy-metal compounds, namely, Chromium Nitrate, using Catla catla (2n = 20, as a test model. The laboratory acclimatized fishes were divided into four groups. Group I served as positive control and the other three as exposed groups for three different time durations of 7, 14 and 21 days and were subjected to uninterrupted sub lethal concentrations (50% of 96 h LC50. The experiments were planned in such a way that fish from all the groups were sacrificed on the same day. The frequencies of micronuclei and bi-nuclei were evaluated comparatively in peripheral erythrocytes. As a result, it was observed that, the fishes and different tissues showed differential sensitivity to the heavy-metal treatment. A significant increase in the frequencies of micronucleated and binucleated cells and percentage increase in DNA tail (pCatla catla during sub lethal toxicity study was also calculated.

  15. Comparison of the effects of hexavalent chromium in the alimentary canal of F344 rats and B6C3F1 mice following exposure in drinking water: implications for carcinogenic modes of action.

    Science.gov (United States)

    Thompson, Chad M; Proctor, Deborah M; Suh, Mina; Haws, Laurie C; Hébert, Charles D; Mann, Jill F; Shertzer, Howard G; Hixon, J Gregory; Harris, Mark A

    2012-01-01

    Exposure to high concentrations of hexavalent chromium (Cr[VI]) in drinking water is reported to induce oral mucosa tumors in F344 rats and intestinal tumors in B6C3F1 mice. To investigate the modes of action underlying these tumors, 90-day drinking water studies (with interim necropsy at day 8) were conducted with concentrations of 0.1-182 mg/l Cr(VI), administered as 0.3-520 mg/l sodium dichromate dihydrate. Blood and tissue samples were analyzed for chromium content, oxidative stress, iron levels, and gross and microscopic lesions. Results for the F344 rats are described herein and compared with results from B6C3F1 mice published previously. After 90 days of exposure, total chromium concentrations in the rat and mouse oral mucosae were comparable, yet significant dose-dependent decreases in the reduced-to-oxidized glutathione ratio (GSH/GSSG) were observed only in rats. In the duodenum, changes in GSH/GSSG were only observed in mice. Levels of 8-hydroxydeoxyguanosine were not increased in the oral or duodenal mucosae of either species. Glutathione levels were increased in the duodenum but decreased in the jejunum of both species, indicating potential differential responses in the intestinal segments. Histiocytic infiltration was observed in the duodenum of both species, yet duodenal cytokines were repressed in mice but increased in rats. Serum and bone marrow iron levels were more decreased in rats than mice. Collectively, these data suggest that Cr(VI)-induced carcinogenesis in the rodent alimentary canal involves oxidative stress; however, differences in histopathology, cytokines, and iron status suggest potential contributions from other factors as well.

  16. One-electron oxidation of mitomycin C and its corresponding peroxyl radicals. A steady-state and pulse radiolysis study

    Science.gov (United States)

    Getoff, Nikola; Solar, Sonja; Quint, Ruth M.

    1997-12-01

    The one-electron oxidation of Mitomycin C (MMC) as well as the formation of the corresponding peroxyl radicals were investigated by both steady-state and pulse radiolysis. The steady-state MMC-radiolysis by OH-attack followed at both absorption bands showed different yields: at 218 nm G i (-MMC) = 3.0 and at 364 nm G i (-MMC) = 3.9, indicating the formation of various not yet identified products, among which ammonia was determined, G(NH 3) = 0.81. By means of pulse radiolysis it was established a total κ (OH + MMC) = (5.8 ± 0.2) × 10 9 dm 3 mol -1 s -1. The transient absorption spectrum from the one-electron oxidized MMC showed absorption maxima at 295 nm ( ɛ = 9950 dm 3 mol -1 cm t-1 ), 410 nm ( ɛ = 1450 dm 3 mol -1 cm -1) and 505 nm ( ɛ = 5420 dm 3 mol -1 cm -1). At 280-320 and 505 nm and above they exhibit in the first 150 μs a first order decay, κ1 = (0.85 ± 0.1) × 10 3 s -1, and followed upto ms time range, by a second order decay, 2 κ = (1.3 ± 0.3) × 10 8 dm 3 mol -1 s -1. Around 410 nm the kinetics are rather mixed and could not be resolved. The steady-state MMC-radiolysis in the presence of oxygen featured a proportionality towards the absorbed dose for both MMC-absorption bands, resulting in a G i (-MMC) = 1.5. Among several products ammonia-yield was determined G(NH 3) = 0.52. The formation of MMC-peroxyl radicals was studied by pulse radiolysis, likewise in neutral aqueous solution, but saturated with a gas mixture of 80% N 2O and 20% O 2. The maxima of the observed transient spectrum are slightly shifted compared to that of the one-electron oxidized MMC-species, namely: 290 nm ( ɛ = 10100 dm 3 mol -1 cm -1), 410 nm ( ɛ = 2900 dm 3 mol -1 cm -1) and 520 nm ( ɛ = 5500 dm 3 mol -1 cm -1). The O 2-addition to the MMC-one-electron oxidized transients was found to be at 290 to 410 nm gk(MMC·OH + O 2) = 5 × 10 7 dm 3 mol -1 s -1, around 480 nm κ = 1.6 × 10 8 dm 3 mol -1 s -1 and at 510 nm and above, κ = 3 × 10 8 dm 3 mol -1 s -1. The

  17. Low oxidation state aluminum-containing cluster anions: LAlH(-) and LAln(-) (n = 2-4, L = N[Si(Me)3]2).

    Science.gov (United States)

    Zhang, Xinxing; Wang, Linjie; Montone, Georgia R; Gill, Ann F; Ganteför, Gerd; Eichhorn, Bryan; Kandalam, Anil K; Bowen, Kit H

    2017-06-14

    Several low oxidation state aluminum-containing cluster anions, LAlH(-) and LAln(-) (n = 2-4, L = N[Si(Me)3]2), were produced via reactions between aluminum hydride cluster anions, AlxHy(-), and hexamethyldisilazane (HMDS). These clusters were characterized by mass spectrometry, anion photoelectron spectroscopy, and density functional theory (DFT) based calculations. Agreement between the experimental and theoretical vertical detachment energies (VDEs) and adiabatic detachment energies (ADEs) validated the computed geometrical structures. Reactions between aluminum hydride cluster anions and ligands promise to be a new synthetic scheme for low oxidation state, ligated aluminum clusters.

  18. The Oxidation State of Fe in MORB Glasses and the Oxygen Fugacity of the Upper Mantle

    Energy Technology Data Exchange (ETDEWEB)

    E Cottrell; K Kelley

    2011-12-31

    Micro-analytical determination of Fe{sup 3+}/{Sigma}Fe ratios in mid-ocean ridge basalt (MORB) glasses using micro X-ray absorption near edge structure ({mu}-XANES) spectroscopy reveals a substantially more oxidized upper mantle than determined by previous studies. Here, we show that global MORBs yield average Fe{sup 3+}/{Sigma}Fe ratios of 0.16 {+-} 0.01 (n = 103), which trace back to primary MORB melts equilibrated at the conditions of the quartz-fayalite-magnetite (QFM) buffer. Our results necessitate an upward revision of the Fe{sup 3+}/{Sigma}Fe ratios of MORBs, mantle oxygen fugacity, and the ferric iron content of the mantle relative to previous wet chemical determinations. We show that only 0.01 (absolute, or < 10%) of the difference between Fe{sup 3+}/{Sigma}Fe ratios determined by micro-colorimety and XANES can be attributed to the Moessbauer-based XANES calibration. The difference must instead derive from a bias between micro-colorimetry performed on experimental vs. natural basalts. Co-variations of Fe{sup 3+}/{Sigma}Fe ratios in global MORB with indices of low-pressure fractional crystallization are consistent with Fe{sup 3+} behaving incompatibly in shallow MORB magma chambers. MORB Fe{sup 3+}/{Sigma}Fe ratios do not, however, vary with indices of the extent of mantle melting (e.g., Na{sub 2}O(8)) or water concentration. We offer two hypotheses to explain these observations: The bulk partition coefficient of Fe{sup 3+} may be higher during peridotite melting than previously thought, and may vary with temperature, or redox exchange between sulfide and sulfate species could buffer mantle melting at {approx} QFM. Both explanations, in combination with the measured MORB Fe{sup 3+}/{Sigma}Fe ratios, point to a fertile MORB source with greater than 0.3 wt.% Fe{sub 2}O{sub 3}.

  19. Solid state welding processes for an oxide dispersion strengthened nickel-chromium-aluminum alloy

    Science.gov (United States)

    Moore, T. J.

    1975-01-01

    Solid-state welding processes were evaluated for joining TD-NiCrAl (Ni-16Cr-4Al-2ThO2) alloy sheet. Both hot-press and resistance spot welding techniques were successfully applied in terms of achieving grain growth across the bond line. Less success was achieved with a resistance seam welding process. In stress-rupture shear and tensile shear tests of lap joints at 1100 C, most failures occurred in the parent material, which indicates that the weld quality was good and that the welds were not a plane of weakness. The overall weld quality was not as good as previously attained with TD-NiCr, probably because the presence of alumina at the faying surfaces and the developmental TD-NiCrAl sheet, which was not of the quality of the TD-NiCr sheet in terms of surface flatness and dimensional control.

  20. Gas sensing properties of tin oxide nanostructures synthesized via a solid-state reaction method

    Energy Technology Data Exchange (ETDEWEB)

    Tan, E T H; Ho, G W [Department of Electrical and Computer Engineering, National University of Singapore, 4 Engineering Drive, 117576 (Singapore); Wong, A S W [Institute of Materials Research and Engineering, A-STAR - Agency for Science, Technology and Research, 3 Research Link, 117602 (Singapore); Kawi, S [Department of Chemical and Biomolecular Engineering, National University of Singapore, 4 Engineering Drive 4, 117576 (Singapore); Wee, A T S [Department of Physics, Surface Science Laboratory, National University of Singapore, 2 Science Drive 3, 117542 (Singapore)], E-mail: elehgw@nus.edu.sg

    2008-06-25

    A high-yield synthesis of SnO{sub 2} nanoparticles via a facile, economical and easily scalable solid-state molten salt synthesis method has been demonstrated. The inorganic additive, molar ratios of chemicals and annealing temperature were found to control the size and porosity of the SnO{sub 2} nanoparticles. The synthesized SnO{sub 2} nanostructures were uniform, well dispersed and exhibited high crystallinity. Hydrogen sensors made from the SnO{sub 2} nanoparticles were found to possess high sensitivity and stability. Other than tailoring the material's structure in terms of size and porosity, another potential method of enhancing the gas sensitivity is functionalization with noble Pd metal.

  1. Poly(ethylene oxide) irradiated in the solid state, melt and aqueous solution—a DSC and WAXD study

    Science.gov (United States)

    Jurkin, Tanja; Pucić, Irina

    2012-09-01

    Interactions of the aggregate state of poly(ethylene oxide), PEO, and γ-irradiation conditions (total dose, atmosphere) on its thermal and crystalline properties were investigated by DSC and WAXD taking into account sample molecular mass and form. In PEO irradiated in the solid state and in the presence of oxygen, chain scission dominated over concurrent crosslinking up to 200 kGy, particularly in PEO powders, due to a large surface being in contact with air. In solid samples the degree of crystallinity and crystallite size increased with the dose up to 50 kGy, probably not just due to partial crystallization upon degradation of amorphous phase, but to recrystallization of broken tie molecules. The least changes in crystallinity and phase transformation temperatures occurred in solid films. A substantial decrease in crystallinity and transformation temperatures without the initial crystallinity increase was achieved in samples that were amorphous on irradiation, at temperatures above the PEO melting temperature and in aqueous solutions. Radiation crosslinking of the PEO aqueous solution in an inert atmosphere is the most suitable way to obtain a lower degree of crystallinity and phase transformation temperatures while preserving mechanical properties.

  2. SPECT/CT Imaging of Pluronic Nanocarriers with Varying Poly(ethylene oxide) Block Length and Aggregation State.

    Science.gov (United States)

    Arranja, Alexandra; Ivashchenko, Oleksandra; Denkova, Antonia G; Morawska, Karolina; van Vlierberghe, Sandra; Dubruel, Peter; Waton, Gilles; Beekman, Freek J; Schosseler, François; Mendes, Eduardo

    2016-03-07

    Optimal biodistribution and prolonged circulation of nanocarriers improve diagnostic and therapeutic effects of enhanced permeability and retention-based nanomedicines. Despite extensive use of Pluronics in polymer-based pharmaceuticals, the influence of different poly(ethylene oxide) (PEO) block length and aggregation state on the biodistribution of the carriers is rather unexplored. In this work, we studied these effects by evaluating the biodistribution of Pluronic unimers and cross-linked micelles with different PEO block size. In vivo biodistribution of (111)In-radiolabeled Pluronic nanocarriers was investigated in healthy mice using single photon emission computed tomography. All carriers show fast uptake in the organs from the reticuloendothelial system followed by a steady elimination through the hepatobiliary tract and renal filtration. The PEO block length affects the initial renal clearance of the compounds and the overall liver uptake. The aggregation state influences the long-term accumulation of the nanocarriers in the liver. We showed that the circulation time and elimination pathways can be tuned by varying the physicochemical properties of Pluronic copolymers. Our results can be beneficial for the design of future Pluronic-based nanomedicines.

  3. Cellulose nanofibril/reduced graphene oxide/carbon nanotube hybrid aerogels for highly flexible and all-solid-state supercapacitors.

    Science.gov (United States)

    Zheng, Qifeng; Cai, Zhiyong; Ma, Zhenqiang; Gong, Shaoqin

    2015-02-11

    A novel type of highly flexible and all-solid-state supercapacitor that uses cellulose nanofibril (CNF)/reduced graphene oxide (RGO)/carbon nanotube (CNT) hybrid aerogels as electrodes and H2SO4/poly(vinyl alcohol) (PVA) gel as the electrolyte was developed and is reported here. These flexible solid-state supercapacitors were fabricated without any binders, current collectors, or electroactive additives. Because of the porous structure of the CNF/RGO/CNT aerogel electrodes and the excellent electrolyte absorption properties of the CNFs present in the aerogel electrodes, the resulting flexible supercapacitors exhibited a high specific capacitance (i.e., 252 F g(-1) at a discharge current density of 0.5 A g(-1)) and a remarkable cycle stability (i.e., more than 99.5% of the capacitance was retained after 1000 charge-discharge cycles at a current density of 1 A g(-1)). Furthermore, the supercapacitors also showed extremely high areal capacitance, areal power density, and energy density (i.e., 216 mF cm(-2), 9.5 mW cm(-2), and 28.4 μWh cm(-2), respectively). In light of its excellent electrical performance, low cost, ease of large-scale manufacturing, and environmental friendliness, the CNF/RGO/CNT aerogel electrodes may have a promising application in the development of flexible energy-storage devices.

  4. Transition Metal Oxides for the Oxygen Reduction Reaction: Influence of the Oxidation States of the Metal and its Position on the Periodic Table.

    Science.gov (United States)

    Toh, Rou Jun; Sofer, Zdeněk; Pumera, Martin

    2015-11-16

    Electrocatalysts have been developed to meet the needs and requirements of renewable energy applications. Metal oxides have been well explored and are promising for this purpose, however, many reports focus on only one or a few metal oxides at once. Herein, thirty metal oxides, which were either commercially available or synthesized by a simple and scalable method, were screened for comparison with regards to their electrocatalytic activity towards the oxygen reduction reaction (ORR). We show that although manganese, iron, cobalt, and nickel oxides generally displayed the ability to enhance the kinetics of oxygen reduction under alkaline conditions compared with bare glassy carbon, there is no significant correlation between the position of a metal on the periodic table and the electrocatalytic performance of its respective metal oxides. Moreover, it was also observed that mixed valent (+2, +3) oxides performed the poorest, compared with their respective pure metal oxides. These findings may be of paramount importance in the field of renewable energy. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Catalytic combustion of methane over alumina-supported palladium: Relationships between the oxidation state, particle size, morphology and activity

    Science.gov (United States)

    Lyubovsky, Maxim R.

    Supported palladium was studied as a catalyst for combustion of natural gas. The influence of variations in temperature and oxygen concentration, of addition of CO and water and of in situ hydrogen reduction on catalyst activity was studied experimentally. The activation energy for methane oxidation over crystalline PdO is about 17.5 kcal/mole and over metallic Pd - 40--45 kcal/mole. The difference in the activation energy is compensated by the preexponential coefficient that is 5--6 orders of magnitude higher for Pd than for PdO. In this work the activity variations under the different reaction conditions were correlated with the corresponding changes in the catalyst oxidation state, particle size and morphology. Formation of metallic hexagonal crystallites 100--200 nm in size was observed by TEM after PdO reduction, which resulted in an increase in the catalyst activity. Redispersion of these metallic crystallites into PdO clusters of 3--5 nm in size occurred during the Pd reoxidation, which resulted in a reversible increase of the catalyst activity on the cooling cycle, known as "negative activation." Activation of the methane molecule is the limiting step of the reaction over both the Pd and the PdO states. We propose that on the Pd surface the reaction occurs through the Langmuir-Hinshelwood mechanism. Under conditions of catalytic combustion the surface is completely covered with oxygen and competitive dissociative adsorption of methane is the limiting step of the process. The high heat of oxygen adsorption explains the high activation energy for the overall process. On the PdO surface the reaction occurs through a redox mechanism. A methane molecule interacts with a surface Pd-O dimer resulting in adsorbed CH3 and OH species. The activation energy of this interaction is about 15 kcal/mole and the probability is low due to the different multiplicity of the initial and final states of the transition complex. Oscillations in the reaction rate under fuel

  6. Ultrasound-assisted extraction and characterization of hydrolytic and oxidative enzymes produced by solid state fermentation.

    Science.gov (United States)

    Szabo, Orsolya Erzsebet; Csiszar, Emilia; Toth, Karolina; Szakacs, George; Koczka, Bela

    2015-01-01

    Ligninolytic and hydrolytic enzymes were produced with six selected fungi on flax substrate by solid state fermentation (SSF). The extracellular enzyme production of the organisms in two SSF media was evaluated by measuring the soluble protein concentration and the filter paper, endoxylanase, 1,4-β-d-glucosidase, 1,4-β-d-endoglucanase, polygalacturonase, lignin peroxidase, manganese peroxidase and laccase activities of the clear culture solutions produced by conventional extraction from the SSF materials. The SSF material of the best enzyme producer (Trichoderma virens TUB F-498) was further investigated to enhance the enzyme recovery by low frequency ultrasound treatment. Performance of both the original and ultrasound macerated crude enzyme mixtures was evaluated in degradation of the colored lignin-containing and waxy materials of raw linen fabric. Results proved that sonication (at 40%, 60% and 80% amplitudes, for 60min) did not result in reduction in the filter paper, lignin peroxidase and laccase activities of the crude enzyme solution, but has a significant positive effect on the efficiency of enzyme extraction from the SSF material. Depending on the parameters of sonication, the enzyme activities in the extracts obtained can be increased up to 129-413% of the original activities measured in the control extracts recovered by a common magnetic stirrer. Sonication also has an effect on both the enzymatic removal of the lignin-containing color materials and hydrophobic surface layer from the raw linen.

  7. Interannual variability in soil nitric oxide emissions over the United States as viewed from space

    Directory of Open Access Journals (Sweden)

    R. C. Hudman

    2010-10-01

    Full Text Available We examine the interannual variability in the NO2 column over North America measured by the Ozone Monitoring Instrument (OMI in 2005–2008. By comparison to a model of soil NOx emissions driven by the North American Regional Reanalysis precipitation and 0–10 cm soil temperature fields, we show the source of this observed interannual variability over much of the central United States in June is fertilizer application. We find that dry, warm conditions followed by convective precipitation induces pulsed emissions of NOx over the agricultural Great Plains. In June 2006 we infer a 50% increase in soil NOx emission and a 30% increase in the tropospheric NO2 column relative to the June 2005–2008 mean. In a case-study of fertilized corn and soybean fields over SE South Dakota, we find an associated rain-induced pulsing event reaching 4.6×1015 molec cm−2, equivalent to a surface concentration of ~2 ppbv. We calculate that soil NOx emissions resulted in a mean daily maximum 8-h ozone enhancement over the agricultural Great Plains of 5 ppbv in June 2006 (with predicted events reaching 16 ppbv compared with a mean enhancement of 3 ppbv for soil NOx in the years 2005–2008.

  8. Interannual variability in soil nitric oxide emissions over the United States as viewed from space

    Science.gov (United States)

    Hudman, R. C.; Russell, A. R.; Valin, L. C.; Cohen, R. C.

    2010-10-01

    We examine the interannual variability in the NO2 column over North America measured by the Ozone Monitoring Instrument (OMI) in 2005-2008. By comparison to a model of soil NOx emissions driven by the North American Regional Reanalysis precipitation and 0-10 cm soil temperature fields, we show the source of this observed interannual variability over much of the central United States in June is fertilizer application. We find that dry, warm conditions followed by convective precipitation induces pulsed emissions of NOx over the agricultural Great Plains. In June 2006 we infer a 50% increase in soil NOx emission and a 30% increase in the tropospheric NO2 column relative to the June 2005-2008 mean. In a case-study of fertilized corn and soybean fields over SE South Dakota, we find an associated rain-induced pulsing event reaching 4.6×1015 molec cm-2, equivalent to a surface concentration of ~2 ppbv. We calculate that soil NOx emis