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Sample records for active uvi reduction

  1. Kinetics of Microbial Reduction of Solid Phase U(VI)

    SciTech Connect

    Liu, Chongxuan; Jeon, Byong Hun; Zachara, John M.; Wang, Zheming; Dohnalkova, Alice; Fredrickson, Jim K.

    2006-10-01

    Sodium boltwoodite (NaUO2SiO3OH ?1.5H2O) was used to assess the kinetics of microbial reduction of solid phase U(VI) by a dissimilatory metal-reducing bacterium (DMRB), Shewanella oneidensis strain MR-1. The bioreduction kinetics was studied with Na-boltwoodite in suspension or within alginate beads. Concentrations of U(VI)tot and cell number were varied to evaluate the coupling of U(VI) dissolution, diffusion, and microbial activity. Batch experiments were performed in a non-growth medium with lactate as electron donor at pH 6.8 buffered with PIPES. Microscopic and spectroscopic analyses with transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), and laser-induced fluorescence spectroscopy (LIFS) collectively indicated that solid phase U(VI) was first dissolved and diffused out of grain interiors before it was reduced on bacterial surfaces and/or within the periplasm. The kinetics of solid phase U(VI) bioreduction was well described by a coupled model of bicarbonate-promoted dissolution of Na-boltwoodite, intraparticle uranyl diffusion, and Monod type bioreduction kinetics with respect to dissolved U(VI) concentration. The results demonstrated the intimate coupling of biological, chemical, and physical processes in microbial reduction of solid phase U(VI).

  2. U(VI) Reduction in Sulfate-Reducing Subsurface Sediments Amended with Ethanol or Acetate

    PubMed Central

    Converse, Brandon J.; Wu, Tao; Findlay, Robert H.

    2013-01-01

    An experiment was conducted with subsurface sediments from Oak Ridge National Laboratory to determine the potential for reduction of U(VI) under sulfate-reducing conditions with either ethanol or acetate as the electron donor. The results showed extensive U(VI) reduction in sediments supplied with either electron donor, where geochemical and microbiological analyses demonstrated active sulfate reduction. PMID:23624470

  3. Influence of magnetite stoichiometry on U(VI) reduction.

    PubMed

    Latta, Drew E; Gorski, Christopher A; Boyanov, Maxim I; O'Loughlin, Edward J; Kemner, Kenneth M; Scherer, Michelle M

    2012-01-17

    Hexavalent uranium (U(VI)) can be reduced enzymatically by various microbes and abiotically by Fe(2+)-bearing minerals, including magnetite, of interest because of its formation from Fe(3+) (oxy)hydroxides via dissimilatory iron reduction. Magnetite is also a corrosion product of iron metal in suboxic and anoxic conditions and is likely to form during corrosion of steel waste containers holding uranium-containing spent nuclear fuel. Previous work indicated discrepancies in the extent of U(VI) reduction by magnetite. Here, we demonstrate that the stoichiometry (the bulk Fe(2+)/Fe(3+) ratio, x) of magnetite can, in part, explain the observed discrepancies. In our studies, magnetite stoichiometry significantly influenced the extent of U(VI) reduction by magnetite. Stoichiometric and partially oxidized magnetites with x ≥ 0.38 reduced U(VI) to U(IV) in UO(2) (uraninite) nanoparticles, whereas with more oxidized magnetites (x < 0.38) and maghemite (x = 0), sorbed U(VI) was the dominant phase observed. Furthermore, as with our chemically synthesized magnetites (x ≥ 0.38), nanoparticulate UO(2) was formed from reduction of U(VI) in a heat-killed suspension of biogenic magnetite (x = 0.43). X-ray absorption and Mössbauer spectroscopy results indicate that reduction of U(VI) to U(IV) is coupled to oxidation of Fe(2+) in magnetite. The addition of aqueous Fe(2+) to suspensions of oxidized magnetite resulted in reduction of U(VI) to UO(2), consistent with our previous finding that Fe(2+) taken up from solution increased the magnetite stoichiometry. Our results suggest that magnetite stoichiometry and the ability of aqueous Fe(2+) to recharge magnetite are important factors in reduction of U(VI) in the subsurface. PMID:22148359

  4. Reduction of U(VI) and Toxic Metals by Desulfovibrio Cytochrome c3

    SciTech Connect

    Wall, Judy D.

    2003-06-01

    The project, ''Reduction of U(VI) and toxic metals by Desulfovibrio cytochrome c3'', is designed to obtain spectroscopic information for or against a functional interaction of cytochrome c3 and uranium in the whole cells. That is, is the cytochrome c3 the uranium reductase? Our approach has been to start with purified cytochrome and determine any unique spectral disturbances during electron flow to U(VI). Then we will attempt to identify these signals emanating from cells actively reducing uranium. This project is being carried out in collaboration with Dr. William Woodruff at the Los Alamos National Laboratory where the spectral experiments are being carried out.

  5. Importance of c-Type cytochromes for U(VI) reduction by Geobacter sulfurreducens

    PubMed Central

    Shelobolina, Evgenya S; Coppi, Maddalena V; Korenevsky, Anton A; DiDonato, Laurie N; Sullivan, Sara A; Konishi, Hiromi; Xu, Huifang; Leang, Ching; Butler, Jessica E; Kim, Byoung-Chan; Lovley, Derek R

    2007-01-01

    Background In order to study the mechanism of U(VI) reduction, the effect of deleting c-type cytochrome genes on the capacity of Geobacter sulfurreducens to reduce U(VI) with acetate serving as the electron donor was investigated. Results The ability of several c-type cytochrome deficient mutants to reduce U(VI) was lower than that of the wild type strain. Elimination of two confirmed outer membrane cytochromes and two putative outer membrane cytochromes significantly decreased (ca. 50–60%) the ability of G. sulfurreducens to reduce U(VI). Involvement in U(VI) reduction did not appear to be a general property of outer membrane cytochromes, as elimination of two other confirmed outer membrane cytochromes, OmcB and OmcC, had very little impact on U(VI) reduction. Among the periplasmic cytochromes, only MacA, proposed to transfer electrons from the inner membrane to the periplasm, appeared to play a significant role in U(VI) reduction. A subpopulation of both wild type and U(VI) reduction-impaired cells, 24–30%, accumulated amorphous uranium in the periplasm. Comparison of uranium-accumulating cells demonstrated a similar amount of periplasmic uranium accumulation in U(VI) reduction-impaired and wild type G. sulfurreducens. Assessment of the ability of the various suspensions to reduce Fe(III) revealed no correlation between the impact of cytochrome deletion on U(VI) reduction and reduction of Fe(III) hydroxide and chelated Fe(III). Conclusion This study indicates that c-type cytochromes are involved in U(VI) reduction by Geobacter sulfurreducens. The data provide new evidence for extracellular uranium reduction by G. sulfurreducens but do not rule out the possibility of periplasmic uranium reduction. Occurrence of U(VI) reduction at the cell surface is supported by the significant impact of elimination of outer membrane cytochromes on U(VI) reduction and the lack of correlation between periplasmic uranium accumulation and the capacity for uranium reduction

  6. Isotopic and Geochemical Tracers for U(VI) Reduction and U Mobility at an in Situ Recovery U Mine.

    PubMed

    Basu, Anirban; Brown, Shaun T; Christensen, John N; DePaolo, Donald J; Reimus, Paul W; Heikoop, Jeffrey M; Woldegabriel, Giday; Simmons, Ardyth M; House, Brian M; Hartmann, Matt; Maher, Kate

    2015-05-19

    In situ recovery (ISR) uranium (U) mining mobilizes U in its oxidized hexavalent form (U(VI)) by oxidative dissolution of U from the roll-front U deposits. Postmining natural attenuation of residual U(VI) at ISR mines is a potential remediation strategy. Detection and monitoring of naturally occurring reducing subsurface environments are important for successful implementation of this remediation scheme. We used the isotopic tracers (238)U/(235)U (δ(238)U), (234)U/(238)U activity ratio, and (34)S/(32)S (δ(34)S), and geochemical measurements of U ore and groundwater collected from 32 wells located within, upgradient, and downgradient of a roll-front U deposit to detect U(VI) reduction and U mobility at an ISR mining site at Rosita, TX, USA. The δ(238)U in Rosita groundwater varies from +0.61‰ to -2.49‰, with a trend toward lower δ(238)U in downgradient wells. The concurrent decrease in U(VI) concentration and δ(238)U with an ε of 0.48‰ ± 0.08‰ is indicative of naturally occurring reducing environments conducive to U(VI) reduction. Additionally, characteristic (234)U/(238)U activity ratio and δ(34)S values may also be used to trace the mobility of the ore zone groundwater after mining has ended. These results support the use of U isotope-based detection of natural attenuation of U(VI) at Rosita and other similar ISR mining sites. PMID:25909757

  7. Effects of Bacillus subtilis on the reduction of U(VI) by nano-Fe0

    NASA Astrophysics Data System (ADS)

    Ding, Congcong; Cheng, Wencai; Sun, Yubing; Wang, Xiangke

    2015-09-01

    The effects of Bacillus subtilis (B. subtilis, a typical model bacterium) on the reduction of U(VI) by nanoscale zero-valent iron (nano-Fe0) were investigated using batch techniques. The reaction products were analysed using spectroscopic techniques, and a kinetics model was developed to elucidate the mechanisms of U(VI) reduction by nano-Fe0. The presence of B. subtilis enhanced the U(VI) sorption rate at pH 3.5-9.5 but inhibited the reduction rate of U(VI) to U(IV) at pH > 4.5. According to the FTIR and XRD analysis, the reduction of U(VI) to U(IV) was inhibited due to the formation of inner-sphere surface complexes between the oxygen-containing functional groups of B. subtilis or extracellular polymeric substances with the Fe(II)/Fe(III) generated by nano-Fe0, which blocked electron transport from the Fe0 core to U(VI). Based on the EXAFS analysis, a fitting of U-Fe shell at ∼3.44 Å revealed inner-sphere bidentate complexes between uranyl and the oxide film of nano-Fe0. For the nano-Fe0 + B. subtilis system, the U-Fe shell (at ∼3.44 Å) and the U-C/P shell (at ∼2.90 Å) further indicated the formation of inner-sphere surface complexes. The kinetics model supported that U(VI) reduction was triggered by U(VI) sorption on the oxide shell of nano-Fe0. The XPS and XANES analyses showed that reductive precipitation was the main mechanism of U(VI) removal by nano-Fe0, whereas the sorption process dominated the removal of U(VI) in the presence of B. subtilis, which was further demonstrated by TEM images.

  8. Influence of Dynamical Conditions on the Reduction of UVI at the Magnetite-Solution Interface

    SciTech Connect

    Ilton, Eugene S.; Boily, Jean F.; Buck, Edgar C.; Skomurski, Frances N.; Rosso, Kevin M.; Cahill, Christopher L.; Bargar, John R.; Felmy, Andrew R.

    2010-01-14

    The heterogeneous reduction of UVI to UIV by ferrous iron is a potentially key process influencing the fate and transport of U in the environment. The reactivity of both sorbed and structural FeII has been studied for numerous substrates, including magnetite. The results from UVI-magnetite experiments have been variable, ranging from no reduction to clear evidence for the formation of UIV. In this contribution, we used XAS and high resolution (+cryogenic) XPS to study the interaction of UVI with nano-particulate magnetite. The results indicated that UVI was partially reduced to UV with no evidence of UIV. However, thermodynamic calculations indicated that mixed-valence U phases with average oxidation states below (V) should have been stable, indicating that the system was not in redox equilibrium. A reaction pathway that involves incorporation of U and stabilization of UV and UVI in secondary phases is invoked to explain the observations.

  9. Reduction of U(VI) Complexes by Anthraquinone Disulfonate: Experiment and Molecular Modeling

    SciTech Connect

    Ainsworth, C.C.; Wang, Z.; Rosso, K.M.; Wagnon, K.; Fredrickson, J.K.

    2004-03-17

    Past studies demonstrate that complexation will limit abiotic and biotic U(VI) reduction rates and the overall extent of reduction. However, the underlying basis for this behavior is not understood and presently unpredictable across species and ligand structure. The central tenets of these investigations are: (1) reduction of U(VI) follows the electron-transfer (ET) mechanism developed by Marcus; (2) the ET rate is the rate-limiting step in U(VI) reduction and is the step that is most affected by complexation; and (3) Marcus theory can be used to unify the apparently disparate U(VI) reduction rate data and as a computational tool to construct a predictive relationship.

  10. Characterization of U(VI) reduction in contaminated sediments with slow-degrading electron donor source

    NASA Astrophysics Data System (ADS)

    Wu, W.; Watson, D. B.; Zhang, G.; Mehlhorn, T.; Lowe, K.; Earles, J.; Phillips, J.; Kelly, S. D.; Boyanov, M.; Kemner, K. M.; Schadt, C.; Criddle, C. S.; Jardine, P. M.; Brooks, S. C.

    2011-12-01

    In order to select sustainable, high efficiency and cost effective electron donor source, oleate and emulsified vegetable oil (EVO) were tested uranium (VI) reduction in comparison with ethanol in microcosms using uranium contaminated sediments and groundwater from the US DOE Oak Ridge Integrated Field Research Challenge (ORIFRC) site. The effect of initial sulfate concentration on U(VI) reduction was also tested. Both oleate and EVO were effective electron donor sources for U(VI) reduction. Accumulation of acetate as a major product and the removal of aqueous U(VI) were observed and were associated with sulfate reduction. Both oleate and EVO supported U(VI) reduction but at slower rates with a comparable but slightly lower extent of reduction than ethanol. X-ray absorption near-edge spectroscopy (XANES) analysis confirmed reduction of U(VI) to U(IV). The extent of U(VI) reduction in solid phase was negatively influenced by aqueous calcium concentration. The majority of electrons of the three substrates were consumed by sulfate reduction, Fe(III) reduction, and methanogenesis. Initial U(VI) concentration in the aqueous phase increased with increased sulfate concentration (1 versus 5 mM), likely due to U(VI) desorption from the solid phase. At the higher initial sulfate concentration more U(VI) was reduced and fewer electrons were used in methanogenesis. Analysis of bacterial and archeal populations using 16S rRNA gene libraries showed a significant increase in Deltaproteobacteria after biostimulation. The microbial community structures developed with oleate and EVO were significantly distinct from those developed with ethanol. Bacteria similar to Desulforegula spp. was predominant for oleate and EVO degradation but were not observed in ethanol-amended microcosms. Known U(VI)-reducing bacteria in the microcosms amended with the three electron donor sources included iron(III) reducing Geobacter spp. but in lower abundances than sulfate-reducing Desulfovibrio spp. The

  11. Isotopic and geochemical tracers for U(VI) reduction and U mobility at an in situ recovery U mine

    DOE PAGESBeta

    Basu, Anirban; Brown, Shaun T.; Christensen, John N.; DePaolo, Donald J.; Reimus, Paul W.; Heikoop, Jeffrey M.; Woldegabriel, Giday; Simmons, Ardyth M.; House, Brian M.; Hartmann, Matt; et al

    2015-05-19

    In situ recovery (ISR) uranium (U) mining mobilizes U in its oxidized hexavalent form (U(VI)) by oxidative dissolution of U from the roll-front U deposits. Post-mining natural attenuation of residual U(VI) at ISR mines is a potential remediation strategy. Detection and monitoring of naturally occurring reducing subsurface environments are important for successful implementation of this remediation scheme. We used the isotopic tracers ²³⁸U/²³⁵U (δ²³⁸U), ²³⁴U/²³⁸U activity ratio, and ³⁴S/³²S (δ³⁴S), and geochemical measurements of U ore and groundwater collected from 32 wells located within, upgradient, and downgradient of a roll-front U deposit to detect U(VI) reduction and U mobility atmore » an ISR mining site at Rosita, TX, USA. The δ²³⁸U in Rosita groundwater varies from 0.61‰ to -2.49‰, with a trend toward lower δ²³⁸U in downgradient wells. The concurrent decrease in U(VI) concentration and δ²³⁸U with an ε of 0.48‰ ± 0.08‰ is indicative of naturally occurring reducing environments conducive to U(VI) reduction. Additionally, characteristic ²³⁴U/²³⁸U activity ratio and δ³⁴S values may also be used to trace the mobility of the ore zone groundwater after mining has ended. These results support the use of U isotope-based detection of natural attenuation of U(VI) at Rosita and other similar ISR mining sites.« less

  12. Cassini UVIS Observations Show Active Saturn's Rings

    NASA Astrophysics Data System (ADS)

    Esposito, L.; Colwell, J. E.; UVIS Team

    2004-12-01

    The Cassini Ultraviolet Imaging Spectrograph (UVIS) is part of the remote sensing payload of the NASA/ESA Cassini spacecraft. This spectrograph includes channels for extreme UV and far UV spectroscopic imaging, high speed photometry of stellar occultations, solar EUV occultation, and a hydrogen/deuterium absorption cell. We report our initial results from UVIS observations of Saturn's rings. Dynamic interactions between neutrals, ions, rings, moons and meteoroids produce a highly structured and time variable Saturn system Oxygen in the Saturn system dominates the magnetosphere. Observed fluctuations indicate close interactions with plasma sources. Stochastic events in the E ring may be the ultimate source. The spectral signature of water ice is seen on Phoebe and in Saturn's rings. Water ice is mixed non-uniformly with darker constituents. The high structure of the UV ring reflectance argues that collisional transport dominates ballistic transport in darkening the rings. Our preliminary results support the idea that rings are recycled fragments of moons: the current processes are more important than history and initial conditions. The spectra along the UVIS SOI radial scan indicate varying amounts of water ice. In the A ring, the ice fraction increases outward to a maximum at the outer edge. This large-scale variation is consistent with initially pure ice that has suffered meteoritic bombardment over the age of the Solar system (Cuzzi and Estrada 1998). We also see variations over scales of 1000 - 3000 km, which cannot be explained by this mechanism. Ballistic transport of spectrally neutral extrinsic pollutants from meteoroids striking the rings has a typical throw distance of 6000 km (Durisen et al 1989), too long to explain this finer structure. We propose a class of smaller renewal events, in which a small moon residing within the rings is shattered by an external impactor (Colwell and Esposito 1993, Barbara and Esposito 2002, Esposito and Colwell 2003). The

  13. Kinetics of U(VI) reduction control kinetics of U(IV) reoxidation

    SciTech Connect

    Senko, J.M.; Minyard, M.L.; Dempsey, B.A.; Roden, E.E.; Yeh, G.-T.; Burgos, W.D.

    2006-04-05

    For the in situ reductive immobilization of U to be an acceptable strategy for the removal of that element from groundwater, the long-term stability of U(IV) must be determined. Rates of biotransformation of Fe species influence the mineralogy of the resulting products (Fredrickson et al., 2003; Senko et al., 2005), and we hypothesize that the rate of U(VI) reduction influences the mineralogy of resultant U(IV) precipitates. We hypothesize that slower rates of U(VI) reduction will yield U(IV) phases that are more resistant to reoxidation, and will therefore be more stable upon cessation of electron donor addition. U(IV) phases formed by relatively slow reduction may be more crystalline or larger in comparison to their relatively rapidly-formed counterparts (Figure 1), thus limiting the reactivity of slowly-formed U(IV) phases toward various oxidants. The physical location of U(IV) precipitates relative to bacterial cells may also limit the reactivity of biogenic U(IV) phases. In this situation, we expect that precipitation of U(IV) within the bacterial cell may protect U(IV) from reoxidation by limiting physical contact between U(IV) and oxidants (Figure 1). We assessed the effect of U(VI) reduction rate on the subsequent reoxidation of biogenic U(IV) and are currently conducting column scale studies to determine whether U(VI) reduction rate can be manipulated by varying the electron donor concentration used to stimulate U(VI) reduction.

  14. U(VI) reduction to mononuclear U(IV) by Desulfitobacterium species.

    PubMed

    Fletcher, Kelly E; Boyanov, Maxim I; Thomas, Sara H; Wu, Qingzhong; Kemner, Kenneth M; Löffler, Frank E

    2010-06-15

    The bioreduction of U(VI) to U(IV) affects uranium mobility and fate in contaminated subsurface environments and is best understood in Gram-negative model organisms such as Geobacter and Shewanella spp. This study demonstrates that U(VI) reduction is a common trait of Gram-positive Desulfitobacterium spp. Five different Desulfitobacterium isolates reduced 100 microM U(VI) to U(IV) in <10 days, whereas U(VI) remained soluble in abiotic and heat-killed controls. U(VI) reduction in live cultures was confirmed using X-ray absorption near-edge structure (XANES) analysis. Interestingly, although bioreduction of U(VI) is almost always reported to yield the uraninite mineral (UO(2)), extended X-ray absorption fine structure (EXAFS) analysis demonstrated that the U(IV) produced in the Desulfitobacterium cultures was not UO(2). The EXAFS data indicated that the U(IV) product was a phase or mineral composed of mononuclear U(IV) atoms closely surrounded by light element shells. This atomic arrangement likely results from inner-sphere bonds between U(IV) and C/N/O- or P/S-containing ligands, such as carbonate or phosphate. The formation of a distinct U(IV) phase warrants further study because the characteristics of the reduced material affect uranium stability and fate in the contaminated subsurface. PMID:20469854

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

    PubMed

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

    2014-09-16

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

  16. Abiotic U(VI) Reduction by Sorbed Fe(II) on Natural Sediments

    SciTech Connect

    Fox, Patricia M.; Davis, James A.; Kukkadapu, Ravi K.; Singer, David M.; Bargar, John R.; Williams, Kenneth H.

    2013-09-15

    Laboratory experiments were performed as a function of aqueous Fe(II) concentration to determine the uptake and oxidation of Fe(II), and Fe(II)-mediated abiotic reduction of U(VI) by aquifer sediments from the Rifle IFRC field site in Colorado, USA. Mössbauer analysis of the sediments spiked with aqueous 57Fe(II) showed that 57Fe(II) was oxidized on the mineral surfaces to 57Fe(III) and most likely formed a nano-particulate Fe(III)-oxide or ferrihydrite-like phase. The extent of 57Fe oxidation decreased with increasing 57Fe(II) uptake, such that 100 % was oxidized at 7.3 μmol/g Fe and 52 % at 39.6 μmol/g Fe, indicating that the sediments had a finite capacity for oxidation of Fe(II). Abiotic U(VI) reduction was observed by XANES spectroscopy only when the Fe(II) uptake was greater than approximately 20 μmol/g and surface-bound Fe(II) was present. The level of U(VI) reduction increased with increasing Fe(II)- loading above this level to a maximum of 18 and 36 % U(IV) at pH 7.2 (40.7 μmol/g Fe) and 8.3 (56.1 μmol/g Fe), respectively in the presence of 400 ppm CO2. Greater U(VI) reduction was observed in CO2 free systems [up to 44 and 54 % at pH 7.2 (17.3 μmol/g Fe) and 8.3 (54.8 μmol/g Fe), respectively] compared to 400 ppm CO2 systems, presumably due to differences in aqueous U(VI) speciation. While pH affects the amount of Fe(II) uptake onto the solid phase, with greater Fe(II) uptake at higher pH, similar amounts of U(VI) reduction were observed at pH 7.2 and 8.3 for a similar Fe(II) uptake. Thus, it appears that abiotic U(VI) reduction is controlled primarily by Fe(II) concentration and aqueous U(VI) speciation. The range of Fe(II) loadings tested in this study are within the range observed in bioreduced sediments, suggesting that Fe(II)-mediated abiotic U(VI) reduction may indeed play a role in field settings.

  17. Abiotic U(VI) reduction by sorbed Fe(II) on natural sediments

    NASA Astrophysics Data System (ADS)

    Fox, Patricia M.; Davis, James A.; Kukkadapu, Ravi; Singer, David M.; Bargar, John; Williams, Kenneth H.

    2013-09-01

    Laboratory experiments were performed as a function of aqueous Fe(II) concentration to determine the uptake and oxidation of Fe(II), and Fe(II)-mediated abiotic reduction of U(VI) by aquifer sediments from the DOE Rifle field research site in Colorado, USA. Mössbauer analysis of the sediments spiked with aqueous 57Fe(II) showed that 57Fe(II) was oxidized on the mineral surfaces to 57Fe(III) and most likely formed a nano-particulate Fe(III)-oxide or ferrihydrite-like phase. The extent of 57Fe oxidation decreased with increasing 57Fe(II) uptake, such that 98% was oxidized at 7.3 μmol/g Fe and 41% at 39.6 μmol/g Fe, indicating that the sediments had a limited capacity for oxidation of Fe(II). Abiotic U(VI) reduction was observed by XANES spectroscopy only when the Fe(II) uptake was greater than approximately 20 μmol/g and surface-bound Fe(II) was present, possibly as oligomeric Fe(II) surface species. The degree of U(VI) reduction increased with increasing Fe(II)-loading above this level to a maximum of 18% and 36% U(IV) at pH 7.2 (40.7 μmol/g Fe) and 8.3 (56.1 μmol/g Fe), respectively in the presence of 400 ppm CO2. Greater U(VI) reduction was observed in CO2-free systems [up to 44% and 54% at pH 7.2 (17.3 μmol/g Fe) and 8.3 (54.8 μmol/g Fe), respectively] compared to 400 ppm CO2 systems, presumably due to differences in aqueous U(VI) speciation. While pH affects the amount of Fe(II) uptake onto the solid phase, with greater Fe(II) uptake at higher pH, similar amounts of U(VI) reduction were observed at pH 7.2 and 8.3 for a similar Fe(II) uptake. Thus, it appears that abiotic U(VI) reduction is controlled primarily by sorbed Fe(II) concentration and aqueous U(VI) speciation. The range of Fe(II) loadings tested in this study are within the range observed in biostimulation experiments at the Rifle site, suggesting that Fe(II)-mediated abiotic U(VI) reduction could play a significant role in field settings.

  18. Reduction of U(VI) to U(IV) by indigenous bacteria in contaminated ground water

    NASA Astrophysics Data System (ADS)

    Abdelouas, A.; Lu, Yongming; Lutze, W.; Nuttall, H. E.

    1998-12-01

    We report on bio-catalyzed reduction and immobilization of U(VI) species (0.25 mg/l to 235 mg/l) in ground water in the presence of high concentrations of nitrate, sulfate and carbonate. We studied ground water from the uranium mill tailings site near Tuba City, Arizona (USA). Experiments with the ground water were conducted in the presence of the Navajo sandstone host rock. Uranium in solution is complexed by carbonate. Two indigenous denitrifying bacteria were identified Pseudomonas aeruginosa and P. stutzeri, and one sulfate reducing bacterium, Shewanella putrefaciens, also known as Fe(III)-reducer. S. putrefaciens can use U(VI) as an electron acceptor, instead of Fe(III). Ethanol was used as the organic carbon source. Microbially mediated reactions are sequential in the order of decreasing redox intensity. Metabolic reduction of nitrate to gaseous species (N 2, N 2O) was complete within 1 week at 16°C. The sulfate concentration remained constant. Some of the U(VI) coprecipitated with aragonite/calcite or was adsorbed on biomass during denitrification. Subsequently, the enzymatically catalyzed reduction of U(VI) to U(IV) was complete within 3 weeks but was accompanied by reduction of sulfate to sulfide. U(IV) precipitated as a uraninite solid solution (U, Ca)O 2, adhering to the bacteria. The final concentration in solution was ≤1 μg/l. U(VI) was not reduced by sulfide. Complexation of U(VI) by carbonate made its reduction by sulfide even slower than in pure water. The bio-catalyzed reaction is the faster process under the conditions given by the composition of the ground water.

  19. U(VI) sorption and reduction kinetics on the magnetite (111) surface

    SciTech Connect

    Singer, David M.; Chatman, Shawn ME; Ilton, Eugene S.; Rosso, Kevin M.; Banfield, Jillian F.; Waychunas, Glenn

    2012-04-03

    Sorption of contaminants onto mineral surfaces is an important process that can restrict their transport in the environment. In the current study, uranium (U) uptake on magnetite (111) was measured as a function of time and solution composition (pH, [CO3]T, [Ca]) under continuous batch-flow conditions. We observed, in real-time and in situ, adsorption and reduction of U(VI) and subsequent growth of UO2 nanoprecipitates using atomic force microscopy (AFM) and newly developed batch-flow U LIII-edge grazing-incidence x-ray absorption spectroscopy near-edge structure (GI-XANES) spectroscopy. U(VI) reduction occurred with and without CO3 present, and coincided with nucleation and growth of particles; maximum sorption loadings were 23 mol m-2 (pH 5) and 27 mol m-2 (pH 10). The U sorption loading was lower when Ca and CO3 were both present and during experiments in which no U(VI) reduction occurred; the maximum U sorption loading was 17 mol m-2 (pH 5 and 10). In situ batch-flow AFM data indicated that UO2 particles achieved a maximum height of 4-5 nm after about 8 hours of exposure, yet lateral growth as aggregates continued up to 300 nm. U uptake is therefore divided into three-stages; (1) initial adsorption of U(VI), (2) reduction of U(VI) to UO2 nanoprecipitates at surface-specific sites after 2-3 hours of exposure, and (3) completion of U(VI) reduction after 6-8 hours, with continuing slow adsorption of U(VI). U(VI) reduction also corresponded to detectable increases in Fe released to solution and surface topography changes, indicating that reduction is coupled to Fe(II) availability at or from the magnetite (111) surface. In addition to providing molecular-scale details about U sorption on magnetite, this work also presents novel advances for collecting surface sensitive molecular-scale information in real-time under batch-flow conditions.

  20. Role of U(VI) Reduction by Geobacter species

    SciTech Connect

    Lovely, Derrick

    2008-12-23

    Previous work had suggested that Acholeplasma palmae has a higher capacity for uranium sorption than other bacteria studied. Sorption studies were performed with cells in suspension in various solutions containing uranium, and results were used to generate uranium-biosorption isotherms. Results from this study showed that the U(VI) sorption capacity of G. uraniireducens was relatively similar in simple solutions, such as sodium chloride or bicarbonate. However, this ability to sorb uranium significantly decreased in groundwater. This suggested that certain chemicals present in the groundwater were inhibiting the ability of cell components of Geobacter to adsorb uranium. It was hypothesized that uranium removal would also be diminished in the bicarbonate solution. However, this did not seem to be the case, as uranium was as easily removed in the bicarbonate solution as in the sodium chloride solution.

  1. Elucidating Geochemical and Biogeochemical U(VI) Reduction Via Soil Sterilization at Oak Ridge, Tennessee

    NASA Astrophysics Data System (ADS)

    Bank, T. L.; Jardine, P. M.; Phelps, T. J.; Ginder-Vogel, M. A.; Fendorf, S. E.; Baldwin, M. E.

    2005-12-01

    The adsorption and reduction of U(VI) onto sterilized and nonsterilized soil from the Oak Ridge Reservation was studied to distinguish biogeochemical versus geochemical effects on metal reduction. The Oak Ridge soil under investigation is a saprolite sequence of interbedded weathered shale and limestone obtained at the capillary fringe with a pH near 7.6. Experiments were conducted on unaltered soils as well as subsamples of the soil that were pre-treated to remove free oxides and/or organic matter. Soils were sterilized by either steam sterilization at 1210C or by γ-irradiation using a Cobalt-60 source with a γ-ray dosage of 20kGy. Sterile and nonsterile U(VI) batch experiments were completed aerobically over a reaction time of 400 hours. The reactions were buffered using 25mM HEPES and NaHCO3. Initial U(VI) concentrations ranged from 0.5 to 10 ppm. The effects of sterilization on bacterial population, soil mineralogy, pH, ζ-potential, cation exchange capacity, redox potential, and soil organic matter (SOM) were identified. Sterilization by irradiation was >99.99% efficient and steam sterilization was approximately 99% efficient. Major mineralogy, soil pH, and clay mineral ζ-potential were unaffected by the sterilization techniques. The cation exchange capacity of the irradiated soils decreased from 40 to 30 cmolc/kg. Sterilization by irradiation caused some degradation of the SOM, as determined by UV-VIS, however the results were practically insignificant due to the small quantity of SOM in the Oak Ridge soil (<0.1%). The redox potential of the soil before and after sterilization is being tested. Results indicate that the removal of U(VI) from solution onto untreated soils was significantly increased in soil sterilized by γ-irradiation compared to nonsterilized soil and suggests that geochemical processes, rather than biogeochemical processes, controlled U(VI) sorption/reduction in these soils. Results of experiments completed using soils pre-treated with H2

  2. Products of abiotic U(VI) reduction by biogenic magnetite and vivianite

    NASA Astrophysics Data System (ADS)

    Veeramani, Harish; Alessi, Daniel S.; Suvorova, Elena I.; Lezama-Pacheco, Juan S.; Stubbs, Joanne E.; Sharp, Jonathan O.; Dippon, Urs; Kappler, Andreas; Bargar, John R.; Bernier-Latmani, Rizlan

    2011-05-01

    Reductive immobilization of uranium by the stimulation of dissimilatory metal-reducing bacteria (DMRB) has been investigated as a remediation strategy for subsurface U(VI) contamination. In those environments, DMRB may utilize a variety of electron acceptors, such as ferric iron which can lead to the formation of reactive biogenic Fe(II) phases. These biogenic phases could potentially mediate abiotic U(VI) reduction. In this work, the DMRB Shewanella putrefaciens strain CN32 was used to synthesize two biogenic Fe(II)-bearing minerals: magnetite (a mixed Fe(II)-Fe(III) oxide) and vivianite (an Fe(II)-phosphate). Analysis of abiotic redox interactions between these biogenic minerals and U(VI) showed that both biogenic minerals reduced U(VI) completely. XAS analysis indicates significant differences in speciation of the reduced uranium after reaction with the two biogenic Fe(II)-bearing minerals. While biogenic magnetite favored the formation of structurally ordered, crystalline UO 2, biogenic vivianite led to the formation of a monomeric U(IV) species lacking U-U associations in the corresponding EXAFS spectrum. To investigate the role of phosphate in the formation of monomeric U(IV) such as sorbed U(IV) species complexed by mineral surfaces, versus a U(IV) mineral, uranium was reduced by biogenic magnetite that was pre-sorbed with phosphate. XAS analysis of this sample also revealed the formation of monomeric U(IV) species suggesting that the presence of phosphate hinders formation of UO 2. This work shows that U(VI) reduction products formed during in situ biostimulation can be influenced by the mineralogical and geochemical composition of the surrounding environment, as well as by the interfacial solute-solid chemistry of the solid-phase reductant.

  3. U(VI) Reduction by Diverse Outer Surface c-Type Cytochromes of Geobacter sulfurreducens

    PubMed Central

    Leavitt, Janet J.; Comolli, Luis R.; Csencsits, Roseann; Janot, Noemie; Flanagan, Kelly A.; Gray, Arianna S.; Leang, Ching; Izallalen, Mounir; Mester, Tünde; Lovley, Derek R.

    2013-01-01

    Early studies with Geobacter sulfurreducens suggested that outer-surface c-type cytochromes might play a role in U(VI) reduction, but it has recently been suggested that there is substantial U(VI) reduction at the surface of the electrically conductive pili known as microbial nanowires. This phenomenon was further investigated. A strain of G. sulfurreducens, known as Aro-5, which produces pili with substantially reduced conductivity reduced U(VI) nearly as well as the wild type, as did a strain in which the gene for PilA, the structural pilin protein, was deleted. In order to reduce rates of U(VI) reduction to levels less than 20% of the wild-type rates, it was necessary to delete the genes for the five most abundant outer surface c-type cytochromes of G. sulfurreducens. X-ray absorption near-edge structure spectroscopy demonstrated that whereas 83% ± 10% of the uranium associated with wild-type cells correspond to U(IV) after 4 h of incubation, with the quintuple mutant, 89% ± 10% of uranium was U(VI). Transmission electron microscopy and X-ray energy dispersion spectroscopy revealed that wild-type cells did not precipitate uranium along pili as previously reported, but U(IV) was precipitated at the outer cell surface. These findings are consistent with those of previous studies, which have suggested that G. sulfurreducens requires outer-surface c-type cytochromes but not pili for the reduction of soluble extracellular electron acceptors. PMID:23934497

  4. Microbial reduction of U(VI) under alkaline conditions: implications for radioactive waste geodisposal.

    PubMed

    Williamson, Adam J; Morris, Katherine; Law, Gareth T W; Rizoulis, Athanasios; Charnock, John M; Lloyd, Jonathan R

    2014-11-18

    Although there is consensus that microorganisms significantly influence uranium speciation and mobility in the subsurface under circumneutral conditions, microbiologically mediated U(VI) redox cycling under alkaline conditions relevant to the geological disposal of cementitious intermediate level radioactive waste, remains unexplored. Here, we describe microcosm experiments that investigate the biogeochemical fate of U(VI) at pH 10-10.5, using sediments from a legacy lime working site, stimulated with an added electron donor, and incubated in the presence and absence of added Fe(III) as ferrihydrite. In systems without added Fe(III), partial U(VI) reduction occurred, forming a U(IV)-bearing non-uraninite phase which underwent reoxidation in the presence of air (O2) and to some extent nitrate. By contrast, in the presence of added Fe(III), U(VI) was first removed from solution by sorption to the Fe(III) mineral, followed by bioreduction and (bio)magnetite formation coupled to formation of a complex U(IV)-bearing phase with uraninite present, which also underwent air (O2) and partial nitrate reoxidation. 16S rRNA gene pyrosequencing showed that Gram-positive bacteria affiliated with the Firmicutes and Bacteroidetes dominated in the post-reduction sediments. These data provide the first insights into uranium biogeochemistry at high pH and have significant implications for the long-term fate of uranium in geological disposal in both engineered barrier systems and the alkaline, chemically disturbed geosphere. PMID:25231875

  5. Metaproteomics Identifies the Protein Machinery Involved in Metal and Radionuclide Reduction in Subsurface Microbiomes and Elucidates Mechanisms and U(VI) Reduction Immobilization

    SciTech Connect

    Pfiffner, Susan M.; Löffler, Frank; Ritalahti, Kirsti; Sayler, Gary; Layton, Alice; Hettich, Robert

    2015-08-31

    The overall goal for this funded project was to develop and exploit environmental metaproteomics tools to identify biomarkers for monitoring microbial activity affecting U speciation at U-contaminated sites, correlate metaproteomics profiles with geochemical parameters and U(VI) reduction activity (or lack thereof), elucidate mechanisms contributing to U(VI) reduction, and provide remediation project managers with additional information to make science-based site management decisions for achieving cleanup goals more efficiently. Although significant progress has been made in elucidating the microbiology contribution to metal and radionuclide reduction, the cellular components, pathway(s), and mechanisms involved in U trans-formation remain poorly understood. Recent advances in (meta)proteomics technology enable detailed studies of complex samples, including environmental samples, which differ between sites and even show considerable variability within the same site (e.g., the Oak Ridge IFRC site). Additionally, site-specific geochemical conditions affect microbial activity and function, suggesting generalized assessment and interpretations may not suffice. This research effort integrated current understanding of the microbiology and biochemistry of U(VI) reduction and capitalize on advances in proteomics technology made over the past few years. Field-related analyses used Oak Ridge IFRC field ground water samples from locations where slow-release substrate biostimulation has been implemented to accelerate in situ U(VI) reduction rates. Our overarching hypothesis was that the metabolic signature in environmental samples, as deciphered by the metaproteome measurements, would show a relationship with U(VI) reduction activity. Since metaproteomic and metagenomic characterizations were computationally challenging and time-consuming, we used a tiered approach that combines database mining, controlled laboratory studies, U(VI) reduction activity measurements, phylogenetic

  6. Reduction of U(VI) Incorporated in the Structure of Hematite

    SciTech Connect

    Ilton, Eugene S.; Lazama Pacheco, Juan S.; Bargar, John R.; Shi, Zhi; Liu, Juan; Kovarik, Libor; Engelhard, Mark H.; Felmy, Andrew R.

    2012-09-04

    U(VI) doped hematite was synthesized and exposed to two different organic reductants with E0 of 0.23 and 0.70 V. A combination of HAADF-TEM and EXAFS provided evidence that uranium was incorporated in hematite in uranate, likely octahedral coordination. XPS indicated that structurally incorporated U(VI) was reduced to U(V), whereas adsorbed U(VI) was reduced to U(IV). Specifically, the experiments indicate that U(V) was the dominant oxidation state of uranium in hematite around Eh -0.24 to -0.28 V and pH 7.7-8.6 for at least up to 5 weeks of reaction time. U(V), but not U(IV), was also detected in hematite at Eh +0.21 V (pH 7.1-7.3). The results support the hypothesis, based on previous experimental and theoretical work, that the stability field of U(V) is widened relative to U(IV) and U(VI) in uranate coordination environments where the coordination number of U is less than 8.

  7. Reduction of U(VI) incorporated in the structure of hematite.

    PubMed

    Ilton, Eugene S; Pacheco, Juan S Lezama; Bargar, John R; Shi, Zhi; Liu, Juan; Kovarik, Libor; Engelhard, Mark H; Felmy, Andrew R

    2012-09-01

    U(VI) doped hematite was synthesized and exposed to two different organic reductants with E(0) of 0.23 and 0.70 V. A combination of HAADF-TEM and EXAFS provided evidence that uranium was incorporated in hematite in uranate, likely octahedral coordination. XPS indicated that structurally incorporated U(VI) was reduced to U(V), whereas non-incorporated U(VI) was reduced to U(IV). Specifically, the experiments indicate that U(V) was the dominant oxidation state of uranium in hematite around Eh -0.24 to -0.28 V and pH 7.7-8.6 for at least up to 5 weeks of reaction time. U(V), but not U(IV), was also detected in hematite at Eh +0.21 V (pH 7.1-7.3). The results support the hypothesis, based on previous experimental and theoretical work, that the stability field of U(V) is widened relative to U(IV) and U(VI) in uranate coordination environments where the coordination number of U is less than 8. PMID:22834714

  8. Dynamic Succession of Groundwater Functional Microbial Communities in Response to Emulsified Vegetable Oil Amendment during Sustained In Situ U(VI) Reduction

    PubMed Central

    Zhang, Ping; Wu, Wei-Min; Van Nostrand, Joy D.; Deng, Ye; He, Zhili; Gihring, Thomas; Zhang, Gengxin; Schadt, Chris W.; Watson, David; Jardine, Phil; Criddle, Craig S.; Brooks, Scott; Marsh, Terence L.; Tiedje, James M.; Arkin, Adam P.

    2015-01-01

    A pilot-scale field experiment demonstrated that a one-time amendment of emulsified vegetable oil (EVO) reduced groundwater U(VI) concentrations for 1 year in a fast-flowing aquifer. However, little is known about how EVO amendment stimulates the functional gene composition, structure, and dynamics of groundwater microbial communities toward prolonged U(VI) reduction. In this study, we hypothesized that EVO amendment would shift the functional gene composition and structure of groundwater microbial communities and stimulate key functional genes/groups involved in EVO biodegradation and reduction of electron acceptors in the aquifer. To test these hypotheses, groundwater microbial communities after EVO amendment were analyzed using a comprehensive functional gene microarray. Our results showed that EVO amendment stimulated sequential shifts in the functional composition and structure of groundwater microbial communities. Particularly, the relative abundance of key functional genes/groups involved in EVO biodegradation and the reduction of NO3−, Mn(IV), Fe(III), U(VI), and SO42− significantly increased, especially during the active U(VI) reduction period. The relative abundance for some of these key functional genes/groups remained elevated over 9 months. Montel tests suggested that the dynamics in the abundance, composition, and structure of these key functional genes/groups were significantly correlated with groundwater concentrations of acetate, NO3−, Mn(II), Fe(II), U(VI), and SO42−. Our results suggest that EVO amendment stimulated dynamic succession of key functional microbial communities. This study improves our understanding of the composition, structure, and function changes needed for groundwater microbial communities to sustain a long-term U(VI) reduction. PMID:25862231

  9. Microbial Reductive Transformation of Phyllosilicate Fe(III) and U(VI) in Fluvial Subsurface Sediments

    SciTech Connect

    Lee, Ji-Hoon; Fredrickson, Jim K.; Kukkadapu, Ravi K.; Boyanov, Maxim I.; Kemner, Kenneth M.; Lin, Xueju; Kennedy, David W.; Bjornstad, Bruce N.; Konopka, Allan; Moore, Dean A.; Resch, Charles T.; Phillips, Jerry L.

    2012-03-14

    The microbial reduction of Fe(III) and U(VI) were investigated in shallow aquifer sediments collected from subsurface Pleistocene flood deposits near the Hanford Reach of the Columbia River in Washington State. Increases in 0.5 N HCl-extractable Fe(II) were observed in incubated sediments and 57Fe Mössbauer spectroscopy revealed that Fe(III) associated with phyllosilicates and pyroxene was reduced to Fe(II). Aqueous uranium(VI) concentrations decreased in incubated Hanford sediments with the rate and extent being greater in sediment amended with organic carbon. X-ray absorption spectroscopy of bioreduced sediments indicated that 67-77% of the U signal was U(VI), probably as an adsorbed species associated with a new or modified reactive mineral phase. Phylotypes within the Deltaproteobacteria were more common in Hanford sediments incubated with U(VI) than without and in U(VI)-free incubations, members of the Clostridiales were dominant with sulfate-reducing phylotypes more common in the sulfate-amended sediments. These results demonstrate the potential for anaerobic reduction phyllosilicate Fe(III) and sulfate in Hanford unconfined aquifer sediments and biotransformations involving reduction and adsorption leading to decreased aqueous U concentrations.

  10. Pilot-Scale In Situ Bioremediation of Uranium in a Highly Contaminated Aquifer. 2. Reduction of U(VI and Geochemical Control of U(VI) Bioavailability

    SciTech Connect

    Wu, Weimin; Carley, Jack M; Gentry, Terry J; Ginder-Vogel, Matthew; Fienen, Michael; Mehlhorn, Tonia L; Yan, Hui; Carroll, Sue L; Pace, Molly; Nyman, Jennifer L; Luo, Jian; Fields, Matthew Wayne; Hickey, Robert; Gu, Baohua; Watson, David B; Cirpka, Olaf; Zhou, Jizhong; Fendorf, Scott; Kitanidis, Peter K; Jardine, Philip M; Criddle, Craig

    2006-07-01

    In situ microbial reduction of soluble U(VI) to sparingly soluble U(IV) was evaluated at the site of the former S-3 Ponds in Area 3 of the U.S. Department of Energy Natural and Accelerated Bioremediation Research Field Research Center, Oak Ridge, TN. After establishing conditions favorable for bioremediation (Wu, et al. Environ. Sci. Technol. 2006, 40, 3988-3995), intermittent additions of ethanol were initiated within the conditioned inner loop of a nested well recirculation system. These additions initially stimulated denitrification of matrix-entrapped nitrate, but after 2 months, aqueous U levels fell from 5 to {approx}1 {micro}M and sulfate reduction ensued. Continued additions sustained U(VI) reduction over 13 months. X-ray near-edge absorption spectroscopy (XANES) confirmed U(VI) reduction to U(IV) within the inner loop wells, with up to 51%, 35%, and 28% solid-phase U(IV) in sediment samples from the injection well, a monitoring well, and the extraction well, respectively. Microbial analyses confirmed the presence of denitrifying, sulfate-reducing, and iron-reducing bacteria in groundwater and sediments. System pH was generally maintained at less than 6.2 with low bicarbonate level (0.75-1.5 mM) and residual sulfate to suppress methanogenesis and minimize uranium mobilization. The bioavailability of sorbed U(VI) was manipulated by addition of low-level carbonate (<5 mM) followed by ethanol (1-1.5 mM). Addition of low levels of carbonate increased the concentration of aqueous U, indicating an increased rate of U desorption due to formation of uranyl carbonate complexes. Upon ethanol addition, aqueous U(VI) levels fell, indicating that the rate of microbial reduction exceeded the rate of desorption. Sulfate levels simultaneously decreased, with a corre sponding increase in sulfide. When ethanol addition ended but carbonate addition continued, soluble U levels increased, indicating faster desorption than reduction. When bicarbonate addition stopped, aqueous U

  11. Pilot-scale in situ bioremedation of uranium in a highly contaminated aquifer. 2. Reduction of u(VI) and geochemical control of u(VI) bioavailability.

    PubMed

    Wu, Wei-Min; Carley, Jack; Gentry, Terry; Ginder-Vogel, Matthew A; Fienen, Michael; Mehlhorn, Tonia; Yan, Hui; Caroll, Sue; Pace, Molly N; Nyman, Jennifer; Luo, Jian; Gentile, Margaret E; Fields, Matthew W; Hickey, Robert F; Gu, Baohua; Watson, David; Cirpka, Olaf A; Zhou, Jizhong; Fendorf, Scott; Kitanidis, Peter K; Jardine, Philip M; Criddle, Craig S

    2006-06-15

    In situ microbial reduction of soluble U(VI) to sparingly soluble U(IV) was evaluated at the site of the former S-3 Ponds in Area 3 of the U.S. Department of Energy Natural and Accelerated Bioremediation Research Field Research Center, Oak Ridge, TN. After establishing conditions favorable for bioremediation (Wu, et al. Environ. Sci. Technol. 2006, 40, 3988-3995), intermittent additions of ethanol were initiated within the conditioned inner loop of a nested well recirculation system. These additions initially stimulated denitrification of matrix-entrapped nitrate, but after 2 months, aqueous U levels fell from 5 to approximately 1 microM and sulfate reduction ensued. Continued additions sustained U(VI) reduction over 13 months. X-ray near-edge absorption spectroscopy (XANES) confirmed U(VI) reduction to U(IV) within the inner loop wells, with up to 51%, 35%, and 28% solid-phase U(IV) in sediment samples from the injection well, a monitoring well, and the extraction well, respectively. Microbial analyses confirmed the presence of denitrifying, sulfate-reducing, and iron-reducing bacteria in groundwater and sediments. System pH was generally maintained at less than 6.2 with low bicarbonate level (0.75-1.5 mM) and residual sulfate to suppress methanogenesis and minimize uranium mobilization. The bioavailability of sorbed U(VI) was manipulated by addition of low-level carbonate (< 5 mM) followed by ethanol (1-1.5 mM). Addition of low levels of carbonate increased the concentration of aqueous U, indicating an increased rate of U desorption due to formation of uranyl carbonate complexes. Upon ethanol addition, aqueous U(VI) levels fell, indicating that the rate of microbial reduction exceeded the rate of desorption. Sulfate levels simultaneously decreased, with a corresponding increase in sulfide. When ethanol addition ended but carbonate addition continued, soluble U levels increased, indicating faster desorption than reduction. When bicarbonate addition stopped

  12. Microbial community changes in response to ethanol or methanol amendments for U(VI) reduction.

    PubMed

    Vishnivetskaya, Tatiana A; Brandt, Craig C; Madden, Andrew S; Drake, Meghan M; Kostka, Joel E; Akob, Denise M; Küsel, Kirsten; Palumbo, Anthony V

    2010-09-01

    Microbial community responses to ethanol, methanol, and methanol plus humics amendments in relationship to U(VI) bioreduction were studied in laboratory microcosm experiments using sediments and ground water from a uranium-contaminated site in Oak Ridge, TN. The type of carbon source added, the duration of incubation, and the sampling site influenced the bacterial community structure upon incubation. Analysis of 16S rRNA gene clone libraries indicated that (i) bacterial communities found in ethanol- and methanol-amended samples with U(VI) reduction were similar due to the presence of Deltaproteobacteria and Betaproteobacteria (members of the families Burkholderiaceae, Comamonadaceae, Oxalobacteraceae, and Rhodocyclaceae); (ii) methanol-amended samples without U(VI) reduction exhibited the lowest diversity and the bacterial community contained 69.2 to 92.8% of the family Methylophilaceae; and (iii) the addition of humics resulted in an increase of phylogenetic diversity of Betaproteobacteria (Rodoferax, Polaromonas, Janthinobacterium, Methylophilales, and unclassified) and Firmicutes (Desulfosporosinus and Clostridium). PMID:20601514

  13. Abiotic Reductive Immobilization of U(VI) by Biogenic Mackinawite

    SciTech Connect

    Veeramani, Harish; Scheinost, Andreas; Monsegue, Niven; Qafoku, Nikolla; Kukkadapu, Ravi K.; Newville, Mathew; Lanzirotti, Anthony; Pruden, Amy; Murayama, Mitsuhiro; Hochella, Michael F.

    2013-03-01

    During subsurface bioremediation of uranium-contaminated sites, indigenous metal and sulfate-reducing bacteria may utilize a variety of electron acceptors, including ferric iron and sulfate that could lead to the formation of various biogenic minerals in-situ. Sulfides, as well as structural and adsorbed Fe(II) associated with biogenic Fe(II)-sulfide phases, can potentially catalyze abiotic U6+ reduction via direct electron transfer processes. In the present work, the propensity of biogenic mackinawite (Fe1+xS, x = 0 to 0.11) to reduce U6+ abiotically was investigated. The biogenic mackinawite produced by Shewanella putrefaciens strain CN32 was characterized by employing a suite of analytical techniques including TEM, SEM, XAS and Mössbauer analyses. Nanoscale and bulk analyses (microscopic and spectroscopic techniques, respectively) of biogenic mackinawite after exposure to U6+ indicate the formation of nanoparticulate UO2. This study suggests the relevance of Fe(II) and sulfide bearing biogenic minerals in mediating abiotic U6+ reduction, an alternative pathway in addition to direct enzymatic U6+ reduction.

  14. Isotopic and geochemical tracers for U(VI) reduction and U mobility at an in situ recovery U mine

    SciTech Connect

    Basu, Anirban; Brown, Shaun T.; Christensen, John N.; DePaolo, Donald J.; Reimus, Paul W.; Heikoop, Jeffrey M.; Woldegabriel, Giday; Simmons, Ardyth M.; House, Brian M.; Hartmann, Matt; Maher, Kate

    2015-05-19

    In situ recovery (ISR) uranium (U) mining mobilizes U in its oxidized hexavalent form (U(VI)) by oxidative dissolution of U from the roll-front U deposits. Post-mining natural attenuation of residual U(VI) at ISR mines is a potential remediation strategy. Detection and monitoring of naturally occurring reducing subsurface environments are important for successful implementation of this remediation scheme. We used the isotopic tracers ²³⁸U/²³⁵U (δ²³⁸U), ²³⁴U/²³⁸U activity ratio, and ³⁴S/³²S (δ³⁴S), and geochemical measurements of U ore and groundwater collected from 32 wells located within, upgradient, and downgradient of a roll-front U deposit to detect U(VI) reduction and U mobility at an ISR mining site at Rosita, TX, USA. The δ²³⁸U in Rosita groundwater varies from 0.61‰ to -2.49‰, with a trend toward lower δ²³⁸U in downgradient wells. The concurrent decrease in U(VI) concentration and δ²³⁸U with an ε of 0.48‰ ± 0.08‰ is indicative of naturally occurring reducing environments conducive to U(VI) reduction. Additionally, characteristic ²³⁴U/²³⁸U activity ratio and δ³⁴S values may also be used to trace the mobility of the ore zone groundwater after mining has ended. These results support the use of U isotope-based detection of natural attenuation of U(VI) at Rosita and other similar ISR mining sites.

  15. Aqueous Complexation Reactions Governing the Rate and Extent of Biogeochemical U(VI) Reduction

    SciTech Connect

    Scott C. Brooks; Wenming Dong; Sue Carroll; James K. Fredrickson; Kenneth M. Kemner; Shelly D. Kelly

    2006-06-01

    The proposed research will elucidate the principal biogeochemical reactions that govern the concentration, chemical speciation, and reactivity of the redox-sensitive contaminant uranium. The results will provide an improved understanding and predictive capability of the mechanisms that govern the biogeochemical reduction of uranium in subsurface environments. In addition, the work plan is designed to: (1) Generate fundamental scientific understanding on the relationship between U(VI) chemical speciation and its susceptibility to biogeochemical reduction reactions. (2) Elucidate the controls on the rate and extent of contaminant reactivity. (3) Provide new insights into the aqueous and solid speciation of U(VI)/U(IV) under representative groundwater conditions.

  16. Electrochemical and spectroscopic evidence on the one-electron reduction of U(VI) to U(V) on magnetite

    SciTech Connect

    Yuan, Ke; Ilton, Eugene S.; Antonio, Mark R.; Li, Zhongrui; Cook, Peter J.; Becker, Udo

    2015-05-19

    Reduction of U(VI) to U(IV) on mineral surfaces has been considered as a one-step two electron process. However, stabilized U(V), with no evidence of U(IV), found in recent studies indicates U(VI) can undergo a one electron reduction to U(V) without further progression to U(IV). We investigated the mechanisms of uranium reduction by reducing U(VI) electrochemically on a magnetite electrode at pH 3.4 . The one electron reduction of U(VI) was first confirmed using the cyclic voltammetry method. Formation of nano-size uranium precipitates on the surface of magnetite at reducing potentials and dissolution of the solids at oxidizing potentials were observed by in situ electrochemical AFM. XPS analysis of the magnetite electrodes polarized in uranium solutions at voltages from 0.1 ~ 0.9 V (vs. Ag/AgCl) showed the presence of only U(V) and U(VI). The highest amount of U(V) relative to U(VI) was prepared at 0.7 V, where the longest average U–Oaxial distance of 2.05 ± 0.01 Å was evident in the same sample revealed by EXAFS analysis. The results demonstrate that the electrochemical reduction of U(VI) on magnetite only yields U(V), even at a potential of 0.9 V, which favors the one-electron reduction mechanism. U(V) did not disproportionate but stabilized on magnetite through precipitation of mixed-valence state U(VI)/U(V) solids.

  17. Microbial Community Changes in Response to Ethanol or Methanol Amendments for U(VI) Reduction

    SciTech Connect

    Vishnivetskaya, Tatiana A; Brandt, Craig C; Madden, Andrew; Drake, Meghan M; Kostka, Joel; Akob, Denise M.; Kusel, Kirsten; Palumbo, Anthony Vito

    2010-01-01

    Microbial community responses to ethanol, methanol and methanol + humics amendments in relationship to uranium bioremediation were studied in laboratory microcosm experiments using sediments and ground water from a uranium-contaminated site in Oak Ridge, Tennessee. Ethanol addition always resulted in uranium reduction at rate of 0.8-1.0 mol l-1 d-1 while methanol addition did so occasionally at rate 0.95 mol l-1 d-1. The type of carbon source added, the duration of incubation, and the sampling site influenced the bacterial community structure upon incubation. Analysis of 16S rRNA gene clone libraries indicated (1) bacterial communities found in ethanol- and methanol-amended samples with U(VI) reduction were similar due to presence of -Proteobacteria, and -Proteobacteria (members of the families Burkholderiaceae, Comamonadaceae, Oxalobacteraceae, and Rhodocyclaceae); (2) methanol-amended samples without U(VI) reduction exhibited the lowest diversity and the bacterial community contained 69.2-92.8% of the family Methylophilaceae; and (3) the addition of humics resulted in an increase of phylogenetic diversity of -Proteobacteria (Rodoferax, Polaromonas, Janthinobacterium, Methylophilales, unclassified) and Firmicutes (Desulfosporosinus, Clostridium).

  18. Electrochemical and Spectroscopic Evidence on the One-Electron Reduction of U(VI) to U(V) on Magnetite.

    PubMed

    Yuan, Ke; Ilton, Eugene S; Antonio, Mark R; Li, Zhongrui; Cook, Peter J; Becker, Udo

    2015-05-19

    Reduction of U(VI) to U(IV) on mineral surfaces is often considered a one-step two-electron process. However, stabilized U(V), with no evidence of U(IV), found in recent studies indicates U(VI) can undergo a one-electron reduction to U(V) without further progression to U(IV). We investigated reduction pathways of uranium by reducing U(VI) electrochemically on a magnetite electrode at pH 3.4. Cyclic voltammetry confirms the one-electron reduction of U(VI) to U(V). Formation of nanosize uranium precipitates on the magnetite surface at reducing potentials and dissolution of the solids at oxidizing potentials are observed by in situ electrochemical atomic force microscopy. XPS analysis of the magnetite electrodes polarized in uranium solutions at voltages from -0.1 to -0.9 V (E(0)(U(VI)/U(V))= -0.135 V vs Ag/AgCl) show the presence of only U(V) and U(VI). The sample with the highest U(V)/U(VI) ratio was prepared at -0.7 V, where the longest average U-O(axial) distance of 2.05 ± 0.01 Å was evident in the same sample revealed by extended X-ray absorption fine structure analysis. The results demonstrate that the electrochemical reduction of U(VI) on magnetite only yields U(V), even at a potential of -0.9 V, which favors the one-electron reduction mechanism. U(V) does not disproportionate but stabilizes on magnetite through precipitation of mixed-valence state U(V)/U(VI) solids. PMID:25893535

  19. Inhibition of a U(VI)- and sulfate-reducing consortia by U(VI).

    PubMed

    Nyman, Jennifer L; Wu, Hsin-I; Gentile, Margaret E; Kitanidis, Peter K; Criddle, Craig S

    2007-09-15

    The stimulation of microbial U(VI) reduction is currently being investigated as a means to reduce uranium's mobility in groundwater, but little is known about the concentration at which U(VI) might inhibit microbial activity, or the effect of U(VI) on bacterial community structure. We investigated these questions with an ethanol-fed U(VI)- and sulfate-reducing enrichment developed from sediment from the site of an ongoing field biostimulation experiment at Area 3 of the Oak Ridge Field Research Center (FRC). Sets of triplicate enrichments were spiked with increasing concentrations of U(VI) (from 49 microm to 9.2 mM). As the U(VI) concentration increased to 224 microM, the culture's production of acetate from ethanol slowed, and at or above 1.6 mM U(VI) little acetate was produced over the time frame of the experiment. An uncoupling inhibition model was applied to the data, and the inhibition coefficient for U(VI), Ku, was found to be approximately 100 microM U(VI), or 24 mg/L, indicating the inhibitory effect is relevant at highly contaminated sites. Microbial community structure at the conclusion of the experiment was analyzed with terminal restriction fragment length polymorphism (T-RFLP) analysis. T-RFs associated with Desulfovibrio-like organisms decreased in relative abundance with increasing U(VI) concentration, whereas Clostridia-like T-RFs increased. PMID:17948804

  20. Plutonium(VI) accumulation and reduction by lichen biomass: correlation with U(VI).

    PubMed

    Ohnuki, Toshihiko; Aoyagi, Hisao; Kitatsuji, Yoshihiro; Samadfam, Mohammad; Kimura, Yasuhiko; William Purvis, O

    2004-01-01

    The uptake of plutonium(VI) and uranium(VI) by lichen biomass was studied in the foliose lichen Parmotrema tinctorum to elucidate the migration behavior of Pu and U in the terrestrial environment. Pu and U uptake by P. tinctorum averaged 0.040+/-0.010 and 0.055+/-0.015 g gdry (-1), respectively, after 96 h incubation with 4.0 x 10(14) mol 1(-1) Pu solutions of pH 3, 4 and 5. SEM observations showed that the accumulated Pu is evenly distributed on the upper and lower surfaces of P. tinctorum, in contrast to U(VI), which accumulated in both cortical and medullary layers. UV/VIS absorption spectroscopy demonstrates that a fraction of Pu(VI) in the solution is reduced to Pu(V) by the organic substances released from P. tinctorum, and the accumulated Pu on the surface is reduced to Pu(IV), while U(VI) keeps the oxidation state of VI. Since the solubility of Pu(IV) hydroxides is very low, reduced Pu(VI) does not penetrate to the medullary layers, but is probably precipitated as Pu(IV) hydroxides on the cortical lichen surface. It is concluded that the uptake and reduction of Pu(VI) by lichens is important to determine the mobilization and oxidation states of Pu in the terrestrial environment. PMID:15381325

  1. Acceleration of Microbially Mediated U(VI) Reduction at a Uranium Mill Tailings Site, Colorado Plateau

    SciTech Connect

    Phil Long; Todd Anderson; Aaron Peacock; Steve Heald; Yun-Juan Chang; Dick Dayvault; Derek R. Lovley; C.T. Resch; Helen Vrionis; Irene Ortiz-Bernad; D.C. White

    2004-03-17

    A second field-scale electron donor amendment experiment was conducted in 2003 at the Old Rifle Uranium Mill Tailings Remedial Action (UMTRA) site in Rifle, Colorado. The objective of the 2003 experiment (done in collaboration with the U.S. Department of Energy's UMTRA Groundwater Project) was to test the hypothesis that amendment of increased concentration of electron donor would result in an increased export of electron donor down gradient which in turn would create a larger zone of down-gradient U(VI) bioreduction sustained over a longer time period relative to the 2002 experiment (Anderson et al. 2003). During the first experiment (2002), {approx}3 mM acetate was amended to subsurface over a period of 3 months in a 15m by 18m by 2.5m volume comprised of 3 upgradient monitoring wells, 20 injection wells, and 15 down-gradient monitoring wells. After an initial one-month phase of metal reduction, bioavailable oxidized Fe was consumed near the injection gallery and the dominant terminal electron accepting process became sulfate reduction, rapidly consuming the injected acetate. For the 2003 experiment, we amended sufficient acetate ({approx}10 mM) to consume available sulfate and export acetate down-gradient where bioavailable oxidized Fe was still present. Data from the experiment indicate that acetate was exported further down gradient, resulting in a larger zone of microbial U(VI) reduction than for the 2002 experiment. Geohydrologic, geochemical, and microbiological data collected during the course of both experiments enable assessment of relative importance of a number of factors controlling the experimental outcomes. Companion posters by Anderson et al. and White et al. provide additional results.

  2. Influence of Reactive Transport on the Reduction of U(VI) in the Presence of Fe(III) and Nitrate: Implications for U(VI) Immobilization by Bioremediation/Bioba

    SciTech Connect

    Wood, Brian D.

    2004-06-01

    The research in FY04 was focused in five specific topics: (1) U(VI) sorption on microbially and abiotically reduced sediments, (2) oxidation of biogenic U(IV) in presence of Fe(II), (3) U(VI) reduction by reduced sediments, (4) kinetics of U(VI) sorption on natural sediments under conditions of flow, and (5) NMR imaging of S. onidensis biofilms in porous media. Two manuscripts are currently in review, and another five (or four?) manuscripts are currently in preparation for submission.

  3. Modeling Reduction of Uranium U(VI) under Variable Sulfate Concentrations by Sulfate-Reducing Bacteria

    PubMed Central

    Spear, John R.; Figueroa, Linda A.; Honeyman, Bruce D.

    2000-01-01

    The kinetics for the reduction of sulfate alone and for concurrent uranium [U(VI)] and sulfate reduction, by mixed and pure cultures of sulfate-reducing bacteria (SRB) at 21 ± 3°C were studied. The mixed culture contained the SRB Desulfovibrio vulgaris along with a Clostridium sp. determined via 16S ribosomal DNA analysis. The pure culture was Desulfovibrio desulfuricans (ATCC 7757). A zero-order model best fit the data for the reduction of sulfate from 0.1 to 10 mM. A lag time occurred below cell concentrations of 0.1 mg (dry weight) of cells/ml. For the mixed culture, average values for the maximum specific reaction rate, Vmax, ranged from 2.4 ± 0.2 μmol of sulfate/mg (dry weight) of SRB · h−1) at 0.25 mM sulfate to 5.0 ± 1.1 μmol of sulfate/mg (dry weight) of SRB · h−1 at 10 mM sulfate (average cell concentration, 0.52 mg [dry weight]/ml). For the pure culture, Vmax was 1.6 ± 0.2 μmol of sulfate/mg (dry weight) of SRB · h−1 at 1 mM sulfate (0.29 mg [dry weight] of cells/ml). When both electron acceptors were present, sulfate reduction remained zero order for both cultures, while uranium reduction was first order, with rate constants of 0.071 ± 0.003 mg (dry weight) of cells/ml · min−1 for the mixed culture and 0.137 ± 0.016 mg (dry weight) of cells/ml · min−1 (U0 = 1 mM) for the D. desulfuricans culture. Both cultures exhibited a faster rate of uranium reduction in the presence of sulfate and no lag time until the onset of U reduction in contrast to U alone. This kinetics information can be used to design an SRB-dominated biotreatment scheme for the removal of U(VI) from an aqueous source. PMID:10966381

  4. Influence of Mn oxides on the reduction of U(VI) by the metal-reducing bacterium Shewanella putrefaciens

    SciTech Connect

    Fredrickson, Jim K.; Zachara, John M.; Kennedy, David W.; Liu, Chongxuan; Duff, Martine C.; Hunter, David; Dohnalkova, Alice

    2002-09-16

    Dissimilatory metal-reducing bacteria (DMRB) enzymatically reduce Fe(III), Mn(III/IV), U(VI), and other polyvalent metals during anaerobic respiration. Previous investigations of the bacterial reduction of U(VI) in the presence of goethite (a-FeOOH) found that, in spite of potential competition as an electron acceptor, goethite had little impact on the bacterial reduction of U(VI) to insoluble U(IV). Mn(III/IV) oxides are also electron acceptors for DMRB but are stronger oxidants than Fe(III) oxides. Differences in the solubility of oxidized Mn and U challenges predictions of their biogeochemical behavior during redox cycling. The potential for Mn oxides to modify the biogeochemical behavior of U during reduction by a subsurface bacterium Shewanella putrefaciens CN32 was investigated using synthetic Mn(III/IV) oxides [pyrolusite ({beta}-MnO{sub 2}), bixbyite (Mn{sub 2}O{sub 3}) and K{sup +}-birnessite (K{sub 4}Mn{sub 14}O{sub 27} {center_dot} 8H{sub 2}O)]. In the absence of bacteria, pyrolusite and bixbyite oxidized biogenic uraninite (UO{sub 2}(s)) to soluble U(VI) species, with bixbyite being the most rapid oxidant. The Mn(III/IV) oxides lowered the bioreduction rate of U(VI) relative to rates in their absence, or in the presence of gibbsite [Al(OH){sub 3}] added as a non-redox reactive surface. Evolved Mn(II) increased with increasing initial U(VI) concentration in the biotic experiments, indicating that valence cycling of U facilitated the reduction of Mn(III/IV). Despite an excess of the Mn oxide, 43-100% of the initial U was bioreduced after extended incubation. Analysis of thin sections of bacterial-Mn oxide suspensions revealed that the reduced U resided in the periplasmic space of the bacterial cells. In the absence of Mn(III/IV) oxides, UO{sub 2}(s) accumulated as copius fine-grained particles external to the cell. These results indicate that the presence of Mn(III/IV) oxides may impede the biological reduction of U(VI) in subsoils and sediments?.

  5. Can microbially-generated hydrogen sulfide account for the rates of U(VI) reduction by a sulfate-reducing bacterium?

    SciTech Connect

    Boonchayaanant, Benjaporn; Gu, Baohua; Wang, Wei; Ortiz, Monica E; Criddle, Craig

    2010-01-01

    In situ remediation of uranium contaminated soil and groundwater is attractive because a diverse range of microbial and abiotic processes reduce soluble and mobile U(VI) to sparingly soluble and immobile U(IV). Often these processes are linked. Sulfate-reducing bacteria (SRB), for example, enzymatically reduce U(VI) to U(IV), but they also produce hydrogen sulfide that can itself reduce U(VI). This study evaluated the relative importance of these processes for Desulfovibrio aerotolerans, a SRB isolated from a U(VI)-contaminated site. For the conditions evaluated, the observed rate of SRB-mediated U(VI) reduction can be explained by the abiotic reaction of U(VI) with the microbially-generated H{sub 2}S. The presence of trace ferrous iron appeared to enhance the extent of hydrogen sulfide-mediated U(VI) reduction at 5 mM bicarbonate, but had no clear effect at 15 mM. During the hydrogen sulfide-mediated reduction of U(VI), a floc formed containing uranium and sulfur. U(VI) sequestered in the floc was not available for further reduction.

  6. Influence of dynamical conditions on the reduction of U(VI) at the magnetite-solution interface.

    PubMed

    Ilton, Eugene S; Boily, Jean-François; Buck, Edgar C; Skomurski, Frances N; Rosso, Kevin M; Cahill, Christopher L; Bargar, John R; Felmy, Andrew R

    2010-01-01

    The heterogeneous reduction of U(VI) to U(IV) by ferrous iron is believed to be a key process influencing the fate and transport of U in the environment. The reactivity of both sorbed and structural Fe(II) has been studied for numerous substrates, including magnetite. Published results from U(VI)-magnetite experiments have been variable, ranging from no reduction to clear evidence for the formation of U(IV). In this contribution, we used XAS and high resolution (+/-cryogenic) XPS to study the interaction of U(VI) with nanoparticulate magnetite. The results indicated that U(VI) was partially reduced to U(V) with no evidence of U(IV). However, thermodynamic calculations indicated that U phases with average oxidation states below (V) should have been stable, indicating that the system was not in redox equilibrium. A reaction pathway that involves incorporation and stabilization of U(V) and U(VI) into secondary phases is invoked to explain the observations. The results suggest an important and previously unappreciated role of U(V) in the fate and transport of uranium in the environment. PMID:20039748

  7. Contribution of Extracellular Polymeric Substances from Shewanella sp. HRCR-1 Biofilms to U(VI) Immobilization

    SciTech Connect

    Cao, Bin; Ahmed, B.; Kennedy, David W.; Wang, Zheming; Shi, Liang; Marshall, Matthew J.; Fredrickson, Jim K.; Isern, Nancy G.; Majors, Paul D.; Beyenal, Haluk

    2011-06-05

    The goal of this study was to quantify the contribution of extracellular polymeric substances (EPS) in U(VI) immobilization by Shewanella sp. HRCR-1. Through comparison of U(VI) immobilization using cells with bound EPS (bEPS) and cells without EPS, we showed that i) bEPS from Shewanella sp. HRCR-1 biofilms contributed significantly to U(VI) immobilization, especially at low initial U(VI) concentrations, through both sorption and reduction; ii) bEPS could be considered as a functional extension of the cells for U(VI) immobilization and they likely play more important roles at initial U(VI) concentrations; and iii) U(VI) reduction efficiency was found to be dependent upon initial U(VI) concentration and the efficiency decreased at lower concentrations. To quantify relative contribution of sorption and reduction in U(VI) immobilization by EPS fractions, we isolated loosely associated EPS (laEPS) and bEPS from Shewanella sp. HRCR-1 biofilms grown in a hollow fiber membrane biofilm reactor and tested their reactivity with U(V). We found that, when in reduced form, the isolated cell-free EPS fractions could reduce U(VI). Polysaccharides in the EPS likely contributed to U(VI) sorption and dominated reactivity of laEPS while redox active components (e.g., outer membrane c-type cytochromes), especially in bEPS, might facilitate U(VI) reduction.

  8. U(VI) reduction at the nano, meso and meter scale: concomitant transition from simpler to more complex biogeochemical processes

    NASA Astrophysics Data System (ADS)

    Veeramani, H.; Hochella, M. F.

    2012-12-01

    Reduction of aqueous hexavalent U(VI) to the sparingly soluble nanoparticulate mineral uraninite [UO2] represents a promising strategy for the in situ immobilization of uranium in contaminated subsurface sediments and groundwater. Studies related to uranium reduction have been extensively carried out at various scales ranging from nano to meso to the meter scale with varying degrees of success. While nanoscale processes involving simple two-electron transfer reactions such as enzymatic microbial U(VI) reduction results in biogenic UO2 formation, mesoscale processes involving minerals and U(VI) are a step up in complexity and have shown varying results ranging from partial uranium reduction to the formation of mixed U(IV)/U(V) species. Although nano- and meso-scale biogeochemical processes have been helpful in predicting the contaminant dynamics at the meter scale, their occurrence is not necessarily apparent in soils and aquifers given the enormous volume of contaminated groundwater to be remediated, among other factors. The formation and long-term stability of biologically reduced uranium at the meter scale is also determined in addition by the complex interplay of aqueous geochemistry, hydrology, soil and sediment mineralogy and microbial community dynamics. For instance, indigenous subsurface microbes often encounter multiple electron acceptors in heterogeneous environments during biostimulation and can catalyze the formation of various reactive biogenic minerals. In such cases, abiotic interactions between U(VI) and reactive biogenic minerals is potentially important because the success of a remediation strategy is contingent upon the speciation of reduced uranium. This presentation will give an overview of uranium reduction ranging from simple nanoscale biological processes to increasingly complex meso and meter scale processes involving abiotic interactions between aqueous uranium and nano-biogenic minerals and the effect of mineralogy and aqueous

  9. Quantitative separation of monomeric U(IV) from UO2 in products of U(VI) reduction

    PubMed Central

    Alessi, Daniel S.; Uster, Benjamin; Veeramani, Harish; Suvorova, Elena I.; Lezama-Pacheco, Juan S.; Stubbs, Joanne E.; Bargar, John R.; Bernier-Latmani, Rizlan

    2012-01-01

    The reduction of soluble hexavalent uranium to tetravalent uranium can be catalyzed by bacteria and minerals. The end-product of this reduction is often the mineral uraninite, which was long assumed to be the only product of U(VI) reduction. However, recent studies report the formation of other species including an adsorbed U(IV) species, operationally referred to as monomeric U(IV). The discovery of monomeric U(IV) is important because the species is likely to be more labile and more susceptible to reoxidation than uraninite. Because there is a need to distinguish between these two U(IV) species, we propose here a wet chemical method of differentiating monomeric U(IV) from uraninite in environmental samples. To calibrate the method, U(IV) was extracted from known mixtures of uraninite and monomeric U(IV) and testted using X-ray absorption spectroscopy (XAS). Monomeric U(IV) was efficiently removed from biomass and Fe(II)-bearing phases by bicarbonate extraction, without affecting uraninite stability. After confirming that the method effectively separates monomeric U(IV) and uraninite, it is further evaluated for a system containing those reduced U species and adsorbed U(VI). The method provides a rapid complement, and in some cases alternative, to XAS analyses for quantifying monomeric U(IV), uraninite, and adsorbed U(VI) species in environmental samples. PMID:22540966

  10. Reduction of Fe(III), Cr(VI), U(VI), and Tc(VII) by Deinococcus radiodurans R1

    PubMed Central

    Fredrickson, J. K.; Kostandarithes, H. M.; Li, S. W.; Plymale, A. E.; Daly, M. J.

    2000-01-01

    Deinococcus radiodurans is an exceptionally radiation-resistant microorganism capable of surviving acute exposures to ionizing radiation doses of 15,000 Gy and previously described as having a strictly aerobic respiratory metabolism. Under strict anaerobic conditions, D. radiodurans R1 reduced Fe(III)-nitrilotriacetic acid coupled to the oxidation of lactate to CO2 and acetate but was unable to link this process to growth. D. radiodurans reduced the humic acid analog anthraquinone-2,6-disulfonate (AQDS) to its dihydroquinone form, AH2DS, which subsequently transferred electrons to the Fe(III) oxides hydrous ferric oxide and goethite via a previously described electron shuttle mechanism. D. radiodurans reduced the solid-phase Fe(III) oxides in the presence of either 0.1 mM AQDS or leonardite humic acids (2 mg ml−1) but not in their absence. D. radiodurans also reduced U(VI) and Tc(VII) in the presence of AQDS. In contrast, Cr(VI) was directly reduced in anaerobic cultures with lactate although the rate of reduction was higher in the presence of AQDS. The results are the first evidence that D. radiodurans can reduce Fe(III) coupled to the oxidation of lactate or other organic compounds. Also, D. radiodurans, in combination with humic acids or synthetic electron shuttle agents, can reduce U and Tc and thus has potential applications for remediation of metal- and radionuclide-contaminated sites where ionizing radiation or other DNA-damaging agents may restrict the activity of more sensitive organisms. PMID:10788374

  11. Reduction of Fe(III), Cr(VI), U(VI), and Tc(VII) by Deinococcus radiodurans R1

    SciTech Connect

    Fredrickson, J.K.; Kostandarithes, H.M.; Li, S.W.; Plymake, A.E.; Daly, M.J.

    2000-05-01

    Deinococcus radiodurans is an exceptionally radiation-resistant microorganism capable of surviving acute exposures to ionizing radiation doses of 15,000 Gy and previously described as having a strictly aerobic respiratory metabolism. Under strict anaerobic conditions, D. radiodurans R1 reduced Fe(III)-nitrilotriacetic acid coupled to the oxidation of lactate to CO{sub 2} and acetate but was unable to link this process to growth. D. radiodurans reduced the humic acid analog anthraquinone-2,6-disulfonate (AQDS) to its dihydroquinone form, AH{sub 2}DS, which subsequently transferred electrons to the Fe(III) oxides hydrous ferric oxide and goethite via a previously described electron shuttle mechanism. D. radiodurans reduced the solid-phase Fe(III) oxides in the presence of either 0.1 mM AQDS or leonardite humic acids (2 mg ml{sup {minus}1}) but not in their absence. D. radiodurans also reduced U(VI) and Tc(VII) in the presence of AQDS. In contrast, Cr(VI) was directly reduced in anaerobic cultures with lactate although the rate of reduction was higher in the presence of AQDS. The results are the first evidence that D. radiodurans can reduce Fe(III) coupled to the oxidation of lactate or other organic compounds. Also, D. radiodurans, in combination with humic acids or synthetic electron shuttle agents, can reduce U and Tc and thus has potential applications for remediation of metal- and radionuclide-contaminated sites where ionizing radiation or other DNA-damaging agents may restrict the activity of more sensitive organisms.

  12. Reduction of Fe(III), Cr(VI), U(VI), and Tc(VII) by Deinococcus radiodurans R1.

    PubMed

    Fredrickson, J K; Kostandarithes, H M; Li, S W; Plymale, A E; Daly, M J

    2000-05-01

    Deinococcus radiodurans is an exceptionally radiation-resistant microorganism capable of surviving acute exposures to ionizing radiation doses of 15,000 Gy and previously described as having a strictly aerobic respiratory metabolism. Under strict anaerobic conditions, D. radiodurans R1 reduced Fe(III)-nitrilotriacetic acid coupled to the oxidation of lactate to CO(2) and acetate but was unable to link this process to growth. D. radiodurans reduced the humic acid analog anthraquinone-2,6-disulfonate (AQDS) to its dihydroquinone form, AH(2)DS, which subsequently transferred electrons to the Fe(III) oxides hydrous ferric oxide and goethite via a previously described electron shuttle mechanism. D. radiodurans reduced the solid-phase Fe(III) oxides in the presence of either 0.1 mM AQDS or leonardite humic acids (2 mg ml(-1)) but not in their absence. D. radiodurans also reduced U(VI) and Tc(VII) in the presence of AQDS. In contrast, Cr(VI) was directly reduced in anaerobic cultures with lactate although the rate of reduction was higher in the presence of AQDS. The results are the first evidence that D. radiodurans can reduce Fe(III) coupled to the oxidation of lactate or other organic compounds. Also, D. radiodurans, in combination with humic acids or synthetic electron shuttle agents, can reduce U and Tc and thus has potential applications for remediation of metal- and radionuclide-contaminated sites where ionizing radiation or other DNA-damaging agents may restrict the activity of more sensitive organisms. PMID:10788374

  13. Influence of Reactive Transport on the Reduction of U(VI) in the Presence of Fe(III) and Nitrate: Implications for U(VI) Immobilization by Bioremediation / Biobarriers- Final Report

    SciTech Connect

    B.D. Wood

    2007-01-01

    Subsurface contamination by metals and radionuclides represent some of the most challenging remediation problems confronting the Department of Energy (DOE) complex. In situ remediation of these contaminants by dissimilatory metal reducing bacteria (DMRB) has been proposed as a potential cost effective remediation strategy. The primary focus of this research is to determine the mechanisms by which the fluxes of electron acceptors, electron donors, and other species can be controlled to maximize the transfer of reductive equivalents to the aqueous and solid phases. The proposed research is unique in the NABIR portfolio in that it focuses on (i) the role of flow and transport in the initiation of biostimulation and the successful sequestration of metals and radionuclides [specifically U(VI)], (ii) the subsequent reductive capacity and stability of the reduced sediments produced by the biostimulation process, and (iii) the potential for altering the growth of biomass in the subsurface by the addition of specific metabolic uncoupling compounds. A scientifically-based understanding of these phenomena are critical to the ability to design successful bioremediation schemes. The laboratory research will employ Shewanella putrefaciens (CN32), a facultative DMRB that can use Fe(III) oxides as a terminal electron acceptor. Sediment-packed columns will be inoculated with this organism, and the reduction of U(VI) by the DMRB will be stimulated by the addition of a carbon and energy source in the presence of Fe(III). Separate column experiments will be conducted to independently examine: (1) the importance of the abiotic reduction of U(VI) by biogenic Fe(II); (2) the influence of the transport process on Fe(III) reduction and U(VI) immobilization, with emphasis on methods for controlling the fluxes of aqueous species to maximize uranium reduction; (3) the reductive capacity of biologically-reduced sediments (with respect to re-oxidation by convective fluxes of O2 and NO3-) and

  14. Fe(III) Reduction and U(VI) Immobilization by Paenibacillus sp. Strain 300A, Isolated from Hanford 300A Subsurface Sediments

    PubMed Central

    Ahmed, Bulbul; Cao, Bin; McLean, Jeffrey S.; Ica, Tuba; Dohnalkova, Alice; Istanbullu, Ozlem; Paksoy, Akin; Fredrickson, Jim K.

    2012-01-01

    A facultative iron-reducing [Fe(III)-reducing] Paenibacillus sp. strain was isolated from Hanford 300A subsurface sediment biofilms that was capable of reducing soluble Fe(III) complexes [Fe(III)-nitrilotriacetic acid and Fe(III)-citrate] but unable to reduce poorly crystalline ferrihydrite (Fh). However, Paenibacillus sp. 300A was capable of reducing Fh in the presence of low concentrations (2 μM) of either of the electron transfer mediators (ETMs) flavin mononucleotide (FMN) or anthraquinone-2,6-disulfonate (AQDS). Maximum initial Fh reduction rates were observed at catalytic concentrations (<10 μM) of either FMN or AQDS. Higher FMN concentrations inhibited Fh reduction, while increased AQDS concentrations did not. We also found that Paenibacillus sp. 300A could reduce Fh in the presence of natural ETMs from Hanford 300A subsurface sediments. In the absence of ETMs, Paenibacillus sp. 300A was capable of immobilizing U(VI) through both reduction and adsorption. The relative contributions of adsorption and microbial reduction to U(VI) removal from the aqueous phase were ∼7:3 in PIPES [piperazine-N,N′-bis(2-ethanesulfonic acid)] and ∼1:4 in bicarbonate buffer. Our study demonstrated that Paenibacillus sp. 300A catalyzes Fe(III) reduction and U(VI) immobilization and that these reactions benefit from externally added or naturally existing ETMs in 300A subsurface sediments. PMID:22961903

  15. Fe(III) reduction and U(VI) immobilization by Paenibacillus sp. strain 300A, isolated from Hanford 300A subsurface sediments.

    PubMed

    Ahmed, Bulbul; Cao, Bin; McLean, Jeffrey S; Ica, Tuba; Dohnalkova, Alice; Istanbullu, Ozlem; Paksoy, Akin; Fredrickson, Jim K; Beyenal, Haluk

    2012-11-01

    A facultative iron-reducing [Fe(III)-reducing] Paenibacillus sp. strain was isolated from Hanford 300A subsurface sediment biofilms that was capable of reducing soluble Fe(III) complexes [Fe(III)-nitrilotriacetic acid and Fe(III)-citrate] but unable to reduce poorly crystalline ferrihydrite (Fh). However, Paenibacillus sp. 300A was capable of reducing Fh in the presence of low concentrations (2 μM) of either of the electron transfer mediators (ETMs) flavin mononucleotide (FMN) or anthraquinone-2,6-disulfonate (AQDS). Maximum initial Fh reduction rates were observed at catalytic concentrations (<10 μM) of either FMN or AQDS. Higher FMN concentrations inhibited Fh reduction, while increased AQDS concentrations did not. We also found that Paenibacillus sp. 300A could reduce Fh in the presence of natural ETMs from Hanford 300A subsurface sediments. In the absence of ETMs, Paenibacillus sp. 300A was capable of immobilizing U(VI) through both reduction and adsorption. The relative contributions of adsorption and microbial reduction to U(VI) removal from the aqueous phase were ∼7:3 in PIPES [piperazine-N,N'-bis(2-ethanesulfonic acid)] and ∼1:4 in bicarbonate buffer. Our study demonstrated that Paenibacillus sp. 300A catalyzes Fe(III) reduction and U(VI) immobilization and that these reactions benefit from externally added or naturally existing ETMs in 300A subsurface sediments. PMID:22961903

  16. Fe(III) Reduction and U(VI) Immobilization by Paenibacillus sp. Strain 300A, Isolated from Hanford 300A Subsurface Sediments

    SciTech Connect

    Ahmed, B.; Cao, B.; McLean, Jeffrey S.; Ica, Tuba; Dohnalkova, Alice; Istanbullu, Ozlem; Paksoy, Akin; Fredrickson, Jim K.; Beyenal, Haluk

    2012-11-07

    A facultative iron-reducing (Fe(III)-reducing) Paenibacillus sp. strain was isolated from Hanford 300A subsurface sediment biofilms that was capable of reducing soluble Fe(III) complexes (Fe(III)-NTA and Fe(III)-citrate) but unable to reduce poorly crystalline ferrihydrite (Fh). However, Paenibacillus sp. 300A was capable of reducing Fh in the presence of low concentrations (2 µM) of either of electron transfer mediators (ETMs) flavin mononucleotide (FMN) or anthraquinone-2,6-disulfonate (AQDS). Maximum initial Fh reduction rates were observed at catalytic concentrations (<10 µM) of either FMN or AQDS. Higher FMN concentrations inhibited Fh reduction, while increased AQDS concentrations did not. We found that Paenibacillus sp. 300A also could reduce Fh in the presence of natural ETMs from Hanford 300A subsurface sediments. In the absence of ETMs, Paenibacillus sp. 300A was capable of immobilizing U(VI) through both reduction and adsorption. The relative contributions of adsorption and microbial reduction to U(VI) removal from the aqueous phase were ~7:3 in PIPES and ~1:4 in bicarbonate buffer. Our study demonstrated that Paenibacillus sp. 300A catalyzes Fe(III) reduction and U(VI) immobilization and that these reactions benefit from externally added or naturally existing ETMs in 300A subsurface sediments.

  17. Development of a biomarker for Geobacter activity and strain composition: Proteogenomic analysis of the citrate synthase protein during bioremediation of U(VI)

    SciTech Connect

    Wilkins, M.J.; Callister, S.J.; Miletto, M.; Williams, K.H.; Nicora, C.D.; Lovley, D.R.; Long, P.E.; Lipton, M.S.

    2010-02-15

    Monitoring the activity of target microorganisms during stimulated bioremediation is a key problem for the development of effective remediation strategies. At the US Department of Energy's Integrated Field Research Challenge (IFRC) site in Rifle, CO, the stimulation of Geobacter growth and activity via subsurface acetate addition leads to precipitation of U(VI) from groundwater as U(IV). Citrate synthase (gltA) is a key enzyme in Geobacter central metabolism that controls flux into the TCA cycle. Here, we utilize shotgun proteomic methods to demonstrate that the measurement of gltA peptides can be used to track Geobacter activity and strain evolution during in situ biostimulation. Abundances of conserved gltA peptides tracked Fe(III) reduction and changes in U(VI) concentrations during biostimulation, whereas changing patterns of unique peptide abundances between samples suggested sample-specific strain shifts within the Geobacter population. Abundances of unique peptides indicated potential differences at the strain level between Fe(III)-reducing populations stimulated during in situ biostimulation experiments conducted a year apart at the Rifle IFRC. These results offer a novel technique for the rapid screening of large numbers of proteomic samples for Geobacter species and will aid monitoring of subsurface bioremediation efforts that rely on metal reduction for desired outcomes.

  18. Development of a biomarker for Geobacter activity and strain composition; Proteogenomic analysis of the citrate synthase protein during bioremediation of U(VI).

    SciTech Connect

    Wilkins, Michael J.; Callister, Stephen J.; Miletto, Marzia; Williams, Kenneth H.; Nicora, Carrie D.; Lovely, Derek R.; Long, Philip E.; Lipton, Mary S.

    2011-01-01

    Monitoring the activity of target microorganisms during stimulated bioremediation is a key problem for the development of effective remediation strategies. At the U.S. Department of Energy’s Integrated Field Research Challenge (IFRC) site in Rifle, CO, the stimulation of Geobacter growth and activity via subsurface acetate addition leads to precipitation of U(VI) from groundwater as U(IV). Citrate synthase (gltA) is a key enzyme in Geobacter central metabolism that controls flux into the TCA cycle. Here, we utilize shotgun proteomic methods to demonstrate that the measurement of gltA peptides can be used to track Geobacter activity and strain evolution during in situ biostimulation. Abundances of conserved gltA peptides tracked Fe(III) reduction and changes in U(VI) concentrations during biostimulation, whereas changing patterns of unique peptide abundances between samples suggested sample-specific strain shifts within the Geobacter population. Abundances of unique peptides indicated potential differences at the strain level between Fe(III)-reducing populations stimulated during in situ biostimulation experiments conducted a year apart at the Rifle IFRC. These results offer a novel technique for the rapid screening of large numbers of proteomic samples for Geobacter species and will aid monitoring of subsurface bioremediation efforts that rely on metal reduction for desired outcomes.

  19. INVESTIGATION OF THE TRANSFORMATION OF URANIUM UNDER IRON-REDUCING CONDITIONS: REDUCTION OF UVI BY BIOGENIC FEII/FEIII HYDROXIDE (GREEN RUST)

    SciTech Connect

    O'Loughlin, Edward J.; Scherer, Michelle M.; Kemner, Kenneth M.

    2006-12-31

    The recent identification of green rusts (GRs) as products of the reduction of FeIII oxyhydroxides by dissimilatory iron-reducing bacteria, coupled with the ability of synthetic (GR) to reduce UVI species to insoluble UO2, suggests that biogenic green rusts (BioGRs) may play an important role in the speciation (and thus mobility) of U in FeIII-reducing environments. The objective of our research was to examine the potential for BioGR to affect the speciation of U under FeIII-reducing conditions. To meet this objective, we designed and executed a hypothesis-driven experimental program to identify key factors leading to the formation of BioGRs as products of dissimilatory FeIII reduction, to determine the key factors controlling the reduction of UVI to UIV by GRs, and to identify the resulting U-bearing mineral phases. The results of this research significantly increase our understanding of the coupling of biotic and abiotic processes with respect to the speciation of U in iron-reducing environments. In particular, the reduction of UVI to UIV by BioGR with the subsequent formation of U-bearing mineral phases may be effective for immobilizing U in suboxic subsurface environments. This information has direct applications to contaminant transport modeling and bioremediation engineering for natural or enhanced in situ remediation of subsurface contamination.

  20. Reduction of U(VI) and Toxic Metals by Desulfovibrio Cytochrome C3

    SciTech Connect

    Wall, Judy D

    2013-04-11

    The central objective of our proposed research was twofold: 1) to investigate the structure-function relationship of Desulfovibrio desulfuricans (now Desulfovibrio alaskensis G20) cytochrome c3 with uranium and 2) to elucidate the mechanism for uranium reduction in vitro and in vivo. Physiological analysis of a mutant of D. desulfuricans with a mutation of the gene encoding the type 1 tetraheme cytochrome c3 had demonstrated that uranium reduction was negatively impacted while sulfate reduction was not if lactate were the electron donor. This was thought to be due to the presence of a branched pathway of electron flow from lactate leading to sulfate reduction. Our experimental plan was to elucidate the structural and mechanistic details of uranium reduction involving cytochrome c3.

  1. Simultaneous adsorption and reduction of U(VI) on reduced graphene oxide-supported nanoscale zerovalent iron.

    PubMed

    Sun, Yubing; Ding, Congcong; Cheng, Wencai; Wang, Xiangke

    2014-09-15

    The reduced graphene oxide-supported nanoscale zero-valent iron (nZVI/rGO) composites were synthesized by chemical deposition method and were characterized by SEM, high resolution TEM, Raman and potentiometric acid-base titrations. The characteristic results showed that the nZVI nanoparticles can be uniformly dispersed on the surface of rGO. The removal of U(VI) on nZVI/rGO composites as a function of contact time, pH and U(VI) initial concentration was investigated by batch technique. The removal kinetics of U(VI) on nZVI and nZVI/rGO were well simulated by a pseudo-first-order kinetic model and pseudo-second-order kinetic model, respectively. The presence of rGO on nZVI nanoparticles increased the reaction rate and removal capacity of U(VI) significantly, which was attributed to the chemisorbed OH(-) groups of rGO and the massive enrichment of Fe(2+) on rGO surface by XPS analysis. The XRD analysis revealed that the presence of rGO retarded the transformation of iron corrosion products from magnetite/maghemite to lepidocrocite. According to the fitting of EXAFS spectra, the UC (at ∼2.9Å) and UFe (at ∼3.2Å) shells were observed, indicating the formation of inner-sphere surface complexes on nZVI/rGO composites. Therefore, the nZVI/rGO composites can be suitable as efficient materials for the in-situ remediation of uranium-contaminated groundwater in the environmental pollution management. PMID:25194557

  2. Biogeochemical Modeling of In Situ U(VI) Reduction and Immobilization with Emulsified Vegetable Oil as the Electron Donor at a Field Site in Oak Ridge, Tennessee

    NASA Astrophysics Data System (ADS)

    Tang, G.; Parker, J.; Wu, W.; Schadt, C. W.; Watson, D. B.; Brooks, S. C.; Orifrc Team

    2011-12-01

    A comprehensive biogeochemical model was developed to quantitatively describe the coupled hydrologic, geochemical and microbiological processes that occurred following injection of emulsified vegetable oil (EVO) as the electron donor to immobilize U(VI) at the Oak Ridge Integrated Field Research Challenge site (ORIFRC) in Tennessee. The model couples the degradation of EVO, production and oxidation of long-chain fatty acids (LCFA), glycerol, hydrogen and acetate, reduction of nitrate, manganese, ferrous iron, sulfate and uranium, and methanoganesis with growth of multiple microbial groups. The model describes the evolution of geochemistry and microbial populations not only in the aqueous phase as typically observed, but also in the mineral phase and therefore enables us to evaluate the applicability of rates from the literature for field scale assessment, estimate the retention and degradation rates of EVO and LCFA, and assess the influence of the coupled processes on fate and transport of U(VI). Our results suggested that syntrophic bacteria or metal reducers might catalyze LCFA oxidation in the downstream locations when sulfate was consumed, and competition between methanogens and others for electron donors and slow growth of methanogen might contribute to the sustained reducing condition. Among the large amount of hydrologic, geochemical and microbiological parameter values, the initial biomass, and the interactions (e.g., inhibition) of the microbial functional groups, and the rate and extent of Mn and Fe oxide reduction appear as the major sources of uncertainty. Our model provides a platform to conduct numerical experiments to study these interactions, and could be useful for further iterative experimental and modeling investigations into the bioreductive immobiliztion of radionuclide and metal contaminants in the subsurface.

  3. Metal reduction by spores of Desulfotomaculum reducens.

    PubMed

    Junier, Pilar; Frutschi, Manon; Wigginton, Nicholas S; Schofield, Eleanor J; Bargar, John R; Bernier-Latmani, Rizlan

    2009-12-01

    The bioremediation of uranium-contaminated sites is designed to stimulate the activity of microorganisms able to catalyze the reduction of soluble U(VI) to the less soluble mineral UO(2). U(VI) reduction does not necessarily support growth in previously studied bacteria, but it typically involves viable vegetative cells and the presence of an appropriate electron donor. We characterized U(VI) reduction by the sulfate-reducing bacterium Desulfotomaculum reducens strain MI-1 grown fermentatively on pyruvate and observed that spores were capable of U(VI) reduction. Hydrogen gas - a product of pyruvate fermentation - rather than pyruvate, served as the electron donor. The presence of spent growth medium was required for the process, suggesting that an unknown factor produced by the cells was necessary for reduction. Ultrafiltration of the spent medium followed by U(VI) reduction assays revealed that the factor's molecular size was below 3 kDa. Pre-reduced spent medium displayed short-term U(VI) reduction activity, suggesting that the missing factor may be an electron shuttle, but neither anthraquinone-2,6-disulfonic acid nor riboflavin rescued spore activity in fresh medium. Spores of D. reducens also reduced Fe(III)-citrate under experimental conditions similar to those for U(VI) reduction. This is the first report of a bacterium able to reduce metals while in a sporulated state and underscores the novel nature of the mechanism of metal reduction by strain MI-1. PMID:19601961

  4. Investigation of the Transformation of Uranium under Iron-Reducing Conditions: Reduction of UVI by Biogenic FeII/FeIII Hydroxide (Green Rust)

    SciTech Connect

    Edward O’Loughlin; Michelle Scherer; Kenneth Kemner; Shelly Kelly

    2004-03-17

    hypotheses: (1) The formation of GRs by dissimilatory Fe{sup III} reduction is controlled by Fe{sup III} speciation, solution composition, and microbial physiology. (2) The chemical composition and structural properties of biogenic GRs are variable and depend on the conditions under which they were formed. (3) The rate of U{sup VI} reduction by biogenic GRs varies depending on their chemical composition and structure, particularly with respect to the Fe{sup II}/Fe{sup III} ratio and the nature of the interlayer anions. (4) The rate of U{sup VI} reduction by a given biogenic GR is affected by the solution composition (e.g., pH, uranium concentration, the concentration of carbonate and other ligands, and the presence of other potential oxidants). Moreover, the solution composition affects both the speciation of U{sup VI} and U{sup IV} and the stability of the GR. (5) The reduction of UVI to UIV can be coupled to dissimilatory FeIII reduction under conditions that promote the formation of biogenic GR and other reactive Fe{sup II} species. The results of this research will increase our understanding of the coupling of biotic and abiotic processes with respect to the speciation of U in Fe{sup III}-reducing environments. This information has direct applications to understanding contaminant transport and the development of in situ bioremediation technologies for treatment of subsurface U contamination.

  5. Influence of Calcium on Microbial Reduction of Solid Phase Uranium (VI)

    SciTech Connect

    Liu, Chongxuan; Jeon, Byong-Hun; Zachara, John M.; Wang, Zheming

    2007-06-27

    The effect of calcium on microbial reduction of a solid phase U(VI), sodium boltwoodite (NaUO2SiO3OH ∙1.5H2O), was evaluated in a culture of a dissimilatory metal-reducing bacterium (DMRB), Shewanella oneidensis strain MR-1. Batch experiments were performed in a non-growth bicarbonate medium with lactate as electron donor at pH 7 buffered with PIPES. Calcium increased both the rate and extent of Na-boltwoodite dissolution by increasing its solubility through the formation of a ternary aqueous calcium-uranyl-carbonate species. The ternary species, however, decreased the rates of microbial reduction of aqueous U(VI). Laser-induced fluorescence spectroscopy (LIFS) and transmission electron microscopy (TEM) revealed that microbial reduction of solid phase U(VI) is a sequentially coupled process of Na-boltwoodite dissolution, U(VI) aqueous speciation, and microbial reduction of dissolved U(VI) to U(IV) that accumulated on bacterial surfaces/periplasm. The overall rates of microbial reduction of solid phase U(VI) can be described by the coupled rates of dissolution and microbial reduction that were both influenced by calcium. The results demonstrated that dissolved U(VI) concentration during microbial reduction was a complex function of solid phase U(VI) dissolution kinetics, aqueous U(VI) speciation, and microbial activity.

  6. Decrease of U(VI) immobilization capability of the facultative anaerobic strain Paenibacillus sp. JG-TB8 under anoxic conditions due to strongly reduced phosphatase activity.

    PubMed

    Reitz, Thomas; Rossberg, Andre; Barkleit, Astrid; Selenska-Pobell, Sonja; Merroun, Mohamed L

    2014-01-01

    Interactions of a facultative anaerobic bacterial isolate named Paenibacillus sp. JG-TB8 with U(VI) were studied under oxic and anoxic conditions in order to assess the influence of the oxygen-dependent cell metabolism on microbial uranium mobilization and immobilization. We demonstrated that aerobically and anaerobically grown cells of Paenibacillus sp. JG-TB8 accumulate uranium from aqueous solutions under acidic conditions (pH 2 to 6), under oxic and anoxic conditions. A combination of spectroscopic and microscopic methods revealed that the speciation of U(VI) associated with the cells of the strain depend on the pH as well as on the aeration conditions. At pH 2 and pH 3, uranium was exclusively bound by organic phosphate groups provided by cellular components, independently on the aeration conditions. At higher pH values, a part (pH 4.5) or the total amount (pH 6) of the dissolved uranium was precipitated under oxic conditions in a meta-autunite-like uranyl phosphate mineral phase without supplying an additional organic phosphate substrate. In contrast to that, under anoxic conditions no mineral formation was observed at pH 4.5 and pH 6, which was clearly assigned to decreased orthophosphate release by the cells. This in turn was caused by a suppression of the indigenous phosphatase activity of the strain. The results demonstrate that changes in the metabolism of facultative anaerobic microorganisms caused by the presence or absence of oxygen can decisively influence U(VI) biomineralization. PMID:25157416

  7. Decrease of U(VI) Immobilization Capability of the Facultative Anaerobic Strain Paenibacillus sp. JG-TB8 under Anoxic Conditions Due to Strongly Reduced Phosphatase Activity

    PubMed Central

    Reitz, Thomas; Rossberg, Andre; Barkleit, Astrid; Selenska-Pobell, Sonja; Merroun, Mohamed L.

    2014-01-01

    Interactions of a facultative anaerobic bacterial isolate named Paenibacillus sp. JG-TB8 with U(VI) were studied under oxic and anoxic conditions in order to assess the influence of the oxygen-dependent cell metabolism on microbial uranium mobilization and immobilization. We demonstrated that aerobically and anaerobically grown cells of Paenibacillus sp. JG-TB8 accumulate uranium from aqueous solutions under acidic conditions (pH 2 to 6), under oxic and anoxic conditions. A combination of spectroscopic and microscopic methods revealed that the speciation of U(VI) associated with the cells of the strain depend on the pH as well as on the aeration conditions. At pH 2 and pH 3, uranium was exclusively bound by organic phosphate groups provided by cellular components, independently on the aeration conditions. At higher pH values, a part (pH 4.5) or the total amount (pH 6) of the dissolved uranium was precipitated under oxic conditions in a meta-autunite-like uranyl phosphate mineral phase without supplying an additional organic phosphate substrate. In contrast to that, under anoxic conditions no mineral formation was observed at pH 4.5 and pH 6, which was clearly assigned to decreased orthophosphate release by the cells. This in turn was caused by a suppression of the indigenous phosphatase activity of the strain. The results demonstrate that changes in the metabolism of facultative anaerobic microorganisms caused by the presence or absence of oxygen can decisively influence U(VI) biomineralization. PMID:25157416

  8. Reduction of uranium by cytochrome c3 of Desulfovibrio vulgaris

    USGS Publications Warehouse

    Lovley, D.R.; Widman, P.K.; Woodward, J.C.; Phillips, E.J.P.

    1993-01-01

    The mechanism for U(VI) reduction by Desulfovibrio vulgaris (Hildenborough) was investigated. The H2-dependent U(VI) reductase activity in the soluble fraction of the cells was lost when the soluble fraction was passed over a cationic exchange column which extracted cytochrome c3. Addition of cytochrome c3 back to the soluble fraction that had been passed over the cationic exchange column restored the U(VI)-reducing capacity. Reduced cytochrome c3 was oxidized by U(VI), as was a c-type cytochrome(s) in whole-cell suspensions. When cytochrome c3 was combined with hydrogenase, its physiological electron donor, U(VI) was reduced in the presence of H2. Hydrogenase alone could not reduce U(VI). Rapid U(VI) reduction was followed by a subsequent slow precipitation of the U(IV) mineral uraninite. Cytochrome c3 reduced U(VI) in a uranium-contaminated surface water and groundwater. Cytochrome c3 provides the first enzyme model for the reduction and biomineralization of uranium in sedimentary environments. Furthermore, the finding that cytochrome c3 can catalyze the reductive precipitation of uranium may aid in the development of fixed-enzyme reactors and/or organisms with enhanced U(VI)-reducing capacity for the bioremediation of uranium- contaminated waters and waste streams.

  9. UVIS Stray Light

    NASA Astrophysics Data System (ADS)

    Petro, Larry

    2009-07-01

    Structures outside the optical path of the detector FOV and the surfaces of optical elements could scatter significant light from bright sources onto the UVIS CCD. Such structures are oversized by typically a few mm relative to the FOV?s beam. The beam footprint of a source outside the FOV can overlap the edges of those structures, which will cause light to be scattered onto the detector. This on orbit test will: 1} verify that release of gravitational stress has not changed the detector mask by comparison with similar ground tests, 2} assess the far wing stray light from a sources outside the CCD FOV, 3} note any sources of stray light in the near and far field that were not noted during ground test, and 4} assess the surface brightness of the off-chip target PSF relative to the on-chip PSF.

  10. WFC3 SS UVIS Spare Tungsten Lamp

    NASA Astrophysics Data System (ADS)

    MacKenty, John

    2012-10-01

    Part of side switch activities.This proposal will verify the operation of the spare UVIS channel calsystem tungsten lamp. Internal flatfields will be obtained in one filter from each of the twelve filter wheels, providing an initial baseline and comparison for those taken with the primary lamp {WF09}. Filters for this proposal were chosen based upon a balance of multiple factors: reasonable countrate with calsystem tungsten lamp {no long exposure times}, science priority of the filter, overall coverage of UVIS wavelength regime, and slot location in the wheel. Exposures will be taken in the default full-frame, four-amp, unbinned readout mode.This proposal corresponds to the spare lamp portion of SS SMOV activity ID: WF09b

  11. UVIS tungsten lamp cross-check

    NASA Astrophysics Data System (ADS)

    Baggett, Sylvia

    2009-07-01

    This proposal will verify the operation of the spare UVIS channel calsystem tungsten lamp. Internal flatfields will be obtained in one filter from each of the twelve filter wheels, providing an initial baseline and comparison for those taken with the primary lamp {WF09, 11422}. Filters for this proposal were chosen based upon a balance of multiple factors: reasonable countrate with calsystem tungsten lamp {no long exposure times}, science priority of the filter, overall coverage of UVIS wavelength regime, and slot location in the wheel. Exposures will be taken in the default full-frame, four-amp, unbinned readout mode.This proposal corresponds to the spare lamp portion of SMOV activity id WFC3-09.

  12. WFC3 SS Uvis SOFA Test

    NASA Astrophysics Data System (ADS)

    MacKenty, John

    2012-10-01

    Part of side switch activities.This proposal will verify the operation of all SOFA filter wheels using the default calsystem tungsten lamp. Internal flatfields will be obtained in one filter from each of the twelve filter wheels, establishing an initial baseline over a broad wavelength range. Subsequent proposals {e.g., WF18, proposal 13206} will obtain full internal flatfield coverage in all UVIS filters. Filters for this proposal were chosen based upon a balance of multiple factors: reasonable countrate with calsystem tungsten lamp {no long exposure times}, science priority of the filter, overall coverage of UVIS wavelength regime, and slot location in the wheel. Exposures will be taken in the default full-frame, four-amp, unbinned readout mode.ID: WF09a

  13. WFC3: UVIS Dark Calibration

    NASA Astrophysics Data System (ADS)

    Bourque, Matthew; Biretta, John A.; Anderson, Jay; Baggett, Sylvia M.; Gunning, Heather C.; MacKenty, John W.

    2014-06-01

    Wide Field Camera 3 (WFC3), a fourth-generation imaging instrument on board the Hubble Space Telescope (HST), has exhibited excellent performance since its installation during Servicing Mission 4 in May 2009. The UVIS detector, comprised of two e2v CCDs, is one of two channels available on WFC3 and is named for its ultraviolet and visible light sensitivity. We present the various procedures and results of the WFC3/UVIS dark calibration, which monitors the health and stability of the UVIS detector, provides characterization of hot pixels and dark current, and produces calibration files to be used as a correction for dark current in science images. We describe the long-term growth of hot pixels and the impacts that UVIS Charge Transfer Efficiency (CTE) losses, postflashing, and proximity to the readout amplifiers have on the population. We also discuss the evolution of the median dark current, which has been slowly increasing since the start of the mission and is currently ~6 e-/hr/pix, averaged across each chip. We outline the current algorithm for creating UVIS dark calibration files, which includes aggressive cosmic ray masking, image combination, and hot pixel flagging. Calibration products are available to the user community, typically 3-5 days after initial processing, through the Calibration Database System (CDBS). Finally, we discuss various improvements to the calibration and monitoring procedures. UVIS dark monitoring will continue throughout and beyond HST’s current proposal cycle.

  14. Characterization of Microbial Activities and U Reduction in a Shallow Aquifer Contaminated by Uranium Mill Tailing

    SciTech Connect

    Elias, Dwayne A.; Krumholz, Lee R.; Wong, D; Long, Philip E.; Suflita, Joseph M.

    2003-05-21

    A Characterization of the Shiprock, NM, uranium mill tailing site focused on the geochemical and microbiological factors governing in-situ uranium-redox reactions. Groundwater and aqueous extracts of sediment samples contained a wide concentration range of sulfate, nitrate, and U(VI) with median values of 21.2 mM, 16.1um, and 2.7 um, respectively. Iron (III) was not detected in groundwater, but a median value of 0.3 mM in sediment extracts was measured. Bacterial diversity down gradient from the disposal pile reflected the predominant geochemistry with relatively high numbers of sulfate-and nitrate-reducing microorganisms, and smaller numbers of acetogenic, methanogenic, nitrate-dependent Fe(II)-oxidizing, Fe(III)-reducing, and sulfide oxidizing bacteria. In aquifer slurry incubations, nitrate reduction was always preferred and had a negative impact on sulfate-, Fe(III)-, and U-reduction rates. We also found that sulfate-reduction rates decreased sharply in the presence of clay, while Fe(III)-reduction increased with no clear impact on U reduction. In the absence of clay, iron and sulfate reduction correlated with concentrations of Fe(III) and sulfate, respectively. Rates of U(VI) loss did not correlate with the concentration of any electron acceptor. With the exception of Fe(III), electron donor amendment was largely unsuccessful in stimulating electron acceptor loss over a 1-week incubation period, suggesting that endogenous forms of organic matter were sufficient to support microbial activity. Our findings suggest that efforts to accelerate biological U reduction should initially focus on stimulating nitrate removal.

  15. Periplasmic Cytochrome c3 of Desulfovibrio vulgaris Is Directly Involved in H2-Mediated Metal but Not Sulfate Reduction

    PubMed Central

    Elias, Dwayne A.; Suflita, Joseph M.; McInerney, Michael J.; Krumholz, Lee R.

    2004-01-01

    Kinetic parameters and the role of cytochrome c3 in sulfate, Fe(III), and U(VI) reduction were investigated in Desulfovibrio vulgaris Hildenborough. While sulfate reduction followed Michaelis-Menten kinetics (Km = 220 μM), loss of Fe(III) and U(VI) was first-order at all concentrations tested. Initial reduction rates of all electron acceptors were similar for cells grown with H2 and sulfate, while cultures grown using lactate and sulfate had similar rates of metal loss but lower sulfate reduction activities. The similarities in metal, but not sulfate, reduction with H2 and lactate suggest divergent pathways. Respiration assays and reduced minus oxidized spectra were carried out to determine c-type cytochrome involvement in electron acceptor reduction. c-type cytochrome oxidation was immediate with Fe(III) and U(VI) in the presence of H2, lactate, or pyruvate. Sulfidogenesis occurred with all three electron donors and effectively oxidized the c-type cytochrome in lactate- or pyruvate-reduced, but not H2-reduced cells. Correspondingly, electron acceptor competition assays with lactate or pyruvate as electron donors showed that Fe(III) inhibited U(VI) reduction, and U(VI) inhibited sulfate loss. However, sulfate reduction was slowed but not halted when H2 was the electron donor in the presence of Fe(III) or U(VI). U(VI) loss was still impeded by Fe(III) when H2 was used. Hence, we propose a modified pathway for the reduction of sulfate, Fe(III), and U(VI) which helps explain why these bacteria cannot grow using these metals. We further propose that cytochrome c3 is an electron carrier involved in lactate and pyruvate oxidation and is the reductase for alternate electron acceptors with higher redox potentials than sulfate. PMID:14711670

  16. Periplasmic Cytochrome c(3) of Desulfovibrio vulgaris Is Directly Involved in H2-Mediated Metal but Not Sulfate Reduction

    SciTech Connect

    Elias, Dwayne A.; Suflita, Joseph M.; McInerney, Michael J.; Krumholz, Lee R.

    2004-01-01

    Kinetic parameters and the role of cytochrome c3 in sulfate, Fe(III), and U(VI) reduction were investigated in Desulfovibrio vulgaris Hildenborough. While sulfate reduction followed Michaelis-Menten kinetics (Km 220 uM), loss of Fe(III) and U(VI) was first-order at all concentrations tested. Initial reduction rates of all electron acceptors were similar for cells grown with H2 and sulfate, while cultures grown using lactate and sulfate had similar rates of metal loss but lower sulfate reduction activities. The similarities in metal, but not sulfate, reduction with H2 and lactate suggest divergent pathways. Respiration assays and reduced minus oxidized spectra were carried out to determine c-type cytochrome involvement in electron acceptor reduction. c-type cytochrome oxidation was immediate with Fe(III) and U(VI) in the presence of H2, lactate, or pyruvate. Sulfidogenesis occurred with all three electron donors and effectively oxidized the c-type cytochrome in lactate or pyruvate-reduced, but not H2-reduced cells. Correspondingly, electron acceptor competition assays with lactate or pyruvate as electron donors showed that Fe(III) inhibited U(VI) reduction, and U(VI) inhibited sulfate loss. However, sulfate reduction was slowed but not halted when H2 was the electron donor in the presence of Fe(III) or U(VI). U(VI) loss was still impeded by Fe(III) when H2 was used. Hence, we propose a modified pathway for the reduction of sulfate, Fe(III), and U(VI) which helps explain why these bacteria cannot grow using these metals. We further propose that cytochrome c3 is an electron carrier involved in lactate and pyruvate oxidation and is the reductase for alternate electron acceptors with higher redox potentials than sulfate.

  17. Uranium Isotopic Fractionation Induced by U(VI) Adsorption Onto Common Aquifer Minerals

    NASA Astrophysics Data System (ADS)

    Jemison, N.; Johnson, T. M.; Shiel, A. E.; Lundstrom, C.

    2014-12-01

    Mining and processing of uranium (U) ore for nuclear energy and weapons has led to U contamination of groundwater. Reduction of soluble, mobile U(VI) to UO2 decreases uranium groundwater concentrations and is an important driver of natural and stimulated attenuation. 238U/235U measurements can be used to monitor and perhaps quantify U(VI) reduction; biological reduction of U(VI) has been shown to produce a ~1.0‰ isotopic fractionation in both laboratory and field settings, with the reduced product enriched in 238U. However, adsorption of U(VI) onto minerals may complicate the use of 238U/235U in this application; adsorption of U(VI) onto Mn oxides induces an isotopic fractionation of 0.2‰ with the sorbed U(VI) depleted in 238U. At present, the isotopic shift produced by adsorption of U(VI) onto other minerals has not yet been explored. This study measures U isotopic fractionation during adsorption onto goethite, birnessite, quartz, illite, and complex aquifer materials. In addition, the effect of U speciation on fractionation is also examined by adsorption of uranyl (UO22+), uranyl carbonato (such as UO2(CO3)22- and UO2(CO3)34-), and calcium uranyl carbonato (Ca2UO2(CO3)3(aq) and CaUO2(CO3)32-) ions to goethite and birnessite. Experiments are carried out with a multi-stage, batch approach, in which a U(VI)-bearing solution is exposed to three stages of adsorption, and the final solution is analyzed by a double-spike MC-ICP-MS method. This increases our ability to resolve among sorbents the extent of fractionation. Early results suggest that uranium adsorption to different minerals produces different isotopic fractionations, with quartz producing little to no fractionation (<0 .05‰), while goethite produces a 0.16‰ isotopic shift (adsorbed U(VI) depleted in 238U).

  18. UVIS CTE Monitor: Star Clusters

    NASA Astrophysics Data System (ADS)

    Noeske, Kai

    2010-09-01

    *** NOTE 2: 2ND CHANGE MAR 26 2011: VISIT 13 HAD FAILED. APPROVED FOR REPETITION. ****** NEW VISIT 14 IS IDENTICAL TO FORMER VISIT 13, WITH EXCEPTIONS THAT SOME SUBEXPOSURES ARE REMOVED. ****** SEE OBSERVING DESCRIPTION FOR DETAILS. ****** NOTE: THIS IS A CHANGED PHASE II PROPOSAL AFTER VISITS 1,2,7 HAD BEEN EXECUTED ****** CHANGES BECAME NECESSARY AFTER ANALYSIS OF INCOMING CALIBRATION DATA FROM 12379 AND 12348 ****** THIS REVISED PHASE II {submission 14FEB2011} ADDS THE EVALUATION OF CHARGE INJECTION***The changes amount to:1} dropping the 3rd epoch {August 2011} of external CTE monitoring {3 orbits}2} simplifying the CTE monitor observations in the second epoch {March 2011}, freeing up 1 orbit3} using the freed up orbits from 1} and 2}, together with two additional external orbits that we were granted, to thoroughly assess the data quality of charge - injected data under realistic observing setups.These charge-injected observations will be obtained during the 2nd epoch of the CTE monitor program, in the March 2011 window.------ Original Text prior to 14 Feb 2011 below this line -----------This program extends the Cycle 17 external CTE calibration {CAL/WFC3 ID 11924} program for WFC3/UVIS over Cycle 18. Targets are {i} the sparse cluster NGC 6791 observed in Cycle 17, to continue a consistent set of observations that allows to isolate the time evolution of the CTE, and {ii} a denser field in 47 Tuc {NGC 104}. The latter will provide data to measure the dependence of the CTE on field crowding. It will also provide a consistent comparison between the CTE evolution of WFC3/UVIS and that of ACS/WFC at the same time into the flight {1 year}, because ACS/WFC CTE data were based on 47 Tuc observations. Additional observations of 47 Tuc in the CVZ will provide a wide range of background levels to measure the background dependence of the UVIS CTE.Goals are {i} the continued monitoring of the time evolution of the WFC3/UVIS CTE, {ii} establishing the detector X

  19. Bicarbonate Impact on U(VI) Bioreduction in a Shallow Alluvial Aquifer

    SciTech Connect

    Long, Philip E.; Williams, Kenneth H.; Davis, James A.; Fox, Patricia M.; Wilkins, Michael J.; Yabusaki, Steven B.; Fang, Yilin; Waichler, Scott R.; Berman, Elena S.; Gupta, Manish; Chandler, Darrell P.; Murray, Christopher J.; Peacock, Aaron D.; Giloteaux, L.; Handley, Kim M.; Lovley, Derek R.; Banfield, Jillian F.

    2015-02-01

    Field-scale biostimulation and desorption tracer experiments conducted in a uranium (U) contaminated, shallow alluvial aquifer have provided insight into the coupling of microbiology, biogeochemistry, and hydrogeology that control U mobility in the subsurface. Initial experiments successfully tested the concept that Fe-reducing bacteria such as Geobacter sp. could enzymatically reduce soluble U(VI) to insoluble U(IV) during in situ electron donor amendment (Anderson et al. 2003, Williams et al. 2011). In parallel, in situ desorption tracer tests using bicarbonate amendment demonstrated rate-limited U(VI) desorption (Fox et al. 2012). These results and prior laboratory studies underscored the importance of enzymatic U(VI)-reduction and suggested the ability to combine desorption and bioreduction of U(VI). Here we report the results of a new field experiment in which bicarbonate-promoted uranium desorption and acetate amendment were combined and compared to an acetate amendment-only experiment in the same experimental plot. Results confirm that bicarbonate amendment to alluvial aquifer desorbs U(VI) and increases the abundance of Ca-uranyl-carbonato complexes. At the same time, that the rate of acetate-promoted enzymatic U(VI) reduction was greater in the presence of added bicarbonate in spite of the increased dominance of Ca-uranyl-carbonato aqueous complexes. A model-simulated peak rate of U(VI) reduction was ~3.8 times higher during acetate-bicarbonate treatment than under acetate-only conditions. Lack of consistent differences in microbial community structure between acetate-bicarbonate and acetate-only treatments suggest that a significantly higher rate of U(VI) reduction the bicarbonate-impacted sediment may be due to a higher intrinsic rate of microbial reduction induced by elevated concentrations of the bicarbonate oxyanion. The findings indicate that bicarbonate amendment may be useful in improving the engineered bioremediation of uranium in aquifers.

  20. Bicarbonate impact on U(VI) bioreduction in a shallow alluvial aquifer

    NASA Astrophysics Data System (ADS)

    Long, Philip E.; Williams, Kenneth H.; Davis, James A.; Fox, Patricia M.; Wilkins, Michael J.; Yabusaki, Steven B.; Fang, Yilin; Waichler, Scott R.; Berman, Elena S. F.; Gupta, Manish; Chandler, Darrell P.; Murray, Chris; Peacock, Aaron D.; Giloteaux, Ludovic; Handley, Kim M.; Lovley, Derek R.; Banfield, Jillian F.

    2015-02-01

    Field-scale biostimulation and desorption tracer experiments conducted in a uranium (U) contaminated, shallow alluvial aquifer have provided insight into the coupling of microbiology, biogeochemistry, and hydrogeology that control U mobility in the subsurface. Initial experiments successfully tested the concept that Fe-reducing bacteria such as Geobacter sp. could enzymatically reduce soluble U(VI) to insoluble U(IV) during in situ electron donor amendment (Anderson et al., 2003; Williams et al., 2011). In parallel, in situ desorption tracer tests using bicarbonate amendment demonstrated rate-limited U(VI) desorption (Fox et al., 2012). These results and prior laboratory studies underscored the importance of enzymatic U(VI)-reduction and suggested the ability to combine desorption and bioreduction of U(VI). Here we report the results of a new field experiment in which bicarbonate-promoted uranium desorption and acetate amendment were combined and compared to an acetate amendment-only experiment in the same experimental plot. Results confirm that bicarbonate amendment to alluvial aquifer sediments desorbs U(VI) and increases the abundance of Ca-uranyl-carbonato complexes. At the same time, the rate of acetate-promoted enzymatic U(VI) reduction was greater in the presence of added bicarbonate in spite of the increased dominance of Ca-uranyl-carbonato aqueous complexes. A model-simulated peak rate of U(VI) reduction was ∼3.8 times higher during acetate-bicarbonate treatment than under acetate-only conditions. Lack of consistent differences in microbial community structure between acetate-bicarbonate and acetate-only treatments suggest that a significantly higher rate of U(VI) reduction in the bicarbonate-impacted sediment may be due to a higher intrinsic rate of microbial reduction induced by elevated concentrations of the bicarbonate oxyanion. The findings indicate that bicarbonate amendment may be useful in improving the engineered bioremediation of uranium in

  1. Interaction of CPR5 with Cell Cycle Regulators UVI4 and OSD1 in Arabidopsis

    PubMed Central

    Bao, Zhilong; Hua, Jian

    2014-01-01

    The impact of cell cycle on plant immunity was indicated by the enhancement of disease resistance with overexpressing OSD1 and UVI4 genes that are negative regulators of cell cycle controller APC (anaphase promoting complex). CPR5 is another gene that is implicated in cell cycle regulation and plant immunity, but its mode of action is not known. Here we report the analysis of genetic requirement for the function of UVI4 and OSD1 in cell cycle progression control and in particular the involvement of CPR5 in this regulation. We show that the APC activator CCS52A1 partially mediates the function of OSD1 and UVI4 in female gametophyte development. We found that the cpr5 mutation suppresses the endoreduplication defect in the uvi4 single mutant and partially rescued the gametophyte development defect in the osd1 uvi4 double mutant while the uvi4 mutation enhances the cpr5 defects in trichome branching and plant disease resistance. In addition, cyclin B1 genes CYCB1;1, CYCB1;2, and CYCB1;4 are upregulated in cpr5. Therefore, CPR5 has a large role in cell cycle regulation and this role has a complex interaction with that of UVI4 and OSD1. This study further indicates an intrinsic link between plant defense responses and cell cycle progression. PMID:24945150

  2. Active{sup 3} noise reduction

    SciTech Connect

    Holzfuss, J.

    1996-06-01

    Noise reduction is a problem being encountered in a variety of applications, such as environmental noise cancellation, signal recovery and separation. Passive noise reduction is done with the help of absorbers. Active noise reduction includes the transmission of phase inverted signals for the cancellation. This paper is about a threefold active approach to noise reduction. It includes the separation of a combined source, which consists of both a noise and a signal part. With the help of interaction with the source by scanning it and recording its response, modeling as a nonlinear dynamical system is achieved. The analysis includes phase space analysis and global radial basis functions as tools for the prediction used in a subsequent cancellation procedure. Examples are given which include noise reduction of speech. {copyright} {ital 1996 American Institute of Physics.}

  3. Identification of simultaneous U(VI) sorption complexes and U(IV) nanoprecipitates on the magnetite (111) surface

    SciTech Connect

    Singer, David M.; Chatman, Shawn ME; Ilton, Eugene S.; Rosso, Kevin M.; Banfield, Jillian F.; Waychunas, Glenn

    2012-04-03

    Sequestration of uranium (U) by magnetite is a potentially important sink for U in natural and contaminated environments. However, molecular-scale controls which favor U(VI) uptake including both adsorption of U(VI) and reduction to U(VI) by magnetite remain poorly understood, in particular the role of U(VI)-CO3-Ca complexes in inhibiting U(VI) reduction. To investigate U uptake pathways on magnetite as a function of U(VI) aqueous speciation, we performed batch sorption experiments on (111) surfaces of natural single crystals under a range of solution conditions (pH 5 and 10; 0.1 mM U(VI); 1 mM NaCl; and with or without 0.5 mM CO3 and 0.1 mM Ca) and characterized surface-associated U using grazing incidence extended x-ray absorption fine structure spectroscopy (GI-EXAFS), grazing incidence x-ray diffraction (GI-XRD), and scanning electron microscopy (SEM). In the absence of both carbonate ([CO3]T, denoted here as CO3) and calcium (Ca), or in the presence of CO3 only, co-existing adsorption of U(VI) surface species and reduction to U(IV) occurs at both pH 5 and 10. In the presence of both CO3 and Ca, only adsorption of U(VI) occur. When U reduction occurs, nanoparticulate UO2 forms only within and adjacent to surface microtopographic features such as crystal boundaries and cracks. This result suggests that U reduction is limited to defect-rich surface regions. Further, at both pH 5 and 10 in the presence of both CO3 and Ca, U(VI)-CO3-Ca ternary surface species develop and U reduction is precluded. These findings extend the range of conditions under which U (VI)-CO3-Ca complexes inhibit U reduction.

  4. Haloes seen in UVIS reflectance

    NASA Astrophysics Data System (ADS)

    Esposito, L. W.; Bradley, E. T.; Colwell, J. E.; Sremcevic, M.

    2012-12-01

    UVIS SOI reflectance spectra show bright 'haloes' around the locations of some of the strongest resonances in Saturn's A ring (Esposito etal 2005). UV spectra constrain the size and composition of the icy ring particles (Bradley etal 2010, 2012). We investigate the Janus 4:3, 5:3, 6:5 and Mimas 5:3 inner Lindblad resonances as well as at the Mimas 5:3 vertical resonance (bending wave location). Models of ring particle regolith evolution (Elliott and Esposito 2010) indicate the deeper regolith is made of older and purer ice. The strong resonances can cause streamline crowding (Lewis and Stewart 2005) which damps the interparticle velocity, allowing temporary clumps to grow, which in turn increase the velocity, eroding the clumps and releasing smaller particles and regolith (see the predator-prey model of Esposito etal 2012). This cyclic behavior, driven by the resonant perturbation from the moon, can yield collision velocities at particular azimuths greater than 1m/sec, sufficient to erode the aggregates (Blum 2006), exposing older, purer materials. Thus, the radial location of the strongest resonances can be where we find both large aggregates and disrupted fragments, in a balance maintained by the periodic moon forcing. If this stirring exposes older, and purer ice, the velocity threshold for eroding the aggregates can explain why only the strongest Lindblad resonances show haloes. Diffusion can explain the morphology of these haloes, although they are not well-resolved spatially by UVIS. Spectra determine the relative contributions of particle size and purity at these locations, for comparison to estimates from the regolith evolution models.

  5. WFC3/UVIS 2.0

    NASA Astrophysics Data System (ADS)

    Deustua, Susana E.; Mack, Jennifer; Bowers, Ariel; and the WFC3/UVIS2.0 Team

    2016-01-01

    WFC3 UVIS data processing pipeline has been improved to provide better precision by implementing chip dependent photometry and cte corrections. The two UVIS CCDs have different characteristics, different QE and different wavelength dependent response functions. Therefore, to improve the photometric precision, new flat fields, zero points, encircled energy curves and aperture corrections were generated. In this presentation we describe these changes, and their effects on data analysis, including using AstroDrizzle. CTE corrections are presented by S. Baggett at this meeting.

  6. Analog VLSI system for active drag reduction

    SciTech Connect

    Gupta, B.; Goodman, R.; Jiang, F.; Tai, Y.C.; Tung, S.; Ho, C.M.

    1996-10-01

    In today`s cost-conscious air transportation industry, fuel costs are a substantial economic concern. Drag reduction is an important way to reduce costs. Even a 5% reduction in drag translates into estimated savings of millions of dollars in fuel costs. Drawing inspiration from the structure of shark skin, the authors are building a system to reduce drag along a surface. Our analog VLSI system interfaces with microfabricated, constant-temperature shear stress sensors. It detects regions of high shear stress and outputs a control signal to activate a microactuator. We are in the process of verifying the actual drag reduction by controlling microactuators in wind tunnel experiments. We are encouraged that an approach similar to one that biology employs provides a very useful contribution to the problem of drag reduction. 9 refs., 21 figs.

  7. Reduction of uranium by Desulfovibrio desulfuricans

    USGS Publications Warehouse

    Lovley, D.R.; Phillips, E.J.P.

    1992-01-01

    The possibility that sulfate-reducing microorganisms contribute to U(VI) reduction in sedimentary environments was investigated. U(VI) was reduced to U(IV) when washed cells of sulfate-grown Desulfovibrio desulfuricans were suspended in a bicarbonate buffer with lactate or H2 as the electron donor. There was no U(VI) reduction in the absence of an electron donor or when the cells were killed by heat prior to the incubation. The rates of U(VI) reduction were comparable to those in respiratory Fe(III)-reducing microorganisms. Azide or prior exposure of the cells to air did not affect the ability of D. desulfuricans to reduce U(VI). Attempts to grow D. desulfuricans with U(VI) as the electron acceptor were unsuccessful. U(VI) reduction resulted in the extracellular precipitation of the U(IV) mineral uraninite. The presence of sulfate had no effect on the rate of U(VI) reduction. Sulfate and U(VI) were reduced simultaneously. Enzymatic reduction of U(VI) by D. desulfuricans was much faster than nonenzymatic reduction of U(VI) by sulfide, even when cells of D. desulfuricans were added to provide a potential catalytic surface for the nonenzymatic reaction. The results indicate that enzymatic U(VI) reduction by sulfate-reducing microorganisms may be responsible for the accumulation of U(IV) in sulfidogenic environments. Furthermore, since the reduction of U(VI) to U(IV) precipitates uranium from solution, D. desulfuricans might be a useful organisms for recovering uranium from contaminated waters and waste streams.

  8. WFC3 UVIS Crosstalk Images

    NASA Astrophysics Data System (ADS)

    Baggett, S.; Hartig, G.; Cheung, E.

    2004-09-01

    This report summarizes the behavior of the Wide Field Camera 3 UVIS channel crosstalk features seen in the first ground-test data from the integrated instrument. There appear to be two types of crosstalk: the first arises from sources at any exposure level (from a few DN up to saturation); the crosstalk from a source in one amp appears in the three other amps as mirror images of the source. The second type arises from highly saturated pixels only; in these cases, the crosstalk appears in the adjoining amp of the same CCD as the source. Both types of crosstalk are highly nonlinear, occur at very low levels (<10DN/ pixel at the default gain of 1.5), and depend upon the bias level, gain, and pixel binning settings. A software workaround to eliminate some of the crosstalk is currently in hand in the form of timing patterns with alternate clamp times. The hardware cause for some of the crosstalk, a common-mode noise susceptibility in the CCD electronics box, has been identified and successfully fixed in the non-flight hardware; the problem is expected to be fixed in the flight hardware later this year. Meanwhile, further tests are underway at the Detector Characterization Lab (DCL at GSFC) to explore additional possible causes of crosstalk in the camera head electronics.

  9. A representative retinoid X receptor antagonist UVI3003 induced teratogenesis in zebrafish embryos.

    PubMed

    Zheng, Liang; Xu, Ting; Li, Daoji; Zhou, Junliang

    2015-03-01

    Retinoid X receptor (RXR) interfering activity has been detected in different water resources. To study RXR disruptor-induced toxicological effects on vertebrates, embryos of zebrafish (Danio rerio) were exposed to a representative RXR antagonist UVI3003. Results showed that the teratogenic index (LC50 /EC50 ) of UVI3003 was as high as 5.4. UVI3003 induced multiple malformations of embryos, including deformed fins, reduced brains, small jaws, bent tails and edema in hearts, the degree of which became more severe with increasing exposure concentration. Although no significant difference was observed in the hatching rates between the exposure group and control, the whole body length was significantly reduced by 6.5% and 8.9% when exposed to 200 and 300 µg l(-1) of UVI3003, respectively. The heart rate also significantly decreased by 8.8-50.2% during exposure. Further experiments revealed that the pharyngula stage was the most sensitive development phase in terms of embryo response to UVI3003. The results demonstrated severe teratogenicity of RXR antagonist in zebrafish embryos and provided important data for ecotoxicological evaluation of RXR antagonists. PMID:25186191

  10. Reduction kinetics of aqueous U(VI) in acidic chloride brines to uraninite by methane, hydrogen or C-graphite under hydrothermal conditions: Implications for the genesis of unconformity-related uranium ore deposits

    NASA Astrophysics Data System (ADS)

    Dargent, Maxime; Truche, Laurent; Dubessy, Jean; Bessaque, Gilles; Marmier, Hervé

    2015-10-01

    The formation of hydrothermal uranium ore deposits involves the reduction of dissolved U(VI)(aq) to uraninite. However, the nature of the reducing agent and the kinetics of such a process are currently unknown. These questions are addressed through dedicated experiments performed under conditions relevant for the genesis of unconformity-related uranium (URU) deposits. We tested the efficiency of the following potential reductants supposed to be involved in the reaction: H2, CH4, C-graphite and dissolved Fe(II). Results demonstrate the great efficiency of H2, CH4 and C-graphite to reduce U(VI)(aq) into uraninite in acidic chloride brines, unlike dissolved Fe(II). Times needed for H2 (1.4 bar), CH4 (2.4 bar) and C-graphite (water/carbon mass ratio = 10) to reduce 1 mM of U(VI)(aq) in an acidic brine (1 m LiCl, pH ≈ 1 fixed by HCl) to uraninite at 200 °C are 12 h, 3 days and 4 months, respectively. The effects of temperature (T) between 100 °C and 200 °C, H2 partial pressure (0.14, 1.4, and 5.4 bar), salinity (0.1, 1 and 3.2 m LiCl) and pH at 25 °C (0.8 and 3.3) on the reduction rate were also investigated. Results show that increasing temperature and H2 partial pressure increase the reaction rate, whereas increasing salinity or pH have the reverse effect. The reduction of uranyl to uraninite follows an apparent zero-order with respect to time, whatever the considered electron donor. From the measured rate constants, the following values of activation energy (Ea), depending on the nature of the electron donor, have been derived: EaC-graphite = 155 ± 3 kJ mol-1, EaCH4 = 143 ± 6 kJ mol-1, and EaH2 = 124 ± 15 kJ mol-1 at T < 150 °C and 32 ± 6 kJ mol-1 at T > 150 °C. An empirical relationship between the reaction rate, the hydrogen partial pressure, the uranyl speciation, and the temperature is also proposed. This allows an estimation of the time of formation of a giant U ore deposit such as McArthur River (Canada). The duration of the mineralizing event is

  11. Impact of phosphate on U(VI) immobilization in the presence of goethite

    NASA Astrophysics Data System (ADS)

    Singh, Abhas; Ulrich, Kai-Uwe; Giammar, Daniel E.

    2010-11-01

    Past mining, processing, and waste disposal activities have left a legacy of uranium-contaminated soil and groundwater. Phosphate addition to subsurface environments can potentially immobilize U(VI) in-situ through interactions with uranium at mineral-water interfaces. Phosphate can induce the precipitation of low solubility U(VI)-phosphates, and it may enhance or inhibit U(VI) adsorption to iron(III) (oxy)hydroxide surfaces. Such surfaces may also facilitate the heterogeneous nucleation of U(VI)-phosphate precipitates. The interactions among phosphate, U(VI), and goethite (α-FeOOH) were investigated in a year-long series of experiments at pH 4. Reaction time, total U(VI), total phosphate, and the presence and absence of goethite were systematically varied to determine their effects on the extent of U(VI) uptake and the dominant uranium immobilization mechanism. Dissolved U(VI) and phosphate concentrations were interpreted within a reaction-based modeling framework that included dissolution-precipitation reactions and a surface complexation model to account for adsorption. The best available thermodynamic data and past surface complexation models were integrated to form an internally consistent framework. Additional evidence for the uptake mechanisms was obtained using scanning electron microscopy and X-ray diffraction. The formation and crystal growth of a U(VI)-phosphate phase, most likely chernikovite, UO 2HPO 4·4H 2O (s), occurred rapidly for initially supersaturated suspensions both with and without goethite. Nucleation appears to occur homogeneously for almost all conditions, even in the presence of goethite, but heterogeneous nucleation was likely at one condition. The U(VI)-phosphate solids exhibited metastability depending on the TOTU:TOTP ratio. At the highest phosphate concentration studied (130 μM), U(VI) uptake was enhanced due to the likely formation of a ternary surface complex for low (˜1 μM) to intermediate (˜10 μM) TOTU concentrations and

  12. Liquor Activity Reduction (LAR) Programme - 12397

    SciTech Connect

    Pether, Colin; Carrol, Phil; Birkett, Eddie; Kibble, Matthew

    2012-07-01

    Waste material from the reprocessing of irradiated fuel has been stored under water for several decades leading to the water becoming highly radioactive. As a critical enabler to the decommissioning strategy for the Sellafield site, the Liquor Activity Reduction (LAR) programme has been established to provide a processing route for this highly radioactive liquor. This paper reviews the progress that has been made since the start of routine LAR transfer cycles (July 2010) and follows on from the earlier paper presented at WM2011. The paper focuses on the learning from the first full year of routine LAR transfer cycles and the application of this learning to the wider strategies for the treatment of further radioactive liquid effluents on the Sellafield site. During this period over 100,000 Curies of radioactivity has been safely removed and treated. The past year has witnessed the very successful introduction of the LAR programme. This has lead to hazard reduction at MSSS and demonstration that the SIXEP facility can meet the significantly increased challenge that the LAR programme represents. Part of the success has been the ability to predict and deliver a realistic production schedule with the availability of the MSSS, EDT and SIXEP facilities being central to this. Most importantly, the LAR programme has been successful in bringing together key stakeholders to deliver this work while integrating with the existing, day to day, demands of the Sellafield site. (authors)

  13. International Space Station (ISS) Risk Reduction Activities

    NASA Technical Reports Server (NTRS)

    Fodroci, Michael

    2011-01-01

    As the assembly of the ISS nears completion, it is worthwhile to step back and review some of the actions pursued by the Program in recent years to reduce risk and enhance the safety and health of ISS crewmembers, visitors, and space flight participants. While the ISS requirements and initial design were intended to provide the best practicable levels of safety, it is always possible to reduce risk -- given the determination and commitment to do so. The following is a summary of some of the steps taken by the ISS Program Manager, by our International Partners, by hardware and software designers, by operational specialists, and by safety personnel to continuously enhance the safety of the ISS. While decades of work went into developing the ISS requirements, there are many things in a Program like the ISS that can only be learned through actual operational experience. These risk reduction activities can be divided into roughly three categories: (1) Areas that were initially noncompliant which have subsequently been brought into compliance or near compliance (i.e., Micrometeoroid and Orbital Debris [MMOD] protection, acoustics) (2) Areas where initial design requirements were eventually considered inadequate and were subsequently augmented (i.e., Toxicity Level 4 materials, emergency hardware and procedures) (3) Areas where risks were initially underestimated, and have subsequently been addressed through additional mitigation (i.e., Extravehicular Activity [EVA] sharp edges, plasma shock hazards) Due to the hard work and cooperation of many parties working together across the span of nearly a decade, the ISS is now a safer and healthier environment for our crew, in many cases exceeding the risk reduction targets inherent in the intent of the original design. It will provide a safe and stable platform for utilization and discovery.

  14. Diffusion of U(VI) in Opalinus Clay: Influence of temperature and humic acid

    NASA Astrophysics Data System (ADS)

    Joseph, C.; Van Loon, L. R.; Jakob, A.; Steudtner, R.; Schmeide, K.; Sachs, S.; Bernhard, G.

    2013-05-01

    activation energy for the diffusion of U(VI) through Opalinus Clay of 10 kJ/mol was calculated. The observed increased Kd and De values for U(VI)aqueous at 60 °C compensated each other to almost equal values of the apparent diffusion coefficient Da at 25 and 60 °C. Hence, an elevated temperature of 60 °C does not impact the migration of U(VI) through OPA significantly.

  15. Characterization of UVIS traps with CI

    NASA Astrophysics Data System (ADS)

    Sabbi, Elena

    2013-10-01

    The charge transfer efficiency {CTE} of the WFC3/UVIS channel is declining as damage from radiation is accumulating. The impact of CTE losses on scientific data can be mitigated by removing the charge-trailing at pixel level. This program is designed to identify and characterize the traps responsible for the charge losses and to monitor the grouth of the trap number with time.

  16. Biotransformation involved in sustained reductive removal of uranium in contaminant aquifers

    SciTech Connect

    Lovley, Derek R.

    2005-06-01

    This report summarizes progress made from August 2004 to July 2005. During this period research focused primarily on obtaining a better understanding of the factors controlling the reduction of U(VI) during in situ uranium bioremediation as well as investigating the potential for using electrodes as an alternative electron donor to promote in situ uranium reduction. Analysis of the 2003 experiment at the field study site in Rifle, CO was completed. The results demonstrated the substantial heterogeneity of the zone undergoing bioremediation, both in terms of geochemistry and microbiology. The lack of U(VI) reduction under sulfate-reducing conditions was clearly documented. The need for more detailed sampling both with time and with depth in the aquifer was demonstrated. For the first time a comparison between the composition of the microbial community in the sediments and the microbes in the corresponding groundwater was attempted. The findings from this study are important not only in further demonstrating the potential for in situ uranium bioremediation, but also for indicating how methods and sampling approaches should be improved in the future. A manuscript summarizing these findings has been accepted for publication in Applied and Environmental Microbiology. In summer of 2004 a new field experiment was conducted at the Rifle site. A novel feature of this study was much more intensive sampling in order to better define the progression of microbial processes during in situ uranium bioremediation. The results demonstrated that stimulation of in situ uranium bioremediation with added acetate was a repeatable phenomenon and that U(VI) reduction was clearly linked to the presence and activity of microorganisms in the family Geobacteraceae. A manuscript summarizing these results is in preparation. A surprising result of the field studies at the Rifle site was that although Geobacter species actively reduced U(VI) in the groundwater, removing it from solution, a high

  17. Ultraviolet Observations of Phoebe from the Cassini UVIS

    NASA Technical Reports Server (NTRS)

    Hendrix, Amanda R.; Hansen, Candice J.

    2007-01-01

    Observations of Saturn's distant moon Phoebe were made at far-ultraviolet (FUV) (1100-1900 A) and extreme-ultraviolet (EUV) (600-1100 A) wavelengths by the Cassini Ultraviolet Imaging Spectrograph (UVIS) during the Cassini spacecraft flyby on June 11, 2004. These are the first UV spectra of Phoebe and the first detection of water ice on a Solar System surface using FUV wavelengths. The characteristics of water ice in the FUV are presented, and Hapke models are used to interpret the spectra in terms of composition and grain size; the use of both areal and intimate mixing models is explored. Non-ice species used in these models include carbon, ice tholin, Triton tholin, poly-HCN and kerogen. Satisfactory disk-integrated fits are obtained for intimate mixtures of approx.10% H2O plus a non-ice species. Spatially resolved regions of higher (approx.20%) and lower (approx.5%) H2O ice concentrations are also detected. Phoebe does not display any evidence of volatile activity. Upper limits on atomic oxygen and carbon are 5 x 10(exp 11) and 2 x 10(exp 12) atoms/sq. cm, respectively, for solar photon scattering. The UVIS detection of water ice on Phoebe, and the ice amounts detected, are consistent with IR measurements and contribute to the evidence for a Phoebe origin in the outer Solar System rather than in the main asteroid belt.

  18. A Mixed-Valent Uranium Phosphonate Framework Containing U(IV) , U(V) , and U(VI).

    PubMed

    Chen, Lanhua; Zheng, Tao; Bao, Songsong; Zhang, Linjuan; Liu, Hsin-Kuan; Zheng, Limin; Wang, Jianqiang; Wang, Yaxing; Diwu, Juan; Chai, Zhifang; Albrecht-Schmitt, Thomas E; Wang, Shuao

    2016-08-16

    It is shown that U(V) O2 (+) ions can reside at U(VI) O2 (2+) lattice sites during mild reduction and crystallization process under solvothermal conditions, yielding a complicated and rare mixed-valent uranium phosphonate compound that simultaneously contains U(IV) , U(V) , and U(VI) . The presence of uranium with three oxidation states was confirmed by various characterization techniques, including X-ray crystallography, X-ray photoelectron, electron paramagnetic resonance, FTIR, UV/Vis-NIR absorption, and synchrotron radiation X-ray absorption spectroscopy, and magnetism measurements. PMID:27356283

  19. Role of U(VI) Adsorption in U(VI) Reduction by Geobacter Species.

    SciTech Connect

    None, None

    2009-03-09

    Previous work had suggested that Acholeplasma palmae has a higher capacity for uranium sorption than other bacteria studied. Sorption studies were performed with cells in suspension in various solutions containing uranium and results were used to generate uranium-biosorption isotherms.

  20. U(VI) behaviour in hyperalkaline calcite systems

    NASA Astrophysics Data System (ADS)

    Smith, Kurt F.; Bryan, Nicholas D.; Swinburne, Adam N.; Bots, Pieter; Shaw, Samuel; Natrajan, Louise S.; Mosselmans, J. Frederick W.; Livens, Francis R.; Morris, Katherine

    2015-01-01

    The behaviour of U(VI) in hyperalkaline fluid/calcite systems was studied over a range of U(VI) concentrations (5.27 × 10-5 μM to 42.0 μM) and in two high pH systems, young and old synthetic cement leachate in batch sorption experiments. These systems were selected to be representative of young- (pH 13.3) and old-stage (pH 10.5) leachate evolution within a cementitious geological disposal facility. Batch sorption experiments, modelling, extended X-ray absorption fine structure spectroscopy, electron microscopy, small angle X-ray scattering and luminescence spectroscopy were used to define the speciation of U(VI) across the systems of study. At the lowest concentrations (5.27 × 10-5 μM 232U(VI)) significant U removal was observed for both old and young cement leachates, and this was successfully modelled using a first order kinetic adsorption modelling approach. At higher concentrations (>4.20 μM) in the young cement leachate, U(VI) showed no interaction with the calcite surface over an 18 month period. Small angle X-ray scattering techniques indicated that at high U concentrations (42.0 μM) and after 18 months, the U(VI) was present in a colloidal form which had little interaction with the calcite surface and consisted of both primary and aggregated particles with a radius of 7.6 ± 1.1 and 217 ± 24 Å, respectively. In the old cement leachate, luminescence spectroscopy identified two surface binding sites for U(VI) on calcite: in the system with 0.21 μM U(VI), a liebigite-like Ca2UO2(CO3)3 surface complex was identified; at higher U(VI) concentrations (0.42 μM), a second binding site of undetermined coordination was identified. At elevated U(VI) concentrations (>2.10 μM) in old cement leachate, both geochemical data and luminescence spectroscopy suggested that surface mediated precipitation was controlling U(VI) behaviour. A focused ion beam mill was used to create a section across the U(VI) precipitate-calcite interface. Transmission electron

  1. Identification of Simultaneous U(VI) Sorption Complexes and U(IV) Nanoprecipitates on the Magnetite (111) Surface

    SciTech Connect

    Singer, David M.; Chatman, Shawn M.; Ilton, Eugene S.; Rosso, Kevin M.; Banfield, Jillian F.; Waychunas, Glenn A.

    2012-05-10

    Sequestration of uranium (U) by magnetite is a potentially important sink for U in natural and contaminated environments. However, molecular-scale controls that favor U(VI) uptake including both adsorption of U(VI) and reduction to U(IV) by magnetite remain poorly understood, in particular, the role of U(VI)-CO{sub 3}-Ca complexes in inhibiting U(VI) reduction. To investigate U uptake pathways on magnetite as a function of U(VI) aqueous speciation, we performed batch sorption experiments on (111) surfaces of natural single crystals under a range of solution conditions (pH 5 and 10; 0.1 mM U(VI); 1 mM NaNO{sub 3}; and with or without 0.5 mM CO{sub 3} and 0.1 mM Ca) and characterized surface-associated U using grazing incidence extended X-ray absorption fine structure spectroscopy (GI-EXAFS), grazing incidence X-ray diffraction (GI-XRD), and scanning electron microscopy (SEM). In the absence of both carbonate ([CO{sub 3}]T, denoted here as CO{sub 3}) and calcium (Ca), or in the presence of CO{sub 3} only, coexisting adsorption of U(VI) surface species and reduction to U(IV) occurs at both pH 5 and 10. In the presence of both Ca and CO{sub 3}, only U(VI) adsorption (VI) occurs. When U reduction occurs, nanoparticulate UO{sub 2} forms only within and adjacent to surface microtopographic features such as crystal boundaries and cracks. This result suggests that U reduction is limited to defect-rich surface regions. Further, at both pH 5 and 10 in the presence of both CO{sub 3} and Ca, U(VI)-CO{sub 3}-Ca ternary surface species develop and U reduction is inhibited. These findings extend the range of conditions under which U(VI)-CO{sub 3}-Ca complexes inhibit U reduction.

  2. Release of contaminant U(VI) from soils

    SciTech Connect

    Zheng, Zuoping; Wan, Jiamin

    2003-08-20

    The retention, mobility, and bio-availability of U(VI) incontaminated soils depend strongly on release of U(VI). Laboratory batchexperiments were performed to evaluate the factors controlling therelease of U(VI) from contaminated soil at Oak Ridge, Tennessee. We foundthat the ionic strength of the extraction solution strongly affectsrelease of U(VI). Increase in ionic strength shows a strong effect onU(VI) release as indicated by the increase in release rates andassociated release of U(VI) concentrations. We also found that the ratioof solution volume to solid mass (V/M) has a significant impact on therelease of U(VI). Increase in the V/M ratio shows a negligible effect onthe U(VI) release over a 4-day period. However, at Day 30 and Day 120,larger V/M ratios cause greater U(VI) release. The maximum U(VI)concentrations observed in the release experiments are in the range ofschoepite estimated under conditions relevant to the experiments,suggesting that schoepite solubility primarily controls the U(VI)release, but that solubilization and desorption effects cannot bedistinguished using macroscopic methods.

  3. ADSORPTION AND TRANSPORT OF U(VI) IN SUBSURFACE MEDIA

    EPA Science Inventory

    U(VI) adsorption and transport in three natural, heterogeneous subsurface media were investigated in batch and column experiments. The rate of U(VI) adsorption to the natural samples was rapid over the first few hours of the experiments, and then slowed appreciably after twenty-f...

  4. 29 CFR 4043.23 - Active participant reduction.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 29 Labor 9 2014-07-01 2014-07-01 false Active participant reduction. 4043.23 Section 4043.23 Labor Regulations Relating to Labor (Continued) PENSION BENEFIT GUARANTY CORPORATION PLAN TERMINATIONS REPORTABLE EVENTS AND CERTAIN OTHER NOTIFICATION REQUIREMENTS Post-Event Notice of Reportable Events § 4043.23 Active participant reduction....

  5. 29 CFR 4043.23 - Active participant reduction.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 29 Labor 9 2010-07-01 2010-07-01 false Active participant reduction. 4043.23 Section 4043.23 Labor Regulations Relating to Labor (Continued) PENSION BENEFIT GUARANTY CORPORATION PLAN TERMINATIONS REPORTABLE EVENTS AND CERTAIN OTHER NOTIFICATION REQUIREMENTS Post-Event Notice of Reportable Events § 4043.23 Active participant reduction....

  6. Iron Reduction and Radionuclide Immobilization: Kinetic, Thermodynamic and Hydrologic controls & Reaction-Based Modeling - Final Report

    SciTech Connect

    William D. Burgos

    2004-06-18

    Our research focused on (1) microbial reduction of Fe(III) and U(VI) individually, and concomitantly in natural sediments, (2) Fe(III) oxide surface chemistry, specifically with respect to reactions with Fe(II)and U(VI), (3) the influence of humic substances on Fe(III) and U(VI) bioreduction, and on U(VI) complexation, and (4) the development of reaction-based reactive transport biogeochemical models to numerically simulate our experimental results. We have continued our investigations on microbial reduction of Fe(III) oxides. Modeling our earlier experimental results required assumption of a hydrated surface for hematite, more reactive than predicted based on theoretical solubility (Burgos et al.2002). Subsequent studies with Shewanella putrefaciens and Geobacter sulfurreducens confirmed the rates of Fe(III) bioreduction depend on oxide surface area rather than oxide thermodynamic properties (Roden,2003a,b;2004; Burgos et al,2003). We examined the potential for bioreduction of U(VI) by Geobacter sulfurreducens in the presence of synthetic Fe(III) oxides and natural Fe(III) oxide-containing solids (Jeon et al,2004a,b) in which more than 95% of added U(VI) was sorbed to mineral surfaces. The results showed a significant portion of solid-associated U(VI) was resistant to both enzymatic and abiotic (Fe(II)-driven) reduction, but the rate and extent of bioreduction of U(VI) was increased due to the addition of anthraquinone-2,6-disulfonate (AQDS). We conducted long-term semicontinuous culture and column experiments on coupled Fe(III) oxide/U(VI) reduction. These experiments were conducted with natural subsurface sediment from the Oyster site in Virginia, whose Fe content and microbial reducibility are comparable to ORNL FRC sediments (Jeon et al, 2004b). The results conclusively demonstrated the potential for sustained removal of U(VI) from solution via DMRB activity in excess of the U(VI) sorption capacity of the natural mineral assemblages. Jang (2004) demonstrated

  7. Haloes Seen In UVIS Reflectance Spectra

    NASA Astrophysics Data System (ADS)

    Esposito, Larry W.; Bradley, E.; Colwell, J.; Sremcevic, M.

    2012-10-01

    UVIS SOI reflectance spectra show bright ‘haloes’ around the locations of some of the strongest resonances in Saturn’s A ring (Esposito etal 2005). UV spectra constrain the size and composition of the icy ring particles (Bradley etal 2010, 2012). We investigate the Janus 4:3, 5:3, 6:5 and Mimas 5:3 inner Lindblad resonances as well as at the Mimas 5:3 vertical resonance (bending wave location). Models of ring particle regolith evolution (Elliott and Esposito 2010) indicate the deeper regolith is made of older and purer ice. The strong resonances cause streamline crowding (Lewis and Stewart 2005) which damps the interparticle velocity, allowing temporary clumps to grow, which in turn increase the velocity, eroding the clumps and releasing smaller particles and regolith (see the predator-prey model of Esposito etal 2012). This cyclic behavior, driven by the resonant perturbation from the moon, can yield collision velocities greater than 1m/sec, sufficient to erode the aggregates (Blum 2006), exposing older, purer materials. Thus, the radial location of the strongest resonances can be where we find both large aggregates and disrupted fragments, in a balance maintained by the periodic moon forcing. If this stirring exposes older, and purer ice, the velocity threshold for eroding the aggregates can explain why only the strongest Lindblad resonances show haloes. UVIS spectra can determine the relative contributions of particle size and purity at these locations, for comparison to estimates from the regolith evolution models.

  8. Simultaneous reduction of arsenic(V) and uranium(VI) by mackinawite: role of uranyl arsenate precipitate formation.

    PubMed

    Troyer, Lyndsay D; Tang, Yuanzhi; Borch, Thomas

    2014-12-16

    Uranium (U) and arsenic (As) often occur together naturally and, as a result, can be co-contaminants at sites of uranium mining and processing, yet few studies have examined the simultaneous redox dynamics of U and As. This study examines the influence of arsenate (As(V)) on the reduction of uranyl (U(VI)) by the redox-active mineral mackinawite (FeS). As(V) was added to systems containing 47 or 470 μM U(VI) at concentrations ranging from 0 to 640 μM. In the absence of As(V), U was completely removed from solution and fully reduced to nano-uraninite (nano-UO2). While the addition of As(V) did not reduce U uptake, at As(V) concentrations above 320 μM, the reduction of U(VI) was limited due to the formation of a trögerite-like uranyl arsenate precipitate. The presence of U also significantly inhibited As(V) reduction. While less U(VI) reduction to nano-UO2 may take place in systems with high As(V) concentrations, formation of trögerite-like mineral phases may be an acceptable reclamation end point due to their high stability under oxic conditions. PMID:25383895

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

    PubMed

    Hua, Bin; Deng, Baolin

    2008-12-01

    Batch experiments were used to evaluate the reductive immobilization of hexavalent uranium (U(VI)) by synthesized, amorphous iron sulfide (FeS) in the anoxic environment. The tests were initiated by spiking 168.0 microM U(VI) to 0.18 g/L FeS suspensions under a CO2-free condition with pH varied from 5.99 to 10.17. The immobilization rate of U(VI) was determined by monitoring the changes of aqueous U(VI) concentration, and the reduction rate of U(VI) associated with FeS was determined by the difference between the total spiked U(VI) and the extractable amount of U(VI) by 25 mM NaHCO3 solution. The results showed that a rapid removal of U(VI) from the aqueous phase occurred within 1 h under all pH conditions accompanied by a simultaneous release of Fe(ll), whereas the reduction of U(VI) associated with FeS took hours to over a week for completion. The reduction rate was greatly increased with decreasing pH within the examined pH range. Product analysis by X-ray photoelectron spectroscopy showed the formation of U3O8/4O9/UO2, polysulfide, and ferric iron. PMID:19192785

  10. Astrometric Correction for WFC3/UVIS Lithographic-Mask Pattern

    NASA Astrophysics Data System (ADS)

    Kozhurina-Platais, V.; Hammer, D.; Dencheva, N.; Hack, W.

    2013-07-01

    Observations of the central field in Cen taken with large dither patterns and over a large range of HST roll-angles exposed through F606W UVIS filter hav e been used to examine the lithographic-mask pattern imprinted on the WFC3/UVIS detec tor during the manufacturing process. This detector defect introduces fine-scale astrome tric errors at the level of about 0.2 pixel with a complicated spatial structure across the WFC3/ UVIS CCD chips. The fine-scale solution was utilized to construct a 2-D look-up table for co rrection of the WFC3/UVIS lithographic-mask pattern. The astrometric errors due to th is detector defect have been cor- rected down to the ~ 0.05 pixel level. The derived 2-D look-up table can be interpol ated at any point in the WFC3/UVIS image by ST software DrizzlePac / AstroDrizzle. The main results of these calibrations are: 1) new polynomial coefficien ts of geometric distortion for 14 calibrated UVIS filters in the form of Instrument Distortion Co rrection Table (IDCTAB file) were improved to account for the lithographic-mask pattern i n the WFC3/UVIS detector; 2) new derived look-up table in the form of a D2IMFILE, which sig nificantly improves (30-60%) the fine-scale structure in the WFC3/UVIS geometric distorti on; 3) geometric distortion cou- pled with the D2IMFILE and new improved IDCTAB can now be succ essfully corrected to the precision level of ~ 0.05 pixel (2 mas) for the UVIS detector.

  11. Annual waste reduction activities report. Issue 1

    SciTech Connect

    1991-03-18

    This report discusses the waste minimization activities for the Pinellas Plant. The Pinellas Plant deals with low-level radioactive wastes, solvents, scrap metals and various other hazardous materials. This program has realized cost savings through recycling and reuse of materials.

  12. Feedback controllers for broadband active noise reduction

    NASA Astrophysics Data System (ADS)

    Petitjean, Benoit; Legrain, Isabelle

    1994-09-01

    The aim of the present paper is to demonstrate the efficiency of an LQG-based controller for the active control of the acoustic field radiated by a rectangular panel. This topic has been of interest for numerous researchers in the past 10 or 15 years, but very little attention has been paid to broadband disturbances occurring in a relatively high frequency range. These are unfortunately common features of noise perturbations in realistic structures such as airplanes or helicopters. The few articles that deal with this problem provide very scarce experimental results and are related to frequency bands where the structure dynamics is rather poor. From the outset, the problem at hand involves numerous difficulties, such as the modeling of the active structure itself and the possible large size of the controller. In the following, the experimental setup is described, then the controller design procedure is developed and finally some experimental results are shown that prove the efficiency of the method.

  13. Uranium reduction by Shewanella oneidensis MR-1 as a function of NaHCO3 concentration: surface complexation control of reduction kinetics.

    PubMed

    Sheng, Ling; Fein, Jeremy B

    2014-04-01

    It is crucial to determine the controls on the kinetics of U(VI) bioreduction in order to understand and model the fate and mobility of U in groundwater systems and also to enhance the effectiveness of U bioremediation strategies. In this study, we measured the rate of U(VI) reduction by Shewanella oneidensis strain MR-1 as function of NaHCO3 concentration. The experiments demonstrate that increasing concentrations of NaHCO3 in the system lead to slower U(VI) reduction kinetics. The NaHCO3 concentration also strongly affects the speciation of U(VI) on the bacterial cell envelope. We used a thermodynamic surface complexation modeling approach to determine the speciation and concentration of U(VI) adsorbed onto the bacteria as a function of the NaHCO3 concentration in the experimental systems. We observed a strong positive correlation between the measured U(VI) reduction rates and the calculated total concentration of U(VI) surface complexes formed on the bacterial cell envelope. This positive correlation indicates that the speciation and concentration of U(VI) adsorbed on the bacterial cell envelope control the kinetics of U(VI) bioreduction under the experimental conditions. The results of this study serve as a basis for developing speciation-based kinetic rate laws for enzymatic reduction of U(VI) by bacteria. PMID:24576101

  14. REPEATED REDUCTIVE AND OXIDATIVE TREATMENTS ON GRANULAR ACTIVATED CARBON

    EPA Science Inventory

    Fenton oxidation and Fenton oxidation preceded by reduction solutions were applied to granular activated carbon (GAC) to chemically regenerate the adsorbent. No adsorbate was present on the GAC so physicochemical effects from chemically aggressive regeneration of the carbon coul...

  15. 29 CFR 4043.23 - Active participant reduction.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... EVENTS AND CERTAIN OTHER NOTIFICATION REQUIREMENTS Post-Event Notice of Reportable Events § 4043.23 Active participant reduction. (a) Reportable event. A reportable event occurs when the number of active...., facility shutdown or sale); and (2) The number of active participants at the date the reportable...

  16. 29 CFR 4043.23 - Active participant reduction.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... EVENTS AND CERTAIN OTHER NOTIFICATION REQUIREMENTS Post-Event Notice of Reportable Events § 4043.23 Active participant reduction. (a) Reportable event. A reportable event occurs when the number of active...., facility shutdown or sale); and (2) The number of active participants at the date the reportable...

  17. 29 CFR 4043.23 - Active participant reduction.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... EVENTS AND CERTAIN OTHER NOTIFICATION REQUIREMENTS Post-Event Notice of Reportable Events § 4043.23 Active participant reduction. (a) Reportable event. A reportable event occurs when the number of active...., facility shutdown or sale); and (2) The number of active participants at the date the reportable...

  18. Cryogenic Laser Induced U(VI) Fluorescence Studies of a U(VI) Substituted Natural Calcite: Implications to U(VI) Speciation in Contaminated Hanford Sediments

    SciTech Connect

    Wang, Zheming; Zachara, John M.; McKinley, James P.; Smith, Steven C.

    2005-04-14

    Time-resolved laser-induced fluorescence spectroscopy (TRLFS) and imaging spectromicroscopy (TRLFISM) were used to examine the chemical speciation of uranyl in contaminated subsurface sediments from the Hanford Site, Washington. Spectroscopic measurements for contaminant U(VI) were compared to those from a natural, uranyl-bearing calcite (NUC) that had been found via X-ray absorption spectroscopy (XAS) to include uranyl in the same coordination environment as calcium (1). Spectral deconvolution of TRLFS measurements on the NUC revealed the unexpected presence of two distinct chemical environments consistent with published spectra of U(VI)-substituted synthetic calcite and aragonite. Apparently, some U(VI) substitution sites in calcite distorted to exhibit a local, more energetically favorable aragonite structure. TRLFS measurements of the Hanford sediments were similar to the NUC in terms of peak positions and intensity, despite a small CaCO3 content (<0.1 to 3.2 mass%). Spectral deconvolution of the sediment measurements also revealed the presence of U(VI) in calcite and aragonite structural environments. TRLFISM measurements at multiple locations in the different sediments displayed only minor variation indicating a uniform speciation pattern. Collectively, the measurements implied that waste U(VI), long-resident beneath the sampled disposal pond (32 y), had co-precipitated within newly formed carbonates. These results have major implications for the solubility and fate of the contaminated U(VI).

  19. Surface Complexation Modeling of U(VI) Adsorption onto Savannah River Site Sediments

    NASA Astrophysics Data System (ADS)

    Dong, W.; Wan, J.; Tokunaga, T. K.; Denham, M.; Davis, J.; Hubbard, S. S.

    2011-12-01

    The Savannah River Site (SRS) was a U.S. Department of Energy facility for plutonium production during the Cold War. Waste plumes containing low-level radioactivity and acidic waste solutions were discharged to a series of unlined seepage basins in the F-Area of the SRS from 1955 to 1988. Although the site has undergone many years of active remediation, the groundwater remains acidic, and the concentrations of U and other radionuclides are still significantly higher than their Maximum Contaminant Levels (MCLs). The objective of this effort is to understand and predict U(VI) mobility in acidic waste plumes through developing surface complexation models (SCMs). Laboratory batch experiments were conducted to evaluate U adsorption behavior over the pH range of 3.0 to 9.5. Ten sorbent samples were selected including six contaminated sediment samples from three boreholes drilled within the plume and along the groundwater flow direction, two uncontaminated (pristine) sediment samples from a borehole outside of the plume, and two reference minerals, goethite and kaolinite (identified as the dominant minerals in the clay size fraction of the F-Area sediments). The results show that goethite and kaolinite largely control U partitioning behavior. In comparison with the pristine sediment, U(VI) adsorption onto contaminated sediments exhibits adsorption edges shifted toward lower pH by about 1.0 unit (e.g., from pH≈4.5 to pH≈3.5). We developed a SCMs based component additivity (CA) approach, which can successfully predict U(VI) adsorption onto uncontaminated SRS sediments. However, application of the same SCMs based CA approach to contaminated sediments resulted in underestimates of U(VI) adsorption at acidic pH conditions. The model sensitivity analyses indicate that both goethite and kaolinite surfaces co-contributed to U(VI) adsorption under acidic pH conditions. In particular, the exchange sites of clay minerals might play an important role in adsorption of U(VI) at p

  20. Upper Atmospheric Density Retrievals from UVIS Dayglow Observations of Titan

    NASA Astrophysics Data System (ADS)

    Stevens, Michael H.; Evans, J. S.; Ajello, J. M.; Bradley, E. T.; Meier, R. R.; Westlake, J. H.; Waite, J. H.

    2012-10-01

    The Cassini Ultraviolet Imaging Spectrograph (UVIS) observed Titan’s dayside limb on multiple occasions between 2007-2012. The airglow observations reveal the same variety of EUV (600-1150 λ) and FUV (1150-1900 λ) emissions arising from photoelectron impact and photofragmentation of molecular nitrogen (N2) on Earth. Through spectral analysis we extract radiance profiles for each set of UVIS limb emissions in the EUV and FUV, which are attenuated by methane (CH4). Using a terrestrial airglow model adapted to Titan, we derive the N2 and CH4 density profiles using the prescribed solar irradiance for the relevant Cassini orbit and compare the calculated radiance profiles directly with observations. We find that the Titan airglow can be explained by solar driven processes to within the uncertainties of the UVIS observations. Fluctuations in the observed airglow between flybys suggest compositional changes in the background atmosphere. The source of these compositional changes is not yet known, although the interaction of Titan with Saturn’s magnetosphere has been implicated as an important contributing factor. Here we use unique UVIS airglow observations over Titan’s disk to quantify compositional fluctuations with latitude and local time. We furthermore compare N2 and CH4 densities retrieved from the UVIS airglow to in situ observations by the Cassini Ion and Neutral Mass Spectrometer (INMS) and discuss how the UVIS and INMS variations may be related to Titan’s varying plasma environment.

  1. Chromium Isotope Behaviour During Aerobic Microbial Reduction Activities

    NASA Astrophysics Data System (ADS)

    Zhang, Q.; Amor, K.; Porcelli, D.; Thompson, I.

    2014-12-01

    Microbial activity is a very important, and possibly even the dominant, reduction mechanism for many metals in natural water systems. Isotope fractionations during microbial metal reduction can reflect one major mechanism in metal cycling in the environment, and isotopic signatures can be used to identify and quantify reduction processes during biogeochemical cycling in the present environment as well as in the past. There are many Cr (VI)-reducing bacteria that have been discovered and isolated from the environment, and Cr isotopes were found to be fractionated during microbial reduction processes. In this study, Cr reduction experiments have been undertaken to determine the conditions under which Cr is reduced and the corresponding isotope signals that are generated. The experiments have been done with a facultative bacteria Pseudomonas fluorescens LB 300, and several parameters that have potential impact on reduction mechanisms have been investigated. Electron donors are important for bacteria growth and metabolism. One factor that can control the rate of Cr reduction is the nature of the electron donor. The results show that using citrate as an electron donor can stimulate bacteria reduction activity to a large extent; the reduction rate is much higher (15.10 mgˑL-1hour-1) compared with experiments using glucose (6.65 mgˑL-1ˑhour-1), acetate (4.88 mgˑL-1hour-1) or propionate (4.85 mgˑL-1hour-1) as electron donors. Groups with higher electron donor concentrations have higher reduction rates. Chromium is toxic, and when increasing Cr concentrations in the medium, the bacteria reduction rate is also higher, which reflects bacteria adapting to the toxic environment. In the natural environment, under different pH conditions, bacteria may metabolise in different ways. In our experiments with pH, bacteria performed better in reducing Cr (VI) when pH = 8, and there are no significant differences between groups with pH = 4 or pH = 6. To investigate this further, Cr

  2. Redox Interactions of Tc(VII), U(VI), and Np(V) with Microbially Reduced Biotite and Chlorite.

    PubMed

    Brookshaw, Diana R; Pattrick, Richard A D; Bots, Pieter; Law, Gareth T W; Lloyd, Jonathan R; Mosselmans, J Fredrick W; Vaughan, David J; Dardenne, Kathy; Morris, Katherine

    2015-11-17

    Technetium, uranium, and neptunium are contaminants that cause concern at nuclear facilities due to their long half-life, environmental mobility, and radiotoxicity. Here we investigate the impact of microbial reduction of Fe(III) in biotite and chlorite and the role that this has in enhancing mineral reactivity toward soluble TcO4(-), UO2(2+), and NpO2(+). When reacted with unaltered biotite and chlorite, significant sorption of U(VI) occurred in low carbonate (0.2 mM) buffer, while U(VI), Tc(VII), and Np(V) showed low reactivity in high carbonate (30 mM) buffer. On reaction with the microbially reduced minerals, all radionuclides were removed from solution with U(VI) reactivity influenced by carbonate. Analysis by X-ray absorption spectroscopy (XAS) confirmed reductive precipitation to poorly soluble U(IV) in low carbonate conditions and both Tc(VII) and Np(V) in high carbonate buffer were also fully reduced to poorly soluble Tc(IV) and Np(IV) phases. U(VI) reduction was inhibited under high carbonate conditions. Furthermore, EXAFS analysis suggested that in the reaction products, Tc(IV) was associated with Fe, Np(IV) formed nanoparticulate NpO2, and U(IV) formed nanoparticulate UO2 in chlorite and was associated with silica in biotite. Overall, microbial reduction of the Fe(III) associated with biotite and chlorite primed the minerals for reductive scavenging of radionuclides: this has clear implications for the fate of radionuclides in the environment. PMID:26488884

  3. WFC3 SMOV Proposal 11419: UVIS Gain

    NASA Astrophysics Data System (ADS)

    Baggett, S.; Borders, T.

    2009-11-01

    This report summarizes the gain results obtained from the SMOV UVIS Detector Functional program, proposal #11419. Based on internal calibration flatfields, the gain at the nominal 1.5 setting was measured at 1.61, 1.61, 1.63, and 1.62 e-/DN, with errors <0.01 e- /DN, for quadrants A, B, C, and D, respectively. These values are ~3% higher than those measured in ground test images and to date have been stable on-orbit: a preliminary mea- surement of the recent Cycle 17 gain data (proposal 11906, PI Pavlovsky) yielded gains within 1% or better of the SMOV values. The off-nominal gain settings are restricted parameters and unavailable for general use, however, the SMOV proposal obtained data to check these settings on-orbit relative to the nominal 1.5 setting. The values for the off-nominal gains were measured at 1.04, 1.02, 1.04, 1.04 e-/DN and at 2.17, 2.12, 2.17, 2.16 e-/DN for the gain 1.0 and gain 2.0 settings. The exposure times for the gain 4.0 images were erroneously set too low to allow a determination of that setting; the observations were not repeated.

  4. U(VI) bioreduction with emulsified vegetable oil as the electron donor-- Microcosm tests and model development

    SciTech Connect

    Tang, Guoping; Wu, Wei-min; Watson, David B; Parker, Jack C.; Schadt, Christopher Warren; Brooks, Scott C; Shi, Xiaoqing

    2013-01-01

    Microcosm tests were conducted to study U(VI) bioreduction in contaminated sediments with emulsified vegetable oil (EVO) as the electron donor. In the microcosms, EVO was degraded by indigenous microorganisms and stimulated Fe, U, and sulfate bioreduction, and methanogenesis. Removal of aqueous U occurred concurrently with sulfate reduction, with more reduction of total U in the case of higher initial sulfate concentrations. X-ray absorption near-edge spectroscopy (XANES) analysis confirmed U(VI) reduction to U(IV). As the acetate concentration peaked in 10~20 days in oleate microcosms, the maximum was reached in 100~120 days in the EVO microcosms, indicating that EVO hydrolysis was rate-limiting. The acetate accumulation was sustained over 50 days longer in the oleate and EVO than in the ethanol microcosms, suggesting that acetate-utilizing methanogenesis was slower in the cases of oleate and EVO. Both slow hydrolysis and methanogenesis could contribute to potential sustained bioreduction in field application. Biogeochemical models were developed to couple degradation of EVO, production and oxidation of long-chain fatty acids, glycerol, acetate, and hydrogen, reduction of Fe(III), U(VI) and sulfate, and methanogenesis with growth and decay of microbial functional groups. The models were used to simulate the coupled processes in a field test in a companion article.

  5. Radiocesium activity reduction in boar meat by brining.

    PubMed

    Dvorák, P; Kunová, V; Kunová, J; Benová, K

    2008-02-01

    Meat of wild boar with an intial (137)Cs activity concentration of 103 Bq kg(-1) of fresh mass was treated by brining. Dry-salting reduced the (137)Cs activity only by about 12-18%. Subsequent brining was done by using both pure sodium chloride and a mixture of sodium chloride and potassium nitrate. After double-brine exchange, the (137)Cs activity concentration was reduced by at least 72%. The double-brine exchanges were done for two time intervals (the first each 24 h and the second each 7 days). There were no differences in the (137)Cs activity reduction for these two time intervals. From the technological point of view, the repeated exchange of the brine solution represents a relative easy method of (137)Cs activity reduction in contaminated pork meat. PMID:17882446

  6. Proposal for a modification of the UVI risk scale.

    PubMed

    Zaratti, Francesco; Piacentini, Rubén D; Guillén, Héctor A; Cabrera, Sergio H; Liley, J Ben; McKenzie, Richard L

    2014-07-01

    The standardisation of UV information to the public through the UV Index (UVI) has been hugely beneficial since its endorsement by multiple international agencies more than 10 years ago. It has now gained widespread acceptance, and UVI values are available throughout the world from satellite instruments, ground-based measurements, and from forecasts based on model calculations. These have been useful for atmospheric scientists, health professionals (skin and eye specialists), and the general public. But the descriptors and health messages associated with the UVI scale are targeted towards European skin types and UV regimes, and are not directly applicable to the population living closer to the equator, especially for those in the high-altitude Altiplano region of South America. This document arose from discussions at the Latin American Society of Photobiology and Photomedicine's Congress, which was held in Arequipa, Peru, in November 2013. A major outcome of the meeting was the Arequipa Accord, which is intended as a unifying document to ensure co-ordination of UV and health research decisions in Latin America. A plank of that agreement was the need to tailor the UVI scale to make it more relevant to the region and its population. Here we make some suggestions to improve the international applicability of the UVI scale. PMID:24728468

  7. WFC3/UVIS Charge Transfer Efficiency 2009-2015

    NASA Astrophysics Data System (ADS)

    Baggett, S.; Gosmeyer, C.; Noeske, K.

    2015-03-01

    Observations of the globular cluster Ω Cen taken with the WFC3/UVIS F606W over a 5-year time period have been used to create a standard astrometric c atalog in the central region of this cluster. The newly created catalog is then used to examine th e linear part of the WFC3/UVIS distortion solution and to search for variations of the astro metric X&Y scale over time. The variations of the X&Y scale over time have been examined with X&Y positions derived from single UVIS drizzled images, based on Kozhurina-Platais (2 014) geometric distortion solution in the form of the reference IDCTAB file for ST software DrizzleP ac/AstroDrizzle and ST OPUS pipe-line. The main results of this examination are: 1) over the 5-year time period of WFC3 operations, the WFC3/UVIS distortion is found to be tim e-independent; 2) there is no sudden or extreme fluctuations in the WFC3/UVIS astrometri c scale; 3) the geometric distortion solution over this period time is accurate at the l evel of ± 2 mas. 5R 2015wfc..rept....3B

  8. Characterization of the biochemical-pathway of uranium (VI) reduction in facultative anaerobic bacteria.

    PubMed

    Mtimunye, Phalazane J; Chirwa, Evans M N

    2014-10-01

    Cultures of U(VI) reducing bacteria sourced from abandoned uranium mine tailing dam were evaluated for their ability to reduce U(VI) to U(IV). The species in the cultures reduced U(VI) in solutions with initial U(VI) concentration up to 400mgL(-)(1) under a near neutral pH of 6.5. The electron flow pathway and fate of reduced species was also analysed in the individual species in order to evaluate the potential for control and optimisation of the reduction potential at the biochemical level. The results showed that U(VI) reduction in live cells was completely blocked by the NADH-dehydrogenase inhibitor, rotenone (C23H22O6), and thioredoxin inhibitor, cadmium chloride (CdCl2), showing that U(VI) reduction involves the electron flow through NADH-dehydrogenase, a primary electron donor to the electron transport respiratory (ETR) system. Mass balance analysis of uranium species aided by visual and electron microscopy suggest that most U(VI) reduction occurred on the cell surface of the isolated species. This finding indicates the possibility of easy uranium recovery for beneficial use through biological remediation. Should the U(VI) be reduced inside the cell, recovery would require complete disruption of the cells and therefore would be difficult. The study contributes new knowledge on the underlying mechanisms in the U(VI) reduction in facultative anaerobes. PMID:25065785

  9. Cassini UVIS observations of Titan nightglow spectra

    NASA Astrophysics Data System (ADS)

    Ajello, Joseph M.; West, Robert A.; Gustin, Jacques; Larsen, Kristopher; Stewart, A. Ian F.; Esposito, Larry W.; McClintock, William E.; Holsclaw, Gregory M.; Bradley, E. Todd

    2012-12-01

    In this paper we present the first nightside EUV and FUV airglow limb spectra of Titan showing molecular emissions. The Cassini Ultraviolet Imaging Spectrograph (UVIS) observed photon emissions of Titan's day and night limb-airglow and disk-airglow on multiple occasions, including during an eclipse observation. The 71 airglow observations analyzed in this paper show EUV (600-1150 Å) and FUV (1150-1900 Å) atomic multiplet lines and band emissions arising from either photoelectron induced fluorescence and solar photo-fragmentation of molecular nitrogen (N2) or excitation by magnetosphere plasma. The altitude of the peak UV emissions on the limb during daylight occurred inside the thermosphere at the altitude of the topside ionosphere (near 1000 km altitude). However, at night on the limb, a subset of emission features, much weaker in intensity, arise in the atmosphere with two different geometries. First, there is a twilight photoelectron-excited glow that persists with solar depression angle up to 25-30 degrees past the terminator, until the solar XUV shadow height passes the altitude of the topside ionosphere (1000-1200 km). The UV twilight glow spectrum is similar to the dayglow but weaker in intensity. Second, beyond 120° solar zenith angle, when the upper atmosphere of Titan is in total XUV darkness, there is indication of weak and sporadic nightside UV airglow emissions excited by magnetosphere plasma collisions with ambient thermosphere gas, with similar N2 excited features as above in the daylight or twilight glow over an extended altitude range.

  10. Effects of aqueous uranyl speciation on the kinetics of microbial uranium reduction

    NASA Astrophysics Data System (ADS)

    Belli, Keaton M.; DiChristina, Thomas J.; Van Cappellen, Philippe; Taillefert, Martial

    2015-05-01

    The ability to predict the success of the microbial reduction of soluble U(VI) to highly insoluble U(IV) as an in situ bioremediation strategy is complicated by the wide range of geochemical conditions at contaminated sites and the strong influence of aqueous uranyl speciation on the bioavailability and toxicity of U(VI) to metal-reducing bacteria. To determine the effects of aqueous uranyl speciation on uranium bioreduction kinetics, incubations and viability assays with Shewanella putrefaciens strain 200 were conducted over a range of pH and dissolved inorganic carbon (DIC), Ca2+, and Mg2+ concentrations. A speciation-dependent kinetic model was developed to reproduce the observed time series of total dissolved uranium concentration over the range of geochemical conditions tested. The kinetic model yielded the highest rate constant for the reduction of uranyl non-carbonate species (i.e., the 'free' hydrated uranyl ion, uranyl hydroxides, and other minor uranyl complexes), indicating that they represent the most readily reducible fraction of U(VI) despite being the least abundant uranyl species in solution. The presence of DIC, Ca2+, and Mg2+ suppressed the formation of more bioavailable uranyl non-carbonate species and resulted in slower bioreduction rates. At high concentrations of bioavailable U(VI), however, uranium toxicity to S. putrefaciens inhibited bioreduction, and viability assays confirmed that the concentration of non-carbonate uranyl species best predicts the degree of toxicity. The effect of uranium toxicity was accounted for by incorporating the free ion activity model of metal toxicity into the bioreduction rate law. Overall, these results demonstrate that, in the absence of competing terminal electron acceptors, uranium bioreduction kinetics can be predicted over a wide range of geochemical conditions based on the bioavailability and toxicity imparted on U(VI) by solution composition. These findings also imply that the concentration of uranyl non

  11. The variability of Saturn's thermosphere from Cassini/UVIS occultations

    NASA Astrophysics Data System (ADS)

    Koskinen, Tommi; Sandel, Bill R.; Yelle, Roger V.

    2014-11-01

    We present temperature and density profiles that we retrieved from 17 stellar occultations obtained by the Cassini UVIS instrument. These results complement our previous analysis of 15 solar occultations by Saturn’s upper atmosphere. We find that the exospheric temperature ranges from 370 K to 550 K, in agreement with our previous results. The temperature appears to increase with latitude from the equator to the poles by 100 - 150 K, a trend that is also evident in the pressure level altitudes that we derive from the data. We also find evidence for the expansion of the thermosphere by about 500 km between 2005 and 2011 at low to mid northern latitudes. This expansion is probably caused by significant warming of the lower thermosphere that anti-correlates with solar activity. We also present a comparison of our results with the newly available reanalysis of the Voyager UVS results (Vervack and Moses, 2014), and discuss the results in the context of energy deposition and dynamics in Saturn’s upper atmosphere.

  12. Bioreduction of U(VI) in groundwater under anoxic conditions from a decommissioned in situ leaching uranium mine.

    PubMed

    Ding, De-xin; Li, Shi-mi; Hu, Nan; Xu, Fei; Li, Guang-yue; Wang, Yong-dong

    2015-04-01

    To determine whether the U(VI) in groundwater under anoxic conditions at a decommissioned in situ leaching (ISL) uranium mine could be bioreduced, groundwater samples containing suspended sediments were taken from the mine, experimental setup was fabricated, and the jar containing the groundwater in the setup was amended with ethanol and incubated under anoxic conditions. The variations of pH, chemical oxygen demand, nitrate, sulfate, U(VI), and dissolved oxygen (DO) concentrations were monitored during the incubation. U(VI) concentration dropped to 0.043 mg/L when the stimulated microorganisms were active, and it then increased to 0.835 mg/L within 10 days after the metabolism of the stimulated microorganisms was inhibited. The DO variation was observed in the amended jar during the incubation, and the metabolism of the stimulated microorganisms was found to affect the DO concentration. Firmicutes were found to be dominant in the sediments in the amended jar through the 16S rRNA pyrosequencing. The results indicate that it is possible to bioreduce U(VI) in the groundwater under anoxic conditions at the decommissioned ISL uranium mine by adding carbon source into it without removing the oxygen from it. PMID:25341364

  13. Variability in Saturn's upper atmosphere from Cassini/UVIS occultations

    NASA Astrophysics Data System (ADS)

    Koskinen, T. T.; Strobel, D. F.; West, R. A.; Yelle, R. V.

    2015-10-01

    We present new density and temperature profiles based on more than 20 stellar occultations by Saturn's upper atmosphere observed simultaneously by the EUV and FUV channels of the Cassini/UVIS instrument. With these results, more than 40 stellar and solar occultations from Cassini/UVIS [1, 2, 3] and 6 occultations from Voyager/UVS [4] have now been analyzed. The results provide valuable constraints on models of chemistry, dynamics and thermal structure in the upper atmosphere. They are also required to plan for the end of the Cassini mission.

  14. Active viscoelastic matter: from bacterial drag reduction to turbulent solids.

    PubMed

    Hemingway, E J; Maitra, A; Banerjee, S; Marchetti, M C; Ramaswamy, S; Fielding, S M; Cates, M E

    2015-03-01

    A paradigm for internally driven matter is the active nematic liquid crystal, whereby the equations of a conventional nematic are supplemented by a minimal active stress that violates time-reversal symmetry. In practice, active fluids may have not only liquid-crystalline but also viscoelastic polymer degrees of freedom. Here we explore the resulting interplay by coupling an active nematic to a minimal model of polymer rheology. We find that adding a polymer can greatly increase the complexity of spontaneous flow, but can also have calming effects, thereby increasing the net throughput of spontaneous flow along a pipe (a "drag-reduction" effect). Remarkably, active turbulence can also arise after switching on activity in a sufficiently soft elastomeric solid. PMID:25793858

  15. Kinetic Desorption and Sorption of U(VI) During Reactive Transport in a Contaminated Hanford Sediment

    SciTech Connect

    Qafoku, Nik; Zachara, John M.; Liu, Chongxuan; Gassman, Paul L.; Qafoku, Odeta; Smith, Steven C.

    2005-05-12

    Column experiments were conducted to investigate U(VI) desorption and sorption kinetics in a sand-textured, contaminated (22.7 µmol kg-1) capillary fringe sediment that had experienced long-term exposure to U(VI). The clay fraction mineralogy of the sediment was dominated by montmorillonite, muscovite, vermiculite, and chlorite. Saturated column experiments were performed under mildly alkaline/calcareous conditions representative of the Hanford site where uranyl–carbonate and calcium–uranyl–carbonate complexes dominate aqueous speciation. A U(VI) free solution was used to study U(VI) desorption in columns where different flow rates were applied. Uranium(VI) sorption was studied after the desorption of labile contaminant U(VI) using different U(VI) concentrations in the leaching solution. Strong kinetic behavior was observed for both U(VI) desorption and sorption. Although U(VI) is semi–mobile in mildly alkaline, calcareous subsurface environments, our results showed substantial U(VI) sorption, significant retardation during transport, and atypical breakthrough curves with extended tailing. A distributed rate model was applied to describe the effluent data and to allow comparisons between the desorption rate of contaminant U(VI) with the rate of short-term U(VI) sorption. Desorption was the slower process. Our results suggest that U(VI) release and transport in the vadose zone and aquifer system from which the sediment was obtained are kinetically controlled.

  16. The effect of temperature on the speciation of U(VI) in sulfate solutions

    SciTech Connect

    Rao, Linfeng; Tian, Guoxin

    2008-09-15

    Sulfate, one of the inorganic constituents that could be present in the nuclear waste repository, forms complexes with U(VI) and affects its migration in the environment. Results show that the complexation of U(VI) with sulfate is enhanced by the increase in temperature. The effect of temperature on the complexation and speciation of U(VI) in sulfate solutions is discussed.

  17. Charge transfer induced activity of graphene for oxygen reduction

    NASA Astrophysics Data System (ADS)

    Shen, Anli; Xia, Weijun; Zhang, Lipeng; Dou, Shuo; Xia, Zhenhai; Wang, Shuangyin

    2016-05-01

    Tetracyanoethylene (TCNE), with its strong electron-accepting ability, was used to dope graphene as a metal-free electrocatalyst for the oxygen reduction reaction (ORR). The charge transfer process was observed from graphene to TCNE by x-ray photoelectron spectroscopy and Raman characterizations. Our density functional theory calculations found that the charge transfer behavior led to an enhancement of the electrocatalytic activity for the ORR.

  18. Kinetics of Abiotic Uranium(VI) Reduction by Sulfide

    NASA Astrophysics Data System (ADS)

    Hyun, S.; Davis, J. A.; Hayes, K. F.

    2010-12-01

    Uranium(VI) reduction is an important process affecting the radionuclide’s fate under sulfate reducing conditions. In this work, kinetics of abiotic U(VI) reduction by dissolved sulfide was studied using a batch reactor. The effects of solution pH, dissolved carbonate, Ca(II), U(VI), and S(-II) concentration on the reduction kinetics were tested. The ranges of these experimental variables were designed to cover the variation in groundwater chemistry observed at the Old Rifle uranium mill tailings site (Colorado, USA). Dissolved U concentration was monitored as a function of time using inductively coupled plasma-mass spectrometry to measure the rate of U(VI) reduction. Solid phase reduction products were identified using X-ray diffraction, transmission electron microscopy, and X-ray absorption spectroscopy. The results showed that changes in the experimental variables significantly affected U(VI) reduction kinetics by dissolved sulfide. U(VI) reduction occurred under circumneutral pH while no reduction was observed under alkaline conditions. The reduction rate was slowed by increased dissolved carbonate concentration. One solid phase reduction product was identified as nanoscale uraninite (UO2+x(s)). Thermodynamic modeling showed that the dissolved U(VI) aqueous species changed as a function of solution conditions correlated with the change in the reduction rate. These results show that U(VI) aqueous speciation is important in determining abiotic U(VI) reduction kinetics by dissolved sulfide. This study also illustrates the potential importance of dissolved sulfide in field-scale modeling of U reactive transport, and is expected to contribute to the understanding of long-term effects of biostimulation on U transport at the Rifle site.

  19. Operational Definitions and Implementation of WFC3 UVIS Subarrays

    NASA Astrophysics Data System (ADS)

    Lupie, O.; Robinson, M.; Welty, A.; Baggett, W.; McKinney, M.

    2002-12-01

    This technical memo describes the implementation of WFC3 UVIS channel subarrays. The capability described herein allows for both user-defined subarrays and a set of fixed subarray apertures. The precedent and experience for such an implementation are the ACS and STIS instruments.

  20. Transient F Ring Dust Features in Cassini UVIS Solar Occultations

    NASA Astrophysics Data System (ADS)

    Becker, T. M.; Colwell, J. E.; Esposito, L. W.; Attree, N.; Murray, C.

    2015-12-01

    We present results from an investigation of the variable particle size distribution in Saturn's dynamic F ring. We analyze 13 solar occultations observed by the Cassini Ultraviolet Imaging Spectrograph (UVIS), of which 4 occultations show a clear signature of diffracted sunlight. The magnitude and scattering angle of the diffraction signal suggest the presence of a significant population of micron-sized dust particles; however, the lack of a detection of diffracted light in other solar occultations implies that such a population is transient or spatially variable. Initial comparisons with images from the Cassini Imaging Science Subsystem (ISS) suggest that a diffraction signal is detected in UVIS occultations that coincide with a recent collisional event in the F ring core, as seen in the ISS images. This implies that such events release a significant population of dust, which can then be measured by the diffraction signature in the UVIS data. We use a forward-modeling approach to place constraints on the particle size distribution of the F ring during each solar occultation. We present these measurements of the size distribution and our comparisons of the F ring dust population as measured by UVIS with the ISS images of the ring.

  1. Improvement of the Valencia region ultraviolet index (UVI) forecasting system

    NASA Astrophysics Data System (ADS)

    Gómez, I.; Marín, M. J.; Pastor, F.; Estrela, M. J.

    2012-04-01

    The CEAM Foundation (Valencia, Spain) has developed an operational ultraviolet index (UVI) forecasting system based on the Santa Barbara DISORT Atmospheric Radiative Transfer (SBDART) model. The main objective of this system is to provide the general public with a tool to minimize the impact of ultraviolet (UV) radiation, which can cause important human health problems. The system presented in this paper has been developed in collaboration with the Environment Department of the Regional Government of Valencia, and it replaces the one running until 2007. The new system substitutes the previously used Ozone Monitoring Instrument (OMI) observed data with the total ozone column data forecasted from the Global Forecasting System (GFS) model. This has allowed the forecasting period to be increased from only 1 day in the original system to 3 days, with daily updates. The UVI forecast presented herein uses maps to show the hourly daytime evolution of the UV index on selected locations as well as the maximum UVI expected in the area of interest for the following 3 days (D, D+1, and D+2). The locations selected correspond to measurement stations equipped with erythemal radiation instruments. The UVI forecast information, the erythemal radiation experimental data, and other outreach information are supplied to the public through both the CEAM Meteorology and Climatology Program Web page and the Environment Department of the Regional Government of Valencia Web page.

  2. Reduction of salivary tissue factor (thromboplastin) activity by warfarin therapy.

    PubMed

    Zacharski, L R; Rosenstein, R

    1979-03-01

    The coagulant of normal human saliva has been identified as tissue factor (thromboplastin, TF) by virtue of its ability to cause rapid coagulation in plasmas deficient in first-stage coagulation factors and to activate factor x in the presence of factor VII and by virtue of the fact that its activity is expressed only in the presence of factor VII and is inhibited by an antibody to TF. The TF is related to cells and cell fragments in saliva. Salivary TF activity has been found to be significantly reduced in patients taking warfarin. The decline in TF activity during induction of warfarin anticoagulation occurs during the warfarin-induced decline in vitamin-K-dependent clotting factor activity, as judged by the prothrombin time. The decrease in TF activity is not related to a reduction in salivary cell count or total protein content or to a direct effect of warfarin on the assay. It is hypothesized that the mechanism by which warfarin inhibits TF activity may be related to the mechanism by which it inhibits expression of the activity of the vitamin-K-dependent clotting factors. Inhibition of the TF activity may be involved in the antithrombotic effect of warfarin. PMID:760859

  3. Effectiveness of U(VI) Bioremediation by DMRB in Dual Porosity Soils Explored via Numerical Modeling

    NASA Astrophysics Data System (ADS)

    Rotter, B. E.; Barry, A.; Gerhard, J. I.

    2006-12-01

    The use of naturally present dissimilatory metal reducing bacteria (DMRB) is a promising bioremediation option for uranium-contaminated sites. DMRB activity is typically stimulated by introducing an organic carbon source into the subsurface, resulting in bioreduction of highly soluble U(VI) to immobile U(IV). While this process has been demonstrated in the laboratory for simple systems, it is important to understand how its effectiveness is influenced by a variety of natural and engineered processes expected in typical applications. Biogeochemical reactive transport models provide a valuable means for investigating the performance of and parameter sensitivities of these complex systems. A new one-dimensional model for DMRB bioreduction of U(VI) was developed in PHREEQC. The model includes multiple redox processes, U(VI) sorption, and both single and dual porosity domains. The model was applied to a variety of real-site parameterized scenarios in order to explore the impact of (i) modeling approaches, (ii) expected natural variability inherent in porous media systems, and (iii) engineering options for implementation. Examples of the first include diverse approaches to modeling active biomass (1st order vs. non-growth Monod vs. Monod with growth; multiple microbial communities vs. a single community). Examples of the second include diffusion-limited mass transfer between the advective flow region and the immobile micro-matrix region through variations in region porosities, bioreduction rates and mass transfer rate coefficients, as well as aquifer mineralogy. Examples of the third include organic carbon injection regimes (quantity and duration) and their impact on U(IV) reoxidation. These suites of simulations provide valuable insight into key system sensitivities that will guide further model development and upscaling to field scale.

  4. Dinitrogen activation upon reduction of a triiron(II) complex.

    PubMed

    Lee, Yousoon; Sloane, Forrest T; Blondin, Geneviève; Abboud, Khalil A; García-Serres, Ricardo; Murray, Leslie J

    2015-01-26

    Reaction of a trinuclear iron(II) complex, Fe3 Br3 L (1), with KC8 under N2 leads to dinitrogen activation products (2) from which Fe3 (NH)3 L (2-1; L is a cyclophane bridged by three β-diketiminate arms) was characterized by X-ray crystallography. (1) H NMR spectra of the protonolysis product of 2 synthesized under (14) N2 and (15) N2 confirm atmospheric N2 reduction, and ammonia is detected by the indophenol assay (yield ∼30 %). IR and Mössbauer spectroscopy, and elemental analysis on 2 and 2-1 as well as the tri(amido)triiron(II) 3 and tri(methoxo)triiron 4 congeners support our assignment of the reduction product as containing protonated N-atom bridges. PMID:25504859

  5. Tuning the catalytic activity of graphene nanosheets for oxygen reduction reaction via size and thickness reduction.

    PubMed

    Benson, John; Xu, Qian; Wang, Peng; Shen, Yuting; Sun, Litao; Wang, Tanyuan; Li, Meixian; Papakonstantinou, Pagona

    2014-11-26

    Currently, the fundamental factors that control the oxygen reduction reaction (ORR) activity of graphene itself, in particular, the dependence of the ORR activity on the number of exposed edge sites remain elusive, mainly due to limited synthesis routes of achieving small size graphene. In this work, the synthesis of low oxygen content (<2.5±0.2 at. %), few layer graphene nanosheets with lateral dimensions smaller than a few hundred nanometers were achieved using a combination of ionic liquid assisted grinding of high purity graphite coupled with sequential centrifugation. We show for the first time that the graphene nanosheets possessing a plethora of edges exhibited considerably higher electron transfer numbers compared to the thicker graphene nanoplatelets. This enhanced ORR activity was accomplished by successfully exploiting the plethora of edges of the nanosized graphene as well as the efficient electron communication between the active edge sites and the electrode substrate. The graphene nanosheets were characterized by an onset potential of -0.13 V vs Ag/AgCl and a current density of -3.85 mA/cm2 at -1 V, which represent the best ORR performance ever achieved from an undoped carbon based catalyst. This work demonstrates how low oxygen content nanosized graphene synthesized by a simple route can considerably impact the ORR catalytic activity and hence it is of significance in designing and optimizing advanced metal-free ORR electrocatalysts. PMID:25334050

  6. Effects of the Anaerobic Respiration of Shewanella oneidensis MR-1 on the Stability of Extracellular U(VI) Nanofibers

    PubMed Central

    Jiang, Shenghua; Hur, Hor-Gil

    2013-01-01

    Uranium (VI) is considered to be one of the most widely dispersed and problematic environmental contaminants, due in large part to its high solubility and great mobility in natural aquatic systems. We previously reported that under anaerobic conditions, Shewanella oneidensis MR-1 grown in medium containing uranyl acetate rapidly accumulated long, extracellular, ultrafine U(VI) nanofibers composed of polycrystalline chains of discrete meta-schoepite (UO3·2H2O) nanocrystallites. Wild-type MR-1 finally transformed the uranium (VI) nanofibers to uranium (IV) nanoparticles via further reduction. In order to investigate the influence of the respiratory chain in the uranium transformation process, a series of mutant strains lacking a periplasmic cytochrome MtrA, outer membrane (OM) cytochrome MtrC and OmcA, a tetraheme cytochrome CymA anchored to the cytoplasmic membrane, and a trans-OM protein MtrB, were tested in this study. Although all the mutants produced U(VI) nanofibers like the wild type, the transformation rates from U(VI) nanofibers to U(IV) nanoparticles varied; in particular, the mutant with deletion in tetraheme cytochrome CymA stably maintained the uranium (VI) nanofibers, suggesting that the respiratory chain of S. oneidensis MR-1 is probably involved in the stability of extracellular U(VI) nanofibers, which might be easily treated via the physical processes of filtration or flocculation for the remediation of uranium contamination in sediments and aquifers, as well as the recovery of uranium in manufacturing processes. PMID:23719584

  7. Effects of the anaerobic respiration of Shewanella oneidensis MR-1 on the stability of extracellular U(VI) nanofibers.

    PubMed

    Jiang, Shenghua; Hur, Hor-Gil

    2013-01-01

    Uranium (VI) is considered to be one of the most widely dispersed and problematic environmental contaminants, due in large part to its high solubility and great mobility in natural aquatic systems. We previously reported that under anaerobic conditions, Shewanella oneidensis MR-1 grown in medium containing uranyl acetate rapidly accumulated long, extracellular, ultrafine U(VI) nanofibers composed of polycrystalline chains of discrete meta-schoepite (UO(3)·2H2O) nanocrystallites. Wild-type MR-1 finally transformed the uranium (VI) nanofibers to uranium (IV) nanoparticles via further reduction. In order to investigate the influence of the respiratory chain in the uranium transformation process, a series of mutant strains lacking a periplasmic cytochrome MtrA, outer membrane (OM) cytochrome MtrC and OmcA, a tetraheme cytochrome CymA anchored to the cytoplasmic membrane, and a trans-OM protein MtrB, were tested in this study. Although all the mutants produced U(VI) nanofibers like the wild type, the transformation rates from U(VI) nanofibers to U(IV) nanoparticles varied; in particular, the mutant with deletion in tetraheme cytochrome CymA stably maintained the uranium (VI) nanofibers, suggesting that the respiratory chain of S. oneidensis MR-1 is probably involved in the stability of extracellular U(VI) nanofibers, which might be easily treated via the physical processes of filtration or flocculation for the remediation of uranium contamination in sediments and aquifers, as well as the recovery of uranium in manufacturing processes. PMID:23719584

  8. Effect of phosphate on U(VI) sorption to montmorillonite: Ternary complexation and precipitation barriers

    NASA Astrophysics Data System (ADS)

    Troyer, Lyndsay D.; Maillot, Fabien; Wang, Zheming; Wang, Zimeng; Mehta, Vrajesh S.; Giammar, Daniel E.; Catalano, Jeffrey G.

    2016-02-01

    Phosphate addition is a potential treatment method to lower the solubility of U(VI) in soil and groundwater systems by causing U(VI) phosphate precipitation as well as enhancing adsorption. Previous work has shown that iron oxide surfaces may facilitate the nucleation of U(VI) phosphate minerals and, that under weakly acidic conditions, phosphate also enhances U(VI) adsorption to such phases. Like iron oxides, clays are important reactive phases in the subsurface but little is known about the interaction of U(VI) and phosphate with these minerals. The effect of aqueous phosphate on U(VI) binding to Wyoming montmorillonite (SWy-2) in air-equilibrated systems was investigated. Equilibrium U(VI) uptake to montmorillonite was determined at pH 4, 6 and 8 at discrete initial phosphate concentrations between 0 and 100 μM. The observed behavior of U(VI) indicates a transition from adsorption to precipitation with increasing total uranium and phosphate concentrations at all pH values. At the highest phosphate concentration examined at each pH value, a barrier to U(VI) phosphate nucleation is observed. At lower concentrations, phosphate has no effect on macroscopic U(VI) adsorption. To assess the mechanisms of U(VI)-phosphate interactions on smectite surfaces, U(VI) speciation was investigated under selected conditions using laser-induced fluorescence spectroscopy (LIFS) and extended X-ray absorption fine-structure (EXAFS) spectroscopy. Samples above the precipitation threshold display EXAFS and LIFS spectral signatures consistent with the autunite family of U(VI) phosphate minerals. However, at lower U(VI) concentrations, changes in LIFS spectra upon phosphate addition suggest that U(VI)-phosphate ternary surface complexes form on the montmorillonite surface at pH 4 and 6 despite the lack of a macroscopic effect on adsorption. The speciation of solid-associated U(VI) below the precipitation threshold at pH 8 is dominated by U(VI)-carbonate surface complexes. This work

  9. Long-Term International Space Station (ISS) Risk Reduction Activities

    NASA Astrophysics Data System (ADS)

    Fodroci, M. P.; Gafka, G. K.; Lutomski, M. G.; Maher, J. S.

    2012-01-01

    As the assembly of the ISS nears completion, it is worthwhile to step back and review some of the actions pursued by the Program in recent years to reduce risk and enhance the safety and health of ISS crewmembers, visitors, and space flight participants. While the initial ISS requirements and design were intended to provide the best practicable levels of safety, it is always possible to further reduce risk - given the determination, commitment, and resources to do so. The following is a summary of some of the steps taken by the ISS Program Manager, by our International Partners, by hardware and software designers, by operational specialists, and by safety personnel to continuously enhance the safety of the ISS, and to reduce risk to all crewmembers. While years of work went into the development of ISS requirements, there are many things associated with risk reduction in a Program like the ISS that can only be learned through actual operational experience. These risk reduction activities can be divided into roughly three categories: Areas that were initially noncompliant which have subsequently been brought into compliance or near compliance (i.e., Micrometeoroid and Orbital Debris [MMOD] protection, acoustics) Areas where initial design requirements were eventually considered inadequate and were subsequently augmented (i.e., Toxicity Hazard Level- 4 [THL] materials, emergency procedures, emergency equipment, control of drag-throughs) Areas where risks were initially underestimated, and have subsequently been addressed through additional mitigation (i.e., Extravehicular Activity [EVA] sharp edges, plasma shock hazards) Due to the hard work and cooperation of many parties working together across the span of more than a decade, the ISS is now a safer and healthier environment for our crew, in many cases exceeding the risk reduction targets inherent in the intent of the original design. It will provide a safe and stable platform for utilization and discovery for years

  10. Long-Term International Space Station (ISS) Risk Reduction Activities

    NASA Technical Reports Server (NTRS)

    Forroci, Michael P.; Gafka, George K.; Lutomski, Michael G.; Maher, Jacilyn S.

    2011-01-01

    As the assembly of the ISS nears completion, it is worthwhile to step back and review some of the actions pursued by the Program in recent years to reduce risk and enhance the safety and health of ISS crewmembers, visitors, and space flight participants. While the initial ISS requirements and design were intended to provide the best practicable levels of safety, it is always possible to further reduce risk given the determination, commitment, and resources to do so. The following is a summary of some of the steps taken by the ISS Program Manager, by our International Partners, by hardware and software designers, by operational specialists, and by safety personnel to continuously enhance the safety of the ISS, and to reduce risk to all crewmembers. While years of work went into the development of ISS requirements, there are many things associated with risk reduction in a Program like the ISS that can only be learned through actual operational experience. These risk reduction activities can be divided into roughly three categories: Areas that were initially noncompliant which have subsequently been brought into compliance or near compliance (i.e., Micrometeoroid and Orbital Debris [MMOD] protection, acoustics) Areas where initial design requirements were eventually considered inadequate and were subsequently augmented (i.e., Toxicity hazard level-4 materials, emergency procedures, emergency equipment, control of drag-throughs) Areas where risks were initially underestimated, and have subsequently been addressed through additional mitigation (i.e., Extravehicular Activity [EVA] sharp edges, plasma shock hazards). Due to the hard work and cooperation of many parties working together across the span of more than a decade, the ISS is now a safer and healthier environment for our crew, in many cases exceeding the risk reduction targets inherent in the intent of the original design. It will provide a safe and stable platform for utilization and discovery for years to come.

  11. Propulsion Risk Reduction Activities for Nontoxic Cryogenic Propulsion

    NASA Technical Reports Server (NTRS)

    Smith, Timothy D.; Klem, Mark D.; Fisher, Kenneth L.

    2010-01-01

    The Propulsion and Cryogenics Advanced Development (PCAD) Project s primary objective is to develop propulsion system technologies for nontoxic or "green" propellants. The PCAD project focuses on the development of nontoxic propulsion technologies needed to provide necessary data and relevant experience to support informed decisions on implementation of nontoxic propellants for space missions. Implementation of nontoxic propellants in high performance propulsion systems offers NASA an opportunity to consider other options than current hypergolic propellants. The PCAD Project is emphasizing technology efforts in reaction control system (RCS) thruster designs, ascent main engines (AME), and descent main engines (DME). PCAD has a series of tasks and contracts to conduct risk reduction and/or retirement activities to demonstrate that nontoxic cryogenic propellants can be a feasible option for space missions. Work has focused on 1) reducing the risk of liquid oxygen/liquid methane ignition, demonstrating the key enabling technologies, and validating performance levels for reaction control engines for use on descent and ascent stages; 2) demonstrating the key enabling technologies and validating performance levels for liquid oxygen/liquid methane ascent engines; and 3) demonstrating the key enabling technologies and validating performance levels for deep throttling liquid oxygen/liquid hydrogen descent engines. The progress of these risk reduction and/or retirement activities will be presented.

  12. Propulsion Risk Reduction Activities for Non-Toxic Cryogenic Propulsion

    NASA Technical Reports Server (NTRS)

    Smith, Timothy D.; Klem, Mark D.; Fisher, Kenneth

    2010-01-01

    The Propulsion and Cryogenics Advanced Development (PCAD) Project s primary objective is to develop propulsion system technologies for non-toxic or "green" propellants. The PCAD project focuses on the development of non-toxic propulsion technologies needed to provide necessary data and relevant experience to support informed decisions on implementation of non-toxic propellants for space missions. Implementation of non-toxic propellants in high performance propulsion systems offers NASA an opportunity to consider other options than current hypergolic propellants. The PCAD Project is emphasizing technology efforts in reaction control system (RCS) thruster designs, ascent main engines (AME), and descent main engines (DME). PCAD has a series of tasks and contracts to conduct risk reduction and/or retirement activities to demonstrate that non-toxic cryogenic propellants can be a feasible option for space missions. Work has focused on 1) reducing the risk of liquid oxygen/liquid methane ignition, demonstrating the key enabling technologies, and validating performance levels for reaction control engines for use on descent and ascent stages; 2) demonstrating the key enabling technologies and validating performance levels for liquid oxygen/liquid methane ascent engines; and 3) demonstrating the key enabling technologies and validating performance levels for deep throttling liquid oxygen/liquid hydrogen descent engines. The progress of these risk reduction and/or retirement activities will be presented.

  13. Guided cobalamin biosynthesis supports Dehalococcoides mccartyi reductive dechlorination activity

    PubMed Central

    Yan, Jun; Im, Jeongdae; Yang, Yi; Löffler, Frank E.

    2013-01-01

    Dehalococcoides mccartyi strains are corrinoid-auxotrophic Bacteria and axenic cultures that require vitamin B12 (CN-Cbl) to conserve energy via organohalide respiration. Cultures of D. mccartyi strains BAV1, GT and FL2 grown with limiting amounts of 1 µg l−1 CN-Cbl quickly depleted CN-Cbl, and reductive dechlorination of polychlorinated ethenes was incomplete leading to vinyl chloride (VC) accumulation. In contrast, the same cultures amended with 25 µg l−1 CN-Cbl exhibited up to 2.3-fold higher dechlorination rates, 2.8–9.1-fold increased growth yields, and completely consumed growth-supporting chlorinated ethenes. To explore whether known cobamide-producing microbes supply Dehalococcoides with the required corrinoid cofactor, co-culture experiments were performed with the methanogen Methanosarcina barkeri strain Fusaro and two acetogens, Sporomusa ovata and Sporomusa sp. strain KB-1, as Dehalococcoides partner populations. During growth with H2/CO2, M. barkeri axenic cultures produced 4.2 ± 0.1 µg l−1 extracellular cobamide (factor III), whereas the Sporomusa cultures produced phenolyl- and p-cresolyl-cobamides. Neither factor III nor the phenolic cobamides supported Dehalococcoides reductive dechlorination activity suggesting that M. barkeri and the Sporomusa sp. cannot fulfil Dehalococcoides' nutritional requirements. Dehalococcoides dechlorination activity and growth occurred in M. barkeri and Sporomusa sp. co-cultures amended with 10 µM 5′,6′-dimethylbenzimidazole (DMB), indicating that a cobalamin is a preferred corrinoid cofactor of strains BAV1, GT and FL2 when grown with chlorinated ethenes as electron acceptors. Even though the methanogen and acetogen populations tested did not produce cobalamin, the addition of DMB enabled guided biosynthesis and generated a cobalamin that supported Dehalococcoides' activity and growth. Guided cobalamin biosynthesis may offer opportunities to sustain and enhance Dehalococcoides activity in contaminated

  14. Surface complexation modeling of U(VI) sorption to Hanford sediment with varying geochemical conditions

    SciTech Connect

    Um, Wooyong; Serne, R. Jeffrey; Krupka, Kenneth M.

    2007-04-11

    A series of U(VI) adsorption experiments with varying pH, ionic strength, concentrations of dissolved U(VI) and carbonate was conducted to provide a more realistic database for U(VI) adsorption onto near-field vadose zone sediments at the proposed Integrated Disposal Facility (IDF) on the Hanford Site. The distribution coefficient, Kd, for U(VI) in predicted “pure” glass leachate is 0 mL/g because the glass leachate has high sodium and carbonate concentrations and high pH. The zero adsorption result suggests that uranium will exhibit no retardation when the subsurface geochemistry is controlled by glass leachate. However, U(VI) can be sequestrated even when the pH, carbonate and sodium concentrations reached levels similar to “pure” glass leachate, because U(VI) coprecipitates with calcite. When glass leachate interacts with existing porewater or surrounding sediments, sorption is observed and the numerical value of the U(VI) Kd varies significantly. A non-electrostatic, general composite approach for surface complexation modeling was applied and a combination of two U(VI) surface species, monodentate (SOUO2+) and bidentate (SO2UO2(CO3)2-), simulated very well the measured U(VI) adsorption data. The general composite surface complexation model, compared to the constant or single-valued Kd model, more accurately predicted U(VI) adsorption under the varying geochemical conditions expected at the IDF.

  15. Reaction of U-VI with titanium-substituted magnetite: Influence of Ti on U-IV speciation

    SciTech Connect

    Latta, Drew; Pearce, Carolyn I.; Rosso, Kevin M.; Kemner, Kenneth M.; Boyanov, Maxim I.

    2013-07-01

    Reduction of hexavalent uranium (UVI) to less soluble tetravalent uranium (UIV) through enzymatic or abiotic redox reactions has the potential to alter U mobility in subsurface environments. As a ubiquitous natural mineral, magnetite (Fe3O4) is of interest because of its ability to act as a rechargeable reductant for UVI. Natural magnetites are often impure with titanium, and structural Fe3+ replacement by TiIV yields a proportional increase in the relative Fe2+ content in the metal sublattice to maintain bulk charge neutrality. In the absence of oxidation, the Ti content sets the initial bulk Fe2+/Fe3+ ratio (R). Here, we demonstrate that Ti-doped magnetites (Fe3 xTixO4) reduce UVI to UIV. The UVI-Fe2+ redox reactivity was found to be controlled directly by R, but was otherwise independent of Ti content (xTi). However, in contrast to previous studies with pure magnetite where UVI was reduced to nanocrystalline uraninite (UO2), the presence of structural Ti (xTi = 0.25 0.53) results in the formation of UIV species that lack the bidentate U-O2-U bridges of uraninite. Extended x-ray absorption fine structure spectroscopic analysis indicated that the titanomagnetite-bound UIV phase has a novel UIV-Ti binding geometry, different from the coordination of UIV in the mineral brannerite (UIVTi2O6). The observed UIV-Ti coordination at a distance of 3.43 Å suggests a binuclear corner-sharing adsorption/incorporation UIV complex with the solid phase. Furthermore, we explored the effect of oxidation (decreasing R) and solids-to-solution ratio on the reduced UIV phase. The formation of the non-uraninite UIV-Ti phase appears to be controlled by availability of surface Ti sites, rather than R. Our work highlights a previously unrecognized role of Ti in the environmental chemistry of UIV and suggests that further work to characterize the long-term stability of UIV phases formed in the presence of Ti is warranted.

  16. Activated carbon becomes active for oxygen reduction and hydrogen evolution reactions.

    PubMed

    Yan, Xuecheng; Jia, Yi; Odedairo, Taiwo; Zhao, Xiaojun; Jin, Zhao; Zhu, Zhonghua; Yao, Xiangdong

    2016-06-21

    We utilized a facile method for creating unique defects in the activated carbon (AC), which makes it highly active for the oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER). The ORR activity of the defective AC (D-AC) is comparable to the commercial Pt/C in alkaline medium, and the D-AC also exhibits excellent HER activity in acidic solution. PMID:27277286

  17. CASSINI UVIS STELLAR OCCULTATION OBSERVATIONS OF SATURN's RINGS

    SciTech Connect

    Colwell, J. E.; Jerousek, R. G.; Pettis, D.; Bradley, E. T.; Esposito, L. W.; Sremcevic, M.

    2010-12-15

    The Cassini spacecraft's Ultraviolet Imaging Spectrograph (UVIS) includes a high-speed photometer (HSP) that has observed more than 100 stellar occultations by Saturn's rings. Here, we document a standardized technique applied to the UVIS-HSP ring occultation datasets delivered to the Planetary Data System as higher level data products. These observations provide measurements of ring structure that approaches the scale of the largest common ring particles ({approx}5 m). The combination of multiple occultations at different viewing geometries enables reconstruction of the three-dimensional structure of the rings. This inversion of the occultation data depends on accurate calibration of the data so that occultations of different stars taken at different times and under different viewing conditions can be combined to retrieve ring structure. We provide examples of the structure of the rings as seen from several occultations at different incidence angles to the rings, illustrating changes in the apparent structure with viewing geometry.

  18. HST/WFC3: Improvements to the UVIS Dark Calibration

    NASA Astrophysics Data System (ADS)

    Bourque, Matthew; Baggett, Sylvia M.; WFC3 Team

    2016-06-01

    The Hubble Space Telescope (HST) Wide Field Camera 3 (WFC3) UVIS detector, comprised of two e2v CCDs, exhibits an inherent dark current (in the absence of any illumination) presently measured at ~7 e-/hr and increasing at ~1 e-/hr/yr. Additionally, detector degradation due to on-orbit radiation damage generates a continuously increasing though small population of hot pixels (dark current exceeding 54 e-/hr, currently ~4% of each chip). We present the results of the WFC3/UVIS dark calibration, which provides calibration files used as a correction for these detector characteristics. We also discuss the impacts that Charge Transfer Efficiency (CTE) losses and detector post-flashing have on the hot pixel population, as well as various improvements to the calibration procedure that were introduced in the CALWF3 v3.3 pipeline.

  19. The WFC3/UVIS Reference Files : 2. Biases and Darks

    NASA Astrophysics Data System (ADS)

    Martel, A. R.; Baggett, S.; Bushouse, H.; Sabbi, E.

    2008-09-01

    Bias and dark reference files for the Wide Field Camera 3 (WFC3) UVIS flight detector were assembled from ground data acquired in the final thermal vacuum campaign at the Goddard Space Flight Center (GSFC). These represent the first generation of reference files for the UVIS channel and will serve to calibrate the on-orbit data from the early phase of the fourth Servicing Mission Observatory Verification (SMOV4). In this report, we present our methodology for assembling the bias and dark reference data, tabulate the resulting reference files, and discuss their overall features. We also discuss the assignment of their data quality flags. The most up-to-date reference files are available on the STScI WFC3 Web site.

  20. Revisiting Uvis Observations of the Enceladus Water Vapor Plume

    NASA Astrophysics Data System (ADS)

    Portyankina, G.

    2014-12-01

    The Cassini Ultraviolet Imaging Spectrograph (UVIS) onboard Cassini spacecraft observed occultations of several stars and the Sun by the water vapor plume and separate jets emitting from the southern pole of Enceladus [Hansen et al., 2006 and 2011]. During the solar occultation separate collimated gas jets were detected inside the background plume. These observations provide data about water vapor column densities along the line of sight of the UVIS instrument. Monte Carlo simulations and Direct Simulation Monte Carlo (DSMC) are used to model the plume of Enceladus including an option to add multiple jet sources to the general background plume. The models account for molecular collisions, gravitational and Coriolis forces. Jet sources can differ in production rate and velocity distribution of the water molecules emitted. Recent observations of the visible dust plume by the Cassini Imaging Science Subsystem (ISS) identified as many as 98 jet sources located along Tiger stripes [Porco et al. 2014]. We applied the spatial distribution of the sources observed by ISS in our models. The output of the models are the 3-D distribution of water vapor density and surface deposition patterns. Comparison between the simulation results and column densitioes derived from UVIS observations provide constraints on the physical characteristics of the plume and jets.

  1. Phasic motor activity reduction occurring with horizontal rapid eye movements during active sleep in human.

    PubMed

    Kohyama, J; Shimohira, M; Hasegawa, T; Kouji, T; Iwakawa, Y

    1995-01-01

    We describe the phasic reduction of motor activity occurring with horizontal rapid eye movements (REMs) during active sleep in 15 children (12 healthy children and 3 patients with severe brain damage). A REM-related decrease in intercostal muscle activity was demonstrated by averaging integrated surface electromyograms. In the healthy subjects, this reduction had a mean latency from the REM onset of 37.1 ms and a duration of 225.9 ms. This phenomenon was also observed in the 3 patients who had lost cerebral function. We hypothesized a brainstem origin for the effect. A REM-related mentalis muscle activity loss, detected by averaging mentalis muscle twitches, was observed in 10 healthy children among the subjects. This loss began at 59.1 ms before the onset of REMs and lasted for 230.2 ms on average. In addition, a transient decrease in integrated REM activity surrounding mentalis muscle twitches (a twitch-related reduction of REMs) was observed. We discuss the similarity between REM-related phasic reduction of muscle activity obtained for intercostal and mentalis muscles and pontogeniculo-occipital (PGO) wave-related inhibitory postsynaptic potentials reported for feline lumbar and trigeminal motoneurons, respectively. We then assume the presence of a phasic event generator, functioning during active sleep in healthy humans, which triggers at least three generators; that is, the generator of PGO waves (or REMs), motor inhibition, and of motor excitation including muscle twitches. PMID:8751071

  2. Adaptive control of an active seat for occupant vibration reduction

    NASA Astrophysics Data System (ADS)

    Gan, Zengkang; Hillis, Andrew J.; Darling, Jocelyn

    2015-08-01

    The harmful effects on human performance and health caused by unwanted vibration from vehicle seats are of increasing concern. This paper presents an active seat system to reduce the vibration level transmitted to the seat pan and the occupants' body under low frequency periodic excitation. Firstly, the detail of the mechanical structure is given and the active seat dynamics without external load are characterized by vibration transmissibility and frequency responses under different excitation forces. Owing the nonlinear and time-varying behaviour of the proposed system, a Filtered-x least-mean-square (FXLMS) adaptive control algorithm with on-line Fast-block LMS (FBLMS) identification process is employed to manage the system operation for high vibration cancellation performance. The effectiveness of the active seat system is assessed through real-time experimental tests using different excitation profiles. The system identification results show that an accurate estimation of the secondary path is achieved by using the FBLMS on-line technique. Substantial reduction is found for cancelling periodic vibration containing single and multiple frequencies. Additionally, the robustness and stability of the control system are validated through transient switching frequency tests.

  3. Reductive activation of E. coli respiratory nitrate reductase.

    PubMed

    Ceccaldi, Pierre; Rendon, Julia; Léger, Christophe; Toci, René; Guigliarelli, Bruno; Magalon, Axel; Grimaldi, Stéphane; Fourmond, Vincent

    2015-10-01

    Over the past decades, a number of authors have reported the presence of inactive species in as-prepared samples of members of the Mo/W-bisPGD enzyme family. This greatly complicated the spectroscopic studies of these enzymes, since it is impossible to discriminate between active and inactive species on the basis of the spectroscopic signatures alone. Escherichia coli nitrate reductase A (NarGHI) is a member of the Mo/W-bisPGD family that allows anaerobic respiration using nitrate as terminal electron acceptor. Here, using protein film voltammetry on NarGH films, we show that the enzyme is purified in a functionally heterogeneous form that contains between 20 and 40% of inactive species that activate the first time they are reduced. This activation proceeds in two steps: a non-redox reversible reaction followed by an irreversible reduction. By carefully correlating electrochemical and EPR spectroscopic data, we show that neither the two major Mo(V) signals nor those of the two FeS clusters that are the closest to the Mo center are associated with the two inactive species. We also conclusively exclude the possibility that the major "low-pH" and "high-pH" Mo(V) EPR signatures correspond to species in acid-base equilibrium. PMID:26073890

  4. Antibacterial activity of silver bionanocomposites synthesized by chemical reduction route

    PubMed Central

    2012-01-01

    Background The aim of this study is to investigate the functions of polymers and size of nanoparticles on the antibacterial activity of silver bionanocomposites (Ag BNCs). In this research, silver nanoparticles (Ag NPs) were incorporated into biodegradable polymers that are chitosan, gelatin and both polymers via chemical reduction method in solvent in order to produce Ag BNCs. Silver nitrate and sodium borohydride were employed as a metal precursor and reducing agent respectively. On the other hand, chitosan and gelatin were added as a polymeric matrix and stabilizer. The antibacterial activity of different sizes of silver nanoparticles was investigated against Gram-positive and Gram-negative bacteria by the disk diffusion method using Mueller-Hinton Agar. Results The properties of Ag BNCs were studied as a function of the polymer weight ratio in relation to the use of chitosan and gelatin. The morphology of the Ag BNCs films and the distribution of the Ag NPs were also characterized. The diameters of the Ag NPs were measured and their size is less than 20 nm. The antibacterial trait of silver/chitosan/gelatin bionanocomposites was investigated. The silver ions released from the Ag BNCs and their antibacterial activities were scrutinized. The antibacterial activities of the Ag BNC films were examined against Gram-negative bacteria (E. coli and P. aeruginosa) and Gram-positive (S. aureus and M. luteus) by diffusion method using Muller-Hinton agar. Conclusions The antibacterial activity of Ag NPs with size less than 20 nm was demonstrated and showed positive results against Gram-negative and Gram-positive bacteria. The Ag NPs stabilized well in the polymers matrix. PMID:22967920

  5. Enhanced U(VI) release from autunite mineral by aerobic Arthrobacter sp. in the presence of aqueous bicarbonate

    SciTech Connect

    Katsenovich, Yelena P.; Carvajal, Denny A.; Wellman, Dawn M.; Lagos, Leonel E.

    2012-05-01

    The bacterial effect on U(VI) release from the autunite mineral (Ca[(UO2)(PO4)]2•3H2O) was investigated to provide a more comprehensive understanding of the important microbiological processes affecting autunite stability within subsurface bicarbonate-bearing environments. Experiments were performed in a culture of the Arthrobacter oxydans G975 strain, herein referred to as G975, a soil bacterium previously isolated from Hanford Site soil. 91 mg of autunite powder and 50 mL of phosphorous-limiting sterile media were amended with bicarbonate (ranging between 1 and 10 mM) in glass reactor bottles and inoculated with the G975 strain after the dissolution of autunite was at steady state. SEM observations indicated that G975 formed a biofilm on the autunite surface and penetrated the mineral cleavages. The mineral surface colonization by bacteria tended to increase concomitantly with bicarbonate concentrations. Additionally, a sterile culture-ware with inserts was used in non-contact dissolution experiments where autunite and bacteria cells were kept separately. The data suggest that G975 bacteria is able to enhance the release of U(VI) from autunite without direct contact with the mineral. In the presence of bicarbonate, the damage to bacterial cells caused by U(VI) toxicity was reduced, yielding similar values for total organic carbon (TOC) degradation and cell density compared to U(VI)-free controls. The presence of active bacterial cells greatly enhanced the release of U(VI) from autunite in bicarbonate-amended media.

  6. Enhanced U(VI) release from autunite mineral by aerobic Arthrobacter sp. in the presence of aqueous bicarbonate

    SciTech Connect

    Katsenovich, Yelena; Carvajal, Denny A.; Wellman, Dawn M.; Lagos, Leonel

    2012-04-20

    The bacterial effect on U(VI) leaching from the autunite mineral (Ca[(UO{sub 2})(PO{sub 4})]{sub 2} {center_dot} 3H{sub 2}O) was investigated to provide a more comprehensive understanding into important microbiological processes affecting autunite stability within subsurface bicarbonate-bearing environments. Experiments were performed in a culture of G975 Arthrobacter oxydans strain, herein referred to as G975, a soil bacterium previously isolated from Hanford Site soil. 91 mg of autunite powder and 50 mL of phosphorus-limiting sterile media were amended with bicarbonate ranging between 1-10 mM in glass reactor bottles and inoculated with G975 strain after the dissolution of autunite was at steady state. SEM observations indicated G975 formed a biofilm on the autunite surface and penetrated the mineral cleavages. The mineral surface colonization by bacteria tended to increase concomitantly with bicarbonate concentrations. Additionally, a sterile cultureware with inserts was used in non-contact bioleaching experiments where autunite and bacteria cells were kept separately. The data suggest the G975 bacteria is able to enhance U(VI) leaching from autunite without the direct contact with the mineral. In the presence of bicarbonate, the damage to bacterial cells caused by U(VI) toxicity was reduced, yielding similar values for total organic carbon (TOC) degradation and cell density compared to U(VI)-free controls. The presence of active bacterial cells greatly enhanced the U(VI) bioleaching from autunite in bicarbonate-amended media.

  7. The Composition and Structure of Enceladus' Plume from a Cassini UVIS Observation of a Solar Occultation

    NASA Astrophysics Data System (ADS)

    Hansen, C. J.; Shemansky, D. E.; Esposito, L. W.; Stewart, I.; Hendrix, A. R.

    2010-12-01

    The Cassini Ultraviolet Imaging Spectrograph (UVIS) observed an occultation of the sun by Enceladus’ water vapor plume on May 18, 2010. UVIS used its extreme ultraviolet (EUV) channel for this new observation, to detect absorptions in the wavelength range 55 to 110 nm. Molecular nitrogen and water vapor have absorptions in this range. The N2 b(3,0) line is at 97.2 nm, extinguishing the solar H Lyman gamma emission. Cassini’s Ion and Neutral Mass Spectrometer (INMS) detected a species with an atomic mass of 28 amu, which could be CO, C2H4 or N2 [1, 2]. Definitive UVIS detection of N2 was important to clear up this ambiguity, and this was an important goal of the observation, as the presence or lack of N2 is key to models of the geochemistry in the interior [3, 4, 5]. UVIS did not detect N2 and we set an upper limit for the column density of 3 x 10^13 cm^-2. The absorption features in the spectrum are best fit by a water vapor column density of 0.9 x 10^16 cm^-2. This column density is in family with previous UVIS measurements from stellar occultations in 2005 and 2007 at far ultraviolet wavelengths, suggesting that Enceladus’ activity has been stable for the last 5 years [6, 7]. We used fluctuations in the signal to probe the structure of the gas jets again, as was analyzed in the 2007 occultation of zeta Orionis [7]. Gas jets are correlated to the dust jets detected by Cassini’s Imaging Science Subsystem [8]. The path of the sun cut through the jets horizontally at an altitude above the limb of ~15 km at the closest point. The resolution of the solar occultation is higher than the stellar occultation, and collimation of the gas jets observed in the solar occultation is greater than estimated in 2007. The observed collimation allows us to derive a mach number of ~4 for the ratio of the vertical velocity in the jet to the thermal velocity of the plume gas. The new opportunity afforded by this solar occultation is used to further model the structure and

  8. The role of nanopores on U(VI) sorption and redox behavior in U(VI)-contaminated subsurface sediments

    SciTech Connect

    Xu, Huifang; Roden, Eric E.; Kemner, Kenneth M.; Jung, Hun-Bok; Konishi, Hiromi; Boyanov, Maxim; Sun, Yubing; Mishra, Bhoopesh

    2013-10-16

    Most reactive surfaces in clay-dominated sediments are present within nanopores (pores of nm dimension). The behavior of geological fluids and minerals in nanopores is significantly different from those in normal non-nanoporous environments. The effect of nanopore surfaces on U(VI) sorption/desorption and reduction is likely to be significant in clay-rich subsurface environments. Our research results from both model nanopore system and natural sediments from both model system (synthetic nanopore alumina) and sediments from the ORNL Field Research Center prove that U(VI) sorption on nanopore surfaces can be greatly enhanced by nanopore confinement environments. The results from the project provide advanced mechanistic, quantitative information on the physiochemical controls on uranium sorption and redox behavior in subsurface sediments. The influence of nanopore surfaces on coupled uranium sorption/desorption and reduction processes is significant in virtually all subsurface environments, because most reactive surfaces are in fact nanopore surfaces. The results will enhance transfer of our laboratory-based research to a major field research initiative where reductive uranium immobilization is being investigated. Our results will also provide the basic science for developing in-situ colloidal barrier of nanoporous alumina in support of environmental remediation and long term stewardship of DOE sites.

  9. Treatment of activated carbon to enhance catalytic activity for reduction of nitric oxide with ammonia

    SciTech Connect

    Ku, B.J.; Rhee, H.K. . Dept. of Chemical Engineering); Lee, J.K.; Park, D. )

    1994-11-01

    Catalytic activity of activated carbon treated with various techniques was examined in a fixed bed reactor for the reduction of nitric oxide with ammonia at 150 C. Activated carbon derived from coconut shell impregnated with an aqueous solution of ammonium sulfate, further treated with sulfuric acid, dried at 120 C, and then heated in an inert gas stream at 400 C, showed the highest catalytic activity within the range of experimental conditions. The enhancement of catalytic activity of modified activated carbon could be attributed to the increase in the amount of oxygen function groups which increased the adsorption site for ammonia. Catalytic activity of activated carbons depended on the surface area and the oxygen content as well.

  10. Kinetic desorption and sorption of U(VI) during reactive transport in a contaminated Hanford sediment.

    PubMed

    Qafoku, Nikolla P; Zachara, John M; Liu, Chongxuan; Gassman, Paul L; Qafoku, Odeta S; Smith, Steven C

    2005-05-01

    Column experiments were conducted to investigate U(VI) desorption and sorption kinetics in a sand-textured, U(VI)-contaminated (22.7 micromol kg(-1)) capillary fringe sediment from the U.S. Department of Energy (DOE) Hanford site. Saturated column experiments were performed under mildly alkaline conditions representative of the Hanford site where uranyl-carbonate and calcium-uranyl-carbonate complexes dominate aqueous speciation. A U(VI)-free solution was used to study contaminant U(VI) desorption in columns where different flow rates were applied. Sorbed, contaminant U(VI) was partially labile (11.8%), and extended leaching times and water volumes were required for complete desorption of the labile fraction. Uranium-(VI) sorption was studied after the desorption of labile, contaminant U(VI) using different U(VI) concentrations in the leaching solution. Strong kinetic effects were observed for both U(VI) sorption and desorption, with half-life ranging from 8.5 to 48.5 h for sorption and from 39.3 to 150 h for desorption. Although U(VI) is semi-mobile in mildly alkaline, subsurface environments, we observed substantial U(VI) adsorption, significant retardation during transport, and atypical breakthrough curves with extended tailing. A distributed rate model was applied to describe the effluent data and to allow comparisons between the desorption rate of contaminant U(VI) with the rate of shortterm U(VI) sorption. Desorption was the slower process. We speculate that the kinetic behavior results from transport or chemical phenomena within the phyllosilicate-dominated fine fraction present in the sediment. Our results suggest that U(VI) release and transport in the vadose zone and aquifer system from which the sediment was obtained are kinetically controlled. PMID:15926566

  11. Oxygen reduction reaction activity on Pt{111} surface alloys.

    PubMed

    Attard, Gary A; Brew, Ashley; Ye, Jin-Yu; Morgan, David; Sun, Shi-Gang

    2014-07-21

    PtM overlayers (where M=Fe, Co or Ni) supported on Pt{111} are prepared via thermal annealing in either a nitrogen/water or hydrogen ambient of dilute aqueous droplets containing M(Z+) cations directly attached to the electrode. Two different PtM phases are detected depending on the nature of the post-annealing cooling environment. The first of these consists of small (<20 nm), closely packed microcrystals comprised of a central metallic core and a shell (several monolayers thick) of mixed metal oxides/hydroxides. The second type of PtM phase is prepared by cooling in a stream of hydrogen gas. Although this second phase also consists of numerous microcrystals covering the Pt{111} electrode surface, these are both flatter than before and moreover are entirely metallic in character. A positive shift in the onset of PtM oxide formation correlates with increased activity towards the oxygen reduction reaction (ORR), which we ascribe to the greater availability of platinum metallic sites under ORR conditions. PMID:24986646

  12. Digital Signal Processing System for Active Noise Reduction

    NASA Astrophysics Data System (ADS)

    Edmonson, William W.; Tucker, Jerry

    2002-12-01

    different adaptive noise cancellation algorithms and provide an operational prototype to understand the behavior of the system under test. DSP software was required to interface the processor with the data converters using interrupt routines. The goal is to build a complete ANC system that can be placed on a flexible circuit with added memory circuitry that also contains the power supply, sensors and actuators. This work on the digital signal processing system for active noise reduction was completed in collaboration with another ASEE Fellow, Dr. Jerry Tucker from Virginia Commonwealth University, Richmond, VA.

  13. Mitomycin antibiotic reductive potential and related pharmacological activities.

    PubMed

    Pan, S S; Gonzalez, H

    1990-06-01

    Relationships of reductive potential, kinetics of enzymatic reduction, augmented oxygen consumption, and cytotoxicity were determined for seven clinically relevant mitomycin antibiotics. Potentials for one-electron reduction were obtained by cyclic voltammetry analysis in dimethyl sulfoxide with 0.1 M tetraethyl-ammonium perchlorate. These potentials were -0.55 V for N7-acetylmitomycin C, -0.61 V for mitomycin A, -0.75 V for N7-(p-hydroxyphenyl)mitomycin C, -0.79 V for N7-(dimethylamino-methylene)mitomycin C, -0.81 V for N7-(2-(4-nitrophenyldithio)-ethyl)-mitomycin C, -0.81 V for mitomycin C, and -0.89 V for porfiromycin. All seven antibiotics were reduced by xanthine oxidase and NADPH-cytochrome P450 reductase, but the rate of reduction varied for each antibiotic and each enzyme. The less negative the reductive potential of an antibiotic, the more easily that antibiotic was reduced enzymatically. These seven mitomycin antibiotics also augmented oxygen consumption by rat liver microsomes. As with their reduction by xanthine oxidase and NADPH-cytochrome P450 reductase, the less negative the reductive potential of an antibiotic, the more it augmented oxygen consumption. Cytotoxicity of each antibiotic was assessed by defining the IC50 against HCT 116 human colon carcinoma cells. A relationship between the reductive potential of these antibiotics and their cytotoxicity against HCT 116 cells was also observed. PMID:2113607

  14. UVI Cyber-security Workshop Workshop Analysis.

    SciTech Connect

    Kuykendall, Tommie G.; Allsop, Jacob Lee; Anderson, Benjamin Robert; Boumedine, Marc; Carter, Cedric; Galvin, Seanmichael Yurko; Gonzalez, Oscar; Lee, Wellington K.; Lin, Han Wei; Morris, Tyler Jake; Nauer, Kevin S.; Potts, Beth A.; Ta, Kim Thanh; Trasti, Jennifer; White, David R.

    2015-07-08

    The cybersecurity consortium, which was established by DOE/NNSA’s Minority Serving Institutions Partnerships Program (MSIPP), allows students from any of the partner schools (13 HBCUs, two national laboratories, and a public school district) to have all consortia options available to them, to create career paths and to open doors to DOE sites and facilities to student members of the consortium. As a part of this year consortium activities, Sandia National Laboratories and the University of Virgin Islands conducted a week long cyber workshop that consisted of three courses; Digital Forensics and Malware Analysis, Python Programming, and ThunderBird Cup. These courses are designed to enhance cyber defense skills and promote learning within STEM related fields.

  15. Transient groundwater chemistry near a river: Effects on U(VI) transport in laboratory column experiments

    SciTech Connect

    Yin, Jun; Haggerty, Roy; Stoliker, Deborah L.; Kent, Douglas B.; Istok, Jonathan D.; Greskowiak, Janek; Zachara, John M.

    2011-04-05

    In the 300 Area of a U(VI)-contaminated aquifer at Hanford, Washington, USA, inorganic carbon and major cations, which have large impacts on U(VI) transport, change on an hourly and seasonal basis near the Columbia River. Batch and column experiments were conducted to investigate the factors controlling U(VI) adsorption/desorption by changing chemical conditions over time. Low alkalinity and low Ca concentrations (Columbia River water) enhanced adsorption and reduced aqueous concentrations. Conversely, high alkalinity and high Ca concentrations (Hanford groundwater) reduced adsorption and increased aqueous concentrations of U(VI). An equilibrium surface complexation model calibrated using laboratory batch experiments accounted for the decrease in U(VI) adsorption observed with increasing (bi)carbonate concentrations and other aqueous chemical conditions. In the column experiment, alternating pulses of river and groundwater caused swings in aqueous U(VI) concentration. A multispecies multirate surface complexation reactive transport model simulated most of the major U(VI) changes in two column experiments. The modeling results also indicated that U(VI) transport in the studied sediment could be simulated by using a single kinetic rate without loss of accuracy in the simulations. Moreover, the capability of the model to predict U(VI) transport in Hanford groundwater under transient chemical conditions depends significantly on the knowledge of real-time change of local groundwater chemistry.

  16. Transient groundwater chemistry near a river: Effects on U(VI) transport in laboratory column experiments

    USGS Publications Warehouse

    Yin, J.; Haggerty, R.; Stoliker, D.L.; Kent, D.B.; Istok, J.D.; Greskowiak, J.; Zachara, J.M.

    2011-01-01

    In the 300 Area of a U(VI)-contaminated aquifer at Hanford, Washington, USA, inorganic carbon and major cations, which have large impacts on U(VI) transport, change on an hourly and seasonal basis near the Columbia River. Batch and column experiments were conducted to investigate the factors controlling U(VI) adsorption/desorption by changing chemical conditions over time. Low alkalinity and low Ca concentrations (Columbia River water) enhanced adsorption and reduced aqueous concentrations. Conversely, high alkalinity and high Ca concentrations (Hanford groundwater) reduced adsorption and increased aqueous concentrations of U(VI). An equilibrium surface complexation model calibrated using laboratory batch experiments accounted for the decrease in U(VI) adsorption observed with increasing (bi)carbonate concentrations and other aqueous chemical conditions. In the column experiment, alternating pulses of river and groundwater caused swings in aqueous U(VI) concentration. A multispecies multirate surface complexation reactive transport model simulated most of the major U(VI) changes in two column experiments. The modeling results also indicated that U(VI) transport in the studied sediment could be simulated by using a single kinetic rate without loss of accuracy in the simulations. Moreover, the capability of the model to predict U(VI) transport in Hanford groundwater under transient chemical conditions depends significantly on the knowledge of real-time change of local groundwater chemistry. Copyright 2011 by the American Geophysical Union.

  17. Transient groundwater chemistry near a river: Effects on U(VI) transport in laboratory column experiments

    USGS Publications Warehouse

    Yin, Jun; Haggerty, Roy; Stoliker, Deborah L.; Kent, Douglas B.; Istok, Jonathan D.; Greskowiak, Janek; Zachara, John M.

    2011-01-01

    In the 300 Area of a U(VI)-contaminated aquifer at Hanford, Washington, USA, inorganic carbon and major cations, which have large impacts on U(VI) transport, change on an hourly and seasonal basis near the Columbia River. Batch and column experiments were conducted to investigate the factors controlling U(VI) adsorption/desorption by changing chemical conditions over time. Low alkalinity and low Ca concentrations (Columbia River water) enhanced adsorption and reduced aqueous concentrations. Conversely, high alkalinity and high Ca concentrations (Hanford groundwater) reduced adsorption and increased aqueous concentrations of U(VI). An equilibrium surface complexation model calibrated using laboratory batch experiments accounted for the decrease in U(VI) adsorption observed with increasing (bi)carbonate concentrations and other aqueous chemical conditions. In the column experiment, alternating pulses of river and groundwater caused swings in aqueous U(VI) concentration. A multispecies multirate surface complexation reactive transport model simulated most of the major U(VI) changes in two column experiments. The modeling results also indicated that U(VI) transport in the studied sediment could be simulated by using a single kinetic rate without loss of accuracy in the simulations. Moreover, the capability of the model to predict U(VI) transport in Hanford groundwater under transient chemical conditions depends significantly on the knowledge of real-time change of local groundwater chemistry.

  18. Rapid Rather than Gradual Weight Reduction Impairs Hemorheological Parameters of Taekwondo Athletes through Reduction in RBC-NOS Activation

    PubMed Central

    Yang, Woo Hwi; Heine, Oliver; Pauly, Sebastian; Kim, Pilsang; Bloch, Wilhelm; Mester, Joachim; Grau, Marijke

    2015-01-01

    Purpose Rapid weight reduction is part of the pre-competition routine and has been shown to negatively affect psychological and physiological performance of Taekwondo (TKD) athletes. This is caused by a reduction of the body water and an electrolyte imbalance. So far, it is unknown whether weight reduction also affects hemorheological properties and hemorheology-influencing nitric oxide (NO) signaling, important for oxygen supply to the muscles and organs. Methods For this purpose, ten male TKD athletes reduced their body weight by 5% within four days (rapid weight reduction, RWR). After a recovery phase, athletes reduced body weight by 5% within four weeks (gradual weight reduction, GWR). Each intervention was preceded by two baseline measurements and followed by a simulated competition. Basal blood parameters (red blood cell (RBC) count, hemoglobin concentration, hematocrit, mean corpuscular volume, mean cellular hemoglobin and mean cellular hemoglobin concentration), RBC-NO synthase activation, RBC nitrite as marker for NO synthesis, RBC deformability and aggregation parameters were determined on a total of eight investigation days. Results Basal blood parameters were not affected by the two interventions. In contrast to GWR, RWR decreased activation of RBC-NO synthase, RBC nitrite, respective NO concentration and RBC deformability. Additionally, RWR increased RBC aggregation and disaggregation threshold. Conclusion The results point out that a rapid weight reduction negatively affects hemorheological parameters and NO signaling in RBC which might limit performance capacity. Thus, GWR should be preferred to achieve the desired weight prior to a competition to avoid these negative effects. PMID:25875585

  19. Solvent impregnated resin for isolation of U(VI) from industrial wastes

    SciTech Connect

    Karve, M.; Rajgor, R.V.

    2008-07-01

    A solid-phase extraction method based upon impregnation of Cyanex 302 (bis(2,4,4- trimethylpentyl)mono-thio-phosphinic acid) on Amberlite XAD-2 resin is proposed for isolation of U(VI) from uranmicrolite ore tailing samples and industrial effluent samples. U(VI) was sorbed from nitric acid media on the solvent-impregnated resin (SIR) and was recovered completely with 1.0 M HCl. Based upon sorption behavior of U(VI) with Cyanex 302, it was quantitatively sorbed on the SIR in a dynamic method, while the other metal ions were not sorbed by the modified resin. The preparation of impregnated resin is simple, based upon physical interaction of the extractant and solid support, has good sorption capacity for U(VI), and is also reliable for detection of traces of U(VI). (authors)

  20. WFC3/UVIS Dark Current Calibration and Detector Characteristics

    NASA Astrophysics Data System (ADS)

    Bourque, Matthew; Biretta, John A.; Baggett, Sylvia M.; Anderson, Jay; MacKenty, John W.; WFC3 Team

    2015-01-01

    The Hubble Space Telescope (HST) Wide Field Camera 3 (WFC3) is a fourth-generation imaging instrument that was installed during Servicing Mission 4 in May 2009. The WFC3/UVIS detector, comprised of two e2v CCDs, exhibits an inherent dark current (in the absence of any illumination) presently measured at ~6 e-/hr. In addition, detector degradation due to on-orbit radiation damage generates a continuously increasing though small population of hot pixels (dark current exceeding 54 e-/hr, ~4% of each chip) as well as 'sink' pixels (pixels which contain a large number of charge traps). We present the procedures and results of the WFC3/UVIS dark calibration, which provides calibration files used as a correction for these detector characteristics. We discuss the impacts that Charge Transfer Efficiency (CTE) losses and detector post-flashing have on the hot pixel population and overall calibration, as well as the plans for flagging the 'sink' pixels in the calibration pipeline. Finally, we discuss various improvements to the calibration procedure that will increase the accuracy of dark current and hot pixel measurements.

  1. Investigation of U(VI) Adsorption in Quartz-Chlorite Mineral Mixtures

    SciTech Connect

    Wang, Zheming; Zachara, John M.; Shang, Jianying; Jeon, Choong; Liu, Juan; Liu, Chongxuan

    2014-08-25

    A batch and cryogenic laser-induced time-resolved fluorescence spectroscopy investigation of U(VI) adsorbed on quartz-chlorite mixtures with variable mass ratios have been performed under field-relevant uranium concentrations (5x10-7 M and 5x10-6 M) in pH 8.1 synthetic groundwater. The U(VI) adsorption Kd values steadily increased as the mass fraction of chlorite increased, indicating preferential sorption to chlorite. For all mineral mixtures, U(VI) adsorption Kd values were lower than that calculated from the assumption of component additivity; The largest deviation occurred when the mass fractions of the two minerals were equal. U(VI) adsorbed on quartz and chlorite displayed characteristic individual fluorescence spectra that were not affected by mineral mixing. The spectra of U(VI) adsorbed within the mixtures could be simulated by one surface U(VI) species on quartz and two on chlorite. The fluorescence intensity decreased in a nonlinear manner as the adsorbed U(VI) concentration increased with increasing chlorite mass fraction – likely due to ill-defined fluorescence quenching by both structural Fe/Cr in chlorite, and trace amounts of solubilized and re-precipitated Fe/Cr in the aqueous phase. However, the fractional spectral intensities of U(VI) adsorbed on quartz and chlorite followed the same trend of fractional adsorbed U(VI) concentration in each mineral phase; approximate linear correlations in the quartz:chlorite mass ratio ranges of 0.0 - 0.2 and 0.2 - 1.0, offering a method to estimate of U(VI) concentration distribution between the mineral components.

  2. Uranium isotopes fingerprint biotic reduction

    SciTech Connect

    Stylo, Malgorzata; Neubert, Nadja; Wang, Yuheng; Monga, Nikhil; Romaniello, Stephen J.; Weyer, Stefan; Bernier-Latmani, Rizlan

    2015-04-20

    Knowledge of paleo-redox conditions in the Earth’s history provides a window into events that shaped the evolution of life on our planet. The role of microbial activity in paleo-redox processes remains unexplored due to the inability to discriminate biotic from abiotic redox transformations in the rock record. The ability to deconvolute these two processes would provide a means to identify environmental niches in which microbial activity was prevalent at a specific time in paleo-history and to correlate specific biogeochemical events with the corresponding microbial metabolism. Here, we demonstrate that the isotopic signature associated with microbial reduction of hexavalent uranium (U), i.e., the accumulation of the heavy isotope in the U(IV) phase, is readily distinguishable from that generated by abiotic uranium reduction in laboratory experiments. Thus, isotope signatures preserved in the geologic record through the reductive precipitation of uranium may provide the sought-after tool to probe for biotic processes. Because uranium is a common element in the Earth’s crust and a wide variety of metabolic groups of microorganisms catalyze the biological reduction of U(VI), this tool is applicable to a multiplicity of geological epochs and terrestrial environments. The findings of this study indicate that biological activity contributed to the formation of many authigenic U deposits, including sandstone U deposits of various ages, as well as modern, Cretaceous, and Archean black shales. In addition, engineered bioremediation activities also exhibit a biotic signature, suggesting that, although multiple pathways may be involved in the reduction, direct enzymatic reduction contributes substantially to the immobilization of uranium.

  3. Uranium isotopes fingerprint biotic reduction

    DOE PAGESBeta

    Stylo, Malgorzata; Neubert, Nadja; Wang, Yuheng; Monga, Nikhil; Romaniello, Stephen J.; Weyer, Stefan; Bernier-Latmani, Rizlan

    2015-04-20

    Knowledge of paleo-redox conditions in the Earth’s history provides a window into events that shaped the evolution of life on our planet. The role of microbial activity in paleo-redox processes remains unexplored due to the inability to discriminate biotic from abiotic redox transformations in the rock record. The ability to deconvolute these two processes would provide a means to identify environmental niches in which microbial activity was prevalent at a specific time in paleo-history and to correlate specific biogeochemical events with the corresponding microbial metabolism. Here, we demonstrate that the isotopic signature associated with microbial reduction of hexavalent uranium (U),more » i.e., the accumulation of the heavy isotope in the U(IV) phase, is readily distinguishable from that generated by abiotic uranium reduction in laboratory experiments. Thus, isotope signatures preserved in the geologic record through the reductive precipitation of uranium may provide the sought-after tool to probe for biotic processes. Because uranium is a common element in the Earth’s crust and a wide variety of metabolic groups of microorganisms catalyze the biological reduction of U(VI), this tool is applicable to a multiplicity of geological epochs and terrestrial environments. The findings of this study indicate that biological activity contributed to the formation of many authigenic U deposits, including sandstone U deposits of various ages, as well as modern, Cretaceous, and Archean black shales. In addition, engineered bioremediation activities also exhibit a biotic signature, suggesting that, although multiple pathways may be involved in the reduction, direct enzymatic reduction contributes substantially to the immobilization of uranium.« less

  4. Uranium isotopes fingerprint biotic reduction.

    PubMed

    Stylo, Malgorzata; Neubert, Nadja; Wang, Yuheng; Monga, Nikhil; Romaniello, Stephen J; Weyer, Stefan; Bernier-Latmani, Rizlan

    2015-05-01

    Knowledge of paleo-redox conditions in the Earth's history provides a window into events that shaped the evolution of life on our planet. The role of microbial activity in paleo-redox processes remains unexplored due to the inability to discriminate biotic from abiotic redox transformations in the rock record. The ability to deconvolute these two processes would provide a means to identify environmental niches in which microbial activity was prevalent at a specific time in paleo-history and to correlate specific biogeochemical events with the corresponding microbial metabolism. Here, we demonstrate that the isotopic signature associated with microbial reduction of hexavalent uranium (U), i.e., the accumulation of the heavy isotope in the U(IV) phase, is readily distinguishable from that generated by abiotic uranium reduction in laboratory experiments. Thus, isotope signatures preserved in the geologic record through the reductive precipitation of uranium may provide the sought-after tool to probe for biotic processes. Because uranium is a common element in the Earth's crust and a wide variety of metabolic groups of microorganisms catalyze the biological reduction of U(VI), this tool is applicable to a multiplicity of geological epochs and terrestrial environments. The findings of this study indicate that biological activity contributed to the formation of many authigenic U deposits, including sandstone U deposits of various ages, as well as modern, Cretaceous, and Archean black shales. Additionally, engineered bioremediation activities also exhibit a biotic signature, suggesting that, although multiple pathways may be involved in the reduction, direct enzymatic reduction contributes substantially to the immobilization of uranium. PMID:25902522

  5. Uranium isotopes fingerprint biotic reduction

    PubMed Central

    Stylo, Malgorzata; Neubert, Nadja; Wang, Yuheng; Monga, Nikhil; Romaniello, Stephen J.; Weyer, Stefan; Bernier-Latmani, Rizlan

    2015-01-01

    Knowledge of paleo-redox conditions in the Earth’s history provides a window into events that shaped the evolution of life on our planet. The role of microbial activity in paleo-redox processes remains unexplored due to the inability to discriminate biotic from abiotic redox transformations in the rock record. The ability to deconvolute these two processes would provide a means to identify environmental niches in which microbial activity was prevalent at a specific time in paleo-history and to correlate specific biogeochemical events with the corresponding microbial metabolism. Here, we demonstrate that the isotopic signature associated with microbial reduction of hexavalent uranium (U), i.e., the accumulation of the heavy isotope in the U(IV) phase, is readily distinguishable from that generated by abiotic uranium reduction in laboratory experiments. Thus, isotope signatures preserved in the geologic record through the reductive precipitation of uranium may provide the sought-after tool to probe for biotic processes. Because uranium is a common element in the Earth’s crust and a wide variety of metabolic groups of microorganisms catalyze the biological reduction of U(VI), this tool is applicable to a multiplicity of geological epochs and terrestrial environments. The findings of this study indicate that biological activity contributed to the formation of many authigenic U deposits, including sandstone U deposits of various ages, as well as modern, Cretaceous, and Archean black shales. Additionally, engineered bioremediation activities also exhibit a biotic signature, suggesting that, although multiple pathways may be involved in the reduction, direct enzymatic reduction contributes substantially to the immobilization of uranium. PMID:25902522

  6. Study of sorption-retarded U(VI) diffusion in Hanford silt/clay material

    SciTech Connect

    Bai, Jing; Liu, Chongxuan; Ball, William P.

    2009-10-15

    A diffusion cell method was developed to measure the effective aqueous diffusion coefficient for U(VI) under strictly controlled chemical conditions within the inter-particle pores of silt/clay sediment from the DOE Hanford site, WA. "Inward-flux” diffusion studies were conducted in which U(VI) concentrations in both aqueous and solid phases were measured as a function of distance into the cell under conditions of constant concentration at the cell boundaries. A sequential extraction method was developed to measure sorbed U(VI) content in the solid phase, while accounting for the non-negligible extractable background U(VI). U(VI) diffusion data were found to be consistent with a model that assumed that: 1) a single effective aqueous diffusion coefficient could be used to simulate the coupled diffusion of various aqueous U(VI) species, and 2) the local equilibrium assumption (LEA) is appropriate for modeling the effects of sorption under the given experimental conditions. An effective aqueous diffusion coefficient (De) of 1.6x10^-6 cm2/s was obtained under conditions of pH 8.0 and calcite saturation that are relevant to the subsurface conditions at some regions of the Hanford site. The developed experimental techniques provide a practical approach for measuring effective aqueous U(VI) diffusivity in sorptive porous media.

  7. Comparing approaches for simulating the reactive transport of U(VI) in ground water

    USGS Publications Warehouse

    Curtis, G.P.; Kohler, M.; Davis, J.A.

    2009-01-01

    The reactive transport of U(VI) in a well-characterized shallow alluvial aquifer at a former U(VI) mill located near Naturita, CO, was predicted for comparative purposes using a surface complexation model (SCM) and a constant K d approach to simulate U(VI) adsorption. The ground water at the site had U(VI) concentrations that ranged from 0.01 to 20 ??M, alkalinities that ranged from 2.5 to 18 meq/L, and a nearly constant pH of 7.1. The SCM used to simulate U(VI) adsorption was previously determined independently using laboratory batch adsorption experiments. Simulations obtained using the SCM approach were compared with simulations that used a constant K d approach to simulate adsorption using previously determined site-specific K d values. In both cases, the ground water flow and transport models used a conceptual model that was previously calibrated to a chloride plume present at the site. Simulations with the SCM approach demonstrated that the retardation factor varied temporally and spatially because of the differential transport of alkalinity and dissolved U(VI) and the nonlinearity of the U(VI) adsorption. The SCM model also simulated a prolonged slow decline in U(VI) concentration, which was not simulated using a constant K d model. Simulations using the SCM approach and the constant K d approach were similar after 20 years of transport but diverged significantly after 60 years. The simulations demonstrate the need for site-specific geochemical information on U(VI) adsorption to produce credible simulations of future transport. ?? 2009 Springer-Verlag.

  8. The effect of Paecilomyces catenlannulatus on removal of U(VI) by illite.

    PubMed

    Li, Fengbo; Gao, Zhimou; Li, Xiaoyu; Fang, Lejin

    2014-11-01

    The effect of Paecilomyces catenlannulatus (P. catenlannulatus) on removal of U(VI) onto illite as a function of contact time, pH, ionic strength, and solution concentration was conducted by batch techniques. The adsorption kinetics indicated that the removal of U(VI) on illite and illite coated P. catenlannulatus can be fitted by pseudo-second order kinetic model very well. The removal of U(VI) on illite and illite coated P. catenlannulatus increased with increasing pH from 1.0 to 7.0, whereas the decrease of U(VI) adsorption on illite and illite coated P. catenlannulatus was observed at pH > 7.5. The adsorption behavior of U(VI) on illite and illite coated P. catenlannulatus can be simulated by the double diffuse model under various pH conditions. The ionic strength-dependent experiments showed that the removal of U(VI) on illite was outer-sphere surface complexation, whereas the inner-sphere surface complexation predominated the U(VI) adsorption onto illite coated P. catenlannulatus at pH 5.0-7.0. The maximum adsorption capacity of U(VI) on illite and illite coated P. catenlannulatus calculated from Langmuir model at pH 5.0 and T = 298 K was 46.729 and 54.347 mg/g, respectively, revealing enhanced adsorption of U(VI) on illite coated P. catenlannulatus. This paper highlights the effect of microorganism on the removal of radionuclides from aqueous solutions in environmental pollution management. PMID:24998746

  9. Reduction of beta activity from depleted derbies, ingots and crucibles

    SciTech Connect

    Briggs, G.G.; Schonegg, E.; Kato, T.R.

    1984-09-01

    The reduction of beta radiation on uranium ingot and crucible surfaces was demonstrated in the production casting operation by adding a mixture of slag liner material (MgF/sub 2/) and calcium fluoride to the remelt charge. The beta emitters (/sup 234/Th and /sup 234/Pa) are largely discharged with the fluorides into drums during a remote crucible burnout operation; thereby, reducing operator exposure to beta radiation. A production test showed that very low beta radiation from uranium flat castings can be achieved by using derbies recently prepared by reduction. Plant tests with fluoride addition indicate that pickling of derbies may not be necessary for casting uranium flats from a plasma sprayed (ZrO/sub 2/) crucible. Also, ingots produced with fluoride additions had less pipe as compared to standard production technique. 2 references, 5 tables.

  10. HST WFC3/UVIS: charge transfer efficiency monitoring and mitigation

    NASA Astrophysics Data System (ADS)

    Baggett, Sylvia M.; Sosey, Megan L.; Anderson, Jay; Gosmeyer, Catherine; Bourque, Matthew; Bajaj, Varun; Khandrika, Harish G.; Martlin, Catherine; Kozhurina-Platais, Vera; Sabbi, Elena; WFC3 Team

    2016-01-01

    The harsh low-earth orbit environment is known to damage CCD devices and the HST WFC3/UVIS camera is no exception. One consequence of the radiation damage is charge-transfer efficiency (CTE) loss over time. We summarize the level of the CTE losses, the effect on science data, and the pre- and post-observation mitigation options available. Among them is the pixel-based CTE correction, which has been incorporated into the HST automatic data processing pipeline. The pipeline now provides both standard and CTE-corrected data products; observers with older data can re-retrieve their images via the the Mikulski Archive for Space Telescopes (MAST) to obtain the new products.

  11. Enzymatic iron and uranium reduction by sulfate-reducing bacteria

    USGS Publications Warehouse

    Lovley, D.R.; Roden, E.E.; Phillips, E.J.P.; Woodward, J.C.

    1993-01-01

    The potential for sulfate-reducing bacteria (SRB) to enzymatically reduce Fe(III) and U(VI) was investigated. Five species of Desulfovibrio as well as Desulfobacterium autotrophicum and Desulfobulbus propionicus reduced Fe(III) chelated with nitrilotriacetic acid as well as insoluble Fe(III) oxide. Fe(III) oxide reduction resulted in the accumulation of magnetite and siderite. Desulfobacter postgatei reduced the chelated Fe(III) but not Fe(III) oxide. Desulfobacter curvatus, Desulfomonile tiedjei, and Desulfotomaculum acetoxidans did not reduce Fe(III). Only Desulfovibrio species reduced U(VI). U(VI) reduction resulted in the precipitation of uraninite. None of the SRB that reduced Fe(III) or U(VI) appeared to conserve enough energy to support growth from this reaction. However, Desulfovibrio desulfuricans metabolized H2 down to lower concentrations with Fe(III) or U(VI) as the electron acceptor than with sulfate, suggesting that these metals may be preferred electron acceptors at the low H2 concentrations present in most marine sediments. Molybdate did not inhibit Fe(III) reduction by D. desulfuricans. This indicates that the inability of molybdate to inhibit Fe(III) reduction in marine sediments does not rule out the possibility that SRB are important catalysts for Fe(III) reduction. The results demonstrate that although SRB were previously considered to reduce Fe(III) and U(VI) indirectly through the production of sulfide, they may also directly reduce Fe(III) and U(VI) through enzymatic mechanisms. These findings, as well as our recent discovery that the So-reducing microorganism Desulfuromonas acetoxidans can reduce Fe(III), demonstrate that there are close links between the microbial sulfur, iron, and uranium cycles in anaerobic marine sediments. ?? 1993.

  12. Iran’s Activities on Prevention, Treatment and Harm Reduction of Drug Abuse

    PubMed Central

    Saberi Zafarghandi, Mohammad Bagher; Jadidi, Mohsen; Khalili, Narjes

    2015-01-01

    Context: In the present review study, authors investigated Iran’s activities regarding prevention, abuse and harm reduction of drugs nationwide. The issue appears to be important in order to show the trend of activities in the country. Evidence Acquisition: In this report, authors gathered data from different Farsi/English peer review journals issued both in printed and online versions. These journals have been indexed in PubMed, ISI, ISC, SID, Magiran, UN, etc. These are among the most referred and cited databases. Results: Summarizing the data led to three distinguished sections: 1) drug supply reduction activities; 2) drug demand reduction activities; 3) harm reduction activities. Conclusions: As the results showed, the trend of activities was encouraging and some additional activities could be included to future programs relying on early-onset preventions. PMID:26870709

  13. DEVELOPMENT OF HIGH ACTIVITY, CATALYTIC SYSTEMS FOR NOx REDUCTION

    SciTech Connect

    Unknown

    2001-12-01

    This project was directed at an investigation of catalytic NO{sub x} reduction on carbonaceous supports at low temperatures. The experimental work was conducted primarily in a packed bed reactor/gas flow system that was constructed for this work. The analytical techniques employed were mass spectrometry, NO{sub x} chemiluminescence, and gas chromatography. The experimental plan was focused on steady-state reactivity experiments, followed by temperature programmed desorption (TPD) of surface intermediates, and also selected temperature-programmed reaction (TPR) experiments. Both uncatalyzed and catalyzed (potassium-promoted) phenolic resin char, were investigated as well as the catalytic effect of additional CO in the gas phase.

  14. Active Flap Control of the SMART Rotor for Vibration Reduction

    NASA Technical Reports Server (NTRS)

    Hall, Steven R.; Anand, R. Vaidyanathan; Straub, Friedrich K.; Lau, Benton H.

    2009-01-01

    Active control methodologies were applied to a full-scale active flap rotor obtained during a joint Boeing/ DARPA/NASA/Army test in the Air Force National Full-Scale Aerodynamic Complex 40- by 80-foot anechoic wind tunnel. The active flap rotor is a full-scale MD 900 helicopter main rotor with each of its five blades modified to include an on-blade piezoelectric actuator-driven flap with a span of 18% of radius, 25% of chord, and located at 83% radius. Vibration control demonstrated the potential of active flaps for effective control of vibratory loads, especially normal force loads. Active control of normal force vibratory loads using active flaps and a continuous-time higher harmonic control algorithm was very effective, reducing harmonic (1-5P) normal force vibratory loads by 95% in both cruise and approach conditions. Control of vibratory roll and pitch moments was also demonstrated, although moment control was less effective than normal force control. Finally, active control was used to precisely control blade flap position for correlation with pretest predictions of rotor aeroacoustics. Flap displacements were commanded to follow specific harmonic profiles of 2 deg or more in amplitude, and the flap deflection errors obtained were less than 0.2 deg r.m.s.

  15. Reduction of structural weight, costs and complexity of a control system in the active vibration reduction of flexible structures

    NASA Astrophysics Data System (ADS)

    Daraji, A. H.; Hale, J. M.

    2014-09-01

    This paper concerns the active vibration reduction of a flexible structure with discrete piezoelectric sensors and actuators in collocated pairs bonded to its surface. In this study, a new fitness and objective function is proposed to determine the optimal number of actuators, based on variations in the average closed loop dB gain margin reduction for all of the optimal piezoelectric pairs and on the modes that are required to be attenuated using the optimal linear quadratic control scheme. The aim of this study is to find the minimum number of optimally located sensor/actuator pairs, which can achieve the same vibration reduction as a greater number, in order to reduce the cost, complexity and power requirement of the control system. This optimization was done using a genetic algorithm. The technique may be applied to any lightly damped structure, and is demonstrated here by attenuating the first six vibration modes of a flat cantilever plate. It is shown that two sensor/actuator pairs, located and controlled optimally, give almost the same vibration reduction as ten pairs. These results are validated by comparing the open and closed loop time responses and actuator feedback voltages for various numbers of piezoelectric pairs using the ANSYS finite element package and a proportional differential control scheme.

  16. Activity and Stability of Nanoscale Oxygen Reduction Catalysts

    SciTech Connect

    Shao-Horn, Yang

    2015-07-28

    Design of highly active and stable nanoscale catalysts for electro-oxidation of small organic molecules is of great importance to the development of efficient fuel cells. The amount and instability of Pt-based catalysts in the cathode limits the cost, efficiency and lifetime of proton exchange membrane fuel cells. We developed a microscopic understanding of the factors governing activity and stability in Pt and PtM alloys. Experimental efforts were focused on probing the size and shape dependence of ORR activity of Pt-based nanoparticles supported on carbon nanotubes. A microscopic understanding of the activity was achieved by correlating voltammetry and rotating ring disk electrodes to surface atomic and electronic structures, which were elucidated predominantly by high-resolution transmission electron microscopy (HRTEM), Scanning transmission electron microscopy energy dispersive X-ray Spectroscopy (STEM-EDS) and synchrotron X-ray absorption spectroscopy (XAS).

  17. Sustained Reduction of Cerebellar Activity in Experimental Epilepsy

    PubMed Central

    Rijkers, Kim; Moers-Hornikx, Véronique M. P.; Hemmes, Roelof J.; Aalbers, Marlien W.; Temel, Yasin; Vles, Johan S. H.; Hoogland, Govert

    2015-01-01

    Clinical and experimental evidence suggests a role for the cerebellum in seizure control, while no data are available on cerebellar activity between seizures. We hypothesized that interictal regional activity of the deep cerebellar nuclei is reduced in epilepsy and tested this in an animal model by using ΔFosB and cytochrome oxidase (COX) (immuno)histochemistry. The expression of these two markers of neuronal activity was analysed in the dentate nucleus (DN), interpositus nucleus (IN), and fastigial nucleus (FN) of the cerebellum of fully amygdala kindled rats that were sacrificed 48 hours after their last seizure. The DN and FN of kindled rats exhibited 25 to 29% less ΔFosB immunopositive cells than their respective counterpart in sham controls (P < 0.05). COX expression in the DN and FN of kindled animals was reduced by 32 to 33% compared to respective control values (P < 0.05). These results indicate that an epileptogenic state is characterized by decreased activity of deep cerebellar nuclei, especially the DN and FN. Possible consequences may include a decreased activation of the thalamus, contributing to further seizure spread. Restoration of FN activity by low frequency electrical stimulation is suggested as a possible treatment option in chronic epilepsy. PMID:26417599

  18. U(VI) adsorption on aquifer sediments at the Hanford Site.

    PubMed

    Um, Wooyong; Serne, R Jeffrey; Brown, Christopher F; Last, George V

    2007-08-15

    Aquifer sediments collected via split-spoon sampling in two new groundwater wells in the 200-UP-1 operable unit at the Hanford Site were characterized and showed typical Ringold Unit E Formation properties dominated by gravel and sand. High iron-oxide content in Fe oxide/clay coatings caused the highest U(VI) adsorption as quantified by batch K(d) values, indicating iron oxides are the key solid adsorbent in the 200-UP-1 sediments that affect U(VI) fate and mobility. Even though U(VI) adsorption on the gravel-sized fraction of the sediments is considered to be negligible, careful characterization should be conducted to determine U(VI) adsorption on gravel, because of presence of Fe oxides coatings and diffusion-controlled adsorption into the gravel particles' interior surfaces. A linear adsorption isotherm was observed up to 10(-6) M (238 microg/L) of total U(VI) concentration in batch U(VI) adsorption tests with varying total U(VI) concentrations in spiked groundwater. U(VI) adsorption decreased with increasing concentrations of dissolved carbonate, because strong anionic aqueous uranium-carbonate complexes formed at high pH and high alkalinity conditions. Noticeable uranium desorption hysteresis was observed in a flow-through column experiment, suggesting that desorption K(d) values for aged uranium-contaminated sediments at the Hanford Site can be larger than adsorption K(d) values determined in short-term laboratory experiments and slow uranium release from contaminated sediments into the groundwater is expected. PMID:17499879

  19. U(VI) adsorption on aquifer sediments at the Hanford Site

    NASA Astrophysics Data System (ADS)

    Um, Wooyong; Serne, R. Jeffrey; Brown, Christopher F.; Last, George V.

    2007-08-01

    Aquifer sediments collected via split-spoon sampling in two new groundwater wells in the 200-UP-1 operable unit at the Hanford Site were characterized and showed typical Ringold Unit E Formation properties dominated by gravel and sand. High iron-oxide content in Fe oxide/clay coatings caused the highest U(VI) adsorption as quantified by batch Kd values, indicating iron oxides are the key solid adsorbent in the 200-UP-1 sediments that affect U(VI) fate and mobility. Even though U(VI) adsorption on the gravel-sized fraction of the sediments is considered to be negligible, careful characterization should be conducted to determine U(VI) adsorption on gravel, because of presence of Fe oxides coatings and diffusion-controlled adsorption into the gravel particles' interior surfaces. A linear adsorption isotherm was observed up to 10 - 6 M (238 μg/L) of total U(VI) concentration in batch U(VI) adsorption tests with varying total U(VI) concentrations in spiked groundwater. U(VI) adsorption decreased with increasing concentrations of dissolved carbonate, because strong anionic aqueous uranium-carbonate complexes formed at high pH and high alkalinity conditions. Noticeable uranium desorption hysteresis was observed in a flow-through column experiment, suggesting that desorption Kd values for aged uranium-contaminated sediments at the Hanford Site can be larger than adsorption Kd values determined in short-term laboratory experiments and slow uranium release from contaminated sediments into the groundwater is expected.

  20. Preconcentration of U(VI) ions on few-layered graphene oxide nanosheets from aqueous solutions.

    PubMed

    Zhao, Guixia; Wen, Tao; Yang, Xin; Yang, Shubin; Liao, Jiali; Hu, Jun; Shao, Dadong; Wang, Xiangke

    2012-05-28

    Graphene oxide nanosheets have attracted multidisciplinary attention due to their unique physicochemical properties. Herein, few-layered graphene oxide nanosheets were synthesized from graphite using a modified Hummers method and were characterized by TEM, AFM, Raman spectroscopy, XPS, FTIR spectroscopy, TG-DTA and acid-base titrations. The prepared few-layered graphene oxide nanosheets were used as adsorbents for the preconcentration of U(VI) ions from large volumes of aqueous solutions as a function of pH, ionic strength and temperature. The sorption of U(VI) ions on the graphene oxide nanosheets was strongly dependent on pH and independent of the ionic strength, indicating that the sorption was mainly dominated by inner-sphere surface complexation rather than by outer-sphere surface complexation or ion exchange. The abundant oxygen-containing functional groups on the surfaces of the graphene oxide nanosheets played an important role in U(VI) sorption. The sorption of U(VI) on graphene oxide nanosheets increased with an increase in temperature and the thermodynamic parameters calculated from the temperature-dependent sorption isotherms suggested that the sorption of U(vi) on graphene oxide nanosheets was an endothermic and spontaneous process. The maximum sorption capacities (Q(max)) of U(VI) at pH 5.0 ± 0.1 and T = 20 °C was 97.5 mg g(-1), which was much higher than any of the currently reported nanomaterials. The graphene oxide nanosheets may be suitable materials for the removal and preconcentration of U(VI) ions from large volumes of aqueous solutions, for example, U(VI) polluted wastewater, if they can be synthesized in a cost-effective manner on a large scale in the future. PMID:22473651

  1. Upscaling of U(VI) Desorption and Transport Using Decimeter-Scale Tanks

    SciTech Connect

    Rodriguez, Derrick

    2015-01-28

    Experimental work was used to validate modeling studies and develop multicontinuum models of U(VI) transport in a contaminated aquifer. At the bench scale, it has been shown that U(VI) desorption is rate-limited and that rates are dependent on the bicarbonate concentration. Two decimeter-scale experiments were conducted in order to help establish rigorous upscaling approaches that could be tested at the tracer test and plume scales.

  2. Upscaling of U(VI) Desorption and Transport Using Decimeter-Scale Tanks

    SciTech Connect

    Rodriguez, Derrick

    2014-12-22

    Experimental work was used to validate modeling studies and develop multicontinuum models of U(VI) transport in a contaminated aquifer. At the bench scale, it has been shown that U(VI) desorption is rate-limited and that rates are dependent on the bicarbonate concentration. Two decimeter-scale experiments were conducted in order to help establish rigorous upscaling approaches that could be tested at the tracer test and plume scales.

  3. Study of sorption-retarded U(VI) diffusion in Hanford silt/clay material.

    PubMed

    Bai, Jing; Liu, Chongxuan; Ball, William P

    2009-10-15

    A diffusion cell method was applied to measure the effective pore diffusion coefficient (Dp) for U(VI) under strictly controlled chemical conditions in a silt/clay sediment from the U.S. Department of Energy Hanford site, WA. "Inward-flux" diffusion studies were conducted in which [U(VI)] in both aqueous and solid phases was measured as a function of distance in the diffusion cell under conditions of constant concentration at the cell boundaries. A sequential extraction method was developed to measure sorbed contaminant U(VI) in the solid phase containing extractable background U(VI). The effect of sorption kinetics on U(VI) interparticle diffusion was evaluated by comparing sorption-retarded diffusion models with sorption described either as equilibrium or intraparticle diffusion-limited processes. Both experimental and modeling results indicated that (1) a single pore diffusion coefficient can simulate the diffusion of total aqueous U(VI), and (2) the local equilibrium assumption (LEA) is appropriate for modeling sorption-retarded diffusion under the given experimental conditions. Dp of 1.6-1.7 x 10(-6) cm2/s was estimated in aqueous solution at pH 8.0 and saturated with respect to calcite, as relevant to some subsurface regions of the Hanford site. PMID:19921882

  4. Appetite suppression and weight reduction by a centrally active aminosterol.

    PubMed

    Ahima, Rexford S; Patel, Hiralben R; Takahashi, Nobuhiko; Qi, Yong; Hileman, Stanley M; Zasloff, Michael A

    2002-07-01

    The rise in obesity and its complications has generated enormous interest in the regulation of feeding and body weight. We show that a spermine metabolite of cholesterol (MSI-1436) decreases body weight, specifically fat, by suppressing feeding and preventing the reduction in energy expenditure, hormonal changes, and patterns of neuropeptide expression normally associated with weight loss. MSI-1436 enters the brain after peripheral injection and is more potent when injected into the cerebral ventricle (intracerebroventricular [ICV]). Systemic or ICV MSI-1436 administration induced similar patterns of Fos immunoreactivity in the brain, especially the paraventricular hypothalamic nucleus (PVN). This brain region integrates neural signals from hypothalamic and brain stem nuclei and regulates feeding behavior, autonomic function, and neuroendocrine function. Microinjection of MSI-1436 into the PVN potently suppressed feeding and reduced body weight for several days. Unlike caloric restriction, MSI-1436 decreased mRNA levels of agouti-related peptide and neuropeptide Y in the hypothalamus. These findings indicate that MSI-1436 acts in the brain to regulate food intake and energy expenditure, likely through suppression of orexigenic hypothalamic pathways. PMID:12086938

  5. Substantial Humic Acid Adsorption to Activated Carbon Air Cathodes Produces a Small Reduction in Catalytic Activity.

    PubMed

    Yang, Wulin; Watson, Valerie J; Logan, Bruce E

    2016-08-16

    Long-term operation of microbial fuel cells (MFCs) can result in substantial degradation of activated carbon (AC) air-cathode performance. To examine a possible role in fouling from organic matter in water, cathodes were exposed to high concentrations of humic acids (HA). Cathodes treated with 100 mg L(-1) HA exhibited no significant change in performance. Exposure to 1000 mg L(-1) HA decreased the maximum power density by 14% (from 1310 ± 30 mW m(-2) to 1130 ± 30 mW m(-2)). Pore blocking was the main mechanism as the total surface area of the AC decreased by 12%. Minimization of external mass transfer resistances using a rotating disk electrode exhibited only a 5% reduction in current, indicating about half the impact of HA adsorption was associated with external mass transfer resistance and the remainder was due to internal resistances. Rinsing the cathodes with deionized water did not restore cathode performance. These results demonstrated that HA could contribute to cathode fouling, but the extent of power reduction was relatively small in comparison to large mass of humics adsorbed. Other factors, such as biopolymer attachment, or salt precipitation, are therefore likely more important contributors to long-term fouling of MFC cathodes. PMID:27414751

  6. Identification of proteins capable of metal reduction from the proteome of the Gram-positive bacterium Desulfotomaculum reducens MI-1 using an NADH-based activity assay

    SciTech Connect

    Otwell, Annie E.; Sherwood, Roberts; Zhang, Sheng; Nelson, Ornella D.; Li, Zhi; Lin, Hening; Callister, Stephen J.; Richardson, Ruth E.

    2015-01-01

    Metal reduction capability has been found in numerous species of environmentally abundant Gram-positive bacteria. However, understanding of microbial metal reduction is based almost solely on studies of Gram-negative organisms. In this study, we focus on Desulfotomaculum reducens MI-1, a Gram-positive metal reducer whose genome lacks genes with similarity to any characterized metal reductase. D. reducens has been shown to reduce not only Fe(III), but also the environmentally important contaminants U(VI) and Cr(VI). By extracting, separating, and analyzing the functional proteome of D. reducens, using a ferrozine-based assay in order to screen for chelated Fe(III)-NTA reduction with NADH as electron donor, we have identified proteins not previously characterized as iron reductases. Their function was confirmed by heterologous expression in E. coli. These are the protein NADH:flavin oxidoreductase (Dred_2421) and a protein complex composed of oxidoreductase FAD/NAD(P)-binding subunit (Dred_1685) and dihydroorotate dehydrogenase 1B (Dred_1686). Dred_2421 was identified in the soluble proteome and is predicted to be a cytoplasmic protein. Dred_1685 and Dred_1686 were identified in both the soluble as well as the insoluble (presumably membrane) protein fraction, suggesting a type of membrane-association, although PSORTb predicts both proteins are cytoplasmic. Furthermore, we show that these proteins have the capability to reduce soluble Cr(VI) and U(VI) with NADH as electron donor. This study is the first functional proteomic analysis of D. reducens, and one of the first analyses of metal and radionuclide reduction in an environmentally relevant Gram-positive bacterium.

  7. Aerosol properties in Titan's upper atmosphere from UVIS airglow observations

    NASA Astrophysics Data System (ADS)

    Lavvas, Panayotis; Koskinen, Tommi; Royer, Emilie; Rannou, Pascal; West, Robert A.

    2015-11-01

    Multiple Cassini observations reveal that the abundant aerosol particles in Titan's atmosphere are formed at high altitudes, particularly in the thermosphere [1]. They subsequently fall towards the lower atmosphere, and in their path, their size, shape, and population change in reflection to the variable atmospheric conditions.Although multiple observations can help us retrieve information for the aerosol properties in the lower atmosphere [2], we have limited knowledge for their properties in the altitude range between their formation region in the thermosphere, and the upper region of the main haze layer. UVIS is one of a few instruments that can probe this part of the atmosphere and allow for the retrieval of the aerosol properties.Here we analyze observations of atmospheric airglow that demonstrate the signature of N2 emissions and light scattering from aerosol particles, at different altitudes above 500 km [3]. We fit these observations with a combined model of N2 airglow [4] and atmospheric scattering by gases and aerosols that allows us to separate the pure scattering component and retrieve the aerosol size (distribution) and density. We particularly focus on observations from the T32 flyby that probed high southern latitudes in 2007 and combine good altitude resolution with high signal to noise ratio. We combine these with observations at different phase angles and observing geometry conditions (nadir vs. limb) in order to set better constraints on the aerosol properties.Our preliminary results demonstrate an increase in the average particle size with decreasing altitude in the atmosphere, from about 10 nm at 800 km to ~50 nm at 500 km, and an extinction profile at 185 nm wavelength, similar to the profile derive from UVIS occultation measurements at lower latitudes [5].[1] Lavvas et al. 2013. PNAS, doi/10.1073/pnas.1217059110, and references therein.[2] Tomasko et al. 2008, PSS, 56, p.669; Bellucci et al. 2009, Icarus 201, p.198[3] Ajello et al. 2008, GRL

  8. Uranium(VI) reduction and removal by high performing purified anaerobic cultures from mine soil.

    PubMed

    Chabalala, Simphiwe; Chirwa, Evans M N

    2010-01-01

    Biological uranium reduction was investigated using bacteria isolated from a uranium mine in Limpopo, South Africa. Background uranium concentration in soil from the mine was determined to be 168 mgkg(-1) much higher than the typical background uranium concentration in natural soils (0.30-11.7 mgkg(-1)). Therefore it was expected that the bacteria isolated from the site were resistant to U(VI) toxicity. Preliminary studies using a non-purified consortium from the mine soil showed that U(VI) [uranyl(VI) dioxide, UO(2)(2+)] was reduced and re-oxidized intermittently due to the coexistence of U(VI) reducers and U(VI) oxidisers in the soil. Results from U(VI) reduction by individual species showed that the purified cultures of Pantoea sp., Pseudomonas sp. and Enterobacter sp. reduced U(VI) to U(IV) [U(OH)(4)(aq)] under pH 5-6. Klebsiella sp. had to be eliminated from the cultures since these contributed to the remobilisation of uranium to the hexavelant form. The initial reduction rate determined at 50% point in 30 mgL(-1) batches was highest in Pseudomonas sp. at 30 mgL(-1), followed by Pantoea sp. Rapid reduction was observed in all cultures during the first 6h of incubation with equilibrium conditions obtained only after incubation for 24h. Complete U(VI) reduction was observed at concentrations as high as 200mgL(-1) and up to 88% removal after 24h in batches with an initial added U(VI) concentration of 400 mgL(-1). PMID:19883933

  9. Actively Controlled Landing Gear for Aircraft Vibration Reduction

    NASA Technical Reports Server (NTRS)

    Horta, Lucas G.; Daugherty, Robert H.; Martinson, Veloria J.

    1999-01-01

    Concepts for long-range air travel are characterized by airframe designs with long, slender, relatively flexible fuselages. One aspect often overlooked is ground induced vibration of these aircraft. This paper presents an analytical and experimental study of reducing ground-induced aircraft vibration loads using actively controlled landing gears. A facility has been developed to test various active landing gear control concepts and their performance. The facility uses a NAVY A6-intruder landing gear fitted with an auxiliary hydraulic supply electronically controlled by servo valves. An analytical model of the gear is presented including modifications to actuate the gear externally and test data is used to validate the model. The control design is described and closed-loop test and analysis comparisons are presented.

  10. Reductions in Northeast Refining Activity: Potential Implications for Petroleum Product Markets

    EIA Publications

    2011-01-01

    This report is the Energy Information Administration's (EIA) initial effort to provide information and analysis on the potential impacts on petroleum product markets from reductions in Northeast petroleum refining activity.

  11. Quantitative toxicoproteomic analysis of zebrafish embryos exposed to a retinoid X receptor antagonist UVI3003.

    PubMed

    Zheng, Liang; Yu, Jianlan; Shi, Huahong; Xia, Liang; Xin, Qi; Zhang, Qiang; Zhao, Heng; Luo, Ji; Jin, Wenhai; Li, Daoji; Zhou, Junliang

    2015-09-01

    Retinoid X receptor (RXR) antagonists, including some environmental endocrine disruptors, have a teratogenic effect on vertebrate embryos. To investigate the toxicological mechanism on the protein expression level, a quantitative proteomic study was conducted to analyze the proteome alterations of zebrafish (Danio rerio) embryos exposed to gradient concentrations of a representative RXR antagonist UVI3003. Using isobaric Tags for Relative and Absolute Quantitation (iTRAQ) labeling coupled nano high-performance liquid chromatography-tandem mass spectrometry (nano HPLC-MS/MS), in total 6592 proteins were identified, among which 195 proteins were found to be differentially expressed by more than a two-fold change in exposed groups compared with the control. Gene ontology analysis showed that these differential proteins were mostly involved in anatomical structure development, biosynthetic process, ion binding and oxidoreductase activity. Moreover, the biological pathways of translation, lipoprotein metabolism, cell survival and gluconeogenesis were intensively inhibited after exposure. Some significantly downregulated proteins such as apolipoprotein A-I and vitellogenin and upregulated proteins such as calcium activated nucleotidase 1b, glutathione S-transferase and glucose 6-dehydrogenases showed a strong dose-dependent response. The results provided new insight into the molecular details of RXR antagonist-induced teratogenicity and added novel information of pathways and potential biomarkers for evaluation of RXR interfering activity. PMID:25581642

  12. Real-Time Active Cosmic Neutron Background Reduction Methods

    SciTech Connect

    Mukhopadhyay, Sanjoy; Maurer, Richard; Wolff, Ronald; Mitchell, Stephen; Guss, Paul

    2013-09-01

    Neutron counting using large arrays of pressurized 3He proportional counters from an aerial system or in a maritime environment suffers from the background counts from the primary cosmic neutrons and secondary neutrons caused by cosmic ray-induced mechanisms like spallation and charge-exchange reaction. This paper reports the work performed at the Remote Sensing Laboratory–Andrews (RSL-A) and results obtained when using two different methods to reduce the cosmic neutron background in real time. Both methods used shielding materials with a high concentration (up to 30% by weight) of neutron-absorbing materials, such as natural boron, to remove the low-energy neutron flux from the cosmic background as the first step of the background reduction process. Our first method was to design, prototype, and test an up-looking plastic scintillator (BC-400, manufactured by Saint Gobain Corporation) to tag the cosmic neutrons and then create a logic pulse of a fixed time duration (~120 μs) to block the data taken by the neutron counter (pressurized 3He tubes running in a proportional counter mode). The second method examined the time correlation between the arrival of two successive neutron signals to the counting array and calculated the excess of variance (Feynman variance Y2F)1 in the neutron count distribution from Poisson distribution. The dilution of this variance from cosmic background values ideally would signal the presence of man-made neutrons.2 The first method has been technically successful in tagging the neutrons in the cosmic-ray flux and preventing them from being counted in the 3He tube array by electronic veto—field measurement work shows the efficiency of the electronic veto counter to be about 87%. The second method has successfully derived an empirical relationship between the percentile non-cosmic component in a neutron flux and the Y2F of the measured neutron count distribution. By using shielding materials alone, approximately 55% of the neutron flux

  13. Real-time active cosmic neutron background reduction methods

    NASA Astrophysics Data System (ADS)

    Mukhopadhyay, Sanjoy; Maurer, Richard; Wolff, Ronald; Mitchell, Stephen; Guss, Paul

    2013-09-01

    Neutron counting using large arrays of pressurized 3He proportional counters from an aerial system or in a maritime environment suffers from the background counts from the primary cosmic neutrons and secondary neutrons caused by cosmic ray‒induced mechanisms like spallation and charge-exchange reaction. This paper reports the work performed at the Remote Sensing Laboratory-Andrews (RSL-A) and results obtained when using two different methods to reduce the cosmic neutron background in real time. Both methods used shielding materials with a high concentration (up to 30% by weight) of neutron-absorbing materials, such as natural boron, to remove the lowenergy neutron flux from the cosmic background as the first step of the background reduction process. Our first method was to design, prototype, and test an up-looking plastic scintillator (BC-400, manufactured by Saint Gobain Corporation) to tag the cosmic neutrons and then create a logic pulse of a fixed time duration (~120 μs) to block the data taken by the neutron counter (pressurized 3He tubes running in a proportional counter mode). The second method examined the time correlation between the arrival of two successive neutron signals to the counting array and calculated the excess of variance (Feynman variance Y2F)1 in the neutron count distribution from Poisson distribution. The dilution of this variance from cosmic background values ideally would signal the presence of manmade neutrons.2 The first method has been technically successful in tagging the neutrons in the cosmic-ray flux and preventing them from being counted in the 3He tube array by electronic veto—field measurement work shows the efficiency of the electronic veto counter to be about 87%. The second method has successfully derived an empirical relationship between the percentile non-cosmic component in a neutron flux and the Y2F of the measured neutron count distribution. By using shielding materials alone, approximately 55% of the neutron flux

  14. The Host Galaxies of LoBAL QSOs at Low z: A Perspective from HST UVIS Images

    NASA Astrophysics Data System (ADS)

    Behn, Wyatt Alan; Lazarova, Mariana; Canalizo, Gabriela

    2016-06-01

    We present GALFIT models of a complete optically-selected volume-limited sample of Low-Ionization Broad Absorption Line QSOs (LoBALs) in the redshift range 0.5-0.6 observed with HST WFC3 UVIS F475W. We investigate the morphologies in the rest frame u which map the younger stellar populations. In addition, we present statistics on the number of neighborhood galaxies within 150 kpc and possible trends between clustering and host galaxy properties. This sample of LoBALs is selected from QSOs characterized by their extreme blue-shifted absorption in the Mg II line—which is a signature of high velocity winds towards the observer. Only ~1-3% of optically selected QSOs are LoBALs. Their low fraction could be explained by their orientation or by a short period of outflow manifest in all QSOs during their lifetime. We aim to better understand the possibility of the evolutionary model by studying their morphologies in detail. Previous work on this sample, from images with F125W filter (rest frame i), shows that at least 60% of these objects exhibit signs of recent merger activity. We complement those results with our results from the UVIS observations and neighborhood clustering statistics.

  15. ACTINIC MASK INSPECTION AT THE ALS: RISK REDUCTION ACTIVITIES FOR 2003

    SciTech Connect

    Barty, A; Levesque, R; Ayers, J; Liu, Y; Gullikson, E; Barale, P

    2004-01-05

    This document reports on risk reduction activities performed at the VNL during CY2003 as a part of the Lith-343 actinic inspection project funded by International SEMATECH. The risk reduction activities described in this document comprise deliverable items 3.1.3, 3.1.4, 3.1.5 and 3.1.6 of Amendment 6 to the VNL EUV mask blank technology transfer contract.

  16. Potential Impacts of Reductions in Refinery Activity on Northeast Petroleum Product Markets

    EIA Publications

    2012-01-01

    Potential Impacts of Reductions in Refinery Activity on Northeast Petroleum Product Markets is an update to a previous Energy Information Administration (EIA) report, Reductions in Northeast Refining Activity: Potential Implications for Petroleum Product Markets, released in December 2011. This update analyzes possible market responses and impacts in the event Sunoco's Philadelphia refinery closes this summer, in addition to the recently idled refineries on the East Coast and in the U.S. Virgin Islands.

  17. Development of High Activity, Coal-Derived, Promoted Catalytic Systems for NOx Reduction at Low Temperatures

    SciTech Connect

    J. M. Calo

    1998-05-01

    This project is directed at an investigation of catalytic NO{sub x} reduction mechanisms on coal-derived, activated carbon supports at low temperatures. Promoted carbon systems offer some potentially significant advantages for heterogeneous NO{sub x} reduction. These include: low cost; high activity at low temperatures, which minimizes carbon loss; oxygen resistance; and a support material which can be engineered with respect to porosity, transport and catalyst dispersion characteristics.

  18. Reductant and sequence effects on the morphology and catalytic activity of peptide-capped Au nanoparticles.

    PubMed

    Briggs, Beverly D; Li, Yue; Swihart, Mark T; Knecht, Marc R

    2015-04-29

    The use of peptides as capping ligands for materials synthesis has been widely explored. The ambient conditions of bio-inspired syntheses using molecules such as peptides represent an attractive route for controlling the morphology and activity of nanomaterials. Although various reductants can be used in such syntheses, no comprehensive comparison of the same bio-based ligand with different reductants has been reported. In this contribution, peptides AuBP1, AuBP2, and Pd4 are used in the synthesis of Au nanoparticles. The reductant strength is varied by using three different reducing agents: NaBH4, hydrazine, and ascorbic acid. These changes in reductant produce significant morphological differences in the final particles. The weakest reductant, ascorbic acid, yields large, globular nanoparticles with rough surfaces, whereas the strongest reductant, NaBH4, yields small, spherical, smooth nanomaterials. Studies of 4-nitrophenol reduction using the Au nanoparticles as catalysts reveal a decrease in activation energy for the large, globular, rough materials relative to the small, spherical, smooth materials. These studies demonstrate that modifying the reductant is a simple way to control the activity of peptide-capped nanoparticles. PMID:25839335

  19. Revealing the Origin of Activity in Nitrogen-Doped Nanocarbons towards Electrocatalytic Reduction of Carbon Dioxide.

    PubMed

    Xu, Junyuan; Kan, Yuhe; Huang, Rui; Zhang, Bingsen; Wang, Bolun; Wu, Kuang-Hsu; Lin, Yangming; Sun, Xiaoyan; Li, Qingfeng; Centi, Gabriele; Su, Dangsheng

    2016-05-23

    Carbon nanotubes (CNTs) are functionalized with nitrogen atoms for reduction of carbon dioxide (CO2 ). The investigation explores the origin of the catalyst's activity and the role of nitrogen chemical states therein. The catalysts show excellent performances, with about 90 % current efficiency for CO formation and stability over 60 hours. The Tafel analyses and density functional theory calculations suggest that the reduction of CO2 proceeds through an initial rate-determining transfer of one electron to CO2 , which leads to the formation of carbon dioxide radical anion (CO2 (.-) ). The initial reduction barrier is too high on pristine CNTs, resulting in a very high overpotentials at which the hydrogen evolution reaction dominates over CO2 reduction. The doped nitrogen atoms stabilize the radical anion, thereby lowering the initial reduction barrier and improving the intrinsic activity. The most efficient nitrogen chemical state for this reaction is quaternary nitrogen, followed by pyridinic and pyrrolic nitrogen. PMID:27100272

  20. Characterization of the holographic imaging grating of GOMOS UVIS spectrometer

    NASA Astrophysics Data System (ADS)

    Graeffe, Jussi; Saari, Heikki K.; Astola, Heikki; Rainio, Kari; Mazuray, Lorand; Pierot, Dominique; Craen, Pierre; Gruslin, Michel; Lecat, Jean-Herve; Bonnemason, Francis; Flamand, Jean; Thevenon, Alain

    1996-11-01

    A Finnish-French group has proposed an imaging spectrometer- based instrument for the ENVISAT Earth observation satellite of ESA, which yields a global mapping of the vertical profile of ozone and other related atmospheric gases. The GOMOS instrument works by measuring the UV-visible spectrum of a star that is occulting behind the Earth's atmosphere. The prime contractor of GOMOS is Matra Marconi Space France. The focal plane optics are designed and manufactured by Spacebel Instrumentation S.A. and the holographic grating by Jobin-Yvon. VTT Automation, Measurement Technology has participated in the GOMOS studies since 1989 and is presently responsible for the verification tests of the imaging quality and opto-mechanical interfaces of the holographic imaging grating of GOMOS. The UVIS spectrometer of GOMOS consists of a holographic, aberration corrected grating and of a CCD detector. The alignment of the holographic grating needs as an input very accurate knowledge of the mechanical interfaces. VTT Automation has designed, built and tested a characterization system for the holographic grating. This system combines the accurate optical imaging measurements with the absolute knowledge of the geometrical parameters at the accuracy of plus or minus 10 micrometers which makes the system unique. The developed system has been used for two breadboard gratings and the qualification model grating. The imaging quality results and their analysis together with alignment procedure utilizing of the knowledge of mechanical interfaces is described.

  1. Global Auroral Energy Deposition Derived from Polar UVI Images

    NASA Technical Reports Server (NTRS)

    Fillingim, M. O.; Brittnacher, M. J.; Elsen, R.; Parks, G. K.; Spann, J. F., Jr.; Germany, G. A.

    1997-01-01

    Quantitative measurement of the transfer of energy and momentum to the ionosphere from the solar wind is one of the main objectives of the ISTP program. Global measurement of auroral energy deposition derived from observations of the longer wavelength LBH band emissions made by the Ultraviolet Imager on the Polar spacecraft is one of the key elements in this satellite and ground-based instrument campaign. These "measurements" are inferred by combining information from consecutive images using different filters and have a time resolution on the average of three minutes and are made continuously over a 5 to 8 hour period during each 18 hour orbit of the Polar spacecraft. The energy deposition in the ionosphere from auroral electron precipitation augments are due to Joule heating associated with field aligned currents. Assuming conjugacy of energy deposition between the two hemispheres the total energy input to the ionosphere through electron precipitation can be determined at high time resolution. Previously, precipitating particle measurements along the tracks of low altitude satellites provided only local measurements and the global energy precipitation could be inferred through models but not directly measured. We use the UVI images for the entire month of January 1997 to estimate the global energy deposition at high time resolution. We also sort the energy deposition into sectors to find possible trends, for example, on the dayside and nightside, or the dawn and dusk sides.

  2. Acceleration of Field-Scale Bioreduction of U(VI) in a Shallow Alluvial Aquifer: Temporal and Spatial Evolution of Biogeochemistry

    SciTech Connect

    Long, Phil

    2005-04-20

    Uranium mill tailings sites provide access to uranium-contaminated groundwater at sites that are shallow and low hazard, making it possible to address the following scientific objectives: (1) Determine the dominant electron accepting processes at field sites with long-term metal/rad contamination; (2) Define the biogeochemical transformations that may be important to either natural or accelerated bioremediation under field conditions; and (3) Examine the potential for using biostimulation (electron donor addition) to accelerate reduction of U(VI) to U(IV) at the field scale.

  3. RFI Risk Reduction Activities Using New Goddard Digital Radiometry Capabilities

    NASA Technical Reports Server (NTRS)

    Bradley, Damon; Kim, Ed; Young, Peter; Miles, Lynn; Wong, Mark; Morris, Joel

    2012-01-01

    The Goddard Radio-Frequency Explorer (GREX) is the latest fast-sampling radiometer digital back-end processor that will be used for radiometry and radio-frequency interference (RFI) surveying at Goddard Space Flight Center. The system is compact and deployable, with a mass of about 40 kilograms. It is intended to be flown on aircraft. GREX is compatible with almost any aircraft, including P-3, twin otter, C-23, C-130, G3, and G5 types. At a minimum, the system can function as a clone of the Soil Moisture Active Passive (SMAP) ground-based development unit [1], or can be a completely independent system that is interfaced to any radiometer, provided that frequency shifting to GREX's intermediate frequency is performed prior to sampling. If the radiometer RF is less than 200MHz, then the band can be sampled and acquired directly by the system. A key feature of GREX is its ability to simultaneously sample two polarization channels simultaneously at up to 400MSPS, 14-bit resolution each. The sampled signals can be recorded continuously to a 23 TB solid-state RAID storage array. Data captures can be analyzed offline using the supercomputing facilities at Goddard Space Flight Center. In addition, various Field Programmable Gate Array (FPGA) - amenable radiometer signal processing and RFI detection algorithms can be implemented directly on the GREX system because it includes a high-capacity Xilinx Virtex-5 FPGA prototyping system that is user customizable.

  4. Macroscopic and Microscopic Investigation of U(VI) and Eu(III) Adsorption on Carbonaceous Nanofibers.

    PubMed

    Sun, Yubing; Wu, Zhen-Yu; Wang, Xiangxue; Ding, Congcong; Cheng, Wencai; Yu, Shu-Hong; Wang, Xiangke

    2016-04-19

    The adsorption mechanism of U(VI) and Eu(III) on carbonaceous nanofibers (CNFs) was investigated using batch, IR, XPS, XANES, and EXAFS techniques. The pH-dependent adsorption indicated that the adsorption of U(VI) on the CNFs was significantly higher than the adsorption of Eu(III) at pH < 7.0. The maximum adsorption capacity of the CNFs calculated from the Langmuir model at pH 4.5 and 298 K for U(VI) and Eu(III) were 125 and 91 mg/g, respectively. The CNFs displayed good recyclability and recoverability by regeneration experiments. Based on XPS and XANES analyses, the enrichment of U(VI) and Eu(III) was attributed to the abundant adsorption sites (e.g., -OH and -COOH groups) of the CNFs. IR analysis further demonstrated that -COOH groups were more responsible for U(VI) adsorption. In addition, the remarkable reducing agents of the R-CH2OH groups were responsible for the highly efficient adsorption of U(VI) on the CNFs. The adsorption mechanism of U(VI) on the CNFs at pH 4.5 was shifted from inner- to outer-sphere surface complexation with increasing initial concentration, whereas the surface (co)precipitate (i.e., schoepite) was observed at pH 7.0 by EXAFS spectra. The findings presented herein play an important role in the removal of radionuclides on inexpensive and available carbon-based nanoparticles in environmental cleanup applications. PMID:26998856

  5. Characterization of Hydrogenase and Reductive Dehalogenase Activities of Dehalococcoides ethenogenes Strain 195

    PubMed Central

    Nijenhuis, Ivonne; Zinder, Stephen H.

    2005-01-01

    Dehalococcoides ethenogenes strain 195 reductively dechlorinates tetrachloroethene (PCE) and trichloroethene (TCE) to vinyl chloride and ethene using H2 as an electron donor. PCE- and TCE-reductive dehalogenase (RD) activities were mainly membrane associated, whereas only about 20% of the hydrogenase activity was membrane associated. Experiments with methyl viologen (MV) were consistent with a periplasmic location for the RDs or a component feeding electrons to them. The protonophore uncoupler tetrachlorosalicylanilide did not inhibit reductive dechlorination in cells incubated with H2 and PCE and partially restored activity in cells incubated with the ATPase inhibitor N,N′-dicyclohexylcarbodiimide. Benzyl viologen or diquat (Eo′ ≈ −360 mV) supported reductive dechlorination of PCE or TCE at rates comparable to MV (−450 mV) in cell extracts. PMID:15746376

  6. Sulfur Isotopes as Indicators of Bacterial Sulfate Reduction Processes Influencing Field Scale Uranium Bioremediation

    NASA Astrophysics Data System (ADS)

    Druhan, J. L.; Conrad, M. E.; Williams, K. H.; N'guessan, L.; Long, P. E.; Hubbard, S. S.

    2007-12-01

    An in-situ acetate amendment at a DOE Uranium Mill Tailings Remedial Action (UMTRA) site near Rifle, CO demonstrated successful reduction of aqueous U(VI), to less soluble U(IV) through stimulated microbial activity. U(VI) reduction rates were highest during iron reduction and decreased with the onset of sulfate reduction. However, sustained U(IV) attenuation was observed following subsequent termination of the acetate amendment. These findings illustrate the importance of the transition between iron and sulfate reducing conditions in stimulating bioreduction of uranium. The sulfur isotope compositions of sulfate and sulfide were measured through this transition in order to explore the utility of these data in tracking the extent of microbial sulfate reduction and to assess the stability of sulfide precipitates. Samples for isotopic analyses and aqueous measurements of sulfate, ferrous iron, U(VI) and acetate were collected in one background well and three monitoring wells down-gradient of the acetate injection. Results show an increase of up to 7‰ in the δ34S of sulfate at the onset of sulfate reduction, followed by a return to background δ34S values of -8‰ following cessation of the acetate amendment. The δ34S values of sulfide increased from roughly -20‰ at the onset of sulfate reduction to a maximum of -0.8‰ during peak sulfate removal, followed by a gradual return to values of roughly -28‰ upon cessation of the acetate amendment. These data present a unique perspective on the processes governing the bioreduction experiment in that the sulfate isotopes are a function of both transport and mixing processes, whereas the sulfide isotopes represent biogenic sulfide that is rapidly removed from the aqueous phase. Thus a comparable enrichment in sulfate isotopic data noted in the closest and furthest wells from the injection gallery suggest bioreduction in both of these locations, while a larger increase in sulfide isotopic values in the closest well

  7. U(VI) Adsorption on Aquifer Sediments at the Hanford Site

    SciTech Connect

    Um, Wooyong; Serne, R. Jeffrey; Brown, Christopher F.; Last, George V.

    2007-08-15

    Aquifer core samples collected in three new groundwater wells in the 200-UP-1 operable unit at the Hanford Site were characterized and showed typical Ringold Formation Unit E dominated by gravel and sand. High iron-oxide content in iron (Fe) oxide/clay coatings caused the highest U(VI) adsorption as quantified by Kd values, indicating these hydrous iron oxides are the key solid adsorbent in the 200-UP-1 sediments that affect U(VI) fate and mobility. In batch adsorption tests with varying total U(VI) concentrations in spiked groundwater, a linear isotherm up to 1 ppm of total U(VI) concentration was observed. However, U(VI) adsorption decreased with increasing concentrations of dissolved carbonate, because strong anionic aqueous uranium-carbonate complexes formed at elevated pH and high carbonate conditions. A small amount of uranium desorption hysteresis was observed in a flow-through column experiment, suggesting that desorption Kd values for aged uranium-contaminated sediments at the Hanford Site can be larger than Kd values determined in short-term laboratory experiments and slow uranium release into the groundwater is expected.

  8. Bioreduction of U(VI) and stability of immobilized uranium under suboxic conditions.

    PubMed

    Hu, Nan; Ding, De-xin; Li, Shi-mi; Tan, Xiang; Li, Guang-yue; Wang, Yong-dong; Xu, Fei

    2016-04-01

    In order to study the bioreduction of U(VI) and stability of immobilized uranium under suboxic conditions, microcosm were amended with ethanol, lactate and glucose, and incubated under suboxic conditions. During the incubation, total dissolved U in amended microcosms decreased from 0.95 mg/L to 0.03 mg/L. Pyrosequencing results showed that, the proportion of anaerobic microorganisms capable of reducing U(VI) under suboxic conditions was small compared with that under anoxic conditions; the proportion of aerobic and facultative anaerobic microorganisms capable of consuming the dissolved oxygen was large; and some of the facultative anaerobic microorganisms could reduce U(VI). These results indicated that different microbial communities were responsible for the bioreduction of U(VI) under suboxic and anoxic conditions. After the electron donors were exhausted, total dissolved U in the amended microcosms remained unchanged, while the U(VI)/U(IV) ratio in the solid phase of sediments increased obviously. This implied that the performance of bioreduction of the U(VI) can be maintained under suboxic condition. PMID:26854555

  9. U(VI) Sequestration in Hydroxyapatite Produced by Microbial Glycerol 3-Phosphate Metabolism▿ †

    PubMed Central

    Shelobolina, Evgenya S.; Konishi, Hiromi; Xu, Huifang; Roden, Eric E.

    2009-01-01

    Previous studies have demonstrated the potential for removal of U(VI) from solution via precipitation of U(VI)-bearing calcium-phosphate (Ca-P) minerals coupled to microbial hydrolysis of glycerol phosphate compounds. We evaluated this process in circumneutral-pH groundwater from Area 2 of the U.S. Department of Energy Field Research Center at Oak Ridge National Laboratory. Area 2 groundwater contains high concentrations of dissolved calcium (ca. 4 mM), and thus, release of phosphate during glycerol phosphate metabolism has the potential to create conditions favorable for U(VI) sequestration in Ca-P minerals. Microbial enumeration and isolation studies verified the presence of aerobic and nitrate-reducing glycerol 3-phosphate (G3P)-metabolizing microorganisms in Area 2 sediments. Coprecipitation of U(VI) with Ca-P minerals coupled to microbial G3P hydrolysis was demonstrated in artificial groundwater under aerobic and nitrate-reducing conditions. Transmission electron microscopy analysis and mineral-washing experiments demonstrated that U(VI) was incorporated into the structure of the insoluble Ca-P mineral hydroxyapatite [Ca5(PO4)3OH]. Our results support the idea that U(VI) can be effectively removed from solution in contaminated aquifers through stimulation of microbial organophosphate metabolism. PMID:19633115

  10. High performance of phosphonate-functionalized mesoporous silica for U(VI) sorption from aqueous solution.

    PubMed

    Yuan, Li-Yong; Liu, Ya-Lan; Shi, Wei-Qun; Lv, Yu-Long; Lan, Jian-Hui; Zhao, Yu-Liang; Chai, Zhi-Fang

    2011-07-28

    The renaissance of nuclear energy promotes increasing basic research on the separation and enrichment of nuclear fuel associated radionuclides. Herein, we report the first study for developing mesoporous silica functionalized with phosphonate (NP10) as a sorbent for U(VI) sorption from aqueous solution. The mesoporous silica was synthesized by co-condensation of diethylphosphatoethyltriethoxysilane (DPTS) and tetraethoxysilane (TEOS), using cationic surfactant cetyltrimethylammonium bromide (CTAB) as the template. The synthesized silica nanoparticles were observed to possess a mesoporous structure with a uniform pore diameter of 2.7 nm, and to have good stability and high efficiency for U(VI) sorption from aqueous solution. A maximum sorption capacity of 303 mg g(-1) and fast equilibrium time of 30 min were achieved under near neutral conditions at room temperature. The adsorbed U(VI) can be easily desorbed by using 0.1 mol L(-1) HNO(3), and the reclaimed mesoporous silica can be reused with no decrease of sorption capacity. In addition, the preconcentration of U(VI) from a 100 mL aqueous solution using the functionalized mesoporous silica was also studied. The preconcentration factor was found to be as high as 100, suggesting the vast opportunities of this kind of mesoporous silica for the solid-phase extraction and enrichment of U(VI). PMID:21681327

  11. Determining Individual Mineral Contributions To U(VI) Adsorption In A Contaminated Aquifer Sediment: A Fluorescence Spectroscopy Study

    SciTech Connect

    Wang, Zheming; Zachara, John M.; Boily, Jean F.; Xia, Yuanxian; Resch, Charles T.; Moore, Dean A.; Liu, Chongxuan

    2011-05-15

    The adsorption and speciation of U(VI) was investigated on contaminated, fine grained sediment materials from the Hanford 300 area (SPP1 GWF) in simulated groundwater using cryogenic laser-induced U(VI) fluorescence spectroscopy combined with chemometric analysis. A series of reference minerals (montmorillonite, illite, Michigan chlorite, North Carolina chlorite, California clinochlore, quartz and synthetic 6-line ferrihydrite) was used for comparison that represents the mineralogical constituents of SPP1 GWF. Surface area-normalized Kd values were measured at U(VI) concentrations of 5x10-7 mol L-1 and 5x10-6 mol L-1, respectively, that displayed the following affinity series: 6-line-ferrihydrite > North Carolina chlorite ≈ California clinochlore > Michigan chlorite ≈ quartz > montmorillonite ≈ illite ≈ SPP1 GWF. Both time-resolved spectra and asynchronous two-dimensional (2D) correlation analysis of SPP1 GWF at different delay times indicated that two major adsorbed U(VI) species were present in the sediment that resembled U(VI) adsorbed on quartz and phyllosilicates. Simulations of the normalized fluorescence spectra confirmed that the speciation of SPP1 GWF was best represented by a linear combination of U(VI) adsorbed on quartz (90%) and phyllosilicates (10%). However, the fluorescence quantum yield for U(VI) adsorbed on phyllosilicates was lower than quartz and, consequently, its fractional contribution to speciation may be underestimated. Spectral comparison with literature data suggested that U(VI) exists primarily as inner-sphere U(VI) complexes with surface silanol groups on quartz while U(VI) on phyllosilicates was consistent with the formation of surface U(VI) tricarbonate complexes.

  12. Active sites for NO reduction over Fe-ZSM-5 catalysts.

    PubMed

    Schwidder, M; Santhosh Kumar, M; Brückner, A; Grünert, W

    2005-02-14

    A study of Fe-ZSM-5 catalysts with variable amounts of isolated, oligomeric and heavily aggregated Fe3+ oxo sites (as evidenced by UV-Vis and EPR spectroscopic data) and their catalytic properties in the selective catalytic reduction of NO by isobutane or by NH3 is presented, which allows development of a unified concept of the active Fe sites in these reactions, according to which isolated Fe sites catalyse both SCR reactions while oligomeric sites, though also involved in the selective reduction path, limit the catalyst performance by causing the total oxidation of the reductant. PMID:15685345

  13. Enantioselective CuH-Catalyzed Reductive Coupling of Aryl Alkenes and Activated Carboxylic Acids.

    PubMed

    Bandar, Jeffrey S; Ascic, Erhad; Buchwald, Stephen L

    2016-05-11

    A new method for the enantioselective reductive coupling of aryl alkenes with activated carboxylic acid derivatives via copper hydride catalysis is described. Dual catalytic cycles are proposed, with a relatively fast enantioselective hydroacylation cycle followed by a slower diastereoselective ketone reduction cycle. Symmetrical aryl carboxyclic anhydrides provide access to enantioenriched α-substituted ketones or alcohols with excellent stereoselectivity and functional group tolerance. PMID:27121395

  14. MOF catalysis of Fe(II)-to-Fe(III) reaction for an ultrafast and one-step generation of the Fe2O3@MOF composite and uranium(vi) reduction by iron(ii) under ambient conditions.

    PubMed

    Xiong, Yang Yang; Li, Jian Qiang; Yan, Chang Sheng; Gao, Heng Ya; Zhou, Jian Ping; Gong, Le Le; Luo, Ming Biao; Zhang, Le; Meng, Pan Pan; Luo, Feng

    2016-08-01

    Herein, we demonstrate that Zn-MOF-74 enables the ultrafast and one-step generation of the Fe2O3@MOF composite once Zn-MOF-74 contacts with FeSO4 solution. This unique reaction can be further applied in catalysis of U(vi) reduction by Fe(ii) under ambient conditions. The results provide a highly renovated strategy for U(vi) reduction by Fe(ii) just under ambient conditions, which completely subvert all established methods about U(vi) reduction by Fe(ii) in which O2- and CO2-free conditions are absolutely required. PMID:27380820

  15. Extracellular reduction of uranium via Geobacter conductive pili as a protective cellular mechanism

    PubMed Central

    Cologgi, Dena L.; Lampa-Pastirk, Sanela; Speers, Allison M.; Kelly, Shelly D.; Reguera, Gemma

    2011-01-01

    The in situ stimulation of Fe(III) oxide reduction by Geobacter bacteria leads to the concomitant precipitation of hexavalent uranium [U(VI)] from groundwater. Despite its promise for the bioremediation of uranium contaminants, the biological mechanism behind this reaction remains elusive. Because Fe(III) oxide reduction requires the expression of Geobacter's conductive pili, we evaluated their contribution to uranium reduction in Geobacter sulfurreducens grown under pili-inducing or noninducing conditions. A pilin-deficient mutant and a genetically complemented strain with reduced outer membrane c-cytochrome content were used as controls. Pili expression significantly enhanced the rate and extent of uranium immobilization per cell and prevented periplasmic mineralization. As a result, pili expression also preserved the vital respiratory activities of the cell envelope and the cell's viability. Uranium preferentially precipitated along the pili and, to a lesser extent, on outer membrane redox-active foci. In contrast, the pilus-defective strains had different degrees of periplasmic mineralization matching well with their outer membrane c-cytochrome content. X-ray absorption spectroscopy analyses demonstrated the extracellular reduction of U(VI) by the pili to mononuclear tetravalent uranium U(IV) complexed by carbon-containing ligands, consistent with a biological reduction. In contrast, the U(IV) in the pilin-deficient mutant cells also required an additional phosphorous ligand, in agreement with the predominantly periplasmic mineralization of uranium observed in this strain. These findings demonstrate a previously unrecognized role for Geobacter conductive pili in the extracellular reduction of uranium, and highlight its essential function as a catalytic and protective cellular mechanism that is of interest for the bioremediation of uranium-contaminated groundwater. PMID:21896750

  16. Key Factors Influencing Rates of Heterotrophic Sulfate Reduction in Active Seafloor Hydrothermal Massive Sulfide Deposits

    PubMed Central

    Frank, Kiana L.; Rogers, Karyn L.; Rogers, Daniel R.; Johnston, David T.; Girguis, Peter R.

    2015-01-01

    Hydrothermal vents are thermally and geochemically dynamic habitats, and the organisms therein are subject to steep gradients in temperature and chemistry. To date, the influence of these environmental dynamics on microbial sulfate reduction has not been well constrained. Here, via multivariate experiments, we evaluate the effects of key environmental variables (temperature, pH, H2S, SO42−, DOC) on sulfate reduction rates and metabolic energy yields in material recovered from a hydrothermal flange from the Grotto edifice in the Main Endeavor Field, Juan de Fuca Ridge. Sulfate reduction was measured in batch reactions across a range of physico-chemical conditions. Temperature and pH were the strongest stimuli, and maximum sulfate reduction rates were observed at 50°C and pH 6, suggesting that the in situ community of sulfate-reducing organisms in Grotto flanges may be most active in a slightly acidic and moderate thermal/chemical regime. At pH 4, sulfate reduction rates increased with sulfide concentrations most likely due to the mitigation of metal toxicity. While substrate concentrations also influenced sulfate reduction rates, energy-rich conditions muted the effect of metabolic energetics on sulfate reduction rates. We posit that variability in sulfate reduction rates reflect the response of the active microbial consortia to environmental constraints on in situ microbial physiology, toxicity, and the type and extent of energy limitation. These experiments help to constrain models of the spatial contribution of heterotrophic sulfate reduction within the complex gradients inherent to seafloor hydrothermal deposits. PMID:26733984

  17. Key Factors Influencing Rates of Heterotrophic Sulfate Reduction in Active Seafloor Hydrothermal Massive Sulfide Deposits.

    PubMed

    Frank, Kiana L; Rogers, Karyn L; Rogers, Daniel R; Johnston, David T; Girguis, Peter R

    2015-01-01

    Hydrothermal vents are thermally and geochemically dynamic habitats, and the organisms therein are subject to steep gradients in temperature and chemistry. To date, the influence of these environmental dynamics on microbial sulfate reduction has not been well constrained. Here, via multivariate experiments, we evaluate the effects of key environmental variables (temperature, pH, H2S, [Formula: see text], DOC) on sulfate reduction rates and metabolic energy yields in material recovered from a hydrothermal flange from the Grotto edifice in the Main Endeavor Field, Juan de Fuca Ridge. Sulfate reduction was measured in batch reactions across a range of physico-chemical conditions. Temperature and pH were the strongest stimuli, and maximum sulfate reduction rates were observed at 50°C and pH 6, suggesting that the in situ community of sulfate-reducing organisms in Grotto flanges may be most active in a slightly acidic and moderate thermal/chemical regime. At pH 4, sulfate reduction rates increased with sulfide concentrations most likely due to the mitigation of metal toxicity. While substrate concentrations also influenced sulfate reduction rates, energy-rich conditions muted the effect of metabolic energetics on sulfate reduction rates. We posit that variability in sulfate reduction rates reflect the response of the active microbial consortia to environmental constraints on in situ microbial physiology, toxicity, and the type and extent of energy limitation. These experiments help to constrain models of the spatial contribution of heterotrophic sulfate reduction within the complex gradients inherent to seafloor hydrothermal deposits. PMID:26733984

  18. Active and stable carbon nanotube/nanoparticle composite electrocatalyst for oxygen reduction

    PubMed Central

    Chung, Hoon T.; Won, Jong H.; Zelenay, Piotr

    2013-01-01

    Nanostructured carbon-based materials, such as nitrogen-doped carbon nanotube arrays, Co3O4/nitrogen-doped graphene hybrids and carbon nanotube–graphene complexes have shown respectable oxygen reduction reaction activity in alkaline media. Although certainly promising, the performance of these materials does not yet warrant implementation in the energy conversion/storage devices utilizing basic electrolytes, for example, alkaline fuel cells, metal-air batteries and certain electrolysers. Here we demonstrate a new type of nitrogen-doped carbon nanotube/nanoparticle composite oxygen reduction reaction electrocatalyst obtained from iron acetate as an iron precursor and from cyanamide as a nitrogen and carbon nanotube precursor in a simple, scalable and single-step method. The composite has the highest oxygen reduction reaction activity in alkaline media of any non-precious metal catalysts. When used at a sufficiently high loading, this catalyst also outperforms the most active platinum-based catalysts. PMID:23715281

  19. A Shape-Based Technique for Aurora Oval Segmentation From UVI Images

    NASA Astrophysics Data System (ADS)

    Cao, C.; Newman, T. S.; Germany, G.

    2005-12-01

    A new shape-based method for segmenting the auroral oval from NASA POLAR Ultraviolet Imager (UVI) data is presented. The POLAR mission has produced millions of UVI images, making automated auroral segmentation a beneficial and critical early processing step in analysis of high-latitude ionosphere-thermopshere-magnetosphere (ITM) coupling using auroral images. Past approaches to automatically or semi-automatically segment the auroral oval from UVI imagery include various types of thresholding, histogram-based K-means, and neural network methods. The existing approaches are generally not robust due to the high noise level, the low level of intensity contrast, and the day glow present in some UVI images. A common shortcoming of existing methods is incomplete detection of the auroral oval for some images. In some cases, existing methods can even fail to detect any part of the oval. The method introduced here is more robust to the challenges of the UVI imagery. Recently, we have demonstrated that the auroral oval's shape in UVI images is well-modelled as an elliptic arc. The segmentation method introduced here exploits this finding; we allow shape knowledge to guide auroral processing. The method involves use of a linear least-squares based shape parameter binning approach that operates on pixels determined from an image-specific thresholding step. The binning approach utilizes a modified randomized Hough Transform scheme that is also fast (faster than conventional binning schemes). The approach treats the inner and outer auroral oval boundaries separately and also incorporates heuristics that allow robust differentiation of appropriate inner and outer boundaries. The new method has been tested on more than 1000 aurora images. Results indicate that the method is highly reliable, even in the presence of high image noise, low contrast, and moderate levels of day glow.

  20. WFC3 SMOV Proposal 11450: The Photometric Performance and Calibration of WFC3/UVIS

    NASA Astrophysics Data System (ADS)

    Kalirai, J. S.; MacKenty, J.; Rajan, A.; Baggett, S.; Bohlin, R.; Brown, T.; Deustua, S.; Kimble, R. A.; Riess, A.; Sabbi, E.

    2009-11-01

    We present the photometric calibration of the UVIS camera on WFC3. Following successful instal- lation during Servicing Mission 4, we began a primary calibration program to measure the photo- metric zero points of 37 high priority filters on the UVIS1 CCD. Additional secondary observations obtained as a part of the UVIS Contamination Monitor Program with both UVIS1 and UVIS2 are also analyzed (CAL11426 - Baggett et al. 2009). All measurements are made from a set of high signal-to-noise imaging observations of the white dwarf standards GD 153 (primary program) and GRW+70d5824 (secondary program). We find that the total system throughput of both CCDs is significantly better than expected from the Thermal Vacuum 3 (TV3) testing campaign, with effi- ciency gains of ~10% at the blue and red ends of the spectral coverage, and ~20% near the central wavelength, 5500 Å. Repeat visits in a subset of filters separated by approximately 1 day, 1 week, and 1 month indicate photometric stability in the measured counts to better than 0.5%. We update the Exposure Time Calculator (ETC) with these preliminary results by fitting a smooth curve (2nd order polynomial) to the ratios of the efficiency gains over previous predictions, in the medium and wide band filters. This polynomial is interpolated at a fine wavelength grid and multiplied into the SYNPHOT throughput routines. We also provide photometric zero points for the UVIS camera in three photometric systems, STMAG, ABMAG, and VEGAMAG. A much more detailed Cycle 17 calibration plan, including observations targeting multiple primary standards, and with all filters on both CCDs, begins in October 2009.

  1. Thermodynamic stabilities of U(VI) minerals: Estimated and observed relationships

    SciTech Connect

    Finch, R.J.

    1996-12-31

    Gibbs free energies of formation ({Delta}G{degree}{sub f}) for several structurally related U(VI) minerals are estimated by summing the Gibbs energy contributions from component oxides. The estimated {Delta}G{degree}{sub f} values are used to construct activity-activity (stability) diagrams, and the predicted stability fields are compared with observed mineral occurrences and reaction pathways. With some exceptions, natural occurrences agree well with the mineral stability fields estimated for the systems SiO{sub 2}-CaO-UO{sub 3}-H{sub 2}O and CO{sub 2}-CaO-UO{sub 3}H{sub 2}O, providing confidence in the estimated thermodynamic values. Activity-activity diagrams are sensitive to small differences in {Delta}G{degree}{sub f} values, and mineral compositions must be known accurately, including structurally bound H{sub 2}O. The estimated {Delta}G{degree}{sub f} values are not considered reliable for a few minerals for two major reasons: (1) the structures of the minerals in question are not closely similar to those used to estimate the {Delta}G{sub f}* values of the component oxides, and/or (2) the minerals in question are exceptionally fine grained, leading to large surface energies that increase the effective mineral solubilities. The thermodynamic stabilities of uranium(VI) minerals are of interest for understanding the role of these minerals in controlling uranium concentrations in oxidizing groundwaters associated with uranium ore bodies, uranium mining and mill tailings and geological repositories for nuclear waste.

  2. Uranium Biomineralization By Natural Microbial Phosphatase Activities in the Subsurface

    SciTech Connect

    Taillefert, Martial

    2015-04-01

    This project investigated the geochemical and microbial processes associated with the biomineralization of radionuclides in subsurface soils. During this study, it was determined that microbial communities from the Oak Ridge Field Research subsurface are able to express phosphatase activities that hydrolyze exogenous organophosphate compounds and result in the non-reductive bioimmobilization of U(VI) phosphate minerals in both aerobic and anaerobic conditions. The changes of the microbial community structure associated with the biomineralization of U(VI) was determined to identify the main organisms involved in the biomineralization process, and the complete genome of two isolates was sequenced. In addition, it was determined that both phytate, the main source of natural organophosphate compounds in natural environments, and polyphosphate accumulated in cells could also be hydrolyzed by native microbial population to liberate enough orthophosphate and precipitate uranium phosphate minerals. Finally, the minerals produced during this process are stable in low pH conditions or environments where the production of dissolved inorganic carbon is moderate. These findings suggest that the biomineralization of U(VI) phosphate minerals is an attractive bioremediation strategy to uranium bioreduction in low pH uranium-contaminated environments. These efforts support the goals of the SBR long-term performance measure by providing key information on "biological processes influencing the form and mobility of DOE contaminants in the subsurface".

  3. Using High Performance Computing to Understand Roles of Labile and Nonlabile U(VI) on Hanford 300 Area Plume Longevity

    SciTech Connect

    Lichtner, Peter C.; Hammond, Glenn E.

    2012-07-28

    Evolution of a hexavalent uranium [U(VI)] plume at the Hanford 300 Area bordering the Columbia River is investigated to evaluate the roles of labile and nonlabile forms of U(VI) on the longevity of the plume. A high fidelity, three-dimensional, field-scale, reactive flow and transport model is used to represent the system. Richards equation coupled to multicomponent reactive transport equations are solved for times up to 100 years taking into account rapid fluctuations in the Columbia River stage resulting in pulse releases of U(VI) into the river. The peta-scale computer code PFLOTRAN developed under a DOE SciDAC-2 project is employed in the simulations and executed on ORNL's Cray XT5 supercomputer Jaguar. Labile U(VI) is represented in the model through surface complexation reactions and its nonlabile form through dissolution of metatorbernite used as a surrogate mineral. Initial conditions are constructed corresponding to the U(VI) plume already in place to avoid uncertainties associated with the lack of historical data for the waste stream. The cumulative U(VI) flux into the river is compared for cases of equilibrium and multirate sorption models and for no sorption. The sensitivity of the U(VI) flux into the river on the initial plume configuration is investigated. The presence of nonlabile U(VI) was found to be essential in explaining the longevity of the U(VI) plume and the prolonged high U(VI) concentrations at the site exceeding the EPA MCL for uranium.

  4. An active control system for helicopter vibration reduction by higher harmonic pitch

    NASA Technical Reports Server (NTRS)

    Taylor, R. B.; Farrar, F. A.; Miao, W.

    1980-01-01

    An analytical study defining the basic configuration of an active control system to reduce helicopter vibrations is presented. Theoretical results for a nonlinear four-bladed single rotor helicopter simulation are discussed, showing that vibration reductions on the order of 80-90% for airspeeds up to 150 kn can be expected when using a higher harmonic pitch in an active feedback control system. The rotor performance penalty associated with this level of vibration reduction is about 1-3% and the increase in rotor blade stresses is considered to be low. The location of sensor accelerometers proved to be significant for vibration reductions, and it is noted that the RTSA controller is tolerant of sensor signal noise.

  5. Reduction of helicopter blade-vortex interaction noise by active rotor control technology

    NASA Astrophysics Data System (ADS)

    Yu, Yung H.; Gmelin, Bernd; Splettstoesser, Wolf; Philippe, Jean J.; Prieur, Jean; Brooks, Thomas F.

    Helicopter blade-vortex interaction noise is one of the most severe noise sources and is very important both in community annoyance and military detection. Research over the decades has substantially improved basic physical understanding of the mechanisms generating rotor blade-vortex interaction noise and also of controlling techniques, particularly using active rotor control technology. This paper reviews active rotor control techniques currently available for rotor blade-vortex interaction noise reduction, including higher harmonic pitch control, individual blade control, and on-blade control technologies. Basic physical mechanisms of each active control technique are reviewed in terms of noise reduction mechanism and controlling aerodynamic or structural parameters of a blade. Active rotor control techniques using smart structures/materials are discussed, including distributed smart actuators to induce local torsional or flapping deformations.

  6. Activation energies for oxygen reduction on platinum alloys: theory and experiment.

    PubMed

    Anderson, Alfred B; Roques, Jérôme; Mukerjee, Sanjeev; Murthi, Vivek S; Markovic, Nenad M; Stamenkovic, Vojislav

    2005-01-27

    A combined theoretical and experimental analysis of the electrode potential dependencies of activation energies is presented for the first step in oxygen reduction over platinum and platinum alloy catalysts in both polycrystalline and carbon supported form. Tafel data for several of the catalysts are used to predict potential-dependent activation energies for oxygen reduction over the 0.6-0.9 V range in strong and weak acid. Comparisons with the theoretical curve show good agreement above 0.8 V, suggesting a fairly constant preexponential factor. Arrhenius determinations of activation energies over the 0.7-0.9 V range yield little trend for weak acid, possibly because of the larger uncertainties in the Arrhenius fits, but the strong acid results have smaller uncertainties and for them the measured activation energies trend up with potential. PMID:16851081

  7. Reduction of Helicopter Blade-Vortex Interaction Noise by Active Rotor Control Technology

    NASA Technical Reports Server (NTRS)

    Yu, Yung H.; Gmelin, Bernd; Splettstoesser, Wolf; Brooks, Thomas F.; Philippe, Jean J.; Prieur, Jean

    1997-01-01

    Helicopter blade-vortex interaction noise is one of the most severe noise sources and is very important both in community annoyance and military detection. Research over the decades has substantially improved basic physical understanding of the mechanisms generating rotor blade-vortex interaction noise and also of controlling techniques, particularly using active rotor control technology. This paper reviews active rotor control techniques currently available for rotor blade vortex interaction noise reduction, including higher harmonic pitch control, individual blade control, and on-blade control technologies. Basic physical mechanisms of each active control technique are reviewed in terms of noise reduction mechanism and controlling aerodynamic or structural parameters of a blade. Active rotor control techniques using smart structures/materials are discussed, including distributed smart actuators to induce local torsional or flapping deformations, Published by Elsevier Science Ltd.

  8. QUANTITATIVE STRUCTURE-ACTIVITY RELATIONSHIPS FOR CHEMICAL REDUCTIONS OF ORGANIC CONTAMINANTS

    EPA Science Inventory

    Sufficient kinetic data on abiotic reduction reactions involving organic contaminants are now available that quantitative structure-activity relationships (QSARs) for these reactions can be developed. Over 50 QSARs have been reported, most in just the last few years, and they ar...

  9. RADON REDUCTION TECHNIQUES FOR EXISTING DETACHED HOUSES - TECHNICAL GUIDANCE (THIRD EDITION) FOR ACTIVE SOIL DEPRESSURIZATION SYSTEMS

    EPA Science Inventory

    This technical guidance document is designed to aid in the selection, design, installation and operation of indoor radon reduction techniques using soil depressurization in existing houses. Its emphasis is on active soil depressurization; i.e., on systems that use a fan to depre...

  10. Aminotroponiminates as tunable, redox-active ligands: reversible single electron transfer and reductive dimerisation.

    PubMed

    Lichtenberg, C; Krummenacher, I

    2016-08-21

    Aminotroponiminates (atis) are shown to be redox-active ligands. Under strongly reducing conditions, the result of electron transfer can be controlled by the choice of the metal bound to the ati ligand. Either reversible electron transfer or a reductively induced dimerisation is observed. The latter reaction is (regio- and diastereo-) selective and chemically reversible. PMID:27452905

  11. Cubic anatase TiO2 nanocrystals with enhanced photocatalytic CO2 reduction activity.

    PubMed

    Xu, Quanlong; Yu, Jiaguo; Zhang, Jun; Zhang, Jinfeng; Liu, Gang

    2015-05-01

    Single-crystalline anatase TiO2 nanocubes with exposed {100} and {001} facets, prepared by hydrothermal and calcination methods, display especially high photocatalytic activity toward CO2 reduction to methane and methanol, due to the synergistic effects of better crystallization, a more negative conduction band position and co-exposed {100} and {001} facets. PMID:25864947

  12. Nickel-catalyzed reductive arylation of activated alkynes with aryl iodides

    PubMed Central

    Dorn, Stephanie C. M.; Olsen, Andrew K; Kelemen, Rachel E.; Shrestha, Ruja; Weix, Daniel J.

    2015-01-01

    The direct, regioselective, and stereoselective arylation of activated alkynes with aryl iodides using a nickel catalyst and manganese reductant is described. The reaction conditions are mild (40 °C in MeOH, no acid or base) and an intermediate organomanganese reagent is unlikely. Functional groups tolerated include halides and pseudohalides, free and protected anilines, and a benzyl alcohol. Other activated alkynes including an amide and a ketone also reacted to form arylated products in good yields. PMID:26028781

  13. Active breathing control (ABC): Determination and reduction of breathing-induced organ motion in the chest

    SciTech Connect

    Gagel, Bernd . E-mail: BGagel@UKAachen.de; Demirel, Cengiz M.P.; Kientopf, Aline; Pinkawa, Michael; Piroth, Marc; Stanzel, Sven; Breuer, Christian; Asadpour, Branka; Jansen, Thomas; Holy, Richard; Wildberger, Joachim E.; Eble, Michael J.

    2007-03-01

    Purpose: Extensive radiotherapy volumes for tumors of the chest are partly caused by interfractional organ motion. We evaluated the feasibility of respiratory observation tools using the active breathing control (ABC) system and the effect on breathing cycle regularity and reproducibility. Methods and Materials: Thirty-six patients with unresectable tumors of the chest were selected for evaluation of the ABC system. Computed tomography scans were performed at various respiratory phases starting at the same couch position without patient movement. Threshold levels were set at minimum and maximum volume during normal breathing cycles and at a volume defined as shallow breathing, reflecting the subjective maximal tolerable reduction of breath volume. To evaluate the extent of organ movement, 13 landmarks were considering using commercial software for image coregistration. In 4 patients, second examinations were performed during therapy. Results: Investigating the differences in a normal breathing cycle versus shallow breathing, a statistically significant reduction of respiratory motion in the upper, middle, and lower regions of the chest could be detected, representing potential movement reduction achieved through reduced breath volume. Evaluating interfraction reproducibility, the mean displacement ranged between 0.24 mm (chest wall/tracheal bifurcation) to 3.5 mm (diaphragm) for expiration and shallow breathing and 0.24 mm (chest wall) to 5.25 mm (diaphragm) for normal inspiration. Conclusions: By modifying regularity of the respiratory cycle through reduction of breath volume, a significant and reproducible reduction of chest and diaphragm motion is possible, enabling reduction of treatment planning margins.

  14. Influence of sulfur oxyanions on reductive dehalogenation activities in Desulfomonile tiedjei.

    PubMed Central

    Townsend, G T; Suflita, J M

    1997-01-01

    The inhibition of aryl reductive dehalogenation reactions by sulfur oxyanions has been demonstrated in environmental samples, dehalogenating enrichments, and the sulfate-reducing bacterium Desulfomonile tiedjei; however, this phenomenon is not well understood. We examined the effects of sulfate, sulfite, and thiosulfate on reductive dehalogenation in the model microorganism D. tiedjei and found separate mechanisms of inhibition due to these oxyanions under growth versus nongrowth conditions. Dehalogenation activity was greatly reduced in extracts of cells grown in the presence of both 3-chlorobenzoate, the substrate or inducer for the aryl dehalogenation activity, and either sulfate, sulfite, or thiosulfate, indicating that sulfur oxyanions repress the requisite enzymes. In extracts of fully induced cells, thiosulfate and sulfite, but not sulfate, were potent inhibitors of aryl dehalogenation activity even in membrane fractions lacking the cytoplasmically located sulfur oxyanion reductase. These results suggest that under growth conditions, sulfur oxyanions serve as preferred electron acceptors and negatively influence dehalogenation activity in D. tiedjei by regulating the amount of active aryl dehalogenase in cells. Additionally, in vitro inhibition by sulfur oxyanions is due to the interaction of the reactive species with enzymes involved in dehalogenation and need not involve competition between two respiratory processes for reducing equivalents. Sulfur oxyanions also inhibited tetrachloroethylene dehalogenation by the same mechanisms, further indicating that chloroethylenes are fortuitously dehalogenated by the aryl dehalogenase. The commonly observed inhibition of reductive dehalogenation reactions under sulfate-reducing conditions may be due to similar regulation mechanisms in other dehalogenating microorganisms that contain multiple respiratory activities. PMID:9293011

  15. Effect of 57Fe-goethite Amendment on Microbial Community Composition and Dynamics During the Transition from Iron to Sulfate Reduction

    NASA Astrophysics Data System (ADS)

    Moon, H.; McGuiness, L.; Kukkadapu, R. K.; Peacock, A.; Komlos, J.; Kerkhof, L.; Long, P. E.; Jaffe, P. R.

    2009-12-01

    Due to an increasing interest in microbial biostimulation for the purpose of U(VI) bioreduction, which proceeds via iron reduction, there is a growing need for a better understanding of the associated biogeochemical dynamics. This includes Fe(III) availability as well as the microbial community changes, including the activity of iron-reducers during the biostimulation period even after the onset of sulfate reduction. An up-flow column experiment was conducted with Old Rifle site sediments, where half of the columns had sediment that was augmented with 57Fe-goethite to track minute goethite changes after the onset of sulfate reduction, and to study the effects of increased Fe(III) levels on the overall biostimulation dynamics. The addition of the 57Fe-goethite did not delay the onset of sulfate reduction, but slightly suppressed the overall rate of sulfate reduction and hence acetate utilization. Mossbauer analyses confirmed that there was bioavailable iron present after the onset of sulfate reduction and that iron was still being reduced during sulfate reduction. Addition of the 57Fe-goethite to the sediment had a noticeable effect on the overall composition of the microbial population. 16S rRNA analyses of biostimulatd sediment using TRFLP showed that Geobacter sp. were still active and replicating after sulfate reduction had occurred for over 30 days. DNA fingerprints of the sediment-attached microbial communities were dominated by 5 TRFs, that comprised 25-57 % of the total profile. Augmentation of sediments with the 57Fe-goethite resulted in somewhat higher numbers of Geobacter-like species throughout the experiment, and during sulfate reduction slightly lower numbers of sulfate reducers. These columns also had a slightly improved U(VI) removal efficiency, which might be attributed to the higher Geobacter-like numbers.

  16. HST/WFC3 UVIS Detector: Dark, Charge Transfer Efficiency, and Point Spread Function Calibrations

    NASA Astrophysics Data System (ADS)

    Bourque, Matthew; Anderson, Jay; Baggett, Sylvia; Bowers, Ariel; MacKenty, John W.; Sahu, Kailash C.

    2015-08-01

    Wide Field Camera 3 (WFC3) is a fourth-generation imaging instrument on board the Hubble Space Telescope (HST) that was installed during Servicing Mission 4 in May 2009. As one of two channels available on WFC3, the UVIS detector is comprised of two e2v CCDs and is sensitive to ultraviolet and visible light. Here we provide updates to the characterization and monitoring of the UVIS performance and stability. We present the long-term growth of the dark current and the hot pixel population, as well as the evolution of Charge Transfer Efficiency (CTE). We also discuss updates to the UVIS dark calibration products, which are used to correct for dark current in science images. We examine the impacts of CTE losses and outline some techniques to mitigate CTE effects during and after observation by use of post-flash and pixel-based CTE corrections. Finally, we summarize an investigation of WFC3/UVIS Point Spread Functions (PSFs) and their potential use for characterizing the focus of the instrument.

  17. Compositional Variations from UVIS Observations of Titan's Dayglow and Comparisons with in situ INMS Observations

    NASA Astrophysics Data System (ADS)

    Stevens, M. H.; Evans, J. S.; Ajello, J. M.; Bradley, E. T.; Meier, R. R.; Westlake, J. H.; Waite, J. H., Jr.

    2012-04-01

    The Cassini Ultraviolet Imaging Spectrograph (UVIS) observed Titan’s dayside limb on multiple occasions between 2007 and 2011. The airglow observations reveal the same variety of EUV (600-1150Å) and FUV (1150-1900Å) emissions arising from photoelectron excitation and photofragmentation of molecular nitrogen (N2) on Earth. Through spectral analysis we extract radiance profiles for each set of UVIS limb emissions in the EUV and FUV, which are attenuated by methane (CH4). Using a terrestrial airglow model adapted to Titan, we derive the N2 and CH4 density profiles using the prescribed solar irradiance for the relevant Cassini orbit and compare the calculated radiance profiles directly with observations. We find that the UVIS airglow observations can be explained by solar driven processes, although fluctuations in the observed airglow between flybys suggest compositional changes in the background atmosphere. We compare the compositional variations inferred from the UVIS airglow to in situ observations by the Cassini Ion and Neutral Mass Spectrometer (INMS) from the same Titan orbit and discuss how the variations may be related to Titan’s varying plasma environment.

  18. Uranium(VI) reduction by nanoscale zero-valent iron in anoxic batch systems: The role of Fe(II) and Fe(III)

    SciTech Connect

    Yan, Sen; Chen, Yongheng; Xiang, Wu; Bao, Zhengyu; Liu, Chongxuan; Deng, Baolin

    2014-12-01

    The role of Fe(II) and Fe(III) on U(VI) reduction by nanoscale zerovalent iron (nanoFe0) was investigated using two iron chelators 1,10-phenanthroline and triethanolamine (TEA) under a CO2-free anoxic condition. The results showed U(VI) reduction was strongly inhibited by 1,10-phenanthroline and TEA in a pH range from 6.92 to 9.03. For instance, at pH 6.92 the observed U(VI) reduction rates decreased by 80.7% and 82.3% in the presence of 1,10-phenanthroline and TEA, respectively. The inhibition was attributed to the formation of stable complexes between 1,10-phenanthroline and Fe(II) or TEA and Fe(III). In the absence of iron chelators, U(VI) reduction can be enhanced by surface-bound Fe(II) on nanoFe0. Our results suggested that Fe(III) and Fe(II) probably acted as an electron shuttle to mediate the transfer of electrons from nanoFe0 to U(VI), therefore a combined system with Fe(II), Fe(III) and nanoFe0 can facilitate the U(VI) reductive immobilization in the contaminated groundwater.

  19. Lewis Base Activation of Silyl Acetals: Iridium-Catalyzed Reductive Horner-Wadsworth-Emmons Olefination.

    PubMed

    Dakarapu, Udaya Sree; Bokka, Apparao; Asgari, Parham; Trog, Gabriela; Hua, Yuanda; Nguyen, Hiep H; Rahman, Nawal; Jeon, Junha

    2015-12-01

    A Lewis base promoted deprotonative pronucleophile addition to silyl acetals has been developed and applied to the iridium-catalyzed reductive Horner-Wadsworth-Emmons (HWE) olefination of esters and the chemoselective reduction of the resulting enoates. Lewis base activation of silyl acetals generates putative pentacoordinate silicate acetals, which fragment into aldehydes, silanes, and alkoxides in situ. Subsequent deprotonative metalation of phosphonate esters followed by HWE with aldehydes furnishes enoates. This operationally convenient, mechanistically unique protocol converts the traditionally challenging aryl, alkenyl, and alkynyl esters to homologated enoates at room temperature within a single vessel. PMID:26566189

  20. Intracellular reduction/activation of a disulfide switch in thiosemicarbazone iron chelators.

    PubMed

    Akam, Eman A; Chang, Tsuhen M; Astashkin, Andrei V; Tomat, Elisa

    2014-10-01

    Iron scavengers (chelators) offer therapeutic opportunities in anticancer drug design by targeting the increased demand for iron in cancer cells as compared to normal cells. Prochelation approaches are expected to avoid systemic iron depletion as chelators are liberated under specific intracellular conditions. In the strategy described herein, a disulfide linkage is employed as a redox-directed switch within the binding unit of an antiproliferative thiosemicarbazone prochelator, which is activated for iron coordination following reduction to the thiolate chelator. In glutathione redox buffer, this reduction event occurs at physiological concentrations and half-cell potentials. Consistent with concurrent reduction and activation, higher intracellular thiol concentrations increase cell susceptibility to prochelator toxicity in cultured cancer cells. The reduction of the disulfide switch and intracellular iron chelation are confirmed in cell-based assays using calcein as a fluorescent probe for paramagnetic ions. The resulting low-spin Fe(III) complex is identified in intact Jurkat cells by EPR spectroscopy measurements, which also document a decreased concentration of active ribonucleotide reductase following exposure to the prochelator. Cell viability and fluorescence-based assays show that the iron complex presents low cytotoxicity and does not participate in intracellular redox chemistry, indicating that this antiproliferative chelation strategy does not rely on the generation of reactive oxygen species. PMID:25100578

  1. Vibration reduction in helicopter rotors using an active control surface located on the blade

    NASA Technical Reports Server (NTRS)

    Millott, T. A.; Friedmann, P. P.

    1992-01-01

    A feasibility study of vibration reduction in a four-bladed helicopter rotor using individual blade control (IBC), which is implemented by an individually controlled aerodynamic surface located on each blade, is presented. For this exploratory study, a simple offset-hinged spring restrained model of the blade is used with fully coupled flap-lag-torsional dynamics for each blade. Deterministic controllers based on local and global system models are implemented to reduce 4/rev hub loads using both an actively controlled aerodynamic surface on each blade as well as conventional IBC, where the complete blade undergoes cyclic pitch change. The effectiveness of the two approaches for simultaneous reduction of the 4/rev hub shears and hub moments is compared. Conventional IBC requires considerably more power to achieve approximately the same level of vibration reduction as that obtained by implementing IBC using an active control surface located on the outboard segment of the blade. The effect of blade torsional flexibility on the vibration reduction effectiveness of the actively controlled surface was also considered and it was found that this parameter has a very substantial influence.

  2. Intracellular reduction/activation of a disulfide switch in thiosemicarbazone iron chelators

    PubMed Central

    Akam, Eman A.; Chang, Tsuhen M.; Astashkin, Andrei V.

    2014-01-01

    Iron scavengers (chelators) offer therapeutic opportunities in anticancer drug design by targeting the increased demand for iron in cancer cells as compared to normal cells. Prochelation approaches are expected to avoid systemic iron depletion as chelators are liberated under specific intracellular conditions. In the strategy described herein, a disulfide linkage is employed as a redox-directed switch within the binding unit of an antiproliferative thiosemicarbazone prochelator, which is activated for iron coordination following reduction to the thiolate chelator. In glutathione redox buffer, this reduction event occurs at physiological concentrations and half-cell potentials. Consistent with concurrent reduction and activation, higher intracellular thiol concentrations increase cell susceptibility to prochelator toxicity in cultured cancer cells. The reduction of the disulfide switch and intracellular iron chelation are confirmed in cell-based assays using calcein as a fluorescent probe for paramagnetic ions. The resulting low-spin Fe(III) complex is identified in intact Jurkat cells by EPR spectroscopy measurements, which also document a decreased concentration of active ribonucleotide reductase following exposure to the prochelator. Cell viability and fluorescence-based assays show that the iron complex presents low cytotoxicity and does not participate in intracellular redox chemistry, indicating that this antiproliferative chelation strategy does not rely on the generation of reactive oxygen species. PMID:25100578

  3. Characterization of U(VI) Sorption-Desorption Processes and Model Upscaling

    SciTech Connect

    Bai, Jing; Dong, Wenming; Ball, William P.

    2006-10-12

    The objectives of the overall collaborative EMSP effort (with which this project is associated) were to characterize sorption and desorption processes of U(VI) on pristine and contaminated Hanford sediments over a range of sediment facies and materials properties and to relate such characterization both to fundamental molecular-scale understanding and field-scale models of geochemistry and mass transfer. The research was intended to provide new insights on the mechanisms of U(VI) retardation at Hanford, and to allow the development of approaches by which laboratory-developed geochemical models could be upscaled for defensible field-scale predictions of uranium transport in the environment. Within this broader context, objectives of the JHU-based project were to test hypotheses regarding the coupled roles of adsorption and impermeable-zone diffusion in controlling the fate and transport of U(VI) species under conditions of comparatively short-term exposure. In particular, this work tested the following hypotheses: (1) the primary adsorption processes in the Hanford sediment over the pH range of 7 to 10 are surface complexation reactions of aqueous U(VI) hydroxycarbonate and carbonate complexes with amphoteric edge sites on detrital phyllosilicates in the silt/clay size fraction; (2) macroscopic adsorption intensity (at given aqueous conditions) is a function of mineral composition and aquatic chemistry; and (3) equilibrium sorption and desorption to apply in short-term, laboratory-spiked pristine sediments; and (4) interparticle diffusion can be fully understood in terms of a model that couples molecular diffusion of uranium species in the porewater with equilibrium sorption under the relevant aqueous conditions. The primary focus of the work was on developing and applying both models and experiments to test the applicability of "local equilibrium" assumptions in the modeling interpretation of sorption retarded interparticle diffusion, as relevant to processes of U(VI

  4. Trend in the Catalytic Activity of Transition Metals for the Oxygen Reduction Reaction by Lithium

    SciTech Connect

    Dathar, Gopi Krishna Phani; Shelton Jr, William Allison; Xu, Ye

    2012-01-01

    Periodic density functional theory (DFT) calculations indicate that the intrinsic activity of Au, Ag, Pt, Pd, Ir, and Ru for the oxygen reduction reaction by Li (Li-ORR) forms a volcano-like trend with respect to the adsorption energy of oxygen, with Pt and Pd being the most active. The trend is based on two mechanisms: the reduction of molecular O{sub 2} on Au and Ag and of atomic O on the remaining metals. Step edges are found to be more active for catalyzing the Li-ORR than close-packed surfaces. Our findings identify important considerations in the design of catalyst-promoted air cathodes for nonaqueous Li-air batteries.

  5. Probing the interaction of U(vi) with phosphonate-functionalized mesoporous silica using solid-state NMR spectroscopy.

    PubMed

    Uribe, Eva C; Mason, Harris E; Shusterman, Jennifer A; Bruchet, Anthony; Nitsche, Heino

    2016-06-21

    The fundamental interaction of U(vi) with diethylphosphatoethyl triethoxysilane functionalized SBA-15 mesoporous silica is studied by macroscopic batch experiments and solid-state NMR spectroscopy. DPTS-functionalized silica has been shown to extract U(vi) from nitric acid solutions at or above pH 3. Extraction is dependent on pH and ionic strength. Single-pulse (31)P NMR on U(vi) contacted samples revealed that U(vi) only interacts with a fraction of the ligands present on the surface. At pH 4 the U(vi) extraction capacity of the material is limited to 27-37% of the theoretical capacity, based on ligand loading. We combined single pulse (31)P NMR on U(vi)-contacted samples with batch studies to measure a ligand-to-metal ratio of approximately 2 : 1 at pH 3 and 4. Batch studies and cross-polarization NMR measurements reveal that U(vi) binds to deprotonated phosphonate and/or silanol sites. We use (31)P-(31)P DQ-DRENAR NMR studies to compare the average dipolar coupling between phosphorus spins for both U(vi)-complexed and non-complexed ligand environments. These measurements reveal that U(vi) extraction is not limited by inadequate surface distribution of ligands, but rather by low stability of the surface phosphonate complex. PMID:27265020

  6. The U(VI) speciation influenced by a novel Paenibacillus isolate from Mont Terri Opalinus clay.

    PubMed

    Lütke, Laura; Moll, Henry; Bachvarova, Velina; Selenska-Pobell, Sonja; Bernhard, Gert

    2013-05-21

    Bacterial cell walls have a high density of ionizable functional groups available for U(VI) binding, hence have a great potential to affect the speciation of this contaminant in the environment. The studied strain of the genus Paenibacillus is a novel isolate originating from the Mont Terri Opalinus clay formations (Switzerland) which are currently investigated as a potential host rock for future nuclear waste storage. U(VI) binding to the cell surface functional groups was studied by potentiometry combined with time-resolved laser-induced fluorescence spectroscopy (TRLFS). Four bacterial U(VI) surface complexes were identified: R-COO-UO2(+), R-O-PO3-UO2, R-O-PO3H-UO2(+), and (R-O-PO3)2-UO2(2-). The corresponding complex stability constants were calculated to be 5.33 ± 0.08, 8.89 ± 0.04, 12.92 ± 0.05, and 13.62 ± 0.08, respectively. Hence UO2(2+) displays a moderate to strong interaction with the bacterial surface functional groups. In the acidic pH range (pH 3) UO2(2+) binding onto the cell envelope is governed by coordination to hydrogen phosphoryl sites. Upon increasing the pH an increasing coordination of UO2(2+) to carboxylic and deprotonated phosphoryl sites was found. At a pH greater than 7 uranyl hydroxides dominate the speciation. Additionally the bacteria-mediated release of inorganic phosphate in dependence on [U(VI)] at different pH values was studied to assess the influence of phosphate release on U(VI) mobilization. PMID:23508301

  7. Green synthesis of gold nanoparticles using aspartame and their catalytic activity for p-nitrophenol reduction

    NASA Astrophysics Data System (ADS)

    Wu, Shufen; Yan, Songjing; Qi, Wei; Huang, Renliang; Cui, Jing; Su, Rongxin; He, Zhimin

    2015-05-01

    We demonstrated a facile and environmental-friendly approach to form gold nanoparticles through the reduction of HAuCl4 by aspartame. The single-crystalline structure was illustrated by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The energy-dispersive X-ray spectroscopy (EDS) and Fourier transform infrared (FTIR) results indicated that aspartame played a pivotal role in the reduction and stabilization of the gold crystals. The crystals were stabilized through the successive hydrogen-bonding network constructed between the water and aspartame molecules. Additionally, gold nanoparticles synthesized through aspartame were shown to have good catalytic activity for the reduction of p-nitrophenol to p-aminophenol in the presence of NaBH4.

  8. Green synthesis of gold nanoparticles using aspartame and their catalytic activity for p-nitrophenol reduction.

    PubMed

    Wu, Shufen; Yan, Songjing; Qi, Wei; Huang, Renliang; Cui, Jing; Su, Rongxin; He, Zhimin

    2015-01-01

    We demonstrated a facile and environmental-friendly approach to form gold nanoparticles through the reduction of HAuCl4 by aspartame. The single-crystalline structure was illustrated by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The energy-dispersive X-ray spectroscopy (EDS) and Fourier transform infrared (FTIR) results indicated that aspartame played a pivotal role in the reduction and stabilization of the gold crystals. The crystals were stabilized through the successive hydrogen-bonding network constructed between the water and aspartame molecules. Additionally, gold nanoparticles synthesized through aspartame were shown to have good catalytic activity for the reduction of p-nitrophenol to p-aminophenol in the presence of NaBH4. PMID:25991916

  9. Identification of proteins capable of metal reduction from the proteome of the Gram-positive bacterium Desulfotomaculum reducens MI-1 using an NADH-based activity assay

    PubMed Central

    Otwell, A.E.; Sherwood, R.W.; Zhang, S.; Nelson, O.D.; Li, Z.; Lin, H.; Callister, S.J.; Richardson, R.E.

    2015-01-01

    Summary Understanding of microbial metal reduction is based almost solely on studies of Gram-negative organisms. In this study, we focus on Desulfotomaculum reducens MI-1, a Gram-positive metal reducer whose genome lacks genes with similarity to any characterized metal reductase. Using non-denaturing separations and mass spectrometry identification, in combination with a colorimetric screen for chelated Fe(III)-NTA reduction with NADH as electron donor, we have identified proteins from the D. reducens proteome not previously characterized as iron reductases. Their function was confirmed by heterologous expression in E. coli. Furthermore, we show that these proteins have the capability to reduce soluble Cr(VI) and U(VI) with NADH as electron donor. The proteins identified are NADH:flavin oxidoreductase (Dred_2421) and a protein complex composed of oxidoreductase FAD/NAD(P)-binding subunit (Dred_1685) and dihydroorotate dehydrogenase 1B (Dred_1686). Dred_2421 was identified in the soluble proteome and is predicted to be a cytoplasmic protein. Dred_1685 and Dred_1686 were identified in both the soluble as well as the insoluble protein fraction, suggesting a type of membrane-association, although PSORTb predicts both proteins are cytoplasmic. This study is the first functional proteomic analysis of D. reducens and one of the first analyses of metal and radionuclide reduction in an environmentally relevant Gram-positive bacterium. PMID:25389064

  10. Determining individual mineral contributions to U(VI) adsorption in a contaminated aquifer sediment: A fluorescence spectroscopy study

    NASA Astrophysics Data System (ADS)

    Wang, Zheming; Zachara, John M.; Boily, Jean-François; Xia, Yuanxian; Resch, Tom C.; Moore, Dean A.; Liu, C.

    2011-05-01

    The adsorption and speciation of U(VI) was investigated on contaminated, fine grained sediment materials from the Hanford 300 area (SPP1 GWF) in simulated groundwater using cryogenic laser-induced U(VI) fluorescence spectroscopy combined with chemometric analysis. A series of reference minerals (montmorillonite, illite, Michigan chlorite, North Carolina chlorite, California clinochlore, quartz and synthetic 6-line ferrihydrite) was used for comparison that represents the mineralogical constituents of SPP1 GWF. Surface area-normalized Kd values were measured at U(VI) concentrations of 5 × 10 -7 and 5 × 10 -6 mol L -1 that displayed the following affinity series: 6-line-ferrihydrite > North Carolina chlorite ≈ California clinochlore > quartz ≈ Michigan chlorite > illite > montmorillonite. Both time-resolved spectra and asynchronous two-dimensional (2D) correlation analysis of SPP1 GWF at different delay times indicated that two major adsorbed U(VI) species were present in the sediment that resembled U(VI) adsorbed on quartz and phyllosilicates. Simulations of the normalized fluorescence spectra confirmed that the speciation of SPP1 GWF was best represented by a linear combination of U(VI) adsorbed on quartz (90%) and phyllosilicates (10%). However, the fluorescence quantum yield for U(VI) adsorbed on phyllosilicates was lower than quartz and, consequently, its fractional contribution to speciation may be underestimated. Spectral comparison with literature data suggested that U(VI) exist primarily as inner-sphere complexes with surface silanol groups on quartz and as surface U(VI) tricarbonate complexes on phyllosilicates.

  11. A multi-scale magnetotail reconnection event at Saturn and associated flows: Cassini/UVIS observations

    NASA Astrophysics Data System (ADS)

    Radioti, A.; Grodent, D.; Jia, X.; Gérard, J.-C.; Bonfond, B.; Pryor, W.; Gustin, J.; Mitchell, D. G.; Jackman, C. M.

    2016-01-01

    We present high-resolution Cassini/UVIS (Ultraviolet Imaging Spectrograph) observations of Saturn's aurora during May 2013 (DOY 140-141). The observations reveal an enhanced auroral activity in the midnight-dawn quadrant in an extended local time sector (∼02 to 05 LT), which rotates with an average velocity of ∼45% of rigid corotation. The auroral dawn enhancement reported here, given its observed location and brightness, is most probably due to hot tenuous plasma carried inward in fast moving flux tubes returning from a tail reconnection site to the dayside. These flux tubes could generate intense field-aligned currents that would cause aurora to brighten. However, the origin of tail reconnection (solar wind or internally driven) is uncertain. Based mainly on the flux variations, which do not demonstrate flux closure, we suggest that the most plausible scenario is that of internally driven tail reconnection which operates on closed field lines. The observations also reveal multiple intensifications within the enhanced region suggesting an x-line in the tail, which extends from 02 to 05 LT. The localised enhancements evolve in arc and spot-like small scale features, which resemble vortices mainly in the beginning of the sequence. These auroral features could be related to plasma flows enhanced from reconnection which diverge into multiple narrow channels then spread azimuthally and radially. We suggest that the evolution of tail reconnection at Saturn may be pictured by an ensemble of numerous narrow current wedges or that inward transport initiated in the reconnection region could be explained by multiple localised flow burst events. The formation of vortical-like structures could then be related to field-aligned currents, building up in vortical flows in the tail. An alternative, but less plausible, scenario could be that the small scale auroral structures are related to viscous interactions involving small-scale reconnection.

  12. Reductive dehalogenation of disinfection byproducts by an activated carbon-based electrode system.

    PubMed

    Li, Yuanqing; Kemper, Jerome M; Datuin, Gwen; Akey, Ann; Mitch, William A; Luthy, Richard G

    2016-07-01

    Low molecular weight, uncharged, halogenated disinfection byproducts (DBPs) are poorly removed by the reverse osmosis and advanced oxidation process treatment units often applied for further treatment of municipal wastewater for potable reuse. Granular activated carbon (GAC) treatment effectively sorbed 22 halogenated DBPs. Conversion of the GAC to a cathode within an electrolysis cell resulted in significant degradation of the 22 halogenated DBPs by reductive electrolysis at -1 V vs. Standard Hydrogen Electrode (SHE). The lowest removal efficiency over 6 h electrolysis was for trichloromethane (chloroform; 47%) but removal efficiencies were >90% for 13 of the 22 DBPs. In all cases, DBP degradation was higher than in electrolysis-free controls, and degradation was verified by the production of halides as reduction products. Activated carbons and charcoal were more effective than graphite for electrolysis, with graphite featuring poor sorption for the DBPs. A subset of halogenated DBPs (e.g., haloacetonitriles, chloropicrin) were degraded upon sorption to the GAC, even without electrolysis. Using chloropicrin as a model, experiments indicated that this loss was attributable to the partial reduction of sorbed chloropicrin from reducing equivalents in the GAC. Reducing equivalents depleted by these reactions could be restored when the GAC was treated by reductive electrolysis. GAC treatment of an advanced treatment train effluent for potable reuse effectively reduced the concentrations of chloroform, bromodichloromethane and dichloroacetonitrile measured in the column influent to below the method detection limits. Treatment of the GAC by reductive electrolysis at -1 V vs. SHE over 12 h resulted in significant degradation of the chloroform (63%), bromodichloromethane (96%) and dichloroacetonitrile (99%) accumulated on the GAC. The results suggest that DBPs in advanced treatment train effluents could be captured and degraded continuously by reductive electrolysis

  13. Suppression of oxygen reduction reaction activity on Pt-based electrocatalysts from ionomer incorporation

    NASA Astrophysics Data System (ADS)

    Shinozaki, Kazuma; Morimoto, Yu; Pivovar, Bryan S.; Kocha, Shyam S.

    2016-09-01

    The impact of Nafion on the oxygen reduction reaction (ORR) activity is studied for Pt/C and Pt-alloy/C catalysts using thin-film rotating disk electrode (TF-RDE) methods in 0.1 M HClO4. Ultrathin uniform catalyst layers and standardized activity measurement protocols are employed to obtain accurate and reproducible ORR activity. Nafion lowers the ORR activity which plateaus with increasing loading on Pt catalysts. Pt particle size is found not to have significant influence on the extent of the SA decrease upon Nafion incorporation. Catalysts using high surface area carbon (HSC) support exhibit attenuated activity loss resulting from lower ionomer coverage on catalyst particles located within the deep pores. The impact of metallic composition on the activity loss due to Nafion incorporation is also discussed.

  14. Experimental evaluation of leaky least-mean-square algorithms for active noise reduction in communication headsets

    NASA Astrophysics Data System (ADS)

    Cartes, David A.; Ray, Laura R.; Collier, Robert D.

    2002-04-01

    An adaptive leaky normalized least-mean-square (NLMS) algorithm has been developed to optimize stability and performance of active noise cancellation systems. The research addresses LMS filter performance issues related to insufficient excitation, nonstationary noise fields, and time-varying signal-to-noise ratio. The adaptive leaky NLMS algorithm is based on a Lyapunov tuning approach in which three candidate algorithms, each of which is a function of the instantaneous measured reference input, measurement noise variance, and filter length, are shown to provide varying degrees of tradeoff between stability and noise reduction performance. Each algorithm is evaluated experimentally for reduction of low frequency noise in communication headsets, and stability and noise reduction performance are compared with that of traditional NLMS and fixed-leakage NLMS algorithms. Acoustic measurements are made in a specially designed acoustic test cell which is based on the original work of Ryan et al. [``Enclosure for low frequency assessment of active noise reducing circumaural headsets and hearing protection,'' Can. Acoust. 21, 19-20 (1993)] and which provides a highly controlled and uniform acoustic environment. The stability and performance of the active noise reduction system, including a prototype communication headset, are investigated for a variety of noise sources ranging from stationary tonal noise to highly nonstationary measured F-16 aircraft noise over a 20 dB dynamic range. Results demonstrate significant improvements in stability of Lyapunov-tuned LMS algorithms over traditional leaky or nonleaky normalized algorithms, while providing noise reduction performance equivalent to that of the NLMS algorithm for idealized noise fields.

  15. Experimental evaluation of leaky least-mean-square algorithms for active noise reduction in communication headsets.

    PubMed

    Cartes, David A; Ray, Laura R; Collier, Robert D

    2002-04-01

    An adaptive leaky normalized least-mean-square (NLMS) algorithm has been developed to optimize stability and performance of active noise cancellation systems. The research addresses LMS filter performance issues related to insufficient excitation, nonstationary noise fields, and time-varying signal-to-noise ratio. The adaptive leaky NLMS algorithm is based on a Lyapunov tuning approach in which three candidate algorithms, each of which is a function of the instantaneous measured reference input, measurement noise variance, and filter length, are shown to provide varying degrees of tradeoff between stability and noise reduction performance. Each algorithm is evaluated experimentally for reduction of low frequency noise in communication headsets, and stability and noise reduction performance are compared with that of traditional NLMS and fixed-leakage NLMS algorithms. Acoustic measurements are made in a specially designed acoustic test cell which is based on the original work of Ryan et al. ["Enclosure for low frequency assessment of active noise reducing circumaural headsets and hearing protection," Can. Acoust. 21, 19-20 (1993)] and which provides a highly controlled and uniform acoustic environment. The stability and performance of the active noise reduction system, including a prototype communication headset, are investigated for a variety of noise sources ranging from stationary tonal noise to highly nonstationary measured F-16 aircraft noise over a 20 dB dynamic range. Results demonstrate significant improvements in stability of Lyapunov-tuned LMS algorithms over traditional leaky or nonleaky normalized algorithms, while providing noise reduction performance equivalent to that of the NLMS algorithm for idealized noise fields. PMID:12002860

  16. Role of active site loop in coenzyme binding and flavin reduction in cytochrome P450 reductase.

    PubMed

    Mothersole, Robert G; Meints, Carla E; Louder, Alex; Wolthers, Kirsten R

    2016-09-15

    Cytochrome P450 reductase (CPR) contains a loop within the active site (comprising Asp(634), Ala(635), Arg(636) and Asn(637); human CPR numbering) that relocates upon NADPH binding. Repositioning of the loop triggers the reorientation of an FAD-shielding tryptophan (Trp(679)) to a partially stacked conformer, reducing the energy barrier for displacement of the residue by the NADPH nicotinamide ring: an essential step for hydride transfer. We used site-directed mutagenesis and kinetic analysis to investigate if the amino acid composition of the loop influences the catalytic properties of CPR. The D634A and D634N variants elicited a modest increase in coenzyme binding affinity coupled with a 36- and 10-fold reduction in cytochrome c(3+) turnover and a 17- and 3-fold decrease in the pre-steady state rate of flavin reduction. These results, in combination with a reduction in the kinetic isotope effect for hydride transfer, suggest that diminished activity is due to destabilization of the partially stacked conformer of Trp(677) and slower release of NADP(+). In contrast, R636A, R636S and an A635G/R636S double mutant led to a modest increase in cytochrome c(3+) reduction, which is linked to weaker coenzyme binding and faster interflavin electron transfer. A potential mechanism by which Arg(636) influences catalysis is discussed. PMID:27461959

  17. Highly active Pd-In/mesoporous alumina catalyst for nitrate reduction.

    PubMed

    Gao, Zhenwei; Zhang, Yonggang; Li, Deyi; Werth, Charles J; Zhang, Yalei; Zhou, Xuefei

    2015-04-01

    The catalytic reduction of nitrate is a promising technology for groundwater purification because it transforms nitrate into nitrogen and water. Recent studies have mainly focused on new catalysts with higher activities for the reduction of nitrate. Consequently, metal nanoparticles supported on mesoporous metal oxides have become a major research direction. However, the complex surface chemistry and porous structures of mesoporous metal oxides lead to a non-uniform distribution of metal nanoparticles, thereby resulting in a low catalytic efficiency. In this paper, a method for synthesizing the sustainable nitrate reduction catalyst Pd-In/Al2O3 with a dimensional structure is introduced. The TEM results indicated that Pd and In nanoparticles could efficiently disperse into the mesopores of the alumina. At room temperature in CO2-buffered water and under continuous H2 as the electron donor, the synthesized material (4.9 wt% Pd) was the most active at a Pd-In ratio of 4, with a first-order rate constant (k(obs) = 0.241 L min(-1) g(cata)(-1)) that was 1.3× higher than that of conventional Pd-In/Al2O3 (5 wt% Pd; 0.19 L min(-1) g(cata)(-1)). The Pd-In/mesoporous alumina is a promising catalyst for improving the catalytic reduction of nitrate. PMID:25600582

  18. On the occurrence of anoxic microniches, denitrification, and sulfate reduction in aerated activated sludge

    SciTech Connect

    Schramm, A.; Santegoeds, C.M.; Nielsen, H.K.; Ploug, H.; Wagner, M.; Pribyl, M.; Wanner, J.; Amann, R.; De Beer, D.

    1999-09-01

    A combination of different methods was applied to investigate the occurrence of anaerobic processes in aerated activated sludge. Microsensor measurements (O{sub 2}, NO{sub 2}{sup {minus}}, NO{sub 3}{sup {minus}}, and H{sub 2}S) were performed on single sludge flocs to detect anoxic niches, nitrate reduction, or sulfate reduction on a microscale. Incubations of activated sludge with {sup 15}NO{sub 3}{sup {minus}} and {sup 35}SO{sub 4}{sup 2{minus}} were used to determine denitrification and sulfate reduction rates on a batch scale. In four of six investigated sludges, no anoxic zones developed during aeration, and consequently denitrification rates were very low. However, in two sludges anoxia in flocs coincided with significant denitrification rates. Sulfate reduction could not be detected in any sludge in either the microsensor or the batch investigation, not even under short-term anoxic conditions. In contrast, the presence of sulfate-reducing bacteria was shown by fluorescence in situ hybridization with 16S rRNA-targeted oligonucleotide probes and by PCR-based detection of genes coding for the dissimilatory sulfite reductase. A possible explanation for the absence of advection, i.e., facilitated by flow through pores and channels. This possibility is suggested by the irregularity of some oxygen profiles and by confocal laser scanning microscopy of the three-dimensional floc structures, which showed that flocs from the two sludges in which anoxic zones were found were apparently denser than flocs from the other sludges.

  19. Key amino acids of arabidopsis VKOR in the activity of phylloquinone reduction and disulfide bond formation.

    PubMed

    Yang, Xiao-Jian; Cui, Hao-Ran; Yu, Zhi-Bo; Du, Jia-Jia; Xu, Jia-Ning; Wang, Xiao-Yun

    2015-01-01

    Many proteins in chloroplast are regulated through the disulfide bond/thiol transformation to realize their activities. A homologue of VKOR (Vitamin K epoxide reductase) in Arabidopsis chloroplast is found to catalyze the disulfide bond formation in vivo and to mediate the specific phylloquinone reduction in vitro. It is also called LTO1 (Lumen Thiol Oxidoreductase 1). Investigations about functions and essential amino acid residues of AtVKOR have important theoretical significance to clarify the chloroplast redox regulation mechanism. In this study, several amino acids in the VKOR domain of AtVKOR were identified to be involved in binding of phylloquinone. Site-directed mutagenesis was used to study the function of these positions. The results suggested that residues Ser77, Leu87, Phe137 and Leu141 were quite important in the binding and catalyzing the reduction of phylloquinone. These residues were also involved in the electron transferring and disulfide bond formation of substrate proteins by motility assays in vivo, suggesting that the binding of phylloquinone not only affected the delivery of electrons to phylloquinone but also affected the whole electron transfer process. The conserved cysteines in the AtVKOR domain also played critical roles in phylloquinone reduction. When each of the four conserved cysteines was mutated to alanine, the mutants lost reduction activity entirely, suggesting that the four conserved cysteines played crucial roles in the electron transfer process. PMID:25267254

  20. Shortened cecropin A-melittin hybrids. Significant size reduction retains potent antibiotic activity.

    PubMed

    Andreu, D; Ubach, J; Boman, A; Wåhlin, B; Wade, D; Merrifield, R B; Boman, H G

    1992-01-20

    We have earlier reported two 26-residue antibacterial peptides made up from different segments of cecropin A (CA) and melittin (M). We now report a substantial reduction in size at the C-terminal section of the highly active hybrid CA(1-8)M(1-18), leading to a series of 20-, 18- and 15-residue analogs with antibiotic properties similar to the larger molecule. In particular, the 15-residue hybrids CA(1-7)M(2-9), CA(1-7)M(4-11) and CA(1-7)M(5-12) are the shortest cecropin-based peptide antibiotics described so far, with antibacterial activity and spectra similar or better than cecropin A and a 60% reduction in size. Their reduced size and highly alpha-helical structure require an alternative mechanism for their interaction with bacterial membranes. PMID:1733777

  1. INVITED PAPER: Application of an active device for helicopter noise reduction in JAXA

    NASA Astrophysics Data System (ADS)

    Saito, Shigeru; Kobiki, Noboru; Tanabe, Yasutada

    2010-02-01

    Important issues in noise problems for current helicopters are described. An active tab (AT) was developed as a new active device for noise/vibration reduction under research cooperation between Japan Aerospace Exploration Agency (JAXA) and Kawada Industries, Inc. The wind tunnel test was conducted in order to investigate the effectiveness of the AT on the aeroacoustic characteristics of a helicopter. From the wind tunnel test, the capability of reducing blade vortex interaction (BVI) noise by an AT was verified. A new control law using instantaneous pressure change on a blade during BVI phenomena was introduced and applied to the wind tunnel testing. This new control law shows reasonable controllability for helicopter noise reduction. Furthermore, in order to analyze noise characteristics, the advanced computational fluid dynamics (CFD) code named JAXA_ov3d was developed in JAXA and extended to include CFD-CSD (computational structure dynamics) coupling by using the beam theory for blade deformation.

  2. Dioxygen Binding, Activation, and Reduction to H2O by Cu Enzymes.

    PubMed

    Solomon, Edward I

    2016-07-01

    Oxygen intermediates in copper enzymes exhibit unique spectroscopic features that reflect novel geometric and electronic structures that are key to reactivity. This perspective will describe: (1) the bonding origin of the unique spectroscopic features of the coupled binuclear copper enzymes and how this overcomes the spin forbiddenness of O2 binding and activates monooxygenase activity, (2) how the difference in exchange coupling in the non-coupled binuclear Cu enzymes controls the reaction mechanism, and (3) how the trinuclear Cu cluster present in the multicopper oxidases leads to a major structure/function difference in enabling the irreversible reductive cleavage of the O-O bond with little overpotential and generating a fully oxidized intermediate, different from the resting enzyme studied by crystallography, that is key in enabling fast PCET in the reductive half of the catalytic cycle. PMID:27299802

  3. Depressive symptoms among older adults: long-term reduction after a physical activity intervention.

    PubMed

    Motl, Robert W; Konopack, James F; McAuley, Edward; Elavsky, Steriani; Jerome, Gerald J; Marquez, David X

    2005-08-01

    We examined the effects of two physical activity modes on depressive symptoms over a 5-year period among older adults and change in physical self-esteem as a mediator of changes in depressive symptoms. Formerly sedentary, older adults (N = 174) were randomly assigned into 6-month conditions of either walking or low-intensity resistance/flexibility training. Depressive symptoms and physical self-esteem were measured before and after the 6-month intervention, and 12 and 60 months after intervention initiation. Depressive symptoms scores were decreased immediately after the intervention, followed by a sustained reduction for 12 and 60 months after intervention initiation; there was no differential pattern of change between the physical activity modes. Change in physical self-esteem predicted change in depressive symptoms. This study supports the effectiveness of an exercise intervention for the sustained reduction of depressive symptoms among sedentary older adults and physical self-esteem as a potential mediator of this effect. PMID:16049630

  4. Comparison of U(VI) adsorption onto nanoscale zero-valent iron and red soil in the presence of U(VI)-CO3/Ca-U(VI)-CO3 complexes.

    PubMed

    Zhang, Zhibin; Liu, Jun; Cao, Xiaohong; Luo, Xuanping; Hua, Rong; Liu, Yan; Yu, Xiaofeng; He, Likai; Liu, Yunhai

    2015-12-30

    The influence of U(VI)-CO3 and Ca-U(VI)-CO3 complexes on U(VI) adsorption onto red soil and nanoscale zero-valent iron (NZVI) was investigated using batch adsorption and fixed-bed column experiments to simulate the feasibility of NZVI as the reactive medium in permeable- reactive barriers (PRB) for in situ remediation of uranium-contaminated red soils. The adsorption capacity (qe) and distribution constant (Kd) of NZVI and red soil decreased with increasing pH, dissolved carbonate and calcium concentrations, but the qe and Kd values of NZVI were 5-10 times higher than those of red soil. The breakthrough pore volume (PV) values increased with the decrease of pH, dissolved carbonate and calcium concentration; however, the breakthrough PV values of the PRB column filled with 5% NZVI were 2.0-3.5 times higher than the 100% red soil column. The U(VI)-CO3 complexes adsorbed onto the surface of red soil/NZVI (≡SOH) to form SO-UO2CO3(-) or SO-UO2 (CO3)2(3-). XPS and XRD analysis further confirmed the reduction of U(VI) to U(IV) and the formation of FeOOH on NZVI surfaces. The findings of this study are significant to the remediation of uranium-contaminated red soils and the consideration of practical U(VI) species in the natural environment. PMID:26280584

  5. Reduction of Floor Shock Vibration by Active Momentum Exchange Impact Damper

    NASA Astrophysics Data System (ADS)

    Son, Lovely; Yamada, Keisuke; Hara, Susumu; Utsuno, Hideo; Matsuhisa, Hiroshi

    This paper proposes an active control type of momentum exchange impact damper (AMEID) and its application to reducing shock vibration of the floor. The floor is modeled as a one-degree-of-freedom system. The active component of AMEID is realized by using a linear motor. The controller design of AMEID is based on the LQR optimal control theory. The simulation results show that the performance of AMEID is not affected by the mass ratio. In addition, the performance of AMEID is compared with the conventional passive momentum exchange impact damper (PMEID), the active mass damper (AMD) and the conventional active control method in reducing the floor shock vibration. It is shown that the shock reduction performance obtained by AMEID is larger than that obtained by PMEID. The power consumption and the stroke of the actuator for AMEID are lower than those of AMD. Furthermore, the transmitted force obtained by AMEID is smaller than that of the conventional active control.

  6. Localized, Non-Harmonic Active Flap Motions for Low Frequency In-Plane Rotor Noise Reduction

    NASA Technical Reports Server (NTRS)

    Sim, Ben W.; Potsdam, Mark; Kitaplioglu, Cahit; LeMasurier, Philip; Lorber, Peter; Andrews, Joseph

    2012-01-01

    A first-of-its-kind demonstration of the use of localized, non-harmonic active flap motions, for suppressing low frequency, in-plane rotor noise, is reported in this paper. Operational feasibility is verified via testing of the full-scale AATD/Sikorsky/UTRC active flap demonstration rotor in the NFAC's 40- by 80-Foot anechoic wind tunnel. Effectiveness of using localized, non-harmonic active flap motions are compared to conventional four-per-rev harmonic flap motions, and also active flap motions derived from closed-loop acoustics implementations. All three approaches resulted in approximately the same noise reductions over an in-plane three-by-three microphone array installed forward and near in-plane of the rotor in the nearfield. It is also reported that using an active flap in this localized, non-harmonic manner, resulted in no more that 2% rotor performance penalty, but had the tendency to incur higher hub vibration levels.

  7. Reduction of the Radiating Sound of a Submerged Finite Cylindrical Shell Structure by Active Vibration Control

    PubMed Central

    Kim, Heung Soo; Sohn, Jung Woo; Jeon, Juncheol; Choi, Seung-Bok

    2013-01-01

    In this work, active vibration control of an underwater cylindrical shell structure was investigated, to suppress structural vibration and structure-borne noise in water. Finite element modeling of the submerged cylindrical shell structure was developed, and experimentally evaluated. Modal reduction was conducted to obtain the reduced system equation for the active feedback control algorithm. Three Macro Fiber Composites (MFCs) were used as actuators and sensors. One MFC was used as an exciter. The optimum control algorithm was designed based on the reduced system equations. The active control performance was then evaluated using the lab scale underwater cylindrical shell structure. Structural vibration and structure-borne noise of the underwater cylindrical shell structure were reduced significantly by activating the optimal controller associated with the MFC actuators. The results provide that active vibration control of the underwater structure is a useful means to reduce structure-borne noise in water. PMID:23389344

  8. Effect of the mechanical activation on size reduction of crystalline acetaminophen drug particles.

    PubMed

    Biazar, Esmaeil; Beitollahi, Ali; Rezayat, S Mehdi; Forati, Tahmineh; Asefnejad, Azadeh; Rahimi, Mehdi; Zeinali, Reza; Ardeshir, Mahmoud; Hatamjafari, Farhad; Sahebalzamani, Ali; Heidari, Majid

    2009-01-01

    The decrease in particle size may offer new properties to drugs. In this study, we investigated the size reduction influence of the acetaminophen (C(8)H(9)O(2)N) particles by mechanical activation using a dry ball mill. The activated samples with the average size of 1 microm were then investigated in different time periods with the infrared (IR), inductively coupled plasma (ICP), atomic force microscopy (AFM), and X-ray diffraction (XRD) methods. The results of the IR and XRD images showed no change in the drug structure after the mechanical activation of all samples. With the peak height at full width at half maximum from XRD and the Scherrer equation, the size of the activated crystallite samples illustrated that the AFM images were in sound agreement with the Scherrer equation. According to the peaks of the AFM images, the average size of the particles in 30 hours of activation was 24 nm with a normal particle distribution. The ICP analysis demonstrated the presence of tungsten carbide particle impurities after activation from the powder sample impacting with the ball and jar. The greatest reduction in size was after milling for 30 hours. PMID:20054432

  9. Highly branched PtCu bimetallic alloy nanodendrites with superior electrocatalytic activities for oxygen reduction reactions

    NASA Astrophysics Data System (ADS)

    Fu, Shaofang; Zhu, Chengzhou; Shi, Qiurong; Xia, Haibing; Du, Dan; Lin, Yuehe

    2016-02-01

    Morphology control is a promising strategy to improve the catalytic performance of Pt-based catalysts. In this work, we reported a facile synthesis of PtCu bimetallic alloy nanodendrites using Brij 58 as a template. The highly branched structures and porous features offer relatively large surface areas, which is beneficial to the enhancement of the catalytic activity for oxygen reduction reactions in fuel cells. In addition, the elimination of carbon supports showed an important effect on the stability of the catalysts. By tuning the ratio of Pt and Cu precursors, PtCu nanodendrites were almost four times more active on the basis of an equivalent Pt mass for oxygen reduction reactions than the commercial Pt/C catalyst.Morphology control is a promising strategy to improve the catalytic performance of Pt-based catalysts. In this work, we reported a facile synthesis of PtCu bimetallic alloy nanodendrites using Brij 58 as a template. The highly branched structures and porous features offer relatively large surface areas, which is beneficial to the enhancement of the catalytic activity for oxygen reduction reactions in fuel cells. In addition, the elimination of carbon supports showed an important effect on the stability of the catalysts. By tuning the ratio of Pt and Cu precursors, PtCu nanodendrites were almost four times more active on the basis of an equivalent Pt mass for oxygen reduction reactions than the commercial Pt/C catalyst. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07682j

  10. A General Method for Multimetallic Platinum Alloy Nanowires as Highly Active and Stable Oxygen Reduction Catalysts.

    PubMed

    Bu, Lingzheng; Ding, Jiabao; Guo, Shaojun; Zhang, Xu; Su, Dong; Zhu, Xing; Yao, Jianlin; Guo, Jun; Lu, Gang; Huang, Xiaoqing

    2015-11-25

    An unconventional class of high-performance Pt alloy multimetallic nanowires (NWs) is produced by a general method. The obtained PtNi NWs exhibit amazingly specific and mass oxygen reduction reaction (ORR) activities with improvement factors of 51.1 and 34.6 over commercial Pt/C catalysts, respectively, and are also stable in ORR conditions, making them among the most efficient electrocatalysts for ORR. PMID:26459261

  11. Microbial Reduction of Uranium under Iron- and Sulfate-reducing Conditions: Effect of Amended Goethite on Microbial Community Composition and Dynamics

    SciTech Connect

    Moon, Hee Sun; McGuinness, L.; Kukkadapu, Ravi K.; Peacock, Aaron D.; Komlos, John; Kerkhoff, Lee; Long, Philip E.; Jaffe, Peter R.

    2010-07-01

    There is a growing need for a better understanding of the biogeochemical dynamics involved in microbial U(VI) reduction due to an increasing interest in using biostimulation via electron donor addition as a means to remediate uranium contaminated sites. U(VI) reduction has been observed to be maximized during iron reducing conditions and to decrease upon commencement of sulfate reducing conditions. There are many unknowns regarding the impact of iron/sulfate biogeochemistry on U(VI) reduction. This includes Fe(III) availability as well as the microbial community changes, including the activity of iron-reducers during the uranium biostimulation period even after the onset of sulfate reduction. Up-flow column experiments were conducted with Old Rifle site sediments containing Fe-oxides, Fe-clays, and sulfate rich groundwater. Half of the columns had sediment that was augmented with small amounts of small-particle 57Fe-goethite to track continuously minute goethite changes, and to study the effects of increased Fe(III) levels on the overall biostimulation dynamics. The addition of the 57Fe-goethite did not delay the onset of sulfate reduction, but slightly suppressed the overall rate of sulfate reduction and hence acetate utilization, it did not affect the bacterial numbers of Geobacter-like species throughout the experiment, but did lower the numbers of sulfate reducers in the sediments. 57Fe-Mössbauer analyses (a 57Fe-specific technique) confirmed that there was bioavailable iron present after the onset of sulfate reduction and that iron was still being reduced during sulfate reduction. Addition of the 57Fe-goethite to the sediment had a noticeable effect on the overall composition of the microbial population. 16S rRNA analyses of biostimulated sediment using TRFLP (terminal restriction fragment length polymorphism) showed that Geobacter sp. (a known Fe-reducer) was still active and replicating during the period of significant sulfate reduction. DNA fingerprints of

  12. Reduction of hexavalent chromium by Sphaerotilus natans a filamentous micro-organism present in activated sludges.

    PubMed

    Caravelli, Alejandro H; Giannuzzi, Leda; Zaritzky, Noemí E

    2008-08-15

    Wastewaters produced by various industries may contain undesirable amounts of hexavalent chromium (Cr(VI)), as chromate and dichromate, a hazardous metal affecting flora and animals of aquatic ecosystems as well as human health. One removal strategy comprises the microbial reduction of Cr(VI) to Cr(III), a less soluble chemical species that is less toxic than Cr(VI). In this work, the ability to reduce Cr(VI) of Sphaerotilus natans, a filamentous bacterium usually found in activated sludge systems, was evaluated. In aerobic conditions, S. natans was able to efficiently reduce Cr(VI) to Cr(III) from dichromate solutions ranging between 4.5 and 80 mg Cr(VI)l(-1) in the presence of a carbonaceous source. A simultaneous evaluation of the microbial respiratory activity inhibition was also carried out to analyze the toxic effect of Cr(VI). Cr(VI) reduction by S. natans was mathematically modeled; chromium(VI) reduction rate depended on both Cr(VI) concentration and active biomass concentration. Although it is known that S. natans removes heavy metal cations such as Cr(III) by biosorption, the ability of this micro-organism to reduce Cr(VI), which behaves as an oxyanion in aqueous solutions, is a novel finding. The distinctive capacity to reduce Cr(VI) to Cr(III) than remain soluble or precipitated becomes S. natans a potential micro-organism to decontaminate wastewaters. PMID:18215460

  13. Enhanced Activity of Nanocrystalline Zeolites for Selective Catalytic Reduction of NOx

    SciTech Connect

    Sarah C. Larson; Vicki H. Grassian

    2006-12-31

    Nanocrystalline zeolites with discrete crystal sizes of less than 100 nm have different properties relative to zeolites with larger crystal sizes. Nanocrystalline zeolites have improved mass transfer properties and very large internal and external surface areas that can be exploited for many different applications. The additional external surface active sites and the improved mass transfer properties of nanocrystalline zeolites offer significant advantages for selective catalytic reduction (SCR) catalysis with ammonia as a reductant in coal-fired power plants relative to current zeolite based SCR catalysts. Nanocrystalline NaY was synthesized with a crystal size of 15-20 nm and was thoroughly characterized using x-ray diffraction, electron paramagnetic resonance spectroscopy, nitrogen adsorption isotherms and Fourier Transform Infrared (FT-IR) spectroscopy. Copper ions were exchanged into nanocrystalline NaY to increase the catalytic activity. The reactions of nitrogen dioxides (NO{sub x}) and ammonia (NH{sub 3}) on nanocrystalline NaY and CuY were investigated using FT-IR spectroscopy. Significant conversion of NO{sub 2} was observed at room temperature in the presence of NH{sub 3} as monitored by FT-IR spectroscopy. Copper-exchanged nanocrystalline NaY was more active for NO{sub 2} reduction with NH{sub 3} relative to nanocrystalline NaY.

  14. Hierarchically porous carbons with optimized nitrogen doping as highly active electrocatalysts for oxygen reduction

    NASA Astrophysics Data System (ADS)

    Liang, Hai-Wei; Zhuang, Xiaodong; Brüller, Sebastian; Feng, Xinliang; Müllen, Klaus

    2014-09-01

    Development of efficient, low-cost and stable electrocatalysts as the alternative to platinum for the oxygen reduction reaction is of significance for many important electrochemical devices, such as fuel cells, metal-air batteries and chlor-alkali electrolysers. Here we report a highly active nitrogen-doped, carbon-based, metal-free oxygen reduction reaction electrocatalyst, prepared by a hard-templating synthesis, for which nitrogen-enriched aromatic polymers and colloidal silica are used as precursor and template, respectively, followed by ammonia activation. Our protocol allows for the simultaneous optimization of both porous structures and surface functionalities of nitrogen-doped carbons. Accordingly, the prepared catalysts show the highest oxygen reduction reaction activity (half-wave potential of 0.85 V versus reversible hydrogen electrode with a low loading of 0.1 mg cm-2) in alkaline media among all reported metal-free catalysts. Significantly, when used for constructing the air electrode of zinc-air battery, our metal-free catalyst outperforms the state-of the-art platinum-based catalyst.

  15. Hierarchically porous carbons with optimized nitrogen doping as highly active electrocatalysts for oxygen reduction.

    PubMed

    Liang, Hai-Wei; Zhuang, Xiaodong; Brüller, Sebastian; Feng, Xinliang; Müllen, Klaus

    2014-01-01

    Development of efficient, low-cost and stable electrocatalysts as the alternative to platinum for the oxygen reduction reaction is of significance for many important electrochemical devices, such as fuel cells, metal-air batteries and chlor-alkali electrolysers. Here we report a highly active nitrogen-doped, carbon-based, metal-free oxygen reduction reaction electrocatalyst, prepared by a hard-templating synthesis, for which nitrogen-enriched aromatic polymers and colloidal silica are used as precursor and template, respectively, followed by ammonia activation. Our protocol allows for the simultaneous optimization of both porous structures and surface functionalities of nitrogen-doped carbons. Accordingly, the prepared catalysts show the highest oxygen reduction reaction activity (half-wave potential of 0.85 V versus reversible hydrogen electrode with a low loading of 0.1 mg cm(-2)) in alkaline media among all reported metal-free catalysts. Significantly, when used for constructing the air electrode of zinc-air battery, our metal-free catalyst outperforms the state-of the-art platinum-based catalyst. PMID:25229121

  16. Stable platinum nanoclusters on genomic DNA–graphene oxide with a high oxygen reduction reaction activity

    PubMed Central

    Tiwari, Jitendra N.; Nath, Krishna; Kumar, Susheel; Tiwari, Rajanish N.; Kemp, K. Christian; Le, Nhien H.; Youn, Duck Hyun; Lee, Jae Sung; Kim, Kwang S.

    2013-01-01

    Nanosize platinum clusters with small diameters of 2–4 nm are known to be excellent catalysts for the oxygen reduction reaction. The inherent catalytic activity of smaller platinum clusters has not yet been reported due to a lack of preparation methods to control their size (<2 nm). Here we report the synthesis of platinum clusters (diameter ≤1.4 nm) deposited on genomic double-stranded DNA–graphene oxide composites, and their high-performance electrocatalysis of the oxygen reduction reaction. The electrochemical behaviour, characterized by oxygen reduction reaction onset potential, half-wave potential, specific activity, mass activity, accelerated durability test (10,000 cycles) and cyclic voltammetry stability (10,000 cycles) is attributed to the strong interaction between the nanosize platinum clusters and the DNA–graphene oxide composite, which induces modulation in the electronic structure of the platinum clusters. Furthermore, we show that the platinum cluster/DNA–graphene oxide composite possesses notable environmental durability and stability, vital for high-performance fuel cells and batteries. PMID:23900456

  17. Two-dimensional structure Au nanosheets are super active for the catalytic reduction of 4-nitrophenol.

    PubMed

    Zhang, Yan; Cui, Zhimin; Li, Lidong; Guo, Lin; Yang, Shihe

    2015-06-14

    Two-dimensional structure Au nanosheets with a polygon morphology and controlled thicknesses of ∼15 nm, ∼35 nm, and ∼50 nm were successfully synthesized by a one-step solution reduction method. Scanning and transmission electron microscopy (SEM and TEM), selected area electron diffraction (SEAD) analyses, and X-ray diffraction (XRD) were used to thoroughly study the structure and the formation mechanism of the nanosheets. The catalytic activity of the Au nanosheets was investigated for the reduction of 4-nitrophenol (4-NP) by UV-visible absorption spectroscopy. Against all expectation, the Au nanosheets with such a big lateral (more than 1 μm) size exhibited superior catalytic activity on the selective reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) in the presence of NaBH4. On the other hand, the catalytic activity does closely depend on the thickness of the nanosheets; that is, it decreases with increasing thickness. The reaction can be completed in less than 1 min when catalyzed by Au nanosheets about 15 nm thick. The 100% conversion efficiency was further demonstrated after two catalytic cycles with the thinnest Au nanosheets. PMID:25971868

  18. Catalytic Activity of Platinum Monolayer on Iridium and Rhenium Alloy Nanoparticles for the Oxygen Reduction Reaction

    SciTech Connect

    Karan, Hiroko I.; Sasaki, Kotaro; Kuttiyiel, Kurian; Farberow, Carrie A.; Mavrikakis, Manos; Adzic, Radoslav R.

    2012-05-04

    A new type of electrocatalyst with a core–shell structure that consists of a platinum monolayer shell placed on an iridium–rhenium nanoparticle core or platinum and palladium bilayer shell deposited on that core has been prepared and tested for electrocatalytic activity for the oxygen reduction reaction. Carbon-supported iridium–rhenium alloy nanoparticles with several different molar ratios of Ir to Re were prepared by reducing metal chlorides dispersed on Vulcan carbon with hydrogen gas at 400 °C for 1 h. These catalysts showed specific electrocatalytic activity for oxygen reduction reaction comparable to that of platinum. The activities of PtML/PdML/Ir2Re1, PtML/Pd2layers/Ir2Re1, and PtML/Pd2layers/Ir7Re3 catalysts were, in fact, better than that of conventional platinum electrocatalysts, and their mass activities exceeded the 2015 DOE target. Our density functional theory calculations revealed that the molar ratio of Ir to Re affects the binding strength of adsorbed OH and, thereby, the O2 reduction activity of the catalysts. The maximum specific activity was found for an intermediate OH binding energy with the corresponding catalyst on the top of the volcano plot. The monolayer concept facilitates the use of much less platinum than in other approaches. Finally, the results with the PtML/PdML/Ir2Re electrocatalyst indicate that it is a promising alternative to conventional Pt electrocatalysts in low-temperature fuel cells.

  19. A Strategy to Promote the Electrocatalytic Activity of Spinels for Oxygen Reduction by Structure Reversal.

    PubMed

    Wu, Guangping; Wang, Jun; Ding, Wei; Nie, Yao; Li, Li; Qi, Xueqiang; Chen, Siguo; Wei, Zidong

    2016-01-22

    The electrocatalytic performance of a spinel for the oxygen reduction reaction (ORR) can be significantly promoted by reversing its crystalline structure from the normal to the inverse. As the spinel structure reversed, the activation and cleavage of O-O bonds are accelerated owing to a dissimilarity effect of the distinct metal atoms co-occupying octahedral sites. The Co(II)Fe(III)Co(III)O4 spinel with the Fe and Co co-occupying inverse structure exhibits an excellent ORR activity, which even exceeds that of the state-of-the-art commercial Pt/C by 42 mV in alkaline medium. PMID:26663768

  20. Ag–Fe2O3 nanocomposites with enhanced catalytic activity for reduction of 4-nitrophenol

    NASA Astrophysics Data System (ADS)

    Liu, Shiben; Chen, Yingjie; Dong, Lifeng

    2016-07-01

    Hybrid nanostructures can be multifunctional and even possess enhanced properties. Ag–Fe2O3 nanocomposites and Ag nanoparticles (NPs) were fabricated and applied to catalyze the reduction of 4-nitrophenol. Compared with Ag NPs, Ag–Fe2O3 nanocomposites demonstrated enhanced catalytic activities. Furthermore, due to their magnetic properties, Ag–Fe2O3 nanocomposites could be easily separated from the reaction mixture and recycled through an external magnetic field. These findings will help us design hybrid nanostructures with catalytic activity and explore other potential applications of magnetic nanocomposites.

  1. Structure-activity relationship in high-performance iron-based electrocatalysts for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Song, Ping; Wang, Ying; Pan, Jing; Xu, Weilin; Zhuang, Lin

    2015-12-01

    A sustainable Iron (Fe), Nitrogen (N) co-doped high performance Fe-Nx/C electrocatalyst for oxygen reduction reaction (ORR) is synthesized simply based on nitric acid oxidation of cheap carbon black. The obtained optimal nonprecious metal electrocatalyst shows high ORR performance in both alkaline and acidic conditions and possesses appreciable performance/price ratio due to its low cost. Furthermore, the structure-activity relationship of different active sites on Fe-Nx/C is revealed systematically: Fe-N4/2-C > Fe4-N-C > N-C >> Fe4-C ≥ C, from both experimental and theoretical points of view.

  2. New stereoselective titanium reductive amination synthesis of 3-amino and polyaminosterol derivatives possessing antimicrobial activities.

    PubMed

    Salmi, Chanaz; Loncle, Celine; Vidal, Nicolas; Letourneux, Yves; Brunel, Jean Michel

    2008-03-01

    A series of 3-amino and polyaminosterol analogues of squalamine and trodusquemine were synthesized involving a new stereoselective titanium reductive amination reaction in high chemical yields of up to 95% in numerous cases. These derivatives were evaluated for their in vitro antimicrobial properties against human pathogens. Activity was highly dependent on the different compounds' structures involved and best results have been obtained with aminosterol derivatives 4b, 4e and 6i exhibiting activities against yeasts, Gram positive and Gram negative bacteria at average concentrations of 6.25-12.5 microg/mL. PMID:17566609

  3. An ene reductase from Clavispora lusitaniae for asymmetric reduction of activated alkenes.

    PubMed

    Ni, Yan; Yu, Hui-Lei; Lin, Guo-Qiang; Xu, Jian-He

    2014-03-01

    A putative ene reductase gene from Clavispora lusitaniae was heterologously overexpressed in Escherichia coli, and the encoded protein (ClER) was purified and characterized for its biocatalytic properties. This NADPH-dependent flavoprotein was identified with reduction activities toward a diverse range of activated alkenes including conjugated enones, enals, maleimide derivative and α,β-unsaturated carboxylic esters. The purified ClER exhibited a relatively high activity of 7.3 U mg(prot)⁻¹ for ketoisophorone while a remarkable catalytic efficiency (k(cat)/K(m)=810 s⁻¹ mM⁻¹) was obtained for 2-methyl-cinnamaldehyde due to the high affinity. A series of prochiral activated alkenes were stereoselectively reduced by ClER furnishing the corresponding saturated products in up to 99% ee. The practical applicability of ClER was further evaluated for the production of (R)-levodione, a valuable chiral compound, from ketoisophorone. Using the crude enzyme of ClER and glucose dehydrogenase (GDH), 500 mM of ketoisophorone was efficiently converted to (R)-levodione with excellent stereoselectivity (98% ee) within 1h. All these positive features demonstrate a high synthetic potential of ClER in the asymmetric reduction of activated alkenes. PMID:24564901

  4. Enhancing Electrocatalytic Oxygen Reduction on Nitrogen-Doped Graphene by Active Sites Implantation

    NASA Astrophysics Data System (ADS)

    Feng, Leiyu; Yang, Lanqin; Huang, Zujing; Luo, Jingyang; Li, Mu; Wang, Dongbo; Chen, Yinguang

    2013-11-01

    The shortage of nitrogen active sites and relatively low nitrogen content result in unsatisfying eletrocatalytic activity and durability of nitrogen-doped graphene (NG) for oxygen reduction reaction (ORR). Here we report a novel approach to substantially enhance electrocatalytic oxygen reduction on NG electrode by the implantation of nitrogen active sites with mesoporous graphitic carbon nitride (mpg-C3N4). Electrochemical characterization revealed that in neutral electrolyte the resulting NG (I-NG) exhibited super electrocatalytic activity (completely 100% of four-electron ORR pathway) and durability (nearly no activity change after 100000 potential cyclings). When I-NG was used as cathode catalyst in microbial fuel cells (MFCs), power density and its drop percentage were also much better than the NG and Pt/C ones, demonstrating that the current I-NG was a perfect alternative to Pt/C and offered a new potential for constructing high-performance and less expensive cathode which is crucial for large-scale application of MFC technology.

  5. Enhancing Electrocatalytic Oxygen Reduction on Nitrogen-Doped Graphene by Active Sites Implantation

    PubMed Central

    Feng, Leiyu; Yang, Lanqin; Huang, Zujing; Luo, Jingyang; Li, Mu; Wang, Dongbo; Chen, Yinguang

    2013-01-01

    The shortage of nitrogen active sites and relatively low nitrogen content result in unsatisfying eletrocatalytic activity and durability of nitrogen-doped graphene (NG) for oxygen reduction reaction (ORR). Here we report a novel approach to substantially enhance electrocatalytic oxygen reduction on NG electrode by the implantation of nitrogen active sites with mesoporous graphitic carbon nitride (mpg-C3N4). Electrochemical characterization revealed that in neutral electrolyte the resulting NG (I-NG) exhibited super electrocatalytic activity (completely 100% of four-electron ORR pathway) and durability (nearly no activity change after 100000 potential cyclings). When I-NG was used as cathode catalyst in microbial fuel cells (MFCs), power density and its drop percentage were also much better than the NG and Pt/C ones, demonstrating that the current I-NG was a perfect alternative to Pt/C and offered a new potential for constructing high-performance and less expensive cathode which is crucial for large-scale application of MFC technology. PMID:24264379

  6. The Validation of an Active Control Intervention for Mindfulness Based Stress Reduction (MBSR)

    PubMed Central

    MacCoon, Donal G.; Imel, Zac E.; Rosenkranz, Melissa A.; Sheftel, Jenna G.; Weng, Helen Y.; Sullivan, Jude C.; Bonus, Katherine A.; Stoney, Catherine M.; Salomons, Tim V.; Davidson, Richard J.; Lutz, Antoine

    2011-01-01

    Most of the extant literature investigating the health effects of mindfulness interventions relies on wait-list control comparisons. The current article specifies and validates an active control condition, the Health Enhancement Program (HEP), thus providing the foundation necessary for rigorous investigations of the relative efficacy of Mindfulness Based Stress Reduction (MBSR) and for testing mindfulness as an active ingredient. 63 participants were randomized to either MBSR (n=31) or HEP (n=32). Compared to HEP, MBSR led to reductions in thermal pain ratings in the mindfulness- but not the HEP-related instruction condition (η2=.18). There were significant improvements over time for general distress (η2=.09), anxiety (η2=.08), hostility (η2=.07), and medical symptoms (η2=.14), but no effects of intervention. Practice was not related to change. HEP is an active control condition for MBSR while remaining inert to mindfulness. These claims are supported by results from a pain task. Participant-reported outcomes (PROs) replicate previous improvements to well-being in MBSR, but indicate that MBSR is no more effective than a rigorous active control in improving these indices. These results emphasize the importance of using an active control condition like HEP in studies evaluating the effectiveness of MBSR. PMID:22137364

  7. Enhancement of oxygen reduction reaction activities by Pt nanoclusters decorated on ordered mesoporous porphyrinic carbons

    DOE PAGESBeta

    Sun-Mi Hwang; Choi, YongMan; Kim, Min Gyu; Sohn, Young-Jun; Cheon, Jae Yeong; Joo, Sang Hoon; Yim, Sung-Dae; Kuttiyiel, Kurian A.; Sasaki, Kotaro; Adzic, Radoslav R.; et al

    2016-03-08

    The high cost of Pt-based membrane electrode assemblies (MEAs) is a critical hurdle for the commercialization of polymer electrolyte fuel cells (PEFCs). Recently, non-precious metal-based catalysts (NPMCs) have demonstrated much enhanced activity but their oxygen reduction reaction (ORR) activity is still inferior to that of Pt-based catalysts resulting in a much thicker electrode in the MEA. For the reduction of mass transport and ohmic overpotential we adopted a new concept of catalyst that combines an ultra-low amount of Pt nanoclusters with metal–nitrogen (M–Nx) doped ordered mesoporous porphyrinic carbon (FeCo–OMPC(L)). The 5 wt% Pt/FeCo–OMPC(L) showed a 2-fold enhancement in activities comparedmore » to a higher loading of Pt. Our experimental results supported by first-principles calculations indicate that a trace amount of Pt nanoclusters on FeCo–OMPC(L) significantly enhances the ORR activity due to their electronic effect as well as geometric effect from the reduced active sites. Finally, in terms of fuel cell commercialization, this class of catalysts is a promising candidate due to the limited use of Pt in the MEA.« less

  8. Uranium(VI) Reduction by Nanoscale Zerovalent Iron in Anoxic Batch Systems

    SciTech Connect

    Yan, Sen; Hua, Bin; Bao, Zhengyu; Yang, John; Liu, Chongxuan; Deng, Baolin

    2010-11-17

    This study investigated the influences of pH, bicarbonate, and calcium on U(VI) adsorption and reduction by synthetic nanosize zero valent iron (nano Fe0) particles under an anoxic condition. The results showed that about 87.1%, 82.7% and 78.3% of U(VI) could be reduced within 96 hours in the presence of 10 mM bicarbonate at pHs 6.92, 8.03 and 9.03, respectively. The rates of U(VI) reduction and adsorption by nano Fe0, however, varied significantly with increasing pH and concentrations of bicarbonate and/or calcium. Solid phase analysis by X-ray photoelectron spectroscopy confirmed the formation of UO2 and iron (hydr)oxides as a result of the redox interactions between adsorbed U(VI) and nano Fe0. This study highlights the potential important role of groundwater chemical composition in controlling the rates of U(VI) reductive immobilization using nano Fe0 in subsurface environments.

  9. Reaction-Based Reactive Transport Modeling of Fe(III) and U(V) Reduction

    SciTech Connect

    Burgos, William D.; Roden, Eric E.; Yeh, Gour-Tsyh

    2005-06-01

    Our new research project (started Fall 2004) was funded by a grant to The Pennsylvania State University, University of Central Florida, and The University of Alabama in the Integrative Studies Element of the NABIR Program (DE-FG04-ER63914/63915/63196). Our previous NABIR project (DE-FG02-01ER63180/63181/63182, funded within the Biotransformation Element) focused on (1) microbial reduction of Fe(III) and U(VI) individually, and concomitantly in natural sediments, (2) Fe(III) oxide surface chemistry, specifically with respect to reactions with Fe(II) and U(VI), (3) the influence of humic substances on Fe(III) and U(VI) bioreduction, and on U(VI) complexation, and (4) the development of reaction-based reactive transport biogeochemical models to numerically simulate our experimental results. The new project focuses on the development of a mechanistic understanding and quantitative models of coupled Fe(III)/U(VI) reduction in FRC Area 2 sediments. This work builds on our previous studies of microbial Fe(III) and U(VI) reduction, and is directly aligned with the Scheibe et al. NABIR FRC Field Project at Area 2.

  10. High performance of phosphate-functionalized graphene oxide for the selective adsorption of U(VI) from acidic solution

    NASA Astrophysics Data System (ADS)

    Liu, Xia; Li, Jiaxing; Wang, Xiangxue; Chen, Changlun; Wang, Xiangke

    2015-11-01

    In this study, phosphate-functionalized graphene oxide (PGO) was prepared by grafting triethyl phosphite onto the surface of GO using Arbuzov reaction. The as-prepared PGO was characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, Fourier transformed infrared spectroscopy and Zeta potential. The application of the PGO to remove U(VI) from aqueous solution was investigated with a maximum adsorption capacity of 251.7 mg/g at pH = 4.0 ± 0.1 and T = 303 K. The adsorption mechanism was also investigated by X-ray photoelectron spectroscopy analysis, indicating a chemical adsorption of U(VI) on PGO surface. Moreover, experimental results gave a better removal efficiency toward U(VI) on PGO surface than other heavy metal ions at acidic solution, indicating the selective extraction of U(VI) from environmental pollutants.

  11. Reduction of hexavalent chromium using Aerva lanata L.: elucidation of reduction mechanism and identification of active principles.

    PubMed

    Poonkuzhali, K; Rajeswari, V; Saravanakumar, T; Viswanathamurthi, P; Park, Seung-Moon; Govarthanan, M; Sathishkumar, P; Palvannan, T

    2014-05-15

    The effluent discharge treatment for controlling the environment from non biodegradable metal contaminants using plant extract is an efficient technique. The reduction of hexavalent chromium by abundantly available weed, Aerva lanata L. was investigated using batch equilibrium technique. The variables studied were Cr(VI) concentration, Aerva lanata L. dose, contact time, pH, temperature and agitation speed. Cyclic voltammetry and ICP-MS analysis confirmed the reduction of Cr(VI) to Cr(III). Electrochemical analysis proved that, the chromium has not been degraded and the valency of the chromium has only been changed. ICP-MS analysis shows that 100ng/L of hexavalent chromium was reduced to 97.01ng/L trivalent chromium. These results suggest that components present in the Aerva lanata L. are responsible for the reduction of Cr(VI) to Cr(III). The prime components ferulic acid, kaempherol and β-carboline present in the Aerva lanata L. may be responsible for the reduction of Cr(VI) as evident from LC-MS analysis. PMID:24681590

  12. Influence of ammonium availability on expression of nifD and amtB genes during biostimulation of a U(VI) contaminated aquifer: implications for U(VI) removal and monitoring the metabolic state of Geobacteraceae

    SciTech Connect

    Mouser, Paula J.; N'Guessan, A. Lucie; Elifantz, Hila; Holmes, Dawn E.; Williams, Kenneth H; Wilkins, Michael J.; Long, Philip E.; Lovley, Derek R.

    2009-03-25

    The influence of ammonium availability on bacterial community structure and the physiological status of Geobacter species during in situ bioremediation of uranium-contaminated groundwater was evaluated. Ammonium concentrations varied by 2 orders of magnitude (<4 to 400 ?M) across the study site. Analysis of 16S rRNA sequences suggested that ammonium may have been one factor influencing the community composition prior to acetate amendment with Rhodoferax species predominating over Geobacter species with higher ammonium and Dechloromonas species dominating at the site with lowest ammonium. However, once acetate was added and dissimilatory metal reduction was stimulated, Geobacter species became the predominant organisms at all locations. Rates of U(VI) reduction appeared to be more related to acetate concentrations rather than ammonium levels. In situ mRNA transcript abundance of the nitrogen fixation gene, nifD, and the ammonium transporter gene, amtB, in Geobacter species indicated that ammonium was the primary source of nitrogen during uranium reduction. The abundance of amtB was inversely correlated to ammonium levels, whereas nifD transcript levels were similar across all sites examined. These results suggest that nifD and amtB expression are closely regulated in response to ammonium availability to ensure an adequate supply of nitrogen while conserving cell resources. Thus, quantifying nifD and amtB transcript expression appears to be a useful approach for monitoring the nitrogen-related physiological status of subsurface Geobacter species. This study also emphasizes the need for more detailed analysis of geochemical and physiological interactions at the field scale in order to adequately model subsurface microbial processes during bioremediation.

  13. UVIS CCD EPER CTE measurements performed during the April 2007 Ambient Calibration campaign (SMS UV02S01)

    NASA Astrophysics Data System (ADS)

    Robberto, Massimo

    The UVIS spare detector (UVIS build 2) has been installed in WFC3 and used for a short ambient ground test campaign in April 2007. Tests have been performed using the Extended Pixel Edge Response (EPER) measure of the Charge Transfer Efficiency. In this ISR I describe the methods and results of the test. The Charge Transfer Efficiency appears to be higher than 99.9999%, in agreement with previous DCL measures.

  14. Enhancement of sludge reduction and methane production by removing extracellular polymeric substances from waste activated sludge.

    PubMed

    Nguyen, Minh Tuan; Mohd Yasin, Nazlina Haiza; Miyazaki, Toshiki; Maeda, Toshinari

    2014-12-01

    The management of waste activated sludge (WAS) recycling is a concern that affects the development of the future low-carbon society, particularly sludge reduction and biomass utilization. In this study, we investigated the effect of removing extracellular polymeric substances (EPS), which play important roles in the adhesion and flocculation of WAS, on increased sludge disintegration, thereby enhancing sludge reduction and methane production by anaerobic digestion. EPS removal from WAS by ethylenediaminetetraacetic acid (EDTA) significantly enhanced sludge reduction, i.e., 49 ± 5% compared with 27 ± 1% of the control at the end the digestion process. Methane production was also improved in WAS without EPS by 8881 ± 109 CH4 μmol g(-1) dry-weight of sludge. Microbial activity was determined by denaturing gradient gel electrophoresis and real-time polymerase chain reaction, which showed that the hydrolysis and acetogenesis stages were enhanced by pretreatment with 2% EDTA, with a larger methanogenic community and better methane production. PMID:25277968

  15. U(VI) bioreduction with emulsified vegetable oil as the electron donor-Model application to a field test

    SciTech Connect

    Tang, Guoping; Watson, David B; Wu, Wei-min; Schadt, Christopher Warren; Parker, Jack C; Brooks, Scott C

    2013-01-01

    A one-time 2-hour emulsified vegetable oil (EVO) injection in a fast flowing aquifer decreased U discharge to a stream for over a year. Using a comprehensive biogeochemical model developed in the companion article based on microcosm tests, we approximately matched the observed acetate, nitrate, Fe, U, and sulfate concentrations, and described the major evolution trends of multiple microbial functional groups in the field test. While the lab-determined parameters were generally applicable in the field-scale simulation, the EVO hydrolysis rate constant was estimated to be an order of magnitude greater in the field than in the microcosms. The model predicted substantial biomass (sulfate reducers) and U(IV) accumulation near the injection wells and along the side boundaries of the treatment zone where electron donors (long-chain fatty acids) from the injection wells met electron acceptors (sulfate) from the surrounding environment. While EVO retention and hydrolysis characteristics were expected to control treatment longevity, modeling results indicated that electron acceptors such as sulfate may not only compete for electrons but also play a conducive role in degrading complex substrates and enhancing U(VI) reduction and immobilization. As a result, the spacing of the injection wells could be optimized for effective sustainable bioremediation.

  16. Is dihydrolipoic acid among the reductive activators of parasite CysHis proteases?

    PubMed

    Lockwood, Thomas D

    2008-04-01

    Activities of mature CysHis proteases depend upon relative rates of oxidations vs. reductions of catalytic sulfur by multiple enzymatic and non-enzymatic reactions. CysHis peptidolysis is inhibited by Fe3+ but not Fe2+. Others report the paradox that malarial parasites require exogenous free lipoic acid (LA) from human host, although the apicoplast organelle produces it. Extra-cellular LA disulfide can be taken up and reduced to dihydrolipoic acid (DHLA) by reductases of any cell type. Here, the opposing effects of DHLA vs. Fe3+ on the falcipain-2 hemoglobinase were investigated employing Z-Phe-Arg-AMC substrate. Despite limited solubility, non-regenerated DHLA (10 microM, threshold 2 microM) was found to be the most potent activator of the air-inactivated (sulfoxygenated) protease discovered thus far. Activation was preemptively opposed by Fe3+, but not Fe2+. However, cruzain from T. cruzi, and cathepsin B from mammal were indistinguishable in their responsiveness to DHLA and Fe redox. Thus, DHLA activation vs. Fe3+ inhibition is not unique to falcipain-2 or apicomplexans but is rather a primordial feature of CysHis peptidolysis. Free LA and/or unassociated lipoylated enzyme subunits could be among multiple pathways shuttling reducing equivalents to reduction of proteins, including CysHis proteases. It is discussed that opposing DHLA-Fe3+ modification of plasmodial proteolysis might be a specialized adaptation to intra-erythrocytic growth. PMID:18068706

  17. Aligned carbon nanotube with electro-catalytic activity for oxygen reduction reaction

    DOEpatents

    Liu, Di-Jia; Yang, Junbing; Wang, Xiaoping

    2010-08-03

    A catalyst for an electro-chemical oxygen reduction reaction (ORR) of a bundle of longitudinally aligned carbon nanotubes having a catalytically active transition metal incorporated longitudinally in said nanotubes. A method of making an electro-chemical catalyst for an oxygen reduction reaction (ORR) having a bundle of longitudinally aligned carbon nanotubes with a catalytically active transition metal incorporated throughout the nanotubes, where a substrate is in a first reaction zone, and a combination selected from one or more of a hydrocarbon and an organometallic compound containing an catalytically active transition metal and a nitrogen containing compound and an inert gas and a reducing gas is introduced into the first reaction zone which is maintained at a first reaction temperature for a time sufficient to vaporize material therein. The vaporized material is then introduced to a second reaction zone maintained at a second reaction temperature for a time sufficient to grow longitudinally aligned carbon nanotubes over the substrate with a catalytically active transition metal incorporated throughout the nanotubes.

  18. A modified oxic-settling-anaerobic activated sludge process using gravity thickening for excess sludge reduction

    NASA Astrophysics Data System (ADS)

    Wang, Jun; Li, Shi-Yu; Jiang, Feng; Wu, Ke; Liu, Guang-Li; Lu, Hui; Chen, Guang-Hao

    2015-09-01

    Oxic-settling-anaerobic process (OSA) was known as a cost-effective way to reduce the excess sludge production with simple upgrade of conventional activated sludge process (CAS). A low oxidation-reduction potential (ORP) level was the key factor to sludge decay and lysis in the sludge holding tank of the OSA process. However, the ORP control with nitrogen purge or chemical dosing in the OSA process would induce extra expense and complicate the operation. Hence, in this study, a sludge holding tank using gravity thickening was applied to OSA process to reduce the excess sludge production without any ORP control. Results showed that the modified OSA process not only reduced the excess sludge production effectively but also improved the sludge settleability without affected the treatment capacity. The reduction of the excess sludge production in the modified OSA process resulted from interactions among lots of factors. The key element of the process was the gravity thickening sludge holding tank.

  19. A modified oxic-settling-anaerobic activated sludge process using gravity thickening for excess sludge reduction

    PubMed Central

    Wang, Jun; Li, Shi-Yu; Jiang, Feng; Wu, Ke; Liu, Guang-Li; Lu, Hui; Chen, Guang-Hao

    2015-01-01

    Oxic-settling-anaerobic process (OSA) was known as a cost-effective way to reduce the excess sludge production with simple upgrade of conventional activated sludge process (CAS). A low oxidation-reduction potential (ORP) level was the key factor to sludge decay and lysis in the sludge holding tank of the OSA process. However, the ORP control with nitrogen purge or chemical dosing in the OSA process would induce extra expense and complicate the operation. Hence, in this study, a sludge holding tank using gravity thickening was applied to OSA process to reduce the excess sludge production without any ORP control. Results showed that the modified OSA process not only reduced the excess sludge production effectively but also improved the sludge settleability without affected the treatment capacity. The reduction of the excess sludge production in the modified OSA process resulted from interactions among lots of factors. The key element of the process was the gravity thickening sludge holding tank. PMID:26350761

  20. Probing the interaction of U(VI) with phosphonate-functionalized mesoporous silica using solid-state NMR spectroscopy

    DOE PAGESBeta

    Uribe, Eva C.; Mason, Harris E.; Shusterman, Jennifer A.; Bruchet, Anthony; Nitsche, Heino

    2016-05-30

    The fundamental interaction of U(VI) with diethylphosphatoethyl triethoxysilane functionalized SBA-15 mesoporous silica is studied by macroscopic batch experiments and solid-state NMR spectroscopy. DPTS-functionalized silica has been shown to extract U(VI) from nitric acid solutions at or above pH 3. Extraction is dependent on pH and ionic strength. Single-pulse 31P NMR on U(VI) contacted samples revealed that U(VI)only interacts with a fraction of the ligands present on the surface. At pH 4 the U(VI) extraction capacity of the material is limited to 27–37% of the theoretical capacity, based on ligand loading. We combined single pulse 31P NMR on U(VI)-contacted samples withmore » batch studies to measure a ligand-to-metal ratio of approximately 2 : 1 at pH 3 and 4. Batch studies and cross-polarization NMR measurements reveal that U(VI) binds to deprotonated phosphonate and/or silanol sites. We use 31P–31P DQ-DRENAR NMR studies to compare the average dipolar coupling between phosphorus spins for both U(VI)-complexed and non-complexed ligand environments. Furthermore, these measurements reveal that U(VI) extraction is not limited by inadequate surface distribution of ligands, but rather by low stability of the surface phosphonate complex.« less

  1. Drag and lift reduction of a 3D bluff-body using active vortex generators

    NASA Astrophysics Data System (ADS)

    Aider, Jean-Luc; Beaudoin, Jean-François; Wesfreid, José Eduardo

    2010-05-01

    In this study, a passive flow control experiment on a 3D bluff-body using vortex generators (VGs) is presented. The bluff-body is a modified Ahmed body (Ahmed in J Fluids Eng 105:429-434 1983) with a curved rear part, instead of a slanted one, so that the location of the flow separation is no longer forced by the geometry. The influence of a line of non-conventional trapezoïdal VGs on the aerodynamic forces (drag and lift) induced on the bluff-body is investigated. The high sensitivity to many geometric (angle between the trapezoïdal element and the wall, spanwise spacing between the VGs, longitudinal location on the curved surface) and physical (freestream velocity) parameters is clearly demonstrated. The maximum drag reduction is -12%, while the maximum global lift reduction can reach more than -60%, with a strong dependency on the freestream velocity. For some configurations, the lift on the rear axle of the model can be inverted (-104%). It is also shown that the VGs are still efficient even downstream of the natural separation line. Finally, a dynamic parameter is chosen and a new set-up with motorized vortex generators is proposed. Thanks to this active device. The optimal configurations depending on two parameters are found more easily, and a significant drag and lift reduction (up to -14% drag reduction) can be reached for different freestream velocities. These results are then analyzed through wall pressure and velocity measurements in the near-wake of the bluff-body with and without control. It appears that the largest drag and lift reduction is clearly associated to a strong increase of the size of the recirculation bubble over the rear slant. Investigation of the velocity field in a cross-section downstream the model reveals that, in the same time, the intensity of the longitudinal trailing vortices is strongly reduced, suggesting that the drag reduction is due to the breakdown of the balance between the separation bubble and the longitudinal vortices

  2. Boreal winter comparison of auroral images from Polar UVI and IMAGE FUV

    NASA Astrophysics Data System (ADS)

    Spann, J. F.; Germany, G.; Maddox, W.; Fillingim, M.; Parks, G.; Mende, S.

    2004-12-01

    Same-scene images made with Polar UVI and IMAGE FUV are compared for the boreal winter of 2000-2001. The results of the comparison are used to determine whether the use of both instruments could lead to a better evaluation of the average precipitation and total energy input than with either one individually. These results are a part of a broader investigation to quantitatively compare conjugate images using both instruments and to correlate observed asymmetries with solar wind and seasonal parameters.

  3. Establishing a relationship between activity reduction in human perirhinal cortex and priming.

    PubMed

    Voss, Joel L; Hauner, Katherina K Y; Paller, Ken A

    2009-09-01

    Perirhinal neurons exhibit reduced firing rates with stimulus repetition, a phenomenon termed "repetition suppression." However, relationships between perirhinal repetition suppression and behavioral expressions of memory remain unclear. We used anatomically constrained functional magnetic resonance imaging (fMRI) to assess relationships between perirhinal activity and priming, a type of implicit memory. Priming was expressed as speeded animacy judgments for old versus new words. Concurrently, old words elicited less neural activity in bilateral perirhinal cortex. The magnitude of the left perirhinal activity reduction selectively predicted the magnitude of behavioral priming in an across-subjects hierarchical linear regression analysis. These findings have implications for considering how perirhinal cortex may contribute to different neurocognitive functions, possibly including both implicit memory and familiarity-based recognition. This study documents the first evidence linking behavioral measures of priming to information processing in perirhinal cortex. PMID:19405122

  4. Elucidating the activity of stepped Pt single crystals for oxygen reduction.

    PubMed

    Bandarenka, Aliaksandr S; Hansen, Heine A; Rossmeisl, Jan; Stephens, Ifan E L

    2014-07-21

    The unexpectedly high measured activity of Pt[n(111) × (111)] and Pt[n(111) × (100)] stepped single crystal surfaces towards the oxygen reduction reaction (ORR) is explained utilizing the hydroxyl binding energy as the activity descriptor. Using this descriptor (estimated using experimental data obtained by different groups), a well-defined Sabatier-type volcano is observed for the activities measured for the Pt[n(111) × (111)] and Pt[n(111) × (100)] stepped single crystals, in remarkable agreement with earlier theoretical studies. We propose that the observed destabilisation of *OH species at these surfaces is due to the decreased solvation of the adsorbed hydroxyl intermediates on adjacent terrace sites. PMID:24643715

  5. Catalytic activity trends of oxygen reduction reaction for nonaqueous Li-air batteries.

    PubMed

    Lu, Yi-Chun; Gasteiger, Hubert A; Shao-Horn, Yang

    2011-11-30

    We report the intrinsic oxygen reduction reaction (ORR) activity of polycrystalline palladium, platinum, ruthenium, gold, and glassy carbon surfaces in 0.1 M LiClO(4) 1,2-dimethoxyethane via rotating disk electrode measurements. The nonaqueous Li(+)-ORR activity of these surfaces primarily correlates to oxygen adsorption energy, forming a "volcano-type" trend. The activity trend found on the polycrystalline surfaces was in good agreement with the trend in the discharge voltage of Li-O(2) cells catalyzed by nanoparticle catalysts. Our findings provide insights into Li(+)-ORR mechanisms in nonaqueous media and design of efficient air electrodes for Li-air battery applications. PMID:22044022

  6. Improved oxygen reduction activity on Pt3Ni(111) via increased surface site availability.

    PubMed

    Stamenkovic, Vojislav R; Fowler, Ben; Mun, Bongjin Simon; Wang, Guofeng; Ross, Philip N; Lucas, Christopher A; Marković, Nenad M

    2007-01-26

    The slow rate of the oxygen reduction reaction (ORR) in the polymer electrolyte membrane fuel cell (PEMFC) is the main limitation for automotive applications. We demonstrated that the Pt3Ni(111) surface is 10-fold more active for the ORR than the corresponding Pt(111) surface and 90-fold more active than the current state-of-the-art Pt/C catalysts for PEMFC. The Pt3Ni(111) surface has an unusual electronic structure (d-band center position) and arrangement of surface atoms in the near-surface region. Under operating conditions relevant to fuel cells, its near-surface layer exhibits a highly structured compositional oscillation in the outermost and third layers, which are Pt-rich, and in the second atomic layer, which is Ni-rich. The weak interaction between the Pt surface atoms and nonreactive oxygenated species increases the number of active sites for O2 adsorption. PMID:17218494

  7. Palladium–platinum core-shell icosahedra with substantially enhanced activity and durability towards oxygen reduction

    SciTech Connect

    Wang, Xue; Choi, Sang-Il; Roling, Luke T.; Luo, Ming; Ma, Cheng; Zhang, Lei; Chi, Miaofang; Liu, Jingyue; Xie, Zhaoxiong; Herron, Jeffrey A.; Mavrikakis, Manos; Xia, Younan

    2015-07-02

    Conformal deposition of platinum as ultrathin shells on facet-controlled palladium nanocrystals offers a great opportunity to enhance the catalytic performance while reducing its loading. Here we report such a system based on palladium icosahedra. Owing to lateral confinement imposed by twin boundaries and thus vertical relaxation only, the platinum overlayers evolve into a corrugated structure under compressive strain. For the core-shell nanocrystals with an average of 2.7 platinum overlayers, their specific and platinum mass activities towards oxygen reduction are enhanced by eight- and sevenfold, respectively, relative to a commercial catalyst. Density functional theory calculations indicate that the enhancement can be attributed to the weakened binding of hydroxyl to the compressed platinum surface supported on palladium. After 10,000 testing cycles, the mass activity of the core-shell nanocrystals is still four times higher than the commercial catalyst. Ultimately, these results demonstrate an effective approach to the development of electrocatalysts with greatly enhanced activity and durability.

  8. Palladium-platinum core-shell icosahedra with substantially enhanced activity and durability towards oxygen reduction

    NASA Astrophysics Data System (ADS)

    Wang, Xue; Choi, Sang-Il; Roling, Luke T.; Luo, Ming; Ma, Cheng; Zhang, Lei; Chi, Miaofang; Liu, Jingyue; Xie, Zhaoxiong; Herron, Jeffrey A.; Mavrikakis, Manos; Xia, Younan

    2015-07-01

    Conformal deposition of platinum as ultrathin shells on facet-controlled palladium nanocrystals offers a great opportunity to enhance the catalytic performance while reducing its loading. Here we report such a system based on palladium icosahedra. Owing to lateral confinement imposed by twin boundaries and thus vertical relaxation only, the platinum overlayers evolve into a corrugated structure under compressive strain. For the core-shell nanocrystals with an average of 2.7 platinum overlayers, their specific and platinum mass activities towards oxygen reduction are enhanced by eight- and sevenfold, respectively, relative to a commercial catalyst. Density functional theory calculations indicate that the enhancement can be attributed to the weakened binding of hydroxyl to the compressed platinum surface supported on palladium. After 10,000 testing cycles, the mass activity of the core-shell nanocrystals is still four times higher than the commercial catalyst. These results demonstrate an effective approach to the development of electrocatalysts with greatly enhanced activity and durability.

  9. Chemical and enzymatic reductive activation of acylfulvene to isomeric cytotoxic reactive intermediates

    PubMed Central

    Pietsch, Kathryn E.; Neels, James F.; Yu, Xiang; Gong, Jiachang; Sturla, Shana J.

    2011-01-01

    Acylfulvenes, a class of semisynthetic analogues of the sesquiterpene natural product illudin S, are cytotoxic towards cancer cells. The minor structural changes between illudin S and AFs translate to an improved therapeutic window in preclinical cell-based assays and xenograft models. AFs are, therefore, unique tools for addressing the chemical and biochemical basis of cytotoxic selectivity. AFs elicit cytotoxic responses by alkylation of biological targets, including DNA. While AFs are capable of direct alkylation, cytosolic reductive bioactivation to an electrophilic intermediate is correlated with enhanced cytotoxicity. Data obtained in this study illustrates chemical aspects of the process of AF activation. By tracking reaction mechanisms with stable isotope-labeled reagents, enzymatic versus chemical activation pathways for AF were compared for reactions involving the NADPH-dependent enzyme prostaglandin reductase 1 (PTGR1) or sodium borohydride, respectively. These two processes resulted in isomeric products that appear to give rise to similar patterns of DNA modification. The chemically activated isomer has been newly isolated and chemically characterized in this study, including an assessment of its relative stereochemistry, and stability at varying pH and under bioassay conditions. In mammalian cancer cells, this chemically activated analog was shown to not rely on further cellular activation to significantly enhance cytotoxic potency, in contrast to the requirements of AF. On the basis of this study, we anticipate that the chemically activated form of AF will serve as a useful chemical probe for evaluating biomolecular interactions independent of enzyme-mediated activation. PMID:21939268

  10. Controlled reduction of red mud waste to produce active systems for environmental applications: heterogeneous Fenton reaction and reduction of Cr(VI).

    PubMed

    Costa, Regina C C; Moura, Flávia C C; Oliveira, Patrícia E F; Magalhães, Fabiano; Ardisson, José D; Lago, Rochel M

    2010-02-01

    In this work, controlled reduction of red mud with H(2) was used to produce active systems for two different environmental applications, i.e. the heterogeneous Fenton reaction and the reduction of Cr(VI). Mössbauer, powder X-ray diffraction, thermal analyses and scanning electron microscopy analyses showed that at different temperatures, i.e. 300, 400, 500 and 600 degrees C, H(2) reduces red mud to different phases, mainly Fe(3)O(4), Fe(0)/Fe(3)O(4) and Fe(0). These Fe phases are dispersed on Al, Si and Ti oxides present in the red mud and show high reactivity towards two environmental applications, i.e. the heterogeneous Fenton reaction and the reduction of Cr(VI). Reduction with H(2) at 400 degrees C showed the best results for the oxidation of the model dye methylene blue with H(2)O(2) at neutral pH due to the presence of the composite Fe(0)/Fe(3)O(4). The reduced red mud at 500-600 degrees C produced Fe(0) highly active for the reduction of Cr(VI) in aqueous medium. Another feature of these red mud based system is that after deactivation due to extensive use they can be completely regenerated by simple treatment with H(2). PMID:20060564

  11. HST/WFC3: Evolution of the UVIS Channel's Charge Transfer Efficiency

    NASA Astrophysics Data System (ADS)

    Gosmeyer, Catherine; Baggett, Sylvia M.; Anderson, Jay; WFC3 Team

    2016-06-01

    The Wide Field Camera 3 (WFC3) on the Hubble Space Telescope (HST) contains both an IR and a UVIS channel. After more than six years on orbit, the UVIS channel performance remains stable; however, on-orbit radiation damage has caused the charge transfer efficiency (CTE) of UVIS's two CCDs to degrade. This degradation is seen as vertical charge 'bleeding' from sources during readout and its effect evolves as the CCDs age. The WFC3 team has developed software to perform corrections that push the charge back to the sources, although it cannot recover faint sources that have been bled out entirely. Observers can mitigate this effect in various ways such as by placing sources near the amplifiers, observing bright targets, and by increasing the total background to at least 12 electrons, either by using a broader filter, lengthening exposure time, or post-flashing. We present results from six years of calibration data to re-evaluate the best level of total background for mitigating CTE loss and to re-verify that the pixel-based CTE correction software is performing optimally over various background levels. In addition, we alert observers that CTE-corrected products are now available for retrieval from MAST as part of the CALWF3 v3.3 pipeline upgrade.

  12. Pharmacologic reduction in tumor necrosis factor activity of pulmonary alveolar macrophages.

    PubMed

    Leeper-Woodford, S K; Fisher, B J; Sugerman, H J; Fowler, A A

    1993-02-01

    Tumor necrosis factor-alpha (TNF), an inflammatory cytokine released by macrophages, may be a mediator of lung injury during septicemia. We previously reported that the cyclooxygenase inhibitor ibuprofen and histamine receptor antagonists cimetidine (H2 antagonist) and diphenhydramine (H1 antagonist) attenuate lung injury and reduce circulating TNF surges during porcine sepsis. Since pulmonary alveolar macrophages (PAM) may participate in early sepsis by producing TNF, we hypothesized that the TNF activity of PAM is reduced by ibuprofen, cimetidine, and diphenhydramine. To test this, we examined changes in PAM-derived TNF bioactivity and cell viability of freshly isolated porcine PAM during exposure to bacterial endotoxin (LPS), ibuprofen, cimetidine, and diphenhydramine. The TNF activity (% L929 cytotoxicity of PAM conditioned medium) was elevated in LPS-stimulated PAM cultures (15 to 25% increase at 1 to 6 h and 40 to 43% increase at 6 to 48 h, compared with non-LPS-stimulated cultures), and ibuprofen (150 micrograms/ml) added with LPS decreased the TNF activity for 24 h (20 to 28% reduction at 1 to 24 h). Ibuprofen added 1 h after LPS was less effective in reducing the PAM-derived TNF activity (20 to 22% reduction at 2 to 6 h). Cimetidine (112 micrograms/ml) reduced the TNF activity of LPS-stimulated PAM cultures during the first 4 h of LPS exposure (15 to 24% decrease at 1 to 4 h). Diphenhydramine (150 micrograms/ml) attenuated the PAM-derived TNF activity but also decreased viability of PAM, indicating a toxic effect of this agent on PAM.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:8093999

  13. Characterization of redox activity in resting and activated mast cells by reduction and reoxidation of lipophilic nitroxides.

    PubMed

    Suzuki-Nishimura, T; Swartz, H M

    1998-10-01

    1. We measured redox systems in resting and activated rat peritoneal mast cells under anoxia by using the redox metabolism of free doxyl stearic acid (5DS) and phosphatidylcholine with two 5DS molecules esterified to the glycerol (di5DSPC). 2. In the absence of oxygen, 5DS and di5DSPC were reduced to the corresponding hydroxylamines by resting mast cells, with apparent first-order kinetics of 0.085 and 0.078/min, respectively. 3. The activation of mast cells induced by compound 48/80 and bradykinin did not affect the rates of reduction of the nitroxides, and therefore the activation appeared not to be closely coupled to the redox system of these cells; this finding implies that ischemia is unlikely to affect histamine release from mast cells. 4. The oxidation of the nitroxides by the mast cells was very fast and may be nonenzymatic. 5. We concluded that nitroxides can be useful probes of redox metabolism in the mast cells but, because the characteristics of the cellular reduction-reoxidation systems differed from that of other cells, the use of this approach in other cells will require careful characterization of the redox metabolism of nitroxides in those cells. PMID:9792226

  14. Reduction of urease activity by interaction with the flap covering the active site.

    PubMed

    Macomber, Lee; Minkara, Mona S; Hausinger, Robert P; Merz, Kenneth M

    2015-02-23

    With the increasing appreciation for the human microbiome coupled with the global rise of antibiotic resistant organisms, it is imperative that new methods be developed to specifically target pathogens. To that end, a novel computational approach was devised to identify compounds that reduce the activity of urease, a medically important enzyme of Helicobacter pylori, Proteus mirabilis, and many other microorganisms. Urease contains a flexible loop that covers its active site; Glide was used to identify small molecules predicted to lock this loop in an open conformation. These compounds were screened against the model urease from Klebsiella aerogenes, and the natural products epigallocatechin and quercetin were shown to inhibit at low and high micromolar concentrations, respectively. These molecules exhibit a strong time-dependent inactivation of urease that was not due to their oxygen sensitivity. Rather, these compounds appear to inactivate urease by reacting with a specific Cys residue located on the flexible loop. Substitution of this cysteine by alanine in the C319A variant increased the urease resistance to both epigallocatechin and quercetin, as predicted by the computational studies. Protein dynamics are integral to the function of many enzymes; thus, identification of compounds that lock an enzyme into a single conformation presents a useful approach to define potential inhibitors. PMID:25594724

  15. Reduction of Urease Activity by Interaction with the Flap Covering the Active Site

    PubMed Central

    Macomber, Lee; Minkara, Mona S.; Hausinger, Robert P.; Merz, Kenneth M.

    2015-01-01

    With the increasing appreciation for the human microbiome coupled with the global rise of antibiotic resistant organisms, it is imperative that new methods be developed to specifically target pathogens. To that end, a novel computational approach was devised to identify compounds that reduce the activity of urease, a medically important enzyme of Helicobacter pylori, Proteus mirabilis, and many other microorganisms. Urease contains a flexible loop that covers its active site; Glide was used to identify small molecules predicted to lock this loop in an open conformation. These compounds were screened against the model urease from Klebsiella aerogenes and the natural products epigallocatechin and quercetin were shown to inhibit at low and high micromolar concentrations, respectively. These molecules exhibit a strong time-dependent inactivation of urease that was not due to their oxygen sensitivity. Rather, these compounds appear to inactivate urease by reacting with a specific Cys residue located on the flexible loop. Substitution of this cysteine by alanine in the C319A variant increased the urease resistance to both epigallocatechin and quercetin, as predicted by the computational studies. Protein dynamics are integral to the function of many enzymes; thus, identification of compounds that lock an enzyme into a single conformation presents a useful approach to define potential inhibitors. PMID:25594724

  16. Impact of Polymer Electrolyte Membrane Degradation Products on Oxygen Reduction Reaction Activity for Platinum Electrocatalysts

    SciTech Connect

    Christ, J. M.; Neyerlin, K. C.; Wang, H.; Richards, R.; Dinh, H. N.

    2014-10-30

    The impact of model membrane degradation compounds on the relevant electrochemical parameters for the oxygen reduction reaction (i.e. electrochemical surface area and catalytic activity), was studied for both polycrystalline Pt and carbon supported Pt electrocatalysts. Model compounds, representing previously published, experimentally determined polymer electrolyte membrane degradation products, were in the form of perfluorinated organic acids that contained combinations of carboxylic and/or sulfonic acid functionality. Perfluorinated carboxylic acids of carbon chain length C1 – C6 were found to have an impact on electrochemical surface area (ECA). The longest chain length acid also hindered the observed oxygen reduction reaction (ORR) performance, resulting in a 17% loss in kinetic current (determined at 0.9 V). Model compounds containing sulfonic acid functional groups alone did not show an effect on Pt ECA or ORR activity. Lastly, greater than a 44% loss in ORR activity at 0.9V was observed for diacid model compounds DA-Naf (perfluoro(2-methyl-3-oxa-5-sulfonic pentanoic) acid) and DA-3M (perfluoro(4-sulfonic butanoic) acid), which contained both sulfonic and carboxylic acid functionalities.

  17. Impact of Polymer Electrolyte Membrane Degradation Products on Oxygen Reduction Reaction Activity for Platinum Electrocatalysts

    DOE PAGESBeta

    Christ, J. M.; Neyerlin, K. C.; Wang, H.; Richards, R.; Dinh, H. N.

    2014-10-30

    The impact of model membrane degradation compounds on the relevant electrochemical parameters for the oxygen reduction reaction (i.e. electrochemical surface area and catalytic activity), was studied for both polycrystalline Pt and carbon supported Pt electrocatalysts. Model compounds, representing previously published, experimentally determined polymer electrolyte membrane degradation products, were in the form of perfluorinated organic acids that contained combinations of carboxylic and/or sulfonic acid functionality. Perfluorinated carboxylic acids of carbon chain length C1 – C6 were found to have an impact on electrochemical surface area (ECA). The longest chain length acid also hindered the observed oxygen reduction reaction (ORR) performance, resultingmore » in a 17% loss in kinetic current (determined at 0.9 V). Model compounds containing sulfonic acid functional groups alone did not show an effect on Pt ECA or ORR activity. Lastly, greater than a 44% loss in ORR activity at 0.9V was observed for diacid model compounds DA-Naf (perfluoro(2-methyl-3-oxa-5-sulfonic pentanoic) acid) and DA-3M (perfluoro(4-sulfonic butanoic) acid), which contained both sulfonic and carboxylic acid functionalities.« less

  18. Highly active oxygen reduction non-platinum group metal electrocatalyst without direct metal-nitrogen coordination

    NASA Astrophysics Data System (ADS)

    Strickland, Kara; Miner, Elise; Jia, Qingying; Tylus, Urszula; Ramaswamy, Nagappan; Liang, Wentao; Sougrati, Moulay-Tahar; Jaouen, Frédéric; Mukerjee, Sanjeev

    2015-06-01

    Replacement of noble metals in catalysts for cathodic oxygen reduction reaction with transition metals mostly create active sites based on a composite of nitrogen-coordinated transition metal in close concert with non-nitrogen-coordinated carbon-embedded metal atom clusters. Here we report a non-platinum group metal electrocatalyst with an active site devoid of any direct nitrogen coordination to iron that outperforms the benchmark platinum-based catalyst in alkaline media and is comparable to its best contemporaries in acidic media. In situ X-ray absorption spectroscopy in conjunction with ex situ microscopy clearly shows nitrided carbon fibres with embedded iron particles that are not directly involved in the oxygen reduction pathway. Instead, the reaction occurs primarily on the carbon-nitrogen structure in the outer skin of the nitrided carbon fibres. Implications include the potential of creating greater active site density and the potential elimination of any Fenton-type process involving exposed iron ions culminating in peroxide initiated free-radical formation.

  19. Enhanced photocatalytic CO₂-reduction activity of electrospun mesoporous TiO₂ nanofibers by solvothermal treatment.

    PubMed

    Fu, Junwei; Cao, Shaowen; Yu, Jiaguo; Low, Jingxiang; Lei, Yongpeng

    2014-06-28

    Photocatalytic reduction of CO2 into renewable hydrocarbon fuels using semiconductor photocatalysts is considered as a potential solution to the energy deficiency and greenhouse effect. In this work, mesoporous TiO2 nanofibers with high specific surface areas and abundant surface hydroxyl groups are prepared using an electrospinning strategy combined with a subsequent calcination process, followed by a solvothermal treatment. The solvothermally treated mesoporous TiO2 nanofibers exhibit excellent photocatalytic performance on CO2 reduction into hydrocarbon fuels. The significantly improved photocatalytic activity can be attributed to the enhanced CO2 adsorption capacity and the improved charge separation after solvothermal treatment. The highest activity is achieved for the sample with a 2-h solvothermal treatment, showing 6- and 25-fold higher CH4 production rate than those of TiO2 nanofibers without solvothermal treatment and P25, respectively. This work may also provide a prototype for studying the effect of solvothermal treatment on the structure and photocatalytic activity of semiconductor photocatalysts. PMID:24809306

  20. Highly active oxygen reduction non-platinum group metal electrocatalyst without direct metal–nitrogen coordination

    PubMed Central

    Strickland, Kara; Miner, Elise; Jia, Qingying; Tylus, Urszula; Ramaswamy, Nagappan; Liang, Wentao; Sougrati, Moulay-Tahar; Jaouen, Frédéric; Mukerjee, Sanjeev

    2015-01-01

    Replacement of noble metals in catalysts for cathodic oxygen reduction reaction with transition metals mostly create active sites based on a composite of nitrogen-coordinated transition metal in close concert with non-nitrogen-coordinated carbon-embedded metal atom clusters. Here we report a non-platinum group metal electrocatalyst with an active site devoid of any direct nitrogen coordination to iron that outperforms the benchmark platinum-based catalyst in alkaline media and is comparable to its best contemporaries in acidic media. In situ X-ray absorption spectroscopy in conjunction with ex situ microscopy clearly shows nitrided carbon fibres with embedded iron particles that are not directly involved in the oxygen reduction pathway. Instead, the reaction occurs primarily on the carbon–nitrogen structure in the outer skin of the nitrided carbon fibres. Implications include the potential of creating greater active site density and the potential elimination of any Fenton-type process involving exposed iron ions culminating in peroxide initiated free-radical formation. PMID:26059552

  1. Active twist control methodology for vibration reduction of a helicopter with dissimilar rotor system

    NASA Astrophysics Data System (ADS)

    Pawar, Prashant M.; Jung, Sung Nam

    2009-03-01

    In this work, an active vibration reduction of hingeless composite rotor blades with dissimilarity is investigated using the active twist concept and the optimal control theory. The induced shear strain on the actuation mechanism by the piezoelectric constant d15 from the PZN-8% PT-based single-crystal material is used to achieve more active twisting to suppress the extra vibrations. The optimal control algorithm is based on the minimization of an objective function comprised of quadratic functions of vibratory hub loads and voltage control harmonics. The blade-to-blade dissimilarity is modeled using the stiffness degradation of composite blades. The optimal controller is applied to various possible dissimilarities arising from different damage patterns of composite blades. The governing equations of motion are derived using Hamilton's principle. The effects of composite materials and smart actuators are incorporated into the comprehensive aeroelastic analysis system. Numerical results showing the impact of addressing the blade dissimilarities on hub vibrations and voltage inputs required to suppress the vibrations are demonstrated. It is observed that all vibratory shear forces are reduced considerably and the major harmonics of moments are reduced significantly. However, the controller needs further improvement to suppress 1/rev moment loads. A mechanism to achieve vibration reduction for the dissimilar rotor system has also been identified.

  2. Active vibration reduction by optimally placed sensors and actuators with application to stiffened plates by beams

    NASA Astrophysics Data System (ADS)

    Daraji, A. H.; Hale, J. M.

    2014-10-01

    This study concerns new investigation of active vibration reduction of a stiffened plate bonded with discrete sensor/actuator pairs located optimally using genetic algorithms based on a developed finite element modeling. An isotropic plate element stiffened by a number of beam elements on its edges and having a piezoelectric sensor and actuator pair bonded to its surfaces is modeled using the finite element method and Hamilton’s principle, taking into account the effects of piezoelectric mass, stiffness and electromechanical coupling. The modeling is based on the first order shear deformation theory taking into account the effects of bending, membrane and shear deformation for the plate, the stiffening beam and the piezoelectric patches. A Matlab finite element program has been built for the stiffened plate model and verified with ANSYS and also experimentally. Optimal placement of ten piezoelectric sensor/actuator pairs and optimal feedback gain for active vibration reduction are investigated for a plate stiffened by two beams arranged in the form of a cross. The genetic algorithm was set up for optimization of sensor/actuator placement and feedback gain based on the minimization of the optimal linear quadratic index as an objective function to suppress the first six modes of vibration. Comparison study is presented for active vibration reduction of a square cantilever plate stiffened by crossed beams with two sensor/actuator configurations: firstly, ten piezoelectric sensor/actuator pairs are located in optimal positions; secondly, a piezoelectric layer of single sensor/actuator pair covering the whole of the stiffened plate as a SISO system.

  3. An ultrastable bimetallic carbide as platinum electrocatalyst support for highly active oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Yan, Zaoxue; Zhang, Mingmei; Xie, Jimin; Shen, Pei Kang

    2015-11-01

    Stable bimetallic carbide (Fe2MoC) with graphitized carbon (GC) as matrix has been synthesized through an ion-exchange method. The Pt nanoparticles are loaded on the GC-Fe2MoC composite to form Pt/GC-Fe2MoC electrocatalyst which shows much higher activity and stability than those of commercial Pt/C for oxygen reduction reaction in acidic media. The excellent performances of Pt/GC-Fe2MoC are mainly due to the inherent stability of GC-Fe2MoC and the promotion effect between Fe2MoC and Pt.

  4. Iron (III) reduction: A novel activity of the human NAD(P)H:oxidoreductase

    SciTech Connect

    Onyenwoke, Rob U.; Wiegel, Juergen . E-mail: jwiegel@uga.edu

    2007-02-09

    NAD(P)H:quinone oxidoreductase (NQO1; EC 1.6.99.2) catalyzes a two-electron transfer involved in the protection of cells from reactive oxygen species. These reactive oxygen species are often generated by the one-electron reduction of quinones or quinone analogs. We report here on the previously unreported Fe(III) reduction activity of human NQO1. Under steady state conditions with Fe(III) citrate, the apparent Michaelis-Menten constant (K{sub m}{sup app}) was {approx}0.3nM and the apparent maximum velocity (V{sub max}{sup app}) was 16Umg{sup -1}. Substrate inhibition was observed above 5nM. NADH was the electron donor, K{sub m}{sup app}=340{mu}M and V{sub max}{sup app}=46Umg{sup -1}. FAD was also a cofactor with a K{sub m}{sup app} of 3.1{mu}M and V{sub max}{sup app} of 89Umg{sup -1}. The turnover number for NADH oxidation was 25s{sup -1}. Possible physiological roles of the Fe(III) reduction by this enzyme are discussed.

  5. Hybrid feedforward-feedback active noise reduction for hearing protection and communication.

    PubMed

    Ray, Laura R; Solbeck, Jason A; Streeter, Alexander D; Collier, Robert D

    2006-10-01

    A hybrid active noise reduction (ANR) architecture is presented and validated for a circumaural earcup and a communication earplug. The hybrid system combines source-independent feedback ANR with a Lyapunov-tuned leaky LMS filter (LyLMS) improving gain stability margins over feedforward ANR alone. In flat plate testing, the earcup demonstrates an overall C-weighted total noise reduction of 40 dB and 30-32 dB, respectively, for 50-800 Hz sum-of-tones noise and for aircraft or helicopter cockpit noise, improving low frequency (<100 Hz) performance by up to 15 dB over either control component acting individually. For the earplug, a filtered-X implementation of the LyLMS accommodates its nonconstant cancellation path gain. A fast time-domain identification method provides a high-fidelity, computationally efficient, infinite impulse response cancellation path model, which is used for both the filtered-X implementation and communication feedthrough. Insertion loss measurements made with a manikin show overall C-weighted total noise reduction provided by the ANR earplug of 46-48 dB for sum-of-tones 80-2000 Hz and 40-41 dB from 63 to 3000 Hz for UH-60 helicopter noise, with negligible degradation in attenuation during speech communication. For both hearing protectors, a stability metric improves by a factor of 2 to several orders of magnitude through hybrid ANR. PMID:17069300

  6. Effects of a TiC substrate on the catalytic activity of Pt for NO reduction.

    PubMed

    Chu, Xingli; Fu, Zhaoming; Li, Shasha; Zhang, Xilin; Yang, Zongxian

    2016-05-11

    Density functional theory calculations are used to elucidate the catalytic properties of a Pt monolayer supported on a TiC(001) substrate (Pt/TiC) toward NO reduction. It is found that the compound system of Pt/TiC has a good stability due to the strong Pt-TiC interaction. The diverse dissociation paths (namely the direct dissociation mechanism and the dimeric mechanism) are investigated. The transition state searching calculations suggest that NO has strong diffusion ability and small activation energy for dissociation on the Pt/TiC. For NO reduction on the Pt/TiC surface, we have found that the direct dissociation mechanisms (NO + N + O → NO2 + N and NO + N + O → N2 + O + O) are easier with a smaller dissociation barrier than those on the Pt(111) surface; and the dimeric process (NO + NO → (NO)2 → N2O + O → N2 + O + O) is considered to be dominant or significant with even a lower energy barrier than that of the direct dissociation. The results show that Pt/TiC can serve as an efficient catalyst for NO reduction. PMID:27117987

  7. Active Vibration Control for Helicopter Interior Noise Reduction Using Power Minimization

    NASA Technical Reports Server (NTRS)

    Mendoza, J.; Chevva, K.; Sun, F.; Blanc, A.; Kim, S. B.

    2014-01-01

    This report describes work performed by United Technologies Research Center (UTRC) for NASA Langley Research Center (LaRC) under Contract NNL11AA06C. The objective of this program is to develop technology to reduce helicopter interior noise resulting from multiple gear meshing frequencies. A novel active vibration control approach called Minimum Actuation Power (MAP) is developed. MAP is an optimal control strategy that minimizes the total input power into a structure by monitoring and varying the input power of controlling sources. MAP control was implemented without explicit knowledge of the phasing and magnitude of the excitation sources by driving the real part of the input power from the controlling sources to zero. It is shown that this occurs when the total mechanical input power from the excitation and controlling sources is a minimum. MAP theory is developed for multiple excitation sources with arbitrary relative phasing for single or multiple discrete frequencies and controlled by a single or multiple controlling sources. Simulations and experimental results demonstrate the feasibility of MAP for structural vibration reduction of a realistic rotorcraft interior structure. MAP control resulted in significant average global vibration reduction of a single frequency and multiple frequency excitations with one controlling actuator. Simulations also demonstrate the potential effectiveness of the observed vibration reductions on interior radiated noise.

  8. Mechanisms of Active Aerodynamic Load Reduction on a Rotorcraft Fuselage With Rotor Effects

    NASA Technical Reports Server (NTRS)

    Schaeffler, Norman W.; Allan, Brian G.; Jenkins, Luther N.; Yao, Chung-Sheng; Bartram, Scott M.; Mace, W. Derry; Wong, Oliver D.; Tanner, Philip E.

    2016-01-01

    The reduction of the aerodynamic load that acts on a generic rotorcraft fuselage by the application of active flow control was investigated in a wind tunnel test conducted on an approximately 1/3-scale powered rotorcraft model simulating forward flight. The aerodynamic mechanisms that make these reductions, in both the drag and the download, possible were examined in detail through the use of the measured surface pressure distribution on the fuselage, velocity field measurements made in the wake directly behind the ramp of the fuselage and computational simulations. The fuselage tested was the ROBIN-mod7, which was equipped with a series of eight slots located on the ramp section through which flow control excitation was introduced. These slots were arranged in a U-shaped pattern located slightly downstream of the baseline separation line and parallel to it. The flow control excitation took the form of either synthetic jets, also known as zero-net-mass-flux blowing, and steady blowing. The same set of slots were used for both types of excitation. The differences between the two excitation types and between flow control excitation from different combinations of slots were examined. The flow control is shown to alter the size of the wake and its trajectory relative to the ramp and the tailboom and it is these changes to the wake that result in a reduction in the aerodynamic load.

  9. Adsorption of U(VI) on sericite in the presence of Bacillus subtilis: A combined batch, EXAFS and modeling techniques

    NASA Astrophysics Data System (ADS)

    Sun, Yubing; Zhang, Rui; Ding, Congcong; Wang, Xiangxue; Cheng, Wencai; Chen, Changlun; Wang, Xiangke

    2016-05-01

    The effect of Bacillus subtilis (B. subtilis) on the adsorption of U(VI) onto sericite was investigated using batch, EXAFS and modeling techniques. The batch adsorption indicated that the increased adsorption of U(VI) on sericite + B. subtilis systems at pH < 5.0 was predominantly attributed to the formation of inner-sphere complexes between U(VI) and surface functional groups of B. subtilis, whereas the inhibited adsorption was observed at pH > 6.0 due to the combination of deprotonated carboxyl groups of B. subtilis with the hydroxyl of sericite. The slightly enhanced adsorption of U(VI) on sericite + B. subtilis with increasing CO2 contents at pH < 6.0 was ascribed to the electrostatic attraction between positively charged U(VI) species (UO22+ species) and negatively charged surface of sericite + B. subtilis, whereas the U(VI) adsorption sharply decreased at pH > 7.0 owing to electrostatic repulsion between negatively charged sericite + B. subtilis and negatively charged U(VI) species such as UO2(OH)3- or UO2(CO3)22- species. According to EXAFS analysis, the increased adsorption mechanism of U(VI) on sericite + B. subtilis at pH 4.0 was attributed to the formation of U-P shell, whereas the bidentate inner-sphere surface complexes was also observed at pH 7.0 due to the formation of U-C shell (2.92 Å) and/or U-Si/Al (3.18 Å) shell. Under the range of allowable error, the pH-dependent and isothermal adsorption of U(VI) on sericite + B. subtilis can be fitted by surface complexation modeling using ion exchange and surface complexation reaction by using equilibrium parameters obtained from each binary systems. These findings are important to understand the fate and transport of U(VI) on the mineral-bacteria ternary systems in the near-surface environment.

  10. A Computational Study of BVI Noise Reduction Using Active Twist Control

    NASA Technical Reports Server (NTRS)

    Fogarty, David E.; Wilbur, Matthew L.; Sekula, Martin K.

    2010-01-01

    The results of a computational study examining the effects of active-twist control on blade-vortex interaction (BVI) noise using the Apache Active Twist Rotor are presented. The primary goal of this activity is to reduce BVI noise during a low-speed descent flight condition using active-twist control. Rotor aeroelastic behavior was modeled using the Comprehensive Analytical Model of Rotorcraft Aerodynamics and Dynamics code and the rotor noise was predicted using the acoustics code PSU-WOPWOP. The accuracy of the analysis was validated through comparisons with experimental acoustic data for the first generation Active Twist Rotor at an advance ratio of mu=0.14. The application of active-twist to the main rotor blade system consisted of harmonic actuation frequencies ranging from 2P to 5P, control phase angles from 0' to 360 , and tip-twist amplitudes ranging from 0.5 to 4.0 . The acoustic analysis was conducted for a single low-speed flight condition of advance ratio =0.14 and shaft angle-of-attack, c^=+6 , with BVI noise levels predicted on a flat plane of observers located 1.1 rotor diameters beneath the rotor. The results indicated reductions of up to 11dB in BVI noise using 1.25 tip-twist amplitude with negligible effects on 4P vertical hub shear.

  11. Segregated Pt on Pd nanotubes for enhanced oxygen reduction activity in alkaline electrolyte.

    PubMed

    St John, Samuel; Atkinson, Robert W; Dyck, Ondrej; Sun, Cheng-Jun; Zawodzinski, Thomas A; Papandrew, Alexander B

    2015-12-01

    Nanoscaled Pt domains were integrated with Pd nanotubes via vapor deposition to yield a highly active electrocatalyst for the oxygen reduction reaction (ORR) in alkaline media. The surface-area-normalized ORR activity of these bi-metallic Pt-on-Pd nanotubes (PtPdNTs) was nearly 6× the corresponding carbon-supported Pt nanoparticle (Pt/C) activity at 0.9 V vs. RHE (1.5 vs. 0.24 mA cmmetal(-2), respectively). Furthermore, the high specific activity of the PtPdNTs was achieved without sacrificing mass-normalized activity, which is more than twice that of Pt/C (0.333 A mgPtPdNT(-1)vs. 0.141 A mgPt/C(-1)) and also greater than that of Pd/C (0.221 A mgPd/C(-1)). We attribute the enhancements in specific and mass activity to modifications of the segregated Pt electronic structure and to nanoscale porosity, respectively. PMID:26553367

  12. Atomic Ordering Enhanced Electrocatalytic Activity of Nanoalloys for Oxygen Reduction Reaction

    SciTech Connect

    Loukrakpam, Rameshwori; Shan, Shiyao; Petkov, Valeri; Yang, Lefu; Luo, Jin; Zhong, Chuan-Jian

    2013-10-01

    For oxygen reduction reaction (ORR) over alloy electrocatalysts, the understanding of how the atomic arrangement of the metal species in the nanocatalysts is responsible for the catalytic enhancement is challenging for achieving better design and tailoring of nanoalloy catalysts. This paper reports results of an investigation of the atomic structures and the electrocatalytic activities of ternary and binary nanoalloys, aiming at revealing a fundamental insight into the unique atomic-scale structure-electrocatalytic activity relationship. PtIrCo catalyst and its binary counterparts (PtCo and PtIr) are chosen as a model system for this study. The effect of thermochemical treatment temperature on the atomic-scale structure of the catalysts was examined as a useful probe to the structure-activity correlation. The structural characterization of the binary and ternary nanoalloy catalysts was performed by combining surface sensitive techniques such as XPS and 3D atomic ordering sensitive techniques such as high-energy X-ray diffraction (HE-XRD) coupled to atomic pair distribution function (PDF) analysis (HE-XRD/PDFs) and computer simulations. The results show that the thermal treatment temperature tunes the nanoalloy’s atomic and chemical ordering in a different way depending on the chemical composition, leading to differences in the nanoalloy’s mass and specific activities. A unique structural tunability of the atomic ordering in a platinum-iridium-cobalt nanoalloy has been revealed for enhancing greatly the electrocatalytic activity toward oxygen reduction reaction, which has significant implication for rational design and nanoengineering of advanced catalysts for electrochemical energy conversion and storage.

  13. Progress Towards Fuselage Drag Reduction via Active Flow Control: A Combined CFD and Experimental Effort

    NASA Technical Reports Server (NTRS)

    Schaefler, Norman W.; Allan, Brian G.; Lienard, Caroline; LePape, Arnaud

    2010-01-01

    A combined computational and experimental effort has been undertaken to study fuselage drag reduction on a generic, non-proprietary rotorcraft fuselage by the application of active ow control. Fuselage drag reduction is an area of research interest to both the United States and France and this area is being worked collaboratively as a task under the United States/France Memorandum of Agreement on Helicopter Aeromechanics. In the first half of this task, emphasis is placed on the US generic fuselage, the ROBIN-mod7, with the experimental work being conducted on the US side and complementary US and French CFD analysis of the baseline and controlled cases. Fuselage simulations were made using Reynolds-averaged Navier-Stokes ow solvers and with multiple turbulence models. Comparisons were made to experimental data for numerical simulations of the isolated fuselage and for the fuselage as installed in the tunnel, which includes modeling of the tunnel contraction, walls, and support fairing. The numerical simulations show that comparisons to the experimental data are in good agreement when the tunnel and model support are included. The isolated fuselage simulations compare well to each other, however, there is a positive shift in the centerline pressure when compared to the experiment. The computed flow separation locations on the rear ramp region had only slight differences with and without the tunnel walls and model support. For the simulations, the flow control slots were placed at several locations around the flow separation lines as a series of eight slots that formed a nearly continuous U-shape. Results from the numerical simulations resulted in an estimated 35% fuselage drag reduction from a steady blowing flow control configuration and a 26% drag reduction for unsteady zero-net-mass flow control configuration. Simulations with steady blowing show a delayed flow separation at the rear ramp of the fuselage that increases the surface pressure acting on the ramp

  14. Deriving the Structure and Composition of Enceladus’ Plume from Cassini UVIS Observations

    NASA Astrophysics Data System (ADS)

    Hansen, Candice; Esposito, Larry; Colwell, Josh; Hendrix, Amanda; Portyankina, Ganna; Shemansky, Don; West, Robert

    2015-11-01

    Cassini’s Ultraviolet Imaging Spectrograph (UVIS) has observed 4 stellar and one solar occultation by Enceladus’ water vapor plume. The July 2005 occultation observation established that water is the primary constituent of the plume [1], and allowed us to calculate the flux of water coming from the plume; the 2007 occultation showed super-sonic jets of gas imbedded within the plume [2]. The solar occultation observation set upper limits for N2 as a constituent of the plume and provided higher resolution data on the jets [3]. On 19 October 2011, epsilon and zeta Orionis were simultaneously occulted by the plume. The stars were in separate pixels on the detector, separated by 24 mrad, or ~20 km, with the lower altitude star (epsilon Orionis) 18 km above the limb at its closest point. The profile at two altitudes shows evidence for a new gas jet location, possibly between dust jet #50 and #51 identified in [4].Results from the assemblage of these data sets, with implications for the composition and vertical structure of the plume and jets, will be described. Gas being expelled from the “tiger stripe” fissures is largely on a vertical escape trajectory away from Enceladus. Upper limits are set for water vapor near the limb at latitudes well away from the south pole at 3 x 1015 cm-2. Upper limits are set for the amount of ethylene and H2 in the plume, two species of interest to the chemistry of the plume [5]. No hydrogen or oxygen emission features have been observed from Enceladus’ water vapor plume, in contrast to the purported plumes at Europa, probably due to the very different plasma environment at Saturn. Data have now been processed consistently for all occultations with slightly different results for water vapor supply to the Saturn magnetosphere than previously reported. Overall, eruptive activity has been steady to within ~20% from 2005 to 2011.References: [1] Hansen, C. J. et al., Science 311:1422 (2006). Hansen, C. J. et al., Nature 456:477 (2008

  15. Enhanced electrocatalytic activity of nitrogen-doped olympicene/graphene hybrids for the oxygen reduction reaction.

    PubMed

    Hou, Xiuli; Zhang, Peng; Li, Shuang; Liu, Wei

    2016-08-17

    Developing inexpensive and non-precious metal electrocatalysts for the oxygen reduction reaction (ORR) is among the major goals in fuel cells. Herein, by using density-functional theory calculations, we show that N-doped olympicene/graphene hybrids exhibit unexpectedly high ORR catalytic activity-even comparable to that of the Pt(111) surface. Both graphitic-type and pyridine-type N-doped olympicene/graphene hybrids are highly active for the ORR and have good CO tolerance. The formation of the second H2O molecule is the rate-determining step for the ORR with the graphitic-type hybrid, whereas on the pyridine-type hybrid, it is the formation of OOH. Note that N-doped olympicene/graphene hybrid materials combine the high reactivity of olympicene and the high electrical conductivity of graphene, which allows them to be potentially used as low-cost and non-precious-metal ORR catalysts. PMID:27499058

  16. Enhanced oxygen reduction activity and solid oxide fuel cell performance with a nanoparticles-loaded cathode.

    PubMed

    Zhang, Xiaomin; Liu, Li; Zhao, Zhe; Tu, Baofeng; Ou, Dingrong; Cui, Daan; Wei, Xuming; Chen, Xiaobo; Cheng, Mojie

    2015-03-11

    Reluctant oxygen-reduction-reaction (ORR) activity has been a long-standing challenge limiting cell performance for solid oxide fuel cells (SOFCs) in both centralized and distributed power applications. We report here that this challenge has been tackled with coloading of (La,Sr)MnO3 (LSM) and Y2O3 stabilized zirconia (YSZ) nanoparticles within a porous YSZ framework. This design dramatically improves ORR activity, enhances fuel cell output (200-300% power improvement), and enables superior stability (no observed degradation within 500 h of operation) from 600 to 800 °C. The improved performance is attributed to the intimate contacts between nanoparticulate YSZ and LSM particles in the three-phase boundaries in the cathode. PMID:25686380

  17. Porous Dendritic Platinum Nanotubes with Extremely High Activity and Stability for Oxygen Reduction Reaction

    PubMed Central

    Zhang, Gaixia; Sun, Shuhui; Cai, Mei; Zhang, Yong; Li, Ruying; Sun, Xueliang

    2013-01-01

    Controlling the morphology of Pt nanostructures can provide opportunities to greatly increase their activity and stability. Porous dendritic Pt nanotubes were successfully synthesized by a facile, cost-effective aqueous solution method at room temperature in large scale. These unique structures are porous, hollow, hierarchical, and single crystalline, which not only gives them a large surface area with high catalyst utilization, but also improves mass transport and gas diffusion. These novel Pt structures exhibited significantly improved catalytic activity (4.4 fold) for oxygen reduction reaction (ORR) and greatly enhanced durability (6.1 fold) over that of the state-of-the-art commercial Pt/C catalyst. This work provides a promising approach to the design of highly efficient next-generation electrocatalysts. PMID:23524665

  18. New mechanistically based model for predicting reduction of biosolids waste by ozonation of return activated sludge.

    PubMed

    Isazadeh, Siavash; Feng, Min; Urbina Rivas, Luis Enrique; Frigon, Dominic

    2014-04-15

    Two pilot-scale activated sludge reactors were operated for 98 days to provide the necessary data to develop and validate a new mathematical model predicting the reduction of biosolids production by ozonation of the return activated sludge (RAS). Three ozone doses were tested during the study. In addition to the pilot-scale study, laboratory-scale experiments were conducted with mixed liquor suspended solids and with pure cultures to parameterize the biomass inactivation process during exposure to ozone. The experiments revealed that biomass inactivation occurred even at the lowest doses, but that it was not associated with extensive COD solubilization. For validation, the model was used to simulate the temporal dynamics of the pilot-scale operational data. Increasing the description accuracy of the inactivation process improved the precision of the model in predicting the operational data. PMID:24572272

  19. Selective nitrogen doping in graphene: Enhanced catalytic activity for the oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Wang, Xianlong; Hou, Zhufeng; Ikeda, Takashi; Huang, Sheng-Feng; Terakura, Kiyoyuki; Boero, Mauro; Oshima, Masaharu; Kakimoto, Masa-Aki; Miyata, Seizo

    2011-12-01

    The structural and electronic properties of N-doped zigzag graphene ribbons with various ratios of dihydrogenated to monohydrogenated edge carbons are investigated within the density functional theory framework. We find that the stability of graphitic N next to the edge, which is claimed to play important roles in the catalytic activity in our previous work, will be enhanced with increasing the concentration of dihydrogenated carbons. Furthermore, the dihydrogenated edge carbons turn out to be easily converted into monohydrogenated ones in the presence of oxygen molecules at room temperature. Based on our results, we propose a possible way to enhance the oxygen reduction catalytic activity of N-doped graphene by controlling the degrees of hydrogenation of edge carbons. The characteristic features in the x-ray absorption and emission spectra for each specific N site considered here will also be given.

  20. The Origin of the Catalytic Activity of a Metal Hydride in CO2 Reduction.

    PubMed

    Kato, Shunsuke; Matam, Santhosh Kumar; Kerger, Philipp; Bernard, Laetitia; Battaglia, Corsin; Vogel, Dirk; Rohwerder, Michael; Züttel, Andreas

    2016-05-10

    Atomic hydrogen on the surface of a metal with high hydrogen solubility is of particular interest for the hydrogenation of carbon dioxide. In a mixture of hydrogen and carbon dioxide, methane was markedly formed on the metal hydride ZrCoHx in the course of the hydrogen desorption and not on the pristine intermetallic. The surface analysis was performed by means of time-of-flight secondary ion mass spectroscopy and near-ambient pressure X-ray photoelectron spectroscopy, for the in situ analysis. The aim was to elucidate the origin of the catalytic activity of the metal hydride. Since at the initial stage the dissociation of impinging hydrogen molecules is hindered by a high activation barrier of the oxidised surface, the atomic hydrogen flux from the metal hydride is crucial for the reduction of carbon dioxide and surface oxides at interfacial sites. PMID:27061237

  1. Temporal separation of catalytic activities allows anti-Markovnikov reductive functionalization of terminal alkynes

    NASA Astrophysics Data System (ADS)

    Li, Le; Herzon, Seth B.

    2014-01-01

    There is currently great interest in the development of multistep catalytic processes in which one or several catalysts act sequentially to rapidly build complex molecular structures. Many enzymes—often the inspiration for new synthetic transformations—are capable of processing a single substrate through a chain of discrete, mechanistically distinct catalytic steps. Here, we describe an approach to emulate the efficiency of these natural reaction cascades within a synthetic catalyst by the temporal separation of catalytic activities. In this approach, a single catalyst exhibits multiple catalytic activities sequentially, allowing for the efficient processing of a substrate through a cascade pathway. Application of this design strategy has led to the development of a method to effect the anti-Markovnikov (linear-selective) reductive functionalization of terminal alkynes. The strategy of temporal separation may facilitate the development of other efficient synthetic reaction cascades.

  2. Understanding Iron-based catalysts with efficient Oxygen reduction activity from first-principles calculations

    NASA Astrophysics Data System (ADS)

    Hafiz, Hasnain; Barbiellini, B.; Jia, Q.; Tylus, U.; Strickland, K.; Bansil, A.; Mukerjee, S.

    2015-03-01

    Catalysts based on Fe/N/C clusters can support the oxygen-reduction reaction (ORR) without the use of expensive metals such as platinum. These systems can also prevent some poisonous species to block the active sites from the reactant. We have performed spin-polarized calculations on various Fe/N/C fragments using the Vienna Ab initio Simulation Package (VASP) code. Some results are compared to similar calculations obtained with the Gaussian code. We investigate the partial density of states (PDOS) of the 3d orbitals near the Fermi level and calculate the binding energies of several ligands. Correlations of the binding energies with the 3d electronic PDOS's are used to propose electronic descriptors of the ORR associated with the 3d states of Fe. We also suggest a structural model for the most active site with a ferrous ion (Fe2+) in the high spin state or the so-called Doublet 3 (D3).

  3. Reduction Sensitive Lipid Conjugates of Tenofovir: Synthesis, Stability, and Antiviral Activity.

    PubMed

    Giesler, Kyle E; Marengo, Jose; Liotta, Dennis C

    2016-08-11

    The therapeutic value of numerous small molecules hinges on their ability to permeate the plasma membrane. This is particularly true for tenofovir (TFV), adefovir, and other antiviral nucleosides that demonstrate potent antiviral activity but poor bioavailability. Using TFV as a model substrate, we hybridized two disparate prodrug strategies to afford novel reduction-sensitive lipid conjugates of TFV that exhibit subnanomolar activity toward HIV-1 and are stable in human plasma for more than 24 h with a therapeutic index approaching 30000. These compounds significantly rival the clinically approved formulation of TFV and revitalize the potential of disulfide-bearing prodrugs which have seen limited in vitro and in vivo success since their debut over 20 years ago. We further demonstrate the utility of these conjugates as a tool to indirectly probe the enzymatic hydrolysis of phosphonomonoesters that may further advance the development of other prodrug strategies for nucleosides, peptides, and beyond. PMID:27405794

  4. Effects of metabolic uncouplers on excess sludge reduction and microbial products of activated sludge.

    PubMed

    Fang, Fang; Hu, Hai-Lan; Qin, Min-Min; Xue, Zhao-Xia; Cao, Jia-Shun; Hu, Zhi-Rong

    2015-06-01

    The present study investigated the influences of three metabolic uncouplers (pCP, oCP and oNP) on excess activated sludge reduction and microbial products of extracellular polymeric substances (EPS) and intracellular storage product (polyhydroxybutyrate, PHB) in short-term tests. Results showed sludge was reduced 58.2%, 59.8% and 80.8%, respectively, at pCP, oCP and oNP concentrations of 20mg/L. The dosage of three uncouplers had no obviously influences on COD removal and sludge settleability, but had significant inhibition effect on ammonia removal, especially for oNP. Low concentration of pCP and oNP (5mg/L) dosing resulted in protein and polysaccharide content increased in EPS, however, they were decreased at high pCP and oNP concentrations (>5mg/L). To oCP, the protein content in EPS was increased linearly with oCP concentration. Furthermore, metabolic uncouplers addition stimulated the production of PHB. Among three uncouplers, oCP could be an alternative uncoupler for sludge reduction in activated sludge process. PMID:25746471

  5. Classic Maya civilization collapse associated with reduction in tropical cyclone activity

    NASA Astrophysics Data System (ADS)

    Medina, M. A.; Polanco-Martinez, J. M.; Lases-Hernández, F.; Bradley, R. S.; Burns, S. J.

    2013-12-01

    In light of the increased destructiveness of tropical cyclones observed over recent decades one might assume that an increase and not a decrease in tropical cyclone activity would lead to societal stress and perhaps collapse of ancient cultures. In this study we present evidence that a reduction in the frequency and intensity of tropical Atlantic cyclones could have contributed to the collapse of the Maya civilization during the Terminal Classic Period (TCP, AD. 800-950). Statistical comparisons of a quantitative precipitation record from the Yucatan Peninsula (YP) Maya lowlands, based on the stalagmite known as Chaac (after the Mayan God of rain and agriculture), relative to environmental proxy records of El Niño/Southern Oscillation (ENSO), tropical Atlantic sea surface temperatures (SSTs), and tropical Atlantic cyclone counts, suggest that these records share significant coherent variability during the TCP and that summer rainfall reductions between 30 and 50% in the Maya lowlands occurred in association with decreased Atlantic tropical cyclones. Analysis of modern instrumental hydrological data suggests cyclone rainfall contributions to the YP equivalent to the range of rainfall deficits associated with decreased tropical cyclone activity during the collapse of the Maya civilization. Cyclone driven precipitation variability during the TCP, implies that climate change may have triggered Maya civilization collapse via freshwater scarcity for domestic use without significant detriment to agriculture. Pyramid in Tikal, the most prominent Maya Kingdom that collapsed during the Terminal Classic Period (circa C.E. 800-950) Rainfall feeding stalagmites inside Rio Secreto cave system, Yucatan, Mexico.

  6. RF probe recovery time reduction with a novel active ringing suppression circuit

    PubMed Central

    Peshkovsky, A.S.; Forguez, J.; Cerioni, L.; Pusiol, D.J.

    2005-01-01

    A simple Q-damper device for active probe recovery time reduction is introduced along with a straightforward technique for the circuit's component value optimization. The device is inductively coupled to a probe through a coupling transformer positioned away from the main coil, which makes the design independent of the coil type being used. The Q-damper is a tuned circuit, which is resonant at the same frequency as the probe and can be actively interrupted. When the circuit is interrupted, it is detuned and, thereby, is uncoupled from the probe, which operates normally. Turning the device on leads to re-coupling of the circuits and causes splitting of the probe's resonance line, which can be observed through its drive port. A resistance of an appropriate value is introduced into the Q-damper circuit, resulting in smoothing of the resonance splitting into one broad line, representing the coupled system's low-Q state, in which the energy stored in the main coil is efficiently dissipated. The circuit's component values are optimized by monitoring the shape of this low-Q state. Probe recovery time reduction by, approximately, an order of magnitude has been obtained with this device. Application of the device during an NQR experiment led to an increase in the signal-to-noise ratio by a factor of 4.9. PMID:16111906

  7. Early Reduction of Microglia Activation by Irradiation in a Model of Chronic Glaucoma

    PubMed Central

    Bosco, Alejandra; Crish, Samuel D.; Steele, Michael R.; Romero, Cesar O.; Inman, Denise M.; Horner, Philip J.; Calkins, David J.; Vetter, Monica L.

    2012-01-01

    Glaucoma is a neurodegenerative disease that results in the progressive decline and ultimate death of retinal ganglion cells (RGCs). While multiple risk factors are associated with glaucoma, the mechanisms leading to onset and progression of the disease remain unknown. Molecular analysis in various glaucoma models has revealed involvement of non-neuronal cell populations, including astrocytes, Mueller glia and microglia, at early stages of glaucoma. High-dose irradiation was reported to have a significant long-term protective effect in the DBA/2J (D2) mouse model of glaucoma, although the cellular and molecular basis for this effect remains unclear. In particular, the acute effects of irradiation on specific cell populations, including non-neuronal cells, in the D2 retina and nerve have not been assessed. Here we report that irradiation induces transient reduction in proliferating microglia within the optic nerve head and glial lamina within the first week post-irradiation. This was accompanied by reduced microglial activation, with no effect on astrocyte gliosis in those regions. At later stages we confirm that early high-dose irradiation of the mouse head results in improvement of axonal structural integrity and anterograde transport function, without reduction of intraocular pressure. Thus reduced microglial activation induced by irradiation at early stages is associated with reduced optic nerve and retinal neurodegeneration in the D2 mouse model of glaucoma. PMID:22952717

  8. Aircraft panel with sensorless active sound power reduction capabilities through virtual mechanical impedances

    NASA Astrophysics Data System (ADS)

    Boulandet, R.; Michau, M.; Micheau, P.; Berry, A.

    2016-01-01

    This paper deals with an active structural acoustic control approach to reduce the transmission of tonal noise in aircraft cabins. The focus is on the practical implementation of the virtual mechanical impedances method by using sensoriactuators instead of conventional control units composed of separate sensors and actuators. The experimental setup includes two sensoriactuators developed from the electrodynamic inertial exciter and distributed over an aircraft trim panel which is subject to a time-harmonic diffuse sound field. The target mechanical impedances are first defined by solving a linear optimization problem from sound power measurements before being applied to the test panel using a complex envelope controller. Measured data are compared to results obtained with sensor-actuator pairs consisting of an accelerometer and an inertial exciter, particularly as regards sound power reduction. It is shown that the two types of control unit provide similar performance, and that here virtual impedance control stands apart from conventional active damping. In particular, it is clear from this study that extra vibrational energy must be provided by the actuators for optimal sound power reduction, mainly due to the high structural damping in the aircraft trim panel. Concluding remarks on the benefits of using these electrodynamic sensoriactuators to control tonal disturbances are also provided.

  9. Porous Silica-Coated Gold Nanorods: A Highly Active Catalyst for the Reduction of 4-Nitrophenol.

    PubMed

    Mohanta, Jagdeep; Satapathy, Smithsagar; Si, Satyabrata

    2016-02-01

    The successful coating of thin porous silica layers of various thicknesses [(10±1), (12±1), and (14±1) nm] on cetyl trimethylammonium bromide (CTAB) capped gold nanorods was achieved through a modified Stöber procedure. The resulting material was applied as a novel catalyst for the reduction of 4-nitrophenol. The catalytic activities of the gold nanorods increased up to eight times after coating with a layer of porous silica and the reaction followed a zero-order kinetics, having a rate constant as high as 2.92×10(-1) mol L(-1) min(-1). The spectral changes during the reduction reaction of 4-nitrophenol were observed within a very short span of time and a complete conversion to 4-aminophenol occured within 5-6 mins, including the induction period of ≈2 mins. The reusability of the catalyst was studied by running the catalytic reaction during five consecutive cycles with good efficiency without destroying the nanostructure. The methodology can be effectively applied to the development of composite catalysts with highly enhanced catalytic activity. PMID:26663755

  10. Structural Insight into Activation Mechanism of Toxoplasma gondii Nucleoside Triphosphate Diphosphohydrolases by Disulfide Reduction*

    PubMed Central

    Krug, Ulrike; Zebisch, Matthias; Krauss, Michel; Sträter, Norbert

    2012-01-01

    The intracellular parasite Toxoplasma gondii produces two nucleoside triphosphate diphosphohydrolases (NTPDase1 and -3). These tetrameric, cysteine-rich enzymes require activation by reductive cleavage of a hitherto unknown disulfide bond. Despite a 97% sequence identity, both isozymes differ largely in their ability to hydrolyze ATP and ADP. Here, we present crystal structures of inactive NTPDase3 as an apo form and in complex with the product AMP to resolutions of 2.0 and 2.2 Å, respectively. We find that the enzyme is present in an open conformation that precludes productive substrate binding and catalysis. The cysteine bridge 258–268 is identified to be responsible for locking of activity. Crystal structures of constitutively active variants of NTPDase1 and -3 generated by mutation of Cys258–Cys268 show that opening of the regulatory cysteine bridge induces a pronounced contraction of the whole tetramer. This is accompanied by a 12° domain closure motion resulting in the correct arrangement of all active site residues. A complex structure of activated NTPDase3 with a non-hydrolyzable ATP analog and the cofactor Mg2+ to a resolution of 2.85 Å indicates that catalytic differences between the NTPDases are primarily dictated by differences in positioning of the adenine base caused by substitution of Arg492 and Glu493 in NTPDase1 by glycines in NTPDase3. PMID:22130673

  11. Tau reduction prevents Aβ-induced axonal transport deficits by blocking activation of GSK3β

    PubMed Central

    Xu, Jordan C.; Fomenko, Vira; Miyamoto, Takashi; Suberbielle, Elsa; Knox, Joseph A.; Ho, Kaitlyn; Kim, Daniel H.; Yu, Gui-Qiu

    2015-01-01

    Axonal transport deficits in Alzheimer’s disease (AD) are attributed to amyloid β (Aβ) peptides and pathological forms of the microtubule-associated protein tau. Genetic ablation of tau prevents neuronal overexcitation and axonal transport deficits caused by recombinant Aβ oligomers. Relevance of these findings to naturally secreted Aβ and mechanisms underlying tau’s enabling effect are unknown. Here we demonstrate deficits in anterograde axonal transport of mitochondria in primary neurons from transgenic mice expressing familial AD-linked forms of human amyloid precursor protein. We show that these deficits depend on Aβ1–42 production and are prevented by tau reduction. The copathogenic effect of tau did not depend on its microtubule binding, interactions with Fyn, or potential role in neuronal development. Inhibition of neuronal activity, N-methyl-d-aspartate receptor function, or glycogen synthase kinase 3β (GSK3β) activity or expression also abolished Aβ-induced transport deficits. Tau ablation prevented Aβ-induced GSK3β activation. Thus, tau allows Aβ oligomers to inhibit axonal transport through activation of GSK3β, possibly by facilitating aberrant neuronal activity. PMID:25963821

  12. DEVELOPMENT OF HIGH ACTIVITY, COAL-DERIVED, PROMOTED CATALYTIC SYSTEMS FOR NOx REDUCTION AT LOW TEMPERATURES

    SciTech Connect

    Joseph M. Calo

    2000-07-21

    This project is directed at an investigation of catalytic NO{sub x} reduction mechanisms on coal-derived, activated carbon supports at low temperatures. Promoted carbon systems offer some potentially significant advantages for heterogeneous NO{sub x} reduction. These include: low cost; high activity at low temperatures, which minimizes carbon loss; oxygen resistance; and a support material which can be engineered with respect to porosity, transport and catalyst dispersion characteristics. During the reporting period, the following has been accomplished: (1) Steady-state reactivity studies in the packed bed reactor were extended to the NO/CO-carbon reaction system as a function of temperature and NO and CO concentrations. It was found that the NO reaction rate increased in the presence of CO, and the apparent activation energy decreased to about 75 {+-} 8 kJ/mol. In addition, the influence of mass transfer limitations were noted at low NO and CO concentrations. (2) The packed bed reactor/gas flow system has been applied to performing post-reaction temperature programmed desorption (TPD) studies of intermediate surface complexes following steady-state reaction. It was found that the amount of CO-evolving intermediate surface complexes exceeded that of the N{sub 2}-evolving surface complexes, and that both increased with reaction temperature. The TPD spectra indicates that both types of complexes desorb late, suggesting that they have high desorption activation energies. Plans for the next reporting period include extending the temperature programmed desorption studies in the packed bed reactor system to the NO/CO reaction system, including exposure to just CO, as well as NO/CO mixtures.

  13. Microtubules Accelerate the Kinase Activity of Aurora-B by a Reduction in Dimensionality

    PubMed Central

    Noujaim, Michael; Bechstedt, Susanne; Wieczorek, Michal; Brouhard, Gary J.

    2014-01-01

    Aurora-B is the kinase subunit of the Chromosome Passenger Complex (CPC), a key regulator of mitotic progression that corrects improper kinetochore attachments and establishes the spindle midzone. Recent work has demonstrated that the CPC is a microtubule-associated protein complex and that microtubules are able to activate the CPC by contributing to Aurora-B auto-phosphorylation in trans. Aurora-B activation is thought to occur when the local concentration of Aurora-B is high, as occurs when Aurora-B is enriched at centromeres. It is not clear, however, whether distributed binding to large structures such as microtubules would increase the local concentration of Aurora-B. Here we show that microtubules accelerate the kinase activity of Aurora-B by a “reduction in dimensionality.” We find that microtubules increase the kinase activity of Aurora-B toward microtubule-associated substrates while reducing the phosphorylation levels of substrates not associated to microtubules. Using the single molecule assay for microtubule-associated proteins, we show that a minimal CPC construct binds to microtubules and diffuses in a one-dimensional (1D) random walk. The binding of Aurora-B to microtubules is salt-dependent and requires the C-terminal tails of tubulin, indicating that the interaction is electrostatic. We show that the rate of Aurora-B auto-activation is faster with increasing concentrations of microtubules. Finally, we demonstrate that microtubules lose their ability to stimulate Aurora-B when their C-terminal tails are removed by proteolysis. We propose a model in which microtubules act as scaffolds for the enzymatic activity of Aurora-B. The scaffolding activity of microtubules enables rapid Aurora-B activation and efficient phosphorylation of microtubule-associated substrates. PMID:24498282

  14. Adsorption and desorption of U(VI) on functionalized graphene oxides: a combined experimental and theoretical study.

    PubMed

    Sun, Yubing; Yang, Shubin; Chen, Yue; Ding, Congcong; Cheng, Wencai; Wang, Xiangke

    2015-04-01

    The adsorption and desorption of U(VI) on graphene oxides (GOs), carboxylated GOs (HOOC-GOs), and reduced GOs (rGOs) were investigated by batch experiments, EXAFS technique, and computational theoretical calculations. Isothermal adsorptions showed that the adsorption capacities of U(VI) were GOs > HOOC-GOs > rGOs, whereas the desorbed amounts of U(VI) were rGOs > GOs > HOOC-GOs by desorption kinetics. According to EXAFS analysis, inner-sphere surface complexation dominated the adsorption of U(VI) on GOs and HOOC-GOs at pH 4.0, whereas outer-sphere surface complexation of U(VI) on rGO was observed at pH 4.0, which was consistent with surface complexation modeling. Based on the theoretical calculations, the binding energy of [G(···)UO2](2+) (8.1 kcal/mol) was significantly lower than those of [HOOC-GOs(···)UO2](2+) (12.1 kcal/mol) and [GOs-O(···)UO2](2+) (10.2 kcal/mol), suggesting the physisorption of UO2(2+) on rGOs. Such high binding energy of [GOs-COO(···)UO2](+) (50.5 kcal/mol) revealed that the desorption of U(VI) from the -COOH groups was much more difficult. This paper highlights the effect of the hydroxyl, epoxy, and carboxyl groups on the adsorption and desorption of U(VI), which plays an important role in designing GOs for the preconcentration and removal of radionuclides in environmental pollution cleanup applications. PMID:25761122

  15. ESTIMATION OF MICROBIAL REDUCTIVE TRANSFORMATION RATES FOR CHLORINATED BENZENES AND PHENOLS USING A QUANTITATIVE STRUCTURE-ACTIVITY RELATIONSHIP APPROACH

    EPA Science Inventory

    A set of literature data was used to derive several quantitative structure-activity relationships (QSARs) to predict the rate constants for the microbial reductive dehalogenation of chlorinated aromatics. Dechlorination rate constants for 25 chloroaromatics were corrected for th...

  16. Removal of micropollutants and reduction of biological activity in a full scale reclamation plant using ozonation and activated carbon filtration.

    PubMed

    Reungoat, J; Macova, M; Escher, B I; Carswell, S; Mueller, J F; Keller, J

    2010-01-01

    Pharmaceutical compounds are found in secondary treated effluents up to microg L(-1) levels and therefore discharged into surface waters. Since the long term effects of these compounds on the environment and human health are, to date, largely unknown, implementation of advanced treatment of wastewaters is envisaged to reduce their discharge. This is of particular relevance where surface waters are used as drinking water sources and when considering indirect potable reuse. This study aimed at assessing the removal of organic micropollutants and the concurrent reduction of their biological activity in a full scale reclamation plant treating secondary effluent. The treatment consists of 6 stages: denitrification, pre-ozonation, coagulation/flocculation/dissolved air flotation and filtration (DAFF), main ozonation, activated carbon filtration and final ozonation for disinfection. For that purpose, representative 24-hour composite samples were collected after each stage. The occurrence of 85 compounds was monitored by LC/MS-MS. A battery of 6 bioassays was also used as a complementary tool to evaluate non-specific toxicity and 5 specific toxic modes of action. Results show that, among the 54 micropollutants quantified in the influent water, 50 were removed to below their limit of quantification representing more than 90% of concentration reduction. Biological activity was reduced, depending on the specific response that was assessed, from a minimum of 62% (AhR response) to more than 99% (estrogenicity). The key processes responsible for the plant's performances were the coagulation/flocculation/DAFF, main ozonation and activated carbon filtration. The effect of these 3 processes varied from one compound or bioassay to another but their combination was almost totally responsible for the overall observed reduction. Bioassays yielded complementary information, e.g. estrogenic compounds were not detected in the secondary effluent by chemical analysis, but the samples had an

  17. DEVELOPMENT OF HIGH ACTIVITY, COAL-DERIVED, PROMOTED CATALYTIC SYSTEMS FOR NOx REDUCTION AT LOW TEMPERATURES

    SciTech Connect

    Joseph M. Calo

    2000-07-19

    This project is directed at an investigation of catalytic NO{sub x} reduction mechanisms on coal-derived, activated carbon supports at low temperatures. Promoted carbon systems offer some potentially significant advantages for heterogeneous NO{sub x} reduction. These include: low cost; high activity at low temperatures, which minimizes carbon loss; oxygen resistance; and a support material which can be engineered with respect to porosity, transport and catalyst dispersion characteristics. During the reporting period, the following has been accomplished: (1) A packed bed reactor/gas flow system has been tested and applied to performing NO-carbon reactivity studies. This system employs a Kin-Tek gas calibration/mixing system for varying NO and CO concentrations in the feed gas to the packed bed, a NO{sub x} chemiluminescence analyzer (ThermoElectron, Model 10), and a quadrupole mass spectrometer (Ametek). This system is used for both steady-state reactivity studies, as well as mechanistic studies on the effects of NO and CO in the gas phase on intermediate oxygen surface complex populations on the carbon substrates. (2) Reactivity studies of the NO-carbon system have been performed as a function of temperature and NO concentration. It was found that apparent activation energy in the ''high temperature'' regime of 180 {+-} 10 kJ/mol agrees well with corresponding values reported in the literature. At the low NO concentrations used, it was observed that the reaction is not strictly first order in NO. In addition, the influence of mass transfer limitations were noted at high temperatures and low NO concentrations. Plans for the next reporting period include applications of the packed bed reactor system to perform temperature programmed desorption studies of the reaction of the NO-carbon reaction, and to reactivity studies of the NO/CO reaction system.

  18. Experimental Study of Active Techniques for Blade/Vortex Interaction Noise Reduction

    NASA Astrophysics Data System (ADS)

    Kobiki, Noboru; Murashige, Atsushi; Tsuchihashi, Akihiko; Yamakawa, Eiichi

    This paper presents the experimental results of the effect of Higher Harmonic Control (HHC) and Active Flap on the Blade/Vortex Interaction (BVI) noise. Wind tunnel tests were performed with a 1-bladed rotor system to evaluate the simplified BVI phenomenon avoiding the complicated aerodynamic interference which is characteristically and inevitably caused by a multi-bladed rotor. Another merit to use this 1-bladed rotor system is that the several objective active techniques can be evaluated under the same condition installed in the same rotor system. The effects of the active techniques on the BVI noise reduction were evaluated comprehensively by the sound pressure, the blade/vortex miss distance obtained by Laser light Sheet (LLS), the blade surface pressure distribution and the tip vortex structure by Particle Image Velocimetry (PIV). The correlation among these quantities to describe the effect of the active techniques on the BVI conditions is well obtained. The experiments show that the blade/vortex miss distance is more dominant for BVI noise than the other two BVI governing factors, such as blade lift and vortex strength at the moment of BVI.

  19. NMDA receptor hypofunction produces concomitant firing rate potentiation and burst activity reduction in the prefrontal cortex

    PubMed Central

    Jackson, Mark E.; Homayoun, Houman; Moghaddam, Bita

    2004-01-01

    Cognitive deficits associated with frontal lobe dysfunction are a determinant of long-term disability in schizophrenia and are not effectively treated with available medications. Clinical studies show that many aspects of these deficits are transiently induced in healthy individuals treated with N-methyl-d-aspartate (NMDA) antagonists. These findings and recent genetic linkage studies strongly implicate NMDA receptor deficiency in schizophrenia and suggest that reversing this deficiency is pertinent to treating the cognitive symptoms of schizophrenia. Despite the wealth of behavioral data on the effects of NMDA antagonist treatment in humans and laboratory animals, there is a fundamental lack of understanding about the mechanisms by which a general state of NMDA deficiency influences the function of cortical neurons. Using ensemble recording in freely moving rats, we found that NMDA antagonist treatment, at doses that impaired working memory, potentiated the firing rate of most prefrontal cortex neurons. This potentiation, which correlated with expression of behavioral stereotypy, resulted from an increased number of irregularly discharged single spikes. Concurrent with the increase in spike activity, there was a significant reduction in organized bursting activity. These results identify two distinct mechanisms by which NMDA receptor deficiency may disrupt frontal lobe function: an increase in disorganized spike activity, which may enhance cortical noise and transmission of disinformation; and a decrease in burst activity, which reduces transmission efficacy of cortical neurons. These findings provide a physiological basis for the NMDA receptor deficiency model of schizophrenia and may clarify the nature of cortical dysfunction in this disease. PMID:15159546

  20. A unique platinum-graphene hybrid structure for high activity and durability in oxygen reduction reaction

    PubMed Central

    Wang, Chengming; Ma, Liang; Liao, Lingwen; Bai, Song; Long, Ran; Zuo, Ming; Xiong, Yujie

    2013-01-01

    It remains a grand challenge to achieve both high activity and durability in Pt electrocatalysts for oxygen reduction reaction (ORR) in fuel cells. Here we develop a class of Pt highly concave cubic (HCC) nanocrystals, which are enriched with high-index facets, to enable high ORR activity. The durability of HCC nanocrystals can be significantly improved via assembly with graphene. Meanwhile, the unique hybrid structure displays further enhanced specific activity, which is 7-fold greater than the state-of-the-art Pt/C catalysts. Strikingly, it exhibits impressive performance in terms of half-wave potential (E1/2). The E1/2 of 0.967 V at the Pt loading as low as 46 μg cm−2, which stands as 63 mV higher than that of the Pt/C catalysts, is slightly superior to the record observed for the most active porous Pt-Ni catalyst in literature. This work paves the way to designing high-performance electrocatalysts by modulating their surface and interface with loading substrates. PMID:23999570

  1. Effects of combining biological treatment and activated carbon on hexavalent chromium reduction.

    PubMed

    Orozco, A M Ferro; Contreras, E M; Zaritzky, N E

    2011-02-01

    The objectives of the present work were: (a) to analyze the Cr(VI) removal by combining activated sludge (AS) with powdered activated carbon (PAC), (b) to analyze the effect of PAC and Cr(VI) on the growth kinetics of activated sludge, and (c) to determine if the combined method (AS-PAC) for Cr(VI) removal can be considered additive or synergistic with respect to the individual processes. Chromate removal was improved by increasing PAC concentrations in both PAC and AS-PAC systems. Cr(VI) removal using the AS-PAC system was higher than using AS or PAC. The increase of Cr(VI) caused longer lag phase and lower observed specific growth rate (μ(obs)), biomass yield (Y(X/S)), and specific growth substrate consumption rate (q(S)) of activated sludge; additionally, PAC did not enhance the growth kinetic parameters (μ(obs), Y(X/S), q(S)). Cr(VI) reduction in AS-PAC system was the result of the additive effect of each individual Cr(VI) removal process. PMID:21123053

  2. Platinum multicubes prepared by ni(2+) -mediated shape evolution exhibit high electrocatalytic activity for oxygen reduction.

    PubMed

    Ma, Liang; Wang, Chengming; Xia, Bao Yu; Mao, Keke; He, Jiawei; Wu, Xiaojun; Xiong, Yujie; Lou, Xiong Wen David

    2015-05-01

    Pt(100) facets are generally considered less active for the oxygen reduction reaction (ORR). Reported herein is a unique Pt-branched structure, a multicube, whose surface is mostly enclosed by {100} facets but contains high-index facets at the small junction area between the adjacent cubic components. The synthesis is accomplished by a Ni(2+) -mediated facet evolution from high-index {311} to {100} facets on the frameworks of multipods. Despite the high {100} facet coverage, the Pt multicubes exhibit impressive ORR activity in terms of half-wave potential and current density nearly to the level of the most active Pt-based catalysts, while the durability of catalysts is well retained. The facet evolution creates a set of samples with tunable ratios of high-index to low-index facets. The results reveal that the excellent ORR performance of Pt multicubes is a combined result of active sites by high-index facets and low resistance by flat surface. It is anticipated that this work will offer a new approach to facet-controlled synthesis and ORR catalysts design. PMID:25756931

  3. Ultrathin Icosahedral Pt-Enriched Nanocage with Excellent Oxygen Reduction Reaction Activity.

    PubMed

    He, Dong Sheng; He, Daping; Wang, Jing; Lin, Yue; Yin, Peiqun; Hong, Xun; Wu, Yuen; Li, Yadong

    2016-02-10

    Cost-efficient utilization of Pt in the oxygen reduction reaction (ORR) is of great importance for the potential industrial scale demand of proton-exchange membrane fuel cells. Designing a hollow structure of a Pt catalyst offers a great opportunity to enhance the electrocatalytic performance and maximize the use of precious Pt. Herein we report a routine to synthesize ultrathin icosahedral Pt-enriched nanocages. In detail, the Pt atoms were conformally deposited on the surface of Pd icosahedral seeds, followed by selective removal of the Pd core by a concentrated HNO3 solution. The icosahedral Pt-enriched nanocage that is a few atomic layers thick includes the merits of abundant twin defects, an ultrahigh surface/volume ratio, and an ORR-favored Pt{111} facet, all of which have been demonstrated to be promoting factors for ORR. With a 10 times higher specific activity and 7 times higher mass activity, this catalyst shows more extraordinary ORR activity than the commercial Pt/C. The ORR activity of icosahedral Pt-enriched nanocages outperforms the cubic and octahedral nanocages reported in the literature, demonstrating the superiority of the icosahedral nanocage structure. PMID:26808073

  4. Solubility data for U(VI) hydroxide and Np(IV) hydrous oxide: application of MCC-3 methodology

    SciTech Connect

    Krupka, K.M.; Rai, D.; Fulton, R.W.; Strickert, R.G.

    1984-10-01

    Experiments based on a modified MCC-3S test method were conducted to investigate the solubility of U(VI) hydroxide (the mineral schoepite) and Np(IV) hydrous oxide at ambient temperature. The solubility of U(VI) hydroxide was investigated in carbonate-free, oxidizing aqueous solutions in the pH range of 3 to 11. The measured concentrations of dissolved U confirm the amphoteric behavior of U(VI) hydroxide solid and the importance of anionic U(VI) hydroxyl complexes in accurately calculating the solubilities of U(VI) solids under basic pH conditions. the effect of fluoride complexation on the solubility of Np(IV) hydrous oxide was studied in carbonate-free, near-neutral to alkaline solutions that contained 100 ppM total F. For solutions in which sodium dithionite (Na/sub 2/S/sub 2/O/sub 4/) and metallic Fe were used as reducing agents, the addition of 100 ppM F had no measurable effect on the solubility of Np(IV) hydrous oxide.

  5. Effect of Subgrid Heterogeneity on Scaling Geochemical and Biogeochemical Reactions: A Case of U(VI) Desorption

    SciTech Connect

    Liu, Chongxuan; Shang, Jianying; Shan, Huimei; Zachara, John M.

    2014-02-04

    The effect of subgrid heterogeneity in sediment properties on the rate of uranyl[U(VI)] desorption was investigated using a sediment collected from the US Department of Energy Hanford site. The sediment was sieved into 7 grain size fractions that each exhibited different U(VI) desorption properties. Six columns were assembled using the sediment with its grain size fractions arranged in different spatial configurations to mimic subgrid heterogeneity in reactive transport properties. The apparent rate of U(VI) desorption varied significantly in the columns. Those columns with sediment structures leading to preferential transport had much lower rates of U(VI) desorption than those with relatively homogeneous transport. Modeling analysis indicated that the U(VI) desorption model and parameters characterized from well-mixed reactors significantly over-predicted the measured U(VI) desorption in the columns with preferential transport. A dual domain model, which operationally separates reactive transport properties into two subgrid domains improved the predictions significantly. A similar effect of subgrid heterogeneity, albeit at a less degree, was observed for denitrification, which also occurred in the columns. The results imply that subgrid heterogeneity is an important consideration in extrapolating reaction rates from the laboratory to field.

  6. Active Aerodynamic Load Reduction on a Rotorcraft Fuselage With Rotor Effects: A CFD Validation Effort

    NASA Technical Reports Server (NTRS)

    Allan, Brian G.; Schaeffler, Norman W.; Jenkins, Luther N.; Yao, Chung-Sheng; Wong, Oliver D.; Tanner, Philip E.

    2015-01-01

    A rotorcraft fuselage is typically designed with an emphasis on operational functionality with aerodynamic efficiency being of secondary importance. This results in a significant amount of drag during high-speed forward flight that can be a limiting factor for future high-speed rotorcraft designs. To enable higher speed flight, while maintaining a functional fuselage design (i.e., a large rear cargo ramp door), the NASA Rotary Wing Project has conducted both experimental and computational investigations to assess active flow control as an enabling technology for fuselage drag reduction. This paper will evaluate numerical simulations of a flow control system on a generic rotorcraft fuselage with a rotor in forward flight using OVERFLOW, a structured mesh Reynolds-averaged Navier-Stokes flow solver developed at NASA. The results are compared to fuselage forces, surface pressures, and PN flow field data obtained in a wind tunnel experiment conducted at the NASA Langley 14-by 22-Foot Subsonic Tunnel where significant drag and download reductions were demonstrated using flow control. This comparison showed that the Reynolds-averaged Navier-Stokes flow solver was unable to predict the fuselage forces and pressure measurements on the ramp for the baseline and flow control cases. While the CFD was able to capture the flow features, it was unable to accurately predict the performance of the flow control.

  7. Reductive dehalogenation activity of indigenous microorganism in sediments of the Hackensack River, New Jersey.

    PubMed

    Sohn, Seo Yean; Häggblom, Max M

    2016-07-01

    Organohalogen pollutants are of concern in many river and estuarine environments, such as the New York-New Jersey Harbor estuary and its tributaries. The Hackensack River is contaminated with various metals, hydrocarbons and halogenated organics, including polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins. In order to examine the potential for microbial reductive dechlorination by indigenous microorganisms, sediment samples were collected from five different estuarine locations along the Hackensack River. Hexachlorobenzene (HCB), hexabromobenzene (HBB), and pentachloroaniline (PCA) were selected as model organohalogen pollutants to assess anaerobic dehalogenating potential. Dechlorinating activity of HCB and PCA was observed in sediment microcosms for all sampling sites. HCB was dechlorinated via pentachlorobenzene (PeCB) and trichlorobenzene (TriCB) to dichlorobenzene (DCB). PCA was dechlorinated via tetrachloroaniline (TeCA), trichloroanilines (TriCA), and dichloroanilines (DCA) to monochloroaniline (MCA). No HBB debromination was observed over 12 months of incubation. However, with HCB as a co-substrate slow HBB debromination was observed with production of tetrabromobenzene (TeBB) and tribromobenzene (TriBB). Chloroflexi specific 16S rRNA gene PCR-DGGE followed by sequence analysis detected Dehalococcoides species in sediments of the freshwater location, but not in the estuarine site. Analysis targeting 12 putative reductive dehalogenase (rdh) genes showed that these were enriched concomitant with HCB or PCA dechlorination in freshwater sediment microcosms. PMID:27108041

  8. Hydrodynamic sensing does not facilitate active drag reduction in the golden shiner (Notemigonus crysoleucas).

    PubMed

    McHenry, M J; Michel, K B; Stewart, W; Müller, U K

    2010-04-01

    The lateral line system detects water flow, which allows fish to orient their swimming with respect to hydrodynamic cues. However, it is unclear whether this sense plays a role in the control of propulsion. Hydrodynamic theory suggests that fish could reduce drag by coordinating the motion of the head relative to detected flow signals. To test this hypothesis, we performed measurements of undulatory kinematics during steady swimming in the golden shiner (Notemigonus crysoleucas) at three speeds (4.5, 11.0 and 22.0 cm s(-1)). We found that the phase shift between yaw angle and lateral velocity (20.5+/-13.1 deg., N=5) was significantly greater than the theoretical optimum (0 deg.) and the amplitude of these variables created a hydrodynamic index (H=0.05+/-0.03, N=6) that was less than an order of magnitude below the theoretical prediction. Furthermore, we repeated these measurements after pharmacologically ablating the lateral line hair cells and found that drag reduction was not adversely influenced by disabling the lateral line system. Therefore, flow sensing does not facilitate active drag reduction. However, we discovered that ablating the lateral line causes the envelope of lateral displacement to nearly double at the envelope's most narrow point for swimming at 4.5 cm s(-1). Therefore, fish may use hydrodynamic sensing to modulate the lateral amplitude of slow undulatory swimming, which could allow rapid responses to changes in environmental flow. PMID:20348343

  9. Electrocatalytic activities of alkyne-functionalized copper nanoparticles in oxygen reduction in alkaline media

    NASA Astrophysics Data System (ADS)

    Liu, Ke; Song, Yang; Chen, Shaowei

    2014-12-01

    Stable alkyne-capped copper nanoparticles were prepared by chemical reduction of copper acetate with sodium borohydride in the presence of alkyne ligands. Transmission electron microscopic measurements showed that nanoparticles were well dispersed with a diameter in the range of 4-6 nm. FTIR and photoluminescence spectroscopic measurements confirmed the successful attachment of the alkyne ligands onto the nanoparticle surface most likely forming Cu-Ctbnd interfacial bonds. XPS measurements indicated the formation of a small amount of CuO in the nanoparticles with a satellite peak where the binding energy red-shifted with increasing Cu(II) concentration. Cu2O was also detected in the nanoparticles. Similar results were observed with commercial CuO nanoparticles. Electrochemical studies showed that the as-prepared alkyne-capped copper nanoparticles exhibited apparent electrocatalytic activity in oxygen reduction in alkaline media, a performance that was markedly better than those reported earlier with poly- or single-crystalline copper electrodes; and the fraction of peroxides in the final products decreased with decreasing concentration of oxide components in the nanoparticles.

  10. N2O reduction by the mu4-sulfide-bridged tetranuclear CuZ cluster active site.

    PubMed

    Chen, Peng; Gorelsky, Serge I; Ghosh, Somdatta; Solomon, Edward I

    2004-08-13

    Nitrous oxide (N2O) reduction is a chemical challenge both in the selective oxidation of organic substrates by N2O and in the removal of N2O as a green-house gas. The reduction of N2O is thermodynamically favorable but kinetically inert, and requires activating transition-metal centers. In biological systems, N2O reduction is the last step in the denitrification process of the bacterial nitrogen cycle and is accomplished by the enzyme nitrous oxide reductase, whose active site consists of a micro4-sulfide-bridged tetranuclear CuZ cluster which has many unusual spectroscopic features. Recent studies have developed a detailed electronic-structure description of the resting CuZ cluster, determined its catalytically relevant state, and provided insight into the role of this tetranuclear copper cluster in N2O activation and reduction. PMID:15307074

  11. Concentration Effects of Polymer Electrolyte Membrane Degradation Products on Oxygen Reduction Activity for Three Platinum Catalysts

    DOE PAGESBeta

    Christ, J. M.; Neyerlin, K. C.; Richards, R.; Dinh, H. N.

    2014-10-04

    A rotating disk electrode (RDE) along with cyclic voltammetry (CV) and linear sweep voltammetry (LSV), were used to investigate the impact of two model compounds representing degradation products of Nafion and 3M perfluorinated sulfonic acid membranes on the electrochemical surface area (ECA) and oxygen reduction reaction (ORR) activity of polycrystalline Pt, nano-structured thin film (NSTF) Pt (3M), and Pt/Vulcan carbon (Pt/Vu) (TKK) electrodes. ORR kinetic currents (measured at 0.9 V and transport corrected) were found to decrease linearly with the log of concentration for both model compounds on all Pt surfaces studied. Ultimately, model compound adsorption effects on ECA weremore » more abstruse due to competitive organic anion adsorption on Pt surfaces superimposing with the hydrogen underpotential deposition (HUPD) region.« less

  12. Reduction in Power Consumption for Full-Color Active Matrix Organic Light-Emitting Devices

    NASA Astrophysics Data System (ADS)

    Kanno, Hiroshi; Hamada, Yuji; Nishimura, Kazuki; Okumoto, Kenji; Saito, Nobuo; Mameno, Kazunobu; Shibata, Kenichi

    2006-09-01

    The active matrix organic light-emitting diode (AMOLED) is expected to serve as next generation flat panels display with the outstanding features of wide viewing angle, vivid images, and quick response. For practical use of full-color AMOLEDs in mobile devices, it is essential to reduce the power consumption, which is generally higher than that of liquid crystal displays (LCDs). For this aim, a red, green, blue, and white (RGBW) pixel format combined with an RGB color filter array (RGBW format) with a common white emission layer (EML) has been developed. We find that the RGBW format can successfully reduce the power consumption of a full-color AMOLED by nearly half that of a conventionally filtered RGB pixel format. This improved power consumption is almost equal to the power consumption of a same-sized LCD. The RGBW format is a promising technique for the further reduction of the power consumption of a full-color AMOLED.

  13. Repetition-Related Reductions in Neural Activity during Emotional Simulations of Future Events

    PubMed Central

    2015-01-01

    Simulations of future experiences are often emotionally arousing, and the tendency to repeatedly simulate negative future outcomes has been identified as a predictor of the onset of symptoms of anxiety. Nonetheless, next to nothing is known about how the healthy human brain processes repeated simulations of emotional future events. In this study, we present a paradigm that can be used to study repeated simulations of the emotional future in a manner that overcomes phenomenological confounds between positive and negative events. The results show that pulvinar nucleus and orbitofrontal cortex respectively demonstrate selective reductions in neural activity in response to frequently as compared to infrequently repeated simulations of negative and positive future events. Implications for research on repeated simulations of the emotional future in both non-clinical and clinical populations are discussed. PMID:26390294

  14. Reduction of Free Edge Peeling Stress of Laminated Composites Using Active Piezoelectric Layers

    PubMed Central

    Huang, Bin; Kim, Heung Soo

    2014-01-01

    An analytical approach is proposed in the reduction of free edge peeling stresses of laminated composites using active piezoelectric layers. The approach is the extended Kantorovich method which is an iterative method. Multiterms of trial function are employed and governing equations are derived by taking the principle of complementary virtual work. The solutions are obtained by solving a generalized eigenvalue problem. By this approach, the stresses automatically satisfy not only the traction-free boundary conditions, but also the free edge boundary conditions. Through the iteration processes, the free edge stresses converge very quickly. It is found that the peeling stresses generated by mechanical loadings are significantly reduced by applying a proper electric field to the piezoelectric actuators. PMID:25025088

  15. Nitride stabilized PtNi core-shell nanocatalyst for high oxygen reduction activity.

    PubMed

    Kuttiyiel, Kurian A; Sasaki, Kotaro; Choi, Yongman; Su, Dong; Liu, Ping; Adzic, Radoslav R

    2012-12-12

    We describe a route to the development of novel PtNiN core-shell catalysts with low Pt content shell and inexpensive NiN core having high activity and stability for the oxygen reduction reaction (ORR). The PtNiN synthesis involves nitriding Ni nanoparticles and simultaneously encapsulating it by 2-4 monolayer-thick Pt shell. The experimental data and the density functional theory calculations indicate nitride has the bifunctional effect that facilitates formation of the core-shell structures and improves the performance of the Pt shell by inducing both geometric and electronic effects. Synthesis of inexpensive NiN cores opens up possibilities for designing of various transition metal nitride based core-shell nanoparticles for a wide range of applications in energy conversion processes. PMID:23194259

  16. NASA Propulsion Concept Studies and Risk Reduction Activities for Resource Prospector Lander

    NASA Technical Reports Server (NTRS)

    Trinh, Huu P.; Williams, Hunter; Burnside, Chris

    2015-01-01

    The Resource Prospector mission is to investigate the Moon's polar regions in search of volatiles. The government-version lander concept for the mission is composed of a braking stage and a liquid-propulsion lander stage. A propulsion trade study concluded with a solid rocket motor for the braking stage while using the 4th-stage Peacekeeper (PK) propulsion components for the lander stage. The mechanical design of the liquid propulsion system was conducted in concert with the lander structure design. A propulsion cold-flow test article was fabricated and integrated into a lander development structure, and a series of cold flow tests were conducted to characterize the fluid transient behavior and to collect data for validating analytical models. In parallel, RS-34 PK thrusters to be used on the lander stage were hot-fire tested in vacuum conditions as part of risk reduction activities.

  17. Concentration Effects of Polymer Electrolyte Membrane Degradation Products on Oxygen Reduction Activity for Three Platinum Catalysts

    SciTech Connect

    Christ, J. M.; Neyerlin, K. C.; Richards, R.; Dinh, H. N.

    2014-10-04

    A rotating disk electrode (RDE) along with cyclic voltammetry (CV) and linear sweep voltammetry (LSV), were used to investigate the impact of two model compounds representing degradation products of Nafion and 3M perfluorinated sulfonic acid membranes on the electrochemical surface area (ECA) and oxygen reduction reaction (ORR) activity of polycrystalline Pt, nano-structured thin film (NSTF) Pt (3M), and Pt/Vulcan carbon (Pt/Vu) (TKK) electrodes. ORR kinetic currents (measured at 0.9 V and transport corrected) were found to decrease linearly with the log of concentration for both model compounds on all Pt surfaces studied. Ultimately, model compound adsorption effects on ECA were more abstruse due to competitive organic anion adsorption on Pt surfaces superimposing with the hydrogen underpotential deposition (HUPD) region.

  18. Infrared observation of thermally activated oxide reduction within Al/SiOx/Si tunnel diodes

    NASA Astrophysics Data System (ADS)

    Brendel, R.; Hezel, R.

    1992-05-01

    Electron-beam-evaporated aluminum/silicon oxide/silicon tunnel diodes with an initial oxide thickness of 1.3 nm have been annealed for up to 1 h at temperatures from 213 to 369 °C. They have been investigated by infrared grazing internal reflection (GIR) spectroscopy and current-voltage measurements. The measured IR spectra were analyzed by computer modeling. All spectral features could be explained self-consistently within a Al/AlOy/SiOx/Si layer model. In the as-deposited state less than 0.6 monolayers of Al—O bonds are formed at the Al/SiOx interface. A thermally activated reduction of the ultrathin oxide film by Al was observed. The changes in the current-voltage curves induced by slight annealing (1 min at 213 °C) are accompanied by changes in the insulator-bonding structure, which GIR is sensitive enough to detect.

  19. Activation reduction in anterior temporal cortices during repeated recognition of faces of personal acquaintances.

    PubMed

    Sugiura, M; Kawashima, R; Nakamura, K; Sato, N; Nakamura, A; Kato, T; Hatano, K; Schormann, T; Zilles, K; Sato, K; Ito, K; Fukuda, H

    2001-05-01

    Repeated recognition of the face of a familiar individual is known to show semantic repetition priming effect. In this study, normal subjects were repeatedly presented faces of their colleagues, and the effect of repetition on the regional cerebral blood flow change was measured using positron emission tomography. They repeated a set of three tasks: the familiar-face detection (F) task, the facial direction discrimination (D) task, and the perceptual control (C) task. During five repetitions of the F task, familiar faces were presented six times from different views in a pseudorandom order. Activation reduction through the repetition of the F tasks was observed in the bilateral anterior (anterolateral to the polar region) temporal cortices which are suggested to be involved in the access to the long-term memory concerning people. The bilateral amygdala, the hypothalamus, and the medial frontal cortices, were constantly activated during the F tasks, and considered to be associated with the behavioral significance of the presented familiar faces. Constant activation was also observed in the bilateral occipitotemporal regions and fusiform gyri and the right medial temporal regions during perception of the faces, and in the left medial temporal regions during the facial familiarity detection task, which are consistent with the results of previous functional brain imaging studies. The results have provided further information about the functional segregation of the anterior temporal regions in face recognition and long-term memory. PMID:11304083

  20. In situ probing of the active site geometry of ultrathin nanowires for the oxygen reduction reaction

    DOE PAGESBeta

    Liu, Haiqing; Wong, Stanislaus S.; An, Wei; Li, Yuanyuan; Frenkel, Anatoly I.; Sasaki, Kotaro; Koenigsmann, Christopher; Su, Dong; Anderson, Rachel M.; Crooks, Richard M.; et al

    2015-09-24

    To create truly effective electrocatalysts for the cathodic reaction governing proton exchange membrane fuel cells (PEMFC), namely the oxygen reduction reaction (ORR), necessitates an accurate and detailed structural understanding of these electrocatalysts, especially at the nanoscale, and to precisely correlate that structure with demonstrable performance enhancement. To address this key issue, we have combined and interwoven theoretical calculations with experimental, spectroscopic observations in order to acquire useful structural insights into the active site geometry with implications for designing optimized nanoscale electrocatalysts with rationally predicted properties. Specifically, we have probed ultrathin (~2 nm) core–shell Pt~Pd9Au nanowires, which have been previously shownmore » to be excellent candidates for ORR in terms of both activity and long-term stability, from the complementary perspectives of both DFT calculations and X-ray absorption spectroscopy (XAS). The combination and correlation of data from both experimental and theoretical studies has revealed for the first time that the catalytically active structure of our ternary nanowires can actually be ascribed to a PtAu~Pd configuration, comprising a PtAu binary shell and a pure inner Pd core. Moreover, we have plausibly attributed the resulting structure to a specific synthesis step, namely the Cu underpotential deposition (UPD) followed by galvanic replacement with Pt. Thus, the fundamental insights gained into the performance of our ultrathin nanowires from our demonstrated approach will likely guide future directed efforts aimed at broadly improving upon the durability and stability of nanoscale electrocatalysts in general.« less

  1. Early reduction in toe flexor strength is associated with physical activity in elderly men

    PubMed Central

    Suwa, Masataka; Imoto, Takayuki; Kida, Akira; Yokochi, Takashi

    2016-01-01

    [Purpose] To compare the toe flexor, hand grip and knee extensor strengths of young and elderly men, and to examine the association between toe flexor strength and physical activity or inactivity levels. [Subjects and Methods] Young (n=155, 18–23 years) and elderly (n=60, 65–88 years) men participated in this study. Toe flexor, hand grip, and knee extensor strength were measured. Physical activity (time spent standing/walking per day) and inactivity (time spent sitting per day) were assessed using a self-administered questionnaire. [Results] Toe flexor, hand grip, and knee extensor strength of the elderly men were significantly lower than those of the young men. Standing/walking and sitting times of the elderly men were lower than those of the young men. Toe flexor strength correlated with hand grip and knee extensor strength in both groups. In elderly men, toe flexor strength correlated with standing/walking time. In comparison to the young men’s mean values, toe flexor strength was significantly lower than knee extensor and hand grip strength in the elderly group. [Conclusion] The results suggest that age-related reduction in toe flexor strength is greater than those of hand grip and knee extensor strengths. An early loss of toe flexor strength is likely associated with reduced physical activity in elderly men. PMID:27313353

  2. Isolated metal active site concentration and stability control catalytic CO2 reduction selectivity.

    PubMed

    Matsubu, John C; Yang, Vanessa N; Christopher, Phillip

    2015-03-01

    CO2 reduction by H2 on heterogeneous catalysts is an important class of reactions that has been studied for decades. However, atomic scale details of structure-function relationships are still poorly understood. Particularly, it has been suggested that metal particle size plays a unique role in controlling the stability of CO2 hydrogenation catalysts and the distribution of active sites, which dictates reactivity and selectivity. These studies often have not considered the possible role of isolated metal active sites in the observed dependences. Here, we utilize probe molecule diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) with known site-specific extinction coefficients to quantify the fraction of Rh sites residing as atomically dispersed isolated sites (Rhiso), as well as Rh sites on the surface of Rh nanoparticles (RhNP) for a series of TiO2 supported Rh catalysts. Strong correlations were observed between the catalytic reverse water gas shift turn over frequency (TOF) and the fraction of Rhiso sites and between catalytic methanation TOF and the fraction of RhNP sites. Furthermore, it was observed that reaction condition-induced disintegration of Rh nanoparticles, forming Rhiso active sites, controls the changing reactivity with time on stream. This work demonstrates that isolated atoms and nanoparticles of the same metal on the same support can exhibit uniquely different catalytic selectivity in competing parallel reaction pathways and that disintegration of nanoparticles under reaction conditions can play a significant role in controlling stability. PMID:25671686

  3. In situ probing of the active site geometry of ultrathin nanowires for the oxygen reduction reaction

    SciTech Connect

    Liu, Haiqing; Wong, Stanislaus S.; An, Wei; Li, Yuanyuan; Frenkel, Anatoly I.; Sasaki, Kotaro; Koenigsmann, Christopher; Su, Dong; Anderson, Rachel M.; Crooks, Richard M.; Adzic, Radoslav R.; Liu, Ping

    2015-09-24

    To create truly effective electrocatalysts for the cathodic reaction governing proton exchange membrane fuel cells (PEMFC), namely the oxygen reduction reaction (ORR), necessitates an accurate and detailed structural understanding of these electrocatalysts, especially at the nanoscale, and to precisely correlate that structure with demonstrable performance enhancement. To address this key issue, we have combined and interwoven theoretical calculations with experimental, spectroscopic observations in order to acquire useful structural insights into the active site geometry with implications for designing optimized nanoscale electrocatalysts with rationally predicted properties. Specifically, we have probed ultrathin (~2 nm) core–shell Pt~Pd9Au nanowires, which have been previously shown to be excellent candidates for ORR in terms of both activity and long-term stability, from the complementary perspectives of both DFT calculations and X-ray absorption spectroscopy (XAS). The combination and correlation of data from both experimental and theoretical studies has revealed for the first time that the catalytically active structure of our ternary nanowires can actually be ascribed to a PtAu~Pd configuration, comprising a PtAu binary shell and a pure inner Pd core. Moreover, we have plausibly attributed the resulting structure to a specific synthesis step, namely the Cu underpotential deposition (UPD) followed by galvanic replacement with Pt. Thus, the fundamental insights gained into the performance of our ultrathin nanowires from our demonstrated approach will likely guide future directed efforts aimed at broadly improving upon the durability and stability of nanoscale electrocatalysts in general.

  4. Synthesis of highly active and dual-functional electrocatalysts for methanol oxidation and oxygen reduction reactions

    NASA Astrophysics Data System (ADS)

    Zhao, Qi; Zhang, Geng; Xu, Guangran; Li, Yingjun; Liu, Baocang; Gong, Xia; Zheng, Dafang; Zhang, Jun; Wang, Qin

    2016-12-01

    The promising Pt-based ternary catalyst is crucial for polymer electrolyte membrane fuel cells (PEMFCs) due to improving catalytic activity and durability for both methanol oxidation reaction and oxygen reduction reaction. In this work, a facile strategy is used for the synthesis ternary RuMPt (M = Fe, Co, Ni, and Cu) nanodendrities catalysts. The ternary RuMPt alloys exhibit enhanced specific and mass activity, positive half-wave potential, and long-term stability, compared with binary Pt-based alloy and the commercial Pt/C catalyst, which is attributed to the high electron density and upshifting of the d-band center for Pt atoms, and synergistic catalytic effects among Pt, M, and Ru atoms by introducing a transition metal. Impressively, the ternary RuCoPt catalyst exhibits superior mass activity (801.59 mA mg-1) and positive half-wave potential (0.857 V vs. RHE) towards MOR and ORR, respectively. Thus, the RuMPt nanocomposite is a very promising material to be used as dual electrocatalyst in the application of PEMFCs.

  5. In Situ Probing of the Active Site Geometry of Ultrathin Nanowires for the Oxygen Reduction Reaction.

    PubMed

    Liu, Haiqing; An, Wei; Li, Yuanyuan; Frenkel, Anatoly I; Sasaki, Kotaro; Koenigsmann, Christopher; Su, Dong; Anderson, Rachel M; Crooks, Richard M; Adzic, Radoslav R; Liu, Ping; Wong, Stanislaus S

    2015-10-01

    To create truly effective electrocatalysts for the cathodic reaction governing proton exchange membrane fuel cells (PEMFC), namely the oxygen reduction reaction (ORR), necessitates an accurate and detailed structural understanding of these electrocatalysts, especially at the nanoscale, and to precisely correlate that structure with demonstrable performance enhancement. To address this key issue, we have combined and interwoven theoretical calculations with experimental, spectroscopic observations in order to acquire useful structural insights into the active site geometry with implications for designing optimized nanoscale electrocatalysts with rationally predicted properties. Specifically, we have probed ultrathin (∼2 nm) core-shell Pt∼Pd9Au nanowires, which have been previously shown to be excellent candidates for ORR in terms of both activity and long-term stability, from the complementary perspectives of both DFT calculations and X-ray absorption spectroscopy (XAS). The combination and correlation of data from both experimental and theoretical studies has revealed for the first time that the catalytically active structure of our ternary nanowires can actually be ascribed to a PtAu∼Pd configuration, comprising a PtAu binary shell and a pure inner Pd core. Moreover, we have plausibly attributed the resulting structure to a specific synthesis step, namely the Cu underpotential deposition (UPD) followed by galvanic replacement with Pt. Hence, the fundamental insights gained into the performance of our ultrathin nanowires from our demonstrated approach will likely guide future directed efforts aimed at broadly improving upon the durability and stability of nanoscale electrocatalysts in general. PMID:26402364

  6. Photocatalytic reduction synthesis of SrTiO3-graphene nanocomposites and their enhanced photocatalytic activity

    PubMed Central

    2014-01-01

    SrTiO3-graphene nanocomposites were prepared via photocatalytic reduction of graphene oxide by UV light-irradiated SrTiO3 nanoparticles. Fourier transformed infrared spectroscopy analysis indicates that graphene oxide is reduced into graphene. Transmission electron microscope observation shows that SrTiO3 nanoparticles are well assembled onto graphene sheets. The photocatalytic activity of as-prepared SrTiO3-graphene composites was evaluated by the degradation of acid orange 7 (AO7) under a 254-nm UV irradiation, revealing that the composites exhibit significantly enhanced photocatalytic activity compared to the bare SrTiO3 nanoparticles. This can be explained by the fact that photogenerated electrons are captured by graphene, leading to an increased separation and availability of electrons and holes for the photocatalytic reaction. Hydroxyl (·OH) radicals were detected by the photoluminescence technique using terephthalic acid as a probe molecule and were found to be produced over the irradiated SrTiO3 nanoparticles and SrTiO3-graphene composites; especially, an enhanced yield is observed for the latter. The influence of ethanol, KI, and N2 on the photocatalytic efficiency was also investigated. Based on the experimental results, ·OH, h+, and H2O2 are suggested to be the main active species in the photocatalytic degradation of AO7 by SrTiO3-graphene composites. PACS 61.46. + w; 78.67.Bf; 78.66.Sq PMID:25050089

  7. Electrochemical activation of commercial polyacrylonitrile-based carbon fiber for the oxygen reduction reaction.

    PubMed

    Xu, Haibo; Xia, Guangsen; Liu, Haining; Xia, Shuwei; Lu, Yonghong

    2015-03-28

    Nitrogen (N)-doped carbon and its non-noble metal composite replacing platinum-based oxygen reduction reaction (ORR) electrocatalysts still have some fundamental problems that remain. Here the micron-sized commercial polyacrylonitrile-based carbon fiber (PAN-CF) electrode was modified using an electrochemical method, converting its inherent pyridinic-N into 2-pyridone (or 2-hydroxyl pyridine) functional group existing in three-dimensional active layers with remarkable ORR catalytic activity and stability. The carbon atom adjacent to the nitrogen and oxygen atoms is prone to act as an active site to efficiently catalyze a two-electron ORR process. However, after coordinating pyridone to the Cu(2+) ion, together with the electrochemical reaction, the chemical redox between Cu(+) and ORR intermediates synergistically tends towards a four-electron pathway in alkaline solution. In different medium, the complexation and dissociation can induce the charge transfer and reconstruction among proton, metal ion and pyridone functionalities, eventually leading to the changes of ORR performance. PMID:25712410

  8. Palladium-platinum core-shell icosahedra with substantially enhanced activity and durability towards oxygen reduction.

    PubMed

    Wang, Xue; Choi, Sang-Il; Roling, Luke T; Luo, Ming; Ma, Cheng; Zhang, Lei; Chi, Miaofang; Liu, Jingyue; Xie, Zhaoxiong; Herron, Jeffrey A; Mavrikakis, Manos; Xia, Younan

    2015-01-01

    Conformal deposition of platinum as ultrathin shells on facet-controlled palladium nanocrystals offers a great opportunity to enhance the catalytic performance while reducing its loading. Here we report such a system based on palladium icosahedra. Owing to lateral confinement imposed by twin boundaries and thus vertical relaxation only, the platinum overlayers evolve into a corrugated structure under compressive strain. For the core-shell nanocrystals with an average of 2.7 platinum overlayers, their specific and platinum mass activities towards oxygen reduction are enhanced by eight- and sevenfold, respectively, relative to a commercial catalyst. Density functional theory calculations indicate that the enhancement can be attributed to the weakened binding of hydroxyl to the compressed platinum surface supported on palladium. After 10,000 testing cycles, the mass activity of the core-shell nanocrystals is still four times higher than the commercial catalyst. These results demonstrate an effective approach to the development of electrocatalysts with greatly enhanced activity and durability. PMID:26133469

  9. Palladium–platinum core-shell icosahedra with substantially enhanced activity and durability towards oxygen reduction

    DOE PAGESBeta

    Wang, Xue; Choi, Sang-Il; Roling, Luke T.; Luo, Ming; Ma, Cheng; Zhang, Lei; Chi, Miaofang; Liu, Jingyue; Xie, Zhaoxiong; Herron, Jeffrey A.; et al

    2015-07-02

    Conformal deposition of platinum as ultrathin shells on facet-controlled palladium nanocrystals offers a great opportunity to enhance the catalytic performance while reducing its loading. Here we report such a system based on palladium icosahedra. Owing to lateral confinement imposed by twin boundaries and thus vertical relaxation only, the platinum overlayers evolve into a corrugated structure under compressive strain. For the core-shell nanocrystals with an average of 2.7 platinum overlayers, their specific and platinum mass activities towards oxygen reduction are enhanced by eight- and sevenfold, respectively, relative to a commercial catalyst. Density functional theory calculations indicate that the enhancement can bemore » attributed to the weakened binding of hydroxyl to the compressed platinum surface supported on palladium. After 10,000 testing cycles, the mass activity of the core-shell nanocrystals is still four times higher than the commercial catalyst. Ultimately, these results demonstrate an effective approach to the development of electrocatalysts with greatly enhanced activity and durability.« less

  10. Density Functional Theory Study of Oxygen Reduction Activity on Ultrathin Platinum Nanotubes

    SciTech Connect

    Matanovic, Ivana; Kent, Paul; Garzon, Fernando; Henson, Neil J.

    2012-07-13

    The structure, stability, and catalytic activity of a number of single- and double-wall platinum (n,m) nanotubes ranging in diameter from 0.3 to 2.0 nm were studied using plane-wave based density functional theory in the gas phase and water environment. The change in the catalytic activity toward the oxygen reduction reaction (ORR) with the size and chirality of the nanotube was studied by calculating equilibrium adsorption potentials for ORR intermediates and by constructing free energy diagrams in the ORR dissociative mechanism network. In addition, the stability of the platinum nanotubes is investigated in terms of electrochemical dissolution potentials and by determining the most stable state of the material as a function of pH and potential, as represented in Pourbaix diagrams. Our results show that the catalytic activity and the stability toward electrochemical dissolution depend greatly on the diameter and chirality of the nanotube. On the basis of the estimated overpotentials for ORR, we conclude that smaller, approximately 0.5 nm in diameter single-wall platinum nanotubes consistently show a huge, up to 400 mV larger overpotential than platinum, indicating very poor catalytic activity toward ORR. This is the result of substantial structural changes induced by the adsorption of any chemical species on these tubes. Single-wall n = m platinum nanotubes with a diameter larger than 1 nm have smaller ORR overpotentials than bulk platinum for up to 180 mV and thus show improved catalytic activity relative to bulk. We also predict that these nanotubes can endure the highest cell potentials but dissolution potentials are still for 110 mV lower than for the bulk, indicating a possible corrosion problem.

  11. Reprint of: Active subspaces for sensitivity analysis and dimension reduction of an integrated hydrologic model

    NASA Astrophysics Data System (ADS)

    Jefferson, Jennifer L.; Gilbert, James M.; Constantine, Paul G.; Maxwell, Reed M.

    2016-05-01

    Integrated hydrologic models coupled to land surface models require several input parameters to characterize the land surface and to estimate energy fluxes. Uncertainty of input parameter values is inherent in any model and the sensitivity of output to these uncertain parameters becomes an important consideration. To better understand these connections in the context of hydrologic models, we use the ParFlow-Common Land Model (PF-CLM) to estimate energy fluxes given variations in 19 vegetation and land surface parameters over a 144-hour period of time. Latent, sensible and ground heat fluxes from bare soil and grass vegetation were estimated using single column and tilted-v domains. Energy flux outputs, along with the corresponding input parameters, from each of the four scenario simulations were evaluated using active subspaces. The active subspace method considers parameter sensitivity by quantifying a weight for each parameter. The method also evaluates the potential for dimension reduction by identifying the input-output relationship through the active variable - a linear combination of input parameters. The aerodynamic roughness length was the most important parameter for bare soil energy fluxes. Multiple parameters were important for energy fluxes from vegetated surfaces and depended on the type of energy flux. Relationships between land surface inputs and output fluxes varied between latent, sensible and ground heat, but were consistent between domain setup (i.e., with or without lateral flow) and vegetation type. A quadratic polynomial was used to describe the input-output relationship for these energy fluxes. The reduced-dimension model of land surface dynamics can be compared to observations or used to solve the inverse problem. Considering this work as a proof-of-concept, the active subspace method can be applied and extended to a range of domain setups, land cover types and time periods to obtain a reduced-form representation of any output of interest

  12. Update on Risk Reduction Activities for a Liquid Advanced Booster for NASA's Space Launch System

    NASA Technical Reports Server (NTRS)

    Crocker, Andrew M.; Doering, Kimberly B; Meadows, Robert G.; Lariviere, Brian W.; Graham, Jerry B.

    2015-01-01

    The stated goals of NASA's Research Announcement for the Space Launch System (SLS) Advanced Booster Engineering Demonstration and/or Risk Reduction (ABEDRR) are to reduce risks leading to an affordable Advanced Booster that meets the evolved capabilities of SLS; and enable competition by mitigating targeted Advanced Booster risks to enhance SLS affordability. Dynetics, Inc. and Aerojet Rocketdyne (AR) formed a team to offer a wide-ranging set of risk reduction activities and full-scale, system-level demonstrations that support NASA's ABEDRR goals. For NASA's SLS ABEDRR procurement, Dynetics and AR formed a team to offer a series of full-scale risk mitigation hardware demonstrations for an affordable booster approach that meets the evolved capabilities of the SLS. To establish a basis for the risk reduction activities, the Dynetics Team developed a booster design that takes advantage of the flight-proven Apollo-Saturn F-1. Using NASA's vehicle assumptions for the SLS Block 2, a two-engine, F-1-based booster design delivers 150 mT (331 klbm) payload to LEO, 20 mT (44 klbm) above NASA's requirements. This enables a low-cost, robust approach to structural design. During the ABEDRR effort, the Dynetics Team has modified proven Apollo-Saturn components and subsystems to improve affordability and reliability (e.g., reduce parts counts, touch labor, or use lower cost manufacturing processes and materials). The team has built hardware to validate production costs and completed tests to demonstrate it can meet performance requirements. State-of-the-art manufacturing and processing techniques have been applied to the heritage F-1, resulting in a low recurring cost engine while retaining the benefits of Apollo-era experience. NASA test facilities have been used to perform low-cost risk-reduction engine testing. In early 2014, NASA and the Dynetics Team agreed to move additional large liquid oxygen/kerosene engine work under Dynetics' ABEDRR contract. Also led by AR, the

  13. Activation of the nickel-deficient carbon monoxide dehydrogenase from Rhodospirillum rubrum: Kinetic characterization and reductant requirement

    SciTech Connect

    Ensign, S.A.; Campbell, M.J.; Ludden, P.W. )

    1990-02-27

    The requirements for and kinetics of the activation of the nickel-deficient (apo) CO dehydrogenase from Rhodospirillum rubrum by exogenous nickel have been investigated. The activation is strictly dependent upon the presence of a low-potential one-electron reductant. Sodium dithionite and reduced methylviologen are suitable reductants, whereas reduced indigo carmine and the two-electron reductants sodium borohydride, NADH, and dithiothreitol are ineffective in stimulating activation. The midpoint potential for activation was observed at approximately {minus}475 mV. The ability of a reductant to stimulate activation is correlated with the reduced state of the enzyme Fe{sub 4}-S{sub 4} centers. The activation follows apparent first-order kinetics in a saturable fashion, yielding a rate constant of 0.157 min{sup {minus}1} at saturating concentration of nickel. The initial rate at which the enzyme is activated by NiCl{sub 2} is also a saturable process, yielding a dissociation constant (K{sub D}) of 755 {mu}M for the initial association of nickel and enzyme. Cadmium(II), zinc(II), cobalt(II), and iron(II) are competitive inhibitors of nickel activation with inhibition constants of 2.44, 4.16, 175, and 349 {mu}M, respectively. Manganese(II), calcium(II), and magnesium(II) exhibit no inhibition of activation.

  14. Influence of pulsed mechanical activation of hematite-graphite-aluminum powder mixtures on the reduction of iron oxides

    NASA Astrophysics Data System (ADS)

    Bodrova, L. E.; Vatolin, N. A.; Pastukhov, E. A.; Petrova, S. A.; Popova, E. A.; Zakharov, R. G.

    2011-11-01

    To decrease the temperature of direct iron reduction by carbon and aluminum, short-term pulsed mechanical activation (PMA) of an Fe2O3 + Cgr + Al powder mixture is perfumed during sound-frequency shock loading by a flat activating plunger. The PMA efficiency for powders in comparable with mechanical activation in high-energy ball mills in a decrease in the activation time and retaining the chemical purity of a powder composition.

  15. Particle Sizes in Saturn’s Rings from Diffraction Signals in Cassini UVIS Occultation Data

    NASA Astrophysics Data System (ADS)

    Becker, Tracy M.; Colwell, Joshua E.; Esposito, Larry W.; Attree, Nicholas O.; Murray, Carl D.

    2015-11-01

    Since its arrival at Saturn in 2004, the Cassini spacecraft has illuminated many aspects of the planet’s extensive ring system, including its vast range of particle sizes. Constraints on the particle size distribution are critical for understanding the evolution of the ring system. Our investigation focuses on modeling diffraction signals in occultation data from the Cassini Ultraviolet Imaging Spectrograph (UVIS) to measure the population of the smallest particles in Saturn’s rings.Occultation data from Cassini’s Radio Science Subsystem and the Visual and Infrared Mapping Spectrometer also provide measurements of the size distribution. The amount of light diffracted by the occulting particles is a reflection of the ratio of the wavelength of light and the radius of the particles. We can utilize the diffraction signals at different wavelengths measured by different instruments to describe the particle size distribution of Saturn’s rings.The UVIS wavelength bandpass, 51.2-180 nm, is the shortest of these instruments, making it most sensitive to the smallest particles. We model the diffraction signals detected in stellar occultation data at ring edges and find that Saturn’s outer A ring lacks any significant population of sub-mm particles, but the average size of the smallest particles decreases from ~1.5 cm at the Encke Gap to ~4 mm at the outer edge of the A ring. Diffraction spikes have also been identified at the edge of the B ring and at sharp edges of ringlets in the C ring and Cassini Division, suggestive of mm-sized particles throughout the rings. We analyze solar occultations by the F ring and sporadically detect diffracted light, indicating the population of sub-mm particles responsible for the diffraction is transient or spatially variable. Comparisons with images from the Cassini Imaging Science Subsystem suggest that these diffraction signals coincide with nearby collisional events in the F ring core. This may indicate that such events release

  16. Modeling of the Enceladus water vapor jets for interpreting UVIS star and solar occultation observations

    NASA Astrophysics Data System (ADS)

    Portyankina, Ganna; Esposito, Larry W.; Aye, Klaus-Michael; Hansen, Candice J.

    2015-11-01

    One of the most spectacular discoveries of the Cassini mission is jets emitting from the southern pole of Saturn’s moon Enceladus. The composition of the jets is water vapor and salty ice grains with traces of organic compounds. Jets, merging into a wide plume at a distance, are observed by multiple instruments on Cassini. Recent observations of the visible dust plume by the Cassini Imaging Science Subsystem (ISS) identified as many as 98 jet sources located along “tiger stripes” [Porco et al. 2014]. There is a recent controversy on the question if some of these jets are “optical illusion” caused by geometrical overlap of continuous source eruptions along the “tiger stripes” in the field of view of ISS [Spitale et al. 2015]. The Cassini’s Ultraviolet Imaging Spectrograph (UVIS) observed occultations of several stars and the Sun by the water vapor plume of Enceladus. During the solar occultation separate collimated gas jets were detected inside the background plume [Hansen et al., 2006 and 2011]. These observations directly provide data about water vapor column densities along the line of sight of the UVIS instrument and could help distinguish between the presence of only localized or also continuous sources. We use Monte Carlo simulations and Direct Simulation Monte Carlo (DSMC) to model the plume of Enceladus with multiple (or continuous) jet sources. The models account for molecular collisions, gravitational and Coriolis forces. The models result in the 3-D distribution of water vapor density and surface deposition patterns. Comparison between the simulation results and column densities derived from UVIS observations provide constraints on the physical characteristics of the plume and jets. The specific geometry of the UVIS observations helps to estimate the production rates and velocity distribution of the water molecules emitted by the individual jets.Hansen, C. J. et al., Science 311:1422-1425 (2006); Hansen, C. J. et al, GRL 38:L11202 (2011

  17. Sulfur isotopes as indicators of amended bacterial sulfate reduction processes influencing field scale uranium bioremediation.

    PubMed

    Druhan, Jennifer L; Conrad, Mark E; Williams, Kenneth H; N'Guessan, Lucie; Long, Philip E; Hubbard, Susan S

    2008-11-01

    Aqueous uranium (U(VI)) concentrations in a contaminated aquifer in Rifle Colorado have been successfully lowered through electron donor amended bioreduction. Samples collected during the acetate amendment experiment were analyzed for aqueous concentrations of Fe(ll), sulfate, sulfide, acetate, U(VI), and delta(34)S of sulfate and sulfide to explore the utility of sulfur isotopes as indicators of in situ acetate amended sulfate and uranium bioreduction processes. Enrichment of up to 7% per hundred in delta(34)S of sulfate in down-gradient monitoring wells indicates a transition to elevated bacterial sulfate reduction. A depletion in Fe(II), sulfate, and sulfide concentrations atthe height of sulfate reduction, along with an increase in the delta(34)S of sulfide to levels approaching the delta(34)S values of sulfate, indicates sulfate limited conditions concurrent with a rebound in U(VI) concentrations. Upon cessation of acetate amendment, sulfate and sulfide concentrations increased, while delta(34)S values of sulfide returned to less than -20% per hundred and sulfate delta(34)S decreased to near-background values, indicating lower levels of sulfate reduction accompanied by a corresponding drop in U(VI). Results indicate a transition between electron donor and sulfate-limited conditions at the height of sulfate reduction and suggest stability of biogenic FeS precipitates following the end of acetate amendment. PMID:19031870

  18. Sulfur Isotopes as Indicators of Amended Bacterial Sulfate Reduction Processes Influencing Field Scale Uranium Bioremediation

    SciTech Connect

    Druhan, Jennifer L.; Conrad, Mark E.; Williams, Kenneth H.; N'Guessan, A. Lucie; Long, Philip E.; Hubbard, Susan S.

    2008-11-01

    Aqueous uranium (U(VI)) concentrations in a contaminated aquifer in Rifle Colorado have been successfully lowered through electron donor amended bioreduction. Samples collected during the acetate amendment experiment were analyzed for aqueous concentrations of Fe(II), sulfate, sulfide, acetate, U(VI), and δ34S of sulfate and sulfide to explore the utility of sulfur isotopes as indicators of in situ acetate amended sulfate and uranium bioreduction processes. Enrichment of up to 7‰ in δ34S of sulfate in down-gradient monitoring wells indicates a transition to elevated bacterial sulfate reduction. A depletion in Fe(II), sulfate, and sulfide concentrations at the height of sulfate reduction, along with an increase in the δ34S of sulfide to levels approaching the d34S values of sulfate, indicates sulfate limited conditions concurrent with a rebound in U(VI) concentrations. Upon cessation of acetate amendment, sulfate and sulfide concentrations increased, while δ34S values of sulfide returned to less than -20‰ and sulfate δ34S decreased to near-background values, indicating lower levels of sulfate reduction accompanied by a corresponding drop in U(VI). Results indicate a transition between electron donor and sulfate-limited conditions at the height of sulfate reduction and suggest stability of biogenic FeS precipitates following the end of acetate amendment.

  19. Afferent input-associated reduction of muscle activity in microgravity environment.

    PubMed

    Kawano, F; Nomura, T; Ishihara, A; Nonaka, I; Ohira, Y

    2002-01-01

    Responses of electromyogram (EMG) of soleus, lateral portion of gastrocnemius (LG) and tibialis anterior (TA), and both afferent and efferent neurograms at the L(5) segmental level of the spinal cord, to altered gravity levels created by the parabolic flight of a jet airplane were investigated in adult rats. The EMG activity in antigravity soleus muscle gradually increased when the gravity was elevated from 1-G to 1.5-G (+23%) and 2-G (+67%) during the ascending phase of parabolic flight. The activity decreased approximately 72% from the 1-G level immediately when the rat was exposed to microgravity. The EMG level was maintained low during the 20-s microgravity, but it was restored immediately once the gravity level was increased to 1.5-G and then 1-G during the descending and recovery phase. The EMG level of LG also increased gradually when the gravity level was elevated and the level then decreased when the rat was exposed to microgravity (P>0.05). However, the activity level during the 20-s microgravity was identical to that obtained at 1-G. The EMG level of TA even increased insignificantly in response to the exposure to microgravity. The responses of afferent neurogram were similar to those of soleus EMG, even though the magnitude of the reduction of integrated neurogram level in response to microgravity exposure was small (approximately 26% vs. 1-G level) relative to that of soleus EMG. The level of efferent neurogram was also decreased, but only approximately 9% vs. 1-G level, during the 20-s microgravity. The data in the current study suggest that the afferent input is closely associated with the gravity-dependent muscular activity. PMID:12379265

  20. Preliminary Experiments on Noise Reduction in Cavities Using Active Impedance Changes

    NASA Astrophysics Data System (ADS)

    LACOUR, O.; GALLAND, M. A.; THENAIL, D.

    2000-02-01

    This paper reports experiments on the active control of enclosed sound fields via wall impedance changes. Two methods previously developed allow one to implement practically active acoustic impedances: the first is referred to as “direct” control and permits precise realizations for harmonic excitations, while the second is a hybrid passive/active feedback control well suited for random noise treatments. The two techniques have been already presented [1]; the contribution of this work relies on testing the efficiency of both systems in silencing two enclosures through experimental analyses, subsequently compared with classical analytical description. The first test cavity is one-dimensional; a global sound reduction is achieved by the hybrid system for a broadband primary excitation. The second system is a reactangular three-dimensional cavity closed by a simply supported elastic plate. The noise source is an external load applied at one point of the plate. Different impedance values are successively assigned, their effect being estimated through a global sound level indicator. Attention is also given to plate vibration changes, which may occur. Three typical behaviours of the plate-cavity system are investigated. A first experiment involves an excitation at an acoustic resonance and induces a weak plate-cavity coupling. The second, also at an acoustic resonance of the cavity, yields a strong coupling while the third corresponds to an off-resonance excitation. The hybrid feedback control system provides useful attenuation for all cases, and shows also a promising behaviour when dealing with broadband excitations. It confirms the interest of the method when classical feedforward active control fails, i.e., when reliable prior information of the undesired disturbance is not available.

  1. Synthesis of Pt-Ni/graphene via in situ reduction and its enhanced catalyst activity for methanol oxidation.

    PubMed

    Li, Lihong; Wu, Yuen; Lu, Jun; Nan, Caiyun; Li, Yadong

    2013-09-01

    A simple in situ reduction approach was used to obtain Pt3Ni/reduced graphene oxide (rGO) with dominant {111} facets. The catalytic activity of Pt-Ni/rGO toward methanol electro-oxidation was studied by performing cyclic voltammetry. The Pt3Ni/rGO nanocatalysts exhibited improved catalytic activity and durability. PMID:23863973

  2. Experimental and Modeling Study of Sorption-Retarded U(VI) Diffusion in a Hanford Silt/Clay Material

    NASA Astrophysics Data System (ADS)

    Bai, J.; Liu, C.; Ball, W. P.

    2008-12-01

    Two types of "inward-flux" diffusion cell systems immersed in finite- and infinite- volume liquid systems were designed to study U(VI) diffusion in a silt/clay size Hanford sediment material at pH 8.0 (±0.1) and in equilibrium with calcite solids and atmospheric CO2. U(VI) concentrations at the cell boundaries were monitored during the cell operation, and the spatial profiles of U(VI) concentrations in both the pore water and the solid phase in the cell media were measured at the end of the cell operation. Results show that while sorption equilibrium was maintained in the "infinite-volume" cell system, strong non-equilibrium occurred in the cells of the "finite-volume" systems, where desorption from solids near the cell-solution interface was important. Rate limitations to sorption and desorption were also independently measured in batch sorption and desorption experiments. A distributed first-order rate model was applied to model U(VI) sorption/desorption kinetics in the batch and the two types of diffusion cell systems. Sensitivity analysis on the modeling confirmed that local equilibrium of sorption was reasonably valid for the infinite-volume system, but less valid for the finite-volume case, presumably because of the greater importance of desorption, and/or the lower U(VI) in the finite-volume system. With proper accounting for non-equilibrium sorption, both types of cells provided good experimental measure of effective diffusion rates. The use of tritiated water (HTO) tracer provided independent measurement of the tortuosity factor, allowing calculation of molecular diffusion coefficients for the dominant U(VI) species, principally Ca2(UO2)(CO3)30 and Ca(UO2)(CO3)32-.

  3. Adsorption characteristics of U(VI) on Fe(III)Cr(III) (oxy)hydroxides synthesized at different temperatures.

    PubMed

    Ahn, Hyangsig; Jo, Ho Young; Lee, Young Jae; Kim, Geon-Young

    2016-07-01

    In this study, the adsorption behavior of U(VI) on (oxy)hydroxides synthesized at different temperatures (25 and 75 °C) was investigated. Four (oxy)hydroxides were synthesized by drying slurries of Fe(III) and Fe(III)Cr(III) (oxy)hydroxide in a vacuum desiccator (25 °C) or in an oven (75 °C). Batch adsorption tests were conducted using the (oxy)hydroxides thus synthesized and groundwater containing uranium ions. In general, the U(VI) removal fraction significantly increased with increasing pH from 3 to 5, remained constant with increasing pH from 5 to 9, and decreased at pH greater than 9, regardless of the type of (oxy)hydroxides and solid-to-liquid ratio. The effect of pH on the U(VI) removal fraction was more significant at a low solid-to-liquid ratio. The oven-dried Fe(III) (oxy)hydroxide exhibited a U(VI) removal fraction lower than that of the vacuum-dried one, whereas the oven-dried Fe(III)Cr(III) (oxy)hydroxide exhibited a U(VI) removal fraction higher than that exhibited by the vacuum-dried one. X-ray photoelectron spectroscopy (XPS) analysis results indicated that the difference in the U(VI) removal fraction is attributed to the dissolution and precipitation of the Fe(III) (oxy)hydroxide during oven drying and dehydration of the Fe(III)Cr(III) (oxy)hydroxide during oven drying. PMID:27060782

  4. Catalytic Reduction of 4-Nitrophenol Using Silver Nanoparticles with Adjustable Activity.

    PubMed

    Kästner, Claudia; Thünemann, Andreas F

    2016-07-26

    We report on the development of ultrasmall core-shell silver nanoparticles synthesized by an upscaled modification of the polyol process. It is foreseen to use these thoroughly characterized particles as reference material to compare the catalytic and biological properties of functionalized silver nanoparticles. Small-angle X-ray scattering (SAXS) analysis reveals a narrow size distribution of the silver cores with a mean radius of Rc = 3.0 nm and a distribution width of 0.6 nm. Dynamic light scattering (DLS) provides a hydrodynamic radius of RH = 10.0 nm and a PDI of 0.09. The particles' surface is covered with poly(acrylic acid) (PAA) forming a shell with a thickness of 7.0 nm, which provides colloidal stability lasting for more than 6 months at ambient conditions. The PAA can be easily exchanged by biomolecules to modify the surface functionality. Replacements of PAA with glutathione (GSH) and bovine serum albumin (BSA) have been performed as examples. We demonstrate that the silver particles effectively catalyze the reduction of 4-nitrophenol to 4-aminophenol with sodium borohydride. With PAA as stabilizer, the catalytic activity of 436 ± 24 L g(-1) s(-1) is the highest reported in the literature for silver nanoparticles. GSH and BSA passivate the surface substantially, resulting in a catalytic activity of 77.6 ± 0.9 and 3.47 ± 0.50 L g(-1) s(-1), respectively. PMID:27380382

  5. Logarithmic InGaAs detectors with global shutter and active dark current reduction

    NASA Astrophysics Data System (ADS)

    Ni, Yang; Arion, Bogdan; Bouvier, Christian; Noguier, Vincent

    2015-05-01

    In this paper, we present newly developed logarithmic InGaAs detectors with global shuttering and also an active dark current reduction technique to ensure ambient temperature operation without TEC for industrial applications. The newly released detectors come with both VGA (15um pitch) and QVGA (25um pitch) resolutions, giving the possibility to use lens less than 1-inch size. The logarithmic response is obtained by using solar-cell mode InGaAs photodiodes. The VGA and QVGA ROICs have 3 analog memories inside each pixel which permit, except the classic ITR, IWR and CDS modes, a new differential imaging mode which can be a useful feature in active imaging systems. The photodiode frontend circuit, in pure voltage mode, is made with non-inverting amplifier instead of CTIA. The reason of this choice is that the exposure time can be shortened without need of excessive power consumption as in CTIA front-end. We think that this arrangement associated with true CDS could match the noise performance of CTIA based one. VGA and QVGA ROICs have been designed and manufactured by using 0.18um 1P4M CMOS process. Both ROIC have been tested with success and match the design targets. The first batch of both detectors is under fabrication and will be presented during the conference.

  6. Reduction of computational complexity in the image/video understanding systems with active vision

    NASA Astrophysics Data System (ADS)

    Kuvich, Gary

    2003-10-01

    The vision system evolved not only as a recognition system, but also as a sensory system for reaching, grasping and other motion activities. In advanced creatures, it became a component of prediction function, allowing creation of environmental models and activity planning. Fast information processing and decision making is vital for any living creature, and requires reduction of informational and computational complexities. The brain achieves this goal using symbolic coding, hierarchical compression, and selective processing of visual information. Network-Symbolic representation, where both systematic structural / logical methods and neural / statistical methods are the parts of a single mechanism, is the most feasible for such models. It converts visual information into the relational Network-Symbolic structures, instead of precise computations of a 3-dimensional models. Narrow foveal vision provides separation of figure from ground, object identification, semantic analysis, and precise control of actions. Rough wide peripheral vision identifies and tracks salient motion, guiding foveal system to salient objects. It also provides scene context. Objects with rigid bodies and other stable systems have coherent relational structures. Hierarchical compression and Network-Symbolic transformations derive more abstract structures that allow invariably recognize a particular structure as an exemplar of class. Robotic systems equipped with such smart vision will be able effectively navigate in any environment, understand situation, and act accordingly.

  7. Reduction-responsive multifunctional hyperbranched polyaminoglycosides with excellent antibacterial activity, biocompatibility and gene transfection capability.

    PubMed

    Huang, Yajun; Ding, Xiaokang; Qi, Yu; Yu, Bingran; Xu, Fu-Jian

    2016-11-01

    There is an increasing demand in developing of multifunctional materials with good antibacterial activity, biocompatibility and drug/gene delivery capability for next-generation biomedical applications. To achieve this purpose, in this work series of hydroxyl-rich hyperbranched polyaminoglycosides of gentamicin, tobramycin, and neomycin (HP and SS-HP with redox-responsive disulfide bonds) were readily synthesized via ring-opening reactions in a one-pot manner. Both HP and SS-HP exhibit high antibacterial activity toward Escherichia coli and Staphylococcus aureus. Meanwhile, the hemolysis assay of the above materials shows good biocompatibility. Moreover, SS-HPs show excellent gene transfection efficiency in vitro due to the breakdown of reduction-responsive disulfide bonds. For an in vivo anti-tumor assay, the SS-HP/p53 complexes exhibit potent inhibition capability to the growth of tumors. This study provides a promising approach for the design of next-generation multifunctional biomedical materials. PMID:27561884

  8. Proteolytic activity of Enterococcus faecalis VB63F for reduction of allergenicity of bovine milk proteins.

    PubMed

    Biscola, V; Tulini, F L; Choiset, Y; Rabesona, H; Ivanova, I; Chobert, J-M; Todorov, S D; Haertlé, T; Franco, B D G M

    2016-07-01

    With the aim of screening proteolytic strains of lactic acid bacteria to evaluate their potential for the reduction of allergenicity of the major bovine milk proteins, we isolated a new proteolytic strain of Enterococcus faecalis (Ent. faecalis VB63F) from raw bovine milk. The proteases produced by this strain had strong activity against caseins (αS1-, αS2-, and β-casein), in both skim milk and sodium caseinate. However, only partial hydrolysis of whey proteins was observed. Proteolysis of Na-caseinate and whey proteins, observed after sodium dodecyl sulfate-PAGE, was confirmed by analysis of peptide profiles by reversed-phase HPLC. Inhibition of proteolysis with EDTA indicated that the proteases produced by Ent. faecalis VB63F belonged to the group of metalloproteases. The optimal conditions for their activity were 42°C and pH 6.5. The majority of assessed virulence genes were absent in Ent. faecalis VB63F. The obtained results suggest that Ent. faecalis VB63F could be efficient in reducing the immunoreactivity of bovine milk proteins. PMID:27179865

  9. Ordered mesoporous porphyrinic carbons with very high electrocatalytic activity for the oxygen reduction reaction

    PubMed Central

    Cheon, Jae Yeong; Kim, Taeyoung; Choi, YongMan; Jeong, Hu Young; Kim, Min Gyu; Sa, Young Jin; Kim, Jaesik; Lee, Zonghoon; Yang, Tae-Hyun; Kwon, Kyungjung; Terasaki, Osamu; Park, Gu-Gon; Adzic, Radoslav R.; Joo, Sang Hoon

    2013-01-01

    The high cost of the platinum-based cathode catalysts for the oxygen reduction reaction (ORR) has impeded the widespread application of polymer electrolyte fuel cells. We report on a new family of non-precious metal catalysts based on ordered mesoporous porphyrinic carbons (M-OMPC; M = Fe, Co, or FeCo) with high surface areas and tunable pore structures, which were prepared by nanocasting mesoporous silica templates with metalloporphyrin precursors. The FeCo-OMPC catalyst exhibited an excellent ORR activity in an acidic medium, higher than other non-precious metal catalysts. It showed higher kinetic current at 0.9 V than Pt/C catalysts, as well as superior long-term durability and MeOH-tolerance. Density functional theory calculations in combination with extended X-ray absorption fine structure analysis revealed a weakening of the interaction between oxygen atom and FeCo-OMPC compared to Pt/C. This effect and high surface area of FeCo-OMPC appear responsible for its significantly high ORR activity. PMID:24056308

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

    NASA Astrophysics Data System (ADS)

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

    2014-10-01

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

  11. Surface complexation modeling of U(VI) adsorption by aquifer sediments from a former mill tailings site at Rifle, Colorado

    SciTech Connect

    Hyun, S. P.; Fox, Patricia M.; Davis, James A.; Campbell, Kate M.; Hayes, Kim F.; Long, Philip E.

    2009-12-15

    U(VI) adsorption by two aquifer sediment samples was studied under oxic conditions as a function of pH, U(VI), Ca, and dissolved carbonate concentration. Background-A (BKG-A) sediment was collected upstream of a former uranium mill-tailings site at Rifle, Colorado, and Little Rusty Composite (LRC) was collected on site but with low U contamination. Batch adsorption experiments were performed using artificial groundwater solutions prepared to simulate the field groundwater composition in equilibrium with specific partial pressures of carbon dioxide. To encompass the geochemical conditions of the alluvial aquifer at the site, the experimental conditions ranged from 6.8×10-8 to 10-5 M in [U(VI)]tot, 7.2 to 8.0 in pH, 3.0×10-3 to 6.0×10-3 M in [Ca2+], and 0.05 to 2.6% in partial pressure of carbon dioxide. The sediment was extracted with a dilute bicarbonate/carbonate solution to determine the background labile U(VI) already present in the sediment. A semi-empirical surface complexation model was developed to describe U(VI) adsorption using FITEQL4. The non-electrostatic, generalized composite surface complexation model successfully simulated U(VI) adsorption over the range of groundwater conditions at the Old Rifle site, using a two-site, two-reaction fitting scheme. The sensitivity of model parameters to background U(VI) concentration on the two samples was evaluated. U(VI) adsorption experiments were also performed using a sand fraction of BKG-A separated through repeated sonication and wet-sieving. Surface area normalized Kd for the bulk and sand fraction indicated similar reactivity for both. The surface complexation model developed in this work is expected to contribute to the prediction of fate and transport of U(VI) in the alluvial aquifer at the Old Rifle site, and to assist in the simulation of biostimulation field experiments performed at the site.

  12. Mechanism of enhanced nitrate reduction via micro-electrolysis at the powdered zero-valent iron/activated carbon interface.

    PubMed

    Luo, Jinghuan; Song, Guangyu; Liu, Jianyong; Qian, Guangren; Xu, Zhi Ping

    2014-12-01

    Nitrate reduction by zero-valent iron (Fe(0)) powder always works well only at controlled pH lower than 4 due to the formation of iron (hydr)oxides on its surface. Fe(0) powder combined with activated carbon (AC), i.e., Fe(0)/AC micro-electrolysis system, was first introduced to enhance nitrate reduction in aqueous solution. Comparative study was carried out to investigate nitrate reduction by Fe(0)/AC system and Fe(0) under near-neutral conditions, showing that the Fe(0)/AC system successfully reduced nitrate even at initial pH 6 with the reduction efficiency of up to 73%, whereas for Fe(0) only ∼10%. The effect of Fe(0) to AC mass ratio on nitrate reduction efficiency was examined. Easier nitrate reduction was achieved with more contact between Fe(0) and AC as the result of decreasing Fe(0) to AC mass ratio. Ferrous ion and oxidation-reduction potential were measured to understand the mechanism of enhanced nitrate reduction by Fe(0)/AC micro-electrolysis. The results suggest that a relative potential difference drives much more electrons from Fe(0) to AC, thus generating adsorbed atomic hydrogen which makes it possible for nitrate to be reduced at near-neural pH. Fe(0)/AC micro-electrolysis thus presents a great potential for practical application in nitrate wastewater treatment without excessive pH adjustment. PMID:25217726

  13. Maternal obesity is associated with a reduction in placental taurine transporter activity

    PubMed Central

    Ditchfield, A M; Desforges, M; Mills, T A; Glazier, J D; Wareing, M; Mynett, K; Sibley, C P; Greenwood, S L

    2015-01-01

    Background/Objectives: Maternal obesity increases the risk of poor pregnancy outcome including stillbirth, pre-eclampsia, fetal growth restriction and fetal overgrowth. These pregnancy complications are associated with dysfunctional syncytiotrophoblast, the transporting epithelium of the human placenta. Taurine, a β-amino acid with antioxidant and cytoprotective properties, has a role in syncytiotrophoblast development and function and is required for fetal growth and organ development. Taurine is conditionally essential in pregnancy and fetal tissues depend on uptake of taurine from maternal blood. We tested the hypothesis that taurine uptake into placental syncytiotrophoblast by the taurine transporter protein (TauT) is lower in obese women (body mass index (BMI)⩾30 kg m−2) than in women of ideal weight (BMI 18.5–24.9 kg m−2) and explored potential regulatory factors. Subjects/Methods: Placentas were collected from term (37–42-week gestation), uncomplicated, singleton pregnancies from women with BMI 19–49 kg m−2. TauT activity was measured as the Na+-dependent uptake of 3H-taurine into placental villous fragments. TauT expression in membrane-enriched placental samples was investigated by western blot. In vitro studies using placental villous explants examined whether leptin or IL-6, adipokines/cytokines that are elevated in maternal obesity, regulates TauT activity. Results: Placental TauT activity was significantly lower in obese women (BMI⩾30) than women of ideal weight (P<0.03) and inversely related to maternal BMI (19–49 kg m−2; P<0.05; n=61). There was no difference in TauT expression between placentas of ideal weight and obese class III (BMI⩾40) subjects. Long-term exposure (48 h) of placental villous explants to leptin or IL-6 did not affect TauT activity. Conclusions: Placental TauT activity at term is negatively related to maternal BMI. We propose that the reduction in placental TauT activity in maternal obesity

  14. Enhancement of activity of RuSex electrocatalyst by modification with nanostructured iridium towards more efficient reduction of oxygen

    NASA Astrophysics Data System (ADS)

    Dembinska, Beata; Kiliszek, Malgorzata; Elzanowska, Hanna; Pisarek, Marcin; Kulesza, Pawel J.

    2013-12-01

    Electrocatalytic activity of carbon (Vulcan XC-72) supported selenium-modified ruthenium, RuSex/C, nanoparticles for reduction of oxygen was enhanced through intentional decoration with iridium nanostructures (dimensions, 2-3 nm). The catalytic materials were characterized in oxygenated 0.5 mol dm-3 H2SO4 using cyclic and rotating ring disk voltammetric techniques as well as using transmission electron microscopy and scanning electron microscopy equipped with X-ray dispersive analyzer. Experiments utilizing gas diffusion electrode aimed at mimicking conditions existing in the low-temperature fuel cell. Upon application of our composite catalytic system, the reduction of oxygen proceeded at more positive potentials, and higher current densities were observed when compared to the behavior of the simple iridium-free system (RuSex/C) investigated under the analogous conditions. The enhancement effect was more pronounced than that one would expect from simple superposition of voltammetric responses for the oxygen reduction at RuSex/C and iridium nanostructures studied separately. Nanostructured iridium acted here as an example of a powerful catalyst for the reduction of H2O2 (rather than O2) and, when combined with such a moderate catalyst as ruthenium-selenium (for O2 reduction), it produced an integrated system of increased electrocatalytic activity in the oxygen reduction process. The proposed system retained its activity in the presence of methanol that could appear in a cathode compartment of alcohol fuel cell.

  15. A novel method to measure both the reductive and the radical scavenging activity in a linoleic acid model system.

    PubMed

    Lindenmeier, Michael; Burkon, Alexander; Somoza, Veronika

    2007-12-01

    The aim of this study was to develop a combined method for measuring the total antioxidant activity, the reductive and the radical scavenging activity. Linoleic acid was used as the substrate for an iron-initiated lipid peroxidation to measure the total antioxidant activity. In addition, methyl esters of linoleic acid hydroperoxides were used as substrates to measure the reductive antioxidant activity. The radical scavenging antioxidant activity was calculated by subtracting the reductive antioxidative activity from the total antioxidative activity. As representative examples, the antioxidants alpha-tocopherol, ascorbic acid, trans-resveratrol and L-glutathione as well as commonly used food additives such as 2(3)-tert-butyl-4-hydroxyanisole (BHA) and 2,6-bis(1,1-dimethylethyl)-4-methylphenol (BHT) were analyzed. The results for the novel antioxidation test showed that alpha-tocopherol, BHA and BHT are primarily acting as radical scavengers, whereas ascorbic acid and L-glutathione show a strong reductive capacity. As linoleic acid as well as its hydroperoxides both are present in foods and in the organism, the test presented here can be considered representative of radical reactions occurring in food matrixes and in vivo. Further experiments are required to document the comprehensive applicability in foods and in vivo. PMID:17680718

  16. Reduction of training costs using active classification in fused hyperspectral and LiDAR data

    NASA Astrophysics Data System (ADS)

    Wuttke, Sebastian; Schilling, Hendrik; Middelmann, Wolfgang

    2012-11-01

    This paper presents a novel approach for the reduction of training costs in classification with co-registered hyperspectral (HS) and Light Detection and Ranging (LiDAR) data using an active classification framework. Fully automatic classification can be achieved by unsupervised learning, which is not suited for adjustment to specific classes. On the other hand, supervised classification with predefined classes needs a lot of training examples, which need to be labeled with the ground truth, usually at a significant cost. The concept of active classification alleviates these problems by the use of a selection strategy: only selected samples are ground truth labeled and used as training data. One common selection strategy is to incorporate in a first step the current state of the classification algorithm and choose only the examples for which the expected information gain is maximized. In the second step a conventional classification algorithm is trained using this data. By alternating between these two steps the algorithm reaches high classification accuracy results with less training samples and therefore lower training costs. The approach presented in this paper involves the user in the active selection strategy and the k-NN algorithm is chosen for classification. The results further benefit from fusing the heterogeneous information of HS and LiDAR data within the classification algorithm. For this purpose, several HS features, such as vegetation indices, and LiDAR features, such as relative height and roughness, are extracted. This increases the separability between different classes and reduces the dimensionality of the HS data. The practicability and performance of this framework is shown for the detection and separation of different kinds of vegetation, e.g. trees and grass in an urban area of Berlin. The HS data was obtained by the SPECIM AISA Eagle 2 sensor, LiDAR data by Riegl LMS Q560.

  17. MURMoT. Design and Application of Microbial Uranium Reduction Monitoring Tools

    SciTech Connect

    Loffler, Frank E.; Ritalahti, Kirsti; Sanford, Robert A.; Lundstrom, Craig C.; Johnson, Thomas M.; Kemner, Kenneth; Boyanov, Maxim

    2009-07-01

    Uranium (U) contamination in the subsurface is a major remediation challenge at many DOE sites. Traditional site remedies present enormous costs to DOE; hence, enhanced bioremediation technologies (i.e., biostimulation and bioaugmentation) combined with monitoring efforts are being considered as cost-effective corrective actions to address subsurface contamination. This research effort improved understanding of the microbial U reduction process and developed new tools for monitoring microbial activities. Application of these tools will promote science-based site management decisions that achieve contaminant detoxification, plume control, and long-term stewardship in the most efficient manner. The overarching hypothesis was that the design, validation and application of a suite of new molecular and biogeochemical tools advance process understanding, and improve environmental monitoring regimes to assess and predict in situ U immobilization. Accomplishments: This project (i) advanced nucleic acid-based approaches to elucidate the presence, abundance, dynamics, spatial distribution, and activity of metal- and radionuclide-detoxifying bacteria; (ii) developed proteomics workflows for detection of metal reduction biomarker proteins in laboratory cultures and contaminated site groundwater; (iii) developed and demonstrated the utility of U isotopic fractionation using high precision mass spectrometry to quantify U(VI) reduction for a range of reduction mechanisms and environmental conditions; and (iv) validated the new tools using field samples from U-contaminated IFRC sites, and demonstrated their prognostic and diagnostic capabilities in guiding decision making for environmental remediation and long-term site stewardship.

  18. MURMoT. Design and Application of Microbial Uranium Reduction Monitoring Tools

    SciTech Connect

    Loeffler, Frank E.

    2014-12-31

    Uranium (U) contamination in the subsurface is a major remediation challenge at many DOE sites. Traditional site remedies present enormous costs to DOE; hence, enhanced bioremediation technologies (i.e., biostimulation and bioaugmentation) combined with monitoring efforts are being considered as cost-effective corrective actions to address subsurface contamination. This research effort improved understanding of the microbial U reduction process and developed new tools for monitoring microbial activities. Application of these tools will promote science-based site management decisions that achieve contaminant detoxification, plume control, and long-term stewardship in the most efficient manner. The overarching hypothesis was that the design, validation and application of a suite of new molecular and biogeochemical tools advance process understanding, and improve environmental monitoring regimes to assess and predict in situ U immobilization. Accomplishments: This project (i) advanced nucleic acid-based approaches to elucidate the presence, abundance, dynamics, spatial distribution, and activity of metal- and radionuclide-detoxifying bacteria; (ii) developed proteomics workflows for detection of metal reduction biomarker proteins in laboratory cultures and contaminated site groundwater; (iii) developed and demonstrated the utility of U isotopic fractionation using high precision mass spectrometry to quantify U(VI) reduction for a range of reduction mechanisms and environmental conditions; and (iv) validated the new tools using field samples from U-contaminated IFRC sites, and demonstrated their prognostic and diagnostic capabilities in guiding decision making for environmental remediation and long-term site stewardship.

  19. Cassini UVIS Results from Occultations of Stars by Saturn's Icy Moons

    NASA Astrophysics Data System (ADS)

    Hansen, Candice; Hendrix, A.

    2009-09-01

    The Cassini Ultraviolet Imaging Spectrograph (UVIS) has observed occultations of stars by Enceladus, Tethys, Dione, Rhea and Iapetus. Stellar occultations are a sensitive probe for gases and have been extremely valuable for understanding the composition (predominantly water), flux and structure of Enceladus’ plume [1, 2]. More recently we have been looking for trace gases in the plume such as ethylene and methanol. A much-anticipated solar occultation will be observed next year to quantify the existence and amount of N2. At Tethys and Iapetus upper limits are set for the column densities of local volatiles (water, O2, CO2, and CO), all of which have absorption features at far ultraviolet wavelengths. The Rhea occultation data, in addition to setting upper limits on surrounding gases, have been analyzed to look for the presence of the debris disk reported by Cassini's MIMI instrument [3]. No material was detected with 2 sigma certainty, however the low optical depth of the material suggests that the probability of its detection by UVIS is < 1 in 1000. An occultation of epsilon Canis Majoris by Dione will take place in September 2009. Results of that occultation will be presented. This work was partially supported by the Jet Propulsion Laboratory, California Institute of Technology, under a contract with the National Aeronautics and Space Administration. [1] Hansen, C. J. et al., Science 311:1422 (2006). [2] Hansen, C. J. et al., Nature 456 (2008). [3] Jones, G. H. et al., Science 319:1380 (2008).

  20. WFC3: Understanding and Mitigating UVIS Charge Transfer Efficiency Losses and IR Persistence Effects

    NASA Astrophysics Data System (ADS)

    Baggett, Sylvia M.; Anderson, J.; Long, K. S.; MacKenty, J. W.; Noeske, K.; Biretta, J. A.; WFC3 Team

    2014-01-01

    A panchromatic instrument, Wide Field Camera 3 (WFC3) contains a UVIS channel with a 4096x4096 pixel e2v CCD array as well as an IR channel with a 1014x1014 Rockwell Scientific HgCdTe focal plane array (FPA). Both detectors have been performing well on-orbit since the installation of the instrument in the Hubble Space Telescope (HST) in May 2009. However, as expected, the harsh low-earth orbit environment has been damaging the UVIS CCDs, resulting in a progressive loss of charge transfer efficiency (CTE) over time. We summarize the magnitude of the CTE losses, the effect on science data, and the pre- and post-observation mitigation options available. The IR FPA does not suffer from accumulating radiation damage but it does exhibit persistence i.e. an after-glow from sources in previous exposures, an anomaly commonly seen in these types of IR arrays. We summarize the characteristics of persistence in WFC3, suggest methods for reducing the effects during observation planning, and describe the calibration products which are available via the Mikulski Archive for Space Telescopes (MAST) for addressing persistence in IR science data.

  1. A New Statistical Convection Model Derived from SuperDARN and Polar UVI Observations

    NASA Astrophysics Data System (ADS)

    Ruohoniemi, J. M.; Greenwald, R. A.; Liou, K.

    2001-12-01

    Since the inception of the SuperDARN concept of coordinated multi-radar observations of ionospheric convection in 1993 a vast database of primary measurements has been accumulated. Following on earlier work with data collected from the Goose Bay radar in the pre-SuperDARN era, we have applied this database to the statistical characterization of the global pattern of high-latitude convection. For a subset of the measurements it is possible to order the velocity according to the geometry of the UVI auroral oval as this is inferred from observations with the Polar UVI instrument. In this talk we will review the derivation of the new convection model and discuss the results of sorting by solar wind and auroral geometry. We find that certain features, obscured in the usual bin-averaging approach, are more pronounced when proper account is taken of the variability of structures in the convection pattern. We compare with previous work and discuss the application of the new model in situations where information on the auroral geometry is present, absent, or can be reasonably inferred from proxy observations.

  2. A New Statistical Convection Model Derived from SuperDARN and Polar UVI Observations

    NASA Astrophysics Data System (ADS)

    Ruohoniemi, J. M.; Greenwald, R. A.; Liou, K.; Shepherd, S. G.

    2002-05-01

    Since the inception of the SuperDARN concept of coordinated multi-radar observations of ionospheric convection in 1993 a vast database of primary measurements has been accumulated. Following on earlier work with data collected from the Goose Bay radar in the pre-SuperDARN era, we have applied this database to the statistical characterization of the global pattern of high-latitude convection. For a subset of the measurements it is possible to order the velocity according to the geometry of the UVI auroral oval as this is inferred from observations with the Polar UVI instrument. In this talk we will review the derivation of the new convection model and discuss the results of sorting by solar wind and auroral geometry. We find that certain features, obscured in the usual bin-averaging approach, are more pronounced when proper account is taken of the variability of structures in the convection pattern. We compare with previous work and discuss the application of the new model in situations where information on the auroral geometry is present, absent, or can be reasonably inferred from proxy observations.

  3. Cassini UVIS Observations of the Io Plasma Torus. 4; Modeling Temporal and Azimuthal Variability

    NASA Technical Reports Server (NTRS)

    Steffl, A. J.; Delamere, P. A.; Bagenal, F.

    2008-01-01

    In this fourth paper in a series, we present a model of the remarkable temporal and azimuthal variability of the Io plasma torus observed during the Cassini encounter with Jupiter. Over a period of three months, the Cassini Ultraviolet Imaging Spectrograph (UVIS) observed a dramatic variaton in the average torus composition. Superimposed on this long-term variation, is a 10.07-hour periodicity caused by azimuthal variation in plasma composition subcorotating relative to System III longitude. Quite surprisingly, the amplitude of the azimuthal variation appears to be modulated at the beat frequency between the System III period and the observed 10.07-hour period. Previously, we have successfully modeled the months-long compositional change by supposing a factor of three increase in the amount of material supplied to Io's extended neutral clouds. Here, we extend our torus chemistry model to include an azimuthal dimension. We postulate the existence of two azimuthal variations in the number of superthermal electrons in the torus: a primary variation that subcorotates with a period of 10.07 hours and a secondary variation that remains fixed in System III longitude. Using these two hot electron variations, our model can reproduce the observed temporal and azimuthal variations observed by Cassini UVIS.

  4. Spectroscopic studies of U(VI) sorption at the kaolinite-water interface. Final report

    SciTech Connect

    Thompson, H.A.; Parks, G.A.; Brown, G.E. Jr.

    1994-06-01

    Efficient use of U as a resource and safe handling, recycling and disposal of U-containing wastes require an understanding of the factors controlling the fate of U, where fate refers to the destination of U, typically expressed as an environmental medium or a process phase. The sorption process constitutes a change in elemental fate. Partitioning of an element from solution to a solid phase, or sorption, can be divided into three broad categories: adsorption, surface precipitation, and absorption. Extended X-ray absorption fine structure (EXAFS), a type of X-ray absorption spectroscopy (XAS), offers the possibility for distinguishing among different modes of sorption by characterizing the atomic environment of the sorbing element. In this study, the authors use EXAFS to determine the structure of U(VI) sorption complexes at the kaolinite-water interface. In Chapter One, they present an overview of selected aspects of U structural chemistry as a basis for considering the structural environment of U at the solid-water interface. To evaluate the utility of XAS for characterization of the structural environment of U(VI) at the solid-water interface, they have carried out an in-depth analysis of XAS data from U(VI)-containing solid and solution model compounds, which they describe in Chapter Two. In Chapter three, they consider sorption of U by kaolinite as a means of effecting the removal of U from surface collection pond waters on the Rocky Flats Plant site in northern Colorado.

  5. Molecular nitrogen and methane density retrievals from Cassini UVIS dayglow observations of Titan's upper atmosphere

    NASA Astrophysics Data System (ADS)

    Stevens, Michael H.; Evans, J. Scott; Lumpe, Jerry; Westlake, Joseph H.; Ajello, Joseph M.; Bradley, E. Todd; Esposito, Larry W.

    2015-02-01

    We retrieve number densities of molecular nitrogen (N2) and methane (CH4) from Titan's upper atmosphere using the UV dayglow. We use Cassini Ultraviolet Imaging Spectrograph (UVIS) limb observations from 800 to 1300 km of the N I 1493 Å and N II 1085 Å multiplets, both produced directly from photofragmentation of N2. UVIS N2 and CH4 densities are in agreement with measurements from Cassini's Ion Neutral Mass Spectrometer (INMS) from the same flyby if INMS densities are scaled up by a factor of 3.0 as reported in previous studies. Analysis of three Cassini flybys of Titan shows that (1) the CH4 homopause on Titan is between 900 and 1100 km, (2) upper atmospheric temperatures vary by less than 10 K over 6 h at the same geographic location and (3) from 1100 to 1700 local solar time temperatures also vary by less than 10 K. The capability of retrieving the global-scale composition from these data complements existing techniques and significantly advances the study of upper atmospheric variability at Titan and for any other atmosphere with a detectable UV dayglow.

  6. Bio-inspired electron-delivering system for reductive activation of dioxygen at metal centres towards artificial flavoenzymes.

    PubMed

    Roux, Yoann; Ricoux, Rémy; Avenier, Frédéric; Mahy, Jean-Pierre

    2015-01-01

    Development of artificial systems, capable of delivering electrons to metal-based catalysts for the reductive activation of dioxygen, has been proven very difficult for decades, constituting a major scientific lock for the elaboration of environmentally friendly oxidation processes. Here we demonstrate that the incorporation of a flavin mononucleotide (FMN) in a water-soluble polymer, bearing a locally hydrophobic microenvironment, allows the efficient reduction of the FMN by NADH. This supramolecular entity is then capable of catalysing a very fast single-electron reduction of manganese(III) porphyrin by splitting the electron pair issued from NADH. This is fully reminiscent of the activity of natural reductases such as the cytochrome P450 reductases with kinetic parameters, which are three orders of magnitude faster compared with other artificial systems. Finally, we show as a proof of concept that the reduced manganese porphyrin activates dioxygen and catalyses the oxidation of organic substrates in water. PMID:26419885

  7. Bio-inspired electron-delivering system for reductive activation of dioxygen at metal centres towards artificial flavoenzymes

    PubMed Central

    Roux, Yoann; Ricoux, Rémy; Avenier, Frédéric; Mahy, Jean-Pierre

    2015-01-01

    Development of artificial systems, capable of delivering electrons to metal-based catalysts for the reductive activation of dioxygen, has been proven very difficult for decades, constituting a major scientific lock for the elaboration of environmentally friendly oxidation processes. Here we demonstrate that the incorporation of a flavin mononucleotide (FMN) in a water-soluble polymer, bearing a locally hydrophobic microenvironment, allows the efficient reduction of the FMN by NADH. This supramolecular entity is then capable of catalysing a very fast single-electron reduction of manganese(III) porphyrin by splitting the electron pair issued from NADH. This is fully reminiscent of the activity of natural reductases such as the cytochrome P450 reductases with kinetic parameters, which are three orders of magnitude faster compared with other artificial systems. Finally, we show as a proof of concept that the reduced manganese porphyrin activates dioxygen and catalyses the oxidation of organic substrates in water. PMID:26419885

  8. Incorporation of Np(V) and U(VI) in carbonate and sulfate minerals crystallized from aqueous solution

    NASA Astrophysics Data System (ADS)

    Balboni, Enrica; Morrison, Jessica M.; Wang, Zheming; Engelhard, Mark H.; Burns, Peter C.

    2015-02-01

    The neptunyl Np(V)O2+ and uranyl U(VI)O22+ ions are soluble in groundwater, although their interaction with minerals in the subsurface may impact their mobility. One mechanism for the immobilization of actinyl ions in the subsurface is co-precipitation in low-temperature minerals that form naturally, or that are induced to form as part of a remediation strategy. Important differences in the crystal-chemical behavior of the Np(V) neptunyl and U(VI) uranyl ions suggest their behavior towards incorporation into growing crystals may differ significantly. Using a selection of low-temperature minerals synthesized in aqueous systems under ambient conditions, this study examines the factors that impact the structural incorporation of the Np(V) neptunyl and U(VI) uranyl ions in carbonate and sulfate minerals. Calcite (CaCO3), aragonite (CaCO3), gypsum (CaSO4·2H2O), strontianite (SrCO3), cerussite (PbCO3), celestine (SrSO4), and anglesite (PbSO4) were synthesized from aqueous solutions containing either 400-1000 ppm of U(VI) or Np(V) relative to the divalent cation present in the system. The synthetic products were investigated by inductively coupled plasma mass spectrometry, luminescence and time resolved luminescence spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscopy. Amongst the carbonate minerals, calcite significantly favors Np(V) incorporation over U(VI). U(VI) and Np(V) are incorporated in aragonite and strontianite in similar amounts, whereas cerussite did not incorporate either U(VI) or Np(V) under the synthesis conditions. The sulfate minerals weakly interact with the actinyl ions, relative to the carbonate minerals. Incorporation of U(VI) and Np(V) in celestine was observed at the level of a few tens of ppm; anglesite and gypsum did not incorporate detectable U(VI) or Np(V). Luminescence spectra of the uranyl incorporated in aragonite and strontianite are consistent with a uranyl unit coordinated by three bidentate CO32- groups

  9. Polydopamine-Coated Manganese Complex/Graphene Nanocomposite for Enhanced Electrocatalytic Activity Towards Oxygen Reduction

    PubMed Central

    Parnell, Charlette M.; Chhetri, Bijay; Brandt, Andrew; Watanabe, Fumiya; Nima, Zeid A.; Mudalige, Thilak K.; Biris, Alexandru S.; Ghosh, Anindya

    2016-01-01

    Platinum electrodes are commonly used electrocatalysts for oxygen reduction reactions (ORR) in fuel cells. However, this material is not economical due to its high cost and scarcity. We prepared an Mn(III) catalyst supported on graphene and further coated with polydopamine, resulting in superior ORR activity compared to the uncoated PDA structures. During ORR, a peak potential at 0.433 V was recorded, which is a significant shift compared to the uncoated material’s −0.303 V (both versus SHE). All the materials reduced oxygen in a wide pH range via a four-electron pathway. Rotating disk electrode and rotating ring disk electrode studies of the polydopamine-coated material revealed ORR occurring via 4.14 and 4.00 electrons, respectively. A rate constant of 6.33 × 106 mol−1s−1 was observed for the polydopamine-coated material–over 4.5 times greater than the uncoated nanocomposite and superior to those reported for similar carbon-supported metal catalysts. Simply integrating an inexpensive bioinspired polymer coating onto the Mn-graphene nanocomposite increased ORR performance significantly, with a peak potential shift of over +730 mV. This indicates that the material can reduce oxygen at a higher rate but with lower energy usage, revealing its excellent potential as an ORR electrocatalyst in fuel cells. PMID:27528439

  10. Reduction of Death Certificate Only (DCO) Registrations by Active Follow Back.

    PubMed

    Turano, LM; Laudico, AV; Esteban, DB; Pisani, P; Parkin, DM

    2002-01-01

    Death certificates are an important source of information for cancer registries that help to improve completeness of case finding. In many countries where routine mortality data are considered of poor quality, this source is often regarded as being of little value. We evaluated the contribution of death certificates to the total number of registrations in the years 1993-1997, in the Manila Cancer Registry (MCR). We compared the "standard" practice of retrieving clinical information if the death certificate was completed in a hospital, with active search of additional information from the deceased's relatives when the death was certified at home.The standard procedure allowed us to reduce the proportion of cases registered from a death certificate by 5%. The improvement varied significantly among the most common sites with a reduction of 10% for lymphomas to less than 1% for cancers of the cervix.The proportion of liver cancers registered from a death certificate only (DCO), originally 47%, was reduced to 29% by contacting relatives of the deceased patients. In countries with limited investment in information systems, death certificates, even when recognised as being of poor quality, are an important source of information for cancer registries. PMID:12718591

  11. Polydopamine-Coated Manganese Complex/Graphene Nanocomposite for Enhanced Electrocatalytic Activity Towards Oxygen Reduction.

    PubMed

    Parnell, Charlette M; Chhetri, Bijay; Brandt, Andrew; Watanabe, Fumiya; Nima, Zeid A; Mudalige, Thilak K; Biris, Alexandru S; Ghosh, Anindya

    2016-01-01

    Platinum electrodes are commonly used electrocatalysts for oxygen reduction reactions (ORR) in fuel cells. However, this material is not economical due to its high cost and scarcity. We prepared an Mn(III) catalyst supported on graphene and further coated with polydopamine, resulting in superior ORR activity compared to the uncoated PDA structures. During ORR, a peak potential at 0.433 V was recorded, which is a significant shift compared to the uncoated material's -0.303 V (both versus SHE). All the materials reduced oxygen in a wide pH range via a four-electron pathway. Rotating disk electrode and rotating ring disk electrode studies of the polydopamine-coated material revealed ORR occurring via 4.14 and 4.00 electrons, respectively. A rate constant of 6.33 × 10(6) mol(-1)s(-1) was observed for the polydopamine-coated material-over 4.5 times greater than the uncoated nanocomposite and superior to those reported for similar carbon-supported metal catalysts. Simply integrating an inexpensive bioinspired polymer coating onto the Mn-graphene nanocomposite increased ORR performance significantly, with a peak potential shift of over +730 mV. This indicates that the material can reduce oxygen at a higher rate but with lower energy usage, revealing its excellent potential as an ORR electrocatalyst in fuel cells. PMID:27528439

  12. An Overview of Propulsion Concept Studies and Risk Reduction Activities for Robotic Lunar Landers

    NASA Technical Reports Server (NTRS)

    Trinh, Huu P.; Story, George; Burnside, Chris; Kudlach, Al

    2010-01-01

    In support of designing robotic lunar lander concepts, the propulsion team at NASA Marshall Space Flight Center (MSFC) and the Johns Hopkins University Applied Physics Laboratory (APL), with participation from industry, conducted a series of trade studies on propulsion concepts with an emphasis on light-weight, advanced technology components. The results suggest a high-pressure propulsion system may offer some benefits in weight savings and system packaging. As part of the propulsion system, a solid rocket motor was selected to provide a large impulse to reduce the spacecraft s velocity prior to the lunar descent. In parallel to this study effort, the team also began technology risk reduction testing on a high thrust-to-weight descent thruster and a high-pressure regulator. A series of hot-fire tests was completed on the descent thruster in vacuum conditions at NASA White Sands Test Facility (WSTF) in New Mexico in 2009. Preparations for a hot-fire test series on the attitude control thruster at WSTF and for pressure regulator testing are now underway. This paper will provide an overview of the concept trade study results along with insight into the risk mitigation activities conducted to date.

  13. Gold-doped graphene: A highly stable and active electrocatalysts for the oxygen reduction reaction

    SciTech Connect

    Stolbov, Sergey Alcántara Ortigoza, Marisol

    2015-04-21

    In addressing the growing need of renewable and sustainable energy resources, hydrogen-fuel-cells stand as one of the most promising routes to transform the current energy paradigm into one that integrally fulfills environmental sustainability. Nevertheless, accomplishing this technology at a large scale demands to surpass the efficiency and enhance the cost-effectiveness of platinum-based cathodes, which catalyze the oxygen reduction reaction (ORR). In this work, our first-principles calculations show that Au atoms incorporated into graphene di-vacancies form a highly stable and cost-effective electrocatalyst that is, at the same time, as or more (dependently of the dopant concentration) active toward ORR than the best-known Pt-based electrocatalysts. We reveal that partial passivation of defected-graphene by gold atoms reduces the reactivity of C dangling bonds and increases that of Au, thus optimizing them for catalyzing the ORR and yielding a system of high thermodynamic and electrochemical stabilities. We also demonstrate that the linear relation among the binding energies of the reaction intermediates assumed in computational high-throughput material screening does not hold, at least for this non-purely transition-metal material. We expect Au-doped graphene to finally overcome the cathode-related challenge hindering the realization of hydrogen-fuel cells as the leading means of powering transportation and portable devices.

  14. Formulation and particle size reduction improve bioavailability of poorly water-soluble compounds with antimalarial activity.

    PubMed

    Wang, Hongxing; Li, Qigui; Reyes, Sean; Zhang, Jing; Xie, Lisa; Melendez, Victor; Hickman, Mark; Kozar, Michael P

    2013-01-01

    Decoquinate (DQ) is highly effective at killing malaria parasites in vitro; however, it is extremely insoluble in water. In this study, solid dispersion method was used for DQ formulation which created a suitable physical form of DQ in aqueous phase for particle manipulation. Among many polymers and surfactants tested, polyvinylpyrrolidone 10, a polymer, and L- α -phosphatidylcholine or polysorbate, two surfactants, were chosen as DQ formulation components. The formulation particles were reduced to a mean size between 200 to 400 nm, which was stable in aqueous medium for at least three weeks. Pharmacokinetic (PK) studies showed that compared to DQ microparticle suspension, a nanoparticle formulation orally dosed to mice showed a 14.47-fold increase in area under the curve (AUC) of DQ plasma concentration and a 4.53-fold increase in AUC of DQ liver distribution. WR 299666, a poorly water-soluble compound with antimalarial activity, was also tested and successfully made into nanoparticle formulation without undergoing solid dispersion procedure. We concluded that nanoparticles generated by using appropriate formulation components and sufficient particle size reduction significantly increased the bioavailability of DQ and could potentially turn this antimalarial agent to a therapeutic drug. PMID:23766925

  15. Growth and Deposition of Au Nanoclusters on Polymer-wrapped Graphene and Their Oxygen Reduction Activity

    NASA Astrophysics Data System (ADS)

    Fujigaya, Tsuyohiko; Kim, Chaerin; Hamasaki, Yuki; Nakashima, Naotoshi

    2016-02-01

    The development of a non-Pt electrocatalyst with a high performance for the oxygen reduction reaction (ORR) is one of the central issues in polymer electrolyte fuel cells science. Au-nanoparticles (Au-NPs) with a diameter of <2 nm are one of the promising substitutes of Pt-NPs; however, it is still a challenge to synthesize such a small-sized Au-NPs with a narrow diameter distribution on a carbon support without using capping agents. We here describe a facile method to deposit uniform Au-NPs (diameter = 1.6 nm and 3.3 nm) on the stacked-graphene (<10 layers) coated with poly[2,2‧-(2,6-pyridine)-5,5‧-bibenzimidazole] without using any capping agents. The obtained Au-NPs exhibit an excellent ORR activity with the onset potential at -0.11 V and -0.09 V (vs. Ag/AgCl) for 1.6 nm and 3.3 nm, respectively. On the other hand, inhomogeneous Au-NPs with 4.6 nm in average diameter shows the onset potential at -0.15 V (vs. Ag/AgCl).

  16. Enhancing pyridinic nitrogen level in graphene to promote electrocatalytic activity for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Sun, Jiaguang; Wang, Lan; Song, Ranran; Yanga, Shubin

    2016-02-01

    We develop an efficient approach to fabricate nitrogen-doped graphene with tunable pyridinic nitrogen levels (from 1.1 to 1.8 at.%), abundant in-plane holes and high surface areas (623 m2 g-1) via a hydrothermal treatment of graphene oxide with hydrogen peroxide and subsequent annealing under ammonia gas. It is found that the chemical etching is beneficial to the formation of pyridinic nitrogen in graphene during the nitrogen-doping process, which is crucial to enhancing the electrocatalytic properties of graphene for oxygen reduction reaction (ORR). Hence, the optimized NG exhibits good electrocatalytic activity, more positive onset potential than Pt-C (-0.08 V versus -0.09 V), good durability, and high selectivity when it is employed as a metal-free catalyst for ORR. This approach may uncover a mechanism in escalation of pyridinic N atoms doped on the graphene basal edge and provide an efficient platform for the synthesis of a series of heteroatom-doped graphene with tunable heteroatom content for broad applications.

  17. Voice communications in the cockpit noise environment: The role of active noise reduction

    NASA Astrophysics Data System (ADS)

    Wheeler, Peter David

    The topic of voice communications in the cockpit noise environment of modern fast-jet aircraft and helicopters is addressed, and in particular, research undertaken in support of the development of a system for reducing the noise level at the operators' ear is described by acoustic cancellation within the ear defender, known as active noise reduction (ANR). The internal noise spectra of today's high performance fast-jet aircraft and military helicopters is described, and the complex interaction of acoustic noise transmission, speech, and microphone noise pick-up, which produces the total acoustic environment at the aircrews' ears, is discussed. Means of mathematically modelling the audio channel, quantifying the components identified above, and identifying areas of shortfall in performance are derived, leading to a procedure for the development of attenuation requirements, described as the communications audit. A model of the electroacoustic characteristics of the ANR ear defender assembly is presented and the sound field distribution within the ear defender/ear cavity, and its effect upon cancellation performance, is discussed. The extensive laboratory and flight testing of the ANR system that was undertaken is reviewed, paying particular attention to the measurement and analysis techniques employed in such testing. Finally, the performance characteristics of ANR are discussed and compared with the requirements previously established. Design limitations placed upon the system by the constraints of its area of application are described, and the scope for future improvements is considered.

  18. Screening of catalytic oxygen reduction reaction activity of metal-doped graphene by density functional theory

    NASA Astrophysics Data System (ADS)

    Chen, Xin; Chen, Shuangjing; Wang, Jinyu

    2016-08-01

    Graphene doping is a promising direction for developing effective oxygen reduction reaction (ORR) catalysts. In this paper, we computationally investigated the ORR performance of 10 kinds of metal-doped graphene (M-G) catalysts, namely, Al-, Si-, Mn-, Fe-, Co-, Ni-, Pd-, Ag-, Pt-, and Au-G. The results shown that the binding energies of the metal atoms incorporated into the graphene vacancy are higher than their bulk cohesive energies, indicating the formed M-G catalysts are even more stable than the corresponding bulk metal surfaces, and thus avoid the metals dissolution in the reaction environment. We demonstrated that the linear relation among the binding energies of the ORR intermediates that found on metal-based materials does not hold for the M-G catalysts, therefore a single binding energy of intermediate alone is not sufficient to evaluate the ORR activity of an arbitrary catalyst. By analysis of the detailed ORR processes, we predicted that the Au-, Co-, and Ag-G materials can be used as the ORR catalysts.

  19. An active structural acoustic control approach for the reduction of the structure-borne road noise

    NASA Astrophysics Data System (ADS)

    Douville, Hugo; Berry, Alain; Masson, Patrice

    2002-11-01

    The reduction of the structure-borne road noise generated inside the cabin of an automobile is investigated using an Active Structural Acoustic Control (ASAC) approach. First, a laboratory test bench consisting of a wheel/suspension/lower suspension A-arm assembly has been developed in order to identify the vibroacoustic transfer paths (up to 250 Hz) for realistic road noise excitation of the wheel. Frequency Response Function (FRF) measurements between the excitation/control actuators and each suspension/chassis linkage are used to characterize the different transfer paths that transmit energy through the chassis of the car. Second, a FE/BE model (Finite/Boundary Elements) was developed to simulate the acoustic field of an automobile cab interior. This model is used to predict the acoustic field inside the cabin as a response to the measured forces applied on the suspension/chassis linkages. Finally, an experimental implementation of ASAC is presented. The control approach relies on the use of inertial actuators to modify the vibration behavior of the suspension and the automotive chassis such that its noise radiation efficiency is decreased. The implemented algorithm consists of a MIMO (Multiple-Input-Multiple-Output) feedforward configuration with a filtered-X LMS algorithm using an advanced reference signal (width FIR filters) using the Simulink/Dspace environment for control prototyping.

  20. Physiological selectivity and activity reduction of insecticides by rainfall to predatory wasps of Tuta absoluta.

    PubMed

    Barros, Emerson C; Bacci, Leandro; Picanco, Marcelo C; Martins, Júlio C; Rosado, Jander F; Silva, Gerson A

    2015-01-01

    In this study, we carried out three bioassays with nine used insecticides in tomato crops to identify their efficiency against tomato leaf miner Tuta absoluta, the physiological selectivity and the activity reduction of insecticides by three rain regimes to predatory wasps Protonectarina sylveirae and Polybia scutellaris. We assessed the mortality caused by the recommended doses of abamectin, beta-cyfluthrin, cartap, chlorfenapyr, etofenprox, methamidophos, permethrin, phenthoate and spinosad to T. absoluta and wasps at the moment of application. In addition, we evaluated the wasp mortality due to the insecticides for 30 days on plants that did not receive rain and on plants that received 4 or 125 mm of rain. Spinosad, cartap, chlorfenapyr, phenthoate, abamectin and methamidophos caused mortality higher than 90% to T. absoluta, whereas the pyrethroids beta-cyfluthrin, etofenprox and permethrin caused mortality between 8.5% and 46.25%. At the moment of application, all the insecticides were highly toxic to the wasps, causing mortality higher than 80%. In the absence of rain, all the insecticides continued to cause high mortality to the wasps for 30 days after the application. The toxicity of spinosad and methamidophos on both wasp species; beta-cyfluthrin on P. sylveirae and chlorfenapyr and abamectin on P. scutellaris, decreased when the plants received 4 mm of rain. In contrast, the other insecticides only showed reduced toxicity on the wasps when the plants received 125 mm of rain. PMID:25421627

  1. Recent Status of SIM Lite Astrometric Observatory Mission: Flight Engineering Risk Reduction Activities

    NASA Technical Reports Server (NTRS)

    Goullioud, Renaud; Dekens, Frank; Nemati, Bijan; An, Xin; Carson, Johnathan

    2010-01-01

    The SIM Lite Astrometric Observatory is a mission concept for a space-borne instrument to perform micro-arc-second narrow-angle astrometry to search 60 to 100 nearby stars for Earth-like planets, and to perform global astrometry for a broad astrophysics program. The instrument consists of two Michelson stellar interferometers and a telescope. The first interferometer chops between the target star and a set of reference stars. The second interferometer monitors the attitude of the instrument in the direction of the target star. The telescope monitors the attitude of the instrument in the other two directions. The main enabling technology development for the mission was completed during phases A & B. The project is currently implementing the developed technology onto flight-ready engineering models. These key engineering tasks will significantly reduce the implementation risks during the flight phases C & D of the mission. The main optical interferometer components, including the astrometric beam combiner, the fine steering optical mechanism, the path-length-control and modulation optical mechanisms, focal-plane camera electronics and cooling heat pipe, are currently under development. Main assemblies are built to meet flight requirements and will be subjected to flight qualification level environmental testing (random vibration and thermal cycling) and performance testing. This paper summarizes recent progress in engineering risk reduction activities.

  2. False alarm reduction in BSN-based cardiac monitoring using signal quality and activity type information.

    PubMed

    Tanantong, Tanatorn; Nantajeewarawat, Ekawit; Thiemjarus, Surapa

    2015-01-01

    False alarms in cardiac monitoring affect the quality of medical care, impacting on both patients and healthcare providers. In continuous cardiac monitoring using wireless Body Sensor Networks (BSNs), the quality of ECG signals can be deteriorated owing to several factors, e.g., noises, low battery power, and network transmission problems, often resulting in high false alarm rates. In addition, body movements occurring from activities of daily living (ADLs) can also create false alarms. This paper presents a two-phase framework for false arrhythmia alarm reduction in continuous cardiac monitoring, using signals from an ECG sensor and a 3D accelerometer. In the first phase, classification models constructed using machine learning algorithms are used for labeling input signals. ECG signals are labeled with heartbeat types and signal quality levels, while 3D acceleration signals are labeled with ADL types. In the second phase, a rule-based expert system is used for combining classification results in order to determine whether arrhythmia alarms should be accepted or suppressed. The proposed framework was validated on datasets acquired using BSNs and the MIT-BIH arrhythmia database. For the BSN dataset, acceleration and ECG signals were collected from 10 young and 10 elderly subjects while they were performing ADLs. The framework reduced the false alarm rate from 9.58% to 1.43% in our experimental study, showing that it can potentially assist physicians in diagnosing a vast amount of data acquired from wireless sensors and enhance the performance of continuous cardiac monitoring. PMID:25671512

  3. False Alarm Reduction in BSN-Based Cardiac Monitoring Using Signal Quality and Activity Type Information

    PubMed Central

    Tanantong, Tanatorn; Nantajeewarawat, Ekawit; Thiemjarus, Surapa

    2015-01-01

    False alarms in cardiac monitoring affect the quality of medical care, impacting on both patients and healthcare providers. In continuous cardiac monitoring using wireless Body Sensor Networks (BSNs), the quality of ECG signals can be deteriorated owing to several factors, e.g., noises, low battery power, and network transmission problems, often resulting in high false alarm rates. In addition, body movements occurring from activities of daily living (ADLs) can also create false alarms. This paper presents a two-phase framework for false arrhythmia alarm reduction in continuous cardiac monitoring, using signals from an ECG sensor and a 3D accelerometer. In the first phase, classification models constructed using machine learning algorithms are used for labeling input signals. ECG signals are labeled with heartbeat types and signal quality levels, while 3D acceleration signals are labeled with ADL types. In the second phase, a rule-based expert system is used for combining classification results in order to determine whether arrhythmia alarms should be accepted or suppressed. The proposed framework was validated on datasets acquired using BSNs and the MIT-BIH arrhythmia database. For the BSN dataset, acceleration and ECG signals were collected from 10 young and 10 elderly subjects while they were performing ADLs. The framework reduced the false alarm rate from 9.58% to 1.43% in our experimental study, showing that it can potentially assist physicians in diagnosing a vast amount of data acquired from wireless sensors and enhance the performance of continuous cardiac monitoring. PMID:25671512

  4. Catechin-capped gold nanoparticles: green synthesis, characterization, and catalytic activity toward 4-nitrophenol reduction

    PubMed Central

    2014-01-01

    An eco-friendly approach is described for the green synthesis of gold nanoparticles using catechin as a reducing and capping agent. The reaction occurred at room temperature within 1 h without the use of any external energy and an excellent yield (99%) was obtained, as determined by inductively coupled plasma mass spectrometry. Various shapes of gold nanoparticles with an estimated diameter of 16.6 nm were green-synthesized. Notably, the capping of freshly synthesized gold nanoparticles by catechin was clearly visualized with the aid of microscopic techniques, including high-resolution transmission electron microscopy, atomic force microscopy, and field emission scanning electron microscopy. Strong peaks in the X-ray diffraction pattern of the as-prepared gold nanoparticles confirmed their crystalline nature. The catalytic activity of the as-prepared gold nanoparticles was observed in the reduction of 4-nitrophenol to 4-aminophenol in the presence of NaBH4. The results suggest that the newly prepared gold nanoparticles have potential uses in catalysis. PMID:24589224

  5. Catechin-capped gold nanoparticles: green synthesis, characterization, and catalytic activity toward 4-nitrophenol reduction

    NASA Astrophysics Data System (ADS)

    Choi, Yoonho; Choi, Myung-Jin; Cha, Song-Hyun; Kim, Yeong Shik; Cho, Seonho; Park, Youmie

    2014-03-01

    An eco-friendly approach is described for the green synthesis of gold nanoparticles using catechin as a reducing and capping agent. The reaction occurred at room temperature within 1 h without the use of any external energy and an excellent yield (99%) was obtained, as determined by inductively coupled plasma mass spectrometry. Various shapes of gold nanoparticles with an estimated diameter of 16.6 nm were green-synthesized. Notably, the capping of freshly synthesized gold nanoparticles by catechin was clearly visualized with the aid of microscopic techniques, including high-resolution transmission electron microscopy, atomic force microscopy, and field emission scanning electron microscopy. Strong peaks in the X-ray diffraction pattern of the as-prepared gold nanoparticles confirmed their crystalline nature. The catalytic activity of the as-prepared gold nanoparticles was observed in the reduction of 4-nitrophenol to 4-aminophenol in the presence of NaBH4. The results suggest that the newly prepared gold nanoparticles have potential uses in catalysis.

  6. Participation and cardiovascular risk reduction in a voluntary worksite nutrition and physical activity program

    PubMed Central

    Thorndike, Anne N.; Healey, Erica; Sonnenberg, Lillian; Regan, Susan

    2010-01-01

    Objective In a cohort of employees participating in a worksite nutrition and physical activity program, we compared program completion and changes in cardiovascular risk factors by baseline body mass index. Methods In 2007, 774 employees enrolled in a 10 week program at a hospital in Boston, MA. Program completion and change in weight, cholesterol, and blood pressure were compared between obese (BMI≥30), overweight (BMI=25–29.9), and normal weight (BMI<25) participants. Results At baseline, 63% were obese or overweight and had higher blood pressure and cholesterol compared to normal weight participants. Program completion was 82% and did not differ by BMI. Mean weight loss was 1.9 kg at end of program (p<0.001) and 0.4 kg at 1 year (p=0.002). At end of program, participants with BMI≥30 lost 3.0% body weight vs. 2.7% for BMI=25–29.9 and 1.7% for BMI<25 (p<0.001), but weight loss at 1 year did not differ by BMI. Mean cholesterol and blood pressure were lower at end of program and 1 year (p all <0.005) but did not differ by BMI. Conclusions Worksite programs can successfully initiate cardiovascular risk reduction among employees, but more intensive interventions are needed to make significant improvements in the health of higher risk obese employees. PMID:21130804

  7. Growth and Deposition of Au Nanoclusters on Polymer-wrapped Graphene and Their Oxygen Reduction Activity

    PubMed Central

    Fujigaya, Tsuyohiko; Kim, ChaeRin; Hamasaki, Yuki; Nakashima, Naotoshi

    2016-01-01

    The development of a non-Pt electrocatalyst with a high performance for the oxygen reduction reaction (ORR) is one of the central issues in polymer electrolyte fuel cells science. Au-nanoparticles (Au-NPs) with a diameter of <2 nm are one of the promising substitutes of Pt-NPs; however, it is still a challenge to synthesize such a small-sized Au-NPs with a narrow diameter distribution on a carbon support without using capping agents. We here describe a facile method to deposit uniform Au-NPs (diameter = 1.6 nm and 3.3 nm) on the stacked-graphene (<10 layers) coated with poly[2,2′-(2,6-pyridine)-5,5′-bibenzimidazole] without using any capping agents. The obtained Au-NPs exhibit an excellent ORR activity with the onset potential at −0.11 V and −0.09 V (vs. Ag/AgCl) for 1.6 nm and 3.3 nm, respectively. On the other hand, inhomogeneous Au-NPs with 4.6 nm in average diameter shows the onset potential at −0.15 V (vs. Ag/AgCl). PMID:26899591

  8. Myopathic Lamin Mutations Cause Reductive Stress and Activate the Nrf2/Keap-1 Pathway

    PubMed Central

    Dialynas, George; Shrestha, Om K.; Ponce, Jessica M.; Zwerger, Monika; Thiemann, Dylan A.; Young, Grant H.; Moore, Steven A.; Yu, Liping; Lammerding, Jan; Wallrath, Lori L.

    2015-01-01

    Mutations in the human LMNA gene cause muscular dystrophy by mechanisms that are incompletely understood. The LMNA gene encodes A-type lamins, intermediate filaments that form a network underlying the inner nuclear membrane, providing structural support for the nucleus and organizing the genome. To better understand the pathogenesis caused by mutant lamins, we performed a structural and functional analysis on LMNA missense mutations identified in muscular dystrophy patients. These mutations perturb the tertiary structure of the conserved A-type lamin Ig-fold domain. To identify the effects of these structural perturbations on lamin function, we modeled these mutations in Drosophila Lamin C and expressed the mutant lamins in muscle. We found that the structural perturbations had minimal dominant effects on nuclear stiffness, suggesting that the muscle pathology was not accompanied by major structural disruption of the peripheral nuclear lamina. However, subtle alterations in the lamina network and subnuclear reorganization of lamins remain possible. Affected muscles had cytoplasmic aggregation of lamins and additional nuclear envelope proteins. Transcription profiling revealed upregulation of many Nrf2 target genes. Nrf2 is normally sequestered in the cytoplasm by Keap-1. Under oxidative stress Nrf2 dissociates from Keap-1, translocates into the nucleus, and activates gene expression. Unexpectedly, biochemical analyses revealed high levels of reducing agents, indicative of reductive stress. The accumulation of cytoplasmic lamin aggregates correlated with elevated levels of the autophagy adaptor p62/SQSTM1, which also binds Keap-1, abrogating Nrf2 cytoplasmic sequestration, allowing Nrf2 nuclear translocation and target gene activation. Elevated p62/SQSTM1 and nuclear enrichment of Nrf2 were identified in muscle biopsies from the corresponding muscular dystrophy patients, validating the disease relevance of our Drosophila model. Thus, novel connections were made

  9. Model-based Analysis of Mixed Uranium(VI) Reduction by Biotic and Abiotic Pathways During in Situ Bioremediation

    SciTech Connect

    Zhao, Jiao; Scheibe, Timothy D.; Mahadevan, Radhakrishnan

    2013-10-24

    Uranium bioremediation has emerged as a potential strategy of cleanup of radionuclear contamination worldwide. An integrated geochemical & microbial community model is a promising approach to predict and provide insights into the bioremediation of a complicated natural subsurface. In this study, an integrated column-scale model of uranium bioremediation was developed, taking into account long-term interactions between biotic and abiotic processes. It is also combined with a comprehensive thermodynamic analysis to track the fate and cycling of biogenic species. As compared with other bioremediation models, the model increases the resolution of the connection of microbial community to geochemistry and establishes direct quantitative correlation between overall community evolution and geochemical variation, thereby accurately predicting the community dynamics under different sedimentary conditions. The thermodynamic analysis examined a recently identified homogeneous reduction of U(VI) by Fe(II) under dynamic sedimentary conditions across time and space. It shows that the biogenic Fe(II) from Geobacter metabolism can be removed rapidly by the biogenic sulphide from sulfate reducer metabolism, hence constituting one of the reasons that make the abiotic U(VI) reduction thermodynamically infeasible in the subsurface. Further analysis indicates that much higher influent concentrations of both Fe(II) and U(VI) than normal are required to for abiotic U(VI) reduction to be thermodynamically feasible, suggesting that the abiotic reduction cannot be an alternative to the biotic reduction in the remediation of uranium contaminated groundwater.

  10. Report on INL Activities for Uncertainty Reduction Analysis of FY11

    SciTech Connect

    G. Plamiotti; H. Hiruta; M. Salvatores

    2011-09-01

    This report presents the status of activities performed at INL under the ARC Work Package on 'Uncertainty Reduction Analyses' that has a main goal the reduction of uncertainties associated with nuclear data on neutronic integral parameters of interest for the design of advanced fast reactors under consideration by the ARC program. First, an analysis of experiments was carried out. For both JOYO (the first Japanese fast reactor) and ZPPR-9 (a large size zero power plutonium fueled experiment performed at ANL-W in Idaho) the performance of ENDF/B-VII.0 is quite satisfying except for the sodium void configurations of ZPPR-9, but for which one has to take into account the approximation of the modeling. In fact, when one uses a more detailed model (calculations performed at ANL in a companion WP) more reasonable results are obtained. A large effort was devoted to the analysis of the irradiation experiments, PROFIL-1 and -2 and TRAPU, performed at the French fast reactor PHENIX. For these experiments a pre-release of the ENDF/B-VII.1 cross section files was also used, in order to provide validation feedback to the CSWEG nuclear data evaluation community. In the PROFIL experiments improvements can be observed for the ENDF/B-VII.1 capture data in 238Pu, 241Am, 244Cm, 97Mo, 151Sm, 153Eu, and for 240Pu(n,2n). On the other hand, 240,242Pu, 95Mo, 133Cs and 145Nd capture C/E results are worse. For the major actinides 235U and especially 239Pu capture C/E's are underestimated. For fission products, 105,106Pd, 143,144Nd and 147,149Sm are significantly underestimated, while 101Ru and 151Sm are overestimated. Other C/E deviations from unity are within the combined experimental and calculated statistical uncertainty. From the TRAPU analysis, the major improvement is in the predicted 243Cm build-up, presumably due to an improved 242Cm capture evaluation. The COSMO experiment was also analyzed in order to provide useful feedback on fission cross sections. It was found out that ENDF

  11. Aerobic Reduction of Arsenate by a Bacterium Isolated From Activated Sludge

    NASA Astrophysics Data System (ADS)

    Kozai, N.; Ohnuki, T.; Hanada, S.; Nakamura, K.; Francis, A. J.

    2006-12-01

    Microlunatus phosphovorus strain NM-1 is a polyphosphate-accumulating bacterium isolated from activated sludge. This bacterium takes up a large amount of polyphosphate under aerobic conditions and release phosphate ions by hydrolysis of polyphosphate to orthophosphate under anaerobic conditions to derive energy for taking up substrates. To understand the nature of this strain, especially, influence of potential contaminants in sewage and wastewater on growth, we have been investigating behavior of this bacterium in media containing arsenic. The present paper mainly reports reduction of arsenate by this bacterium under aerobic conditions. The strain NM-1 (JCM 9379) was aerobically cultured at 30 °C in a nutrient medium containing 2.5 g/l peptone, 0.5 g/l glucose, 1.5 g/l yeast extract, and arsenic [Na2HAsO4 (As(V)) or Na3AsO3 (As(III))] at concentrations between 0 and 50 mM. The cells collected from arsenic-free media were dispersed in buffer solutions containing 2mM HEPES, 10mM NaCl, prescribed concentrations of As(V), and 0-0.2 percent glucose. Then, this cell suspension was kept at 20 °C under aerobic or anaerobic conditions. The speciation of arsenic was carried out by ion chromatography and ICP-MS. The growth of the strain under aerobic conditions was enhanced by the addition of As(V) at the concentration between 1 and 10 mM. The maximum optical density of the culture in the medium containing 5mM As(V) was 1.4 times greater than that of the control culture. Below the As(V) concentration of 10mM, most of the As(V) was reduced to As(III). The growth of the strain under anaerobic conditions has not been observed so far. The cells in the buffer solutions reduced As(V) under aerobic condition. The reduction was enhanced by the addition of glucose. However, the cell did not reduce As(V) under anaerobic conditions. The strain NM-1 showed high resistance to As(V) and As(III). The maximum optical density of the culture grown in a medium containing 50 mM As(V) was only

  12. Simultaneous BVI noise and vibration reduction in rotorcraft using actively-controlled flaps and including performance considerations

    NASA Astrophysics Data System (ADS)

    Patt, Daniel A.

    This work presents the development and application of an active control approach for reduction of both vibration and noise induced by helicopter rotor blade vortex interaction (BVI). Control is implemented through single or dual actively controlled flaps (ACFs) on each blade. Low-speed helicopter flight is prone to severe BVI, resulting in elevated vibration and noise levels. Existing research has suggested that when some form of active control is used to reduce vibration, noise will increase and vice versa. The present research achieves simultaneous reduction of noise and vibration, and also investigates the physical sources of the observed reduction. The initial portion of this work focused on developing a tool for simulating helicopter noise and vibrations in the BVI flight regime. A method for predicting compressible unsteady blade surface pressure distribution on rotor blades was developed and combined with an enhanced free-wake model and an acoustic prediction tool with provisions for blade flexibility. These elements were incorporated within an aeroelastic analysis featuring fully coupled flap-lag-torsional blade dynamics. Subsequently, control algorithms were developed that were effective for reducing noise and vibration even in the nonlinear BVI flight regime; saturation limits were incorporated constraining flap deflections to specified limits. The resulting simulation was also validated with a wide range of experimental data, achieving excellent correlation. Finally, a number of active control studies were performed. Multi-component vibration reductions of 40--80% could be achieved, while incurring a small noise penalty. Noise was reduced using an onboard feedback microphone; reductions of 4--10 dB on the advancing side were observed on a plane beneath the rotor when using dual flaps. Finally, simultaneous noise and vibration reduction was studied. A reduction of about 5 dB in noise on the advancing side combined with a 60% reduction in vibration was

  13. Solubility data for U(VI) hydroxide and Np(IV) hydrous oxide: application of MCC-3 methodology

    SciTech Connect

    Krupka, K.M.; Rai, D.; Fulton, R.W.; Strickert, R.G.

    1985-01-01

    Experiments based on a modified MCC-3S test method were conducted to investigate the solubility of U(VI) hydroxide (the mineral schoepite) and Np(IV) hydrous oxide at ambient temperature. The solubility of U(VI) hydroxide was investigated in carbonate-free, oxidizing aqueous solutions in the pH range of 3 to 11. The measured concentrations of dissolved U confirm the amphoteric behavior of U(VI) hydroxide solid and the importance of anionic U(VI) solids under basic pH conditions. The effect of fluoride complexation on the solubility of Np(IV) hydrous oxide was studied in carbonate-free, near-neutral to alkaline solutions that contained 100 ppm total F. For solutions in which sodium dithionite (Na2S2O4) and metallic Fe were used as reducing agents, the addition of 100 ppm F had no measurable effect on the solubility of Np(IV) hydrous oxide. 20 references, 1 figure.

  14. Effects of antagonist of retinoid X receptor (UVI3003) on morphology and gene profile of Xenopus tropicalis embryos.

    PubMed

    Zhu, Jingmin; Shi, Huahong; Zhu, Pan; Hu, Lingling; Wu, Lijiao; Yang, Yi; Rotchell, Jeanette M

    2014-07-01

    We exposed Xenopus tropicalis embryos to a selective antagonist of retinoid X receptor (UVI3003). UVI3003 induced multiple malformations at the concentrations of 200-1000 μg/L after 48 h exposure. The most prominent malformations affected brains, eyes, cement gland and fins. UVI3003 also induced variable and divergent malformations at 250-1500 μg/L after 0-24 and 24-48 h exposure. Microarray analysis showed that seven genes (rps15, serp2, fmr1, cyp2e1, lrrc9, ugtla6 and LOC100490188) were differentially regulated in all three treatment groups after 0-24h exposure. The most significantly affected pathway was galactose metabolism. In 24-48 h exposure groups, 18 genes were differentially regulated, mainly comprising components of the PPAR signaling pathway. These results suggested that UVI3003 is teratogenic in amphibian embryos. Differential gene expression suggests that galactose metabolism and PPAR signaling pathways may provide underlying mechanistic detail accounting for the observed malformations. PMID:24950139

  15. Influence of Calcite Solids and Dissolved Calcium on U(VI) Sorption and Desorption in Hanford Subsurface Sediments

    SciTech Connect

    Dong, Wenming; Ball, William P.; Stone, Alan T.; Bai, Jing; Liu, Chongxuan; Wang, Zheming

    2004-03-29

    We have investigated U(VI) sorption and desorption with batch experiments conducted on core samples from the Hanford, WA, site as well as on sub-fractions of these materials and laboratory-grade calcite. In these studies, [U(VI)] was varied between 10- 7 and 10-5 and pH between 7.2 to 10, at constant I (=0.05) and constant PCO2 (10-3.5 atm), using water that was saturated with respect to calcite. A carbonate-free (acetic acid- treated) fraction of silt/clay material showed higher sorption than untreated material, suggesting that carbonates block access to higher affinity sites. Of particular interest was that U(VI) sorption on untreated material was maximum at pH=8.4, with substantially less sorption at lower and higher pH and in contrast to results from calcite free studies, which show strong sorption at pH {approx} 5 to 8. U(VI) speciation results suggest that aqueous-phase Ca2UO2(CO3)3 was the source of the otherwise unexpectedly low sorption at pH <8.4.

  16. A new APE1/Ref-1-dependent pathway leading to reduction of NF-kappaB and AP-1, and activation of their DNA-binding activity.

    PubMed

    Ando, Kozue; Hirao, Satoshi; Kabe, Yasuaki; Ogura, Yuji; Sato, Iwao; Yamaguchi, Yuki; Wada, Tadashi; Handa, Hiroshi

    2008-08-01

    APE1/Ref-1 is thought to be a multifunctional protein involved in reduction-oxidation (redox) regulation and base excision DNA repair, and is required for early embryonic development in mice. APE1/Ref-1 has redox activity and AP endonuclease activity, and is able to enhance DNA-binding activity of several transcription factors, including NF-kappaB, AP-1 and p53, through reduction of their critical cysteine residues. However, it remains elusive exactly how APE1/Ref-1 carries out its essential functions in vivo. Here, we show that APE1/Ref-1 not only reduces target transcription factors directly but also facilitates their reduction by other reducing molecules such as glutathione or thioredoxin. The new activity of APE1/Ref-1, termed redox chaperone activity, is exerted at concentration significantly lower than that required for its redox activity and is neither dependent on its redox activity nor on its AP endonuclease activity. We also show evidence that redox chaperone activity of APE1/Ref-1 is critical to NF-kappaB-mediated gene expression in human cells and is mediated through its physical association with target transcription factors. Thus, APE1/Ref-1 may play multiple roles in an antioxidative stress response pathway through its different biochemical activities. These findings also provide new insight into the mechanism of intracellular redox regulation. PMID:18586825

  17. Effect of chloroethene concentrations and granular activated carbon on reductive dechlorination rates and growth of Dehalococcoides spp.

    PubMed

    Aktaş, Özgür; Schmidt, Kathrin R; Mungenast, Sarah; Stoll, Claudia; Tiehm, Andreas

    2012-01-01

    This study focused on the investigation of (i) the tetrachloroethene (PCE) toxicity threshold of a reductively dechlorinating mixed culture containing Dehalococcoides spp., (ii) the adsorption of PCE on different types of granular activated carbon (GAC), and (iii) the bioavailability and reductive dechlorination in the presence of GAC. The abundance of Dehalococcoides spp. detected by quantitative real-time