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Sample records for neptunium bromides

  1. Neptunium

    NASA Astrophysics Data System (ADS)

    Yoshida, Zenko; Johnson, Stephen G.; Kimura, Takaumi; Krsul, John R.

    The first report on the discovery of neptunium was in 1940 by McMillan and Abelson (1940), although McMillan did the preliminary work in 1939 and published his findings (McMillan, 1939). He did not claim that a new element had been discovered until confirmatory measurements had been undertaken in the following year. The production of neptunium was accomplished by placing a layer of uranium trioxide on paper with several aluminum or paper foils and then exposing this to neutrons from a cyclotron. Examination of the uranium paper sample containing the non-recoiling fraction displayed that two new radioactive components had been created. One component displayed a 23 min half-life, later identified as U-239, while the second exhibited a 2.3 day half-life. Both components decayed via β particle emission. Preliminary chemical analysis was performed to determine the behavior of the 2.3 day component and resulted in the contradictory assignment of this component as that exhibiting an atomic number of 93, but not being transuranic in nature (Segrè, 1939). Segrè noted in his paper that his conclusions were contradictory. However, the following quotation is from his paper, “The necessary conclusion seems to be that the 23 minute uranium decays into a very long-lived 93 and that transuranic elements have not yet been observed.” The primary stumbling block to the proper assignment of the material as transuranic in nature was the lack of observation of any alpha decay activity that would emanate from the daughter product of the beta decay of this new material with an atomic number 93. It was this work by Segrè (1939) that led McMillan and Abelson to revisit the chemical analysis and determine its properties in greater depth.

  2. NEPTUNIUM SOLVENT EXTRACTION PROCESS

    DOEpatents

    Dawson, L.R.; Fields, P.R.

    1959-10-01

    The separation of neptunium from an aqueous solution by solvent extraction and the extraction of neptunium from the solvent solution are described. Neptunium is separated from an aqueous solution containing tetravalent or hexavalent neptunium nitrate, nitric acid, and a nitrate salting out agent, such as sodium nitrate, by contacting the solution with an organic solvent such as diethyl ether. Subsequently, the neptunium nitrate is extracted from the organic solvent extract phase with water.

  3. ELECTRODEPOSITION OF NEPTUNIUM

    DOEpatents

    Seaborg, G.T.; Wahl, A.C.

    1960-08-30

    A process of electrodepositing neptunium from solutions is given which comprises conducting the electrodeposition from an absolute alcohol bath containing a neptunium nitrate and lanthanum nitrate at a potential of approximately 50 volts and a current density of between about 1.8 and 4.7 ma/dm/ sup 2/.

  4. NEPTUNIUM OXIDE PROCESSING

    SciTech Connect

    Jordan, J; Watkins, R; Hensel, S

    2009-05-27

    The Savannah River Site's HB-Line Facility completed a campaign in which fifty nine cans of neptunium oxide were produced and shipped to the Idaho National Laboratory in the 9975 shipping container. The neptunium campaign was divided into two parts: Part 1 which consisted of oxide made from H-Canyon neptunium solution which did not require any processing prior to conversion into an oxide, and Part 2 which consisted of oxide made from additional H-Canyon neptunium solutions which required processing to purify the solution prior to conversion into an oxide. The neptunium was received as a nitrate solution and converted to oxide through ion-exchange column extraction, precipitation, and calcination. Numerous processing challenges were encountered in order make a final neptunium oxide product that could be shipped in a 9975 shipping container. Among the challenges overcome was the issue of scale: translating lab scale production into full facility production. The balance between processing efficiency and product quality assurance was addressed during this campaign. Lessons learned from these challenges are applicable to other processing projects.

  5. Neptunium storage at Hanford

    SciTech Connect

    Alderman, C.J.; Shiraga, S.S.; Schwartz, R.A.; Smith, R.J.; Wootan, D.W.

    1993-06-01

    A decision must be made regarding whether the United State`s stockpile of neptunium should be discarded into the waste stream or kept for the production of Pu-238. Although the cost of long term storage is not inconsequential, to dispose of the material means the closing of our option to maintain control over our Pu-238 stockpile. Within the Fuels and Materials Examination Facility at Hanford there exists a remotely operated facility that can be converted for neptunium storage. This paper describes the facility and the anticipated handling requirements.

  6. METHOD OF SEPARATING NEPTUNIUM

    DOEpatents

    Seaborg, G.T.

    1961-10-24

    plutonium in an aqueous solution containing sulfate ions. The process consists of contacting the solution with an alkali metal bromate, digesting the resulting mixture at 15 to 25 deg C for a period of time not more than that required to oxidize the neptunium, adding lanthanum ions and fluoride ions, and separating the plutonium-containing precipitate thus formed from the supernatant solution. (AEC)

  7. SOLVENT EXTRACTION OF NEPTUNIUM

    DOEpatents

    Butler, J.P.

    1958-08-12

    A process is described for the recovery of neptuniunn from dissolver solutions by solvent extraction. The neptunium containing solution should be about 5N, in nitric acid.and about 0.1 M in ferrous ion. The organic extracting agent is tributyl phosphate, and the neptuniunn is recovered from the organic solvent phase by washing with water.

  8. Results of Neptunium Disposal Testing

    SciTech Connect

    Walker, D.D.

    2003-10-07

    Researchers investigated the neutralization of neptunium solution from H-Canyon Tank 16.4 and the properties of the resulting slurry. This work investigated slurry properties from a single neutralization protocol and limited storage times.

  9. Cyanogen bromide

    Integrated Risk Information System (IRIS)

    Cyanogen bromide ; CASRN 506 - 68 - 3 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic

  10. Vinyl bromide

    Integrated Risk Information System (IRIS)

    Vinyl bromide ; CASRN 593 - 60 - 2 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Eff

  11. Neptunium nitrate solution. Neptunium TiOA - TTA method. Revision 1

    SciTech Connect

    Not Available

    1985-04-01

    An analytical solvent extraction method for separating neptunium from plutonium, americium, curium, uranium, thorium, and fission products using tri-iso-octylamine (TiOA) and thenoyltrifluoroacetone (TTA) is described. Neptunium is separated from the bulk of the plutonium, americium, curium, and fission products by the extraction of neptunium(IV) into RiOA, dissolved in xylene, from an aqueous nitric acid reducing solution. The neptunium bearing organic solution is then scrubbed with a nitric acid reducing solution to achieve further purification. Final purification is obtained by stripping neptunium from tri-iso-octylaminexylene solution into dilute hydrochloric acid and then extracting the neptunium(IV) into TTA dissolved in xylene. A quantitative neptunium measurement is then made by alpha counting and alpha pulse height analysis. Most of the neptunium bearing sample solutions associated with the chemical processing of irradiated uranium are aqueous nitric acid solutions, and with the exception of uranium(IV) are free from interfering materials.

  12. Direct chemical reduction of neptunium oxide to neptunium metal using calcium and calcium chloride

    NASA Astrophysics Data System (ADS)

    Squires, Leah N.; Lessing, Paul

    2016-04-01

    A process of direct reduction of neptunium oxide to neptunium metal using calcium metal as the reducing agent is discussed. After reduction of the oxide to metal, the metal is separated by density from the other components of the reaction mixture and can be easily removed upon cooling. The direct reduction technique consistently produces high purity (98%-99% pure) neptunium metal.

  13. OXIDATIVE METHOD OF SEPARATING PLUTONIUM FROM NEPTUNIUM

    DOEpatents

    Beaufait, L.J. Jr.

    1958-06-10

    A method is described of separating neptunium from plutonium in an aqueous solution containing neptunium and plutonium in valence states not greater than +4. This may be accomplished by contacting the solution with dichromate ions, thus oxidizing the neptunium to a valence state greater than +4 without oxidizing any substantial amount of plutonium, and then forming a carrier precipitate which carries the plutonium from solution, leaving the neptunium behind. A preferred embodiment of this invention covers the use of lanthanum fluoride as the carrier precipitate.

  14. Phonon dynamics of neptunium chalcogenides

    NASA Astrophysics Data System (ADS)

    Aynyas, Mahendra; Rukmangad, Aditi; Arya, Balwant S.; Sanyal, Sankar P.

    2012-06-01

    We have performed phonon calculations of Neptunium Chalcogenides (NpX) (X= S, Se, Te) based on breathing shell model (BSM) which includes breathing motion of electron of the Np-atoms due to f-d hybridization. The model predicts that the short range breathing phenomenon play a dominant role in the phonon properties. We also report, for the first time specific heat for these compounds.

  15. Radiotoxicity of neptunium(V) and neptunium(V)-nitrilotriacetic acid (NTA) complexes towards Chelatobacter heintzii

    SciTech Connect

    Banaszak, J.E. |; Reed, D.T.; Rittmann, B.E.

    1997-03-10

    The objective of this work was to investigate the toxicity mechanisms of neptunium and the neptunium-NTA complex towards Chelatobacter heintzii. The results show that metal toxicity of aquo NpO{sub 2}{sup +} may significantly limit growth of Cl heintzii at free metal ion concentrations greater than {approx} 10{sup {minus}5} M. However, neptunium concentrations {ge} 10{sup {minus}4} M do not cause measurable radiotoxicity effects in C. heintzii when present in the form of a neptunium-NTA complex or colloidal/precipitated neptunium-phosphate. The neptunium-NTA complex, which is stable under aerobic conditions, is destabilized by microbial degradation of NTA. When phosphate was present, degradation of NTA led to the precipitation of a neptunium-phosphate phase.

  16. Packaging and Transportation of Additional Neptunium Oxide

    SciTech Connect

    Watkins, R.; Jordan, J.; Hensel, S.

    2010-05-05

    The Savannah River Site's HB-Line Facility completed a second neptunium oxide production campaign in which nine (9) additional cans of neptunium oxide were produced and shipped to the Idaho National Laboratory and Oak Ridge National Laboratory in the 9975 shipping container. These additional cans were from a different feed solution than the first fifty (50) cans of neptunium oxide that were previously produced and shipped via a Letter of Amendment to the 9975 Safety Analysis Report for Packaging (SARP) content table. This paper will address the challenges associated with demonstrating the neptunium oxide produced from the additional feed solution was equivalent to the original neptunium oxide and within the content description of the Letter of Amendment.

  17. Organometallic neptunium(III) complexes.

    PubMed

    Dutkiewicz, Michał S; Farnaby, Joy H; Apostolidis, Christos; Colineau, Eric; Walter, Olaf; Magnani, Nicola; Gardiner, Michael G; Love, Jason B; Kaltsoyannis, Nikolas; Caciuffo, Roberto; Arnold, Polly L

    2016-08-01

    Studies of transuranic organometallic complexes provide a particularly valuable insight into covalent contributions to the metal-ligand bonding, in which the subtle differences between the transuranium actinide ions and their lighter lanthanide counterparts are of fundamental importance for the effective remediation of nuclear waste. Unlike the organometallic chemistry of uranium, which has focused strongly on U(III) and has seen some spectacular advances, that of the transuranics is significantly technically more challenging and has remained dormant. In the case of neptunium, it is limited mainly to Np(IV). Here we report the synthesis of three new Np(III) organometallic compounds and the characterization of their molecular and electronic structures. These studies suggest that Np(III) complexes could act as single-molecule magnets, and that the lower oxidation state of Np(II) is chemically accessible. In comparison with lanthanide analogues, significant d- and f-electron contributions to key Np(III) orbitals are observed, which shows that fundamental neptunium organometallic chemistry can provide new insights into the behaviour of f-elements. PMID:27442286

  18. Organometallic neptunium(III) complexes

    NASA Astrophysics Data System (ADS)

    Dutkiewicz, Michał S.; Farnaby, Joy H.; Apostolidis, Christos; Colineau, Eric; Walter, Olaf; Magnani, Nicola; Gardiner, Michael G.; Love, Jason B.; Kaltsoyannis, Nikolas; Caciuffo, Roberto; Arnold, Polly L.

    2016-08-01

    Studies of transuranic organometallic complexes provide a particularly valuable insight into covalent contributions to the metal–ligand bonding, in which the subtle differences between the transuranium actinide ions and their lighter lanthanide counterparts are of fundamental importance for the effective remediation of nuclear waste. Unlike the organometallic chemistry of uranium, which has focused strongly on UIII and has seen some spectacular advances, that of the transuranics is significantly technically more challenging and has remained dormant. In the case of neptunium, it is limited mainly to NpIV. Here we report the synthesis of three new NpIII organometallic compounds and the characterization of their molecular and electronic structures. These studies suggest that NpIII complexes could act as single-molecule magnets, and that the lower oxidation state of NpII is chemically accessible. In comparison with lanthanide analogues, significant d- and f-electron contributions to key NpIII orbitals are observed, which shows that fundamental neptunium organometallic chemistry can provide new insights into the behaviour of f-elements.

  19. PRECIPITATION METHOD OF SEPARATION OF NEPTUNIUM

    DOEpatents

    Magnusson, L.B.

    1958-07-01

    A process is described for the separation of neptunium from plutonium in an aqueous solution containing neptunium ions in a valence state not greater than +4, plutonium ioms in a valence state not greater than +4, and sulfate ions. The Process consists of adding hypochlorite ions to said solution in order to preferentially oxidize the neptunium and then adding lanthanum ions and fluoride ions to form a precipitate of LaF/sub 3/ carrying the plutonium, and thereafter separating the supernatant solution from the precipitate.

  20. PACKAGING AND TRANSPORTATION OF NEPTUNIUM OXIDE

    SciTech Connect

    Watkins, R; Steve Hensel, S; Jeffrey Jordan, J

    2009-03-03

    The Savannah River Site's HB-Line Facility completed a campaign in which fifty (50) cans of neptunium oxide were produced and shipped to the Idaho National Laboratory in the 9975 shipping container. This shipping campaign involved the addition of neptunium oxide to the 9975 Safety Analysis Report for Packaging (SARP) as a new content and subsequently a Letter of Amendment to the SARP content table. This paper will address the proper steps which should be taken to add a new content table to a SARP. It will also address the importance of product sampling and understanding the material shipping requirements of a SARP.

  1. Dehydration of plutonium or neptunium trichloride hydrate

    DOEpatents

    Foropoulos, Jr., Jerry; Avens, Larry R.; Trujillo, Eddie A.

    1992-01-01

    A process of preparing anhydrous actinide metal trichlorides of plutonium or neptunium by reacting an aqueous solution of an actinide metal trichloride selected from the group consisting of plutonium trichloride or neptunium trichloride with a reducing agent capable of converting the actinide metal from an oxidation state of +4 to +3 in a resultant solution, evaporating essentially all the solvent from the resultant solution to yield an actinide trichloride hydrate material, dehydrating the actinide trichloride hydrate material by heating the material in admixture with excess thionyl chloride, and recovering anhydrous actinide trichloride is provided.

  2. Dehydration of plutonium or neptunium trichloride hydrate

    DOEpatents

    Foropoulos, J. Jr.; Avens, L.R.; Trujillo, E.A.

    1992-03-24

    A process is described for preparing anhydrous actinide metal trichlorides of plutonium or neptunium by reacting an aqueous solution of an actinide metal trichloride selected from the group consisting of plutonium trichloride or neptunium trichloride with a reducing agent capable of converting the actinide metal from an oxidation state of +4 to +3 in a resultant solution, evaporating essentially all the solvent from the resultant solution to yield an actinide trichloride hydrate material, dehydrating the actinide trichloride hydrate material by heating the material in admixture with excess thionyl chloride, and recovering anhydrous actinide trichloride.

  3. Methyl Bromide Poisoning

    PubMed Central

    Rathus, E. M.; Landy, P. J.

    1961-01-01

    Seven cases of methyl bromide poisoning which occurred amongst workers engaged on a fumigation project are described. The methods adopted for investigation of the environmental situation are discussed and the measurement of blood bromide levels on random samples of workers is suggested as an index of the effectiveness of equipment and working methods. PMID:13739738

  4. DEVELOPMENT OF NDA METHODS FOR NEPTUNIUM METAL

    SciTech Connect

    C. MOSS; ET AL

    2000-10-01

    Many techniques have been developed and applied in the US and other countries for the control of the special nuclear materials (SNM) plutonium and uranium, but no standard methods exist for the determination of neptunium in bulk containers. Such methods are needed because the U.S. Department of Energy requires all Government-owned {sup 237}Np be treated as if it were SNM and the International Atomic Energy Agency is considering how to monitor this material. We present the results of the measurements of several samples of neptunium metal with a variety of techniques. Analysis of passive gamma-ray spectra uniquely identifies the material, provides isotopic ratios for contaminants, such as {sup 243}Am, and may provide information about the shielding, mass, and time since processing. Active neutron interrogation, using the delayed neutron technique in a package monitor, provides useful data even if the neptunium is shielded. The tomographic gamma scanner yields a map of the distribution of the neptunium and shielding in a container. Active photon interrogation with pulses from a 10-MeV linac produces delayed neutrons between pulses, even when the container is heavily shielded. Data from one or more of these techniques can be used to identify the material and estimate a mass in a bulk container.

  5. Neptunium_Oxide_Precipitation_Kinetics_AJohnsen

    SciTech Connect

    Johnsen, A M; Roberts, K E; Prussin, S G

    2012-06-08

    We evaluate the proposed NpO{sub 2}{sup +}(aq)-NpO{sub 2}(cr) reduction-precipitation system at elevated temperatures to obtain primary information on the effects of temperature, ionic strength, O{sub 2} and CO{sub 2}. Experiments conducted on unfiltered solutions at 10{sup -4} M NpO{sub 2}{sup +}(aq), neutral pH, and 200 C indicated that solution colloids strongly affect precipitation kinetics. Subsequent experiments on filtered solutions at 200, 212, and 225 C showed consistent and distinctive temperature-dependent behavior at reaction times {le} 800 hours. At longer times, the 200 C experiments showed unexpected dissolution of neptunium solids, but experiments at 212 C and 225 C demonstrated quasi steady-state neptunium concentrations of 3 x 10{sup -6} M and 6 x 10{sup -6} M, respectively. Solids from a representative experiment analyzed by X-ray diffraction were consistent with NpO{sub 2}(cr). A 200 C experiment with a NaCl concentration of 0.05 M showed a dramatic increase in the rate of neptunium loss. A 200 C experiment in an argon atmosphere resulted in nearly complete loss of aqueous neptunium. Previously proposed NpO{sub 2}{sup +}(aq)-NpO{sub 2}(cr) reduction-precipitation mechanisms in the literature specified a 1:1 ratio of neptunium loss and H{sup +} production in solution over time. However, all experiments demonstrated ratios of approximately 0.4 to 0.5. Carbonate equilibria can account for only about 40% of this discrepancy, leaving an unexpected deficit in H+ production that suggests that additional chemical processes are occurring.

  6. DISSOLUTION OF NEPTUNIUM OXIDE RESIDUES

    SciTech Connect

    Kyser, E

    2009-01-12

    This report describes the development of a dissolution flowsheet for neptunium (Np) oxide (NpO{sub 2}) residues (i.e., various NpO{sub 2} sources, HB-Line glovebox sweepings, and Savannah River National Laboratory (SRNL) thermogravimetric analysis samples). Samples of each type of materials proposed for processing were dissolved in a closed laboratory apparatus and the rate and total quantity of off-gas were measured. Samples of the off-gas were also analyzed. The quantity and type of solids remaining (when visible) were determined after post-dissolution filtration of the solution. Recommended conditions for dissolution of the NpO{sub 2} residues are: Solution Matrix and Loading: {approx}50 g Np/L (750 g Np in 15 L of dissolver solution), using 8 M nitric acid (HNO{sub 3}), 0.025 M potassium fluoride (KF) at greater than 100 C for at least 3 hours. Off-gas: Analysis of the off-gas indicated nitric oxide (NO), nitrogen dioxide (NO{sub 2}) and nitrous oxide (N{sub 2}O) as the only identified components. No hydrogen (H{sub 2}) was detected. The molar ratio of off-gas produced per mole of Np dissolved ranged from 0.25 to 0.4 moles of gas per mole of Np dissolved. A peak off-gas rate of {approx}0.1 scfm/kg bulk oxide was observed. Residual Solids: Pure NpO{sub 2} dissolved with little or no residue with the proposed flowsheet but the NpCo and both sweepings samples left visible solid residue after dissolution. For the NpCo and Part II Sweepings samples the residue amounted to {approx}1% of the initial material, but for the Part I Sweepings sample, the residue amounted to {approx}8 % of the initial material. These residues contained primarily aluminum (Al) and silicon (Si) compounds that did not completely dissolve under the flowsheet conditions. The residues from both sweepings samples contained minor amounts of plutonium (Pu) particles. Overall, the undissolved Np and Pu particles in the residues were a very small fraction of the total solids.

  7. New neptunium(V) borates that exhibit the alexandrite effect.

    PubMed

    Wang, Shuao; Alekseev, Evgeny V; Depmeier, Wulf; Albrecht-Schmitt, Thomas E

    2012-01-01

    A new neptunium(V) borate, K[(NpO(2))B(10)O(14)(OH)(4)], was synthesized using boric acid as a reactive flux. The compound possesses a layered structure in which Np(V) resides in triangular holes, creating a hexagonal-bipyramidal environment around neptunium. This compound is unusual in that it exhibits the Alexandrite effect, a property that is typically restricted to neptunium(IV) compounds. PMID:22145669

  8. Investigation of Neptunium Precipitator Cleanout Options

    SciTech Connect

    Hill, B.C.

    2003-09-08

    Oxalate precipitation followed by filtration is used to prepare plutonium oxalate. Historically, plutonium oxalate has tended to accumulate in the precipitation tanks. These solids are periodically removed by flushing with concentrated (64 percent) nitric acid. The same precipitation tanks will now be used in the processing of neptunium. Literature values indicate that neptunium oxalate may not be as soluble as plutonium oxalate in nitric acid. Although a wide variety of options is available to improve neptunium oxalate solubility for precipitator flushing, most of these options are not practical for use. Many of these options require the use of incompatible or difficult to handle chemicals. Other options would require expensive equipment modifications or are likely to lead to product contamination. Based on review of literature and experimental results, the two best options for flushing the precipitator are (1) 64 percent nitric acid and (2) addition of sodium permanganate follow ed by sodium nitrite. Nitric acid is the easiest option to implement. It is already used in the facility and will not lead to product contamination. Experimental results indicate that neptunium oxalate can be dissolved in concentrated nitric acid (64 percent) at 60 degree C to a concentration of 2.6 to 5.6 grams of Np/liter after at least three hours of heating. A lower concentration (1.1 grams of Np/liter) was measured at 60 degree C after less than two hours of heating. These concentrations are acceptable for flushing if precipitator holdup is low (approximately 100-250 grams), but a second method is required for effective flushing if precipitator holdup is high (approximately 2 kilograms). The most effective method for obtaining higher neptunium concentrations is the use of sodium permanganate followed by the addition of sodium nitrite. There is concern that residual manganese from these flushes could impact product purity. Gas generation during permanganate addition is also a concern

  9. Incorporation of neptunium(VI) into a uranyl selenite.

    PubMed

    Meredith, Nathan A; Polinski, Matthew J; Lin, Jian; Simonetti, Antonio; Albrecht-Schmitt, Thomas E

    2012-10-15

    The incorporation of neptunium(VI) into the layered uranyl selenite Cs[(UO(2))(HSeO(3))(SeO(3))] has yielded the highest level of neptunium uptake in a uranyl compound to date with an average of 12(±3)% substitution of Np(VI) for U(VI). Furthermore, this is the first case in nearly 2 decades of dedicated incorporation studies in which the oxidation state of neptunium has been determined spectroscopically in a doped uranyl compound and also the first time in which neptunium incorporation has resulted in a structural transformation. PMID:23030830

  10. High temperature adsorption process for solidification of plutonium and neptunium

    SciTech Connect

    Korchenkin, K.; Mashkin, A.; Nardova, A.

    1995-12-31

    The problem of plutonium and neptunium converting into solid form has been considered. It was recently been discovered that plutonium and neptunium absorbed well on inorganic porous matrices (silica gel) under definite conditions. In the work presented in this paper plutonium and neptunium sorption on silica gel followed by calcining saturated granules was experimentally investigated. Calcination may proceed at the different temperatures to give the solid dustless plutonium and neptunium compounds suitable both for controlled temporary storage (with possible return radionuclides in nuclear fuel cycle) and for long life disposal.

  11. Neptunium flow-sheet verification at reprocessing plants

    SciTech Connect

    Rance, P.; Chesnay, B.; Killeen, T.; Murray, M.; Nikkinen, M.; Petoe, A.; Plumb, J.; Saukkonen, H.

    2007-07-01

    Due to their fissile nature, neptunium and americium have at least a theoretical potential application as nuclear explosives and their proliferation potential was considered by the IAEA in studies in the late 1990's. This work was motivated by an increased awareness of the proliferation potential of americium and neptunium and a number of emerging projects in peaceful nuclear programmes which could result in an increase in the available quantities of these minor actinides. The studies culminated in proposals for various voluntary measures including the reporting of international transfers of separated americium and neptunium, declarations concerning the amount of separated neptunium and americium held by states and the application of flow-sheet verification to ensure that facilities capable of separating americium or neptunium are operated in a manner consistent with that declared. This paper discusses the issue of neptunium flowsheet verification in reprocessing plants. The proliferation potential of neptunium is first briefly discussed and then the chemistry of neptunium relevant to reprocessing plants described with a view to indicating a number of issues relevant to the verification of neptunium flow-sheets. Finally, the scope of verification activities is discussed including analysis of process and engineering design information, plant monitoring and sampling and the potential application of containment and surveillance measures. (authors)

  12. Dissolution of Neptunium Oxide in Unirradiated Mark 53 Targets

    SciTech Connect

    Rudisill, T.S.

    2002-12-06

    Nine unirradiated Mark 53 targets currently stored at the K-Reactor must be dissolved to allow recovery of the neptunium content. The Mark 53 targets are an aluminum clad, neptunium oxide (NpO2)/aluminum metal cermet used for the production of plutonium-238. The targets will be dissolved in H-Canyon and blended with solutions generated from routine fuel dissolutions for purification by solvent extraction. The increased neptunium concentration should not have a significant effect on the neptunium decontamination factor achieved by the 1st cycle of solvent extraction; however, the neptunium content of the uranium product (1CU) will likely increase in proportion to the increase in the neptunium feed concentration. The recovered neptunium will be combined with the existing inventory of neptunium solution currently stored in H-Canyon. The combined inventory will undergo subsequent purification and conversion to an oxide for shipment to the Oak Ridge National Laboratory where plutonium- 238 will be manufactured using the High Flux Isotope Reactor.

  13. Comparison of neptunium sorption results using batch and column techniques

    SciTech Connect

    Triay, I.R.; Furlano, A.C.; Weaver, S.C.; Chipera, S.J.; Bish, D.L.

    1996-08-01

    We used crushed-rock columns to study the sorption retardation of neptunium by zeolitic, devitrified, and vitric tuffs typical of those at the site of the potential high-level nuclear waste repository at Yucca Mountain, Nevada. We used two sodium bicarbonate waters (groundwater from Well J-13 at the site and water prepared to simulate groundwater from Well UE-25p No. 1) under oxidizing conditions. It was found that values of the sorption distribution coefficient, Kd, obtained from these column experiments under flowing conditions, regardless of the water or the water velocity used, agreed well with those obtained earlier from batch sorption experiments under static conditions. The batch sorption distribution coefficient can be used to predict the arrival time for neptunium eluted through the columns. On the other hand, the elution curves showed dispersivity, which implies that neptunium sorption in these tuffs may be nonlinear, irreversible, or noninstantaneous. As a result, use of a batch sorption distribution coefficient to calculate neptunium transport through Yucca Mountain tuffs would yield conservative values for neptunium release from the site. We also noted that neptunium (present as the anionic neptunyl carbonate complex) never eluted prior to tritiated water, which implies that charge exclusion does not appear to exclude neptunium from the tuff pores. The column experiments corroborated the trends observed in batch sorption experiments: neptunium sorption onto devitrified and vitric tuffs is minimal and sorption onto zeolitic tuffs decreases as the amount of sodium and bicarbonate/carbonate in the water increases.

  14. PERFORMANCE OF THE SAVANNAH RIVER SITE COULOMETER FOR NEPTUNIUM PROCESSACCOUNTABILITY AND NEPTUNIUM OXIDE PRODUCT CHARACTERIZATION

    SciTech Connect

    Holland, M; Patterson Nuessle, P; Sheldon Nichols, S; Joe Cordaro, J; George Reeves, G

    2008-06-04

    The Savannah River Site's (SRS) H-Area B-Line (HB-Line) nuclear facility is processing neptunium solutions for stabilization as an oxide. The oxide will eventually be reprocessed and fabricated into target material and the 237Np irradiated to produce {sup 238}Pu in support of National Aeronautics and Space Administration space program missions. As part of nuclear materials accountability, solution concentrations were measured using a high-precision controlled-potential coulometer developed and manufactured at the SRS for plutonium accountability measurements. The Savannah River Site Coulometer system and measurement methodology for plutonium meets performance standards in ISO 12183-2005, 'Controlled-Potential Coulometric Assay of Plutonium'. The Department of Energy (DOE) does not produce or supply a neptunium metal certified reference material, which makes qualifying a measurement method and determining accuracy and precision difficult. Testing and performance of the Savannah River Site Coulometer indicates that it can be used to measure neptunium process solutions and dissolved neptunium oxide without purification for material control and accountability purposes. Savannah River Site's Material Control and Accountability organization has accepted the method uncertainty for accountability and product characterization measurements.

  15. Transport of neptunium through Yucca Mountain tuffs

    SciTech Connect

    Triay, I.R.; Robinson, B.A.; Mitchell, A.J.; Overly, C.M.; Lopez, R.M.

    1993-12-31

    Neptunium has a high solubility in groundwaters from Yucca Mountain. Uranium in nuclear reactors produces {sup 237}Np which has a half-life of 2.14 {times} 10{sup 6} years. Consequently, the transport of {sup 237}Np through tuffs is of major importance in assessing the performance of a high-level nuclear waste repository at Yucca Mountain. The objective of this work is to determine the amount of Np retardation that is provided by the materials in Yucca Mountain tuffs as a function of groundwater chemistry.

  16. The production of Neptunium-236g.

    PubMed

    Jerome, S M; Ivanov, P; Larijani, C; Parker, D J; Regan, P H

    2014-12-01

    Radiochemical analysis of (237)Np is important in a number of fields, such as nuclear forensics, environmental analysis and measurements throughout the nuclear fuel cycle. However analysis is complicated by the lack of a stable isotope of neptunium. Although various tracers have been used, including (235)Np, (239)Np and even (236)Pu, none are entirely satisfactory. However, (236g)Np would be a better candidate for a neptunium yield tracer, as its long half-life means that it is useable as both a radiometric and mass spectrometric measurements. This radionuclide is notoriously difficult to prepare, and limited in scope. In this paper, we examine the options for the production of (236g)Np, based on work carried out at NPL since 2011. However, this work was primarily aimed at the production of (236)Pu, and not (236g)Np and therefore the rate of production are based on the levels of (236)Pu generated in the irradiation of (i) (238)U with protons, (ii) (235)U with deuterons, (iii) (236)U with protons and (iv) (236)U with deuterons. The derivation of a well-defined cross section is complicated by the relevant paucity of information on the variation of the (236m)Np:(236g)Np production ratio with incident particle energy. Furthermore, information on the purity of (236g)Np so produced is similarly sparse. Accordingly, the existing data is assessed and a plan for future work is presented. PMID:24731718

  17. Neptunium(III) application in extraction chromatography.

    PubMed

    Guérin, Nicolas; Nadeau, Kenny; Larivière, Dominic

    2011-12-15

    This paper describes a novel strategy for actinide separation by extraction chromatography with Np(III) valence adjustment. Neptunium(IV) was reduced to Np(III) using Cr(II) and then selectively separated from uranium (IV) on a TEVA resin. After elution, Np(III) was retained on a DGA resin in order to remove any detrimental chromium impurities. Neptunium(III) formation was demonstrated by the complete and selective elution of Np from TEVA resin (99 ± 7%) in less than 12 mL of 9M HCl from U(IV) (0.7 ± 0.7%). It was determined by UV-visible and kinetic studies that Cr(II) was the only species responsible for the elution of Np(IV) as Np(III) and that the Cr(II) solution could be prepared from 2 to 30 min before its use without the need of complex degassing systems to prevent the oxidation of Np(III) by oxygen. The methodology proposed here with TEVA/DGA resins provides removal of Cr(III) impurities produced at high decontamination factors (2.8 × 10(3) and 7.3 × 10(4) respectively). PMID:22099641

  18. Neptunium Binding Kinetics with Arsenazo(III)

    SciTech Connect

    Leigh R. Martin; Aaron T. Johnson; Stephen P. Mezyk

    2014-08-01

    This document has been prepared to meet FCR&D level 2 milestone M2FT-14IN0304021, “Report on the results of actinide binding kinetics with aqueous phase complexants” This work was carried out under the auspices of the Thermodynamics and Kinetics of Advanced Separations Systems FCR&D work package. The report details kinetics experiments that were performed to measure rates of aqueous phase complexation for pentavalent neptunium with the chromotropic dye Arsenazo III (AAIII). The studies performed were designed to determine how pH, ionic strength and AAIII concentration may affect the rate of the reaction. A brief comparison with hexavalent neptunium is also made. It was identified that as pH was increased the rate of reaction also increased, however increasing the ionic strength and concentration of AAIII had the opposite effect. Interestingly, the rate of reaction of Np(VI) with AAIII was found to be slower than that of the Np(V) reaction.

  19. Surface Complexation of Neptunium(V) with Goethite

    SciTech Connect

    Jerden, James L.; Kropf, A. Jeremy

    2007-07-01

    Batch adsorption experiments in which neptunium-bearing solutions were reacted with goethite (alpha-FeOOH) have been performed to study uptake mechanisms in sodium chloride and calcium-bearing sodium silicate solutions. This paper presents results identifying and quantifying the mechanisms by which neptunium is adsorbed as a function of pH and reaction time (aging). Also presented are results from tests in which neptunium is reacted with goethite in the presence of other cations (uranyl and calcium) that may compete with neptunium for sorption sites. The desorption of neptunium from goethite has been studied by re-suspending the neptunium-loaded goethite samples in solutions containing no neptunium. Selected reacted sorbent samples were analyzed by x-ray absorption spectroscopy (XAS) to determine the oxidation state and molecular speciation of the adsorbed neptunium. Results have been used to establish the pH adsorption edge of neptunium on goethite in sodium chloride and calcium-bearing sodium silicate solutions. The results indicate that neptunium uptake on goethite reaches 95% at a pH of approximately 7 and begins to decrease at pH values greater than 8.5. Distribution coefficients for neptunium sorption range from less than 1000 (moles/kg){sub sorbed} / (moles/kg){sub solution} at pH less than 5.0 to greater than 10,000 (moles/kg){sub sorbed} / (moles/kg){sub solution} at pH greater than 7.0. Distribution coefficients as high as 100,000 (moles/kg){sub sorbed} / (moles/kg){sub solution} were recorded for the tests done in calcite equilibrated sodium silicate solutions. XAS results show that neptunium complexes with the goethite surface mainly as Np(V) (although Np(IV) is prevalent in some of the longer-duration sorption tests). The neptunium adsorbed to goethite shows Np-O bond length of approximately 1.8 angstroms which is representative of the Np-O axial bond in the neptunyl(V) complex. This neptunyl(V) ion is coordinated to 5 or 6 equatorial oxygens with Np

  20. Bromide affecting drinking water mutagenicity.

    PubMed

    Myllykangas, T; Nissinen, T K; Mäki-Paakkanen, J; Hirvonen, A; Vartiainen, T

    2003-11-01

    The effect of bromide on the mutagenicity of artificially recharged groundwater and purified artificially recharged groundwater after chlorine, ozone, hydrogen peroxide, permanganate, and UV treatments alone and in various combinations was studied. The highest mutagenicity was observed after chlorination, while hydrogen peroxide-ozone-chlorine treatment produced the lowest value for both waters. Chlorinated waters, which were spiked with bromide, had up to 3.7 times more mutagenic activity than waters without bromide after every preoxidation method. 3-Chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX) was found to correspond as much as 76% of the overall mutagenicity in the waters not spiked with bromide. MX formation was found to be lower when the treated water contained bromide, implicating the formation of brominated MX analogues. Trihalomethane formation increased when the treated water contained bromide. PMID:13129514

  1. Dissolution of Neptunium Oxide in Unirradiated Mark 53 Targets

    SciTech Connect

    Rudisill, T.S.

    2002-06-07

    Nine unirradiated Mark 53 targets currently stored at the K-Reactor must be dissolved to allow recovery of the neptunium content. The Mark 53 targets are an aluminum clad neptunium oxide (NpO2)/aluminum metal cermet used for the production of plutonium-238. The targets will be dissolved in H-Canyon and blended with solutions generated from routine fuel dissolutions for purification by solvent extraction

  2. Neptunium Disposal to the Savannah River Site Tank Farm

    SciTech Connect

    Walker, D.D.

    2004-02-26

    Researchers investigated the neutralization of an acidic neptunium solution from a Savannah River Site (SRS) processing canyon and the properties of the resulting slurry to determine the feasibility of disposal in the SRS tank farm. The acidic solution displayed no properties that precluded the proposed disposal route. Neutralization of the acidic neptunium forms a 4 wt per cent slurry of precipitated metal hydroxides. The insoluble solids consist largely of iron (92 per cent) and neptunium hydroxides (2 per cent). The concentration of soluble neptunium remaining after neutralization equaled much less than previous solubility measurements predicted. Researchers used an apparatus similar to an Ostwald-type viscometer to estimate the consistency of the neptunium slurry with the solids present. The yield stress and consistency of the 4 wt per cent slurry will allow transfer through the tank farm, although concentration of the insoluble solids above 4 wt per cent may cause significant problems due to increased consistency and yield stress. The consistency of the 4 wt per cent slurry is 7.6 centipoise (cP) with a yield stress less than 1 Pascal (Pa). The neptunium slurry, when combined with actual washed radioactive sludge, slightly reduces the yield stress and consistency of the sludge and produces a combined slurry with acceptable rheological properties for vitrification.

  3. Neptunium(III) copper(I) diselenide

    PubMed Central

    Wells, Daniel M.; Skanthakumar, S.; Soderholm, L.; Ibers, James A.

    2009-01-01

    The title compound, NpCuSe2, is the first ternary neptunium transition-metal chalcogenide. It was synthesized from the elements at 873 K in an evacuated fused-silica tube. Single crystals were grown by vapor transport with I2. NpCuSe2 crystallizes in the LaCuS2 structure type and can be viewed as a stacking of layers of CuSe4 tetra­hedra and of double layers of NpSe7 monocapped trigonal prisms along [100]. Because there are no Se—Se bonds in the structure, the formal oxidation states of Np/Cu/Se may be assigned as +III/+I/−II, respectively. PMID:21582032

  4. Aqueous Zinc Bromide Waste Solidification

    SciTech Connect

    Langton, C.A.

    2002-07-23

    The goal of this study was to select one or more commercially available aqueous sorbents to solidify the zinc bromide solution stored in C-Area, identify the polymer to zinc bromide solution ratio (waste loading) for the selected sorbents, and identify processing issues that require further testing in pilot-scale testing.

  5. Tiotropium Bromide: An Update

    PubMed Central

    Heredia, Josep Lluis

    2009-01-01

    Tiotropium bromide is a once-daily inhaled anticholinergic bronchodilator. It works by blocking the muscarinic receptors in airway smooth muscle. Tiotropium has a wide therapeutic margin, due to its poor gastrointestinal absorption and its very low systemic bioavailability. The drug is mainly indicated in COPD patients. Clinically relevant outcomes such as significant improvements in spirometry, hyperinflation, dyspnea, heath status, acute exacerbations and mortality have been consistently observed in tiotropium clinical trials, and the drug has been shown to reduce the risk of mortality due to cardiac-vascular disease and respiratory failure. The main side effect reported is dryness of the mouth. Some subgroups of asthmatics also seem to respond to anticholinergic drugs: among them, those with the Arg/Arg genotype for the β2-adrenergic receptor and those with a high percentage of neutrophils in sputum. PMID:19461900

  6. Gas Generation Testing of Neptunium Oxide at Elevated Temperature

    SciTech Connect

    Duffey, JM

    2004-01-30

    Elevated temperature gas generation tests have been conducted using neptunium dioxide produced on a laboratory scale using the HB-Line Phase II flowsheet. These tests were performed to determine what effect elevated temperatures would have on the neptunium dioxide in comparison to neptunium dioxide tested at ambient temperature. The headspace gas compositions following storage at elevated temperatures associated with normal conditions of transport (NCT) have been measured. These test results show an increase in hydrogen generation rate at elevated temperature and significant removal of oxygen from the headspace gas. The elevated temperature gas generation tests described in this report involved heating small test vessels containing neptunium dioxide and measuring the headspace gas pressure and composition at the end of the test period. Four samples were used in these tests to evaluate the impact of process variables on the gas generation rate. Two samples were calcined to 600 degrees Celsius and two were calcined to 650 degrees Celsius. Each test vessel contained approximately 9.5 g of neptunium dioxide. Following exposure to 75 per cent relative humidity (RH) for five days, these samples were loaded in air and then heated to between 105 and 115 degrees Celsius for about one month. At the conclusion of the test period, the headspace gas of each container was analyzed using a micro-gas chromatograph installed in the glovebox where the experiments were conducted. The pressure, volume, and composition data for the headspace gas samples were used to calculate average H2 generation rates.

  7. Modified Purex first-cycle extraction for neptunium recovery

    SciTech Connect

    Dinh, Binh; Moisy, Philippe; Baron, Pascal; Calor, Jean-Noel; Espinoux, Denis; Lorrain, Brigitte; Benchikouhne-Ranchoux, Magali

    2008-07-01

    A new PUREX first-cycle flowsheet was devised to enhance the extraction yield of neptunium at the extraction step of this cycle. Simulation results (using a qualified process-simulation tool), le d to raising the nitric acid concentration of the feed from 3 M to 4.5 M to allow extraction of more than 99% of the neptunium. This flowsheet was operated in the shielded process cell of ATALANTE facility using pulsed columns and mixer-settlers banks. A 15 kg quantity of genuine oxide fuel of average burn up of 52 GWd/t with cooling time of nearly five years was treated, and the neptunium extraction yield obtained was greater than 99.6%. (authors)

  8. Neptunium(V) Incorporation/Sorption with Uranium(VI) Alteration Products

    SciTech Connect

    Friese, Judah I.; Douglas, Matthew; Buck, Edgar C.; Clark, Susan B.; Hanson, Brady D.

    2004-04-01

    An initial uranium phase that has been observed to form during the corrosion of spent nuclear fuel is the uranium oxy-hydroxide metaschoepite. It has been proposed that neptunium(V) solubility can be limited by its association with this uranium phase. Metaschoepite has been synthesized in the presence of neptunium(V) over the pH range modeled in the proposed Yucca Mountain geologic repository. Uranium (VI) phaseswere synthesized by varying pH and neptunium concentrations. Results of neptunium association with the uranium alteration phases are presented and the relationship to dissolved neptunium concentrations discussed.

  9. Effect of natural organic materials on cadmium and neptunium sorption

    SciTech Connect

    Kung, K.S.; Triay, I.R.

    1994-10-01

    In a batch sorption study of the effect of naturally occurring organic materials on the sorption of cadmium and neptunium on oxides and tuff surfaces, the model sorbents were synthetic goethite, boehmite, amorphous silicon oxides, and a crushed tuff material from Yucca Mountain, Nevada. An amino acid, 3-(3,4-dihydroxypheny)-DL-alanine (DOPA), and an aquatic-originated fulvic material, Nordic aquatic fulvic acid (NAFA), were used as model organic chemicals. Sorption isotherm results showed that DOPA sorption followed the order aluminum oxide > iron oxide > silicon oxide and that the amount of DOAP sorption for a given sorbent increased as the solution pH was raised. The sorption of cadmium and neptunium on the iron oxide was about ten times higher than that on the aluminum oxide. The sorption of cadmium and neptunium on natural tuff material was much lower than that on aluminum and iron oxides. The sorption of cadmium on iron and aluminum oxides was found to be influenced by the presence of DOPA, and increasing the amount of DOPA coating resulted in higher cadmium sorption on aluminum oxide. However, for iron oxide, cadmium sorption decreased with increasing DOPA concentration. The presence of the model organic materials DOPA and NAFA did not affect the sorption of neptunium on tuff material or on the iron and aluminum oxides. Spectroscopic results indicate that cadmium complexes strongly with DOPA. Therefore, the effect of the organic material, DOPA, on the cadmium sorption is readily observed. However, neptunium is possibly complexed weakly with organic material. Thus, DOPA and NAFA have little effect on neptunium sorption on all sorbents selected for study.

  10. Neptunium redox speciation at the illite surface

    NASA Astrophysics Data System (ADS)

    Marsac, Rémi; Banik, Nidhu lal; Lützenkirchen, Johannes; Marquardt, Christian Michael; Dardenne, Kathy; Schild, Dieter; Rothe, Joerg; Diascorn, Alexandre; Kupcik, Tomas; Schäfer, Thorsten; Geckeis, Horst

    2015-03-01

    Neptunium (Np(V)) sorption onto a purified illite is investigated as a function of pH (3-10) and [NpVO2+]tot(3 × 10-8-3 × 10-4 M) in 0.1 M NaCl under Ar atmosphere. After about one week reaction time, only insignificant variation of Np sorption is observed and the establishment of reaction equilibrium can be assumed. Surprisingly, solid-liquid distribution ratios (Rd) are clearly higher than those measured for Np(V) sorption onto illite under aerobic conditions. The observation that Rd increases with decreasing pe (pe = -log ae-) suggests partial reduction to Np(IV), although measured redox potentials (pe values) at a first glance suggest the predominance of Np(V). Reduction to Np(IV) at the illite surface could indeed be confirmed by X-ray absorption near-edge spectroscopy (XANES). Np speciation in presence of the purified Na-illite under given conditions is consistently described by applying the 2 sites protolysis non-electrostatic surface complexation and cation exchange model. Measured pe data are taken to calculate Np redox state and surface complexation constants for Np(IV) are derived by applying a data fitting procedure. Constants are very consistent with results obtained by applying an existing linear free energy relationship (LFER). Taking Np(IV) surface complexation constants into account shifts the calculated Np(V)/Np(IV) redox borderline in presence of illite surfaces by 3-5 pe units (0.2-0.3 V) towards redox neutral conditions. Our study suggests that Np(V) reduction in presence of a sorbing mineral phase is thermodynamically favored.

  11. Sasse Modeling of First Cycle Neptunium (VI) Recovery Flowsheet

    SciTech Connect

    Laurinat, J. E.

    2006-04-01

    A flowsheet has been proposed to separate neptunium from solutions in H-Canyon Tanks 16.4, 12.5, and 11.7 in the First Cycle solvent extraction banks, in which cerium(IV) (Ce(IV)) serves as an agent to oxidize neptunium to neptunium(VI) (Np(VI)). A SASSE (Spreadsheet Algorithm for Stagewise Solvent Extraction) spreadsheet model indicates that the proposed flowsheet is a feasible method for separating neptunium and uranium from sulfates, thorium, and other metal impurities. The proposed flowsheet calls for stripping the sulfates, thorium, and other metal impurities into the 1AW stream and extracting and then stripping the neptunium and uranium into the 1BP stream. SASSE predicts that separation of thorium from the other actinides can be accomplished with actinide losses of 0.01% or less. It is assumed that other metal impurities such as iron, aluminum, and fission products will follow the thorium into 1AW. Due to an organic/aqueous distribution coefficient that is close to one, SASSE predicts that plutonium(VI) (Pu(VI)) is split between the A Bank and B Bank aqueous output streams, with 27% going to 1AW and 73% going to 1BP. An extrapolated distribution coefficient based on unvalidated Ce(IV) distribution measurements at a single nitrate concentration and a comparison with thorium(IV) (Th(IV)) distributions indicates that Ce(IV) could reflux in 1B Bank. If the Ce(IV) distribution coefficient is lower than would be predicted by this single point extrapolation, but still higher than the distribution coefficient for Th(IV), then Ce(IV) would follow Np(VI) and uranium(VI) (U(VI)) into 1BP. The SASSE model was validated using data from a 1964 oxidizing flowsheet for the recovery of Np(VI) in Second Cycle. For the proposed flowsheet to be effective in recovering neptunium, the addition of approximately 0.025 M ceric ammonium nitrate (Ce(NH4)2(NO3)6) to both the 1AF and 1AS streams is required to stabilize the neptunium in the +6

  12. Precipitation of neptunium dioxide from aqueous solution

    SciTech Connect

    Roberts, K E

    1999-12-01

    Tens of thousands of metric tons of highly radioactive, nuclear waste have been generated in the US. Currently, there is no treatment or disposal facility for these wastes. Of the radioactive elements in high-level nuclear waste, neptunium (Np) is of particular concern because it has a long half-life and may potentially be very mobile in groundwaters associated with a proposed underground disposal site at Yucca Mountain, Nevada. Aqueous Np concentrations observed in previous, short-term solubility experiments led to calculated potential doses exceeding proposed long-term regulatory limits. However, thermodynamic data for Np at 25 C showed that these observed aqueous Np concentrations were supersaturated with respect to crystalline NpO{sub 2}. It was hypothesized that NpO{sub 2} is the thermodynamically stable solid phase in aqueous solution, but it is slow to form in an aqueous solution of NpO{sub 2}{sup +} on the time scale of previous experiments. The precipitation of NpO{sub 2} would provide significantly lower aqueous Np concentrations leading to calculated doses below proposed regulatory limits. To test this hypothesis, solubility experiments were performed at elevated temperature to accelerate any slow precipitation kinetics. Ionic NpO{sub 2}{sup +} (aq) was introduced into very dilute aqueous solutions of NaCl with initial pH values ranging from 6 to 10. The reaction vessels were placed in an oven and allowed to react at 200 C until steady-state aqueous Np concentrations were observed. In all cases, aqueous Np concentrations decreased significantly from the initial value of 10{sup {minus}4} M. The solids that formed were analyzed by x-ray powder diffraction, x-ray absorption spectroscopy, and scanning electron microscopy. The solids were determined to be high-purity crystals of NpO{sub 2}. This is the first time that crystalline NpO{sub 2} has been observed to precipitate from NpO{sub 2}{sup +}(aq) in near-neutral aqueous solutions. The results obtained

  13. Neptunium (VI) and neptunium (VI/V) mixed valence cluster compounds

    SciTech Connect

    May, Iain

    2008-01-01

    Neptunium has three readily accessible oxidation states, IV, V and VI, which can coexist under certain conditions, with the aqueous soluble neptunyl(V) moiety, {l_brace}NpO{sub 2}{r_brace}{sup +}, of most environmental relevance. Careful control of Np chemistry is required during actinide separation processes. In addition, the long half life of the major alpha emitting isotope ({sup 237}Np, t{sub 1/2} = 2.144 x 10{sup 6} years) renders Np a major contributor to the radiotoxicity of nuclear waste as a function of time. Significant quantities of neptunium are generated in nuclear reactors and the current surge in interest in nuclear power will lead to an increase in our need to further understand the chemistry of this element. It is clearly of importance that Np chemistry is well understood and there have been several recent investigations into the structural, spectroscopic and magnetic properties of Np compounds. However, the vast majority of this chemistry has been performed in aqueous solution, prohibiting the use of air and moisture sensitive ligands. This is in stark contrast to uranium and thorium where inert atmosphere chemistry with moisture sensitive donor ligands has flourished, yielding greater insight into the structural and electronic properties of these early actinides. For the uranyl(VI) moiety, {l_brace}UO{sub 2}{r_brace}{sup 2+}, UO{sub 2}Cl{sub 2}(thf){sub 3} (and the desolvated dimer [UO{sub 2}Cl{sub 2}(thf)]{sub 2}) have proven to be excellent moisture-free reagents for inert atmosphere uranyl chemistry. These starting reagents have been used extensively within our group to study soft donor ligand coordination in the uranyl equatorial plane and oxo-activation to Lewis acid coordination. However, until now the absence of such a starting reagent for Np has limited our ability to extend this chemistry any further across the actinide series, which is required if we are to gain a more complete understanding of 5f element chemistry. The synthesis of [Np

  14. Neptunium and plutonium complexes with a sterically encumbered triamidoamine (TREN) scaffold

    DOE PAGESBeta

    Brown, Jessie L.; Gaunt, Andrew J.; King, David M.; Liddle, Stephen T.; Reilly, Sean D.; Scott, Brian L.; Wooles, Ashley J.

    2016-03-11

    Here, the syntheses and characterization of isostructural neptunium(IV) and plutonium(IV) complexes [MIV(TRENTIPS)(Cl)] [An = Np, Pu; TRENTIPS = {N(CH2CH2NSiPri3)3}3] are reported, along with the demonstration that they are likely reduced to the corresponding neptunium(III) and plutonium(III) products [MIII(TRENTIPS)]; this chemistry provides new platforms from which to target a plethora of unprecedented molecular functionalities in transuranic chemistry and the neptunium(IV) molecule is the first structurally characterized neptunium(IV)–amide complex.

  15. Neptunium and plutonium complexes with a sterically encumbered triamidoamine (TREN) scaffold.

    PubMed

    Brown, Jessie L; Gaunt, Andrew J; King, David M; Liddle, Stephen T; Reilly, Sean D; Scott, Brian L; Wooles, Ashley J

    2016-04-01

    The syntheses and characterisation of isostructural neptunium(iv) and plutonium(iv) complexes [An(IV)(TREN(TIPS))(Cl)] [An = Np, Pu; TREN(TIPS) = {N(CH2CH2NSiPr(i)3)3}(3-)] are reported, along with the demonstration that they are likely reduced to the corresponding neptunium(iii) and plutonium(iii) products [An(III)(TREN(TIPS))]; this chemistry provides new platforms from which to target a plethora of unprecedented molecular functionalities in transuranic chemistry and the neptunium(iv) molecule is the first structurally characterised neptunium(iv)-amide complex. PMID:27009799

  16. Speciation-dependent toxicity of neptunium(V) toward chelatobacter heintzii.

    SciTech Connect

    Banaszak, J. E.; Reed, D. T.; Rittmann, B. E.; Chemical Engineering; Northwestern Univ.

    1998-04-15

    This work investigates how chemical speciation controls the toxicity of neptunium and the neptunium-NTA complex toward Chelatobacter heintzii. We studied the effect of aquo and complexed/precipitated neptunium on the growth of C. heintzii in noncomplexing glucose and phosphate-buffered nitrilotriacetic acid (NTA) growth media. Equilibrium chemical speciation modeling and absorption spectroscopy were used to link neptunium speciation to biological growth inhibition. Our results show that metal toxicity of aquo NpO{sub 2}{sup +} significantly limits the growth of C. heintzii at free metal ion concentrations greater than {approx}10{sup -5} M. However, neptunium concentrations {ge}10{sup -4} M do not cause measurable radiotoxicity effects in C. heintzii when present in the form of a neptunium-NTA complex or colloidal/precipitated neptunium phosphate. The neptunium-NTA complex, which is stable under aerobic conditions, is destabilized by microbial degradation of NTA. When phosphate was present, degradation of NTA led to the precipitation of a neptunium-phosphate phase.

  17. Bromide Adsorption by Reference Minerals and Soils

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Bromide, Br-, adsorption behavior was investigated on amorphous Al and Fe oxide, montmorillonite, kaolinite, and temperate and tropical soils. Bromide adsorption decreased with increasing solution pH with minimal adsorption occurring above pH 7. Bromide adsorption was higher for amorphous oxides t...

  18. RAPID MEASUREMENTS OF NEPTUNIUM OXIDATION STATES USING CHROMATOGRAPHIC RESINS

    SciTech Connect

    Diprete, D; C Diprete, C; Mira Malek, M; Eddie Kyser, E

    2009-03-24

    The Savannah River Site's (SRS) H-Canyon facility uses ceric ammonium nitrate (CAN) to separate impure neptunium (Np) from a high sulfate feed stream. The material is processed using a two-pass solvent extraction purification which relies on CAN to oxidize neptunium to Np(VI) during the first pass prior to extraction. Spectrophotometric oxidation-state analyses normally used to validate successful oxidation to Np(VI) prior to extraction were compromised by this feed stream matrix. Therefore, a rapid chromatographic method to validate successful Np oxidation was developed using Eichrom Industries TRU and TEVA{reg_sign} resins. The method was validated and subsequently transferred to existing operations in the process analytical laboratories.

  19. Extraction of Uranium, Neptunium and Plutonium from Caustic Media

    SciTech Connect

    Delmau, Laetitia H.; Bonnesen, Peter V.; Engle, Nancy L.; Raymond, Kenneth N.; Xu, Jade

    2004-03-28

    5 Fundamental research on uranium, neptunium and plutonium separation from alkaline media using solvent extraction is being conducted. Specific extractants for these actinides from alkaline media have been synthesized to investigate the feasibility of selective removal of these elements. Two families of extractants have been studied: terephthalamide and tetra(hydroxybenzyl)ethylene diamine derivatives. Fundamental studies were conducted to characterize their extraction behavior from a wide variety of aqueous conditions. The terephthalamide derivatives exhibit a significant extraction strength along with a discriminatory behavior among the actinides, plutonium being extracted the most strongly. Quantitative extraction of plutonium and moderate extraction of neptunium and uranium was achieved from a simple caustic solution. Interestingly, strontium is also quantitatively extracted by these derivatives. However, their stability to highly caustic solutions still needs to be imp roved. Tetra(hydroxybenzyl)ethylene diamine derivatives exhibit a very good stability to caustic conditions and are currently being studied.

  20. Possible Incorporation of Neptunium in Uranyl (VI) Alteration Phases

    SciTech Connect

    Buck, Edgar C.; McNamara, Bruce K.; Douglas, Matthew; Hanson, Brady D.

    2003-11-25

    This study examines existing data on Np behavior from both spent fuel and borosilicate glass tests in effort to resolve issues concerning the selection of possible solubility limiting phases for neptunium and the methods for detecting neptunium at low levels in spent fuel. These issues were raised in a recent report by Finch and Fortner (2002) that argues that the Np analysis with Electron Energy-Loss Spectroscopy (EELS) reported by Buck et al., (1998) is incorrect and that based on a series of experiments with Np-doped U3O8, NpO2 should be adopted as the solubility controlling phase for Np, in the Yucca Mountain performance assessment model. In this report, we will refute the claim that EELS is unable to detect Np and will suggest that the use of NpO2 as the Np solubility controlling phase is not supported by available scientific data from both spent fuel and borosilicate glass.

  1. Syntheses of neptunium trichloride and measurements of its melting temperature

    NASA Astrophysics Data System (ADS)

    Hayashi, Hirokazu; Takano, Masahide; Kurata, Masaki; Minato, Kazuo

    2013-09-01

    Neptunium trichloride (NpCl3) of high purity was synthesized by the solid state reaction of neptunium nitride with cadmium chloride. Lattice parameters of hexagonal NpCl3 were determined from the powder X-ray diffraction pattern to be a = 0.7428 ± 0.0001 nm and c = 0.4262 ± 0.0003 nm, which fairly agree with the reported values. The melting temperature of NpCl3 was measured on a sample of about 1 mg, hermetically encapsulated in a gold crucible with a differential thermal analyzer. The value determined was 1070 ± 3 K which is close to the recommended value (1075 ± 30 K) derived from the mean value of the melting temperature of UCl3 and of PuCl3.

  2. Plutonium, americium, and neptunium speciation in selected groundwaters

    USGS Publications Warehouse

    Cleveland, J.M.; Rees, T.F.; Nash, K.L.

    1985-01-01

    Speciation was determined at 25 and 90 degree C in four groundwaters from diverse sources: the Sparta aquifer in Louisiana, near the Vacherie salt dome; Mansfield No. 2 well in the Palo Duro Basin, Texas; the Stripa mine in Sweden; and the Waste Isolation Pilot Plant in New Mexico. Neptunium generally was soluble in all waters and was present exclusively as Np(V) and Np(VI), regardless of initial oxidation state. The results indicated that plutonium and neptunium solubilities were determined by the oxidation-reduction properties of the waters, i. e. , their abilities to convert these elements to soluble oxidation states. This was not the case for americium, however; Am(IV) was not detected, and the solubility of this element was determined entirely by the chemical properties of Am(III).

  3. SEPARATION OF NEPTUNIUM FROM PLUTONIUM BY CHLORINATION AND SUBLIMATION

    DOEpatents

    Fried, S.M.

    1958-11-18

    A process is described for separating neptunium from plutonium. The method consists in chlorinating a mixture of the oxides of Np and Pu by contacting the mixture with carbon tetrachloride at about 500 icient laborato C. ln this manner the Np is converted to the tetrachlorlde and the Pu converted to the trichloride. Since NpCl/sub 4/ is more latile than PuCl/sub 3/, the separation ls effected by vaporing sad subsequently condenslng the NpCl/sub 4/.

  4. Uranium and Neptunium Desorption from Yucca Mountain Alluvium

    SciTech Connect

    C.D. Scism; P.W. Reimus; M. Ding; S.J. Chipera

    2006-03-16

    Uranium and neptunium were used as reactive tracers in long-term laboratory desorption studies using saturated alluvium collected from south of Yucca Mountain, Nevada. The objective of these long-term experiments is to make detailed observations of the desorption behavior of uranium and neptunium to provide Yucca Mountain with technical bases for a more realistic and potentially less conservative approach to predicting the transport of adsorbing radionuclides in the saturated alluvium. This paper describes several long-term desorption experiments using a flow-through experimental method and groundwater and alluvium obtained from boreholes along a potential groundwater flow path from the proposed repository site. In the long term desorption experiments, the percentages of uranium and neptunium sorbed as a function of time after different durations of sorption was determined. In addition, the desorbed activity as a function of time was fit using a multi-site, multi-rate model to demonstrate that different desorption rate constants ranging over several orders of magnitude exist for the desorption of uranium from Yucca Mountain saturated alluvium. This information will be used to support the development of a conceptual model that ultimately results in effective K{sub d} values much larger than those currently in use for predicting radionuclide transport at Yucca Mountain.

  5. XAS and TRLIF spectroscopy of uranium and neptunium in seawater.

    PubMed

    Maloubier, Melody; Solari, Pier Lorenzo; Moisy, Philippe; Monfort, Marguerite; Den Auwer, Christophe; Moulin, Christophe

    2015-03-28

    Seawater contains radionuclides at environmental levels; some are naturally present and others come from anthropogenic nuclear activity. In this report, the molecular speciation in seawater of uranium(VI) and neptunium(V) at a concentration of 5 × 10(-5) M has been investigated for the first time using a combination of two spectroscopic techniques: Time-resolved laser-induced fluorescence (TRLIF) for U and extended X-ray absorption fine structure (EXAFS) for U and Np at the LIII edge. In parallel, the theoretical speciation of uranium and neptunium in seawater at the same concentration is also discussed and compared to spectroscopic data. The uranium complex was identified as the neutral carbonato calcic complex UO2(CO3)3Ca2, which has been previously described in other natural systems. In the case of neptunium, the complex identified is mainly a carbonato complex whose exact stoichiometry is more difficult to assess. The knowledge of the actinide molecular speciation and reactivity in seawater is of fundamental interest in the particular case of uranium recovery and more generally regarding the actinide life cycle within the biosphere in the case of accidental release. This is the first report of actinide direct speciation in seawater medium that can complement inventory data. PMID:25689216

  6. Neptunium multipoles and resonant x-ray Bragg diffraction by neptunium dioxide (NpO2)

    NASA Astrophysics Data System (ADS)

    Lovesey, S. W.; Detlefs, C.; Rodríguez-Fernández, A.

    2012-06-01

    The low-temperature ordered state of neptunium dioxide (NpO2) remains enigmatic. After decades of experimental and theoretical efforts, long-range order of a time-odd (magnetic) high-order atomic multipole moment is now generally considered to be the fundamental order parameter, the most likely candidate being a magnetic triakontadipole (rank 5). To date, however, direct experimental observation of the primary order parameter remains outstanding. In the light of new experimental findings, we re-examine the effect of crystal symmetry on the atomic multipoles and the resulting x-ray resonant scattering signature. Our simulations use the crystallographic point group \\bar {3}m (D3d), because corresponding magnetic groups \\bar {3}{m}^{\\prime}, {\\bar {3}}^{\\prime}{m}^{\\prime} and {\\bar {3}}^{\\prime}m are shown by us to be at odds with a wealth of experimental results. In addition to the previously observed (secondary) quadrupole order, we derive expressions for higher-order multipoles that might be observed in future experiments. In particular, magnetic octupole moments are predicted to contribute to Np M2,3 and L2,3 resonant scattering via E2-E2 events. The Lorentzian-squared lineshape observed at the M4 resonance is shown to be the result of the anisotropy of the 3p3/2 core levels. Quantitative comparison of our calculations to the measured data yields a core-hole width Γ = 2.60(7) eV and a core-state exchange energy \\vert \\varepsilon (\\frac{1}{2})\\vert =0.7 6(2) eV.

  7. Neptunium multipoles and resonant x-ray Bragg diffraction by neptunium dioxide (NpO2).

    PubMed

    Lovesey, S W; Detlefs, C; Rodríguez-Fernández, A

    2012-06-27

    The low-temperature ordered state of neptunium dioxide (NpO(2)) remains enigmatic. After decades of experimental and theoretical efforts, long-range order of a time-odd (magnetic) high-order atomic multipole moment is now generally considered to be the fundamental order parameter, the most likely candidate being a magnetic triakontadipole (rank 5). To date, however, direct experimental observation of the primary order parameter remains outstanding. In the light of new experimental findings, we re-examine the effect of crystal symmetry on the atomic multipoles and the resulting x-ray resonant scattering signature. Our simulations use the crystallographic point group ̅3m (D(3d)), because corresponding magnetic groups ̅3m', ̅3'm', and ̅3'm are shown by us to be at odds with a wealth of experimental results. In addition to the previously observed (secondary) quadrupole order, we derive expressions for higher-order multipoles that might be observed in future experiments. In particular, magnetic octupole moments are predicted to contribute to Np M(2,3) and L(2,3) resonant scattering via E2–E2 events. The Lorentzian-squared lineshape observed at the M(4) resonance is shown to be the result of the anisotropy of the 3p(3/2) core levels. Quantitative comparison of our calculations to the measured data yields a core–hole width Γ = 2.60(7) eV and a core-state exchange energy [absolute value]ε(1/2)[absolute value] = 0.76(2) eV. PMID:22652978

  8. Re-evaluating neptunium in uranyl phases derived from corroded spent fuel.

    SciTech Connect

    Fortner, J. A.; Finch, R. J.; Kropf, A. J.; Cunnane, J. C.; Chemical Engineering

    2004-11-01

    Interest in mechanisms that may control radioelement release from corroded commercial spent nuclear fuel (CSNF) has been heightened by the selection of the Yucca Mountain site in Nevada as the repository for high-level nuclear waste in the United States. Neptunium is an important radionuclide in repository models owing to its relatively long half-life and its high aqueous mobility as neptunyl [Np(V)O+2]. The possibility of neptunium sequestration into uranyl alteration phases produced by corroding CSNF would suggest-a process for lowering neptunium concentration and subsequent migration from a geologic repository. However, there remains little experimental evidence that uranyl compounds will, in fact, serve as long-term host phases for the retention of neptunium under conditions expected in a deep geologic repository. To directly explore this possibility, we examined specimens of uranyl alteration phases derived from humid-air-corroded CSNF by X-ray absorption spectroscopy to better determine neptunium uptake in these phases. Although neptunium fluorescence was readily observed from as-received CSNF, it was not observed from the uranyl alteration rind. We establish upper limits for neptunium incorporation into CSNF alteration phases that are significantly below previously reported concentrations obtained by using electron energy loss spectroscopy (EELS). We attribute the discrepancy to a plural-scattering event that creates a spurious EELS peak at the neptunium-MV energy.

  9. Re-Evaluating Neptunium in Uranyl Phases Derived from Corroded Spent Fuel

    SciTech Connect

    Fortner, Jeffrey A.; Finch, Robert J.; Kropf, A. Jeremy; Cunnane, James C.

    2004-11-15

    Interest in mechanisms that may control radioelement release from corroded commercial spent nuclear fuel (CSNF) has been heightened by the selection of the Yucca Mountain site in Nevada as the repository for high-level nuclear waste in the United States. Neptunium is an important radionuclide in repository models owing to its relatively long half-life and its high aqueous mobility as neptunyl [Np(V)O{sub 2}{sup +}]. The possibility of neptunium sequestration into uranyl alteration phases produced by corroding CSNF would suggest a process for lowering neptunium concentration and subsequent migration from a geologic repository. However, there remains little experimental evidence that uranyl compounds will, in fact, serve as long-term host phases for the retention of neptunium under conditions expected in a deep geologic repository. To directly explore this possibility, we examined specimens of uranyl alteration phases derived from humid-air-corroded CSNF by X-ray absorption spectroscopy to better determine neptunium uptake in these phases. Although neptunium fluorescence was readily observed from as-received CSNF, it was not observed from the uranyl alteration rind. We establish upper limits for neptunium incorporation into CSNF alteration phases that are significantly below previously reported concentrations obtained by using electron energy loss spectroscopy (EELS). We attribute the discrepancy to a plural-scattering event that creates a spurious EELS peak at the neptunium-M{sub V} energy.

  10. Evaluation of the Effects of Tank 50H Solids on Dissolved Uranium, Plutonium and Neptunium

    SciTech Connect

    Oji, L.N.

    2003-12-02

    The study of the effects of contacting a simulated salt solution spiked with uranium, plutonium, and neptunium with Tank 50H solids. General findings include: There is no evidence for interaction between Tank 50H solids and uranium from the spiked salt solution. Lack of uranium removal may reflect prior removal of uranium. There is evidence for interaction between Tank 50H solids with plutonium and neptunium as evidenced by loss of these two actinides from the salt solution. The amount of plutonium and neptunium lost from solution increased with an increase in the quantity of Tank 50H solids for a fixed simulant volume. The removal of plutonium and neptunium fit typical sorption isotherms allowing development of loading curves for estimating maximum solids loading. The maximum loading capacities for plutonium and neptunium in the simulants are, respectively, 2.01 and 4.48 micrograms per gram of Tank 50H solids. The oxalate in the Tank 50H solids is not directly responsible for the loss of plutonium and neptunium from the salt solution. The removal of plutonium and neptunium may be attributed to other minor components of the Tank 50H solids. We recommend additional testing to identify the component responsible for the plutonium and neptunium removal.

  11. Neptunium and americium speciation in selected basalt, granite, shale, and tuff ground waters

    USGS Publications Warehouse

    Cleveland, J.M.; Rees, T.F.; Nash, K.L.

    1983-01-01

    Neptunium and americium are relatively insoluble in ground waters containing high sulfate concentrations, particularly at 90??C. The insoluble neptunium species is Np(IV); hence reducing waters should enhance its formation. Americium can exist only in the trivalent state under these conditions, and its solubility also should be representative of that of curium.

  12. Chemical Speciation of Neptunium in Spent Fuel. 1st Progress Report

    SciTech Connect

    Czerwinski, Ken; Sherman, Christi; Reed, Don

    2000-03-02

    This project will examine the chemical speciation of neptunium in spent nuclear fuel. The R&D fields covered by the project include waste host materials and actinide chemistry. Examination of neptunium is chosen since it was identified as a radionuclide of concern by the NERI workshop. Additionally, information on the chemical form of neptunium in spent fuel is lacking. The identification of the neptunium species in spent fuel would allow a greater scientific based understanding of its long-term fate and behavior in waste forms. Research to establish the application and development of X-ray synchrotrons radiation (XSR) techniques to determine the structure of aqueous, adsorbed, and solid actinide species of importance to nuclear considerations is being conducted at Argonne. These studies extend current efforts within the Chemical Technology Division at Argonne National Laboratory to investigate actinide speciation with more conventional spectroscopic and solids characterization (e.g. SEM, TEM, and XRD) methods. Our project will utilize all these techniques for determining neptunium speciation in spent fuel. We intend to determine the chemical species and oxidation state of neptunium in spent fuel and alteration phases. Different types of spent fuel will be examined. Once characterized, the chemical behavior of the identified neptunium species will be evaluated if it is not present in the literature. Special attention will be given to the behavior of the neptunium species under typical repository near-field conditions (elevated temperature, high pH, varying Eh). This will permit a timely inclusion of project results into near-field geochemical models. Additionally, project results and methodologies have applications to neptunium in the environment, or treatment of neptunium containing waste.

  13. Lanthanum Bromide Detectors for Safeguards Measurements

    SciTech Connect

    Wright, J.

    2011-05-25

    Lanthanum bromide has advantages over other popular inorganic scintillator detectors. Lanthanum bromide offers superior resolution, and good efficiency when compared to sodium iodide and lanthanum chloride. It is a good alternative to high purity germanium detectors for some safeguards applications. This paper offers an initial look at lanthanum bromide detectors. Resolution of lanthanum bromide will be compared lanthanum chloride and sodium-iodide detectors through check source measurements. Relative efficiency and angular dependence will be looked at. Nuclear material spectra, to include plutonium and highly enriched uranium, will be compared between detector types.

  14. Radiochemistry of uranium, neptunium and plutonium: an updating

    SciTech Connect

    Roberts, R.A.; Choppin, G.R.; Wild, J.F.

    1986-02-01

    This report presents some procedures used in the radiochemical isolation, purification and/or analysis of uranium, neptunium, and plutonium. In this update of the procedures, we have not attempted to discuss the developments in the chemistry of U, Np, and Pu but have restricted the report to the newer procedures, most of which have resulted from the increased emphasis in environmental concern which requires analysis of extremely small amounts of the actinide element in quite complex matrices. The final section of this report describes several schemes for isolation of actinides by oxidation state.

  15. METHYL BROMIDE ALTERNATIVES FOR VINEYARD REPLANT

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Soil fumigation with methyl bromide is needed by grape growers in central California to control soilborne pests. However, use of methyl bromide is banned and soil fumigation with other chemicals subjects to strict regulations to protect human health and air quality. The objective was to determine,...

  16. Measuring methyl bromide emissions from fields

    SciTech Connect

    Yates, S.R.; Gan, J.; Ernst, F.F.; Yates, M.V.

    1995-12-31

    Methyl bromide is used extensively for pest control. Recent evidence suggests that methyl bromide may react with stratospheric ozone and, due to the Clean Air Act, is scheduled for phase-out within the next 5 to 10 years. As indicated in a recent report from The National Agricultural Pesticide Impact Assessment Program, there will be substantial economic impact on the agricultural community if the use of methyl bromide is restricted. There are several areas of uncertainty concerning the agricultural use of methyl bromide. Foremost is the quantification of mass emitted to the atmosphere from agricultural fields. To address this, two field experiments were conducted to directly measure methyl bromide emissions. In the first experiment, methyl bromide was injected at approximately 25 cm depth and the soil was covered with 1 mil high-density polyethylene plastic. The second experiment was similar except that methyl bromide was injected at approximately 68 cm depth and the soil was not covered. From these experiments, the emission rate into the atmosphere and the subsurface transport of methyl bromide was determined. Both experiments include a field-scale mass balance to verify the accuracy of the flux-measurement methods as well as to check data consistency. The volatilization rate and mass lost was determined from estimates of the degradation and from several atmospheric and chamber flux methods.

  17. 77 FR 35295 - Methyl Bromide; Pesticide Tolerances

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-06-13

    ... AGENCY 40 CFR Part 180 RIN 2070-ZA16 Methyl Bromide; Pesticide Tolerances AGENCY: Environmental... methyl bromide in or on cotton, undelinted seed under the Federal Food, Drug, and Cosmetic Act (FFDCA.... Background In the Federal Register of April 6, 2012 (77 FR 20752) (FRL-9345- 1), EPA issued a proposed...

  18. Dose rate dependence of the speciation of neptunium in irradiated solutions of nitric acid

    SciTech Connect

    Precek, M.; Paulenova, A.; Mincher, B.J.; Mezyk, S.P.

    2013-07-01

    The effects of radiation on the redox speciation of neptunium are of interest due to their impact on the performance of separation of neptunium from highly radioactive solutions of dissolved used nuclear fuel. In this study, the influence of dose rate change from 0.4 kGy/h to 6 kGy/h was examined during irradiation of solutions of initially hexavalent 2.0-2.5 mM neptunium in nitric acid of two different concentrations (0.5 and 1 M). Results indicate that the immediate radiolytic steady-state concentration of neptunium(V) were depressed and its initial radiolytic yield was up to 2-times lower (in 1 M HNO{sub 3} solutions)during irradiations with the higher dose rate. The finding is explained on the basis of the enhancement of the role of oxidizing radicals during the radiolytic process. (authors)

  19. Neurological manifestation of methyl bromide intoxication.

    PubMed

    Suwanlaong, Kanokrat; Phanthumchinda, Kammant

    2008-03-01

    Methyl bromide is a highly toxic gas with poor olfactory warning properties. It is widely used as insecticidal fumigant for dry foodstuffs and can be toxic to central and peripheral nervous systems. Most neurological manifestations of methyl bromide intoxication occur from inhalation. Acute toxicity characterized by headache, dizziness, abdominal pain, nausea, vomiting and visual disturbances. Tremor, convulsion, unconsciousness and permanent brain damage may occur in severe poisoning. Chronic exposure can cause neuropathy, pyramidal and cerebellar dysfunction, as well as neuropsychiatric disturbances. The first case of methyl bromide intoxication in Thailand has been described. The patient was a 24-year-old man who worked in a warehouse of imported vegetables fumigated with methyl bromide. He presented with unstable gait, vertigo and paresthesia of both feet, for two weeks. He had a history of chronic exposure to methyl bromide for three years. His fourteen co-workers also developed the same symptoms but less in severity. Neurological examination revealed ataxic gait, decreased pain and vibratory sense on both feet, impaired cerebellar signs and hyperactive reflex in all extremities. The serum concentration of methyl bromide was 8.18 mg/dl. Electrophysilogical study was normal. Magnetic resonance imaging of the brain (MRI) revealed bilateral symmetrical lesion of abnormal hypersignal intensity on T2 and fluid-attenuation inversion recovery (FLAIR) sequences at bilateral dentate nuclei of cerebellum and periventricular area of the fourth ventricle. This incident stresses the need for improvement of worker education and safety precautions during all stages of methyl bromide fumigation. PMID:18575299

  20. Existing Evidence for the Fate of Neptunium in the Yucca Mountain Repository

    SciTech Connect

    Friese, Judah I. ); Buck, Edgar C. ); McNamara, Bruce K. ); Hanson, Brady D. ); Marschman, Steven C. )

    2003-06-18

    Neptunium, because of its long half life, is an element of long-term interest to the Yucca Mountain repository. The fate of neptunium under repository settings is unknown. This report provides a review and new interpretation of past tests on commercial spent nuclear fuel and experimental evidence on the fate of neptunium. Tests on commercial spent nuclear fuel preformed previously at Pacific Northwest National Laboratory (PNNL) used a bathtub setup by immersing spent fuel in either deionized water or a groundwater typical of those at Yucca Mountain. The main goal of the tests was to determine the different concentrations of radionuclides in solution with different types of cladding defects. Neptunium was not the focus of these tests, nor were the tests designed to study neptunium. Drip tests performed at Argonne National Laboratory (ANL) are unsaturated tests that drip water at different rates on spent fuel. Relatively new tests at ANL examine the corrosion of Np-doped U3O8 in humid air at various temperatures. This review concludes that all tests reported here have analytical problems (i.e., relatively high detection limits for Np) and have been configured such that they limit the ability to interpret the available neptunium data. Past tests on spent nuclear fuel do not unambiguously describe neptunium chemistry as there are multiple mechanisms that may explain the observed behavior in each test. One apparently major shortcoming of most tests is that the extent of fuel reaction was limited by the amount of oxygen present in the system. Further detailed studies under repository-relevant conditions, which include the assumption of a constant 20 percent oxygen atmosphere, are needed to provide the data necessary for the development and validation of models used to predict the long-term fate of neptunium and other radionuclides at Yucca Mountain.

  1. Potassium bromide method of infrared sampling

    USGS Publications Warehouse

    Milkey, R.G.

    1958-01-01

    In the preparation of potassium bromide pressed windows for use in the infrared analysis of solids, severe grinding of the potassium bromide powder may produce strong absorption bands that could interfere seriously with the spectra of the sample. These absorption bands appear to be due to some crystal alteration of the potassium bromide as a result of the grinding process. They were less apt to occur when the coarser powder, which had received a relatively gentle grinding, was used. Window blanks prepared from the coarser powders showed smaller adsorbed water peaks and generally higher over-all transmittance readings than windows pressed from the very fine powders.

  2. Reduction and precipitation of neptunium(V) by sulfate-reducing bacteria.

    SciTech Connect

    Banaszak, J. E.; Rittmann, B. E.; Reed, D. T.

    1999-10-21

    Migration of neptunium, as NpO{sub 2}{sup +}, has been identified as a potentially important pathway for actinide release at nuclear waste repositories and existing sites of subsurface contamination. Reduction of Np(V) to Np(IV) will likely reduce its volubility, resulting in lowered subsurface migration. The ability of sulfate-reducing bacteria (SRB) to utilize Np(V) as an electron acceptor was investigated, because these bacteria are active in many anaerobic aquifers and are known to facilitate the reduction of metals and radionuclides. Pure and mixed cultures of SRB were able to precipitate neptunium during utilization of pyruvate, lactate, and hydrogen as electron donors in the presence and absence of sulfate. The neptunium in the precipitate was identified as Np(IV) using X-ray absorption near edge spectroscopy (XANES) analysis. In mixed-culture studies, the addition of hydrogen to consortia grown by pyruvate fermentation stimulated neptunium reduction and precipitation. Experiments with pure cultures of Desulfovibrio vulgaris, growing by lactate fermentation in the absence of sulfate or by sulfate reduction, confirm that the organism is active in neptunium reduction and precipitation. Based on our results, the activity of SRB in the subsurface may have a significant, and potentially beneficial, impact on actinide mobility by reducing neptunium volubility.

  3. SORPTION OF URANIUM, PLUTONIUM AND NEPTUNIUM ONTO SOLIDS PRESENT IN HIGH CAUSTIC NUCLEAR WASTE STORAGE TANKS

    SciTech Connect

    Oji, L; Bill Wilmarth, B; David Hobbs, D

    2008-05-30

    Solids such as granular activated carbon, hematite and sodium phosphates, if present as sludge components in nuclear waste storage tanks, have been found to be capable of precipitating/sorbing actinides like plutonium, neptunium and uranium from nuclear waste storage tank supernatant liqueur. Thus, the potential may exists for the accumulation of fissile materials in such nuclear waste storage tanks during lengthy nuclear waste storage and processing. To evaluate the nuclear criticality safety in a typical nuclear waste storage tank, a study was initiated to measure the affinity of granular activated carbon, hematite and anhydrous sodium phosphate to sorb plutonium, neptunium and uranium from alkaline salt solutions. Tests with simulated and actual nuclear waste solutions established the affinity of the solids for plutonium, neptunium and uranium upon contact of the solutions with each of the solids. The removal of plutonium and neptunium from the synthetic salt solution by nuclear waste storage tank solids may be due largely to the presence of the granular activated carbon and transition metal oxides in these storage tank solids or sludge. Granular activated carbon and hematite also showed measurable affinity for both plutonium and neptunium. Sodium phosphate, used here as a reference sorbent for uranium, as expected, exhibited high affinity for uranium and neptunium, but did not show any measurable affinity for plutonium.

  4. Geomicrobiological redox cycling of the transuranic element neptunium.

    PubMed

    Law, Gareth T W; Geissler, Andrea; Lloyd, Jonathan R; Livens, Francis R; Boothman, Christopher; Begg, James D C; Denecke, Melissa A; Rothe, Jörg; Dardenne, Kathy; Burke, Ian T; Charnock, John M; Morris, Katherine

    2010-12-01

    Microbial processes can affect the environmental behavior of redox sensitive radionuclides, and understanding these reactions is essential for the safe management of radioactive wastes. Neptunium, an alpha-emitting transuranic element, is of particular importance because of its long half-life, high radiotoxicity, and relatively high solubility as Np(V)O(2)(+) under oxic conditions. Here, we describe experiments to explore the biogeochemistry of Np where Np(V) was added to oxic sediment microcosms with indigenous microorganisms and anaerobically incubated. Enhanced Np removal to sediments occurred during microbially mediated metal reduction, and X-ray absorption spectroscopy showed this was due to reduction to poorly soluble Np(IV) on solids. In subsequent reoxidation experiments, sediment-associated Np(IV) was somewhat resistant to oxidative remobilization. These results demonstrate the influence of microbial processes on Np solubility and highlight the critical importance of radionuclide biogeochemistry in nuclear legacy management. PMID:21047117

  5. Application of the underscreened Kondo lattice model to neptunium compounds

    NASA Astrophysics Data System (ADS)

    Thomas, Christopher; da Rosa Simoes, Acirete S.; Iglesias, J. R.; Lacroix, C.; Coqublin, B.

    2012-12-01

    The coexistence of Kondo effect and ferromagnetic order has been observed in many uranium and neptunium compounds such as UTe or Np2PdGa3. This coexistence can be described within the underscreened Anderson lattice model with two f-electrons and S = 1 spins on each site. After performing the Schrieffer-Wolff transformation on this model, we have obtained an effective Hamiltonian with a f-band term in addition to the Kondo interaction for S = 1 spins. The results indicate a coexistence of Kondo effect and ferromagnetic order, with different relative values of the Kondo TK and Curie TC temperatures. We emphasize here especially the case TK < TC where there is a Kondo behavior below TC and a clear decrease of the magnetization below TK. Such a behavior has been observed in the magnetization curves of NpNiSi2 at low temperatures.

  6. Thermodynamics of neptunium(V) fluoride and sulfate at elevatedtemperatures

    SciTech Connect

    Rao, Linfeng; Tian, Guoxin; Xia, Yuanxian; Friese, Judah I.

    2006-10-31

    Complexation of neptunium(V) with fluoride and sulfate at elevated temperatures was studied by microcalorimetry. Thermodynamic parameters, including the equilibrium constants and enthalpy of protonation of fluoride and sulfate, and the enthalpy of complexation between Np(V) and fluoride and sulfate at 25 - 70 C were determined. Results show that the complexation of Np(V) with fluoride and sulfate is endothermic and that the complexation is enhanced by the increase in temperature - a three-fold increase in the stability constants of NpO{sub 2}F(aq) and NpO{sub 2}SO{sub 4}{sup -} as the temperature is increased from 25 to 70 C.

  7. Complexation of Neptunium(V) with Fluoride at Elevated Temperatures

    SciTech Connect

    Rao, Linfeng; Tian, Guoxin; Xia, Yuanxian; Friese, Judah I.

    2008-06-16

    Complexation of neptunium(V) with fluoride at elevated temperatures was studied by spectrophotometry and microcalorimetry. Two successive complexes, NpO{sub 2}F(aq) and NpO{sub 2}F{sub 2}{sup -}, were identified by spectrophotometry in the temperature range of 10-70 C. Thermodynamic parameters, including the equilibrium constants and enthalpy of complexation between Np(V) and fluoride at 10-70 C were determined. Results show that the complexation of Np(V) with fluoride is endothermic and that the complexation is enhanced by the increase in temperature - a two-fold increase in the stability constants of NpO{sub 2}F(aq) and more than five-fold increase in the stability constants of NpO{sub 2}F{sub 2}{sup -} as the temperature is increased from 10 to 70 C.

  8. Gamma-ray measurements of a 6-kilogram neptunium sphere

    SciTech Connect

    Moss, C. E.; Frankle, C. M.

    2002-01-01

    In order to better determine the properties of {sup 237}Np for criticality safety and nuclear nonproliferation, especially its critical mass, 6070-gram solid sphere was cast on 15 May 2001 in a hot cell. The casting sprue was cut off on a lathe and the casting ground to a final diameter of 8.29 cm. The sphere was enclosed in a spherical tungsten shell 0.523-cm thick to reduce the gamma-ray dose. The neptunium and the tungsten were doubly encapsulated in welded, spherical nickel shells, each 0.381-cm thick. The sprue material was analyzed by mass spectrometry. Here we report the results of the first gamma-ray measurements of this unique item.

  9. Nuclear forensics of a non-traditional sample: Neptunium

    DOE PAGESBeta

    Doyle, Jamie L.; Schwartz, Daniel; Tandon, Lav

    2016-05-16

    Recent nuclear forensics cases have focused primarily on plutonium (Pu) and uranium (U) materials. By definition however, nuclear forensics can apply to any diverted nuclear material. This includes neptunium (Np), an internationally safeguarded material like Pu and U, that could offer a nuclear security concern if significant quantities were found outside of regulatory control. This case study couples scanning electron microscopy (SEM) with quantitative analysis using newly developed specialized software, to evaluate a non-traditional nuclear forensic sample of Np. Here, the results of the morphological analyses were compared with another Np sample of known pedigree, as well as other traditionalmore » actinide materials in order to determine potential processing and point-of-origin.« less

  10. Emission of methyl bromide from biomass burning

    SciTech Connect

    Manoe, S.; Andreae, M.O. )

    1994-03-04

    Bromine is, per atom, far more efficient than chlorine in destroying stratospheric ozone, and methyl bromide is the single largest source of stratospheric bromine. The two main previously known sources of this compound are emissions from the ocean and from the compound's use as an agricultural pesticide. Laboratory biomass combustion experiments showed that methyl bromide was emitted in the smoke from various fuels tested. Methyl bromide was also found in smoke plumes from wildfires in savannas, chaparral, and boreal forest. Global emissions of methyl bromide from biomass burning are estimated to be in the range of 10 to 50 gigagrams per year, which is comparable to the amount produced by ocean emission and pesticide use and represents a major contribution ([approximately]30 percent) to the stratospheric bromine budget.

  11. Growth and characterization of lead bromide crystals

    NASA Technical Reports Server (NTRS)

    Singh, N. B.; Gottlieb, M.; Henningsen, T.; Hopkins, R. H.; Mazelsky, R.; Glicksman, M. E.; Coriell, S. R.; Santoro, G. J.; Duval, W. M. B.

    1992-01-01

    Lead(II) bromide was purified by a combination of directional freezing and zone-refining methods. Differential thermal analysis of the lead bromide showed that a destructive phase transformation occurs below the melting temperature. This transformation causes extensive cracking, making it very difficult to grow a large single crystal. Energy of phase transformation for pure lead bromide was determined to be 24.67 cal/g. To circumvent this limitation, crystals were doped by silver bromide which decreased the energy of phase transformation. The addition of silver helped in achieving the size, but enhanced the inhomogeneity in the crystal. The acoustic attenuation constant was almost identical for the pure and doped (below 3000 ppm) crystals.

  12. Investigation of drug interactions with pinaverium bromide.

    PubMed

    Devred, C; Godeau, P; Guerot, C; Librez, P; Mougeot, G; Orsetti, A; Segrestaa, J M

    1986-01-01

    A series of studies was carried out at 6 centres to investigate possible drug interaction between the spasmolytic, pinaverium bromide, and cardiac glycosides, anticoagulants and hypoglycaemic agents given to patients as part of the long-term treatment of their condition. The results of clinical and laboratory investigations did not show any evidence of pinaverium bromide interfering with the action or activity of any of the drugs studied. PMID:3084176

  13. 49 CFR 173.193 - Bromoacetone, methyl bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 49 Transportation 2 2010-10-01 2010-10-01 false Bromoacetone, methyl bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc. 173.193 Section 173.193 Transportation Other Regulations... bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc. (a) Bromoacetone must...

  14. 49 CFR 173.193 - Bromoacetone, methyl bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 49 Transportation 2 2014-10-01 2014-10-01 false Bromoacetone, methyl bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc. 173.193 Section 173.193 Transportation Other Regulations... bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc. (a) Bromoacetone must...

  15. 49 CFR 173.193 - Bromoacetone, methyl bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 49 Transportation 2 2011-10-01 2011-10-01 false Bromoacetone, methyl bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc. 173.193 Section 173.193 Transportation Other Regulations... bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc. (a) Bromoacetone must...

  16. Neptunium Solubility in the Near-Field Environment of A Proposed Yucca Mountain Repository

    SciTech Connect

    D.C. Sassani

    2004-05-14

    For representing the source-term of a proposed repository at Yucca Mountain, NV, total system performance assessment models evaluate the disequilibrium degradation of the waste forms to capture a bounding rate for radionuclide source-term availability and use solubility constraints that are more representative of longer-term, equilibrium processes to limit radionuclide mass transport from the source-term. These solubility limits capture precipitation processes occurring either as the waste forms alter, or in the near-field environment as chemical conditions evolve. A number of alternative models for solubility controls on dissolved neptunium concentrations have been evaluated. These include idealized models based on precipitation of neptunium as separate oxide minerals and more complex considerations of trace amounts of neptunium being incorporated into the secondary uranyl phases from waste form alteration. Thermodynamic models for neptunium under oxidizing conditions indicate that tetravalent neptunium (NpO{sub 2}) solids are more stable relative to pentavalent (Np{sub 2}O{sub 5}) phases, and thereby set lower dissolved concentrations of neptunyl species. Data on solids and solutions from slow flow through (dripping) tests on spent fuel grains indicate that neptunium is tetravalent in the spent fuel and that over {approx}9 years the neptunium concentrations are near to or below calculated NpO{sub 2} solubility. The possibility of kinetic rate limitations to NpO{sub 2} precipitation has led to temperature-dependent studies of NpO{sub 2} precipitation kinetics and solubility to reduce uncertainties and confirm application of the model.

  17. Metabolism and gastrointestinal absorption of neptunium and protactinium in adult baboons

    SciTech Connect

    Ralston, L.G.; Cohen, N.; Bhattacharyya, M.H.; Larsen, R.P.; Ayres, L.; Oldham, R.D.; Moretti, E.S.

    1985-01-01

    The metabolism of neptunium and protactinium was studied in adult female baboons following intravenous injection and intragastric intubation. Immediately following intravenous injection (10/sup -1/ to 10/sup -10/ mg Np per kg body wt), neptunium cleared rapidly from blood, deposited primarily in the skeleton (54 +- 5%) and liver (3 +- 0.2%), and was excreted predominantly via urine (40 +- 3%). For the first year post injection, neptunium was retained with a biological half-time of approx.100 days in liver and 1.5 +- 0.2 yr in bone. In comparison, injected protactinium (10/sup -9/ mg/kg) was retained in blood in higher concentrations and was initially eliminated in urine to a lesser extent (6 +- 3%). In vivo measurements indicated that protactinium was retained in bone (65 +- 0.3%) with a half-time of 3.5 +- 0.6 yr. Differences in the physicochemical states of the neptunium or protactinium solutions injected did not alter the metabolic behavior of these nuclides. The gastrointestinal absorption value for neptunium in two fasted baboons, sacrificed at 1 day post administration, was determined to be 0.92 +- 0.04%. Of the total amount of neptunium absorbed, 52 +- 3% was retained in bone, 6 +- 2% was in liver, and 42 +- 0.1% was excreted in urine. A method was developed to estimate GI absorption values for both nuclides in baboons which were not sacrificed. Absorption values calculated by this method for neptunium and protactinium in fasted baboons were 1.8 +- 0.8% and 0.65 +- 0.01%, respectively. Values for fed animals were 1 to 2 orders of magnitude less than those for fasted animals. 14 refs., 3 figs., 4 tabs. (DT)

  18. The effect of high ionic strength on neptunium (V) adsorption to a halophilic bacterium

    NASA Astrophysics Data System (ADS)

    Ams, David A.; Swanson, Juliet S.; Szymanowski, Jennifer E. S.; Fein, Jeremy B.; Richmann, Michael; Reed, Donald T.

    2013-06-01

    The mobility of neptunium (V) in subsurface high ionic strength aqueous systems may be strongly influenced by adsorption to the cell wall of the halophilic bacteria Chromohalobacter sp. This study is the first to evaluate the adsorption of neptunium (V) to the surface of a halophilic bacterium as a function of pH from approximately 2 to 10 and at ionic strengths of 2 and 4 M. This is also the first study to evaluate the effects of carbonate complexation with neptunium (V) on adsorption to whole bacterial cells under high pH conditions. A thermodynamically-based surface complexation model was adapted to describe experimental adsorption data under high ionic strength conditions where traditional corrections for aqueous ion activity are invalid. Adsorption of neptunium (V) was rapid and reversible under the conditions of the study. Adsorption was significant over the entire pH range evaluated for both ionic strength conditions and was shown to be dependent on the speciation of the sites on the bacterial surface and neptunium (V) in solution. Adsorption behavior was controlled by the relatively strong electrostatic attraction of the positively charged neptunyl ion to the negatively charged bacterial surface at pH below circum-neutral. At pH above circum-neutral, the adsorption behavior was controlled by the presence of negatively charged neptunium (V) carbonate complexes resulting in decreased adsorption, although adsorption was still significant due to the adsorption of negatively charged neptunyl-carbonate species. Adsorption in 4 M NaClO4 was enhanced relative to adsorption in 2 M NaClO4 over the majority of the pH range evaluated, likely due to the effect of increasing aqueous ion activity at high ionic strength. The protonation/deprotonation characteristics of the cell wall of Chromohalobacter sp. were evaluated by potentiometric titrations in 2 and 4 M NaClO4. Bacterial titration results indicated that Chromohalobacter sp. exhibits similar proton buffering

  19. Effect of Precipitation Conditions on the Specific Surface Area of Neptunium Oxide

    SciTech Connect

    HILL, BENJAMINC.

    2004-06-01

    Neptunium oxalate was precipitated under nominal and bounding HB-Line flowsheet conditions. The nominal case represents expected normal HB-Line operation. The bounding case represents process flowsheet extremes that could occur which are anticipated to decrease particle size and increase surface area. The neptunium oxalate produced under bounding conditions was used to validate the effectiveness of HB-Line calcination conditions. The maximum specific surface area of the neptunium oxide (NpO2) used in gas generation testing was 5.34 m2/g. Experiments were conducted to verify that even under bounding precipitation conditions the SSA of NpO2 produced would remain within the range evaluated during gas generation testing. The neptunium oxalate from nominal and bounding precipitation conditions was calcined at 600 degrees Celsius and 625 degrees Celsius, respectively, to form NpO2. Samples from each batch of neptunium oxalate were calcined for one, two, or four hours. Results indicate that the SSA of NpO2 continues to decrease between one and four hours. After two hours of calcination at 625 degrees Celsius, the SSA of NpO2 from the bounding case meets the surface area requirements for limiting moisture uptake.

  20. Batch sorption results for neptunium transport through Yucca Mountain tuffs. Yucca Mountain Site Characterization Program milestone 3349

    SciTech Connect

    Triay, I.R.; Cotter, C.R.; Huddleston, M.H.; Leonard, D.E.

    1996-09-01

    We studied the sorption of neptunium onto tuffs characteristic of the proposed nuclear waste repository at Yucca Mountain, Nevada. The neptunium was in the Np(V) oxidation state under oxidizing conditions in groundwaters from two wells located close to the repository site (J-13 and UE-25 p No.1). We used devitrified, vitric, zeolitic (with emphasis on clinoptilolite-rich samples), and calcite-rich tuffs characteristic of the geology of the site. Neptunium sorbed well onto calcite and calcite-rich tuffs, indicating that a significant amount of neptunium retardation can be expected under fractured-flow scenarios because of calcite coating of the fractures. Neptunium sorption onto clinoptilolite-rich zeolitic tuffs in J-13 well water (pH from 7 to 8.5) was moderate, increased with decreasing pH, and correlated to surface area and amount of clinoptilolite. Neptunium sorbed poorly onto zeolitic tuffs from UE-25 p No.1 groundwater (pH from 7 to 9) and onto devitrified and vitric tuffs from J-13 and UE-25 p No.1 waters (pH from 7 to 9). Iron oxides appeared to be passivated in tuffs, not seeming to contribute to the observed neptunium sorption, even though neptunium sorption onto synthetic iron oxide is significant.

  1. Neptunium as a Tool for Reducing Proliferation Risks with Plutonium: A Technical Analysis of its Efficiency and its Drawbacks

    SciTech Connect

    Greneche, Dominique; Ng, Selena; Guesdon, Bernard; Vinoche, Richard; Delpech, Marc; Golfier, Herve; Dolci, Florence; Poinot-Salanon, Christine

    2006-07-01

    Introducing neptunium into the nuclear fuel cycle has been proposed in the past as a way to impede the diversion or the direct use of plutonium to fabricate a nuclear explosive device. This paper aims to technically analyze the industrial consequences should this proposal be implemented. Two scenarios are considered: 1) adding neptunium to fresh uranium oxide (UOX) fuel before irradiation in a light water reactor; 2) separating neptunium together with plutonium from used UOX fuel and using this combined oxide to fabricate mixed oxide (MOX) fuel before subsequent irradiation in a light water reactor. In both cases, assembly calculations for a pressurized water reactor using fresh fuel doped with neptunium are presented for a wide range of neptunium proportions. Consequences on core and fuel performances and the fuel cycle are analyzed. These are weighed against the potential proliferation resistance benefits of adding neptunium due to the increased quantity of the plutonium isotope {sup 238}Pu in the discharged fuel, or due to the potentially increased detectability through gamma ray emissions of a plutonium-neptunium oxide mixture. Finally, the proliferation risk presented by neptunium itself is discussed. (authors)

  2. Gastrointestinal absorption of protactinium, uranium, and neptunium in the hamster

    SciTech Connect

    Harrison, J.D.; Stather, J.W.

    1981-10-01

    The gastrointestinal absorption of protactinium, uranium, and neptunium in adult hamsters was measured. The actinide preparations were administered intragastrically and animals were kept 2 to 4 weeks prior to the radiochemical analysis of selected tissue samples. Total absorption was estimated using data for the distribution of the actinides after intravenous injection in soluble form. The values obtained were 3.9 and 0.22% for /sup 231/Pa citrate and /sup 231/Pa fluoride, respectively; 0.77 and 0.11% for /sup 233/U (uranyl) nitrate and /sup 233/U dioxide, respectively; and 0.06 and 0.05% for /sup 237/Np citrate and /sup 237/Np nitrate, respectively. The absorption factors recommended by the International Commission on Radiological Protection for use in calculating annual limits on intake for occupationally exposed workers are: 0.1% for all compounds of Pa; 5 and 0.2% for soluble hexavalent and relatively insoluble tetravalent forms of U, respectively; and 1.0% for all chemical forms of Np. The experimental basis for these values is discussed.

  3. Fate of neptunium in an anaerobic, methanogenic microcosm.

    SciTech Connect

    Banaszak, J. E.

    1998-12-21

    Neptunium is found predominantly as Np(IV) in reducing environments, but Np(V) in aerobic environments. However, currently it is not known how the interplay between biotic and abiotic processes affects Np redox speciation in the environment. In order to evaluate the effect of anaerobic microbial activity on the fate of Np in natural systems, Np(V) was added to a microcosminoculated with anaerobic sediments from a metal-contaminated fresh water lake. The consortium included metal-reducing, sulfate-reducing, and methanogenic microorganisms, and acetate was supplied as the only exogenous substrate. Addition of more than 10{sup {minus}5} M Np did not inhibit methane production. Total Np volubility in the active microcosm, as well as in sterilized control samples, decreased by nearly two orders of magnitude. A combination of analytical techniques, including VIS-NIR absorption spectroscopy and XANES, identified Np(IV) as the oxidation state associated with the sediments. The similar results from the active microcosm and the abiotic controls suggest that microbian y produced Mn(II/HI) and Fe(II) may serve as electron donors for Np reduction.

  4. Speciation of neptunium during sorption and diffusion in natural clay

    NASA Astrophysics Data System (ADS)

    Reich, T.; Amayri, S.; Bӧrner, P. J. B.; Drebert, J.; Frӧhlich, D. R.; Grolimund, D.; Kaplan, U.

    2016-05-01

    In argillaceous rocks, which are considered as a potential host rock for nuclear waste repositories, sorption and diffusion processes govern the migration behaviour of actinides like neptunium. For the safety analysis of such a repository, a molecular-level understanding of the transport and retardation phenomena of radioactive contaminants in the host rock is mandatory. The speciation of Np during sorption and diffusion in Opalinus Clay was studied at near neutral pH using a combination of spatially resolved synchrotron radiation techniques. During the sorption and diffusion experiments, the interaction of 8 μM Np(V) solutions with the clay lead to the formation of spots at the clay-water interface with increased Np concentrations as determined by μ-XRF. Several of these spots are correlated with areas of increased Fe concentration. Np L3-edge μ-XANES spectra revealed that up to 85% of the initial Np(V) was reduced to Np(IV). Pyrite could be identified by μ-XRD as a redox-active mineral phase responsible for the formation of Np(IV). The analysis of the diffusion profile within the clay matrix after an in-diffusion experiment for two months showed that Np(V) is progressively reduced with diffusion distance, i.e. Np(IV) amounted to ≈12% and ≈26% at 30 μm and 525 μm, respectively.

  5. Report on neptunium speciation by NMR and optical spectroscopies

    SciTech Connect

    Tait, C.D.; Palmer, P.D.; Ekberg, S.A.; Clark, D.L.

    1995-11-01

    Hydrolysis and carbonate complexation reactions were examined for NpO{sub 2}{sup 2+} and NpO{sub 2}{sup +} ions by a variety of techniques including potentiometric titration, UV-Vis-NIR and NMR spectroscopy. The equilibrium constant for the reaction 3NpO{sub 2}(CO{sub 3}){sub 3}{sup 4{minus}} + 3H{sup +} {rightleftharpoons} (NpO{sub 2}){sub 3}(CO{sub 3}){sub 6}{sup 6{minus}} + 3HCO{sub 3}{sup {minus}} was determined to be logK = 19.7 ({plus_minus} 0.8) (I = 2.5 m). {sup 17}O NMR spectroscopy of NpO{sub 2}{sup n+} ions (n = 1,2) reveals a readily observable {sup 17}O resonance for n = 2, but not for n = 1. The first hydrolysis constant for NpO{sub 2}{sup +} was studied as a function of temperature, and the functional form for the temperature-dependent equilibrium constant for the reaction written as NpO{sub 2}{sup +} + H{sub 2}O {rightleftharpoons} NpO{sub 2}OH + H{sup +} was found to be logK = 2.28 {minus} 3780/T, where T is in {degree}K. Finally, the temperature dependence of neptunium(V) carbonate complexation constants was studied. For the first carbonate complexation constant, the appropriate functional form was found to be log{beta}{sub 01} = 1.47 + 786/T.

  6. [The clinical pharmacological profile of pinaverium bromide].

    PubMed

    Guslandi, M

    1994-04-01

    Pinaverium bromide is a locally acting spasmolytic agent of the digestive tract. Its mechanism of action relies upon inhibition of calcium ion entrance into smooth muscle cells (calcium-antagonist effect). In humans pinaverium facilitates gastric emptying and decreases intestinal transit time in patients with constipation. Pinaverium is very effective in improving symptoms of irritable bowel syndrome (abdominal pain, gas, diarrhea or constipation). In this respect the drug proved to be significantly superior to placebo, at least as effective as trimebutine and on the whole more active than otilonium and prifinium bromide, being always extremely well tolerated. PMID:8028745

  7. Effects of pinaverium bromide on Oddi's sphincter.

    PubMed

    DiSomma, C; Reboa, G; Patrone, M G; Mortola, G P; Sala, G; Ciampini, M

    1986-01-01

    Twelve to 15 days after cholecystectomy, endocholedochal pressure was measured in ten patients before and one hour after oral administration of 15 mg of pinaverium bromide (six patients) or placebo. The mean endocholedochal pressure was 7.1 +/- 0.25 mmHg before and 3.1 +/- 0.2 mmHg after pinaverium (P less than 0.01), and 7.0 +/- 0.2 and 6.8 +/- 1.2 mmHg in the placebo-treated patients. The results suggest that pinaverium bromide has a specific effect on the common bile duct and probably on Oddi's sphincter. PMID:3815457

  8. Intrinsic formation of nanocrystalline neptunium dioxide under neutral aqueous conditions relevant to deep geological repositories.

    PubMed

    Husar, Richard; Hübner, René; Hennig, Christoph; Martin, Philippe M; Chollet, Mélanie; Weiss, Stephan; Stumpf, Thorsten; Zänker, Harald; Ikeda-Ohno, Atsushi

    2015-01-25

    The dilution of aqueous neptunium carbonate complexes induces the intrinsic formation of nanocrystalline neptunium dioxide (NpO2) particles, which are characterised by UV/Vis and X-ray absorption spectroscopies and transmission electron microscopy. This new route of nanocrystalline NpO2 formation could be a potential scenario for the environmental transport of radionuclides from the waste repository (i.e. under near-field alkaline conditions) to the geological environment (i.e. under far-field neutral conditions). PMID:25479067

  9. Factors Controlling Redox Speciation of Plutonium and Neptunium in Extraction Separation Processes

    SciTech Connect

    Paulenova, Alena; Vandegrift, III, George F.

    2013-09-24

    The objective of the project was to examine the factors controlling redox speciation of plutonium and neptunium in UREX+ extraction in terms of redox potentials, redox mechanism, kinetics and thermodynamics. Researchers employed redox-speciation extractions schemes in parallel to the spectroscopic experiments. The resulting distribution of redox species w studied uring spectroscopic, electrochemical, and spectro-electrochemical methods. This work reulted in collection of data on redox stability and distribution of redox couples in the nitric acid/nitrate electrolyte and the development of redox buffers to stabilize the desired oxidation state of separated radionuclides. The effects of temperature and concentrations on the redox behavior of neptunium were evaluated.

  10. Characterization of Neptunium Oxide Generated Using the HB-Line Phase II Flowsheet

    SciTech Connect

    Duffey, J

    2003-08-29

    Approximately 98 grams of neptunium(IV) oxide (NpO{sub 2}) were produced at the Savannah River Technology Center (SRTC) for use in gas generation tests to support the neptunium stabilization program at the Savannah River Site (SRS). The NpO{sub 2} was produced according to the anticipated HB-Line flowsheet consisting of anion exchange, oxalate precipitation, filtration, and calcination. Characterization of the NpO{sub 2} product to be used in gas generation tests included bulk and tap density measurements, X-ray diffraction, particle size distribution, specific surface area measurements, and moisture analysis.

  11. Zinc Bromide Waste Solution Treatment Options

    SciTech Connect

    Langston, C.A.

    2001-01-16

    The objective of this effort was to identify treatment options for 20,000 gallons of low-level radioactively contaminated zinc bromide solution currently stored in C-Area. These options will be relevant when the solutions are declared waste.

  12. Methyl Bromide Alternatives for Vineyard Replant

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The project is part of the USDA-ARS Pacific Area-Wide Pest Management Program for Methyl Bromide Alternatives. This is the first year of a three-year project. The research was initiated in summer 2007 with a field study planned for October 2007 at the USDA-ARS San Joaquin Valley Agricultural Scienc...

  13. METHYL BROMIDE ALTERNATIVES FOR CALIFORNIA STRAWBERRY NURSERIES

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The effects of methyl bromide (MB) alternative fumigants on soil pests, plant productivity in nursery and fruiting fields, as well as production costs, were evaluated in California strawberry nurseries by an interdisciplinary team. Our trials followed nursery stock through low and high elevation ph...

  14. Challenges in Weed Management Without Methyl Bromide

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Methyl bromide has been used for several decades for pre-plant soil fumigation in high value agricultural and horticultural crops because it can provide broad-spectrum control of insects, nematodes, pathogens, and weeds. However, MeBr has been identified as a powerful ozone-depleting chemical and i...

  15. Methyl bromide emissions from tarped fields

    SciTech Connect

    Cicerone, R.J.; Williams, J.; Wang, N.Y.

    1995-12-31

    Once in the stratosphere, bromine atoms can destroy ozone effectively. Because of this potential effect, certain organobromine compounds including methyl bromide (MeBr) are being controlled or eliminated by national and international regulations. It would be valuable to determine the fraction of MeBr used in soil fumigations that subsequently enters the atmosphere to better assess the need for, and value of, strong regulations. We have designed and conducted several experiments accompanying field fumigations with MeBr/chloropicrin mixtures. In each of three field-fumigation experiments new Irvine, CA in which the fumigated field was covered immediately with plastic tarping, we have deployed static flux chambers on top of the tarping and measured escape fluxes of MeBr. After tarp removal, the same chambers were replaced on the bare soil to continue the measurements. We have also measured soil bromide contents before and after the fumigation. One experiment yielded an escape fraction of 80 to 87% (with 19% remaining as bromide) while the other two experiments yielded escape fractions of 30 to 35% (with about 70% remaining as bromide). This paper will summarize stratospheric bromine chemistry, describe the field experiments and discuss factors that influence emissions, including soil pH, moisture and organic content and injection technique. We acknowledge TriCal, Inc. for many helpful discussions and for professional field applications of MeBr.

  16. Can Georgia growers replace methyl bromide

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The price and availability of methyl bromide is limiting its use on Georgia farms; the need for an alternative is essential for sustainable vegetable production in GA. Three alternatives were evaluated in on-farm trials in the spring 2007 in Tift, Colquitt and Echols Counties. Treatments were replic...

  17. A comparison of the action of otilonium bromide and pinaverium bromide: study conducted under clinical control.

    PubMed

    Defrance, P; Casini, A

    1991-11-01

    We studied 40 patients with irritable bowel syndrome (IBS) which received in a simple-blind fashion otilonium and pinaverium bromide (15 days each drug). During each 15-day period we evaluated: number of pain episodes, intensity of pain, number of bowel movements, side effects. Otilonium bromide, (OB), compared with pinaverium bromide was able to significantly (p less than 0.05) reduce the number of pain attacks, whereas no significant differences were found between the 2 groups as regards the other parameters. The occurrence of side effects was similar in the two treatment courses. We can conclude that the two types of treatment were similarly useful in IBS, although OB seems more effective than pinaverium bromide. PMID:1756286

  18. Sensitive redox speciation of neptunium by CE-ICP-MS.

    PubMed

    Stöbener, Nils; Amayri, Samer; Gehl, Aaron; Kaplan, Ugras; Malecha, Kurtis; Reich, Tobias

    2012-11-01

    Capillary electrophoresis (CE) was used to separate the neptunium oxidation states Np(IV) and Np(V), which are the only oxidation states of Np that are stable under environmental conditions. The CE setup was coupled to an inductively coupled plasma mass spectrometer (Agilent 7500ce) using a Mira Mist CE nebulizer and a Scott-type spray chamber. The combination of the separation capacity of CE with the detection sensitivity of inductively coupled plasma mass spectrometry (ICP-MS) allows identification and quantification of Np(IV) and Np(V) at the trace levels expected in the far field of a nuclear waste repository. Limits of detection of 1 × 10(-9) and 5 × 10(-10) mol L(-1) for Np(IV) and Np(V), respectively, were achieved, with a linear range from 10(-9) to 10(-6) mol L(-1). The method was applied to study the redox speciation of the Np remaining in solution after interaction of 5 × 10(-7) mol L(-1) Np(V) with Opalinus Clay. Under mildly oxidizing conditions, a Np sorption of 31% was found, with all the Np remaining in solution being Np(V). A second sorption experiment performed in the presence of Fe(2+) led to complete sorption of the Np onto the clay. After desorption with HClO(4), a mixture of Np(IV) and Np(V) was found in solution by CE-ICP-MS, indicating that some of the sorbed Np had been reduced to Np(IV) by Fe(2+). PMID:23052867

  19. Experimental study on neptunium migration under in situ geochemical conditions

    NASA Astrophysics Data System (ADS)

    Kumata, M.; Vandergraaf, T. T.

    1998-12-01

    Results are reported for migration experiments performed with Np under in situ geochemical conditions over a range of groundwater flow rates in columns of crushed rock in a specially designed facility at the 240-level of the Underground Research Laboratory (URL) near Pinawa, Manitoba, Canada. This laboratory is situated in an intrusive granitic rock formation, the Lac du Bonnet batholith. Highly altered granitic rock and groundwater were obtained from a major subhorizontal fracture zone at a depth of 250 m in the URL. The granite was wet-crushed and wet-sieved with groundwater from this fracture zone. The 180-850-μm size fraction was selected and packed in 20-cm long, 2.54-cm in diameter Teflon™-lined stainless steel columns. Approximately 30-ml vols of groundwater containing 3HHO and 237Np were injected into the columns at flow rates of 0.3, 1, and 3 ml/h, followed by elution with groundwater, obtained from the subhorizontal fracture, at the same flow rates, for a period of 95 days. Elution profiles for 3HHO were obtained, but no 237Np was detected in the eluted groundwater. After terminating the migration experiments, the columns were frozen, the column material was removed and cut into twenty 1-cm thick sections and each section was analyzed by gamma spectrometry. Profiles of 237Np were obtained for the three columns. A one-dimensional transport model was fitted to the 3HHO breakthrough curves to obtain flow parameters for this experiment. These flow parameters were in turn applied to the 237Np concentration profiles in the columns to produce sorption and dispersion coefficients for Np. The results show a strong dependence of retardation factors ( Rf) on flow rate. The decrease in the retarded velocity of the neptunium ( Vn) varied over one order of magnitude under the geochemical conditions for these experiments.

  20. Spectroscopic investigations of neptunium`s and plutonium`s oxidation states in sol-gel glasses as a function of initial valance and thermal history

    SciTech Connect

    Stump, N.A.; Haire, R.G.; Dai, S.

    1996-12-01

    Several oxidation states of neptunium and plutonium, Pu(III),Pu (IV), PU(VI), Np(IV), Np(V) and Np (VI), were studied in glasses prepared by a sol-gel technology. The oxidation state of these actinides was determined primarily by absorption spectrometry and followed as a function of the solidification process, subsequent aging and thermal treatments. It was determined that the initial oxidation state of the actinides in the starting solutions was essentially maintained through the solidification process to form the glasses. However, during densification and removal of residual solvents at elevated temperatures, both actinides in the different sol-gel products converted completely to their tetravalent states. These results are discussed in terms of our findings in comparable studies that only the tetravalent states of plutonium and neptunium are formed in glasses prepared by dissolving their dioxides in different molten- glass formulations.

  1. Neptunium - Uranium - Plutonium Co-Extraction in TBP-based Solvent Extraction Processes for Spent Nuclear Fuel Recycling

    SciTech Connect

    Arm, S.T.; Abrefah, J.; Lumetta, G.J.; Sinkov, S.I.

    2007-07-01

    The US, through the Global Nuclear Energy Partnership, is currently engaged in efforts aimed at closing the nuclear fuel cycle. Neptunium behavior is important to understand for transuranic recycling because of its complex oxidation chemistry. The Pacific Northwest National Laboratory is investigating neptunium oxidation chemistry in the context of the PUREX process. Neptunium extraction in the PUREX process relies on maintaining either IV or V oxidation states. Qualitative conversion of neptunium(V) to neptunium(VI) was achieved within 5 hours in 6 M nitric acid at 95 deg. C. However, the VI state was not maintained during a batch contact test simulating the PUREX process and neptunium reduced to the V state, rendering it inextractable. Vanadium(V) was found to be effective in maintaining neptunium(VI) by adding it to a simulated irradiated nuclear fuel feed in 6 M nitric acid and to the scrub acid in the batch contact simulation of the PUREX process. Computer simulations of the PUREX process with a typical irradiated nuclear fuel in 6 M nitric acid as feed indicated little impact of the higher acid concentration on the behavior of fission products of moderate extractability. We plan to perform countercurrent tests of this modified PUREX process in the near future. (authors)

  2. EVALUATION OF PROPARGYL BROMIDE AS A SOIL FUMIGANT

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The cut flower and bulb industry has relied heavily upon the use of methyl bromide as a key soil treatment for soilborne pest control. Due to the phase-out of methyl bromide it is important to develop alternatives to manage pests now managed by methyl bromide. The emphasis of this work was to eval...

  3. 21 CFR 522.275 - N-Butylscopolammonium bromide.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 6 2013-04-01 2013-04-01 false N-Butylscopolammonium bromide. 522.275 Section 522....275 N-Butylscopolammonium bromide. (a) Specifications. Each milliliter of solution contains 20 milligrams (mg) N-butylscopolammonium bromide. (b) Sponsor. See No. 000010 in § 510.600(c) of this...

  4. 21 CFR 522.275 - N-Butylscopolammonium bromide.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 6 2011-04-01 2011-04-01 false N-Butylscopolammonium bromide. 522.275 Section 522....275 N-Butylscopolammonium bromide. (a) Specifications. Each milliliter of solution contains 20 milligrams (mg) N-butylscopolammonium bromide. (b) Sponsor. See No. 000010 in § 510.600(c) of this...

  5. 21 CFR 522.275 - N-Butylscopolammonium bromide.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false N-Butylscopolammonium bromide. 522.275 Section 522....275 N-Butylscopolammonium bromide. (a) Specifications. Each milliliter of solution contains 20 milligrams (mg) N-butylscopolammonium bromide. (b) Sponsor. See No. 000010 in § 510.600(c) of this...

  6. 21 CFR 522.275 - N-Butylscopolammonium bromide.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 6 2012-04-01 2012-04-01 false N-Butylscopolammonium bromide. 522.275 Section 522....275 N-Butylscopolammonium bromide. (a) Specifications. Each milliliter of solution contains 20 milligrams (mg) N-butylscopolammonium bromide. (b) Sponsor. See No. 000010 in § 510.600(c) of this...

  7. WEED CONTROL IN THE LIFE AFTER METHYL BROMIDE

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Vegetable growers are losing the soil fumigant methyl bromide. Efforts are on-going to extend the deadline for using methyl bromide until suitable alternatives are developed. Regardless of whether the deadline is extended or not, growers need to begin to study alternatives to methyl bromide and be...

  8. 75 FR 5582 - Methyl Bromide; Amendments to Terminate Uses

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-02-03

    ... AGENCY Methyl Bromide; Amendments to Terminate Uses AGENCY: Environmental Protection Agency (EPA). ACTION... requested by the registrants and accepted by the Agency, of products containing the pesticide methyl bromide... Requests from the registrants listed in Table 2 to amend to terminate post-harvest methyl bromide uses...

  9. 40 CFR 180.124 - Methyl bromide; tolerances for residues.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 24 2014-07-01 2014-07-01 false Methyl bromide; tolerances for... § 180.124 Methyl bromide; tolerances for residues. (a) General. A tolerance is established for residues of the fumigant methyl bromide, including metabolites and degradates, in or on the commodity in...

  10. 7 CFR 305.6 - Methyl bromide fumigation treatment schedules.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 7 Agriculture 5 2010-01-01 2010-01-01 false Methyl bromide fumigation treatment schedules. 305.6..., fumigation with methyl bromide for sapote fruit fly. Regulated citrus fruits originating inside an area... equal concentrations of methyl bromide throughout the chamber, a fan should be placed near the point...

  11. Boronic acid flux synthesis and crystal growth of uranium and neptunium boronates and borates: a low-temperature route to the first neptunium(V) borate.

    PubMed

    Wang, Shuao; Alekseev, Evgeny V; Miller, Hannah M; Depmeier, Wulf; Albrecht-Schmitt, Thomas E

    2010-11-01

    Molten methylboronic acid has been used as a reactive flux to prepare the first neptunium(V) borate, NpO(2)[B(3)O(4)(OH)(2)] (NpBO-1), and the first actinide boronate, UO(2)(CH(3)BO(2))(H(2)O) (UCBO-1). NpBO-1 contains cation-cation interactions between the neptunyl units. In contrast, the presence of the methyl groups in the uranyl boronate leads to a one-dimensional structure. PMID:20919728

  12. Mixed-valent neptunium(IV/V) compound with cation-cation-bound six-membered neptunyl rings.

    PubMed

    Jin, Geng Bang

    2013-11-01

    A new mixed-valent neptunium(IV/V) compound has been synthesized by evaporation of a neptunium(V) acidic solution. The structure of the compound features cation-cation-bound six-membered neptunyl(V) rings. These rings are further connected by Np(IV) ions through cation-cation interactions (CCIs) into a three-dimensional neptunium cationic open framework. This example illustrates the possibility of isolating neptunyl(V) CCI oligomers in inorganic systems using other cations to compete with Np(V) in bonding with the neptunyl oxygen. PMID:24187926

  13. Criticality of a Neptunium-237 sphere surrounded with highly enriched uranium shells and an iron reflector

    SciTech Connect

    Sanchez, R. G.; Loaiza, D. J.; Hayes, D. K.; Kimpland, R. H.

    2004-01-01

    An additional experiment has been performed using the recently cast 6-kg {sup 237}Np sphere. The experiment consisted of surrounding the neptunium sphere with highly enriched uranium and an iron reflector. The purpose of the critical experiment is to provide additional criticality data that can be used to validate criticality safety evaluations involving the deposition of neptunium. It is well known that {sup 237}Np is primarily produced by successive neutron capture events in {sup 235}U or through the (n, 2n) reaction in {sup 238}U. These nuclear reactions lead to the production of {sup 237}U, which decays by beta emission into {sup 237}Np. In addition, in the spent fuel, {sup 241}Am decays by alpha emission into {sup 237}Np. Because {sup 237}Np is a threshold fissioner, the best reflectors for critical systems containing neptunium are those materials that exhibit good neutron scattering properties such as low carbon steel (99 wt % Fe). In this experiment, the iron reflector reduced the amount of uranium used in the critical experiment and increased the importance of the neptunium sphere.

  14. High-temperature X-ray diffraction study of uranium-neptunium mixed oxides.

    PubMed

    Chollet, Mélanie; Belin, Renaud C; Richaud, Jean-Christophe; Reynaud, Muriel; Adenot, Frédéric

    2013-03-01

    Incorporating minor actinides (MAs = Am, Np, Cm) in UO2 fertile blankets is a viable option to recycle them. Despite this applied interest, phase equilibria between uranium and MAs still need to be thoroughly investigated, especially at elevated temperatures. In particular, few reports on the U-Np-O system are available. In the present work, we provide for the first time in situ high-temperature X-ray diffraction results obtained during the oxidation of (U1-yNpy)O2 uranium-neptunium mixed oxides up to 1373 K and discuss subsequent phase transformations. We show that (i) neptunium stabilizes the UO2-type fluorite structure at high temperature and that (ii) the U3O8-type orthorhombic structure is observed in a wide range of compositions. We clearly demonstrate the incorporation of neptunium in this phase, which was a controversial question in previous studies up to now. We believe it is the particular stability of the tetravalent state of neptunium that is responsible for the observed phase relationships. PMID:23409700

  15. The influence of phonon anharmonicity on thermal and elastic properties of neptunium

    NASA Astrophysics Data System (ADS)

    Filanovich, A.; Povzner, A.

    2013-06-01

    A self-consistent thermodynamic model describing the thermal and elastic properties of α- and β-phases of neptunium was developed. The presence of strong phonon anharmonicity of Np is established. The obtained results are in good agreement with the experimental data and enable to predict the Np properties in wide temperature range.

  16. Photoelectron, nuclear gamma-ray and infrared absorption spectroscopic studies of neptunium in sodium silicate glass

    SciTech Connect

    Veal, B.W.; Carnall, W.T.; Dunlap, B.D.; Mitchell, A.W.; Lam, D.J.

    1986-04-01

    The valence state of neptunium ions in sodium silicate glasses prepared under reducing and oxidizing conditions has been investigated by the x-ray photoelectron, Moessbauer and optical absorption spectroscopic techniques. Results indicate that the Np ions are tetravalent in glasses prepared under reducing conditions and pentavalent in glasses prepared under oxidizing conditions.

  17. Gastrointestinal absorption of neptunium in primates: effect of ingested mass, diet, and fasting

    SciTech Connect

    Metivier, H.; Bourges, J.; Fritsch, P.; Nolibe, D.; Masse, R.

    1986-05-01

    Absorption and retention of neptunium were determined in baboons after intragastric administration of neptunium nitrate solutions at pH 1. The effects of mass, diet, and fasting on absorption were studied. At higher mass levels (400-800 micrograms Np/kg), absorption was about 1%; at lower mass intakes (0.0009-0.005 micrograms Np/kg), absorption was reduced by 10- to 20-fold. The addition of an oxidizing agent (Fe3+) increased gastrointestinal absorption and supported the hypothesis of a reduction of Np (V) when loss masses were ingested. Diets depleted of or enriched with hydroxy acids did not modify retention of neptunium but increased urinary excretion with increasing hydroxy acid content. The diet enriched with milk components reduced absorption by a factor of 5. Potatoes increased absorption and retention by a factor 5, not necessarily due to the effect of phytate. Fasting for 12 or 24 h increased retention and absorption by factors of about 3 and 10, respectively. Data obtained in baboons when low masses of neptunium were administered suggest that the f1 factor used by ICRP should be decreased. However, fasting as encountered in certain nutritional habits is a factor to be taken into consideration.

  18. Measurements of atmospheric methyl bromide and bromoform

    SciTech Connect

    Cicerone, R.J.; Heidt, L.E.; Pollock, W.H.

    1988-04-20

    We have measured gaseous methyl bromide (CH/sub 3/Br) and bromoform (CHBr/sub 3/) in air samples that were gathered approximately weekly from five ground-level sites: Point Barrow, Alaska; Mauna Loa Observatory and Cape Kumukahi, Hawaii; Matatula, Samoa; and Kaitorete Spit, New Zealand. Approximately 750 samples have been analyzed for CH/sub 3/Br between January 1985 and October 1987 and 990 samples have been analyzed for CHBr/sub 3/ between early 1984 and September 1987, all by gas chromatography/mass spectroscopy. Methyl bromide concentrations are typically 10--11 parts per trillion (ppt) by volume; there are no clear indications of temporal increases. Bromoform concentrations are typically 2--3 ppt, but large seasonal variations are seen at Point Barrow. copyright American Geophysical Union 1988

  19. Removal of bromide and natural organic matter by anion exchange.

    PubMed

    Hsu, Susan; Singer, Philip C

    2010-04-01

    Bromide removal by anion exchange was explored for various water qualities, process configurations, and resin characteristics. Simulated natural waters containing different amounts of natural organic matter (NOM), bicarbonate, chloride, and bromide were treated with a polyacrylate-based magnetic ion exchange (MIEX) resin on a batch basis to evaluate the effectiveness of the resin for removal of bromide. While bromide removal was achieved to some degree, alkalinity (bicarbonate), dissolved organic carbon (DOC), and chloride were shown to inhibit bromide removal in waters with bromide concentrations of 100 and 300 microg/L. Water was also treated using a two-stage batch MIEX process. Two-stage treatment resulted in only a slight improvement in bromide removal compared to single-stage treatment, presumably due to competition with the high concentration of chloride which is present along with bromide in natural waters. In view of the relatively poor bromide removal results for the MIEX resin, a limited set of experiments was performed using polystyrene resins. DOC and bromide removal were compared by treating model waters with MIEX and two polystyrene resins, Ionac A-641 and Amberlite IRA910. The two polystyrene resins were seen to be more effective for bromide removal, while the MIEX resin was more effective at removing DOC. PMID:20045170

  20. Methyl bromide: Ocean sources, ocean sinks, and climate sensitivity

    SciTech Connect

    Anbar, A.D.; Yung, Y.L.; Chavez, F.P.

    1996-03-01

    This study was performed to examine conflicting conclusions of two previously published studies which estimated the size of oceanic sources of methyl bromide. In addition, the sensitivity of atmospheric methyl bromide to climatic variations was examined. A steady state mass balance model was used to reexamine data from the previous studies. Linear scaling of methyl bromide production rates to chlorophyll content provided agreement between the two models. The results suggest that the open ocean is a small net sink for atmospheric methyl bromide, rather than a large net source. A high rate of biological production of methyl bromide in seawater is also strongly indicated. A coupled ocean-atmosphere model indicated that methyl bromide variations induced by climatic change can be larger than those resulting from 25% variations in anthropogenic sources. Quantifying marine production rates of methyl bromide is suggested as a necessary step in assessing stratospheric ozone loss. 63 refs., 10 figs., 2 tabs.

  1. [Research advances in methyl bromide in the ocean].

    PubMed

    Du, Hui-na; Xie, Wen-xia; Cui, Yu-qian; Chen, Jian-lei; Ye, Si-yuan

    2014-12-01

    Methyl bromide is an important atmospheric trace gas, which plays significant roles in the global warming and atmospheric chemistry. The ocean plays important and complex roles in the global biogeochemical cycles of methyl bromide, not only the source of atmospheric methyl bromide, but also the sink. Therefore, developing the chemical research of the soluble methyl bromide in the ocean, will not only have a certain guiding significance to the atmospheric ozone layer protection, but also provide a theoretical basis for estimating methyl bromide's contribution to the global environmental change on global scale. This paper reviewed the research advances on methyl bromide in the ocean, from the aspects of the biogeochemical cycle of methyl bromide in the ocean, the analysis and determination method, the concentration distribution, the sea-to-air flux and its sources and sinks in the atmosphere. Some deficiencies in the current studies were put forward, and the directions of the future studies were prospected. PMID:25876424

  2. Lattice vibrations in lead bromide and chloride

    NASA Astrophysics Data System (ADS)

    Carabatos-Nédelec, C.; Bréhat, F.; Wyncke, B.

    Lead bromide and lead chloride lattice dynamics studies by polarized IR reflectivity and Raman scattering are reported at room temperature and at 10 K. Reflectivity spectra from 20 to 300 cm -1 have been fitted with a model of the factorized form of the dielectric function. The lattice modes frequencies, damping factors and oscillators strengths are given, as well as the effective charges of the polar modes. The study concludes the ionic character of the compounds.

  3. Methyl bromide users search for science

    SciTech Connect

    Winegar, E.D.

    1995-01-01

    Workers, neighbors and the ozone are protected by regulation from this chemical, but those needing it complain that a solid foundation is lacking for the rules. Although not yet featured on {open_quotes}60 Minutes,{close_quotes} the pesticide methyl bromide is gaining widespread attention because of its central position in debates about worker health and safety, environmental toxics exposure and global ozone depletion.

  4. PLUTONIUM-238 RECOVERY FROM IRRADIATED NEPTUNIUM TARGETS USING SOLVENT EXTRACTION

    SciTech Connect

    Scott Herbst; Terry Todd; Jack Law; Bruce Mincher; Steve Frank; John Swanson

    2006-10-01

    The United States Department of Energy proposes to re-establish a domestic capability for producing plutonium-238 (238Pu) to fuel radioisotope power systems primarily in support of future space missions. A conceptual design report is currently being prepared for a new 238Pu, and neptunium-237 (237Np) target fabrication and processing facility tentatively to be built at the Idaho National Laboratory (INL) in the USA. The facility would be capable of producing at least 5 kg of 238Pu-oxide powder per year. Production of 238Pu requires fabrication of 237Np targets with subsequent irradiation in the existing Advanced Test Reactor (ATR) located at the INL. The targets are 237Np oxide dispersed in a compact of powdered aluminum and clad with aluminum metal. The 238Pu product is separated and purified from the residual 237Np, aluminum matrix, and fission products. The unconverted 237Np is also a valuable starting material and is separated, purified and recycled to the target fabrication process. The proposed baseline method for separating and purifying 238Pu and unconverted 237Np post irradiation is by anion exchange (IX). Separation of Pu from Np by IX was chosen as the baseline method because of the method’s proven ability to produce a quality Pu product and because it is amenable to the relatively small scale, batch type production methods used (small batches of ~200g 238Pu are processed at a time). Multiple IX cycles are required involving substantial volumes of nitric acid and other process solutions which must be cleaned and recycled or disposed of as waste. Acid recycle requires rather large evaporator systems, including one contained in a hot cell for remote operation. Finally, the organic based anion exchange resins are rapidly degraded due to the high a-dose and associated heat production from 238Pu decay, and must be regularly replaced (and disposed of as waste). In summary, IX is time consuming, cumbersome, and requires substantial tankage to accommodate the

  5. Bromate oxidized from bromide during sonolytic ozonation.

    PubMed

    Lu, Ning; Wu, Xue-Fei; Zhou, Ji-Zhi; Huang, Xin; Ding, Guo-Ji

    2015-01-01

    Sonolytic ozonation (US/O3) is an effective way to degrade many pollutants in drinking water as the elevated mass transfer rate of ozone gas and the enhanced forming of hydroxyl radicals (OH). This work investigated the formation of bromate (BrO3(-)) from bromide (Br(-)) in sonolytic ozonation. At neutral pH, the bromate conversion rate ([BrO3(-)]/[Br(-)]0) was increased to 60% by ultrasound at continuous ozone flow (0-0.2Lmin(-1)), much higher than that without ultrasound or without bubbling. This indicates that the promoting effect of sonolysis on BrO3(-) formation is mainly due to the sonolytic decomposition of ozone and the enhancement of gas-liquid transfer. The [BrO3(-)]/[Br(-)]0 was increased with increasing pH. In addition, the reduction of HOBr/OBr(-) with ultrasound demonstrates that bromate may be inhibited as the bromide was formed with the H2O2 generation under ultrasound. This suggests the competition between bromate and bromide during the US/O3 led to the inhibition of bromate formation at high ozone flow. Therefore, our result reveals that the bromate formation under ultrasound is improved remarkably in US/O3 in quick treatment with proper ozone flow (<0.2Lmin(-1)). PMID:24931426

  6. Methyl bromide volatility measurements from treated fields

    SciTech Connect

    Majewski, M.S.; Woodrow, J.E.; Seiber, J.N. |

    1995-12-31

    Methyl bromide is used as an agricultural soil fumigant and concern is growing over the role it may play in the depletion of stratospheric ozone. Methyl bromide is applied using various techniques and little is known about how much of the applied fumigant volatilizes into the atmosphere after application. The post-application volatilization losses of methyl bromide from two fields using different application practices were measured using an aerodynamic-gradient technique. One field was covered with a high-barrier plastic film tarp during application and the other was left uncovered, but the furrows made by the injection shanks were bedded over. The cumulative volatilization losses from the tarped field were 22% of the nominal application within the first 5 days of the experiment and about 32% of the nominal application within 9 days including the one day after the tarp was removed on day 8. The nontarped field lost 89%of the nominal application by volatilization in 5 days. The error associated, with each flux measurement, as well as variations in daily flux losses with differing sampling period lengths show the degree of variability inherent in this type of study.

  7. Methyl bromide fate in fumigated soils

    SciTech Connect

    Anderson, T.A.; Rice, P.J.; Cink, J.H.

    1995-12-31

    Although widespread use of methyl bromide (MeBr) as a sail and structure fumigant has previously been recognized as a potential significant source of atmospheric MeBr, losses have not been well quantified. Our research indicates that, in laboratory studies, MeBr is volatilized rapidly from fumigated soils and that volatility increases with temperature (35{degrees}C > 25{degrees}C and 15{degrees}C) and moisture (0.03 bar and 0.3 bar > 1 bar > 3 bar). Degradation of MeBr in soil, as indicated by production of bromide ion, was also directly related to temperature and moisture. Most of the soil degradation of MeBr in these studies appears to be abiotic based on the observation of toxicity (reduced microbial respiration) in fumigated soils. We also determined the transformation and movement of MeBr in undisturbed soil columns. These studies also indicated that MeBT volatilizes rapidly (> 50% in 48 h) from soil. In addition, MeBr was not detected in the leachate from the soil columns, however, bromide ion was detected at levels above background 48 h after fumigation and peaked at 5 weeks.

  8. A Structural Study of Neptunium-Bearing Uranium Oxides

    NASA Astrophysics Data System (ADS)

    Finch, R. J.

    2002-05-01

    Neptunium is an element of significant concern at several contaminated DOE sites, as well as being potentially the largest long-term contributor of radiation dose to people living near the high-level nuclear-waste repository recently recommended by the President for construction at Yucca Mountain, Nevada. In order to understand potential structural effects of Np substitution into uranium minerals, we have synthesized a series of Np-doped U oxides and present here results of a structural study of Np-doped U3O8 (NpxU3-xO8). Although not a mineral, U3O8 bears significant structural similarities to numerous uranyl minerals with both known and potential importance as radionuclide hosts in the environment (Burns et al., Can. Mineral. 34, 845, 1997). Qualitative chemical analyses of U3O8 powders by energy-dispersive x-ray emission spectroscopy (EDS) in a scanning electron microscope indicate that sample powders are homogeneous at the micrometer scale. Further examinations by electron energy-loss spectroscopy (EELS) and EDS in a transmission electron microscope do not reveal compositional inhomogeneities or discernable variability in the Np:U ratios within samples having Np:U ratios of 1:80 and 1:8. Bulk samples of Np-doped U3O8 powders having Np:U ratios of 1:160, 1:80, 1:25, and 1:8, were also analyzed by X-ray absorption near-edge spectroscopy (XANES), which indicates that Np occupies distorted U sites and is predominantly tetravalent. X-ray powder diffraction (XRD) analyses of pure U3O8 and Np-doped U3O8 show that incorporation of Np into U3O8 affects positions and intensities of diffraction peaks, but that all samples are isostructural with alpha-U3O8. No spurious diffraction peaks are observed in any powder patterns of U3O8 with Np:U from 1:160 to 1:8. Lattice parameters vary smoothly as a function of Np concentration. The c cell parameter (perpendicular to the plane of the structural sheets in U3O8) shows little or no dependence on Np concentration, whereas the a

  9. Europium-doped barium bromide iodide

    SciTech Connect

    Gundiah, Gautam; Hanrahan, Stephen M.; Hollander, Fredrick J.; Bourret-Courchesne, Edith D.

    2009-10-21

    Single crystals of Ba0.96Eu0.04BrI (barium europium bromide iodide) were grown by the Bridgman technique. The title compound adopts the ordered PbCl2 structure [Braekken (1932). Z. Kristallogr. 83, 222-282]. All atoms occupy the fourfold special positions (4c, site symmetry m) of the space group Pnma with a statistical distribution of Ba and Eu. They lie on the mirror planes, perpendicular to the b axis at y = +-0.25. Each cation is coordinated by nine anions in a tricapped trigonal prismatic arrangement.

  10. Boronic Acid Flux Synthesis and Crystal Growth of Uranium and Neptunium Boronates and Borates: A Low Temperature Route to the First Neptunium(V) Borate

    SciTech Connect

    Wang, Shuao; Alekseev, Evgeny V.; Miller, Hannah M.; Depmeier, Wulf; Albrecht-Schmitt, Thomas E.

    2010-10-04

    Molten methylboronic acid has been used as a reactive flux to prepare the first neptunium(V) borate, NpO2[B3O4(OH)2] (NpBO-1), and the first actinide boronate, UO2(CH3BO2)(H2O) (UCBO-1). NpBO-1 contains cation-cation interactions between the neptunyl units. In contrast, the presence of the methyl groups in the uranyl boronate leads to a one-dimensional structure.

  11. Advanced hydrogen electrode for hydrogen-bromide battery

    NASA Technical Reports Server (NTRS)

    Kosek, Jack A.; Laconti, Anthony B.

    1987-01-01

    Binary platinum alloys are being developed as hydrogen electrocatalysts for use in a hydrogen bromide battery system. These alloys were varied in terms of alloy component mole ratio and heat treatment temperature. Electrocatalyst evaluation, performed in the absence and presence of bromide ion, includes floating half cell polarization studies, electrochemical surface area measurements, X ray diffraction analysis, scanning electron microscopy analysis and corrosion measurements. Results obtained to date indicate a platinum rich alloy has the best tolerance to bromide ion poisoning.

  12. Chemical speciation of neptunium in spent fuel. Annual report for period 15 August 1999 to 15 August 2000

    SciTech Connect

    Ken Czerwinski; Don Reed

    2000-09-01

    (B204) This project will examine the chemical speciation of neptunium in spent nuclear fuel. The R&D fields covered by the project include waste host materials and actinide chemistry. Examination of neptunium is chosen since it was identified as a radionuclide of concern by the NERI workshop. Additionally, information on the chemical form of neptunium in spent fuel is lacking. The identification of the neptunium species in spent fuel would allow a greater scientific based understanding of its long-term fate and behavior in waste forms. Research to establish the application and development of X-ray synchrotrons radiation (XSR) techniques to determine the structure of aqueous, adsorbed, and solid actinide species of importance to nuclear considerations is being conducted at Argonne. These studies extend current efforts within the Chemical Technology Division at Argonne National Laboratory to investigate actinide speciation with more conventional spectroscopic and solids characterization (e.g. SEM, TEM, and XRD) methods. Our project will utilize all these techniques for determining neptunium speciation in spent fuel. We intend to determine the chemical species and oxidation state of neptunium in spent fuel and alteration phases. Different types of spent fuel will be examined. Once characterized, the chemical behavior of the identified neptunium species will be evaluated if it is not present in the literature. Special attention will be given to the behavior of the neptunium species under typical repository near-field conditions (elevated temperature, high pH, varying Eh). This will permit a timely inclusion of project results into near-field geochemical models. Additionally, project results and methodologies have applications to neptunium in the environment, or treatment of neptunium containing waste. Another important aspect of this project is the close cooperation between a university and a national laboratory. The PI has a transuranic laboratory at MIT where

  13. Long-term desorption behavior of uranium and neptunium in heterogeneous volcanic tuff materials /

    SciTech Connect

    Dean, Cynthia A.

    2010-05-01

    Uranium and neptunium desorption were studied in long-term laboratory experiments using four well-characterized volcanic tuff cores collected from southeast of Yucca Mountain, Nevada. The objectives of the experiments were to 1. Demonstrate a methodology aimed at characterizing distributions of sorption parameters (attributes of multiple sorption sites) that can be applied to moderately-sorbing species in heterogeneous systems to provide more realistic reactive transport parameters and a more realistic approach to modeling transport in heterogeneous systems. 2. Focus on uranium and neptunium because of their high solubility, relatively weak sorption, and high contributions to predicted dose in Yucca Mountain performance assessments. Also, uranium is a contaminant of concern at many DOE legacy sites and uranium mining sites.

  14. Development of Defined, Minimal, and Complete Media for the Growth of Hyphomicrobium neptunium

    PubMed Central

    Havenner, Jeffrey A.; McCardell, Barbara A.; Weiner, Ronald M.

    1979-01-01

    A complete synthetic medium containing 15 amino acids, a minimal synthetic medium (GAMS) containing 4 amino acids, and a supplemented minimal medium (GAMS + calcium pantothenate) have been developed for the cultivation of Hyphomicrobium neptunium ATCC 15444. Depending on the complexity of the synthetic media, generation times were approximately 2 to 3 times longer, and maximum cell densities were 0.3 to 0.9 log10 lower than in ZoBell marine broth 2216. The fates of 14C-labeled amino acids in GAMS were monitored. Results suggested that H. neptunium was auxotrophic for methionine, utilized glutamic acid as a primary energy source, and readily anabolized and catabolized serine and aspartic acid. Individual amino acid concentrations above 125 mM induced prolonged lag periods, whereas only methionine was not growth limiting at a concentration as low as 2 mM. PMID:16345413

  15. Kinetics of oxidation of pentavalent neptunium by pentavalent vanadium in solutions of nitric acid

    NASA Astrophysics Data System (ADS)

    Precek, Martin; Paulenova, Alena

    2010-03-01

    Management of the oxidation state of neptunium in the reprocessing of spent nuclear fuel by solvent extraction is very important. The kinetics of the oxidation of neptunium(V) by vanadium(V) in solutions of nitrate acid was investigated at constant ionic strength 4M. The reaction rate is first order with respect to Np(V) and V(V). The effects of proton concentration on the apparent second order rate constant k1" was determined for temperature 25°C as k1" = (0.99±0.03)·[H+]1.21M-1s-1. Activation parameters associated with the overall reaction have been calculated; the standard reaction enthalpy and entropy were 52.6±0.9 kJ/mol and -55.8±0.9 J/K/mol respectively.

  16. Theoretical studies on level structures and transition properties of neptunium ions

    NASA Astrophysics Data System (ADS)

    Zhou, W. D.; Dong, C. Z.; Wang, Q. M.; Wang, X. L.; Saber, I. A.

    2012-10-01

    Multiconfiguration Dirac-Fock (MCDF) method was employed to calculate the ionization potentials, ionic radii, excitation energies and oscillator strengths for neptunium ions. In the calculations, main valence correlation effects, Breit interaction and QED effects were taken into account. The good consistency with other available theoretical values demonstrates the validity of the present calculations. These theoretical results therefore can be used to predict some physicochemical properties of Np and its oxides.

  17. Comparison of sample preparation methods for reliable plutonium and neptunium urinalysis using automatic extraction chromatography.

    PubMed

    Qiao, Jixin; Xu, Yihong; Hou, Xiaolin; Miró, Manuel

    2014-10-01

    This paper describes improvement and comparison of analytical methods for simultaneous determination of trace-level plutonium and neptunium in urine samples by inductively coupled plasma mass spectrometry (ICP-MS). Four sample pre-concentration techniques, including calcium phosphate, iron hydroxide and manganese dioxide co-precipitation and evaporation were compared and the applicability of different techniques was discussed in order to evaluate and establish the optimal method for in vivo radioassay program. The analytical results indicate that the various sample pre-concentration approaches afford dissimilar method performances and care should be taken for specific experimental parameters for improving chemical yields. The best analytical performances in terms of turnaround time (6h) and chemical yields for plutonium (88.7 ± 11.6%) and neptunium (94.2 ± 2.0%) were achieved by manganese dioxide co-precipitation. The need of drying ashing (≥ 7h) for calcium phosphate co-precipitation and long-term aging (5d) for iron hydroxide co-precipitation, respectively, rendered time-consuming analytical protocols. Despite the fact that evaporation is also somewhat time-consuming (1.5d), it endows urinalysis methods with better reliability and repeatability compared with co-precipitation techniques. In view of the applicability of different pre-concentration techniques proposed previously in the literature, the main challenge behind relevant method development is pointed to be the release of plutonium and neptunium associated with organic compounds in real urine assays. In this work, different protocols for decomposing organic matter in urine were investigated, of which potassium persulfate (K2S2O8) treatment provided the highest chemical yield of neptunium in the iron hydroxide co-precipitation step, yet, the occurrence of sulfur compounds in the processed sample deteriorated the analytical performance of the ensuing extraction chromatographic separation with chemical

  18. Molecular toolbox for genetic manipulation of the stalked budding bacterium Hyphomonas neptunium.

    PubMed

    Jung, Alexandra; Eisheuer, Sabrina; Cserti, Emöke; Leicht, Oliver; Strobel, Wolfgang; Möll, Andrea; Schlimpert, Susan; Kühn, Juliane; Thanbichler, Martin

    2015-01-01

    The alphaproteobacterium Hyphomonas neptunium proliferates by a unique budding mechanism in which daughter cells emerge from the end of a stalk-like extension emanating from the mother cell body. Studies of this species so far have been hampered by the lack of a genetic system and of molecular tools allowing the regulated expression of target genes. Based on microarray analyses, this work identifies two H. neptunium promoters that are activated specifically by copper and zinc. Functional analyses show that they have low basal activity and a high dynamic range, meeting the requirements for use as a multipurpose expression system. To facilitate their application, the two promoters were incorporated into a set of integrative plasmids, featuring a choice of two different selection markers and various fluorescent protein genes. These constructs enable the straightforward generation and heavy metal-inducible synthesis of fluorescent protein fusions in H. neptunium, thereby opening the door to an in-depth analysis of polar growth and development in this species. PMID:25398860

  19. Effects of Titanium Doping in Titanomagnetite on Neptunium Sorption and Speciation.

    PubMed

    Wylie, E Miller; Olive, Daniel T; Powell, Brian A

    2016-02-16

    Neptunium-237 is a radionuclide of great interest owing to its long half-life (2.14 × 10(6) years) and relative mobility as the neptunyl ion (NpO2(+)) under many surface and groundwater conditions. Reduction to tetravalent neptunium (Np(IV)) effectively immobilizes the actinide in many instances due to its low solubility and strong interactions with natural minerals. One such mineral that may facilitate the reduction of neptunium is magnetite (Fe(2+)Fe(3+)2O4). Natural magnetites often contain titanium impurities which have been shown to enhance radionuclide sorption via titanium's influence on the Fe(2+)/Fe(3+) ratio (R) in the absence of oxidation. Here, we provide evidence that Ti-substituted magnetite reduces neptunyl species to Np(IV). Titanium-substituted magnetite nanoparticles were synthesized and reacted with NpO2(+) under reducing conditions. Batch sorption experiments indicate that increasing Ti concentration results in higher Np sorption/reduction values at low pH. High-resolution transmission electron microscopy of the Ti-magnetite particles provides no evidence of NpO2 nanoparticle precipitation. Additionally, X-ray absorption spectroscopy confirms the nearly exclusive presence of Np(IV) on the titanomagnetite surface and provides supporting data indicating preferential binding of Np to terminal Ti-O sites as opposed to Fe-O sites. PMID:26756748

  20. Molecular Toolbox for Genetic Manipulation of the Stalked Budding Bacterium Hyphomonas neptunium

    PubMed Central

    Jung, Alexandra; Eisheuer, Sabrina; Cserti, Emöke; Leicht, Oliver; Strobel, Wolfgang; Möll, Andrea; Schlimpert, Susan; Kühn, Juliane

    2014-01-01

    The alphaproteobacterium Hyphomonas neptunium proliferates by a unique budding mechanism in which daughter cells emerge from the end of a stalk-like extension emanating from the mother cell body. Studies of this species so far have been hampered by the lack of a genetic system and of molecular tools allowing the regulated expression of target genes. Based on microarray analyses, this work identifies two H. neptunium promoters that are activated specifically by copper and zinc. Functional analyses show that they have low basal activity and a high dynamic range, meeting the requirements for use as a multipurpose expression system. To facilitate their application, the two promoters were incorporated into a set of integrative plasmids, featuring a choice of two different selection markers and various fluorescent protein genes. These constructs enable the straightforward generation and heavy metal-inducible synthesis of fluorescent protein fusions in H. neptunium, thereby opening the door to an in-depth analysis of polar growth and development in this species. PMID:25398860

  1. Influence of dissolved organic substances in groundwater on sorption behavior of americium and neptunium

    SciTech Connect

    Boggs, S. Jr.; Seitz, M.G.

    1984-01-01

    Groundwaters typically contain dissolved organic carbon consisting largely of high molecular weight compounds of humic and fulvic acids. To evaluate whether these dissolved organic substances can enhance the tranport of radionuclides through the groundwater system, experiments were conducted to examine the sorption of americium and neptunium onto crushed basalt in the presence of dissolved humic- and fulvic-acid organic carbon introduced into synthetic groundwater. The partitioning experiments with synthetic groundwater show that increasing the concentration of either humic or fulvic acid in the water has a significant inhibiting effect on sorption of both americium and neptunium. At 22/sup 0/C, adsorption of these radionuclides, as measured by distribution ratios (the ratio of nuclide sorbed onto the solid to nuclide in solution at the end of the experiment), decreased by 25% to 50% by addition of as little as 1 mg/L dissolved organic carbon and by one to two orders of magnitude by addition of 100 to 200 mg/L dissolved organic carbon. Distribution ratios measured in solutions reacted at 90/sup 0/C similarly decreased with the addition of dissolved organic carbon but generally ranged from one to two orders of magnitude higher than those determined in the 22/sup 0/C experiment. These results suggest that organic carbon dissolved in deep groundwaters may significantly enhance the mobility of radionuclides of americium and neptunium. 23 references, 5 figures, 11 tables.

  2. Complexation of neptunium(V) with fluoride in aqueous solutions at elevated temperatures

    SciTech Connect

    Tian, Guoxin; Rao, Linfeng; Xia, Yuanxian; Friese, Judah I.

    2009-02-01

    Over the past several decades, the production and testing of nuclear weapons in the U.S. have created significant amounts of high-level nuclear wastes (HLW) that are currently stored in underground tanks across the U.S. DOE (Department of Energy) sites. Eventually, the HLW will be made into the waste form and disposed of in geological repositories for HLW. Among the radioactive materials, neptunium is of great concern in the post-closure chemical environment in the repository because of the long half-life of 237Np (2.14•106 years) and the high mobility of Np(V), the most stable oxidation state of neptunium. It is estimated that 237Np, together with 129I and 99Tc, will be the major contributors to the potential total annual dose from the repository beyond 10000 years [1]. Due to the high radiation energy released from the HLW, the postclosure repository is expected to remain at elevated temperatures for thousands of years [1]. If the waste package is breached and becomes in contact with groundwater, neptunium, as well as other radioactive materials will be in aqueous solutions at elevated temperatures. Interactions of radioactive materials with the chemical components in groundwater play an important role in determining their migration in the repository. To predict the migration behavior of neptunium, it is necessary to have sufficient and reliable thermodynamic data on its complexation with the ligands that are present in the groundwater of the repository (e.g., OH–, F–, SO42– ,PO43– and CO32) at elevated temperatures. However, such data are scarce and scattered for 25°C, and nearly nonexistent for elevated temperatures [2]. To provide reliable thermodynamic data, we have conducted investigations of the complexation of actinides, including thorium, uranium, neptunium and plutonium, at elevated temperatures. Thermodynamic parameters, including formation constants, enthalpy and heat capacity of complexation are experimentally determined. This paper

  3. Mineralogic controls on aqueous neptunium(V) concentrations in silicate systems

    NASA Astrophysics Data System (ADS)

    Alessi, Daniel S.; Szymanowski, Jennifer E. S.; Forbes, Tori Z.; Quicksall, Andrew N.; Sigmon, Ginger E.; Burns, Peter C.; Fein, Jeremy B.

    2013-02-01

    The presence of radioactive neptunium in commercially spent nuclear fuel is problematic due to its mobility in environmental systems upon oxidation to the pentavalent state. As uranium is the major component of spent fuel, incorporation of neptunium into resulting U(VI) mineral phases would potentially influence its release into environmental systems. Alternatively, aqueous neptunium concentrations may be buffered by solid phase Np2O5. In this study, we investigate both of these controls on aqueous neptunium(V) concentrations. We synthesize two uranyl silicates, soddyite, (UO2)2SiO4·2H2O, and boltwoodite, (K, Na)(UO2)(SiO3OH)·1.5H2O, each in the presence of two concentrations of aqueous Np(V). Electron microscopy and electron diffraction analyses of the synthesized phases show that while significant neptunyl incorporation occurred into soddyite, the Np(V) in the boltwoodite systems largely precipitated as a secondary phase, Np2O5(s). The release of Np(V) from each system into aqueous solution was measured for several days, until steady-state concentrations were achieved. Using existing solubility constants (Ksp) for pure soddyite and boltwoodite, we compared predicted equilibrium aqueous U(VI) concentrations with the U(VI) concentrations released in the solubility experiments. Our experiments reveal that Np(V) incorporation into soddyite increases the concentration of aqueous U in equilibrium with the solid phase, perhaps via the formation of a metastable phase. In the mixed boltwoodite - Np2O5(s) system, the measured aqueous U(VI) activities are consistent with those predicted to be in equilibrium with boltwoodite under the experimental conditions, a result that is consistent with our conclusion that little Np(V) incorporation occurred into the boltwoodite. In the boltwoodite systems, the measured Np concentrations are likely controlled by the presence of Np2O5 nanoparticles, suggesting an additional potential mobility vector for Np in geologic systems. Our

  4. 40 CFR 180.124 - Methyl bromide; tolerances for residues.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 25 2012-07-01 2012-07-01 false Methyl bromide; tolerances for residues. 180.124 Section 180.124 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR PESTICIDE CHEMICAL RESIDUES IN FOOD Specific Tolerances § 180.124 Methyl bromide; tolerances...

  5. An Ill Wind: Methyl Bromide Use Near California Schools, 1998.

    ERIC Educational Resources Information Center

    Ross, Zev; Walker, Bill

    A California study investigates the use of the toxic pesticide methyl bromide near the state's public schools, explains why proposed safety rules have failed to protect children and others from exposure, and examines regions at particular exposure risk. Study results show an increasing exposure to methyl bromide near schools already at risk while…

  6. 40 CFR 180.124 - Methyl bromide; tolerances for residues.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 25 2013-07-01 2013-07-01 false Methyl bromide; tolerances for residues. 180.124 Section 180.124 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR PESTICIDE CHEMICAL RESIDUES IN FOOD Specific Tolerances § 180.124 Methyl bromide; tolerances...

  7. EVALUATING EFFECTS OF NEPTUNIUM ON THE SRS METHOD FOR CONTROLLED POTENTIAL COULOMETRIC ASSAY OF PLUTONIUM IN SULFURIC ACID SUPPORTING ELECTROLYTE

    SciTech Connect

    Holland, M; Sheldon Nichols, S

    2008-05-09

    A study of the impact of neptunium on the coulometric assay of plutonium in dilute sulfuric acid was performed. Weight aliquots of plutonium standard solutions were spiked with purified neptunium solution to evaluate plutonium measurement performance for aliquots with Pu:Np ratios of 50:1, 30:1, 20:1, 15:1, and 10:1. Weight aliquots of the pure plutonium standard solution were measured as controls. Routine plutonium instrument control standards were also measured. The presence of neptunium in plutonium aliquots significantly increases the random uncertainty associated with the plutonium coulometric measurement performed in accordance with ISO12183:2005.7 However, the presence of neptunium does not appear to degrade electrode performance and conditioning as aliquots of pure plutonium that were interspersed during the measurement of the mixed Pu:Np aliquots continued to achieve the historical short-term random uncertainty for the method. Lack of adequate control of the neptunium oxidation state is suspected to be the primary cause of the elevated measurement uncertainty and will be pursued in a future study.

  8. Interaction of methyl bromide with soil.

    PubMed

    Tao, Ting; Maciel, Gary E

    2002-02-15

    Because methyl bromide (CH3Br) is a widely used agricultural fumigant for soil disinfection, it is important to know the chemical behavior and fate of CH3Br as a result of its use for soil treatment. A solid-state 13C NMR study of 13CH3Br-treated soil and soil-component samples shows that methylation of soil organic matter may be the major pathway for degradation of CH3Br in soils. Adsorption of CH3Br on a dried clay like Ca-montmorillonite or kaolinite does not contribute directly to the degradation of CH3Br. The results are interpreted in terms of the chemical structures of separated soil fractions and the nature of the separation procedure. PMID:11878373

  9. Single ion dynamics in molten sodium bromide

    SciTech Connect

    Alcaraz, O.; Trullas, J.; Demmel, F.

    2014-12-28

    We present a study on the single ion dynamics in the molten alkali halide NaBr. Quasielastic neutron scattering was employed to extract the self-diffusion coefficient of the sodium ions at three temperatures. Molecular dynamics simulations using rigid and polarizable ion models have been performed in parallel to extract the sodium and bromide single dynamics and ionic conductivities. Two methods have been employed to derive the ion diffusion, calculating the mean squared displacements and the velocity autocorrelation functions, as well as analysing the increase of the line widths of the self-dynamic structure factors. The sodium diffusion coefficients show a remarkable good agreement between experiment and simulation utilising the polarisable potential.

  10. Degradation of methyl bromide in anaerobic sediments

    USGS Publications Warehouse

    Oremland, R.S.; Miller, L.G.; Strohmaler, F.E.

    1994-01-01

    Methyl bromide (MeBr) was anaerobically degraded in saltmarsh sediments after reaction with sulfide. The product of this nucleophilic substitution reaction was methanethiol, which underwent further chemical and bacterial reactions to form dimethyl sulfide. These two gases appeared transiently during sediment incubations because they were metabolized by methanogenic and sulfate-reducing bacteria. A second, less significant reaction of MeBr was the exchange with chloride, forming methyl chloride, which was also susceptible to attack by sulfide. Incubation of 14C-labeled methyl iodide as an analogue of MeBr resulted in the formation of 14CH4 and 14CO2 and also indicated that sulfate-reducing bacteria as well as methanogens metabolized the methylated sulfur intermediates. These results suggest that exposed sediments with abundant free sulfide, such as coastal salt-marshes, may constitute a sink for atmospheric MeBr.

  11. Glycopyrronium bromide for the treatment of chronic obstructive pulmonary disease.

    PubMed

    Riario-Sforza, Gian Galeazzo; Ridolo, Erminia; Riario-Sforza, Edoardo; Incorvaia, Cristoforo

    2015-02-01

    Glycopyrronium bromide is a new long-acting muscarinic antagonist to be used once-daily, which is approved as a bronchodilator for the symptomatic maintenance treatment of adult patients with chronic obstructive pulmonary disease (COPD). In the Glycopyrronium bromide in chronic Obstructive pulmonary disease airWays trials, treatment with inhaled glycopyrronium bromide at 50 μg once daily achieved a significantly better lung function than placebo, as measured by the trough forced expiratory volume in 1 s in patients with moderate-to-severe COPD. The lung function improvement was maintained for up to 52 weeks. Other improved indexes were dyspnea scores, health status, exacerbation rates and time of exercise endurance. Studies comparing the efficacy of glycopyrronium versus tiotropium bromide found substantial equivalence of the two drugs. Glycopyrronium was generally well tolerated. These data add inhaled glycopyrronium bromide to the treatment of patients with moderate to severe COPD as an effective once-daily LAMA. PMID:25547422

  12. Atmosphere-plant canopy interactions of methyl bromide

    SciTech Connect

    Taylor, G.E. Jr.; Leonard, T.D.; Gustin, M.S.

    1995-12-31

    In the planetary boundary layer, parcels of air containing background and elevated concentrations of methyl bromide commonly pass through plant canopies in managed (agriculture) and natural (forests, grasslands) ecosystems. It is hypothesized that leaf surfaces are a significant sink or methyl bromide on a local and regional scale and that failure to account for this sink results in a significant overestimation of methyl bromide transport to the stratosphere. Using highly controlled environments, studies are investigating the reactivity of leaf surfaces for methyl bromide at elevated and global background concentrations. Estimates of pathway resistances are being calculated and sites of deposition determined. The results indicate that plant canopies are a significant unrecognized sink for methyl bromide in the atmosphere.

  13. 49 CFR 173.193 - Bromoacetone, methyl bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 49 Transportation 2 2012-10-01 2012-10-01 false Bromoacetone, methyl bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc. 173.193 Section 173.193 Transportation Other Regulations Relating to Transportation PIPELINE AND HAZARDOUS MATERIALS SAFETY ADMINISTRATION, DEPARTMENT OF TRANSPORTATION HAZARDOUS MATERIALS...

  14. 49 CFR 173.193 - Bromoacetone, methyl bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 49 Transportation 2 2013-10-01 2013-10-01 false Bromoacetone, methyl bromide, chloropicrin and methyl bromide or methyl chloride mixtures, etc. 173.193 Section 173.193 Transportation Other Regulations Relating to Transportation PIPELINE AND HAZARDOUS MATERIALS SAFETY ADMINISTRATION, DEPARTMENT OF TRANSPORTATION HAZARDOUS MATERIALS...

  15. Selective oxidation of bromide in wastewater brines from hydraulic fracturing.

    PubMed

    Sun, Mei; Lowry, Gregory V; Gregory, Kelvin B

    2013-07-01

    Brines generated from oil and natural gas production, including flowback water and produced water from hydraulic fracturing of shale gas, may contain elevated concentrations of bromide (~1 g/L). Bromide is a broad concern due to the potential for forming brominated disinfection byproducts (DBPs) during drinking water treatment. Conventional treatment processes for bromide removal is costly and not specific. Selective bromide removal is technically challenging due to the presence of other ions in the brine, especially chloride as high as 30-200 g/L. This study evaluates the ability of solid graphite electrodes to selectively oxidize bromide to bromine in flowback water and produced water from a shale gas operation in Southwestern PA. The bromine can then be outgassed from the solution and recovered, as a process well understood in the bromine industry. This study revealed that bromide may be selectively and rapidly removed from oil and gas brines (~10 h(-1) m(-2) for produced water and ~60 h(-1) m(-2) for flowback water). The electrolysis occurs with a current efficiency between 60 and 90%, and the estimated energy cost is ~6 kJ/g Br. These data are similar to those for the chlor-alkali process that is commonly used for chlorine gas and sodium hydroxide production. The results demonstrate that bromide may be selectively removed from oil and gas brines to create an opportunity for environmental protection and resource recovery. PMID:23726709

  16. EFFECT OF COMPOSITION OF SELECTED GROUNDWATERS FROM THE BASIN AND RANGE PROVINCE ON PLUTONIUM, NEPTUNIUM, AND AMERICIUM SPECIATION.

    USGS Publications Warehouse

    Rees, Terry F.; Cleveland, Jess M.; Nash, Kenneth L.

    1984-01-01

    The speciation of plutonium, neptunium, and americium was determined in groundwaters from four sources in the Basin and Range Province: the lower carbonate aquifer, Nevada Test Site (NTS) (Crystal Pool); alluvial fill, Frenchman Flat, NTS (well 5C); Hualapai Valley, Arizona (Red Lake south well); and Tularosa Basin, New Mexico (Rentfrow well). The results were interpreted to indicate that plutonium and, to a lesser extent, neptunium are least soluble in reducing groundwaters containing a large concentration of sulfate ion and a small concentration of strongly complexing anions. The results further emphasize the desirability of including studies such as this among the other site-selection criteria for nuclear waste repositories.

  17. Crystal and Electronic Structures of Neptunium Nitrides Synthesized Using a Fluoride Route

    SciTech Connect

    Silva, G W Chinthaka M; Weck, Dr. Phil F.; Eunja, Dr. Kim; Yeamans, Dr. Charles B.; Cerefice, Gary S.; Sattelberger, Alfred P; Czerwinski, Ken R.

    2012-01-01

    A low-temperature fluoride route was utilized to synthesize neptunium mononitride, NpN. Through the development of this process, two new neptunium nitride species, NpN{sub 2} and Np{sub 2}N{sub 3}, were identified. The NpN{sub 2} and Np{sub 2}N{sub 3} have crystal structures isomorphous to those of UN{sub 2} and U{sub 2}N{sub 3}, respectively. NpN{sub 2} crystallizes in a face-centered cubic CaF{sub 2}-type structure with a space group of Fm3m and a refined lattice parameter of 5.3236(1) {angstrom}. The Np{sub 2}N{sub 3} adopts the body-centered cubic Mn{sub 2}O{sub 3}-type structure with a space group of Ia{bar 3}. Its refined lattice parameter is 10.6513(4) {angstrom}. The NpN synthesis at temperatures {le} 900 C using the fluoride route discussed here was also demonstrated. Previous computational studies of the neptunium nitride system have focused exclusively on the NpN phase because no evidence was reported experimentally on the presence of NpN{sub x} systems. Here, the crystal structures of NpN{sub 2} and Np{sub 2}N{sub 3} are discussed for the first time, confirming the experimental results by density functional calculations (DFT). These DFT calculations were performed within the local-density approximation (LDA+U) and the generalized-gradient approximation (GGA+U) corrected with an effective Hubbard parameter to account for the strong on-site Coulomb repulsion between Np 5f electrons. The effects of the spin-orbit coupling in the GGA+U calculations have also been investigated for NpN{sub 2} and NpN.

  18. Crystal and electronic structures of neptunium nitrides synthesized using a fluoride route.

    PubMed

    Silva, G W Chinthaka; Weck, Philippe F; Kim, Eunja; Yeamans, Charles B; Cerefice, Gary S; Sattelberger, Alfred P; Czerwinski, Kenneth R

    2012-02-15

    A low-temperature fluoride route was utilized to synthesize neptunium mononitride, NpN. Through the development of this process, two new neptunium nitride species, NpN(2) and Np(2)N(3), were identified. The NpN(2) and Np(2)N(3) have crystal structures isomorphous to those of UN(2) and U(2)N(3), respectively. NpN(2) crystallizes in a face-centered cubic CaF(2)-type structure with a space group of Fm3m and a refined lattice parameter of 5.3236(1) Å. The Np(2)N(3) adopts the body-centered cubic Mn(2)O(3)-type structure with a space group of Ia3. Its refined lattice parameter is 10.6513(4) Å. The NpN synthesis at temperatures ≤900 °C using the fluoride route discussed here was also demonstrated. Previous computational studies of the neptunium nitride system have focused exclusively on the NpN phase because no evidence was reported experimentally on the presence of NpN(x) systems. Here, the crystal structures of NpN(2) and Np(2)N(3) are discussed for the first time, confirming the experimental results by density functional calculations (DFT). These DFT calculations were performed within the local-density approximation (LDA+U) and the generalized-gradient approximation (GGA+U) corrected with an effective Hubbard parameter to account for the strong on-site Coulomb repulsion between Np 5f electrons. The effects of the spin-orbit coupling in the GGA+U calculations have also been investigated for NpN(2) and NpN. PMID:22280303

  19. Determination of neptunium in environmental samples by extraction chromatography after valence adjustment.

    PubMed

    Guérin, Nicolas; Langevin, Marc-Antoine; Nadeau, Kenny; Labrecque, Charles; Gagné, Alexandre; Larivière, Dominic

    2010-12-01

    Neptunium(V) ions are unstable in acid media, which limits their extraction on chromatographic resins. We developed a novel analytical method to measure Np by either α-spectrometry or inductively coupled plasma mass spectrometry (ICP-MS) after extraction chromatography as Np(VI). We investigated the reactivity of various oxidizing reagents, and determined the retention capacity of Np(IV, V, and VI) on various extraction chromatographic supports. A simple method using two UTEVA resins was used to rapidly detect Np in soil and sediment samples. PMID:20630769

  20. Unusual redox stability of neptunium in the ionic liquid [Hbet][Tf(2)N].

    PubMed

    Long, Kristy; Goff, George; Runde, Wolfgang

    2014-07-25

    The behavior of neptunium in the ionic liquid betaine bistriflimide, [Hbet][Tf2N], has been studied spectroscopically at room temperature and 60 °C for the first time. An unprecedented complex redox chemistry is observed, with up to three oxidation states (iv, v and vi) and up to six Np species existing simultaneously. Both redox reactions and coordination of betaine are observed for Np(iv), (v) and (vi). Elevating the temperature accelerates the coordination of Np(v) with betaine and reduction reactions slow down. PMID:24752760

  1. The synthesis and characterization of neptunium hydroxysulfate, Np(OH)/sub 2/SO/sub 4/

    SciTech Connect

    Wester, D.W.; Mulak, J.; Banks, R.; Carnall, W.T.

    1982-11-15

    Neptunium (IV) hydroxysulfate, Np(OH)/sub 2/SO/sub 4/, was synthesized using hydrothermal techniques. The X-ray powder diffraction pattern indicates that the compound is isomorphous with the Th(IV) and U(IV) analogs. Cell constants for the three compounds clearly show the effects of the actinide contraction. Visible and near-ir spectra are consistent with the presence of Np(IV) and are compared to spectra of Np(IV) in acidic solution. The ir spectrum contains bands which are assigned to the hydroxy and sulfate groups.

  2. Gastrointestinal absorption of plutonium, uranium and neptunium in fed and fasted adult baboons: Application to humans

    SciTech Connect

    Bhattacharyya, M.H.; Larsen, R.P.; Oldham, R.D.; Moretti, E.S. ); Cohen, N.; Ralston, L.G.; Ayres, L. )

    1992-03-01

    Gastrointestinal (GI) absorption values of plutonium, uranium, and neptunium were determined in fed and fasted adult baboons. A dual isotope method of determining GI absorption, which does not require animal sacrifice, was validated and shown to compare well with the sacrifice method (summation of oral isotope in urine with that in tissues at sacrifice). For all three elements, mean GI absorption values were significantly high (5- to 50-fold) in 24-hour (h)-fasted animals than in fed animals, and GI absorption values for baboons agreed well with those for humans.

  3. Lithium bromide chiller technology in gas processing

    SciTech Connect

    Huey, M.A.; Leppin, D.

    1995-12-31

    Lithium Bromide (LiBr) Absorption Chillers have been in use for more than half a century, mainly in the commercial air conditioning industry. The Gas Research Institute and EnMark Natural Gas Company co-funded a field test to determine the viability of this commercial air conditioning technology in the gas industry. In 1991, a 10 MMCFC natural gas conditioning plant was constructed in Sherman, Texas. The plant was designed to use a standard, off-the-shelf chiller from Trane with a modified control scheme to maintain tight operating temperature parameters. The main objective was to obtain a 40 F dewpoint natural gas stream to meet pipeline sales specifications. Various testing performed over the past three years has proven that the chiller can be operated economically and on a continuous basis in an oilfield environment with minimal operation and maintenance costs. This paper will discuss how a LiBr absorption chiller operates, how the conditioning plant performed during testing, and what potential applications are available for LiBr chiller technology.

  4. Kinetics and Mechanism of the Chlorate-Bromide Reaction.

    PubMed

    Sant'Anna, Rafaela T P; Faria, Roberto B

    2015-11-01

    The chlorate-bromide reaction, ClO3(-) + 6Br(-) + 6H(+) → 3Br2 + Cl(-) + 3H2O, was followed at the Br3(-)/Br2 isosbestic point (446 nm). A fifth-order rate law was found: (1)/3 d[Br2]/dt = k[ClO3(-)][Br(-)][H(+)](3) (k = 5.10 × 10(-6) s(-1) L(4) mol(-4)) at 25 °C and I = 2.4 mol L(-1). At high bromide concentrations, the bromide order becomes close to zero, indicating a saturation profile on bromide concentration, similar to the chloride saturation profile observed in the chlorate-chloride reaction. A mechanism is proposed that considers the formation of the intermediate BrOClO2(2-), similar to the intermediate ClOClO2(2-) proposed in the mechanism of the chlorate-chloride reaction. PMID:26467822

  5. Health and Environmental Effects Profile for methyl bromide

    SciTech Connect

    Not Available

    1986-06-01

    The Health and Environmental Effects Profile for methyl bromide was prepared to support listings of hazardous constituents of a wide range of waste streams under Section 3001 of the Resource Conservation and Recovery Act (RCRA) and to provide health-related limits for emergency actions under Section 101 of the Comprehensive Environmental Response, Compensation and Liability Act (CERCLA). Both published literature and information obtained from Agency program office files were evaluated as they pertained to potential human health, aquatic life, and environmental effects. Quantitative estimates are presented provided sufficient data are available. Methyl bromide has been determined to be a systemic toxicant. An Acceptable Daily Intake (ADI), for methyl bromide is 0.0014 mg/kg/day for oral exposure. The Reportable Quantity (RQ) value for methyl bromide is 100.

  6. The oceans: A source or a sink of methyl bromide?

    SciTech Connect

    Pilinis, C.; King, D.B.; Saltzman, E.S.

    1996-04-15

    The global ocean/atmosphere flux of methyl bromide has been estimated from shipboard measurements of the saturation anomaly. When such data are extrapolated globally on the basis of constant saturation anomaly, the ocean is a net sink for methyl bromide [Lobert et al.]. The same data can also be extrapolated on the basis of steady-state production rate of methyl bromide in the water column, allowing regional and seasonal variations in temperature to affect the saturation anomaly. The authors have carried out this type of extrapolation, and they found that the oceans are a strong net source of methyl bromide to the atmosphere. The difference arises mainly due to slow degradation rates in water of higher latitudes. A reduction of the applied production rate by more than 35% is needed in order to switch the ocean from a source to a sink of methyl bromide. These results demonstrate the sensitivity of current estimates of oceanic flux to assumptions about methyl bromide production and destruction in the water column. 19 refs., 2 fig.

  7. Peak Stripping Methodology for Plutonium Analysis in the Presence of Neptunium

    SciTech Connect

    Hodge, Christ

    2005-05-17

    Quantitative Plutonium analysis depends upon the accurate identification of the assay peak. The Np[Pa] equilibrium pair introduces interfering peaks in {sup 239}Pu, {sup 238}Pu, and {sup 235}U assay peak region. When an interfering peak is present, it negates the assay unless an appropriate technique can be developed to deal with the interference. Peak Stripping is one such technique. Peak stripping involves an algorithm to strip an entire peak from another, resulting in a spectrum that can then be analyzed for the isotope of interest. A simpler method is a ''pseudo-peak-stripping'' whereby the effects of the interfering peak are quantified and those effects are stripped from the assay data. In this case the integrated peak areas are analyzed and corrected. There are two methods presented in this paper. Both assimilate the integrated data for the assay peak regions (in this case {sup 238}Pu, {sup 239}Pu, and {sup 235}U) and for the Neptunium/Protactinium secular equilibrium pair (Np[Pa]). Using Np[Pa] assumes that the Protactinium has come to equilibrium with Neptunium. This requires only {approx}6 months from the time chemical purification. Therefore it is a valid assumption in most cases. A correction is then applied to the assay peak areas to ''strip'' the underlying effects of Np[Pa].

  8. The toxic chemistry of methyl bromide.

    PubMed

    Bulathsinghala, A T; Shaw, I C

    2014-01-01

    Methyl bromide (MeBr) is a chemically reactive compound that has found use as a fire retardant and fumigant used for wood, soil, fruits and grains. Its use is banned in many countries because of its ozone-depleting properties. Despite this ban, the use of MeBr persists in some parts of the world (e.g. New Zealand) due to its important role in maintaining strict biosecurity of exported and imported products. Its high chemical reactivity leads to a broad toxicological profile ranging from acute respiratory toxicity following inhalation exposure, through carcinogenicity to neurotoxicty. In this article, we discuss the chemistry of MeBr in the context of its mechanisms of toxicity. The chemical reactivity of MeBr clearly underlies its toxicity. Bromine (Br) is electronegative and a good leaving group; the δ+ carbon thus facilitates electrophilic methylation of biological molecules including glutathione (GSH) via its δ- sulphur atom, leading to downstream effects due to GSH depletion. DNA alkylation, either directly by MeBr or indirectly due to reduction in GSH-mediated detoxification of reactive alkylating chemical species, might explain the carcinogenicity of MeBr. The neurotoxicity of MeBr is much more difficult to understand, but we speculate that methyl phosphates formed in cells might contribute to its neurone-specific toxicity via cholinesterase inhibition. Finally, evidence reviewed shows that it is unlikely for Br⁻ liberated by the metabolism of MeBr to have any toxicological effect because the Br⁻ dose is very low. PMID:23800997

  9. Electronic structure of the Np MT 5 ( M = Fe, Co, Ni; T = Ga, In) series of neptunium compounds

    NASA Astrophysics Data System (ADS)

    Lukoyanov, A. V.; Shorikov, A. O.; Anisimov, V. I.

    2016-03-01

    Evolution of the electronic structure of the Np MGa5 ( M = Fe, Co, Ni) series of neptunium compounds, whose crystal structure is similar to that of the known family of Pu115 superconductors, was studied by the LDA + U + SO method. The calculations took into account both the strong electron correlations and the spin‒orbit coupling in the 5 f shell of neptunium. For the first time, the electronic structure was calculated for a hypothetical series of compounds in which gallium is replaced with indium. Parameters of the crystal structure of the given series were obtained using the relationship between the parameters of the crystal structure of the earlier-studied compounds PuCoGa5 and PuCoIn5. The analysis of the electronic structure and characteristics of neptunium ions calculated in the framework of the LDA + U + SO method showed that the neptunium ions in Np MIn5 with M = Fe, Co, and Ni should have an electron configuration closer to f 4, but a spin and magnetic characteristics close to those in Np MGa5.

  10. PROCESS FOR EXTRACTING NEPTUNIUM AND PLUTONIUM FROM NITRIC ACID SOLUTIONS OF SAME CONTAINING URANYL NITRATE WITH A TERTIARY AMINE

    DOEpatents

    Sheppard, J.C.

    1962-07-31

    A process of selectively extracting plutonium nitrate and neptunium nitrate with an organic solution of a tertiary amine, away from uranyl nitrate present in an aqueous solution in a maximum concentration of 1M is described. The nitric acid concentration is adjusted to about 4M and nitrous acid is added prior to extraction. (AEC)

  11. Assessment of Ethidium bromide and Ethidium monoazide bromide removal from aqueous matrices by adsorption on cupric oxide nanoparticles.

    PubMed

    Fakhri, Ali

    2014-06-01

    The present study was undertaken to develop an effective adsorbent and to study the adsorption of Ethidium bromide and Ethidium monoazide bromide from aqueous solution using the CuO nanoparticles. The characteristics of CuO nanoparticles were determined and found to have a surface area 89.59m(2)/g. Operational parameters such as pH, contact time and adsorbent concentration, initial concentration and temperature were also studied. The amount of removal increases with the increase in pH from one to seven and reaches the maximum when the pH is nine. Adsorption data fitted well with the Langmuir, Freundlich and Florry-Huggins models. The results show that the best fit was achieved with the Langmuir isotherm equation with maximum adsorption capacities of 0.868 and 0.662mg/g for Ethidium bromide and Ethidium monoazide bromide, respectively. The adsorption process was found to follow pseudo-second-order kinetics. The calculated thermodynamic parameters, namely ΔG, ΔH and ΔS showed that adsorption of Ethidium bromide and Ethidium monoazide bromide was spontaneous and endothermic under examined conditions. PMID:24630576

  12. Loading Capacities for Uranium, Plutonium and Neptunium in High Caustic Nuclear Waste Storage Tanks Containing Selected Sorbents

    SciTech Connect

    OJI, LAWRENCE

    2004-11-16

    In this study the loading capacities of selected actinides onto some of the most common sorbent materials which are present in caustic nuclear waste storage tanks have been determined. Some of these transition metal oxides and activated carbons easily absorb or precipitate plutonium, neptunium and even uranium, which if care is not taken may lead to unwanted accumulation of some of these fissile materials in nuclear waste tanks during waste processing. Based on a caustic synthetic salt solution simulant bearing plutonium, uranium and neptunium and ''real'' nuclear waste supernate solution, the loading capacities of these actinides onto iron oxide (hematite), activated carbon and anhydrous sodium phosphate have been determined. The loading capacities for plutonium onto granular activated carbon and iron oxide (hematite) in a caustic synthetic salt solution were, respectively, 3.4 0.22 plus or minus and 5.5 plus or minus 0.38 microgram per gram of sorbent. The loading capacity for plutonium onto a typical nuclear waste storage tank sludge solids was 2.01 microgram per gram of sludge solids. The loading capacities for neptunium onto granular activated carbon and iron oxide (hematite) in a caustic synthetic salt solution were, respectively, 7.9 plus or minus 0.52 and greater than 10 microgram per gram of sorbent. The loading capacity for neptunium onto a typical nuclear waste storage tank sludge solids was 4.48 microgram per gram of sludge solids. A typical nuclear waste storage tank solid material did not show any significant affinity for uranium. Sodium phosphate showed significant affinity for both neptunium and uranium, with loading capacities of 6.8 and 184.6 plus or minus 18.5 microgram per gram of sorbent, respectively.

  13. Disposition of ( UC)methyl bromide in rats after inhalation

    SciTech Connect

    Bond, J.A.; Dutcher, J.S.; Medinsky, M.A.; Henderson, R.F.; Birnbaum, L.S.

    1985-01-01

    The purpose of this investigation was to determine the disposition and metabolism of ( UC)methyl bromide in rats after inhalation. Male Fischer-344 rats were exposed nose only to a vapor concentration of 337 nmol ( UC)methyl bromide/liter air (9.0 ppm, 25C, 620 torr) for 6 hr. Urine, feces, expired air, and tissues were collected for up to 65 hr after exposure. Elimination of UC as UCO2 was the major route of excretion with about 47% (3900 nmol/rat) of the total ( UC)methyl bromide absorbed excreted by this route. CO2 excretion exhibited a biphasic elimination pattern with 85% of the UCO2 being excreted with a half-time of 3.9 +/- 0.1 hr (anti x +/- SE) and 15% excreted with a half-time of 11.4 +/- 0.2 hr. Half-times for elimination of UC in urine and feces were 9.6 +/- 0.1 and 16.1 +/- 0.1 hr, respectively. By 65 hr after exposure, about 75% of the initial radioactivity had been excreted with 25% remaining in the body. Radioactivity was widely distributed in tissues immediately following exposure with lung (250 nmol equivalents/g), adrenal (240 nmol equivalents/g), and nasal turbinates (110 nmol equivalents/g) containing the highest concentrations of UC. Radioactivity in livers immediately after exposure accounted for about 17% of the absorbed methyl bromide. Radioactivity in all other tissues examined accounted for about 10% of the absorbed methyl bromide. Elimination half-times of UC from tissues were on the order of 1.5 to 8 hr. In all tissues examined, over 90% of the UC in the tissues was methyl bromide metabolities. The data from this study indicate that after inhalation methyl bromide is rapidly metabolized in tissues and readily excreted. 22 references, 4 figures, 4 tables.

  14. LIBS Spectral Data for a Mixed Actinide Fuel Pellet Containing Uranium, Plutonium, Neptunium and Americium

    SciTech Connect

    Judge, Elizabeth J.; Berg, John M.; Le, Loan A.; Lopez, Leon N.; Barefield, James E.

    2012-06-18

    Laser-induced breakdown spectroscopy (LIBS) was used to analyze a mixed actinide fuel pellet containing 75% UO{sub 2}/20% PuO{sub 2}/3% AmO{sub 2}/2% NpO{sub 2}. The preliminary data shown here is the first report of LIBS analysis of a mixed actinide fuel pellet, to the authors knowledge. The LIBS spectral data was acquired in a plutonium facility at Los Alamos National Laboratory where the sample was contained within a glove box. The initial installation of the glove box was not intended for complete ultraviolet (UV), visible (VIS) and near infrared (NIR) transmission, therefore the LIBS spectrum is truncated in the UV and NIR regions due to the optical transmission of the window port and filters that were installed. The optical collection of the emission from the LIBS plasma will be optimized in the future. However, the preliminary LIBS data acquired is worth reporting due to the uniqueness of the sample and spectral data. The analysis of several actinides in the presence of each other is an important feature of this analysis since traditional methods must chemically separate uranium, plutonium, neptunium, and americium prior to analysis. Due to the historic nature of the sample fuel pellet analyzed, the provided sample composition of 75% UO{sub 2}/20% PuO{sub 2}/3% AmO{sub 2}/2% NpO{sub 2} cannot be confirm without further analytical processing. Uranium, plutonium, and americium emission lines were abundant and easily assigned while neptunium was more difficult to identify. There may be several reasons for this observation, other than knowing the exact sample composition of the fuel pellet. First, the atomic emission wavelength resources for neptunium are limited and such techniques as hollow cathode discharge lamp have different dynamics than the plasma used in LIBS which results in different emission spectra. Secondly, due to the complex sample of four actinide elements, which all have very dense electronic energy levels, there may be reactions and

  15. UV photodissociation of methyl bromide and methyl bromide cation studied by velocity map imaging

    SciTech Connect

    Blanchet, Valerie; Samartzis, Peter C.; Wodtke, Alec M.

    2009-01-21

    We employ the velocity map imaging technique to measure kinetic energy and angular distributions of state selected CH{sub 3} (v{sub 2}=0,1,2,3) and Br ({sup 2}P{sub 3/2}, {sup 2}P{sub 1/2}) photofragments produced by methyl bromide photolysis at 215.9 nm. These results show unambiguously that the Br and Br* forming channels result in different vibrational excitations of the umbrella mode of the methyl fragment. Low energy structured features appear on the images, which arise from CH{sub 3}Br{sup +} photodissociation near 330 nm. The excess energy of the probe laser photon is channeled into CH{sub 3}{sup +} vibrational excitation, most probably in the {nu}{sub 4} degenerate bend.

  16. Neptunium(V) adsorption to bacteria at low and high ionic strength

    SciTech Connect

    Ams, David A; Swanson, Juliet S; Reed, Donald T; Fein, Jeremy B

    2010-12-08

    Np(V) is expected to be the predominant oxidation state of neptunium in aerobic natural waters. Np(V), as the NpO{sub 2}{sup +} aquo and associated complexed species, is readily soluble, weakly interacting with geologic media, and has a high redox stability under a relatively wide range of subsurface conditions. These chemical properties, along with a long half-life make it a primary element of concern regarding long-term nuclear waste storage and subsurface contaminant. The fate and transport of neptunium in the environment may be influenced by adsorption onto bacterial surfaces. The adsorption of neptunium to bacterial surfaces ties the mobility of the contaminant to the mobility of the bacterium. In this study, the adsorption of the neptunyl (NpO{sub 2}{sup +}) ion was evaluated at low ionic strength on a common soil bacterium and at high ionic strength on a halophilic bacterium isolated from a briny groundwater near the Waste Isolation Pilot Plant (WIPP) in southeast New Mexico. Adsorption experiments were performed in batch reactors as a function of pH, ionic strength, and bacterialNp mass ratio. Np(V) adsorption was modeled using a surface complexation approach with the mathematical program FITEQL to determine functional group specific binding constants. The data from acid and base titrations of the bacteria were also modeled to estimate the concentrations and deprotonation constants of discrete bacterial surface functional groups. Bacterial functional group characteristics and Np(V) adsorption behavior between the soil bacterium and the halophilic bacterium were compared. These results highlight the key similarities and differences in actinide adsorption behavior in environments of significantly different ionic strength. Similarities in adsorption behavior may be linked to similarities in the characteristics of the moieties between all bacterial cell walls. Differences in adsorption behavior may reflect differences in ionic strength effects, rather than

  17. Neptunium(V) Adsorption to Bacteria at Low and High Ionic Strength

    NASA Astrophysics Data System (ADS)

    Ams, D.; Swanson, J. S.; Reed, D. T.

    2010-12-01

    Np(V) is expected to be the predominant oxidation state of neptunium in aerobic natural waters. Np(V), as the NpO2+ aquo and associated complexed species, is readily soluble, interacts weakly with geologic media, and has a high redox stability under a relatively wide range of subsurface conditions. These chemical properties, along with a long half-life make it a primary element of concern regarding long-term nuclear waste storage and subsurface containment. The fate and transport of neptunium in the environment may be influenced by adsorption onto bacterial surfaces. The adsorption of neptunium to bacterial surfaces ties the mobility of the contaminant to the mobility of the bacterium. In this study, the adsorption of the neptunyl (NpO2+) ion was evaluated at low ionic strength on a common soil bacterium and at high ionic strength on a halophilic bacterium isolated from a briny groundwater near the Waste Isolation Pilot Plant (WIPP) in southeast New Mexico. Adsorption experiments were performed in batch reactors as a function of pH, ionic strength, and bacteria/Np mass ratio. Np(V) adsorption was modeled using a surface complexation approach with the mathematical program FITEQL to determine functional group specific binding constants. The data from acid and base titrations of the bacteria used were also modeled to estimate the concentrations and deprotonation constants of discrete bacterial surface functional groups. Bacterial functional group characteristics and Np(V) adsorption behavior between the soil bacterium and the halophilic bacterium were compared. These results highlight key similarities and differences in actinide adsorption behavior in environments of significantly different ionic strength. The observed adsorption behavior may be linked to similarities and differences in the characteristics of the moieties between the cell walls of common gram-negative soil and halophilic bacteria. Moreover, differences in adsorption behavior may also reflect ionic

  18. Effect of Bromide-Hypochlorite Bactericides on Microorganisms1

    PubMed Central

    Shere, Lewis; Kelley, Maurice J.; Richardson, J. Harold

    1962-01-01

    A new principle in compounding stable, granular bactericidal products led to unique combinations of a water-soluble inorganic bromide salt with a hypochlorite-type disinfectant of either inorganic or organic type. Microbiological results are shown for an inorganic bactericide composed of chlorinated trisodium phosphate containing 3.1% “available chlorine” and 2% potassium bromide, and for an organic bactericide formulated from sodium dichloroisocyanurate so as to contain 13.4% “available chlorine” and 8% potassium bromide. Comparison of these products with their nonbromide counterparts are reported for Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa, Streptococcus lactis, Aerobacter aerogenes, and Proteus vulgaris. Test methods employed were the Chambers test, the A.O.A.C. Germicidal and Detergent Sanitizer-Official test, and the Available Chlorine Germicidal Equivalent Concentration test. The minimal killing concentrations for the bromide-hypochlorite bactericides against this variety of organisms were reduced by a factor 2 to 24 times those required for similar hypochlorite-type disinfectants not containing the bromide. PMID:13977149

  19. Zinc Bromide Combustion: Implications for the Consolidated Incinerator Facility

    SciTech Connect

    Oji, L.N.

    1998-12-16

    In the nuclear industry, zinc bromide (ZnBr2) is used for radiation shielding. At Savannah River Site (SRS) zinc bromide solution, in appropriate configurations and housings, was used mainly for shielding in viewing windows in nuclear reactor and separation areas. Waste stream feeds that will be incinerated at the CIF will occasionally include zinc bromide solution/gel matrices.The CIF air pollution systems control uses a water-quench and steam atomizer scrubber that collects salts, ash and trace metals in the liquid phase. Water is re-circulated in the quench unit until a predetermined amount of suspended solids or dissolved salts are present. After reaching the threshold limit, "dirty liquid", also called "blowdown", is pumped to a storage tank in preparation for treatment and disposal. The air pollution control system is coupled to a HEPA pre-filter/filter unit, which removes particulate matter from the flue gas stream (1).The objective of this report is to review existing literature data on the stability of zinc bromide (ZnBr2) at CIF operating temperatures (>870 degrees C (1600 degrees F) and determine what the combustion products are in the presence of excess air. The partitioning of the combustion products among the quencher/scrubber solution, bottom ash and stack will also be evaluated. In this report, side reactions between zinc bromide and its combustion products with fuel oil were not taken into consideration.

  20. Cross-Coupling of Aromatic Bromides with Allylic Silanolate Salts

    PubMed Central

    Denmark, Scott E; Werner, Nathan S.

    2009-01-01

    The sodium salts of allyldimethylsilanol and 2-butenyldimethylsilanol undergo palladium-catalyzed cross-coupling with a wide variety of aryl bromides to afford allylated and crotylated arenes. The coupling of both silanolates required extensive optimization to deliver the expected products in high yields. The reaction of the allyldimethylsilanolate takes place at 85 °C in DME with allylpalladium chloride dimer (2.5 mol %) to afford 7–95% yields of the allylation products. Both electron-rich and sterically-hindered bromides reacted smoothly, whereas electron-poor bromides cross-coupled in poor yield because of a secondary isomerization to the 1-propenyl isomer (and subsequent polymerization). The 2-butenyldimethylsilanolate (E/Z, 80:20) required additional optimization to maximize the formation of the branched (γ-substitution product). A remarkable influence of added alkenes (dibenzylideneacetone and norbornadiene) led to good selectivities for electron-rich and electron-poor bromides in 4–83% yields. However, bromides containing coordinating groups (particularly in the ortho position) gave lower, and in one case even reversed, selectivity. Configurationally homogeneous E-silanolates gave slightly higher γ-selectivity than the pure Z-silanolates. A unified mechanistic picture involving initial γ-transmetalation followed by direct reductive elimination or σ–π isomerization can rationalize all of the observed trends. PMID:18998687

  1. Electrophysiological study of intravenous pinaverium bromide in cardiology.

    PubMed

    Guerot, C; Khemache, A; Sebbah, J; Noel, B

    1988-01-01

    Pinaverium bromide is a musculotropic spasmolytic agent which acts by inhibiting transmembrane calcium movements, an effect similar to that of verapamil. Because of this, an investigation was carried out to see if it had any electrophysiological effects in patients with various cardiac disorders. In an open study, 10 patients received 2 mg pinaverium bromide intravenously. In a double-blind study, 10 patients received 4 mg pinaverium bromide intravenously and 10 patients placebo. Patients included those with either normal or pathological basal conduction, such as bundle-branch block and 1st degree atrioventricular block. Measurements were made of electrophysiological parameters before and 10 minutes after injection. The results showed that neither of the two doses of pinaverium bromide had any effect on atrial excitability, sino-atrial conduction, node and trunk atrioventricular conduction or on intraventricular conduction. No significant difference was seen in comparison with placebo. Pinaverium bromide had no anti-arrhythmic properties in these studies. Local, cardiac and general clinical tolerability was good in all patients. PMID:3219882

  2. Cetyltrimethyl ammonium bromide assisted hydrothermal growth of hematite hollow cubes

    SciTech Connect

    Wang, Wei-Wei; Yao, Jia-Liang

    2010-11-15

    Hematite hollow cubes have been prepared by forced hydrolysis of ferric chloride solutions under hydrothermal conditions. The effects of reaction time, reaction temperature and cetyltrimethyl ammonium bromide on the transformation process from akageneite to hematite were investigated in detail. The products were characterized by X-ray powder diffraction, scanning electron microscopy and transmission electron microscopy. It is found that cetyltrimethyl ammonium bromide was a critical factor influencing the phase transformation process of akageneite and the final morphology of the as-prepared products. With cetyltrimethyl ammonium bromide, hematite hollow cubes and porous spheres were obtained. Otherwise only dense cubes were observed even prolonging reaction time or increasing reaction temperature. The mechanism was proposed.

  3. Straightforward reductive routes to air-stable uranium(III) and neptunium(III) materials.

    PubMed

    Cross, Justin N; Villa, Eric M; Darling, Victoria R; Polinski, Matthew J; Lin, Jian; Tan, Xiaoyan; Kikugawa, Naoki; Shatruk, Michael; Baumbach, Ryan; Albrecht-Schmitt, Thomas E

    2014-07-21

    Studies of trivalent uranium (U(3+)) and neptunium (Np(3+)) are restricted by the tendency of these ions to oxidize in the presence of air and water, requiring manipulations to be carried out in inert conditions to produce trivalent products. While the organometallic and high-temperature reduction chemistry of U(3+) and, to a much smaller extent, Np(3+) has been explored, the study of the oxoanion chemistry of these species has been limited despite their interesting optical and magnetic properties. We report the synthesis of U(3+) and Np(3+) sulfates by utilizing zinc amalgam as an in situ reductant with absolutely no regard to the exclusion of O2 or water. By employing this method we have developed a family of alkali metal U(3+) and Np(3+) sulfates that are air and water stable. The structures, electronic spectra, and magnetic behavior are reported. PMID:24964279

  4. Young geologist trades neptunium for newspapers as 2012 AGU Mass Media Fellow

    NASA Astrophysics Data System (ADS)

    Adams, Mary Catherine

    2012-05-01

    Though the lure of rocks, minerals, and radioactive elements took her away from her original studies, one geology Ph.D. candidate is returning to her journalism roots this summer as AGU's 2012 Mass Media Science and Engineering Fellow. Jessica Morrison is one of 12 young scientists nationwide who are trading in their lab coats for reporters' notebooks in mid-June as part of the program coordinated by the American Association for the Advancement of Science, which helps young scientists cultivate communication skills to help disseminate scientific information to general audiences. Morrison is a Ph.D. student in the Department of Civil Engineering and Geological Sciences at the University of Notre Dame. She spends her days in a laboratory investigating the geochemistry of actinides, the radioactive elements in the "no man's land" of the periodic table—the section that often gets left off or moved to the bottom. These are elements like uranium, neptunium, and plutonium.

  5. Mineralogical Charecteristics of Yucca Mountain Alluvium and Effects on Neptunium (V) Sorption

    SciTech Connect

    M. Ding; S.J. Chipera; P.W. Reimus

    2006-09-05

    Saturated alluvium is expected to serve as an important natural barrier to radionuclide transport at Yucca Mountain, the proposed geological repository for disposal of high-level nuclear wastes. {sup 237}Np(V) (half-life = 2.4 x 10{sup 5} years) has been identified as one of the radionuclides that could potentially contribute the greatest dose to humans because of its relatively high solubility and weak adsorption to volcanic tuffs under oxidizing conditions. The previous studies suggested that the mineralogical characteristics of the alluvium play an important role in the interaction between Np(V) and the alluvium. The purpose of this study is to further evaluate the mineralogical basis for Neptunium (V) sorption by saturated alluvium located down-gradient of Yucca Mountain.

  6. THERMODYNAMICS OF NEPTUNIUM(V) FLOURIDE AND SULFATE AT ELEVATED TEMPERATURES

    SciTech Connect

    L. Rao; G. Tian; Y. Xia; J.I. Friese

    2006-03-06

    Complexation of neptunium(V) with fluoride and sulfate at elevated, temperatures was studied by microcalorimetry. Thermodynamic parameters, including the equilibrium constants and enthalpy of protonation of fluoride and sulfate, and the enthalpy of complexation between Np(V) and fluoride and sulfate at 25-70 C were determined. Results show that the complexation of Np(V) with fluoride and sulfate is endothermic and that the complexation is enhanced by the increase in temperature--a threefold increase in the stability constants of NpO{sub 2}F(aq) and NpO{sub 2}SO{sub 4}{sup -} as the temperature is increased from 25 to 70 C.

  7. Experimental Measurements of Short-Lived Fission Products from Uranium, Neptunium, Plutonium and Americium

    SciTech Connect

    Metz, Lori A.; Payne, Rosara F.; Friese, Judah I.; Greenwood, Lawrence R.; Kephart, Jeremy D.; Pierson, Bruce D.

    2009-11-01

    Fission yields are especially well characterized for long-lived fission products. Modeling techniques incorporate numerous assumptions and can be used to deduce information about the distribution of short-lived fission products. This work is an attempt to gather experimental (model-independent) data on the short-lived fission products. Fissile isotopes of uranium, neptunium, plutonium and americium were irradiated under pulse conditions at the Washington State University 1 MW TRIGA reactor to achieve ~108 fissions. The samples were placed on a HPGe (high purity germanium) detector to begin counting in less than 3 minutes post irradiation. The samples were counted for various time intervals ranging from 5 minutes to 1 hour. The data was then analyzed to determine which radionuclides could be quantified and compared to the published fission yield data.

  8. Investigation of pyridine/propargyl bromide reaction and strong fluorescence enhancements of the resultant poly(propargyl pyridinium bromide).

    PubMed

    Zhou, Changming; Gao, Yong; Chen, Daoyong

    2012-09-20

    Poly(propargyl pyridinium bromide), a kind of conjugated polyelectrolyte with polyacetylene as the backbone and pyridinium as side groups, was synthesized simply via reaction between pyridine and propargyl bromide under mild conditions. The resultant polymer was characterized by (1)H NMR, elemental analysis, FT-IR, and GPC-MALLS. An alkyne group was confirmed as the end group of the polymer chains by the alkyne/azide click chemistry, which reveals that the polymerization is terminated by the reaction between propargyl bromide and carbon anions. It is known that monosubstituted polyacetylenes reported have very weak fluorescence intensities, which limit their applications. As a monosubstituted polyacetylene, the freshly prepared poly(propargyl pyridinium bromide) also has a very weak fluorescence. However, we confirmed that addition of some anions to the polymer solution in DMF or DMSO leads to the fluorescence enhancements up to 25 times. Besides, heating the polymer solution at a temperature between 70 and 130 °C for longer than 0.5 h greatly enhanced the fluorescence intensity. The interaction with the anions or the heating enhances the effective exciton confinement within the conjugated backbone and thus results in the fluorescence enhancements. After the fluorescence enhancements, poly(propargyl pyridinium bromide) has relatively strong fluorescence emissions, which will make it promising in fluorescence-based applications. PMID:22928912

  9. Oxidation of manganese(II) during chlorination: role of bromide.

    PubMed

    Allard, S; Fouche, L; Dick, J; Heitz, A; von Gunten, U

    2013-08-01

    The oxidation of dissolved manganese(II) (Mn(II)) during chlorination is a relatively slow process which may lead to residual Mn(II) in treated drinking waters. Chemical Mn(II) oxidation is autocatalytic and consists of a homogeneous and a heterogeneous process; the oxidation of Mn(II) is mainly driven by the latter process. This study demonstrates that Mn(II) oxidation during chlorination is enhanced in bromide-containing waters by the formation of reactive bromine species (e.g., HOBr, BrCl, Br2O) from the oxidation of bromide by chlorine. During oxidation of Mn(II) by chlorine in bromide-containing waters, bromide is recycled and acts as a catalyst. For a chlorine dose of 1 mg/L and a bromide level as low as 10 μg/L, the oxidation of Mn(II) by reactive bromine species becomes the main pathway. It was demonstrated that the kinetics of the reaction are dominated by the adsorbed Mn(OH)2 species for both chlorine and bromine at circumneutral pH. Reactive bromine species such as Br2O and BrCl significantly influence the rate of manganese oxidation and may even outweigh the reactivity of HOBr. Reaction orders in [HOBr]tot were found to be 1.33 (±0.15) at pH 7.8 and increased to 1.97 (±0.17) at pH 8.2 consistent with an important contribution of Br2O which is second order in [HOBr]tot. These findings highlight the need to take bromide, and the subsequent reactive bromine species formed upon chlorination, into account to assess Mn(II) removal during water treatment with chlorine. PMID:23859083

  10. Intensification of sonochemical degradation of malachite green by bromide ions.

    PubMed

    Moumeni, Ouarda; Hamdaoui, Oualid

    2012-05-01

    Sonochemical oxidation has been investigated as a viable advanced oxidation process (AOP) for the destruction of various pollutants in water. Ultrasonic irradiation generates ()OH radicals that can recombine, react with other gaseous species present in the cavity, or diffuse out of the bubble into the bulk liquid medium where they are able to react with solute molecules. The extent of degradation of an organic dye such as malachite green (MG) is limited by the quantity of hydroxyl radicals diffused from cavitation bubbles. In this work, the effect of bromide ions on sonolytic degradation of MG was investigated. The obtained results clearly demonstrated the considerable enhancement of sonochemical destruction of MG in the presence of bromide. No significant differences were observed in the presence of chloride and sulfate, excluding the salting-out effect. Positive effect of bromide ions, which increases with increasing bromide level and decreasing MG concentration, is due to the generation of dibromine radical anion (Br(2)(-)) formed by reaction of Br(-) with ()OH radicals followed by rapid complexation with another anion. The generated Br(2)(-) radicals, reactive but less than ()OH, are likely able to migrate far from the cavitation bubbles towards the solution bulk and are suitable for degradation of an organic dye such as MG. Additionally, Br(2)(-) radicals undergo radical-radical recombination at a lesser extent than hydroxyl radicals and would be more available than ()OH for substrate degradation, both at the bubble surface and in the solution bulk. This effect compensates for the lower reactivity of Br(2)(-) compared to ()OH toward organic substrate. Addition of bromide to natural and sea waters induces a slight positive effect on MG degradation. In the absence of bromide, ultrasonic treatment for the removal of MG was promoted in complex matrices such as natural and sea waters. PMID:21911308

  11. Methyl bromide emissions from a covered field: II. Volatilization

    SciTech Connect

    Yates, S.R.; Gan, J.; Ernst, F.F.

    1996-01-01

    An experiment to investigate the environmental fate and transport of methyl bromide in agricultural fields is described. The methyl bromide volatilization rate was determined as a function of time for conditions where methyl bromide was applied at a rate of 843 kg in a 3.5-ha (i.e., 240 kg/ha) field covered with plastic at a depth of 25 cm. Three methods were used to estimate the methyl bromide volatilization rate, including: the aerodynamic, theoretical profile shape and integrated horizontal flux methods. The highest methyl bromide volatilization rates were at the beginning of the experiment. Within the first 24 h, approximately 36% of the applied methyl bromide mass was lost. Diurnally, the largest volatilization rates occurred during the day when temperatures were high and the atmosphere was unstable. Cooler temperatures, light winds, and neutral to stable atmospheric conditions were present at night, reducing the flux. The total emission calculated using these methods was found to be approximately 64% ({+-} 10%) of the applied mass. A mass balance was calculated using each flux estimation technique and several methods for analyzing the data. The average mass recovery using all the flux methods was 867 kg ({+-}83 kg), which was 102.8% ({+-}9.8%) of the applied (i.e., 843 kg). The range in the mass balance percent (i.e., percent of applied mass that is measured) is from 88 to 112%. The averaged mass balance percent for the aerodynamic method, which involved using the measured data directly, was approximately 100.8%. The total emission calculated using the aerodynamic method was found to be approximately 62% ({+-}11%) of the applied mass. 29 refs., 7 figs., 1 tab.

  12. Photochemistry of alkyl bromides trapped in water ice films

    NASA Astrophysics Data System (ADS)

    Schrems, O.; Okaikwei, B.; Bluszcz, Th.

    2012-04-01

    Photochemical reactions of atmospheric trace gases taking place at the surface of atmospheric ice particles and in bulk ice are important in stratospheric and tropospheric chemistry but also in polar and alpine snowpack chemistry. Consequently, the understanding of the uptake und incorporation of atmospheric trace gases in water ice as well as their interactions with water molecules is very important for the understanding of processes which occur in ice particles and at the air/ice interface. Reactive atmospheric trace gases trapped in ice are subject of photochemical reactions when irradiated with solar UV radiation. Among such compounds bromine species are highly interesting due to their potential of depleting ozone both in the stratosphere and troposphere. Organic bromine gases can carry bromine to the stratosphere. Methyl bromide (CH3Br) is the largest bromine carrier to the stratosphere. It has both natural and anthropogenic sources. In this contribution we will present the results of our laboratory studies of alkyl bromides (methyl, bromide (CH3Br), dimethyl bromide (CH2Br2), n-propyl bromide (C3H7Br), 1,2-dibromoethane C2H4Br2)), trapped in water ice. We have simulated the UV photochemistry of these brominated alkanes isolated in ice films kept at 16 K and for comparison in solid argon matrices. The photoproducts formed in the ice have been identified by means of FTIR spectroscopy. Reflection absorption infrared spectroscopy (RAIRS) is especially useful to study nascent ice surfaces, kinetics of adsorption/decomposition, and heterogeneous catalysis. Among the observed photoproducts we could identify carbon monoxide and carbon dioxide for each alkyl bromide studied. The photoproduct HBr is dissociated in the bulk ice. Based on the experimental observations possible reaction mechanisms will be discussed.

  13. Neptunium(V) sorption on quartz and albite in aqueous suspension; Annual progress report

    SciTech Connect

    Kohler, M.; Leckie, J.O.

    1991-10-01

    The behavior of neptunium in the subsurface environment is of interest since neptunium isotopes are included in nuclear waste. Previous work investigated the sorption behavior of Np onto {alpha}-Fe{sub 2}O{sub 3} (hematite), an accessory mineral of the Yucca Mountain repository. The work reported herein involves the much more abundant silicate minerals quartz and albite, and is a logical continuation of the ongoing task. In previous work increased sorption was observed in systems containing hematite and EDTA, a ligand which acts as a surrogate for organic complexing agents. In addition, increased partial pressures of CO{sub 2} are common in many ground waters and the effects of carbonate on sorption of radionuclides have to be studied as well. At concentration levels of 10{sup {minus}7} M, Np(V) does not adsorb strongly on quartz and albite up to pH values of approximately 9 at solid/solution ratios of 30 to 40 g/l. Significant adsorption (> 20%) occurs on both minerals only at pH > 9. Pretreatment of albite affects the sorption behavior of this mineral at pH > 9, possibly due to the formation of secondary mineral phases at the albite surface. EDTA does not adsorb on quartz at concentrations of 10{sup {minus}6} M. In the presence of 50 {mu}M EDTA, Np(V) sorption seems to be restricted. EDTA at the 10{sup {minus}6} M level adsorbs onto albite to an appreciable degree at pH values < 7.5. One {mu}M EDTA has no effect on Np(V) adsorption onto albite. Carbonate species adsorb on quartz and albite, both cases showing a maximum in sorption at pH 6.5 to 7 where HCO{sub 3}{sup {minus}} is the predominant solution species.

  14. Investigation of possible interaction between pinaverium bromide and digoxin.

    PubMed

    Weitzel, O; Seidel, G; Engelbert, S; Berksoy, M; Eberhardt, G; Bode, R

    1983-01-01

    A single-blind study was carried out in 25 patients, who were receiving maintenance therapy for congestive heart failure with digoxin, to investigate the effect on steady-state plasma digoxin levels of concomitant administration of the spasmolytic, pinaverium bromide (50 mg 3-times daily). Patients received pinaverium bromide for 12 days followed by placebo for a further 7 days. Assessment of the results in 21 patients showed no evidence of any statistically significant variations in plasma digoxin levels during either treatment period or in the clinical observations which might indicate drug interaction. PMID:6653138

  15. Action of pinaverium bromide on calmodulin-regulated functions.

    PubMed

    Wuytack, F; De Schutter, G; Casteels, R

    1985-08-01

    Pinaverium bromide at concentrations below 10(-5) M did not inhibit calmodulin-dependent enzymes such as phosphodiesterase and the Ca transport ATPase of the plasma membrane. At higher concentrations the compound interacted with the stimulation of those enzymes by calmodulin and also inhibited the calmodulin-independent activity. A similar inhibitory action was observed for the NaK ATPase. It is concluded that the inhibitory action of pinaverium bromide on smooth muscle concentration at concentrations below 10(-5) M was due to its interaction with the voltage-dependent Ca channels and not to its interference with the calmodulin-dependent activation of the contractile proteins. PMID:2995077

  16. Versatile Route to Arylated Fluoroalkyl Bromide Building Blocks.

    PubMed

    Kaplan, Peter T; Vicic, David A

    2016-02-19

    New difunctionalized and fluoroalkylated silyl reagents have been prepared that react with silver and copper salts to afford active catalysts that can be used to synthesize arylated fluoroalkyl bromide building blocks. It has been shown that the [(phen)Ag(CF2)nBr] intermediates are capable of transferring both the phenanthroline ligand and the fluoroalkyl bromide chain to copper iodide, eliminating the need for a preligated copper salt precursor. The methodology is compatible with various chain lengths of the fluoroalkyl halide functionality. PMID:26820388

  17. Magnesium Lewis Acid Assisted Oxidative Bromoetherification Involving Bromine Transfer from Alkyl Bromides with Aldehydes by Umpolung of Bromide.

    PubMed

    Moriyama, Katsuhiko; Nishinohara, Chihiro; Togo, Hideo

    2016-08-16

    An oxidative bromoetherification involving a bromine transfer from alkyl bromides upon reacting them with aldehydes in a Grignard reaction with a concurrent oxidation of bromide was developed to provide substituted tetrahydrofurans in high yields. This reaction, which proceeds through two types of bromine transfer, was promoted by the addition of a Brønsted acid. Mechanistic studies suggested that a magnesium Lewis acid activates hypobromate, which is generated in situ from the reaction of bromide and Oxone to improve the electrophilicity of the bromonium ion (Br(+) ) for the oxidative bromoetherification of alkenyl alcohols. Furthermore, the magnesium Lewis acid catalyzed oxidative bromoetherification of an alkenyl alcohol proceeded to provide a cyclization product in 92 % yield. PMID:27304660

  18. Nickel-Catalyzed Reductive Cross-Coupling of Aryl Bromides with Alkyl Bromides: Et3N as the Terminal Reductant.

    PubMed

    Duan, Zhengli; Li, Wu; Lei, Aiwen

    2016-08-19

    Reductive cross-coupling has emerged as a direct method for the construction of carbon-carbon bonds. Most cobalt-, nickel-, and palladium-catalyzed reductive cross-coupling reactions to date are limited to stoichiometric Mn(0) or Zn(0) as the reductant. One nickel-catalyzed cross-coupling paradigm using Et3N as the terminal reductant is reported. By using this photoredox catalysis and nickel catalysis approach, a direct Csp(2)-Csp(3) reductive cross-coupling of aryl bromides with alkyl bromides is achieved under mild conditions without stoichiometric metal reductants. PMID:27472556

  19. Radioactive waste forms stabilized by ChemChar gasification: characterization and leaching behavior of cerium, thorium, protactinium, uranium, and neptunium.

    PubMed

    Marrero, T W; Morris, J S; Manahan, S E

    2004-02-01

    The uses of a thermally reductive gasification process in conjunction with vitrification and cementation for the long-term disposal of low level radioactive materials have been investigated. gamma-ray spectroscopy was used for analysis of carrier-free protactinium-233 and neptunium-239 and a stoichiometric amount of cerium (observed cerium-141) subsequent to gasification and leaching, up to 48 days. High resolution ICP-MS was used to analyze the cerium, thorium, and uranium from 46 to 438 days of leaching. Leaching procedures followed the guidance of ASTM Procedure C 1220-92, Standard Test Method for Static Leaching of Monolithic Waste Forms for Disposal of Radioactive Waste. The combination of the thermally reductive pretreatment, vitrification and cementation produced a highly non-leachable form suitable for long-term disposal of cerium, thorium, protactinium, uranium, and neptunium. PMID:14637345

  20. Methyl bromide alternatives for postharvest insect disinfestation of California walnuts

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Before shipment, California inshell walnuts destined for the valuable export market must be disinfested of both field pests (codling moth and navel orangeworm) and common storage pests (Indianmeal moth and red flour beetle). Until recently fumigation with methyl bromide has been the most common dis...

  1. A COMPARISON OF BROMIDE AND NITRATE TRANSPORT IN SOILS

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Sandy soils (with sand content 95-98%) are used for agricultural production, which require careful management of water, chemicals, and nutrients to minimize leaching below the rooting zone. Bromide is used as an indicator of downward transport of soluble nutrients in soils. A leching column study ...

  2. HEALTH AND ENVIRONMENTAL EFFECTS PROFILE FOR METHYL BROMIDE

    EPA Science Inventory

    The Health and Environmental Effects Profile for Methyl Bromide was prepared to support listings of hazardous constituents of a wide range of waste streams under Section 3001 of the Resource Conservation and Recovery Act (RCRA) and to provide health-related limits for emergency a...

  3. Nickel-Catalyzed Reductive Amidation of Unactivated Alkyl Bromides.

    PubMed

    Serrano, Eloisa; Martin, Ruben

    2016-09-01

    A user-friendly, nickel-catalyzed reductive amidation of unactivated primary, secondary, and tertiary alkyl bromides with isocyanates is described. This catalytic strategy offers an efficient synthesis of a wide range of aliphatic amides under mild conditions and with an excellent chemoselectivity profile while avoiding the use of stoichiometric and sensitive organometallic reagents. PMID:27357076

  4. Reactive films for mitigating methyl bromide emissions from fumigated soil

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Emissions of methyl bromide (MeBr) from agricultural fumigation can lead to depletion of the stratospheric ozone layer, and so its use is being phased out. However, as MeBr is still widely used under Critical Use Exemptions, strategies are still required to control such emissions. In this work, nove...

  5. Methyl Bromide Alternatives for Floriculture Production in a Problem Site

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Successful methyl bromide alternatives must manage a variety of pest problems in floriculture and vegetable production systems including weeds, plant-parasitic nematodes, and soil-borne diseases. Methods that may be successful in some situations may be challenged in sites with unusually heavy pest p...

  6. EFFECT OF BROMIDE ION ON FORMATION OF HAAS DURING CHLORINATION

    EPA Science Inventory

    loacetic acids (HAAs) during chlorination and he effects of independent variables, including pH, reaction time, and chlorine dosage. Almost all of the indpendent loaetic acids (HAAs) during chlorin...designed to statistically evaluate the influence of bromide ion on the formatio...

  7. The Fate of Alternative Soil Funigants to Methyl Bromide

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Soil fumigation is an important agricultural practice for the control of soil-borne pests. Since the phase–out of methyl bromide, due to its role in the depletion of stratospheric ozone, several alternatives such as 1,3-dichloropropene (1,3-D), chloropicrin (CP), and dimethyl disulfide (DMDS) are b...

  8. Status of Alternatives for Methyl Bromide in the United States

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Methyl bromide is a fumigant used for disinfestation of soils, commodities and structures. Listed as an ozone-depleting chemical international environmental protocols and the U.S. Clean Air Act require that its use be severely restricted. Although use of this fumigant has fallen considerably, the U....

  9. Weed Control with Methyl Bromide Alternatives: A Review.

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Methyl bromide (MeBr) has been used for several decades for pre-plant soil fumigation in high value agricultural and horticultural crops because it can provide broad-spectrum control of insects, nematodes, pathogens, and weeds. However, MeBr has been identified as a powerful ozone-depleting chemica...

  10. PHYTOREMEDIATON POTENTIALS OF SELECTED TROPICAL PLANTS FOR ETHIDIUM BROMIDE

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Research and development has its own benefits and inconveniences. One of the inconveniences is the generation of enormous quantity of diverse toxic and hazardous wastes and its eventual contamination to soil and groundwater resources. Ethidium bromide (EtBr) is one of the commonly used substances i...

  11. Methyl bromide phase out could affect future reforestation efforts

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Methyl bromide has long been an integral component in producing healthy tree seedlings in forest nurseries of California, Idaho, Montana, Oregon and Washington. The fumigant was supposed to be completely phased out of use in the United States of America by 2005, but many forest nurseries continue to...

  12. REVIEW OF CONTROL OPTIONS FOR METHYL BROMIDE IN COMMODITY TREATMENT

    EPA Science Inventory

    The report describes recent developments in the control of methyl bromide (MeBr) and discusses technical considerations and requirements for and economic feasibility of recovery. (NOTE: MeBr, fumigant for agricultural commodities, is an ozone depleting chemical. The U.S. EPA has ...

  13. Investigation of bromide's spectra by high resolution UV-laser

    NASA Astrophysics Data System (ADS)

    Zhang, Jin; Ma, Jian-guo

    2011-12-01

    Experimental investigation has been carried out for dissociation/ionisation of methyl bromide using time of flight mass spectrometer, then, the mass signals were assigned to H+, CHm+ (m= 0-3), iBr+ (i = 79, 81), and the main processes of multi-photon ionization and dissociation of CH3Br were given.

  14. Calla lily production with methyl bromide alternatives – Year 2

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Cut flower and ornamental bulb industries rely heavily on a methyl bromide/chloropicrin (MB/Pic) mixture as a key pest management tool. The loss of MB will seriously affect the cut flower and bulb industry, and, in the future, will require growers to use alternative fumigants. Past experiments have...

  15. Depleting methyl bromide residues in soil by reaction with bases

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Despite generally being considered the most effective soil fumigant, methyl bromide (MeBr) use is being phased out because its emissions from soil can lead to stratospheric ozone depletion. However, a large amount is still currently used due to Critical Use Exemptions. As strategies for reducing the...

  16. Methyl bromide alternatives for postharvest insect disinfestation of California walnuts

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Before shipment, California inshell walnuts destined for the valuable export market must be disinfested of both field pests (codling moth and navel orangeworm) and common storage pests (Indianmeal moth and red flour beetle). Until recently fumigation with methyl bromide has been the most common disi...

  17. BROMIDE-OXIDANT INTERACTIONS AND THM (TRIHALOMETHANE) FORMATION: A LITERATURE REVIEW

    EPA Science Inventory

    The review focuses on the interactions, not only of bromide and chlorine, but also of bromide and two common oxidation alternatives to chlorine--chlorine dioxide and monochloramine. The data evaluations include discussions of reaction products, potentials for trihalomethane (THM)...

  18. T-type Ca2+ channel modulation by otilonium bromide

    PubMed Central

    Strege, Peter R.; Sha, Lei; Beyder, Arthur; Bernard, Cheryl E.; Perez-Reyes, Edward; Evangelista, Stefano; Gibbons, Simon J.; Szurszewski, Joseph H.

    2010-01-01

    Antispasmodics are used clinically to treat a variety of gastrointestinal disorders by inhibition of smooth muscle contraction. The main pathway for smooth muscle Ca2+ entry is through L-type channels; however, there is increasing evidence that T-type Ca2+ channels also play a role in regulating contractility. Otilonium bromide, an antispasmodic, has previously been shown to inhibit L-type Ca2+ channels and colonic contractile activity. The objective of this study was to determine whether otilonium bromide also inhibits T-type Ca2+ channels. Whole cell currents were recorded by patch-clamp technique from HEK293 cells transfected with cDNAs encoding the T-type Ca2+ channels, CaV3.1 (α1G), CaV3.2 (α1H), or CaV3.3 (α1I) alpha subunits. Extracellular solution was exchanged with otilonium bromide (10−8 to 10−5 M). Otilonium bromide reversibly blocked all T-type Ca2+ channels with a significantly greater affinity for CaV3.3 than CaV3.1 or CaV3.2. Additionally, the drug slowed inactivation in CaV3.1 and CaV3.3. Inhibition of T-type Ca2+ channels may contribute to inhibition of contractility by otilonium bromide. This may represent a new mechanism of action for antispasmodics and may contribute to the observed increased clinical effectiveness of antispasmodics compared with selective L-type Ca2+ channel blockers. PMID:20203058

  19. 40 CFR 721.4090 - Ethanaminium, N-[bis(diethylamino)-methylene]-N-ethyl-, bromide.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Ethanaminium, N- -N-ethyl-, bromide... Substances § 721.4090 Ethanaminium, N- -N-ethyl-, bromide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as ethanaminium, N- -N-ethyl-, bromide (PMN...

  20. 40 CFR 721.4090 - Ethanaminium, N-[bis(diethylamino)-methylene]-N-ethyl-, bromide.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Ethanaminium, N- -N-ethyl-, bromide... Substances § 721.4090 Ethanaminium, N- -N-ethyl-, bromide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as ethanaminium, N- -N-ethyl-, bromide (PMN...

  1. 40 CFR 721.4090 - Ethanaminium, N-[bis(diethylamino)-methylene]-N-ethyl-, bromide.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Ethanaminium, N- -N-ethyl-, bromide... Substances § 721.4090 Ethanaminium, N- -N-ethyl-, bromide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as ethanaminium, N- -N-ethyl-, bromide (PMN...

  2. 40 CFR 721.4090 - Ethanaminium, N-[bis(diethylamino)-methylene]-N-ethyl-, bromide.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Ethanaminium, N- -N-ethyl-, bromide... Substances § 721.4090 Ethanaminium, N- -N-ethyl-, bromide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as ethanaminium, N- -N-ethyl-, bromide (PMN...

  3. 40 CFR 180.519 - Bromide ion and residual bromine; tolerances for residues.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 25 2013-07-01 2013-07-01 false Bromide ion and residual bromine... Tolerances § 180.519 Bromide ion and residual bromine; tolerances for residues. (a) General. The food additives, bromide ion and residual bromine, may be present in water, potable in accordance with...

  4. 40 CFR 180.519 - Bromide ion and residual bromine; tolerances for residues.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 24 2011-07-01 2011-07-01 false Bromide ion and residual bromine... Tolerances § 180.519 Bromide ion and residual bromine; tolerances for residues. (a) General. The food additives, bromide ion and residual bromine, may be present in water, potable in accordance with...

  5. 40 CFR 180.519 - Bromide ion and residual bromine; tolerances for residues.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 25 2012-07-01 2012-07-01 false Bromide ion and residual bromine... Tolerances § 180.519 Bromide ion and residual bromine; tolerances for residues. (a) General. The food additives, bromide ion and residual bromine, may be present in water, potable in accordance with...

  6. 40 CFR 180.519 - Bromide ion and residual bromine; tolerances for residues.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 23 2010-07-01 2010-07-01 false Bromide ion and residual bromine... Tolerances § 180.519 Bromide ion and residual bromine; tolerances for residues. (a) General. The food additives, bromide ion and residual bromine, may be present in water, potable in accordance with...

  7. 40 CFR 180.519 - Bromide ion and residual bromine; tolerances for residues.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 24 2014-07-01 2014-07-01 false Bromide ion and residual bromine... Tolerances § 180.519 Bromide ion and residual bromine; tolerances for residues. (a) General. The food additives, bromide ion and residual bromine, may be present in water, potable in accordance with...

  8. 2-Page Summary for Neptunium solubility in the Near-field Environment of A Proposed Yucca Mountain Repository

    SciTech Connect

    D. Sassani; A. Van Luik; J. Summerson

    2005-03-29

    The total system performance assessment (TSPA) for the proposed repository at Yucca Mountain, NV, includes a wide variety of processes to evaluate the potential release of radionuclides from the Engineered Barrier System into the unsaturated zone of the geosphere. The principal processes controlling radionuclide release and mobilization from the waste forms are captured in the model to assess the dissolved concentrations of radionuclides in the source-term. The TSPA model of the source-term incorporates the far-from-equilibrium dissolution of, for example, spent nuclear fuel (SNF) to capture bounding rates of radionuclide availability as the SNF degrades. In addition, for individual radionuclides, the source-term model evaluates solubility constraints that are more indicative of longer-term, equilibrium processes that can limit the potential mass transport from the source term in those cases. These solubility limits represent phase saturation and precipitation processes that can occur either at the waste form as it alters, or at other locations in the near-field environment (e.g., within the invert) if chemical conditions are different. Identification and selection of applicable constraints for solubility-limited radionuclide concentrations is a primary focus in formulating the source-term model for the TSPA. Neptunium is a long-lived radionuclide that becomes a larger fraction of the potential dose as radioactive decay of other radionuclides proceeds. To delineate appropriate long-term source-term controls on dissolved neptunium concentrations, a number of alternative models have been defined. The models are based on data both collected within the Yucca Mountain Project and taken from published literature, and have been evaluated against independent data sets to assess their applicability. The alternative models encompass ones based on precipitation of neptunium within its own separate oxide phases (i.e., ''pure'' Np-phases), and those where neptunium is

  9. Separation of plutonium and neptunium species by capillary electrophoresis-inductively coupled plasma-mass spectrometry and application to natural groundwater samples.

    PubMed

    Kuczewski, Bernhard; Marquardt, Christian M; Seibert, Alice; Geckeis, Horst; Kratz, Jens Volker; Trautmann, Norbert

    2003-12-15

    Capillary electrophoresis (CE) was coupled to ICPMS in order to combine the good performance of this separation technique with the high sensitivity of the ICPMS for the analysis of plutonium and neptunium oxidation states. The combination of a fused-silica capillary with a MicroMist AR 30-I-FM02 nebulizer and a Cinnabar small-volume cyclonic spray chamber yielded the best separation results. With this setup, it was possible to separate a model element mixture containing neptunium (NpO2(+)), uranium (UO2(2+)), lanthanum (La3+), and thorium (Th4+) in 1 M acetic acid. The same conditions were also suitable for the separation of various oxidation states of plutonium and neptunium in different aqueous samples. All separations were obtained within less than 15 min. A detection limit of 50 ppb identical with 2 x 10(-7) M (3-fold standard deviation of a blank) was achieved. To prove the negligible disturbance of the plutonium and neptunium redox equilibria during the CE separations, plutonium and neptunium speciation by CE-ICPMS in acidic solutions was compared with the results of UV/visible absorption spectroscopy and was found to be in good agreement. The CE-ICPMS system was also applied to study the reduction of Pu(VI) in a humic acid-containing groundwater at different pH values. PMID:14670034

  10. Aluminum electroplating on steel from a fused bromide electrolyte

    SciTech Connect

    Prabhat K. Tripathy; Laura A. Wurth; Eric J. Dufek; Toni Y. Gutknecht; Natalie J. Gese; Paula Hahn; Steven M. Frank; Guy L. Frederickson; J. Stephen Herring

    2014-08-01

    A quaternary bromide bath (LiBr–KBr–CsBr–AlBr3) was used to electro-coat aluminum on steel substrates. The electrolytewas prepared by the addition of AlBr3 into the eutectic LiBr–KBr–CsBr melt. A smooth, thick, adherent and shiny aluminum coating could be obtained with 80 wt.% AlBr3 in the ternary melt. The SEM photographs of the coated surfaces suggest the formation of thick and dense coatings with good aluminum coverage. Both salt immersion and open circuit potential measurement suggested that the coatings did display a good corrosionresistance behavior. Annealing of the coated surfaces, prior to corrosion tests, suggested the robustness of the metallic aluminum coating in preventing the corrosion of the steel surfaces. Studies also indicated that the quaternary bromide plating bath can potentially provide a better aluminumcoating on both ferrous and non-ferrous metals, including complex surfaces/geometries.