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Sample records for aqueous nitrate plutonium

  1. Aqueous nitrate flowsheet optimization and enhancement using the ATLAS facility

    SciTech Connect

    Schreiber, S.B.; Punjak, W.A.; Yarbro, S.L.

    1993-08-01

    The Advanced Testing Line for Actinide Separations (ATLAS) is a pilot plant of all aqueous nitrate plutonium recovery and purification operations within the Los Alamos Plutonium Facility. The main unit operations include dissolution, anion exchange, precipitations, evaporation, calcination, and waste stream polishing. In the current political environment, the emphasis has been redirected from the traditional goal of recovering a pure plutonium product to that of generating ``clean`` effluents while placing the plutonium into a form suitable for long term storage. The ATLAS facility is uniquely suited to fulfill this new role in the development and demonstration of new or revisited technologies. This report summarizes recent work in equipment improvements to the batch dissolver, an evaluation of homogeneous hydroxide precipitations, a demonstration of nitric acid recycle, and the preparation of neptunium and plutonium standards.

  2. 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)

  3. NON-AQUEOUS DISSOLUTION OF MASSIVE PLUTONIUM

    DOEpatents

    Reavis, J.G.; Leary, J.A.; Walsh, K.A.

    1959-05-12

    A method is presented for obtaining non-aqueous solutions or plutonium from massive forms of the metal. In the present invention massive plutonium is added to a salt melt consisting of 10 to 40 weight per cent of sodium chloride and the balance zinc chloride. The plutonium reacts at about 800 deg C with the zinc chloride to form a salt bath of plutonium trichloride, sodium chloride, and metallic zinc. The zinc is separated from the salt melt by forcing the molten mixture through a Pyrex filter.

  4. ARRAYS OF BOTTLES OF PLUTONIUM NITRATE SOLUTION

    SciTech Connect

    Margaret A. Marshall

    2012-09-01

    In October and November of 1981 thirteen approaches-to-critical were performed on a remote split table machine (RSTM) in the Critical Mass Laboratory of Pacific Northwest Laboratory (PNL) in Richland, Washington using planar arrays of polyethylene bottles filled with plutonium (Pu) nitrate solution. Arrays of up to sixteen bottles were used to measure the critical number of bottles and critical array spacing with a tight fitting Plexiglas® reflector on all sides of the arrays except the top. Some experiments used Plexiglas shells fitted around each bottles to determine the effect of moderation on criticality. Each bottle contained approximately 2.4 L of Pu(NO3)4 solution with a Pu content of 105 g Pu/L and a free acid molarity H+ of 5.1. The plutonium was of low 240Pu (2.9 wt.%) content. These experiments were sponsored by Rockwell Hanford Operations because of the lack of experimental data on the criticality of arrays of bottles of Pu solution such as might be found in storage and handling at the Purex Facility at Hanford. The results of these experiments were used “to provide benchmark data to validate calculational codes used in criticality safety assessments of [the] plant configurations” (Ref. 1). Data for this evaluation were collected from the published report (Ref. 1), the approach to critical logbook, the experimenter’s logbook, and communication with the primary experimenter, B. Michael Durst. Of the 13 experiments preformed 10 were evaluated. One of the experiments was not evaluated because it had been thrown out by the experimenter, one was not evaluated because it was a repeat of another experiment and the third was not evaluated because it reported the critical number of bottles as being greater than 25. Seven of the thirteen evaluated experiments were determined to be acceptable benchmark experiments. A similar experiment using uranyl nitrate was benchmarked as U233-SOL-THERM-014.

  5. RECOVERY OF PLUTONIUM FROM AQUEOUS SOLUTIONS

    DOEpatents

    Reber, E.J.

    1959-09-01

    A process is described for recovering plutonium values from aqueous solutions by precipitation on bismuth phosphate. The plutonium is secured in its tetravalent state. bismuth salt is added to the solution, and ant excess of phosphoric acid anions is added to the solution in two approximately equal installments. The rate of addition of the first installment is about two to three times as high as the rate of addition of the second installment, whereby a precipitate of bismuth phosphate forms, the precipitate carrying the plutonium values. The precipitate is separated from the solution.

  6. METHOD OF RECOVERING PLUTONIUM VALUES FROM AQUEOUS SOLUTIONS BY CARRIER PRECIPITATION

    DOEpatents

    James, R.A.; Thompson, S.G.

    1959-11-01

    A process is presented for pretreating aqueous nitric acid- plutonium solutions containing a small quantity of hydrazine that has formed as a decomposition product during the dissolution of neutron-bombarded uranium in nitric acid and that impairs the precipitation of plutonium on bismuth phosphate. The solution is digested with alkali metal dichromate or potassium permanganate at between 75 and 100 deg C; sulfuric acid at approximately 75 deg C and sodium nitrate, oxaiic acid plus manganous nitrate, or hydroxylamine are added to the solution to secure the plutonium in the tetravalent state and make it suitable for precipitation on BiPO/sub 4/.

  7. Benchmark Evaluation of Plutonium Nitrate Solution Arrays

    SciTech Connect

    M. A. Marshall; J. D. Bess

    2011-09-01

    In October and November of 1981 thirteen approach-to-critical experiments were performed on a remote split table machine (RSTM) in the Critical Mass Laboratory of Pacific Northwest Laboratory (PNL) in Richland, Washington, using planar arrays of polyethylene bottles filled with plutonium (Pu) nitrate solution. Arrays of up to sixteen bottles were used to measure the critical number of bottles and critical array spacing with a tight fitting Plexiglas{reg_sign} reflector on all sides of the arrays except the top. Some experiments used Plexiglas shells fitted around each bottles to determine the effect of moderation on criticality. Each bottle contained approximately 2.4 L of Pu(NO3)4 solution with a Pu content of 105 g Pu/L and a free acid molarity H+ of 5.1. The plutonium was of low 240Pu (2.9 wt.%) content. These experiments were performed to fill a gap in experimental data regarding criticality limits for storing and handling arrays of Pu solution in reprocessing facilities. Of the thirteen approach-to-critical experiments eleven resulted in extrapolations to critical configurations. Four of the approaches were extrapolated to the critical number of bottles; these were not evaluated further due to the large uncertainty associated with the modeling of a fraction of a bottle. The remaining seven approaches were extrapolated to critical array spacing of 3-4 and 4-4 arrays; these seven critical configurations were evaluation for inclusion as acceptable benchmark experiments in the International Criticality Safety Benchmark Evaluation Project (ICSBEP) Handbook. Detailed and simple models of these configurations were created and the associated bias of these simplifications was determined to range from 0.00116 and 0.00162 {+-} 0.00006 ?keff. Monte Carlo analysis of all models was completed using MCNP5 with ENDF/BVII.0 neutron cross section libraries. A thorough uncertainty analysis of all critical, geometric, and material parameters was performed using parameter perturbation methods. It was found that uncertainty in the impurities in the polyethylene bottles, reflector position, bottle outer diameter, and critical array spacing had the largest effect. The total uncertainty ranged from 0.00651 to 0.00920 ?keff. Evaluation methods and results will be presented and discussed in greater detail in the full paper.

  8. Catalyzed reduction of nitrate in aqueous solutions

    SciTech Connect

    Haas, P.A.

    1994-08-01

    Sodium nitrate and other nitrate salts in wastes is a major source of difficulty for permanent disposal. Reduction of nitrate using aluminum metal has been demonstrated, but NH{sub 3}, hydrazine, or organic compounds containing oxygen would be advantageous for reduction of nitrate in sodium nitrate solutions. Objective of this seed money study was to determine minimum conditions for reduction. Proposed procedure was batchwise heating of aqueous solutions in closed vessels with monitoring of temperatures and pressures. A simple, convenient apparatus and procedure were demonstrated for observing formation of gaseous products and collecting samples for analyses. The test conditions were 250{degree}C and 1000 psi max. Any useful reduction of sodium nitrate to sodium hydroxide as the primary product was not found. The nitrate present at pHs < 4 as HNO{sub 3} or NH{sub 4}NO{sub 3} is easily decomposed, and the effect of nitromethane at these low pHs was confirmed. When acetic acid or formic acid was added, 21 to 56% of the nitrate in sodium nitrate solutions was reduced by methanol or formaldehyde. With hydrazine and acetic acid, 73 % of the nitrate was decomposed to convert NaNO{sub 3} to sodium acetate. With hydrazine and formic acid, 36% of the nitrate was decomposed. If these products are more acceptable for final disposal than sodium nitrate, the reagents are cheap and the conversion conditions would be practical for easy use. Ammonium acetate or formate salts did not significantly reduce nitrate in sodium nitrate solutions.

  9. SOLVENT EXTRACTION PROCESS FOR SEPARATING URANIUM AND PLUTONIUM FROM AQUEOUS ACIDIC SOLUTIONS OF NEUTRON IRRADIATED URANIUM

    DOEpatents

    Bruce, F.R.

    1962-07-24

    A solvent extraction process was developed for separating actinide elements including plutonium and uranium from fission products. By this method the ion content of the acidic aqueous solution is adjusted so that it contains more equivalents of total metal ions than equivalents of nitrate ions. Under these conditions the extractability of fission products is greatly decreased. (AEC)

  10. Purification of aqueous plutonium chloride solutions via precipitation and washing.

    SciTech Connect

    Stroud, M. A.; Salazar, R. R.; Abney, Kent David; Bluhm, E. A.; Danis, J. A.

    2003-01-01

    Pyrochemical operations at Los Alamos Plutonium Facility (TA-55) use high temperature melt s of calcium chloride for the reduction of plutonium oxide to plutonium metal and hi gh temperature combined melts of sodium chloride and potassium chloride mixtures for the electrorefining purification of plutonium metal . The remaining plutonium and americium are recovered from thes e salts by dissolution in concentrated hydrochloric acid followed by either solvent extraction or io n exchange for isolation and ultimately converted to oxide after precipitation with oxalic acid . Figur e 1 illustrates the current aqueous chloride flow sheet used for plutonium processing at TA-55 .

  11. SEPARATION OF PLUTONIUM

    DOEpatents

    Maddock, A.G.; Smith, F.

    1959-08-25

    A method is described for separating plutonium from uranium and fission products by treating a nitrate solution of fission products, uranium, and hexavalent plutonium with a relatively water-insoluble fluoride to adsorb fission products on the fluoride, treating the residual solution with a reducing agent for plutonium to reduce its valence to four and less, treating the reduced plutonium solution with a relatively insoluble fluoride to adsorb the plutonium on the fluoride, removing the solution, and subsequently treating the fluoride with its adsorbed plutonium with a concentrated aqueous solution of at least one of a group consisting of aluminum nitrate, ferric nitrate, and manganous nitrate to remove the plutonium from the fluoride.

  12. [Photodegradation of atenolol in aqueous nitrate solution].

    PubMed

    Ji, Yue-Fei; Zeng, Chao; Meng, Cui; Yang, Xi; Gao, Shi-Xiang

    2012-02-01

    The aqueous photolysis of beta-blocker atenolol (ATL) using Xe lamp as simulated solar irradiation source was investigated in the presence of nitrate ions. The effects of nitrate ion concentration, solution pH value, and concentration of bicarbonate and humic substance on the photodegradation of ATL were studied. The results showed that photodegradation of ATL in nitrate solution followed pseudo-first-order kinetics. The increasing concentration of nitrate ion promoted the photodegradation rate of ATL. The first-order rate constant increased from 0.002 26 min(-1) to 0.009 4 min(-1) with nitrate concentration increasing from 0 to 5 mmol x L(-1). Acidic or alkaline condition of the solution favored the photodegradation of ATL. Different concentration of bicarbonate showed insignificant effect of the degradation while the increasing concentration of fulvic acid showed inhibiting effect. Hydroxyl radical was determined to be formed during the photolysis process of ATL using isopropanol as molecular probe. The main photoproducts of ATL were identified by using SPE-LC-MS techniques and possible photoinduced degradation pathways in nitrate solution were proposed. PMID:22509585

  13. Process for decomposing nitrates in aqueous solution

    DOEpatents

    Haas, Paul A.

    1980-01-01

    This invention is a process for decomposing ammonium nitrate and/or selected metal nitrates in an aqueous solution at an elevated temperature and pressure. Where the compound to be decomposed is a metal nitrate (e.g., a nuclear-fuel metal nitrate), a hydroxylated organic reducing agent therefor is provided in the solution. In accordance with the invention, an effective proportion of both nitromethane and nitric acid is incorporated in the solution to accelerate decomposition of the ammonium nitrate and/or selected metal nitrate. As a result, decomposition can be effected at significantly lower temperatures and pressures, permitting the use of system components composed of off-the-shelf materials, such as stainless steel, rather than more costly materials of construction. Preferably, the process is conducted on a continuous basis. Fluid can be automatically vented from the reaction zone as required to maintain the operating temperature at a moderate value--e.g., at a value in the range of from about 130.degree.-200.degree. C.

  14. METHOD OF SEPARATING PLUTONIUM

    DOEpatents

    Heal, H.G.

    1960-02-16

    BS>A method of separating plutonium from aqueous nitrate solutions of plutonium, uranium. and high beta activity fission products is given. The pH of the aqueous solution is adjusted between 3.0 to 6.0 with ammonium acetate, ferric nitrate is added, and the solution is heated to 80 to 100 deg C to selectively form a basic ferric plutonium-carrying precipitate.

  15. Chemical treatment of plutonium with hydrogen peroxide before nitrate anion exchange processing. [Reduction to (IV)

    SciTech Connect

    Marsh, S.F.; Gallegos, T.D.

    1987-05-01

    The major aqueous process used to recover and purify plutonium at the Los Alamos Plutonium Facility is anion exchange in nitric acid. This process is highly selective for plutonium; however, all plutonium must be as Pu(IV) to form the strongly sorbed anionic nitrato complex. The previous ''full-reduction treatment'' used at Los Alamos to obtain Pu(IV) results in a three- to fourfold increase in the feed solution volume and the introduction of kilogram quantities of extraneous salts immediately before a process whose function is to remove such impurities. That treatment has been successfully replaced by a single reagent, hydrogen peroxide, which converts all plutonium to Pu(IV), minimally increases the feed volume, and introduces no residual impurities. Safety aspects of this revised chemical treatment are addressed.

  16. PLUTONIUM SEPARATION METHOD

    DOEpatents

    Beaufait, L.J. Jr.; Stevenson, F.R.; Rollefson, G.K.

    1958-11-18

    The recovery of plutonium ions from neutron irradiated uranium can be accomplished by bufferlng an aqueous solutlon of the irradiated materials containing tetravalent plutonium to a pH of 4 to 7, adding sufficient acetate to the solution to complex the uranyl present, adding ferric nitrate to form a colloid of ferric hydroxide, plutonlum, and associated fission products, removing and dissolving the colloid in aqueous nitric acid, oxldizlng the plutonium to the hexavalent state by adding permanganate or dichromate, treating the resultant solution with ferric nitrate to form a colloid of ferric hydroxide and associated fission products, and separating the colloid from the plutonlum left in solution.

  17. Criticality experiments with mixed plutonium and uranium nitrate solution at a plutonium fraction of 0.4 in slab geometry

    SciTech Connect

    Pohl, B.A.; Keeton, S.C.

    1997-09-01

    R. C. Lloyd of PNL has completed and published a series of critical experiments with mixed plutonium- uranium nitrate solutions (Reference 1). This series of critical experiments was part of an extensive program jointly sponsored by the U. S. Department of Energy (DOE) and the Power Reactor and Nuclear Fuel Development Corporation (PNC) of Japan and was carried out in the mid-1980`s. The experiments evaluated here (published as Report PNL-6327) were performed with mixed plutonium- uranium nitrate solution in a variable thickness slab tank with two 106.7 cm square sides and a width that could be varied from 7.6 to 22.8 cm. The objective of these experiments was to obtain experimental data to permit the validation of computer codes for criticality calculations and of cross-section data to minimize the uncertainties inherent therein, so that facility safety, efficiency, and reliability could be enhanced. The concentrations of the solution were about 105, 293, and 435 g(Pu+U)/liter with a ratio of plutonium to total heavy metal (plutonium plus uranium) of about 0. 40 for all eight experiments. Four measurements were made with a water reflector, and four with no reflector. Following the publication of the initial PNL reports, considerable effort was devoted to an extensive reevaluation of this series of experiments by a collaboration of researchers from ORNL, PNL, and PNC (Reference 2). Their work resulted in a more accurate description of the ``as built`` hardware configuration and the materials specifications. For the evaluations in this report, the data published in Reference 2 by Smolen et al. is selected to supersede the original PNL report. Eight experiments have been evaluated and seven (063, 064, 071, 072, 074, 075, and 076) provide benchmark criticality data. Experiment 073 could not achieve criticality within vessel height limitations.

  18. METHOD OF SEPARATION OF PLUTONIUM FROM CARRIER PRECIPITATES

    DOEpatents

    Dawson, I.R.

    1959-09-22

    The recovery of plutonium from fluoride carrier precipitates is described. The precipitate is dissolved in zirconyl nitrate, ferric nitrate, aluminum nitrate, or a mixture of these complexing agents, and the plutonium is then extracted from the aqueous solution formed with a water-immiscible organic solvent.

  19. Depolarized Rayleigh light scattering studies of concentrated aqueous nitrate solutions

    NASA Astrophysics Data System (ADS)

    Carpio, R. A.; Mehicic, M.; Yeager, E.

    1980-12-01

    Interferometric measurements of the reorientational relaxation time of the nitrate anion in concentrated aqueous calcium nitrate and zinc nitrate solutions have been made as a function of temperature and composition. Arrhenius plots of tau for Ca(NO3)2 X H2O, where X = 4, 5, and 5.6 and Zn(NO3)2 5 H2O are linear and yield activation energies in the range of 5.6 to 8.3 Kcal/mole. The data for Ca(NO3)2 3.91 H2O, which cover the most extensive range of viscosity and temperature, were non-Arrhenius and were best fitted by the Vogel-Tamman-Fulcher equation from which an ideal glass transition temperature was derived. The viscosity dependence of tau for both the Ca(NO3)2 and Zn(NO3)2 solutions was found to be between that predicted by the classical Stokes-Einstein equation and that predicted using slip hydrodynamic boundary conditions. Nitrate rotation was found to be slower in Ca(NO3)2 solutions than in the corresponding Zn(NO3)2 solutions.

  20. Depolarized Rayleigh light scattering studies of concentrated aqueous nitrate solutions

    NASA Astrophysics Data System (ADS)

    Carpio, Ronald A.; Mehicic, Mehmed; Yeager, Ernest

    1981-03-01

    Interferometric measurements of the reorientational relaxation time τ of the nitrate anion in concentrated aqueous calcium nitrate and zinc nitrate solutions have been made as a function of temperature and composition. Arrhenius plots of τ for Ca(NO3)2ṡXH2O, where X=4,5, and 5.6 and Zn(NO3)2ṡ5H2O are linear and yield activation energies in the range of 5.6 and 8.3 kcal/mole. The data for Ca(NO3)2ṡ3.91H2O, which cover the most extensive range of viscosity and temperature, were non-Arrhenius and were best fitted by the Vogel-Tamman-Fulcher equation from which an ideal glass transition temperature was derived. The viscosity dependence of τ for both the Ca(NO3)2 and Zn(NO3)2 solutions was found to be between that predicted by the classical Stokes-Einstein equation and that predicted using slip hydrodynamic boundary conditions. Nitrate rotation was found to be slower in Ca(NO3)2 solutions than in the corresponding Zn(NO3)2 solutions.

  1. Basis document for PFP plutonium nitrate ion exchange process in Room 228A

    SciTech Connect

    Risenmay, H.R.

    1997-04-23

    The PFP facility currently has approximately 4300 liters of plutonium nitrate solution in storage. This material will be calcined by the Vertical Denigration Calciner (VDC) located in room 230C. However, part of the material needs to be purified to remove constituents that will interfere with the calcination process. An Ion Exchange process using Reillex{trademark} HPQ anion exchange resin was tested by the Plutonium Process Support Laboratories (PPSL) (I). The Ion exchange process is to be installed in glovebox HC-7 in room 228A/234-5Z. The plutonium separated from the interfering constituents will be in a concentrated condition ready to be calcined by the VDC in room 230C. The oxide product of the VDC will be placed into the 2736-Z vaults for long term storage.

  2. Plutonium-uranium separation in the Purex process using mixtures of hydroxylamine nitrate and ferrous sulfamate

    SciTech Connect

    McKibben, J.M.; Chostner, D.F.; Orebaugh, E.G.

    1983-11-01

    Laboratory studies, followed by plant operation, established that a mixture of hydroxylamine nitrate (HAN) and ferrous sulfamate (FS) is superior to FS used alone as a reductant for plutonium in the Purex first cycle. FS usage has been reduced by about 70% (from 0.12 to 0.04M) compared to the pre-1978 period. This reduced the volume of neutralized waste due to FS by 194 liters/metric ton of uranium (MTU) processed. The new flowsheet also gives lower plutonium losses to waste and at least comparable fission product decontamination. To achieve satisfactory performance at this low concentration of FS, the acidity in the 1B mixer-settler was reduced by using a split-scrub - a low acid scrub in stage one and a higher acid scrub in stage three - to remove acid from the solvent exiting the 1A centrifugal contactor. 8 references, 14 figures, 1 table.

  3. Criticality experiments with a mixed-oxide fuel pin array in plutonium-uranium nitrate solutions

    SciTech Connect

    Lloyd, R.C.; Smolen, G.R.; Matsumoto, T.

    1989-01-01

    A series of critical experiments was completed with an array of mixed-oxide (MOX) fuel pins surrounded by plutonium-uranium nitrate solutions. The experiments were performed under a joint Criticality Data Development Program between the US Department of Energy and the Power Reactor and Nuclear Fuel development Corporation of Japan. The critical experiments were performed in the Critical Mass Laboratory (CML) of the Pacific Northwest Laboratory (PNL). The objectives of these experiments are to provide criticality data for a heterogeneous system of fuel pins moderated with plutonium-uranium and to determine the effectiveness of soluble gadolinium as a neutron absorber for criticality control in optimizing the physical size of equipment. Experiments have been performed in a similar configuration; however, these new experiments provide criticality data for a tighter fuel lump spacing, where soluble neutron poisons are not as effective.

  4. SEPARATION OF PLUTONIUM VALUES FROM OTHER METAL VALUES IN AQUEOUS SOLUTIONS BY SELECTIVE COMPLEXING AND ADSORPTION

    DOEpatents

    Beaton, R.H.

    1960-06-28

    A process is given for separating tri- or tetravalent plutonium from fission products in an aqueous solution by complexing the fission products with oxalate, tannate, citrate, or tartrate anions at a pH value of at least 2.4 (preferably between 2.4 and 4), and contacting a cation exchange resin with the solution whereby the plutonium is adsorbed while the complexed fission products remain in solution.

  5. Criticality experiments with mixed oxide fuel pin arrays in plutonium-uranium nitrate solution

    SciTech Connect

    Lloyd, R.C. ); Smolen, G.R. )

    1988-08-01

    A series of critical experiments was completed with mixed plutonium-uranium solutions having a Pu/(Pu + U) ratio of approximately 0.22 in a boiler tube-type lattice assembly. These experiments were conducted as part of the Criticality Data Development Program between the United States Department of Energy (USDOE) and the Power Reactor and Nuclear Fuel Development Corporation (PNC) of Japan. A complete description of the experiments and data are included in this report. The experiments were performed with an array of mixed oxide fuel pins in aqueous plutonium-uranium solutions. The fuel pins were contained in a boiler tube-type tank and arranged in a 1.4 cm square pitch array which resembled cylindrical geometry. One experiment was perfomed with the fuel pins removed from the vessel. The experiments were performed with a water reflector. The concentration of the solutions in the boiler tube-type tank was varied from 4 to 468 g (Pu + U)/liter. The ratio of plutonium to total heavy metal (plutonium plus uranium) was approximately 0.22 for all experiments.

  6. Plutonium silicate alteration phases produced by aqueous corrosion of borosilicate glass.

    SciTech Connect

    Fortner, J. A.; Mertz, C. J.; Bakel, A. J.; Finch, R. J.; Chamerlain, D. B.

    1999-11-22

    Borosilicate glasses loaded with {approx}10 wt % plutonium were found to produce plutonium-silicate alteration phases upon aqueous corrosion under a range of conditions. The phases observed were generally rich in lanthanide (Ln) elements and were related to the lanthanide orthosilicate phases of the monoclinic Ln{sub 2}SiO{sub 5} type. The composition of the phases was variable regarding [Ln]/[Pu] ratio, depending upon type of corrosion test and on the location within the alteration layer. The formation of these phases likely has implications for the incorporation of plutonium into silicate alteration phases during corrosion of titanate ceramics, high-level waste glasses, and spent nuclear fuel.

  7. Extraction of uranyl nitrate from concentrated aqueous salt solutions by tributyl phosphate

    SciTech Connect

    Pyartman, A.K.; Kopyrin, A.A.; Puzikov, E.A.

    1995-01-01

    Equations have been proposed for describing isotherms of extraction of uranyl nitrate from concentrated aqueous salt solutions by neat tri-n-butyl phosphate, with account taken of variations of activity coefficients of the components in organic phase over a wide range of its compositions. The constants of extraction equilibria, calculated for a standard hypothetical 1 M aqueous solution of uranyl nitrate and the state of pure components in organic phase with a mole fraction of 1, have been determined assuming formation of uranyl nitrate disolvate and trisolvate in the organic phase. The excessive thermodynamic functions of mixing tri-n-butyl phosphate with uranyl nitrate disolvate are presented.

  8. Effects of inhaled plutonium nitrate on bone and liver in dogs

    SciTech Connect

    Dagle, G.E.; Weller, R.E.; Watson, C.R.; Buschbom, R.L.

    1994-04-01

    The life-span biological effects of inhaled soluble, alpha-emitting radionuclides deposited in the skeleton and liver were studied in 5 groups of 20 beagles exposed to initial lung depositions ranging from 0.48 to 518 Bq/g of lung. Average plutonium amounts in the lungs decreased to approximately 1% of the final body deposition in dogs surviving 5 years or more; more than 90% of the final depositions accumulated in the liver and skeleton. The liver-to-skeletal ratio of deposited plutonium was 0.83. The incidence of bone tumors, primarily osteogenic sarcomas causing early mortality, at final group average skeletal depositions of 15.8, 2.1, and 0.5 Bq/g was, respectively, 85%, 50%, and 5%; there were no bone tumors in exposure groups with mean average depositions lower than 0.5 Bq/g. Elevated serum liver enzyme levels were observed in exposure groups down to 1.3 Bq/g. The incidence of liver tumors at final group average liver depositions of 6.9, 1.3, 0.2, and 0.1 Bq/g, was, respectively, 25%, 15%, 15%, and 15%; one hepatoma occurred among 40 control dogs. The risk of the liver cancer produced by inhaled plutonium nitrate was difficult to assess due to the competing risks of life shortening from lung and bone tumors.

  9. SOLVENT EXTRACTION PROCESS FOR PLUTONIUM

    DOEpatents

    Seaborg, G.T.

    1959-04-14

    The separation of plutonium from aqueous inorganic acid solutions by the use of a water immiscible organic extractant liquid is described. The plutonium must be in the oxidized state, and the solvents covered by the patent include nitromethane, nitroethane, nitropropane, and nitrobenzene. The use of a salting out agents such as ammonium nitrate in the case of an aqueous nitric acid solution is advantageous. After contacting the aqueous solution with the organic extractant, the resulting extract and raffinate phases are separated. The plutonium may be recovered by any suitable method.

  10. Extraction of cerium-group lanthanide (III) nitrates from concentrated aqueous salt solutions by tributyl phosphate

    SciTech Connect

    Pyartman, A.K.; Kopyrin, A.A.; Puzikov, E.A.

    1995-01-01

    The extraction equilibrium for a hypothetical standard, designated as 1 M aqueous solution of Ln(III) nitrate and the state of the pure components in organic phase with a mole fraction of 1 have been determined assuming formation of tri- and tetrasolvates of the metal(III) nitrates in organic phase. The excessive thermodynamic functions of mixing tri-n-butyl phosphate with solutions of Ln(III) nitrate trisolvates are presented.

  11. Plutonium (IV) complexation by nitrate in acid solutions of ionic strengths from 2 to 19 molal

    SciTech Connect

    Berg, J.M.; Veirs, D.K.; Vaughn, R.B.; Cisneros, M.A.; Smith, C.A.

    1997-09-01

    Titrations of Pu(IV) with HNO{sub 3} in a series of aqueous HClO{sub 4} solutions ranging in ionic strength from 2 to 19 molal were followed using absorption spectrophotometry. The Pu 5f-5f spectra in the visible and near IR range change with complex formation. At each ionic strength, a series of spectra were obtained by varying nitrate concentration. Each series was deconvoluted into spectra f Pu{sup 4+}(aq), Pu(NO{sub 3}){sup 3+} and Pu(NO{sub 3}){sub 2}{sup 2+} complexes, and simultaneously their formation constants were determined. When corrected for the incomplete dissociation of nitric acid, the ionic strength dependence of each formation constant can be described by two parameters, {beta}{sup 0} and {Delta}{var_epsilon} using the formulae of specific ion interaction theory. The difficulties with extending this analysis to higher nitrate coordination numbers are discussed.

  12. Nitrate anion exchange in 238Pu aqueous scrap recovery operations

    NASA Astrophysics Data System (ADS)

    Pansoy-Hjelvik, M. E.; Silver, G. L.; Reimus, M. A. H.; Ramsey, K. B.

    1999-01-01

    Strong base, nitrate anion exchange (IX) is crucial to the purification of 238Pu solution feedstocks with gross levels of impurities. This paper discusses the work involved in bench scale experiments to optimize the nitrate anion exchange process. In particular, results are presented of experiments conducted to a) demonstrate that high levels of impurities can be separated from 238Pu solutions via nitrate anion exchange and, b) work out chemical pretreatment methodology to adjust and maintain 238Pu in the IV oxidation state to optimize the Pu(IV)-hexanitrato anionic complex sorption to Reillex-HPQ resin. Additional experiments performed to determine the best chemical treatment methodology to enhance recovery of sorbed Pu from the resin and VIS-NIR absorption studies to determine the steady state equilibrium of Pu(IV), Pu(III), and Pu(VI) in nitric acid are discussed.

  13. Method of separating thorium from plutonium

    DOEpatents

    Clifton, D.G.; Blum, T.W.

    1984-07-10

    A method is described for chemically separating plutonium from thorium. Plutonium and thorium to be separated are dissolved in an aqueous feed solution, preferably as the nitrate salts. The feed solution is acidified and sodium nitrite is added to the solution to adjust the valence of the plutonium to the +4 state. A chloride salt, preferably sodium chloride, is then added to the solution to induce formation of an anionic plutonium chloride complex. The anionic plutonium chloride complex and the thorium in solution are then separated by ion exchange on a strong base anion exchange column.

  14. Method of separating thorium from plutonium

    DOEpatents

    Clifton, David G.; Blum, Thomas W.

    1984-01-01

    A method of chemically separating plutonium from thorium. Plutonium and thorium to be separated are dissolved in an aqueous feed solution, preferably as the nitrate salts. The feed solution is acidified and sodium nitrite is added to the solution to adjust the valence of the plutonium to the +4 state. A chloride salt, preferably sodium chloride, is then added to the solution to induce formation of an anionic plutonium chloride complex. The anionic plutonium chloride complex and the thorium in solution are then separated by ion exchange on a strong base anion exchange column.

  15. Method of separating thorium from plutonium

    DOEpatents

    Clifton, D.G.; Blum, T.W.

    A method of chemically separating plutonium from thorium is claimed. Plutonium and thorium to be separated are dissolved in an aqueous feed solution, preferably as the nitrate salts. The feed solution is acidified and sodium nitrite is added to the solution to adjust the valence of the plutonium to the +4 state. A chloride salt, preferably sodium chloride, is then added to the solution to induce formation of an anionic plutonium chloride complex. The anionic plutonium chloride complex and the thorium in solution are then separated by ion exchange on a strong base anion exchange column.

  16. Synthesis and structures of plutonyl nitrate complexes: is plutonium heptavalent in PuO3(NO3)2(-) ?

    PubMed

    Maurice, Rmi; Renault, Eric; Gong, Yu; Rutkowski, Philip X; Gibson, John K

    2015-03-01

    Gas-phase plutonium nitrate anion complexes were produced by electrospray ionization (ESI) of a plutonium nitrate solution. The ESI mass spectrum included species with all four of the common oxidation states of plutonium: Pu(III), Pu(IV), Pu(V), and Pu(VI). Plutonium nitrate complexes were isolated in a quadrupole ion trap and subjected to collision-induced dissociation (CID). CID of complexes of the general formula PuOx(NO3)y(-) resulted in the elimination of NO2 to produce PuOx+1(NO3)y-1(-), which in most cases corresponds to an increase in the oxidation state of plutonium. Plutonyl species, Pu(V)O2(NO3)2(-) and Pu(VI)O2(NO3)3(-), were produced from Pu(III)(NO3)4(-) and Pu(IV)(NO3)5(-), respectively, by the elimination of two NO2 molecules. CID of Pu(VI)O2(NO3)3(-) resulted in NO2 elimination to yield PuO3(NO3)2(-), in which the oxidation state of plutonium could be VII, a known oxidation state in condensed phase but not yet in the gas phase. Density functional theory confirmed the nature of Pu(V)O2(NO3)2(-) and Pu(VI)O2(NO3)3(-) as plutonyl(V/VI) cores coordinated by bidentate equatorial nitrate ligands. The computed structure of PuO3(NO3)2(-) is essentially a plutonyl(VI) core, Pu(VI)O2(2+), coordinated in the equatorial plane by two nitrate ligands and one radical oxygen atom. The computations indicate that in the ground spin-orbit free state of PuO3(NO3)2(-), the unpaired electron of the oxygen atom is antiferromagnetically coupled to the spin-triplet state of the plutonyl core. The results indicate that Pu(VII) is not a readily accessible oxidation state in the gas phase, despite that it is stable in solution and solids, but rather that a Pu(VI)-O bonding configuration is favored, in which an oxygen radical is involved. PMID:25695878

  17. Extraction of nitric acid, uranyl nitrate, and bismuth nitrate from aqueous nitric acid solutions with CMPO

    SciTech Connect

    Spencer, B.B.

    1995-08-01

    DOE sponsored development of the transuranium extraction (TRUEX) process for removing actinides from radioactive wastes. The solvent is a mixture of CMPO and TBP. Since the extraction characteristics of CMPO are not as well understood as those of TBP, the extraction of nitric acid, uranyl nitrate, and bismuth nitrate with CMPO (dissolved in n-dodecane) were studied. Results indicate that CMPO extracts nitric acid with a 1:1 stoichiometry; equilibrium constant is 2. 660{plus_minus}0.092 at 25 C, and extraction enthalpy is -5. 46{plus_minus}0.46 kcal/mol. Slope analysis indicates that uranyl nitrate extracts with a mixed equilibria of 1:1 and 2:1 stoichiometries in nearly equal proportion. Equil. constant of the 2: 1 extraction was 1.213 {times} 10{sup 6}{plus_minus}3.56 {times} 10{sup 4} at 25 C; reaction enthalpy was -9.610{plus_minus}0.594 kcal/mol. Nitration complexation constant is 8.412{plus_minus}0.579, with an enthalpy of -10.72{plus_minus}1.87 kcal/mol. Bismuth nitrate also extracts with a mixed equilibria of (perhaps) 1:1 and 2:1 stoichiometries. A 2:1 extraction equilibrium and a nitrate complexation adequately model the data. Kinetics and enthalpies were also measured.

  18. Ab initio investigation of the aqueous solvation of the nitrate ion.

    PubMed

    Pruitt, Spencer R; Brorsen, Kurt R; Gordon, Mark S

    2015-10-28

    The surface affinity of the nitrate ion in aqueous clusters is investigated with a variety of theoretical methods. A sampling of structures in which the nitrate ion is solvated by 32 water molecules is optimized using second order Møller-Plesset perturbation theory (MP2). Four of these MP2 optimized structures are used as starting points for fully ab initio molecular dynamics simulations at the dispersion corrected restricted Hartree-Fock (RHF-D) level of theory. The nitrate ion solvated by 16, 32, and 64 water molecules is also investigated with umbrella sampling molecular dynamics simulations using QM/MM methodology, where the nitrate ion is modeled with MP2 and the water molecules are described using either the non-empirical effective fragment potential (EFP) or the empirical TIP5P potential. The turning point between surface and interior solvation of the nitrate ion is predicted to lie around a cluster size of 64 water molecules. PMID:26412597

  19. Computer simulation of absorption heat pump using aqueous lithium bromide and ternary nitrate mixtures

    NASA Astrophysics Data System (ADS)

    Ally, Moonis R.

    1988-06-01

    A new aqueous ternary mixture consisting of 53 wt percent LiNO3, 28 wt percent KNO3, and 19 wt percent NaNO3 is available for high-temperature heat pump applications. The pressure-composition-temperature and the specific enthalpy-concentration-temperature data in the form of correlated polynomial expressions are used in a computer program to simulate results of a temperature amplifier heat pump with LiBr/H2O and ternary nitrate/H2O mixtures as working fluids. In the absence of adequate thermophysical data for the fluids, the study serves as a best guess first approximation. The results show that the ternary nitrate mixture potentially has approximately a 10 percent advantage in COP and a 15 percent advantage in temperature lifts over aqueous LiBr at high temperatures. Ternary nitrates are hampered by crystallization at low waste heat temperatures and cannot operate competitively in the low lift and waste heat temperature regions. The potential performance advantage at high temperatures for the ternary nitrate mixture is sufficiently attractive to justify additional work to obtain adequate thermodynamic transport and corrosion data.

  20. Plutonium

    NASA Astrophysics Data System (ADS)

    Clark, David L.; Hecker, Siegfried S.; Jarvinen, Gordon D.; Neu, Mary P.

    The element plutonium occupies a unique place in the history of chemistry, physics, technology, and international relations. After the initial discovery based on submicrogram amounts, it is now generated by transmutation of uranium in nuclear reactors on a large scale, and has been separated in ton quantities in large industrial facilities. The intense interest in plutonium resulted fromthe dual-use scenario of domestic power production and nuclear weapons - drawing energy from an atomic nucleus that can produce a factor of millions in energy output relative to chemical energy sources. Indeed, within 5 years of its original synthesis, the primary use of plutonium was for the release of nuclear energy in weapons of unprecedented power, and it seemed that the new element might lead the human race to the brink of self-annihilation. Instead, it has forced the human race to govern itself without resorting to nuclear war over the past 60 years. Plutonium evokes the entire gamut of human emotions, from good to evil, from hope to despair, from the salvation of humanity to its utter destruction. There is no other element in the periodic table that has had such a profound impact on the consciousness of mankind.

  1. Radiolysis of hexavalent plutonium in solutions of uranyl nitrate containing fission product simulants

    NASA Astrophysics Data System (ADS)

    Rance, Peter J. W.; Zilberman, B. Ya.; Akopov, G. A.

    2000-07-01

    The effect of the inherent radioactivity on the chemical state of plutonium ions in solution was recognized very shortly after the first macroscopic amounts of plutonium became available and early studies were conducted as part of the Manhattan Project. However, the behavior of plutonium ions, in nitric acid especially, has been found to be somewhat complex, so much so that a relatively modern summary paper included the comment that, "The vast amount of work carried out in nitric acid solutions can not be adequately summarized. Suffice it to say results in these solutions are plagued with irreproducibility and induction periods…" Needless to say, the presence of other ions in solution, as occurs when irradiated nuclear fuel is dissolved, further complicates matters. The purpose of the work described below was to add to the rather small amount of qualitative data available relating to the radiolytic behavior of plutonium in solutions of irradiated nuclear fuel.

  2. Kinetic studies of nitrate removal from aqueous solution using granular chitosan-Fe(III) complex.

    PubMed

    Hu, Qili; Chen, Nan; Feng, Chuanping; Zhang, Jing; Hu, Weiwu; Lv, Long

    2016-01-01

    In the present study, a granular chitosan-Fe(III) complex was prepared as a feasible adsorbent for the removal of nitrate from an aqueous solution. There was no significant change in terms of nitrate removal efficiency over a wide pH range of 3-11. Nitrate adsorption on the chitosan-Fe(III) complex followed the Langmuir-Freundlich isotherm model. In order to more accurately reflect adsorption and desorption behaviors at the solid/solution interface, kinetic model I and kinetic model II were proposed to simulate the interfacial process in a batch system. Nitrate adsorption on the chitosan-Fe(III) complex followed the pseudo-first-order kinetic model and kinetic model I. The proposed half-time could provide useful information for optimizing process design. Adsorption and desorption rate constants obtained from kinetic model I and kinetic model II were beneficial to understanding the interfacial process and the extent of adsorption reaction. Kinetic model I and kinetic model II implied that nitrate uptake exponentially approaches a limiting value. PMID:26942545

  3. Efficient frequency conversion by stimulated Raman scattering in a sodium nitrate aqueous solution

    NASA Astrophysics Data System (ADS)

    Ganot, Yuval; Bar, Ilana

    2015-09-01

    Frequency conversion of laser beams, based on stimulated Raman scattering (SRS) is an appealing technique for generating radiation at new wavelengths. Here, we investigated experimentally the SRS due to a single pass of a collimated frequency-doubled Nd:YAG laser beam (532 nm) through a saturated aqueous solution of sodium nitrate (NaNO3), filling a 50 cm long cell. These experiments resulted in simultaneous generation of 1st (564 nm) and 2nd (599 nm) Stokes beams, corresponding to the symmetric stretching mode of the nitrate ion, ν1(NO3-), with 40 and 12 mJ/pulse maximal converted energies, equivalent to 12% and 4% efficiencies, respectively, for a 340 mJ/pulse pump energy. The results indicate that the pump and SRS beams were thermally defocused and that four-wave mixing was responsible for the second order Stokes process onset.

  4. Anisole Nitration During Gamma-Irradiation of Aqueous Nitrite and Nitrate Solutions: Free Radical Versus Ionic Mechanisms

    SciTech Connect

    Gracy Elias; Bruce J. Mincher; Leigh R. Martin; Stephen P. Mezyk; Thomas D. Cullen

    2010-04-01

    The nitration of aromatic compounds in the condensed phase is of interest to nuclear waste treatment applications. This chapter discusses our investigation of radiolytic aromatic nitration mechanisms in the condensed phase toward understanding the nitration products created during nuclear fuel reprocessing. The nitration reactions of anisole, a model aromatic compound, were studied in ?-irradiated acidic nitrate, neutral nitrate, and neutral nitrite solutions. The nitrated anisole product distributions were the same with and without radiation in acidic solution, although more products were formed with radiation. In the irradiated acidic condensed phase, radiation-enhanced nitrous acid-catalyzed nitrosonium ion electrophilic aromatic substitution followed by oxidation reactions dominated over radical addition reactions. Neutral nitrate anisole solutions were dominated by mixed nitrosonium/nitronium ion electrophilic aromatic substitution reactions, but with lower product yields. Irradiation of neutral nitrite anisole solution resulted in a statistical substitution pattern for nitroanisole products, suggesting non-electrophilic free radical reactions involving the •NO2 radical.

  5. Aqueous nitrate waste treatment: Technology comparison, cost/benefit, and market analysis

    SciTech Connect

    Not Available

    1994-01-01

    The purpose of this analysis is to provide information necessary for the Department of Energy (DOE) to evaluate the practical utility of the Nitrate to Ammonia and Ceramic or Glass (NAC/NAG/NAX) process, which is under development in the Oak Ridge National Laboratory. The NAC/NACx/NAX process can convert aqueous radioactive nitrate-laden waste to a glass, ceramic, or grout solid waste form. The tasks include, but are not limited to, the following: Identify current commercial technologies to meet hazardous and radiological waste disposal requirements. The technologies may be thermal or non-thermal but must be all inclusive (i.e., must convert a radionuclide-containing nitrate waste with a pH around 12 to a stable form that can be disposed at permitted facilities); evaluate and compare DOE-sponsored vitrification, grouting, and minimum additive waste stabilization projects for life-cycle costs; compare the technologies above with respect to material costs, capital equipment costs, operating costs, and operating efficiencies. For the NAC/NAG/NAX process, assume aluminum reactant is government furnished and ammonia gas may be marketed; compare the identified technologies with respect to frequency of use within DOE for environmental management applications with appropriate rationale for use; Assess the potential size of the DOE market for the NAC/NAG/NAX process; assess and off-gas issues; and compare with international technologies, including life-cycle estimates.

  6. EXTRACTION METHOD FOR SEPARATING URANIUM, PLUTONIUM, AND FISSION PRODUCTS FROM COMPOSITIONS CONTAINING SAME

    DOEpatents

    Seaborg, G.T.

    1957-10-29

    Methods for separating plutonium from the fission products present in masses of neutron irradiated uranium are reported. The neutron irradiated uranium is first dissolved in an aqueous solution of nitric acid. The plutonium in this solution is present as plutonous nitrate. The aqueous solution is then agitated with an organic solvent, which is not miscible with water, such as diethyl ether. The ether extracts 90% of the uraryl nitrate leaving, substantially all of the plutonium in the aqueous phase. The aqueous solution of plutonous nitrate is then oxidized to the hexavalent state, and agitated with diethyl ether again. In the ether phase there is then obtained 90% of plutonium as a solution of plutonyl nitrate. The ether solution of plutonyl nitrate is then agitated with water containing a reducing agent such as sulfur dioxide, and the plutonium dissolves in the water and is reduced to the plutonous state. The uranyl nitrate remains in the ether. The plutonous nitrate in the water may be recovered by precipitation.

  7. SEPARATION OF URANIUM, PLUTONIUM AND FISSION PRODUCTS

    DOEpatents

    Nicholls, C.M.; Wells, I.; Spence, R.

    1959-10-13

    The separation of uranium and plutonium from neutronirradiated uranium is described. The neutron-irradiated uranium is dissolved in nitric acid to provide an aqueous solution 3N in nitric acid. The fission products of the solution are extruded by treating the solution with dibutyl carbitol substantially 1.8N in nitric acid. The organic solvent phase is separated and neutralized with ammonium hydroxide and the plutonium reduced with hydroxylamine base to the trivalent state. Treatment of the mixture with saturated ammonium nitrate extracts the reduced plutonium and leaves the uranium in the organic solvent.

  8. Anisole nitration during gamma-irradiation of aqueous nitrite and nitrate solutions: Free radical versus ionic mechanisms

    SciTech Connect

    Gracy Elias; Bruce J. Mincher; Leigh R. Martin; Stephen P. Mezyk; Thomas Cullen

    2010-04-01

    Radiolytic aromatic nitration mechanisms in the condensed phase are ubiquitous, and especially of interest in atmospheric aerosol chemistry, water treatment by advanced oxidation technologies, and nuclear fuel reprocessing. Here, the radiolytically-induced nitration reactions of anisole, the simplest aryl alkyl ether, were investigated in ?-irradiated acidic nitrate solution, and in neutral nitrate and nitrite solutions. The nitrated anisole product distribution was the same with and without radiation in acidic solution, although more products were formed as a result of irradiation. This suggests that the mechanism of nitration in acidic solution is nitronium ion- induced electrophilic aromatic substitution. The rate of production of nitrated products in neutral nitrate solution was much lower, although the distribution of isomers was similar to that expected for nitronium ion electrophilic nitration. In contrast, the product distribution in neutral nitrite solution approached a statistically random substitution pattern, suggesting a non-electrophilic free radical reaction involving •NO2 radical. When hydroxyl radical (•OH) was scavenged by varying the initial nitrite concentration, the concentration of nitrated products increased with increasing nitrite, indicating that the reaction was probably one of direct •NO2 radical addition. However, this latter mechanism will not be important in acidic solutions, such as those often encountered in atmospheric aerosols or ?-irradiated nuclear fuel reprocessing solutions, due to low amounts of produced •NO2 radical and the low reaction rate constants for the •NO2 radical with aromatic compounds.

  9. SEPARATION OF URANIUM, PLUTONIUM, AND FISSION PRODUCTS

    DOEpatents

    Spence, R.; Lister, M.W.

    1958-12-16

    Uranium and plutonium can be separated from neutron-lrradiated uranium by a process consisting of dissolvlng the lrradiated material in nitric acid, saturating the solution with a nitrate salt such as ammonium nitrate, rendering the solution substantially neutral with a base such as ammonia, adding a reducing agent such as hydroxylamine to change plutonium to the trivalent state, treating the solution with a substantially water immiscible organic solvent such as dibutoxy diethylether to selectively extract the uranium, maklng the residual aqueous solutlon acid with nitric acid, adding an oxidizing agent such as ammonlum bromate to oxidize the plutonium to the hexavalent state, and selectlvely extracting the plutonium by means of an immlscible solvent, such as dibutoxy dlethyletber.

  10. [Adsorption Characteristics of Nitrate and Phosphate from Aqueous Solution on Zirconium-Hexadecyltrimethylammonium Chloride Modified Activated Carbon].

    PubMed

    Zheng, Wen-jing; Lin, Jian-wei; Zhan, Yan-hui; Wang, Hong

    2015-06-01

    A novel adsorbent material, i.e., zirconium-cationic surfactant modified activated carbon (ZrSMAC) was prepared by loading zirconium hydroxide and hexadecyltrimethylammonium chloride (CTAC) on activated carbon, and was used as an adsorbent for nitrate and phosphate removal from aqueous solution. The adsorption characteristics of nitrate and phosphate on ZrSMAC from aqueous solution were investigated in batch mode. Results showed that the ZrSMAC was effective for nitrate and phosphate removal from aqueous solution. The pseudo-second-order kinetic model fitted both the nitrate and phosphate kinetic experimental data well. The equilibrium isotherm data of nitrate adsorption onto the ZrSMAC were well fitted to the Langmuir, Dubinin-Radushkevich (D-R) and Freundlich isotherm models. The equilibrium isotherm data of phosphate adsorption onto the ZrSMAC could be described by the Langmuir and,D- R isotherm models. According to the Langmuir isotherm model, the maximum nitrate and phosphate adsorption capacities for the ZrSMAC were 7.58 mg x g(-1) and 10.9 mg x g(-1), respectively. High pH value was unfavorable for nitrate and phosphate adsorption onto the ZrSMAC. The presence of Cl-, HCO3- and SO4(2-) in solution reduced the nitrate and phosphate adsorption capacities for the ZrSMAC. The nitrate adsorption capacity for the ZrSMAC was reduced by the presence of coexisting phosphate in solution, and the phosphate adsorption capacity for the ZrSMAC was also reduced by the presence of coexisting nitrate in solution. About 90% of nitrate adsorbed on the ZrSMAC could be desorbed in 1 mol x L(-1) NaCl solution, and about 78% of phosphate adsorbed on the ZrSMAC could be desorbed in 1 mol x L(-1) NaOH solution. The adsorption mechanism of nitrate on the ZrSMAC included the anion exchange interactions and electrostatic attraction, and the adsorption mechanism of phosphate on the ZrSMAC included the ligand exchange interaction, electrostatic attraction and anion exchange interaction. PMID:26387324

  11. Efficient frequency conversion by stimulated Raman scattering in a sodium nitrate aqueous solution

    SciTech Connect

    Ganot, Yuval E-mail: ibar@bgu.ac.il; Bar, Ilana E-mail: ibar@bgu.ac.il

    2015-09-28

    Frequency conversion of laser beams, based on stimulated Raman scattering (SRS) is an appealing technique for generating radiation at new wavelengths. Here, we investigated experimentally the SRS due to a single pass of a collimated frequency-doubled Nd:YAG laser beam (532 nm) through a saturated aqueous solution of sodium nitrate (NaNO{sub 3}), filling a 50 cm long cell. These experiments resulted in simultaneous generation of 1st (564 nm) and 2nd (599 nm) Stokes beams, corresponding to the symmetric stretching mode of the nitrate ion, ν{sub 1}(NO{sub 3}{sup −}), with 40 and 12 mJ/pulse maximal converted energies, equivalent to 12% and 4% efficiencies, respectively, for a 340 mJ/pulse pump energy. The results indicate that the pump and SRS beams were thermally defocused and that four-wave mixing was responsible for the second order Stokes process onset.

  12. Extraction of rare-earth metal(III) nitrates by neutral organophosphorus compounds from concentrated aqueous salt solutions

    SciTech Connect

    Pyartman, A.K.; Puzikov, E.A.

    1995-07-20

    Equations describing isotherms of extraction of rare-earth metal(III) nitrates by neutral organo-phosphorus compounds over a wide range of component concentrations in aqueous and organic phases have been proposed. Constants of phase extraction and empirical parameters characterizing the influence of organic phase composition on the activity coefficients of the components have been presented.

  13. Nitrate

    Integrated Risk Information System (IRIS)

    Nitrate ; CASRN 14797 - 55 - 8 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 Effects

  14. Criticality Experiments with Mixed Plutonium and Uranium Nitrate Solution at a Plutonium Fraction of 0.5 in Annular Cylindrical Geometry

    SciTech Connect

    Lloyd, RC

    1988-04-01

    A series of critical experiments was completed with mixed plutonium-uranium solutions having Pu/(Pu + U) ratios of approximately 0.5. These experiments were a part of the Criticality Data Development Program between the United States Department of Energy (USDOE), and the Power Reactor and Nuclear Fuel Development Corporation (PNC) of Japan. A complete description of, and data from, the experiments are included in this report. The experiments were performed with mixed plutonium-uranium solutions in annular cylindrical geometry. The measurements were made with a water reflector. The central region included a concrete annular cylinder containing B{sub 4}C. Interior to the concrete insert was a stainless steel bottle containing plutonium-uranium solution. The concentration of the solution in the annular region was varied from 116 to 433 g (Pu + U)/liter. The ratio of plutonium to total heavy metal (plutonium plus uranium) was 52% for all experiments.

  15. Adsorption of nitrate from aqueous solution by magnetic amine-crosslinked biopolymer based corn stalk and its chemical regeneration property.

    PubMed

    Song, Wen; Gao, Baoyu; Xu, Xing; Wang, Fang; Xue, Nan; Sun, Shenglei; Song, Wuchang; Jia, Ruibao

    2016-03-01

    A novel adsorbent of magnetic amine-crosslinked biopolymer based corn stalk (MAB-CS) was synthesized and used for nitrate removal from aqueous solution. The characters and adsorption mechanisms of this bio-adsorbent were determined by using VSM, TGA, XRD, SEM, TEM, FT-IR and XPS, respectively. The results revealed that the saturated magnetization of MAB-CS reached 6.25 emu/g. Meanwhile, the studies of various factors indicated that this novel magnetic bio-adsorbent performed well over a considerable wide pH range of 6.0 ∼ 9.0, and the presence of PO4(3-) and SO4(2-) would markedly decrease the nitrate removal efficiency. Furthermore, the nitrate adsorption by MAB-CS perfectly fitted the Langmuir isotherm model (R(2)=0.997-0.999) and pseudo second order kinetic model (R(2)=0.953-0.995). The calculated nitrate adsorption capacity of MAB-CS was 102.04 mg/g at 318 K by Langmuir model, and thermodynamic study showed that nitrate adsorption is an spontaneous endothermic process. The regeneration experiments indicated its merit of regeneration and stability with the recovery efficient of 118 ∼ 147%. By integrating the experimental results, it was found that the removal of nitrate was mainly via electrostatic attraction and ion exchange. And this novel bio-adsorbent prepared in this work could achieve effective removal of nitrate and rapid separation from effluents simultaneously. PMID:26561752

  16. Criticality Experiments with Mixed Plutonium and Uranium Nitrate Solution at a Plutonium Fraction of 0.4 in Slab and Cylindrical Geometry

    SciTech Connect

    Lloyd, RC

    1988-04-01

    A series of critical experiments was completed with mixed plutonium-uranium solutions having Pu/(Pu + U) ratios of approximately 0.4. These experiments were a part of the Criticality Data Development Program between the United States Department of Energy (USDOE), and the Power Reactor and Nuclear Fuel Development Corporation (PNC) of Japan. A complete description of, and data from, the experiments are included in this report. The experiments were performed with mixed plutonium-uranium solutions in cylinqrical and slab geometries and included measurements with a water reflector, a concrete reflector, and without an added reflector. The concentration was varied from 105 to 436 g (Pu + U)/liter. The ratio of plutonium to total heavy metal (plutonium plus uranium) was 0.4 for all experiments.

  17. Criticality experiments with mixed plutonium and uranium nitrate solution at a plutonium fraction of 0.5 in slab and cylindrical geometry

    SciTech Connect

    Lloyd, R.C.

    1986-12-01

    A series of critical experiments was completed with mixed plutonium-uranium solutions having Pu/(Pu + U) ratios of approximately 0.5. These experiments were a part of the Criticality Data Development Program between the United States Department of Energy (USDOE), and the Power Reactor and Nuclear Fuel Development Corporation (PNC) of Japan. A complete description of, and data from, the experiments are included in this report. The experiments were performed with mixed plutonium-uranium solutions in cylindrical and slab geometries and included measurements with a water reflector, a concrete reflector, and without an added reflector. The concentration was varied from 112 to 332 g (Pu + U)/liter. The ratio of plutonium to total heavy metal (plutonium plus uranium) was 52% for all experiments.

  18. Caffeine as non-toxic corrosion inhibitor for copper in aqueous solutions of potassium nitrate

    NASA Astrophysics Data System (ADS)

    Fallavena, Thuanny; Antonow, Muriel; Gonalves, Reinaldo Simes

    2006-11-01

    Different electrochemical methods were employed in order to confirm the ability of caffeine (1,3,7-trimethylxanthine) to inhibit the corrosion processes of copper in aqueous potassium nitrate solutions in the absence and in the presence of chloride. Some experiments were repeated in potassium perchlorate in order to compare the influence of the medium. The interaction between the organic compound and the electrode surface occurs independently of the electrode potential. However, maximum interaction was observed at 0.0 V (Ag/AgCl) in aerated solutions, and at -0.25 V (Ag/AgCl) in deaerated solutions. The presence of the organic compound adsorbed on the electrode surface was confirmed by comparing the voltammograms of copper electrode in the absence and presence of 1.5 mmol L -1 of dissolved caffeine. The same results were observed by comparing polarization curves in the absence and in the presence of caffeine. Anodic currents decrease noticeably in the presence of the organic compound. Chronoamperometric experiments were conclusive to prove the inhibitor capability of caffeine to decrease the corrosion dissolution processes of copper under anodic polarization.

  19. Release of nitrous acid and nitrogen dioxide from nitrate photolysis in acidic aqueous solutions.

    PubMed

    Scharko, Nicole K; Berke, Andrew E; Raff, Jonathan D

    2014-10-21

    Nitrate (NO3(-)) is an abundant component of aerosols, boundary layer surface films, and surface water. Photolysis of NO3(-) leads to NO2 and HONO, both of which play important roles in tropospheric ozone and OH production. Field and laboratory studies suggest that NO3¯ photochemistry is a more important source of HONO than once thought, although a mechanistic understanding of the variables controlling this process is lacking. We present results of cavity-enhanced absorption spectroscopy measurements of NO2 and HONO emitted during photodegradation of aqueous NO3(-) under acidic conditions. Nitrous acid is formed in higher quantities at pH 2-4 than expected based on consideration of primary photochemical channels alone. Both experimental and modeled results indicate that the additional HONO is not due to enhanced NO3(-) absorption cross sections or effective quantum yields, but rather to secondary reactions of NO2 in solution. We find that NO2 is more efficiently hydrolyzed in solution when it is generated in situ during NO3(-) photolysis than for the heterogeneous system where mass transfer of gaseous NO2 into bulk solution is prohibitively slow. The presence of nonchromophoric OH scavengers that are naturally present in the environment increases HONO production 4-fold, and therefore play an important role in enhancing daytime HONO formation from NO3(-) photochemistry. PMID:25271384

  20. Aqueous atmospheric chemistry: formation of 2,4-dinitrophenol upon nitration of 2-nitrophenol and 4-nitrophenol in solution.

    PubMed

    Vione, Davide; Maurino, Valter; Minero, Claudio; Pelizzetti, Ezio

    2005-10-15

    Field studies have shown that the powerful phytotoxic agent 2,4-dinitrophenol is very likely to form in the atmospheric aqueous phase upon nitration of 2-nitrophenol or 4-nitrophenol. However, until now, the nitration pathway and the relative importance of the two mononitrophenols as sources of 2,4-dinitrophenol were not known. The present study shows that 2,4-dinitrophenol formation from mononitrophenols can take place upon photolysis and photooxidation of nitrite/nitrous acid (NO2-/HONO) and that nitrogen dioxide plays a key role in the process. A possible pathway might be the reaction between light-excited mononitrophenols (both 2- and 4-isomers) and nitrogen dioxide, in the presence of oxygen. As an alternative, nitration might involve *NO3 + *NO2. Possible sources of nitrogen dioxide in the atmospheric aqueous phase are dissolution from the gas phase and oxidation of NO2-. In the latter case, however, it is necessary that NO2- oxidation is faster than the oxidation of mononitrophenols. This would happen, for instance, in the presence of hematite under irradiation. Radiation absorption and scattering by hematite would also inhibit the direct photolysis of nitrophenols. The formation rate and the yield of 2,4-dinitrophenol are slightly higher when starting from 2-nitrophenol than those from 4-nitrophenol, but they are compensated by the higher concentration of 4-nitrophenol in the atmospheric aqueous phase. PMID:16295857

  1. Criticality Experiments with Mixed Plutonium and Uranium Nitrate Solution at a Plutonium Fraction of 0.2 and 1.0 in Annular Cylindrical Geometry

    SciTech Connect

    Lloyd, RC

    1988-04-01

    A series of critical experiments was completed with mixed plutoniumuranium solutions having Pu/(Pu + U) ratios of approximately 0.2 and 1.0. These experiments were a part of the Criticality Data Development Program between the United States Department of Energy (USDOE), and the Power Reactor and Nuclear Fuel Development Corporation (PNC) of Japan. A complete description of, and data from, the experiments are included in this report. The experiments were performed with mixed plutonium-uranium solutions in annular cylindrical geometry. The measurements were made with a water reflector. The central region included a concrete, polyethylene or void annular cylindrical insert. Interior to the insert was a stainless steel bottle containing plutonium-uranium solution or a void region. In one experiment the central region was filled with a solid cadmium-covered polyethylene insert. The concentration of the solution in the annular region was varied from 61 to 489 g (Pu + U)/liter. The ratio of plutonium to total heavy metal (plutonium plus uranium) was 0.22 or 0.97 for all experiments.

  2. Catalytic liquid-phase hydrogenation of aqueous nitrate solutions: A kinetic investigation

    SciTech Connect

    Pintar, A.; Batista, J.; Levec, J.; Kajiuchi, Toshio

    1996-12-31

    Liquid-phase reduction using a solid Pd/Cu bimetallic catalyst provides a potential technique for the removal of nitrates from waters. Kinetic measurements were performed in an isothermal semi-batch slurry reactor operating at atmospheric pressure. The proposed intrinsic rate expression for nitrate disappearance is based on the conventional Langmuir-Hinshelwood kinetic approach, considering both equilibrium nitrate as well as dissociative hydrogen adsorption processes to different types of active sites, and assuming an irreversible bimolecular surface reaction between adsorbed reactant species to be the rate-controlling step. The apparent activation energy for catalytic liquid-phase nitrate reduction and the heat of nitrate adsorption, in the temperature range 280.5-293 K, were found to be 47 and -22 kJ/mol, respectively. 6 refs., 3 figs.

  3. Automated determination of nitrate plus nitrite in aqueous samples with flow injection analysis using vanadium (III) chloride as reductant.

    PubMed

    Wang, Shu; Lin, Kunning; Chen, Nengwang; Yuan, Dongxing; Ma, Jian

    2016-01-01

    Determination of nitrate in aqueous samples is an important analytical objective for environmental monitoring and assessment. Here we report the first automatic flow injection analysis (FIA) of nitrate (plus nitrite) using VCl3 as reductant instead of the well-known but toxic cadmium column for reducing nitrate to nitrite. The reduced nitrate plus the nitrite originally present in the sample react with the Griess reagent (sulfanilamide and N-1-naphthylethylenediamine dihydrochloride) under acidic condition. The resulting pink azo dye can be detected at 540 nm. The Griess reagent and VCl3 are used as a single mixed reagent solution to simplify the system. The various parameters of the FIA procedure including reagent composition, temperature, volume of the injection loop, and flow rate were carefully investigated and optimized via univariate experimental design. Under the optimized conditions, the linear range and detection limit of this method are 0-100 µM (R(2)=0.9995) and 0.1 µM, respectively. The targeted analytical range can be easily extended to higher concentrations by selecting alternative detection wavelengths or increasing flow rate. The FIA system provides a sample throughput of 20 h(-1), which is much higher than that of previously reported manual methods based on the same chemistry. National reference solutions and different kinds of aqueous samples were analyzed with our method as well as the cadmium column reduction method. The results from our method agree well with both the certified value and the results from the cadmium column reduction method (no significant difference with P=0.95). The spiked recovery varies from 89% to 108% for samples with different matrices, showing insignificant matrix interference in this method. PMID:26695325

  4. Aqueous biphasic plutonium oxide extraction process with pH and particle control

    DOEpatents

    Chaiko, D.J.; Mensah-Biney, R.

    1997-04-29

    A method is described for simultaneously partitioning a metal oxide and silica from a material containing silica and the metal oxide, using a biphasic aqueous medium having immiscible salt and polymer phases. 2 figs.

  5. Selective decomposition of aqueous nitrate into nitrogen using iron deposited bimetals.

    PubMed

    Liou, Ya Hsuan; Lin, Chin Jung; Weng, Shih Chi; Ou, Hsin Hung; Lo, Shang Lien

    2009-04-01

    In the case of the reduction of nitrate in groundwater, the problem is how to convert nitrate [N(+V)] selectively to nontoxic dinitrogen [N(O)] and not to completely reduced ammonia [N(-III)]. Unfortunately, near 100% of the total nitrogen in nitrate is reductively converted to ammonia using naked zerovalent iron (ZVI) thus far reported. In this study, deposition of noble metals (Pt, Pd, and Au) and Cu on iron surface to offer favorable pathways for nitrate reduction was fabricated using either the complete mixing orthe successive method with spontaneous redox reactions. The prepared samples were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy/energy disperse X-ray spectroscopy, and electrochemical analysis. The formation of N2 from the reduction of nitrate was confirmed by residual gas analyzer coupled to a high vacuum system. Based on the experimental results, the ZVI deposited Pd and Cu closely is suggested to promote the abstraction of oxygen from NOx by adsorbed atomic hydrogen on the Cu surface, and enhance N2 formation on the Pd surface. An optimum N2 selectivity of approximately 30% obtained in the alkaline solution containing nitrate using 0.3 wt.% Pd-0.5 wt% Cu/Fe is evident. For groundwater treatment, iron deposited Pd and Cu could facilitate the development of a process requiring neither a massive addition of chemicals nor complex equipment. PMID:19452905

  6. Simultaneous electrochemical determination of nitrate and nitrite in aqueous solution using Ag-doped zeolite-expanded graphite-epoxy electrode.

    PubMed

    Manea, Florica; Remes, Adriana; Radovan, Ciprian; Pode, Rodica; Picken, Stephen; Schoonman, Joop

    2010-11-15

    In this work a new electrochemical sensor based on an Ag-doped zeolite-expanded graphite-epoxy composite electrode (AgZEGE) was evaluated as a novel alternative for the simultaneous quantitative determination of nitrate and nitrite in aqueous solutions. Cyclic voltammetry was used to characterize the electrochemical behavior of the electrode in the presence of individual or mixtures of nitrate and nitrite anions in 0.1M Na(2)SO(4) supporting electrolyte. Linear dependences of current versus nitrate and nitrite concentrations were obtained for the concentration ranges of 1-10mM for nitrate and 0.1-1mM for nitrite using cyclic voltammetry (CV), chronoamperometry (CA), and multiple-pulsed amperometry (MPA) procedures. The comparative assessment of the electrochemical behavior of the individual anions and mixtures of anions on this modified electrode allowed determining the working conditions for the simultaneous detection of the nitrite and nitrate anions. Applying MPA allowed enhancement of the sensitivity for direct and indirect nitrate detection and also for nitrite detection. The proposed sensor was applied in tap water samples spiked with known nitrate and nitrite concentrations and the results were in agreement with those obtained by a comparative spectrophotometric method. This work demonstrates that using multiple-pulse amperometry with the Ag-doped zeolite-expanded graphite-epoxy composite electrode provides a real opportunity for the simultaneous detection of nitrite and nitrate in aqueous solutions. PMID:21035645

  7. An Electronic Tongue Designed to Detect Ammonium Nitrate in Aqueous Solutions

    PubMed Central

    Campos, Inmaculada; Pascual, Lluis; Soto, Juan; Gil-Sánchez, Luis; Martínez-Máñez, Ramón

    2013-01-01

    An electronic tongue has been developed to monitor the presence of ammonium nitrate in water. It is based on pulse voltammetry and consists of an array of eight working electrodes (Au; Pt; Rh; Ir; Cu; Co; Ag and Ni) encapsulated in a stainless steel cylinder. In a first step the electrochemical response of the different electrodes was studied in the presence of ammonium nitrate in water in order to further design the wave form used in the voltammetric tongue. The response of the electronic tongue was then tested in the presence of a set of 15 common inorganic salts; i.e.; NH4NO3; MgSO4; NH4Cl; NaCl; Na2CO3; (NH4)2SO4; MgCl2; Na3PO4; K2SO4; K2CO3; CaCl2; NaH2PO4; KCl; NaNO3; K2HPO4. A PCA plot showed a fairly good discrimination between ammonium nitrate and the remaining salts studied. In addition Fuzzy Art map analyses determined that the best classification was obtained using the Pt; Co; Cu and Ni electrodes. Moreover; PLS regression allowed the creation of a model to correlate the voltammetric response of the electrodes with concentrations of ammonium nitrate in the presence of potential interferents such as ammonium chloride and sodium nitrate. PMID:24145916

  8. Nitrate adsorption from aqueous solution using granular chitosan-Fe3+ complex

    NASA Astrophysics Data System (ADS)

    Hu, Qili; Chen, Nan; Feng, Chuanping; Hu, WeiWu

    2015-08-01

    In the present study, In order to efficiently remove nitrate, granular chitosan-Fe3+ complex with high chemical stability and good environmental adaptation was synthesized through precipitation method and characterized using SEM, XRD, BET and FTIR. The nitrate adsorption performance was evaluated by batch experiments. The results indicated that granular chitosan-Fe3+ complex was an amorphous and mesoporous material. The BET specific surface area and average pore size were 8.98 m2 g-1 and 56.94 Å, respectively. The point of zero charge was obtained at pH 5. The maximum adsorption capacity reached 8.35 mg NO3--N g-1 based on Langmuir-Freundlich model. Moreover, no significant change in the nitrate removal efficiency was observed in the pH range of 3.0-10.0. The adverse influence of sulphate on nitrate removal was the most significant, followed by bicarbonate and fluoride, whereas chloride had slightly adverse effect. Adsorption process followed the pseudo-second-order kinetic model, and the experimental equilibrium data were fitted well with the Langmuir-Freundlich and D-R isotherm models. Thermodynamic parameters revealed that nitrate adsorption was a spontaneous and exothermic process. Granular chitosan-Fe3+ complex could be effectively regenerated by NaCl solution.

  9. An electronic tongue designed to detect ammonium nitrate in aqueous solutions.

    PubMed

    Campos, Inmaculada; Pascual, Lluis; Soto, Juan; Gil-Sánchez, Luis; Martínez-Máez, Ramón

    2013-01-01

    An electronic tongue has been developed to monitor the presence of ammonium nitrate in water. It is based on pulse voltammetry and consists of an array of eight working electrodes (Au; Pt; Rh; Ir; Cu; Co; Ag and Ni) encapsulated in a stainless steel cylinder. In a first step the electrochemical response of the different electrodes was studied in the presence of ammonium nitrate in water in order to further design the wave form used in the voltammetric tongue. The response of the electronic tongue was then tested in the presence of a set of 15 common inorganic salts; i.e.; NH₄NO₃; MgSO₄; NH₄Cl; NaCl; Na₂CO₃; (NH₄)₂SO₄; MgCl₂; Na₃PO₄; K₂SO₄; K₂CO₃; CaCl₂; NaH₂PO₄; KCl; NaNO₃; K₂HPO₄. A PCA plot showed a fairly good discrimination between ammonium nitrate and the remaining salts studied. In addition Fuzzy Art map analyses determined that the best classification was obtained using the Pt; Co; Cu and Ni electrodes. Moreover; PLS regression allowed the creation of a model to correlate the voltammetric response of the electrodes with concentrations of ammonium nitrate in the presence of potential interferents such as ammonium chloride and sodium nitrate. PMID:24145916

  10. CONCENTRATION PROCESS FOR PLUTONIUM IONS, IN AN OXIDATION STATE NOT GREATER THAN +4, IN AQUEOUS ACID SOLUTION

    DOEpatents

    Seaborg, G.T.; Thompson, S.G.

    1960-06-14

    A process for concentrating plutonium is given in which plutonium is first precipitated with bismuth phosphate and then, after redissolution, precipitated with a different carrier such as lanthanum fluoride, uranium acetate, bismuth hydroxide, or niobic oxide.

  11. Aqueous Binary Lanthanide(III) Nitrate Ln(NO3)3 Electrolytes Revisited: Extended Pitzer and Bromley Treatments

    SciTech Connect

    Chatterjee, Sayandev; Campbell, Emily L.; Neiner, Doinita; Pence, Natasha; Robinson, Troy; Levitskaia, Tatiana G.

    2015-09-11

    To date, only limited thermodynamic models describing activity coefficients of the aqueous solutions of lanthanide ions are available. This work expands the existing experimental osmotic coefficient data obtained by classical isopiestic technique for the aqueous binary trivalent lanthanide nitrate Ln(NO3)3 solutions using a combination of water activity and vapor pressure osmometry measurements. The combined osmotic coefficient database for each aqueous lanthanide nitrate at 25°C, consisting of literature available data as well as data obtained in this work, was used to test the validity of Pitzer and Bromley thermodynamic models for the accurate prediction of mean molal activity coefficients of the Ln(NO3)3 solutions in wide concentration ranges. The new and improved Pitzer and Bromley parameters were calculated. It was established that the Ln(NO3)3 activity coefficients in the solutions with ionic strength up to 12 mol kg-1 can be estimated by both Pitzer and single-parameter Bromley models, even though the latter provides for more accurate prediction, particularly in the lower ionic strength regime (up to 6 mol kg-1). On the other hand for the concentrated solutions, the extended three-parameter Bromley model can be employed to predict the Ln(NO3)3 activity coefficients with remarkable accuracy. The accuracy of the extended Bromley model in predicting the activity coefficients was greater than ~95% and ~90% for all solutions with the ionic strength up to 12 mol kg-1 and and 20 mol kg-1, respectively. This is the first time that the activity coefficients for concentrated lanthanide solutions have been predicted with such a remarkable accuracy.

  12. Carcinogenesis and Inflammatory Effects of Plutonium-Nitrate Retention in an Exposed Nuclear Worker and Beagle Dogs.

    SciTech Connect

    Nielsen, Christopher E.; Wang, Xihai; Robinson, Robert J.; Brooks, Antone L.; Lovaglio, Jamie A.; Patton, Kristin M.; McComish, Stacey; Tolmachev, Sergei Y.; Morgan, William F.

    2014-01-01

    The genetic and inflammatory response pathways elicited following plutonium exposure in archival lung tissue of an occupationally exposed human and experimentally exposed beagle dogs were investigated. These pathways include: tissue injury, apoptosis and gene expression modifications related to carcinogenesis and inflammation. In order to determine which pathways are involved, multiple lung samples from a plutonium exposed worker (Case 0269), a human control (Case 0385), and plutonium exposed beagle dogs were examined using histological staining and immunohistochemistry. Examinations were performed to identify target tissues at risk of radiation-induced fibrosis, inflammation, and carcinogenesis. Case 0269 showed interstitial fibrosis in peripheral and subpleural regions of the lung, but no pulmonary tumors. In contrast, the dogs with similar and higher doses showed pulmonary tumors primarily in brochiolo-alveolar, peripheral and subpleural alveolar regions. The TUNEL assay showed slight elevation of apoptosis in tracheal mucosa, tumor cells, and nuclear debris was present in the inflammatory regions of alveoli and lymph nodes of both the human and the dogs. The expression of apoptosis and a number of chemokine/cytokine genes was slightly but not significantly elevated in protein or gene levels compared to that of the control samples. In the beagles, mucous production was increased in the airway epithelial goblet cells and glands of trachea, and a number of chemokine/cytokine genes showed positive immunoreactivity. This analysis of archival tissue from an accidentally exposed worker and in a large animal model provides valuable information on the effects of long-term retention of plutonium in the respiratory tract and the histological evaluation study may impact mechanistic studies of radiation carcinogenesis.

  13. Plutonium Chemistry in the UREX+ Separation Processes

    SciTech Connect

    ALena Paulenova; George F. Vandegrift, III; Kenneth R. Czerwinski

    2009-10-01

    The project "Plutonium Chemistry in the UREX+ Separation Processes” is led by Dr. Alena Paulenova of Oregon State University under collaboration with Dr. George Vandegrift of ANL and Dr. Ken Czerwinski of the University of Nevada at Las Vegas. The objective of the project is to examine the chemical speciation of plutonium in UREX+ (uranium/tributylphosphate) extraction processes for advanced fuel technology. Researchers will analyze the change in speciation using existing thermodynamics and kinetic computer codes to examine the speciation of plutonium in aqueous and organic phases. They will examine the different oxidation states of plutonium to find the relative distribution between the aqueous and organic phases under various conditions such as different concentrations of nitric acid, total nitrates, or actinide ions. They will also utilize techniques such as X-ray absorbance spectroscopy and small-angle neutron scattering for determining plutonium and uranium speciation in all separation stages. The project started in April 2005 and is scheduled for completion in March 2008.

  14. Coordination and hydrolysis of plutonium ions in aqueous solution using Car-Parrinello molecular dynamics free energy simulations.

    PubMed

    Odoh, Samuel O; Bylaska, Eric J; de Jong, Wibe A

    2013-11-27

    Car-Parrinello molecular dynamics (CPMD) simulations have been used to examine the hydration structures, coordination energetics, and the first hydrolysis constants of Pu(3+), Pu(4+), PuO2(+), and PuO2(2+) ions in aqueous solution at 300 K. The coordination numbers and structural properties of the first shell of these ions are in good agreement with available experimental estimates. The hexavalent PuO2(2+) species is coordinated to five aquo ligands while the pentavalent PuO2(+) complex is coordinated to four aquo ligands. The Pu(3+) and Pu(4+) ions are both coordinated to eight water molecules. The first hydrolysis constants obtained for Pu(3+) and PuO2(2+) are 6.65 and 5.70, respectively, all within 0.3 pH unit of the experimental values (6.90 and 5.50, respectively). The hydrolysis constant of Pu(4+), 0.17, disagrees with the value of -0.60 in the most recent update of the Nuclear Energy Agency Thermochemical Database (NEA-TDB) but supports recent experimental findings. The hydrolysis constant of PuO2(+), 9.51, supports the experimental results of Bennett et al. [Radiochim. Acta 1992, 56, 15]. A correlation between the pKa of the first hydrolysis reaction and the effective charge of the plutonium center was found. PMID:24168210

  15. Coordination and Hydrolysis of Plutonium Ions in Aqueous Solution using Car-Parrinello Molecular Dynamics Free Energy Simulations

    SciTech Connect

    Odoh, Samuel O.; Bylaska, Eric J.; De Jong, Wibe A.

    2013-11-27

    Car-Parrinello molecular dynamics (CPMD) simulations have been used to examine the hydration structures, coordination energetics and the first hydrolysis constants of Pu3+, Pu4+, PuO2+ and PuO22+ ions in aqueous solution at 300 K. The coordination numbers and structural properties of the first shell of these ions are in good agreement with available experimental estimates. The hexavalent PuO22+ species is coordinated to 5 aquo ligands while the pentavalent PuO2+ complex is coordinated to 4 aquo ligands. The Pu3+ and Pu4+ ions are both coordinated to 8 water molecules. The first hydrolysis constants obtained for Pu3+ and PuO22+ are 6.65 and 5.70 respectively, all within 0.3 pH units of the experimental values (6.90 and 5.50 respectively). The hydrolysis constant of Pu4+, 0.17, disagrees with the value of -0.60 in the most recent update of the Nuclear Energy Agency Thermochemical Database (NEA-TDB) but supports recent experimental findings. The hydrolysis constant of PuO2+, 9.51, supports the experimental results of Bennett et al. (Radiochim. Act. 1992, 56, 15). A correlation between the pKa of the first hydrolysis reaction and the effective charge of the plutonium center was found.

  16. Chemical species of plutonium in Hanford radioactive tank waste

    SciTech Connect

    Barney, G.S.

    1997-10-22

    Large quantities of radioactive wastes have been generated at the Hanford Site over its operating life. The wastes with the highest activities are stored underground in 177 large (mostly one million gallon volume) concrete tanks with steel liners. The wastes contain processing chemicals, cladding chemicals, fission products, and actinides that were neutralized to a basic pH before addition to the tanks to prevent corrosion of the steel liners. Because the mission of the Hanford Site was to provide plutonium for defense purposes, the amount of plutonium lost to the wastes was relatively small. The best estimate of the amount of plutonium lost to all the waste tanks is about 500 kg. Given uncertainties in the measurements, some estimates are as high as 1,000 kg (Roetman et al. 1994). The wastes generally consist of (1) a sludge layer generated by precipitation of dissolved metals from aqueous wastes solutions during neutralization with sodium hydroxide, (2) a salt cake layer formed by crystallization of salts after evaporation of the supernate solution, and (3) an aqueous supernate solution that exists as a separate layer or as liquid contained in cavities between sludge or salt cake particles. The identity of chemical species of plutonium in these wastes will allow a better understanding of the behavior of the plutonium during storage in tanks, retrieval of the wastes, and processing of the wastes. Plutonium chemistry in the wastes is important to criticality and environmental concerns, and in processing the wastes for final disposal. Plutonium has been found to exist mainly in the sludge layers of the tanks along with other precipitated metal hydrous oxides. This is expected due to its low solubility in basic aqueous solutions. Tank supernate solutions do not contain high concentrations of plutonium even though some tanks contain high concentrations of complexing agents. The solutions also contain significant concentrations of hydroxide which competes with other potential complexants. The sodium nitrate and sodium phosphate salts that form most of the salt cake layers have little interaction with plutonium in the wastes and contain relatively small plutonium concentrations. For these reasons the authors consider plutonium species in the sludges and supernate solutions only. The low concentrations of plutonium in waste tank supernate solutions and in the solid sludges prevent identification of chemical species of plutonium by ordinary analytical techniques. Spectrophotometric measurements are not sensitive enough to identify plutons oxidation states or complexes in these waste solutions. Identification of solid phases containing plutonium in sludge solids by x-ray diffraction or by microscopic techniques would be extremely difficult. Because of these technical problems, plutonium speciation was extrapolated from known behavior observed in laboratory studies of synthetic waste or of more chemically simple systems.

  17. Concentration dependence of the structure of aqueous solutions of lutetium nitrate according to X-ray diffraction

    NASA Astrophysics Data System (ADS)

    Smirnov, P. R.; Grechin, O. V.; Trostin, V. N.

    2014-02-01

    Aqueous solutions of lutetium nitrate over a wide range of concentrations are studied by X-ray diffraction under standard temperature and pressure. The low-angle peaks in experimental scattering intensity curves are interpreted. It is shown that the structure of these solutions can be of two types. It is found that a saturated solution and solutions concentrated to a molar ratio of 1: 20 have a quasi-crystalline structure resulting from interionic interactions. It is determined that dilute solutions form a water-like structure characterized by a tetrahedral network of hydrogen bonds between the water molecules. It is found that low-angle peaks also appear in the intensity curves of dilute solutions; this proves that the so-called "long-range" order is preserved in these solutions. It is revealed that in all the studied systems, the contributions to the total scattering pattern that are responsible for the occurrence of pre-peaks are intercationic interactions.

  18. Preparation of activated carbons from Iris tectorum employing ferric nitrate as dopant for removal of tetracycline from aqueous solutions.

    PubMed

    Li, Gang; Zhang, Dongsheng; Wang, Man; Huang, Ji; Huang, Lihui

    2013-12-01

    Ferric nitrate was employed to modify activated carbon prepared from Iris tectorum during H₃PO₄ activation and ability of prepared activated carbon for removal of tetracycline (TC) was investigated. The properties of the activated carbon samples with or without ferric nitrate, ITAC-Fe and ITAC, were measured by scanning electron microscopy (SEM), N₂ adsorption/desorption isotherms, Fourier transform infrared spectroscopy (FTIR) and Boehm's titration. The results showed that mixing with iron increased the BET surface area, total pore volume and the adsorption capacity as compared to the original carbon. FTIR and Boehm's titration suggested that ITAC-Fe was characteristic of more acidic functional groups than ITAC. Adsorption of TC on both samples exhibited a strong pH-dependent behavior and adsorption capacity reduced rapidly with the increasing solution pH. The adsorption kinetics agreed well with the pseudo-second-order model and the adsorption isotherms data were well described by Langmuir model with the maximum adsorption capacity of 625.022 mg/g for ITAC and 769.231 mg/g for ITAC-Fe. The present work suggested that ITAC-Fe could be used to remove tetracycline effectively from aqueous solutions. PMID:24021870

  19. Synthesis of palladium nanoparticles by sonochemical reduction of palladium(II) nitrate in aqueous solution.

    PubMed

    Nemamcha, Abderrafik; Rehspringer, Jean-Luc; Khatmi, Djameledine

    2006-01-12

    The sonochemical synthesis of stable palladium nanoparticles has been achieved by ultrasonic irradiation of palladium(II) nitrate solution. The starting solutions were prepared by the addition of different concentrations of palladium(II) nitrate in ethylene glycol and poly(vinylpyrrolidone) (PVP). The resulting mixtures were irradiated with ultrasonic 50 kHz waves in a glass vessel for 180 min. The UV-visible absorption spectroscopy and pH measurements revealed that the reduction of Pd(II) to metallic Pd has been successfully achieved and that the obtained suspensions have a long shelf life. The protective effect of PVP was studied using Fourier transform infrared (FT-IR) spectroscopy. It has been found that, in the presence of ethylene glycol, the stabilization of the nanoparticles results from the adsorption of the PVP chain on the palladium particle surface via the coordination of the PVP carbonyl group to the palladium atoms. The effect of the initial Pd(II) concentration on the Pd nanoparticle morphology has been investigated by transmission electron microscopy. It has been shown that the increase of the Pd(II)/PVP molar ratio from 0.13 x 10(-3) to 0.53 x 10(-3) decreases the number of palladium nanoparticles with a slight increase in particle size. For the highest Pd(II)/PVP value, 0.53 x 10(-3), the reduction reaction leads to the unexpected smallest nanoparticles in the form of aggregates. PMID:16471546

  20. Efficient perovskite solar cells fabricated using an aqueous lead nitrate precursor.

    PubMed

    Hsieh, Tsung-Yu; Wei, Tzu-Chien; Wu, Kuan-Lin; Ikegami, Masashi; Miyasaka, Tsutomu

    2015-09-01

    A novel, aqueous precursor system (Pb(NO3)2 + water) is developed to replace conventional (PbI2 + DMF) for fabricating methylammonium lead iodide (MAPbI3) perovskite solar cells (PSCs). When the morphology and surface coverage of the Pb(NO3)2 film was controlled during coating, a power conversion efficiency of 12.58% under standard conditions (AM1.5, 100 mW cm(-2)) was achieved for the PSC. PMID:26203787

  1. Alloy 22 Localized Corrosion Susceptibility In Aqueous Solutions Of Chloride And Nitrate Salts Of Sodium And Potassium At 110 - 150?C

    SciTech Connect

    Felker, S; Hailey, P D; Lian, T; Staggs, K J; Gdowski, G E

    2006-01-17

    Alloy 22 (a nickel-chromium-molybdenum-tungsten alloy) is being investigated for use as the outer barrier of waste containers for a high-level nuclear waste repository in the thick unsaturated zone at Yucca Mountain, Nevada. Experiments were conducted to assess crevice corrosion of Alloy 22 in de-aerated aqueous solutions of chloride and nitrate salts of potassium and sodium in the temperature range 110-150 C (some limited testing was also conducted at 90 C). Electrochemical tests were run in neutral salt solutions without acid addition and others were run in salt solutions with an initial hydrogen ion concentration of 10{sup -4} molal. The Alloy 22 specimens were weld prism specimens and de-aeration was performed with nitrogen gas. No evidence of crevice corrosion was observed in the range 125-150 C. In the 120 to 160 C temperature range, the anionic concentration of stable aqueous solutions is dominated by nitrate relative to chloride. At nominally 120 C, the minimum nitrate to chloride ratio is about 4.5, and it increases to about 22 at nominally 155 C. The absence of localized corrosion susceptibility in these solutions is attributed to the known inhibiting effect of the nitrate anion. At 110 C, aqueous solutions can have dissolved chloride in excess of nitrate. Localized corrosion was observed at nitrate to chloride ratios up to 1.0, the highest ratio tested. The extent of localized corrosion was confined to the crevice region of the samples, and was limited for nitrate to chloride ratios greater than or equal to 0.3. Aqueous solution chemistry studies indicate that nitrate to chloride ratios of less than 0.5 are possible for temperatures up to nominally 116 C. However, the exact upper temperature limit is unknown and no electrochemical testing was done at these temperatures. Limited comparison between 8 m Cl aqueous solutions of Na + K on the one hand and Ca on the other indicated similar electrochemical E{sub crit} values and similar morphology of attack, again limited to the crevice region. However, the 24 hr E{sub corr} value was higher for the Ca based solution; this is probably due to the higher acidity of this solution (Ca{sup 2+} is slightly hydrolyzing). Intermediate-term corrosion potential (E{sub corr}) measurements indicate that moderately acidic conditions are required to achieve elevated E{sub corr} values.

  2. Measurements of Al(NO sub 3 ) sub 3 activities in aqueous nitrate solutions

    SciTech Connect

    Chaiko, D.J.; Fredrickson, D.R.; Difilippo, A.A.; Smidt, S.M.; Vandegrift, G.F. ); Tasker, I.R. )

    1992-01-01

    Aluminum nitrate activity coefficient obtained by vapor pressure osmometry are compared with activity coefficients derived from nitric acid extraction measurements using Bromley's correlation. This solvent extraction approach was possible because of the poor extraction of Al{sup 3+}(D{sub Al} {le} 10{sup {minus}3}) by the chosen solvents. The solvent compositions were 0.25M CMPO (octyl(phenyl)-N,N-diisobutylcarbamoyl-methylphosphine oxide) in tetrachloroethylene (TCE) and 0.25M CMPO with 0.75M tributyle phosphate (TBP) in TCE. In both approaches, nitric acid was used to supress the hydrolysis of Al{sup 3+}. At high ionic strengths, the two techniques yielded very similar activity coefficients for Al(NO{sub 3}){sub 3}. However, at intermediate and very low ionic strengths, the two procedures produced activity coefficients which differed considerably from each other. 2 figures, 3 tables, 18 references.

  3. Measurements of Al(NO{sub 3}){sub 3} activities in aqueous nitrate solutions

    SciTech Connect

    Chaiko, D.J.; Fredrickson, D.R.; Difilippo, A.A.; Smidt, S.M.; Vandegrift, G.F.; Tasker, I.R.

    1992-09-01

    Aluminum nitrate activity coefficient obtained by vapor pressure osmometry are compared with activity coefficients derived from nitric acid extraction measurements using Bromley`s correlation. This solvent extraction approach was possible because of the poor extraction of Al{sup 3+}(D{sub Al} {le} 10{sup {minus}3}) by the chosen solvents. The solvent compositions were 0.25M CMPO (octyl(phenyl)-N,N-diisobutylcarbamoyl-methylphosphine oxide) in tetrachloroethylene (TCE) and 0.25M CMPO with 0.75M tributyle phosphate (TBP) in TCE. In both approaches, nitric acid was used to supress the hydrolysis of Al{sup 3+}. At high ionic strengths, the two techniques yielded very similar activity coefficients for Al(NO{sub 3}){sub 3}. However, at intermediate and very low ionic strengths, the two procedures produced activity coefficients which differed considerably from each other. 2 figures, 3 tables, 18 references.

  4. Measurements of Al(NO 3) 3 activities in aqueous nitrate solutions

    NASA Astrophysics Data System (ADS)

    Chaiko, D. J.; Tasker, I. R.; Fredrickson, D. R.; Difilippo, A. A.; Smidt, S. M.; Vandegrift, G. F.

    Aluminum nitrate activity coefficients obtained by vapor pressure osmometry are compared with activity coefficients derived from nitric acid extraction measurements and Bromley's correlation. This solvent extraction approach was possible because of the poor extraction of Al 3+ (distribution ratio ≤ 10 3) by the chosen solvents. The solvents compositions were 0.25M CMPO (octyl(phenyl)-N, N-diisobutylcarbamoyl methylphosphine oxide) in tetrachloroethylene (TCE) and 0.25M CMPO with 0.75M tributyl phosphate (TBP) in TCE. In both approaches, nitric acid was used to supress the hydrolysis of Al 3+. At high ionic strengths, the two techniques yielded very similar activity coefficients for Al(NO 3) 3. However, at intermediate and very low ionic strengths, the two procedures produced considerably different activity coefficients.

  5. Studies on Nylon-66 membrane using aqueous solutions of potassium and lead nitrate salts as permeants

    NASA Astrophysics Data System (ADS)

    Kumar, Manoj; Ram, Bali

    2015-03-01

    Measurements on hydrodynamic and electro-osmotic permeability of water and aqueous solutions of KNO3 and Pb(NO3)2 in the concentration (C) range of 10 -4 10^{-4} M to 10 -3 10^{-3} M are made across the Nylon-66 membrane. The data obtained are used to ascertain the form of transport equation using the theory of non-equilibrium thermodynamics. Conductance of membrane equilibrated with water and aqueous solutions are measured and the data are used to estimate phenomenological coefficients. These phenomenological coefficients are used to determine the average pore radius, the average number of pores and the membrane constant. Zeta potentials are evaluated using electro-osmotic permeability and membrane-permeant conductance data to understand the electrical nature of the membrane-permeant interface. It is observed that hydrodynamic permeability and electro-osmotic permeability depend linearly on the applied pressure difference and the potential difference, respectively.

  6. Continuous plutonium dissolution apparatus

    DOEpatents

    Meyer, F.G.; Tesitor, C.N.

    1974-02-26

    This invention is concerned with continuous dissolution of metals such as plutonium. A high normality acid mixture is fed into a boiler vessel, vaporized, and subsequently condensed as a low normality acid mixture. The mixture is then conveyed to a dissolution vessel and contacted with the plutonium metal to dissolve the plutonium in the dissolution vessel, reacting therewith forming plutonium nitrate. The reaction products are then conveyed to the mixing vessel and maintained soluble by the high normality acid, with separation and removal of the desired constituent. (Official Gazette)

  7. Kinetics and spectroscopy of the NO/sub 3/ radical in aqueous ceric nitrate-nitric acid solutions

    SciTech Connect

    Wine, P.H.; Mauldin, R.L. III; Thorn, R.P.

    1988-03-10

    A pulsed laser photolysis-long-path absorption apparatus has been employed to investigate the kinetics and spectroscopy of the NO/sub 3/ radical in aqueous nitric acid solution. NO/sub 3/ was prepared by photolysis of cerium ammonium nitrate, Ce(N-H/sub 4/)/sub 2/(NO/sub 3/)/sub 6/. Much lower NO/sub 3/ concentrations were employed than in all previous work on this well-studied photochemical system. Important new findings are (1) the NO/sub 3/(aq) extinction coefficient is considerably larger than previously thought, (2) the appearance of NO/sub 3/ following absorption of a laser photon occurs on a time scale that is fast compared to our 50-ns time resolution, and (3) low concentrations of NO/sub 3/ and other reactive species result in background NO/sub 3/ decay rates which are about an order of magnitude slower than any reported previously. New rate data are reported for the reaction of NO/sub 3/ with Ce(III) and for the reaction SO/sub 4//sup -/ + NO/sub 3//sup -/ ..-->.. NO/sub 3/ + SO/sub 4//sup 2 -/.

  8. ELECTRODEPOSITION OF PLUTONIUM

    DOEpatents

    Wolter, F.J.

    1957-09-10

    A process of electrolytically recovering plutonium from dilute aqueous solutions containing plutonium ions comprises electrolyzing the solution at a current density of about 0.44 ampere per square centimeter in the presence of an acetate-sulfate buffer while maintaining the pH of the solution at substantially 5 and using a stirred mercury cathode.

  9. METHOD OF REDUCING PLUTONIUM COMPOUNDS

    DOEpatents

    Johns, I.B.

    1958-06-01

    A method is described for reducing plutonium compounds in aqueous solution from a higher to a lower valence state. This reduction of valence is achieved by treating the aqueous solution of higher valence plutonium compounds with hydrogen in contact with an activated platinum catalyst.

  10. /sup 252/Cf-source-driven neutron noise measurements of subcriticality for a slab tank containing aqueous Pu-U nitrate

    SciTech Connect

    Mihalczo, J.T.; Blakeman, E.D.; Ragan, G.E.; Kryter, R.C.; Robinson, R.C.; Seino, H.

    1987-08-01

    In order to study nuclear criticality safety related to the development of fast breeder technology, /sup 252/Cf-source-driven neutron noise analysis measurements were performed with a Pu-U nitrate solution in a slab tank of various heights and thickness varying 11.43 cm to 19.05 cm. The results and conclusions of these experiments are (1) a capability to measure the subcriticality of a multiplying system of slab geometry to a k/sub eff/ as low as 0.7 was demonstrated, (2) calculated neutron multiplication factors agreed with those from the experiments within approx.0.02, and (3) the applicability of the method for plutonium solution systems was demonstrated. This paper describes measurements in which the height of the slab was varied for a fixed thickness and the thickness varied for a fixed height, which are the first applications of this measurement method to slab geometry.

  11. Heavy-metal-induced Inhibition of Aspergillus niger nitrate reductase: Applications for Rapid Contaminant Detection in Aqueous Samples

    SciTech Connect

    Apel, William Arnold; Aiken, Abigail Marie; Peyton, Brent Michael; Petersen, James N.

    2003-03-01

    Enzyme inhibition assays have the potential to rapidly screen and identify heavy metals in environmental samples. Inhibition of nitrate reductase (NR) was examined as a method for detecting toxic metals. The activity of NR (EC 1.6.6.2) from Aspergillus niger was assayed as a function of metal concentration in the presence of Cd2+, Cr3+, Cr6+, Cu2+, Ni2+, Pb2+, and Zn2+. NR exhibited sensitivity to these metals at concentrations below 10 µM. Various buffers were screened for their ability to protect NR activity from metal inhibition, and 3-(N-morpholino) propanesulfonic acid (MOPS) was selected as the buffering system for the NR assays as it exhibited the least interference with metal inhibition, thus providing increased assay sensitivity. The hypothesis that chelating agents could prevent the inhibition of NR activity by metal ions was also tested. Results indicated that 10 mM ethylenediaminetetraacetic acid (EDTA) could protect NR activity from inhibition by Cr3+, Cu2+, Cd2+, Ni2+, and Zn2+ at concentrations below 100 µM, but that the EDTA had no effect on NR inhibition by Cr6+. An amount of 10 mM nitrilotriacetic acid (NTA) prevented NR inhibition by Cd2+, Cu2+, Ni2+, Pb2+, and Zn2+ at metal concentrations below 100 µM. However, 10 mM NTA was unable to protect the enzyme from inhibition by either Cr3+ or Cr6+. These results indicated that through specific metal chelation, a NR-based method for individually quantifying Cr3+ and Cr6+ species in aqueous solutions could be developed. The ability to restore activity to NR which been previously inhibited by exposure to 100 µM Pb2+, Cd2+, Zn2+, Cu2+, and Cr3+ was explored to determine whether NR activity could be recovered by EDTA additions for use in consecutive metal inhibition assays. The results showed NR activity could not be regained after exposure to Cr3+ or Cu2+, but did partially recover activity after Cd2+, Pb2+, and Zn2+ exposure.

  12. Chemical Reactivity of alpha-Pinene-derived Products in the Aqueous Phase: Implications on the Fate of Organic Nitrates

    NASA Astrophysics Data System (ADS)

    Rindelaub, J. D.; Hostetler, M. A.; Lipton, M. A.; Shepson, P. B.

    2014-12-01

    The production of organic nitrates has significant atmospheric importance due to the impact on regional air quality by influencing NOx lifetimes and ozone formation. Additionally, these low volatility compounds readily partition into the particle phase and are important contributors to secondary organic aerosol. Once in the aerosol phase, organic nitrates undergo further chemical reactions that govern their fate in the atmosphere and, consequently, their impact on air quality. Recent research indicates that the presence of water on aerosol particles has a major impact on the reactivity of organic nitrates and that condensed phase hydrolysis leads to the destruction of organic nitrate species, depending on structure. Despite this knowledge, the chemical mechanisms, products, product reactivity and volatility are still uncertain, negatively impacting our understanding of aerosol phase processing and the contribution to air quality. To further understand the atmospheric impact of aerosol phase hydrolysis, we analyzed both condensed phase hydrolysis reactions involving alpha-pinene-derived standards and alpha-pinene photochemical chamber reaction filter samples, using a suite of spectroscopic and mass spectrometric techniques. We were able to measure the pH-dependent hydrolysis rate constants for several types of organic nitrates and identify specific reaction products. The chemistry involved exhibits a strong dependence on pH, providing important mechanistic clues. The results of this study will significantly contribute to our knowledge of aerosol phase chemistry and the impact on regional air quality with respect to the fate of organic nitrate species.

  13. CONCENTRATION AND DECONTAMINATION OF SOLUTIONS CONTAINING PLUTONIUM VALUES BY BISMUTH PHOSPHATE CARRIER PRECIPITATION METHODS

    DOEpatents

    Seaborg, G.T.; Thompson, S.G.

    1960-08-23

    A process is given for isolating plutonium present in the tetravalent state in an aqueous solution together with fission products. First, the plutonium and fission products are coprecipitated on a bismuth phosphate carrier. The precipitate obtained is dissolved, and the plutonium in the solution is oxidized to the hexavalent state (with ceric nitrate, potassium dichromate, Pb/ sub 3/O/sub 4/, sodium bismuthate and/or potassium dichromate). Thereafter a carrier for fission products is added (bismuth phosphate, lanthanum fluoride, ceric phosphate, bismuth oxalate, thorium iodate, or thorium oxalate), and the fission-product precipitation can be repeated with one other of these carriers. After removal of the fission-product-containing precipitate or precipitates. the plutonium in the supernatant is reduced to the tetravalent state (with sulfur dioxide, hydrogen peroxide. or sodium nitrate), and a carrier for tetravalent plutonium is added (lanthanum fluoride, lanthanum hydroxide, lanthanum phosphate, ceric phosphate, thorium iodate, thorium oxalate, bismuth oxalate, or niobium pentoxide). The plutonium-containing precipitate is then dissolved in a relatively small volume of liquid so as to obtain a concentrated solution. Prior to dissolution, the bismuth phosphate precipitates first formed can be metathesized with a mixture of sodium hydroxide and potassium carbonate and plutonium-containing lanthanum fluorides with alkali-metal hydroxide. In the solutions formed from a plutonium-containing lanthanum fluoride carrier the plutonium can be selectively precipitated with a peroxide after the pH was adjusted preferably to a value of between 1 and 2. Various combinations of second, third, and fourth carriers are discussed.

  14. Solvent extraction system for plutonium colloids and other oxide nano-particles

    SciTech Connect

    Soderholm, Lynda; Wilson, Richard E; Chiarizia, Renato; Skanthakumar, Suntharalingam

    2014-06-03

    The invention provides a method for extracting plutonium from spent nuclear fuel, the method comprising supplying plutonium in a first aqueous phase; contacting the plutonium aqueous phase with a mixture of a dielectric and a moiety having a first acidity so as to allow the plutonium to substantially extract into the mixture; and contacting the extracted plutonium with second a aqueous phase, wherein the second aqueous phase has a second acidity higher than the first acidity, so as to allow the extracted plutonium to extract into the second aqueous phase. The invented method facilitates isolation of plutonium polymer without the formation of crud or unwanted emulsions.

  15. High-rate intercalation capability of NaTi2(PO4)3/C composite in aqueous lithium and sodium nitrate solutions

    NASA Astrophysics Data System (ADS)

    Vujković, Milica; Mitrić, Miodrag; Mentus, Slavko

    2015-08-01

    The nanodispersed NaTi2(PO4)3/C composite containing 20-25 wt.% of in-situ formed carbon, was synthesized by gel combustion procedure followed by a heat treatment at 650, 700 and 750 °C. The samples calcined at 700 and 750 °C displayed crystalline nasicon structure. They were subjected to the investigation of intercalation/deintercalation kinetics in aqueous NaNO3 and LiNO3 solutions, using cyclic voltammetry and galvanostatic charging/discharging measurements. As regards to the effect of electrolyte composition, the reactions were evidenced to be roughly twice faster in sodium nitrate than in lithium nitrate solution. Among the samples treated at 700 and 750 °C, better performance was evidenced for the sample treated at lower temperature. Coulombic capacity in NaNO3 solution at charging rate 1C amounted to ∼70 mAh g-1 and ∼55 mAh g-1 for the sample calcined at 700 and 750 °C, respectively, and displayed surprisingly slight dependence on charging rate up to even 100C.

  16. Structural characterization of zinc(II) chloride in aqueous solution and in the protic ionic liquid ethyl ammonium nitrate by x-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    D'Angelo, Paola; Zitolo, Andrea; Ceccacci, Francesca; Caminiti, Ruggero; Aquilanti, Giuliana

    2011-10-01

    Extended x-ray absorption fine structure (EXAFS) spectroscopy has been used to investigate the species and structures existing in a series of ZnCl2-H2O-NaCl solutions with different chloride/zinc ratios and in a solution of ZnCl2 in the protic ionic liquid ethyl ammonium nitrate (EAN). The average coordination numbers and distances of zinc species were determined from the analysis of the EXAFS data. In aqueous solution the number of chloride ions tightly bounded to Zn2+ is significantly related to the chloride/zinc ratio, and no inner complex formation between Zn2+ and Cl- ions has been detected for low ZnCl2 concentration (0.1 and 0.2 M). Conversely, in the same concentration range (0.13 M) the ZnCl2 species do not dissociate in EAN and the Zn2+ first coordination shell has two chloride ions and is completed by two oxygen atoms of the nitrate anion. The results of this investigation show that notwithstanding the existence of similar characteristics between EAN and water, the solvation properties of the two solvents are markedly different.

  17. PROCESS OF SEPARATING PLUTONIUM FROM URANIUM

    DOEpatents

    Brown, H.S.; Hill, O.F.

    1958-09-01

    A process is presented for recovering plutonium values from aqueous solutions. It comprises forming a uranous hydroxide precipitate in such a plutonium bearing solution, at a pH of at least 5. The plutonium values are precipitated with and carried by the uranium hydroxide. The carrier precipitate is then redissolved in acid solution and the pH is adjusted to about 2.5, causing precipitation of the uranous hydroxide but leaving the still soluble plutonium values in solution.

  18. PROCESS OF SEPARATING PLUTONIUM VALUES BY ELECTRODEPOSITION

    DOEpatents

    Whal, A.C.

    1958-04-15

    A process is described of separating plutonium values from an aqueous solution by electrodeposition. The process consists of subjecting an aqueous 0.1 to 1.0 N nitric acid solution containing plutonium ions to electrolysis between inert metallic electrodes. A current density of one milliampere io one ampere per square centimeter of cathode surface and a temperature between 10 and 60 d C are maintained. Plutonium is electrodeposited on the cathode surface and recovered.

  19. METHOD FOR RECOVERING PLUTONIUM VALUES FROM SOLUTION USING A BISMUTH HYDROXIDE CARRIER PRECIPITATE

    DOEpatents

    Faris, B.F.

    1961-04-25

    Carrier precipitation processes for separating plutonium values from aqueous solutions are described. In accordance with the invention a bismuth hydroxide precipitate is formed in the plutonium-containing solution, thereby carrying plutonium values from the solution.

  20. Subchronic inhalation of carbon tetrachloride alters the tissue retention of acutely inhaled plutonium-239 nitrate in F344 rats and syrian golden hamsters

    SciTech Connect

    Benson, J.M.; Barr, E.B.; Lundgren, D.L.

    1995-12-01

    Carbon tetrachloride (CCl{sub 4}) has been used extensively in the nuclear weapons industry, so it is likely that nuclear plant workers have been exposed to both CCl{sub 4} and plutonium compounds. Future exposures may occur during {open_quotes}cleanup{close_quotes} operations at weapons productions sites such as the Hanford, Washington, and Rocky Flats, Colorado, facilities. Inhalation of 20 and 100 ppm CCl{sub 4} by hamsters reduces uptake of {sup 239}Pu solubilized from lung, shunting the {sup 239}Pu to the skeleton.

  1. Isothermal decomposition of hydroxylamine and hydroxylamine nitrate in aqueous solutions in the temperature range 80-160 degrees C.

    PubMed

    Liu, Lijun; Papadaki, Maria; Pontiki, Eleni; Stathi, Panagiota; Rogers, William J; Mannan, M Sam

    2009-06-15

    Hydroxylamine (HA) and hydroxylamine nitrate (HAN) have been involved independently in several tragic accidents, which incurred numerous fatalities and injuries. Following these incidents, adiabatic calorimetry and computational chemistry research was conducted on those compounds, suggesting potential reaction pathways of their decomposition, but the mechanism of their unstable behavior, still have not been completely understood. In the present work, isothermal decomposition tests were performed accompanied with HPLC, ion chromatography and UV analyses in the temperature range 80-160 degrees C. Condition-dependent autocatalytic decompositions were demonstrated for HA and HAN, and an intermediate formation has been observed that is most likely responsible for their autocatalytic behavior. These findings corroborate previously reported computational chemistry results. PMID:19027229

  2. Thermochemical nitrate destruction

    DOEpatents

    Cox, John L.; Hallen, Richard T.; Lilga, Michael A.

    1992-01-01

    A method is disclosed for denitrification of nitrates and nitrates present in aqueous waste streams. The method comprises the steps of (1) identifying the concentration nitrates and nitrites present in a waste stream, (2) causing formate to be present in the waste stream, (3) heating the mixture to a predetermined reaction temperature from about 200.degree. C. to about 600.degree. C., and (4) holding the mixture and accumulating products at heated and pressurized conditions for a residence time, thereby resulting in nitrogen and carbon dioxide gas, and hydroxides, and reducing the level of nitrates and nitrites to below drinking water standards.

  3. PROCESS OF ELIMINATING HYDROGEN PEROXIDE IN SOLUTIONS CONTAINING PLUTONIUM VALUES

    DOEpatents

    Barrick, J.G.; Fries, B.A.

    1960-09-27

    A procedure is given for peroxide precipitation processes for separating and recovering plutonium values contained in an aqueous solution. When plutonium peroxide is precipitated from an aqueous solution, the supernatant contains appreciable quantities of plutonium and peroxide. It is desirable to process this solution further to recover plutonium contained therein, but the presence of the peroxide introduces difficulties; residual hydrogen peroxide contained in the supernatant solution is eliminated by adding a nitrite or a sulfite to this solution.

  4. Plutonium controversy

    SciTech Connect

    Richmond, C.R.

    1980-01-01

    The toxicity of plutonium is discussed, particularly in relation to controversies surrounding the setting of radiation protection standards. The sources, amounts of, and exposure pathways of plutonium are given and the public risk estimated. (ACR)

  5. ION EXCHANGE ADSORPTION PROCESS FOR PLUTONIUM SEPARATION

    DOEpatents

    Boyd, G.E.; Russell, E.R.; Taylor, M.D.

    1961-07-11

    Ion exchange processes for the separation of plutonium from fission products are described. In accordance with these processes an aqueous solution containing plutonium and fission products is contacted with a cation exchange resin under conditions favoring adsorption of plutonium and fission products on the resin. A portion of the fission product is then eluted with a solution containing 0.05 to 1% by weight of a carboxylic acid. Plutonium is next eluted with a solution containing 2 to 8 per cent by weight of the same carboxylic acid, and the remaining fission products on the resin are eluted with an aqueous solution containing over 10 per cent by weight of sodium bisulfate.

  6. Effect of Y(III) distribution between aqueous nitrate and organic D2EHPA solutions on the Y(III) precipitation stripping using oxalic acid

    SciTech Connect

    Iglesias, M.; Antico, E.; Salvado, V.; Masana, A.; Valiente, M.

    1999-03-01

    The solvent extraction process of yttrium(III) from nitrate media by di(2-ethylhexyl) phosphoric acid (D2EHPA, represented as HA) has been studied as a first step to accomplish the homogeneous precipitation of yttrium oxalate from an organic metal loaded D2EHPA solution. The analysis of liquid-liquid distribution data at low metal concentrations determined YA{sub 3{center_dot}}2HA as the only metal organic species formed during the extraction, with a formation constant of log{beta} = 16.410 {+-} 0.055. A polymerization of such organic metal species was observed at high metal loading of the organic phase. A comparison of these results with previous studies carried out in chloride or perchlorate media reveals a strong influence of the aqueous medium on the metal species formed in the organic phase, affecting mostly the stoichiometry of such species. The homogeneous precipitation of yttrium as yttrium oxalate using oxalic acid has been carried out as direct recovery of the metal from the organic solution. The observed precipitation-stripping kinetics has been related to the formation of organic yttrium species. The acidity of the stripping solution and the oxalic acid concentration also affects the kinetics and the precipitation yield. The morphology and particle size distribution of the powders obtained support the mentioned influence of the precipitation-stripping kinetics.

  7. METHOD OF PREPARING PLUTONIUM TETRAFLUORIDE

    DOEpatents

    Beede, R.L.; Hopkins, H.H. Jr.

    1959-11-17

    C rystalline plutonium tetrafluoride is precipitated from aqueous up to 1.6 N mineral acid solutions of a plutorium (IV) salt with fluosilicic acid anions, preferably at room temperature. Hydrogen fluoride naay be added after precipitation to convert any plutonium fluosilicate to the tetrafluoride and any silica to fluosilicic acid. This process results in a purer product, especially as to iron and aluminum, than does the precipitation by the addition of hydrogen fluoride.

  8. IODATE METHOD FOR PURIFYING PLUTONIUM

    DOEpatents

    Stoughton, R.W.; Duffield, R.B.

    1958-10-14

    A method is presented for removing radioactive fission products from aqueous solutions containing such fission products together with plutonium. This is accomplished by incorporating into such solutions a metal iodate precipitate to remove fission products which form insoluble iodates. Suitable metal iodates are those of thorium and cerium. The plutonium must be in the hexavalent state and the pH of the solution must be manintained at less than 2.

  9. Polymerization of Pu(IV) in aqueous nitric acid solutions

    SciTech Connect

    Toth, L.M.; Friedman, H.A.; Osborne, M.M.

    1980-10-01

    The polymerization of Pu(IV) in aqueous nitric acid solutions has been studied spectrophotometrically both to establish the influence of large UO{sub 2}(NO{sub 3}){sub 2} concentrations on the polymerization rates and, more generally, to review the influence of the major parameters on the polymer reaction. Typically, experiments have been performed at 50{sup 0}C and with 0.05 M Pu in nitric acid solutions that vary in acidity from 0.07 to 0.4 M. An induction period usually precedes the polymer growth stage during which time nucleation of primary hydrolysis products occurs. Uranyl nitrate retards the polymerization reaction by approximately 35% in spite of the counteracting influence of the nitrate ions associated with this solute. The rate of polymer formation, expressed as d(percent polymer)/dt, has been shown to depend on the total plutonium concentration in reactions where the Pu(IV) concentration remained constant; and it is therefore suggested that the polymer reaction rate is not first order with respect to the concentration of plutonium as was previously thought. It has been shown further that accurate acid determinations on stock reagents are essential in order to obtain reliable polymerization experiments. Satisfactory procedures for these analyses did not exist, so appropriate modifications to the iodate precipitation methods were developed. The most ideal plutonium reagent material has been shown to be crystalline Pu(IV) nitrate because it can be added directly to acid solutions without the occurrence of unintentional hydrolysis reactions.

  10. Purification of alkali metal nitrates

    DOEpatents

    Fiorucci, Louis C.; Gregory, Kevin M.

    1985-05-14

    A process is disclosed for removing heavy metal contaminants from impure alkali metal nitrates containing them. The process comprises mixing the impure nitrates with sufficient water to form a concentrated aqueous solution of the impure nitrates, adjusting the pH of the resulting solution to within the range of between about 2 and about 7, adding sufficient reducing agent to react with heavy metal contaminants within said solution, adjusting the pH of the solution containing reducing agent to effect precipitation of heavy metal impurities and separating the solid impurities from the resulting purified aqueous solution of alkali metal nitrates. The resulting purified solution of alkali metal nitrates may be heated to evaporate water therefrom to produce purified molten alkali metal nitrate suitable for use as a heat transfer medium. If desired, the purified molten form may be granulated and cooled to form discrete solid particles of alkali metal nitrates.

  11. LITERATURE REVIEW FOR OXALATE OXIDATION PROCESSES AND PLUTONIUM OXALATE SOLUBILITY

    SciTech Connect

    Nash, C.

    2012-02-03

    A literature review of oxalate oxidation processes finds that manganese(II)-catalyzed nitric acid oxidation of oxalate in precipitate filtrate is a viable and well-documented process. The process has been operated on the large scale at Savannah River in the past, including oxidation of 20 tons of oxalic acid in F-Canyon. Research data under a variety of conditions show the process to be robust. This process is recommended for oxalate destruction in H-Canyon in the upcoming program to produce feed for the MOX facility. Prevention of plutonium oxalate precipitation in filtrate can be achieved by concentrated nitric acid/ferric nitrate sequestration of oxalate. Organic complexants do not appear practical to sequester plutonium. Testing is proposed to confirm the literature and calculation findings of this review at projected operating conditions for the upcoming campaign. H Canyon plans to commence conversion of plutonium metal to low-fired plutonium oxide in 2012 for eventual use in the Mixed Oxide Fuel (MOX) Facility. The flowsheet includes sequential operations of metal dissolution, ion exchange, elution, oxalate precipitation, filtration, and calcination. All processes beyond dissolution will occur in HB-Line. The filtration step produces an aqueous filtrate that may have as much as 4 M nitric acid and 0.15 M oxalate. The oxalate needs to be removed from the stream to prevent possible downstream precipitation of residual plutonium when the solution is processed in H Canyon. In addition, sending the oxalate to the waste tank farm is undesirable. This report addresses the processing options for destroying the oxalate in existing H Canyon equipment.

  12. WET METHOD OF PREPARING PLUTONIUM TRIBROMIDE

    DOEpatents

    Davidson, N.R.; Hyde, E.K.

    1958-11-11

    S> The preparation of anhydrous plutonium tribromide from an aqueous acid solution of plutonium tetrabromide is described, consisting of adding a water-soluble volatile bromide to the tetrabromide to provide additional bromide ions sufficient to furnish an oxidation-reduction potential substantially more positive than --0.966 volt, evaporating the resultant plutonium tribromides to dryness in the presence of HBr, and dehydrating at an elevated temperature also in the presence of HBr.

  13. Thermochemical nitrate destruction

    DOEpatents

    Cox, J.L.; Hallen, R.T.; Lilga, M.A.

    1992-06-02

    A method is disclosed for denitrification of nitrates and nitrites present in aqueous waste streams. The method comprises the steps of (1) identifying the concentration nitrates and nitrites present in a waste stream, (2) causing formate to be present in the waste stream, (3) heating the mixture to a predetermined reaction temperature from about 200 C to about 600 C, and (4) holding the mixture and accumulating products at heated and pressurized conditions for a residence time, thereby resulting in nitrogen and carbon dioxide gas, and hydroxides, and reducing the level of nitrates and nitrites to below drinking water standards.

  14. RECOVERY OF PLUTONIUM BY CARRIER PRECIPITATION

    DOEpatents

    Goeckermann, R.H.

    1961-04-01

    A process is given for recovering plutonium from an aqueous nitric acid zirconium-containing solution of an acidity between 0.2 and 1 N by adding fluoride anions (1.5 to 5 mg/l) and precipitating the plutonium with an excess of hydrogen peroxide at from 53 to 65 deg C.

  15. Simultaneous removal of cadmium and nitrate in aqueous media by nanoscale zerovalent iron (nZVI) and Au doped nZVI particles.

    PubMed

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

    2014-10-15

    Nanoscale zerovalent iron (nZVI) has demonstrated high efficacy for treating nitrate or cadmium (Cd) contamination, but its efficiency for simultaneous removal of nitrate and Cd has not been investigated. This study evaluated the reactivity of nZVI to the co-contaminants and by-product formation, employed different catalysts to reduce nitrite yield from nitrate, and examined the transformation of nZVI after reaction. Nitrate reduction resulted in high solution pH, negatively charged surface of nZVI, formation of Fe3O4 (a stable transformation of nZVI), and no release of ionic iron. Increased pH and negative charge contributed to significant increase in Cd(II) removal capacity (from 40 mg/g to 188 mg/g) with nitrate present. In addition, nitrate reduction by nZVI could be catalyzed by Cd(II): while 30% of nitrate was reduced by nZVI within 2 h in the absence of Cd(II), complete nitrate reduction was observed in the presence of 40 mg-Cd/L due to the formation of Cd islands (Cd(0) and CdO) on the nZVI particles. While nitrate was reduced mostly to ammonium when Cd(II) was not present or at Cd(II) concentrations ≥ 40 mg/L, up to 20% of the initial nitrate was reduced to nitrite at Cd(II) concentrations < 40 mg/L. Among nZVI particles doped with 1 wt. % Cu, Ag, or Au, nZVI deposited with 1 wt. % Au reduced nitrite yield to less than 3% of the initial nitrate, while maintaining a high Cd(II) removal capacity. PMID:24999115

  16. LABORATORY INVESTIGATIONS OF INTERACTIONS OF IRRADIATED O-XYLENE/NOX/SO2/AIR MIXTURES WITH AQUEOUS MEDIA CONTAINING SODIUM FLUORIDE, SODIUM TRIFLUOROACETATE, AMMONIUM NITRATE AND HYDROGEN PEROXIDE

    EPA Science Inventory

    Laboratory experiments were conducted to investigate interactions between complex air mixtures and aqueous films containing hydrolysis products of hydrochlorofluorocarbon (HCFC) and hydrofluorocarbon (HFC) oxidation products. he experiments consisted of exposing aqueous films con...

  17. 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.

  18. Thermochemical nitrate reduction

    SciTech Connect

    Cox, J.L.; Lilga, M.A.; Hallen, R.T.

    1992-09-01

    A series of preliminary experiments was conducted directed at thermochemically converting nitrate to nitrogen and water. Nitrates are a major constituent of the waste stored in the underground tanks on the Hanford Site, and the characteristics and effects of nitrate compounds on stabilization techniques must be considered before permanent disposal operations begin. For the thermochemical reduction experiments, six reducing agents (ammonia, formate, urea, glucose, methane, and hydrogen) were mixed separately with {approximately}3 wt% NO{sub 3}{sup {minus}} solutions in a buffered aqueous solution at high pH (13); ammonia and formate were also mixed at low pH (4). Reactions were conducted in an aqueous solution in a batch reactor at temperatures of 200{degrees}C to 350{degrees}C and pressures of 600 to 2800 psig. Both gas and liquid samples were analyzed. The specific components analyzed were nitrate, nitrite, nitrous oxide, nitrogen, and ammonia. Results of experimental runs showed the following order of nitrate reduction of the six reducing agents in basic solution: formate > glucose > urea > hydrogen > ammonia {approx} methane. Airnmonia was more effective under acidic conditions than basic conditions. Formate was also effective under acidic conditions. A more thorough, fundamental study appears warranted to provide additional data on the mechanism of nitrate reduction. Furthermore, an expanded data base and engineering feasibility study could be used to evaluate conversion conditions for promising reducing agents in more detail and identify new reducing agents with improved performance characteristics.

  19. Modified titrimetric determination of plutonium using photometric end-point detection

    SciTech Connect

    Baughman, W.J.; Dahlby, J.W.

    1980-04-01

    A method used at LASL for the accurate and precise assay of plutonium metal was modified for the measurement of plutonium in plutonium oxides, nitrate solutions, and in other samples containing large quantities of plutonium in oxidized states higher than +3. In this modified method, the plutonium oxide or other sample is dissolved using the sealed-reflux dissolution method or other appropriate methods. Weighed aliquots, containing approximately 100 mg of plutonium, of the dissolved sample or plutonium nitrate solution are fumed to dryness with an HC1O/sub 4/-H/sub 2/SO/sub 4/ mixture. The dried residue is dissolved in dilute H/sub 2/SO/sub 4/, and the plutonium is reduced to plutonium (III) with zinc metal. The excess zinc metal is dissolved with HCl, and the solution is passed through a lead reductor column to ensure complete reduction of the plutonium to plutonium (III). The solution, with added ferroin indicator, is then titrated immediately with standardized ceric solution to a photometric end point. For the analysis of plutonium metal solutions, plutonium oxides, and nitrate solutions, the relative standard deviation are 0.06, 0.08, and 0.14%, respectively. Of the elements most likely to be found with the plutonium, only iron, neptunium, and uranium interfere. Small amounts of uranium and iron, which titrate quantitatively in the method, are determined by separate analytical methods, and suitable corrections are applied to the plutonium value. 4 tables, 4 figures.

  20. Extraction of rare earth metal(III) nitrates with trialkylmethylammonium nitrate from multicomponent solutions containing ammonium nitrate

    SciTech Connect

    Pyartman, A.K.; Puzikov, E.A.; Bogatov, K.B.

    1994-10-20

    A study has been made of the extraction of rare earth elements (III) (praseodymium-lutetium, yttrium) by trialkylmethylammonium nitrate in kerosine (1.10 M) from binary and multicomponent solutions containing 1.0-3.0 M of ammonium nitrate. Physicochemical and mathematical models have been proposed for the distribution of individual lanthanides (III) depending on the composition of the initial raw material and on the total REE(III) and ammonium nitrate concentrations in the aqueous phase. The optimal concentration ranges for total REE and ammonium nitrate in the aqueous phase have been found for separating complex REE concentrates by using trialkylmethylammonium nitrate in the diluent.

  1. PROCESS OF REMOVING PLUTONIUM VALUES FROM SOLUTION WITH GROUP IVB METAL PHOSPHO-SILICATE COMPOSITIONS

    DOEpatents

    Russell, E.R.; Adamson, A.W.; Schubert, J.; Boyd, G.E.

    1957-10-29

    A process for separating plutonium values from aqueous solutions which contain the plutonium in minute concentrations is described. These values can be removed from an aqueous solution by taking an aqueous solution containing a salt of zirconium, titanium, hafnium or thorium, adding an aqueous solution of silicate and phosphoric acid anions to the metal salt solution, and separating, washing and drying the precipitate which forms when the two solutions are mixed. The aqueous plutonium containing solution is then acidified and passed over the above described precipi-tate causing the plutonium values to be adsorbed by the precipitate.

  2. EXTRACTION OF TETRAVALENT PLUTONIUM VALUES WITH METHYL ETHYL KETONE, METHYL ISOBUTYL KETONE ACETOPHENONE OR MENTHONE

    DOEpatents

    Seaborg, G.T.

    1961-08-01

    A process is described for extracting tetravalent plutonium from an aqueous acid solution with methyl ethyl ketone, methyl isobutyl ketone, or acetophenone and with the extraction of either tetravalent or hexavalent plutonium into menthone. (AEC)

  3. Production of gas phase NO₂ and halogens from the photochemical oxidation of aqueous mixtures of sea salt and nitrate ions at room temperature.

    PubMed

    Richards, Nicole K; Finlayson-Pitts, Barbara J

    2012-10-01

    Nitrate and halide ions coexist in a number of environmental systems, including sea salt particles, the Arctic snowpack, and alkaline dry lakes. However, little is known about potential synergisms between halide and nitrate ions. The effect of sea salt on NO(3)(-) photochemistry at 311 nm was investigated at 298 K using thin films of deliquesced NaNO(3)-synthetic sea salt mixtures. Gas phase NO(2), NO, and halogen products were measured as a function of photolysis time using NO(y) chemiluminescence and atmospheric pressure ionization mass spectrometry (API-MS). The production of NO(2) increases with the halide-to-nitrate ratio, and is similar to that for mixtures of NaCl with NaNO(3). Gas phase halogen production also increased with the halide-to-nitrate ratio, consistent with NO(3)(-) photolysis yielding OH which oxidizes halide ions in the film. Yields of gas phase halogens and NO were strongly dependent on the acidity of the solution, while that of NO(2) was not. An additional halogen formation mechanism in the dark involving molecular HNO(3) is proposed that may be important in other systems such as reactions on surfaces. These studies show that the yield of Br(2) relative to NO(2) during photolysis of halide-nitrate mixtures could be as high as 35% under some atmospheric conditions. PMID:22506935

  4. Thermal Stability Studies of Candidate Decontamination Agents for Hanford’s Plutonium Finishing Plant Plutonium-Contaminated Gloveboxes

    SciTech Connect

    Scheele, Randall D.; Cooper, Thurman D.; Jones, Susan A.; Ewalt, John R.; Compton, James A.; Trent, Donald S.; Edwards, Matthew K.; Kozelisky, Anne E.; Scott, Paul A.; Minette, Michael J.

    2005-09-29

    This report provides the results of PNNL's and Fluor's studies of the thermal stabilities of potential wastes arising from decontamination of Hanford's Plutonium Finishing Plant's plutonium contaminated gloveboxes. The candidate wastes arising from the decontamination technologies ceric nitrate/nitric acid, RadPro, Glygel, and Aspigel.

  5. Nitrate reduction

    DOEpatents

    Dziewinski, Jacek J. (Los Alamos, NM); Marczak, Stanislaw (Los Alamos, NM)

    2000-01-01

    Nitrates are reduced to nitrogen gas by contacting the nitrates with a metal to reduce the nitrates to nitrites which are then contacted with an amide to produce nitrogen and carbon dioxide or acid anions which can be released to the atmosphere. Minor amounts of metal catalysts can be useful in the reduction of the nitrates to nitrites. Metal salts which are formed can be treated electrochemically to recover the metals.

  6. Nitrate and periplasmic nitrate reductases

    PubMed Central

    Sparacino-Watkins, Courtney; Stolz, John F.; Basu, Partha

    2014-01-01

    The nitrate anion is a simple, abundant and relatively stable species, yet plays a significant role in global cycling of nitrogen, global climate change, and human health. Although it has been known for quite some time that nitrate is an important species environmentally, recent studies have identified potential medical applications. In this respect the nitrate anion remains an enigmatic species that promises to offer exciting science in years to come. Many bacteria readily reduce nitrate to nitrite via nitrate reductases. Classified into three distinct types – periplasmic nitrate reductase (Nap), respiratory nitrate reductase (Nar) and assimilatory nitrate reductase (Nas), they are defined by their cellular location, operon organization and active site structure. Of these, Nap proteins are the focus of this review. Despite similarities in the catalytic and spectroscopic properties Nap from different Proteobacteria are phylogenetically distinct. This review has two major sections: in the first section, nitrate in the nitrogen cycle and human health, taxonomy of nitrate reductases, assimilatory and dissimilatory nitrate reduction, cellular locations of nitrate reductases, structural and redox chemistry are discussed. The second section focuses on the features of periplasmic nitrate reductase where the catalytic subunit of the Nap and its kinetic properties, auxiliary Nap proteins, operon structure and phylogenetic relationships are discussed. PMID:24141308

  7. PROCESS FOR SEPARATING PLUTONIUM BY REPEATED PRECIPITATION WITH AMPHOTERIC HYDROXIDE CARRIERS

    DOEpatents

    Faris, B.F.

    1960-04-01

    A multiple carrier precipitation method is described for separating and recovering plutonium from an aqueous solution. The hydroxide of an amphoteric metal is precipitated in an aqueous plutonium-containing solution. This precipitate, which carries plutonium, is then separated from the supernatant liquid and dissolved in an aqueous hydroxide solution, forming a second plutonium- containing solution. lons of an amphoteric metal which forms an insoluble hydroxide under the conditions existing in this second solution are added to the second solution. The precipitate which forms and which carries plutonium is separated from the supernatant liquid. Amphoteric metals which may be employed are aluminum, bibmuth, copper, cobalt, iron, lanthanum, nickel, and zirconium.

  8. Extraction of rare-earth(III) nitrates by trialkylmethylammonium nitrate from multicomponent solutions

    SciTech Connect

    Pyartman, A.K.; Kopyrin, A.A.; Puzikov, E.A.

    1994-05-20

    Extraction of rare-earth metal(III) (REM) [praseodymium-lutetium, yttrium(III)] nitrates by solutions of trialkylmethylammonium nitrate in kerosene (0.4-1.0 M) was studied. It was established that di- and trisolvates are formed in the organic phase. Extraction constants were determined. Physicochemical and mathematical models were developed to describe the extraction of REM(III) nitrates from binary and multicomponent aqueous solutions. The range of REM nitrate concentrations in the aqueous providing optimal conditions for extraction separation of REM by trialkylmethylammonium nitrate solutions in kerosene was established.

  9. SEPARATION OF PLUTONIUM FROM LANTHANUM BY CHELATION-EXTRACTION

    DOEpatents

    James, R.A.; Thompson, S.G.

    1958-12-01

    Plutonium can be separated from a mixture of plutonlum and lanthanum in which the lanthanum to plutonium molal ratio ls at least five by adding the ammonium salt of N-nitrosoarylhydroxylamine to an aqueous solution having a pH between about 3 and 0.2 and containing the plutonium in a valence state of at least +3, to form a plutonium chelate compound of N-nitrosoarylhydroxylamine. The plutonium chelate compound may be recovered from the solution by extracting with an immiscible organic solvent such as chloroform.

  10. METHOD OF IMPROVING THE CARRIER PRECIPITATION OF PLUTONIUM

    DOEpatents

    Kamack, H.J.; Balthis, J.H.

    1958-12-01

    Plutonium values can be recovered from acidic solutlons by adding lead nitrate, hydrogen fluoride, lantha num nitrate, and sulfurlc acid to the solution to form a carrler preclpitate. The lead sulfate formed improves the separatlon characteristics of the lanthanum fluoride carrier precipitate,

  11. CONVERSION OF PLUTONIUM TRIFLUORIDE TO PLUTONIUM TETRAFLUORIDE

    DOEpatents

    Fried, S.; Davidson, N.R.

    1957-09-10

    A large proportion of the trifluoride of plutonium can be converted, in the absence of hydrogen fluoride, to the tetrafiuoride of plutonium. This is done by heating plutonium trifluoride with oxygen at temperatures between 250 and 900 deg C. The trifiuoride of plutonium reacts with oxygen to form plutonium tetrafluoride and plutonium oxide, in a ratio of about 3 to 1. In the presence of moisture, plutonium tetrafluoride tends to hydrolyze at elevated temperatures and therefore it is desirable to have the process take place under anhydrous conditions.

  12. PLUTONIUM CARRIER METATHESIS WITH ORGANIC REAGENT

    DOEpatents

    Thompson, S.G.

    1958-07-01

    A method is described for converting a plutonium containing bismuth phosphate carrier precipitate Into a compositton more readily soluble in acid. The method consists of dissolving the bismuth phosphate precipitate in an aqueous solution of alkali metal hydroxide, and adding one of a certaia group of organic compounds, e.g., polyhydric alcohols or a-hydrorycarboxylic acids. The mixture is then heated causiing formation of a bismuth hydroxide precipitate containing plutonium which may be readily dissolved in nitric acid for further processing.

  13. SEPARATION OF RUTHENIUM FROM AQUEOUS SOLUTIONS

    DOEpatents

    Callis, C.F.; Moore, R.L.

    1959-09-01

    >The separation of ruthenium from aqueous solutions containing uranium plutonium, ruthenium, and fission products is described. The separation is accomplished by providing a nitric acid solution of plutonium, uranium, ruthenium, and fission products, oxidizing plutonium to the hexavalent state with sodium dichromate, contacting the solution with a water-immiscible organic solvent, such as hexone, to extract plutonyl, uranyl, ruthenium, and fission products, reducing with sodium ferrite the plutonyl in the solvent phase to trivalent plutonium, reextracting from the solvent phase the trivalent plutonium, ruthenium, and some fission products with an aqueous solution containing a salting out agent, introducing ozone into the aqueous acid solution to oxidize plutonium to the hexavalent state and ruthenium to ruthenium tetraoxide, and volatizing off the ruthenium tetraoxide.

  14. Plutonium story

    SciTech Connect

    Seaborg, G T

    1981-09-01

    The first nuclear synthesis and identification (i.e., the discovery) of the synthetic transuranium element plutonium (isotope /sup 238/Pu) and the demonstration of its fissionability with slow neutrons (isotope /sup 239/Pu) took place at the University of California, Berkeley, through the use of the 60-inch and 37-inch cyclotrons, in late 1940 and early 1941. This led to the development of industrial scale methods in secret work centered at the University of Chicago's Metallurgical Laboratory and the application of these methods to industrial scale production, at manufacturing plants in Tennessee and Washington, during the World War II years 1942 to 1945. The chemical properties of plutonium, needed to devise the procedures for its industrial scale production, were studied by tracer and ultramicrochemical methods during this period on an extraordinarily urgent basis. This work, and subsequent investigations on a worldwide basis, have made the properties of plutonium very well known. Its well studied electronic structure and chemical properties give it a very interesting position in the actinide series of inner transition elements.

  15. Plutonium Story

    DOE R&D Accomplishments Database

    Seaborg, G. T.

    1981-09-01

    The first nuclear synthesis and identification (i.e., the discovery) of the synthetic transuranium element plutonium (isotope /sup 238/Pu) and the demonstration of its fissionability with slow neutrons (isotope /sup 239/Pu) took place at the University of California, Berkeley, through the use of the 60-inch and 37-inch cyclotrons, in late 1940 and early 1941. This led to the development of industrial scale methods in secret work centered at the University of Chicago's Metallurgical Laboratory and the application of these methods to industrial scale production, at manufacturing plants in Tennessee and Washington, during the World War II years 1942 to 1945. The chemical properties of plutonium, needed to devise the procedures for its industrial scale production, were studied by tracer and ultramicrochemical methods during this period on an extraordinarily urgent basis. This work, and subsequent investigations on a worldwide basis, have made the properties of plutonium very well known. Its well studied electronic structure and chemical properties give it a very interesting position in the actinide series of inner transition elements.

  16. PRECIPITATION METHOD OF SEPARATING PLUTONIUM FROM CONTAMINATING ELEMENTS

    DOEpatents

    Duffield, R.B.

    1959-02-24

    S>A method is described for separating plutonium, in a valence state of less than five, from an aqueous solution in which it is dissolved. The niethod consists in adding potassium and sulfate ions to such a solution while maintaining the solution at a pH of less than 7.1, and isolating the precipitate of potassium plutonium sulfate thus formed.

  17. COMPLEX FLUORIDES OF PLUTONIUM AND AN ALKALI METAL

    DOEpatents

    Seaborg, G.T.

    1960-08-01

    A method is given for precipitating alkali metal plutonium fluorides. such as KPuF/sub 5/, KPu/sub 2/F/sub 9/, NaPuF/sub 5/, and RbPuF/sub 5/, from an aqueous plutonium(IV) solution by adding hydrogen fluoride and alkali-metal- fluoride.

  18. PROCESS USING POTASSIUM LANTHANUM SULFATE FOR FORMING A CARRIER PRECIPITATE FOR PLUTONIUM VALUES

    DOEpatents

    Angerman, A.A.

    1958-10-21

    A process is presented for recovering plutonium values in an oxidation state not greater than +4 from fluoride-soluble fission products. The process consists of adding to an aqueous acidic solution of such plutonium values a crystalline potassium lanthanum sulfate precipitate which carries the plutonium values from the solution.

  19. METHOD FOR SEPARATING PLUTONIUM AND FISSION PRODUCTS EMPLOYING AN OXIDE AS A CARRIER FOR FISSION PRODUCTS

    DOEpatents

    Davies, T.H.

    1961-07-18

    Carrier precipitation processes for separating plutonium values from uranium fission products are described. Silicon dioxide or titanium dioxide in a finely divided state is added to an acidic aqueous solution containing hexavalent plutonium ions together with ions of uranium fission products. The supernatant solution containing plutonium ions is then separated from the oxide and the fission products associated therewith.

  20. PLUTONIUM ALLOYS

    DOEpatents

    Chynoweth, W.

    1959-06-16

    The preparation of low-melting-point plutonium alloys is described. In a MgO crucible Pu is placed on top of the lighter alloying metal (Fe, Co, or Ni) and the temperature raised to 1000 or 1200 deg C. Upon cooling, the alloy slug is broke out of the crucible. With 14 at. % Ni the m.p. is 465 deg C; with 9.5 at. % Fe the m.p. is 410 deg C; and with 12.0 at. % Co the m.p. is 405 deg C. (T.R.H.) l6262 l6263 ((((((((Abstract unscannable))))))))

  1. METHOD FOR DISSOLVING LANTHANUM FLUORIDE CARRIER FOR PLUTONIUM

    DOEpatents

    Koshland, D.E. Jr.; Willard, J.E.

    1961-08-01

    A method is described for dissolving lanthanum fluoride precipitates which is applicable to lanthanum fluoride carrier precipitation processes for recovery of plutonium values from aqueous solutions. The lanthanum fluoride precipitate is contacted with an aqueous acidic solution containing dissolved zirconium in the tetravalent oxidation state. The presence of the zirconium increases the lanthanum fluoride dissolved and makes any tetravalent plutonium present more readily oxidizable to the hexavalent state. (AEC)

  2. Aqueous complexation of thorium(IV), uranium(IV), neptunium(IV), plutonium(III/IV), and cerium(III/IV) with DTPA.

    PubMed

    Brown, M Alex; Paulenova, Alena; Gelis, Artem V

    2012-07-16

    Aqueous complexation of Th(IV), U(IV), Np(IV), Pu(III/IV), and Ce(III/IV) with DTPA was studied by potentiometry, absorption spectrophotometry, and cyclic voltammetry at 1 M ionic strength and 25 °C. The stability constants for the 1:1 complex of each trivalent and tetravalent metal were calculated. From the potentiometric data, we report stability constant values for Ce(III)DTPA, Ce(III)HDTPA, and Th(IV)DTPA of log β(101) = 20.01 ± 0.02, log β(111) = 22.0 ± 0.2, and log β(101) = 29.6 ± 1, respectively. From the absorption spectrophotometry data, we report stability constant values for U(IV)DTPA, Np(IV)DTPA, and Pu(IV)DTPA of log β(101) = 31.8 ± 0.1, 32.3 ± 0.1, and 33.67 ± 0.02, respectively. From the cyclic voltammetry data, we report stability constant values for Ce(IV) and Pu(III) of log β(101) = 34.04 ± 0.04 and 20.58 ± 0.04, respectively. The values obtained in this work are compared and discussed with respect to the ionic radius of each cationic metal. PMID:22738207

  3. Dopaminium nitrate

    PubMed Central

    Gatfaoui, Sofian; Marouani, Houda; Roisnel, Thierry; Dhaouadi, Hassouna

    2014-01-01

    The asymmetric unit of the title salt [systematic name: 2-(3,4-di­hydroxy­phen­yl)ethanaminium nitrate], C8H12NO2 +·NO3 −, contains two independent cations and two independent nitrate anions. The crystal structure consists of discrete nitrate ions stacked in layers parallel to (010). These layers are linked via the dopaminium cations by O—H⋯O, N—H⋯O and weak C—H⋯O hydrogen bonds, forming a three-dimensional supra­molecular network. PMID:24860376

  4. Extraction of selected transplutonium(III) and lanthanide(III) ions by dihexyl-N,N-diethylcarbamoylmethylphosphonate from aqueous nitrate media

    SciTech Connect

    Horwitz, E.P.; Muscatello, A.C.; Kalina, D.G.; Kaplan, L.

    1981-05-01

    The extraction behavior of selected transplutonium(III) and lanthanide(III) ions from nitrate solution was studied using relatively pure dihexyl-N,N-diethylcarbamoylmethylphosphonate (DHDECMP). The data obtained for Am(III) and Eu(III) using DHDECMP were compared with analogous measurements obtained with dibutyl butylphosphonate (DB(BP)) and in certain cases with dihexyl-N,N-diethylcarbamoylethylphosphonate (DHDECEP). It was found that both the nitrate and extractant concentration dependencies were third power. The K/sub d/'s for Am(III) and for Eu(III) measured from low acid LiNO/sub 3/ solutions were similar for DHDECMP, DHDECEP, and DB(BP), thus giving no evidence for any significant chelation effect for DHDECMP. Significant differences among DHDECMP, DHDECEP, and DB(BP) are found for the extraction of Am(III) and Eu(III) from 1 to 5 M HNO/sub 3/. These differences are explained by the ability of DHDECMP (and to a lesser extent, DHDECEP) to buffer itself against HNO/sub 3/ by protonation of the amide group. The K/sub d/'s for Am(III) through Fm(III) and for La(III) through Lu(III) measured from LiNO/sub 3/ and HNO/sub 3/ using DHDECMP show a definite tetrad effect when plotted as a function of Z. The K/sub d/'s for the lanthanides generally decrease with Z whereas the K/sub d/'s for the transplutonium elements change very little with Z.

  5. Evaluation of nitrate destruction methods

    SciTech Connect

    Taylor, P.A.; Kurath, D.E.; Guenther, R.

    1993-03-30

    A wide variety of high nitrate-concentration aqueous mixed [radioactive and Resource Conservation and Recovery Act (RCRA) hazardous] wastes are stored at various US Department of Energy (DOE) facilities. These wastes will ultimately be solidified for final disposal, although the waste acceptance criteria for the final waste form is still being determined. Because the nitrates in the wastes will normally increase the volume or reduce the integrity of all of the waste forms under consideration for final disposal, nitrate destruction before solidification of the waste will generally be beneficial. This report describes and evaluates various technologies that could be used to destroy the nitrates in the stored wastes. This work was funded by the Department of Energy`s Office of Technology Development, through the Chemical/Physical Technology Support Group of the Mixed Waste Integrated Program. All the nitrate destruction technologies will require further development work before a facility could be designed and built to treat the majority of the stored wastes. Several of the technologies have particularly attractive features: the nitrate to ammonia and ceramic (NAC) process produces an insoluble waste form with a significant volume reduction, electrochemical reduction destroys nitrates without any chemical addition, and the hydrothermal process can simultaneously treat nitrates and organics in both acidic and alkaline wastes. These three technologies have been tested using lab-scale equipment and surrogate solutions. At their current state of development, it is not possible to predict which process will be the most beneficial for a particular waste stream.

  6. PRODUCTION OF PLUTONIUM METAL

    DOEpatents

    Lyon, W.L.; Moore, R.H.

    1961-01-17

    A process is given for producing plutonium metal by the reduction of plutonium chloride, dissolved in alkali metal chloride plus or minus aluminum chloride, with magnesium or a magnesium-aluminum alloy at between 700 and 800 deg C and separating the plutonium or plutonium-aluminum alloy formed from the salt.

  7. Processing of Non-PFP Plutonium Oxide in Hanford Plants

    SciTech Connect

    Jones, Susan A.; Delegard, Calvin H.

    2011-03-10

    Processing of non-irradiated plutonium oxide, PuO2, scrap for recovery of plutonium values occurred routinely at Hanford’s Plutonium Finishing Plant (PFP) in glovebox line operations. Plutonium oxide is difficult to dissolve, particularly if it has been high-fired; i.e., calcined to temperatures above about 400°C and much of it was. Dissolution of the PuO2 in the scrap typically was performed in PFP’s Miscellaneous Treatment line using nitric acid (HNO3) containing some source of fluoride ion, F-, such as hydrofluoric acid (HF), sodium fluoride (NaF), or calcium fluoride (CaF2). The HNO3 concentration generally was 6 M or higher whereas the fluoride concentration was ~0.5 M or lower. At higher fluoride concentrations, plutonium fluoride (PuF4) would precipitate, thus limiting the plutonium dissolution. Some plutonium-bearing scrap also contained PuF4 and thus required no added fluoride. Once the plutonium scrap was dissolved, the excess fluoride was complexed with aluminum ion, Al3+, added as aluminum nitrate, Al(NO3)3•9H2O, to limit collateral damage to the process equipment by the corrosive fluoride. Aluminum nitrate also was added in low quantities in processing PuF4.

  8. IMPROVED PROCESS OF PLUTONIUM CARRIER PRECIPITATION

    DOEpatents

    Faris, B.F.

    1959-06-30

    This patent relates to an improvement in the bismuth phosphate process for separating and recovering plutonium from neutron irradiated uranium, resulting in improved decontamination even without the use of scavenging precipitates in the by-product precipitation step and subsequently more complete recovery of the plutonium in the product precipitation step. This improvement is achieved by addition of fluomolybdic acid, or a water soluble fluomolybdate, such as the ammonium, sodium, or potassium salt thereof, to the aqueous nitric acid solution containing tetravalent plutonium ions and contaminating fission products, so as to establish a fluomolybdate ion concentration of about 0.05 M. The solution is then treated to form the bismuth phosphate plutonium carrying precipitate.

  9. STRIPPING PROCESS FOR PLUTONIUM

    DOEpatents

    Kolodney, M.

    1959-10-01

    A method for removing silver, nickel, cadmium, zinc, and indium coatings from plutonium objects while simultaneously rendering the plutonium object passive is described. The coated plutonium object is immersed as the anode in an electrolyte in which the plutonium is passive and the coating metal is not passive, using as a cathode a metal which does not dissolve rapidly in the electrolyte. and passing an electrical current through the electrolyte until the coating metal is removed from the plutonium body.

  10. Recovery of Plutonium by Carrier Precipitation

    DOEpatents

    Goeckermann, R. H.

    1961-04-01

    The recovery of plutonium from an aqueous nitric acid Zr-containing solution of 0.2 to 1N acidity is accomplished by adding fluoride anions (1.5 to 5 mg/l), and precipitating the Pu with an excess of H/sub 2/0/sub 2/ at 53 to 65 deg C. (AEC)

  11. Mechanistic Features of the TiO2 Heterogeneous Photocatalysis of Arsenic and Uranyl Nitrate in Aqueous Suspensions Studied by the Stopped-Flow Technique.

    PubMed

    Meichtry, Jorge M; Levy, Ivana K; Mohamed, Hanan H; Dillert, Ralf; Bahnemann, Detlef W; Litter, Marta I

    2016-03-16

    The dynamics of the transfer of electrons stored in TiO2 nanoparticles to As(III) , As(V) , and uranyl nitrate in water was investigated by using the stopped-flow technique. Suspensions of TiO2 nanoparticles with stored trapped electrons (etrap (-) ) were mixed with solutions of acceptor species to evaluate the reactivity by following the temporal evolution of etrap (-) by the decrease in the absorbance at λ=600 nm. The results indicate that As(V) and As(III) cannot be reduced by etrap (-) under the reaction conditions. In addition, it was observed that the presence of As(V) and As(III) strongly modified the reaction rate between O2 and etrap (-) : an increase in the rate was observed if As(V) was present and a decrease in the rate was observed in the presence of As(III) . In contrast with the As system, U(VI) was observed to react easily with etrap (-) and U(IV) formation was observed spectroscopically at λ=650 nm. The possible competence of U(VI) and NO3 (-) for their reduction by etrap (-) was analyzed. The inhibition of the U(VI) photocatalytic reduction by O2 could be attributed to the fast oxidation of U(V) and/or U(IV) . PMID:26710930

  12. Anion Recognition Triggered Nanoribbon-Like Self-Assembly: A Fluorescent Chemosensor for Nitrate in Acidic Aqueous Solution and Living Cells.

    PubMed

    Yang, Yaping; Chen, Shiyan; Ni, Xin-Long

    2015-07-21

    A water-soluble π-conjugated bispyridinium phenylenevinylene-based fluorogenic probe has been developed as a novel fluorescent chemosensor for highly selective, sensitive, and rapid detection of NO3(-) anion in acidic aqueous media. This system self-assembles to a nanoribbon as a result of ionic interaction. The positively charged chemosensor generates a nearly instantaneous significant fluorescence signal (475 vs 605 nm) in response to NO3(-) in the green/yellow spectral region, with a large Stokes shift (130 nm). The fluorescence changes can be attributed to the self-aggregation of the sensor triggered by ionic interaction, which occurs as a consequence of the subtle cooperation of electrostatic ionic bonding, van der Waals forces, and π-stacking of the π-conjugated aromatic moieties. Importantly, this chemosensor has been employed for the first time for the fluorescence detection of intracellular NO3(-) anion in cultured cells. PMID:26084357

  13. FLAME DENITRATION AND REDUCTION OF URANIUM NITRATE TO URANIUM DIOXIDE

    DOEpatents

    Hedley, W.H.; Roehrs, R.J.; Henderson, C.M.

    1962-06-26

    A process is given for converting uranyl nitrate solution to uranium dioxide. The process comprises spraying fine droplets of aqueous uranyl nitrate solution into a hightemperature hydrocarbon flame, said flame being deficient in oxygen approximately 30%, retaining the feed in the flame for a sufficient length of time to reduce the nitrate to the dioxide, and recovering uranium dioxide. (AEC)

  14. PRECIPITATION METHOD OF SEPARATING PLUTONIUM FROM CONTAMINATING ELEMENTS

    DOEpatents

    Sutton, J.B.

    1958-02-18

    This patent relates to an improved method for the decontamination of plutonium. The process consists broadly in an improvement in a method for recovering plutonium from radioactive uranium fission products in aqueous solutions by decontamination steps including byproduct carrier precipitation comprising the step of introducing a preformed aqueous slurry of a hydroxide of a metal of group IV B into any aqueous acidic solution which contains the plutonium in the hexavalent state, radioactive uranium fission products contaminant and a by-product carrier precipitate and separating the metal hydroxide and by-product precipitate from the solution. The process of this invention is especially useful in the separation of plutonium from radioactive zirconium and columbium fission products.

  15. PROCESS OF SEPARATING URANIUM FROM AQUEOUS SOLUTION BY SOLVENT EXTRACTION

    DOEpatents

    Warf, J.C.

    1958-08-19

    A process is described for separating uranium values from aqueous uranyl nitrate solutions. The process consists in contacting the uramium bearing solution with an organic solvent, tributyl phosphate, preferably diluted with a less viscous organic liquida whereby the uranyl nitrate is extracted into the organic solvent phase. The uranvl nitrate may be recovered from the solvent phase bv back extracting with an aqueous mediuin.

  16. Method for aqueous radioactive waste treatment

    DOEpatents

    Bray, Lane A.; Burger, Leland L.

    1994-01-01

    Plutonium, strontium, and cesium found in aqueous waste solutions resulting from nuclear fuel processing are removed by contacting the waste solutions with synthetic zeolite incorporating up to about 5 wt % titanium as sodium titanate in an ion exchange system. More than 99.9% of the plutonium, strontium, and cesium are removed from the waste solutions.

  17. Method for aqueous radioactive waste treatment

    DOEpatents

    Bray, L.A.; Burger, L.L.

    1994-03-29

    Plutonium, strontium, and cesium found in aqueous waste solutions resulting from nuclear fuel processing are removed by contacting the waste solutions with synthetic zeolite incorporating up to about 5 wt % titanium as sodium titanate in an ion exchange system. More than 99.9% of the plutonium, strontium, and cesium are removed from the waste solutions. 3 figures.

  18. Method for dissolving delta-phase plutonium

    DOEpatents

    Karraker, David G.

    1992-01-01

    A process for dissolving plutonium, and in particular, delta-phase plutonium. The process includes heating a mixture of nitric acid, hydroxylammonium nitrate (HAN) and potassium fluoride to a temperature between 40.degree. and 70.degree. C., then immersing the metal in the mixture. Preferably, the nitric acid has a concentration of not more than 2M, the HAN approximately 0.66M, and the potassium fluoride 0.1M. Additionally, a small amount of sulfamic acid, such as 0.1M can be added to assure stability of the HAN in the presence of nitric acid. The oxide layer that forms on plutonium metal may be removed with a non-oxidizing acid as a pre-treatment step.

  19. Extraction of lanthanide(III) and yttrium nitrates by trialkylmethylammonium nitrate from multicomponent solutions

    SciTech Connect

    Pyartman, A.K.; Kopyrin, A.A.; Puzikov, E.A.

    1995-07-01

    The extraction of lanthanide(III) and yttrium nitrates from multicomponent solutions by trialkylmethylammonium nitrate at 298.15 K and pH 2 is examined. Physicochemical and mathematical models describing the distributions of lanthanide(III) (Pr-Lu) and Y in multicomponent solutions as a function of the total metal concentration in the aqueous phase and concentrate composition are presented.

  20. PREPARATION OF PLUTONIUM TRIFLUORIDE

    DOEpatents

    Burger, L.L.; Roake, W.E.

    1961-07-11

    A process of producing plutonium trifluoride by reacting dry plutonium(IV) oxalate with chlorofluorinated methane or ethane at 400 to 450 deg C and cooling the product in the absence of oxygen is described.

  1. METHOD OF SEPARATING PLUTONIUM

    DOEpatents

    Brown, H.S.; Hill, O.F.

    1958-02-01

    Plutonium hexafluoride is a satisfactory fluorinating agent and may be reacted with various materials capable of forming fluorides, such as copper, iron, zinc, etc., with consequent formation of the metal fluoride and reduction of the plutonium to the form of a lower fluoride. In accordance with the present invention, it has been found that the reactivity of plutonium hexafluoride with other fluoridizable materials is so great that the process may be used as a method of separating plutonium from mixures containing plutonium hexafluoride and other vaporized fluorides even though the plutonium is present in but minute quantities. This process may be carried out by treating a mixture of fluoride vapors comprising plutonium hexafluoride and fluoride of uranium to selectively reduce the plutonium hexafluoride and convert it to a less volatile fluoride, and then recovering said less volatile fluoride from the vapor by condensation.

  2. 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.

  3. 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.

  4. PLUTONIUM-THORIUM ALLOYS

    DOEpatents

    Schonfeld, F.W.

    1959-09-15

    New plutonium-base binary alloys useful as liquid reactor fuel are described. The alloys consist of 50 to 98 at.% thorium with the remainder plutonium. The stated advantages of these alloys over unalloyed plutonium for reactor fuel use are easy fabrication, phase stability, and the accompanying advantuge of providing a means for converting Th/sup 232/ into U/sup 233/.

  5. PLUTONIUM-239 AND AMERICIUM-241 UPTAKE BY PLANTS FROM SOIL

    EPA Science Inventory

    Alfalfa was grown in soil contaminated with plutonium-239 dioxide (239PuO2) at a concentration of 29.7 nanocuries per gram (nCi/g). In addition to alfalfa, radishes, wheat, rye, and tomatoes were grown in soils contaminated with americium-241 nitrate (241Am(NO3)3) at a concentrat...

  6. BASIC PEROXIDE PRECIPITATION METHOD OF SEPARATING PLUTONIUM FROM CONTAMINANTS

    DOEpatents

    Seaborg, G.T.; Perlman, I.

    1959-02-10

    A process is described for the separation from each other of uranyl values, tetravalent plutonium values and fission products contained in an aqueous acidic solution. First the pH of the solution is adjusted to between 2.5 and 8 and hydrogen peroxide is then added to the solution causing precipitation of uranium peroxide which carries any plutonium values present, while the fission products remain in solution. Separation of the uranium and plutonium values is then effected by dissolving the peroxide precipitate in an acidic solution and incorporating a second carrier precipitate, selective for plutonium. The plutonium values are thus carried from the solution while the uranium remains flissolved. The second carrier precipitate may be selected from among the group consisting of rare earth fluorides, and oxalates, zirconium phosphate, and bismuth lihosphate.

  7. History and stabilization of the Plutonium Finishing Plant (PFP) complex, Hanford Site

    SciTech Connect

    Gerber, M.S., Fluor Daniel Hanford

    1997-02-18

    The 231-Z Isolation Building or Plutonium Metallurgy Building is located in the Hanford Site`s 200 West Area, approximately 300 yards north of the Plutonium Finishing Plant (PFP) (234-5 Building). When the Hanford Engineer Works (HEW) built it in 1944 to contain the final step for processing plutonium, it was called the Isolation Building. At that time, HEW used a bismuth phosphate radiochemical separations process to make `AT solution,` which was then dried and shipped to Los Alamos, New Mexico. (AT solution is a code name used during World War II for the final HEW product.) The process was carried out first in T Plant and the 224-T Bulk Reduction Building and B Plant and the 224-B Bulk Reduction Building. The 224-T and -B processes produced a concentrated plutonium nitrate stream, which then was sent in 8-gallon batches to the 231-Z Building for final purification. In the 231-Z Building, the plutonium nitrate solution underwent peroxide `strikes` (additions of hydrogen peroxide to further separate the plutonium from its carrier solutions), to form the AT solution. The AT solution was dried and shipped to the Los Alamos Site, where it was made into metallic plutonium and then into weapons hemispheres.` The 231-Z Building began `hot` operations (operations using radioactive materials) with regular runs of plutonium nitrate on January 16, 1945.

  8. METHOD OF SEPARATING PLUTONIUM FROM LANTHANUM FLUORIDE CARRIER

    DOEpatents

    Watt, G.W.; Goeckermann, R.H.

    1958-06-10

    An improvement in oxidation-reduction type methods of separating plutoniunn from elements associated with it in a neutron-irradiated uranium solution is described. The method relates to the separating of plutonium from lanthanum ions in an aqueous 0.5 to 2.5 N nitric acid solution by 'treating the solution, at room temperature, with ammonium sulfite in an amount sufficient to reduce the hexavalent plutonium present to a lower valence state, and then treating the solution with H/sub 2/O/sub 2/ thereby forming a tetravalent plutonium peroxide precipitate.

  9. PLUTONIUM-ZIRCONIUM ALLOYS

    DOEpatents

    Schonfeld, F.W.; Waber, J.T.

    1960-08-30

    A series of nuclear reactor fuel alloys consisting of from about 5 to about 50 at.% zirconium (or higher zirconium alloys such as Zircaloy), balance plutonium, and having the structural composition of a plutonium are described. Zirconium is a satisfactory diluent because it alloys readily with plutonium and has desirable nuclear properties. Additional advantages are corrosion resistance, excellent fabrication propenties, an isotropie structure, and initial softness.

  10. PREPARATION OF PLUTONIUM HALIDES

    DOEpatents

    Davidson, N.R.; Katz, J.J.

    1958-11-01

    A process ls presented for the preparation of plutonium trihalides. Plutonium oxide or a compound which may be readily converted to plutonlum oxide, for example, a plutonium hydroxide or plutonlum oxalate is contacted with a suitable halogenating agent. Speciflc agents mentioned are carbon tetrachloride, carbon tetrabromide, sulfur dioxide, and phosphorus pentachloride. The reaction is carried out under superatmospberic pressure at about 300 icient laborato C.

  11. Trawsfynydd Plutonium Estimate

    SciTech Connect

    Reid, Bruce D.; Gerlach, David C.; Heasler, Patrick G.; Livingston, J.

    2009-11-20

    Report serves to document an estimate of the cumulative plutonium production of the Trawsfynydd Unit II reactor (Traws II) over its operating life made using the Graphite Isotope Ratio Method (GIRM). The estimate of the plutonium production in Traws II provided in this report has been generated under blind conditions. In other words, the estimate ofthe Traws II plutonium production has been generated without the knowledge of the plutonium production declared by the reactor operator (Nuclear Electric). The objective of this report is to demonstrate that the GIRM can be employed to serve as an accurate tool to verify weapons materials production declarations.

  12. PREPARATION OF PLUTONIUM

    DOEpatents

    Kolodney, M.

    1959-07-01

    Methods are presented for the electro-deposition of plutonium from fused mixtures of plutonium halides and halides of the alkali metals and alkaline earth metals. Th salts, preferably chlorides and with the plutonium prefer ably in the trivalent state, are placed in a refractory crucible such as tantalum or molybdenam and heated in a non-oxidizing atmosphere to 600 to 850 deg C, the higher temperatatures being used to obtain massive plutonium and the lower for the powder form. Electrodes of graphite or non reactive refractory metals are used, the crucible serving the cathode in one apparatus described in the patent.

  13. Use of Gadolinium as a Primary Criticality Control in Disposing Waste Containing Plutonium at SRS

    SciTech Connect

    Andrew, Vincent

    2005-01-04

    Use of gadolinium as a neutron poison has been proposed for disposing of several metric tons of excess plutonium at the Savannah River Site (SRS). The plutonium will first be dissolved in nitric acid in small batches. Gadolinium nitrate will then be added to the plutonium nitrate solution. The Gd-poisoned plutonium solution will be neutralized and transferred to large under-ground tanks. The pH of small batches of neutralized plutonium solution will be adjusted prior to addition of the glass frit for eventual production as glass logs. The use of gadolinium as the neutron poison would minimize the number of glass logs generated from this disposition. The primary criticality safety concerns regarding the disposal process are: (1) maintaining neutron moderation under all processing conditions since gadolinium has a very large absorption cross section for thermal neutrons, (2) characteristics of plutonium and gadolinium precipitation during the neutralization process, (3) mixing characteristics of the precipitate to ensure that plutonium would remain homogeneously mixed with gadolinium, and (4) potential separation of plutonium and gadolinium during nitric and formic acids addition. A number of experiments were conducted at the Savannah River National Laboratory to study the behavior of plutonium and gadolinium at various stages of the disposition process.

  14. SEPARATION OF FISSION PRODUCT VALUES FROM THE HEXAVALENT PLUTONIUM BY CARRIER PRECIPITATION

    DOEpatents

    Davies, T.H.

    1959-12-15

    An improved precipitation of fission products on bismuth phosphate from an aqueous mineral acid solution also containing hexavalent plutonium by incorporating, prior to bismuth phosphate precipitation, from 0.05 to 2.5 grams/ liter of zirconium phosphate, niobium oxide. and/or lanthanum fluoride is described. The plutonium remains in solution.

  15. Evaluation of the Magnesium Hydroxide Treatment Process for Stabilizing PFP Plutonium/Nitric Acid Solutions

    SciTech Connect

    Gerber, Mark A.; Schmidt, Andrew J.; Delegard, Calvin H.; Silvers, Kurt L.; Baker, Aaron B.; Gano, Susan R.; Thornton, Brenda M.

    2000-09-28

    This document summarizes an evaluation of the magnesium hydroxide [Mg(OH)2] process to be used at the Hanford Plutonium Finishing Plant (PFP) for stabilizing plutonium/nitric acid solutions to meet the goal of stabilizing the plutonium in an oxide form suitable for storage under DOE-STD-3013-99. During the treatment process, nitric acid solutions bearing plutonium nitrate are neutralized with Mg(OH)2 in an air sparge reactor. The resulting slurry, containing plutonium hydroxide, is filtered and calcined. The process evaluation included a literature review and extensive laboratory- and bench-scale testing. The testing was conducted using cerium as a surrogate for plutonium to identify and quantify the effects of key processing variables on processing time (primarily neutralization and filtration time) and calcined product properties.

  16. Evaluation of nitrate and nitrite destruction/separation technologies

    SciTech Connect

    Hobbs, D.T.

    1997-08-29

    This report describes and evaluates four types of nitrate and nitrite destruction and separation technologies that could be used to treat the aqueous, alkaline, nitrate-bearing mixed waste that is generated by the In-Tank Precipitation (ITP) process at the Savannah River Site (SRS). The technologies considered in this report include thermal, hydrothermal, chemical, and electrochemical technologies.

  17. Method for improved decomposition of metal nitrate solutions

    DOEpatents

    Haas, Paul A.; Stines, William B.

    1983-10-11

    A method for co-conversion of aqueous solutions of one or more heavy metal nitrates wherein thermal decomposition within a temperature range of about 300.degree. to 800.degree. C. is carried out in the presence of about 50 to 500% molar concentration of ammonium nitrate to total metal.

  18. Method for improved decomposition of metal nitrate solutions

    DOEpatents

    Haas, P.A.; Stines, W.B.

    1981-01-21

    A method for co-conversion of aqueous solutions of one or more heavy metal nitrates is described, wherein thermal decomposition within a temperature range of about 300 to 800/sup 0/C is carried out in the presence of about 50 to 500% molar concentration of ammonium nitrate to total metal.

  19. DELTA PHASE PLUTONIUM ALLOYS

    DOEpatents

    Cramer, E.M.; Ellinger, F.H.; Land. C.C.

    1960-03-22

    Delta-phase plutonium alloys were developed suitable for use as reactor fuels. The alloys consist of from 1 to 4 at.% zinc and the balance plutonium. The alloys have good neutronic, corrosion, and fabrication characteristics snd possess good dimensional characteristics throughout an operating temperature range from 300 to 490 deg C.

  20. Electrodeposition of Plutonium

    SciTech Connect

    Kelley, H.M.

    2002-10-30

    Equipment for electrolytic deposition of plutonium from molten salt solutions was designed and built and was tested with cerium as a stand-in for plutonium. The electrolysis cell is a graphite crucible that serves as the anode; the cathode is a molybdenum rod. This paper discusses results of that test.

  1. PLUTONIUM-CERIUM ALLOY

    DOEpatents

    Coffinberry, A.S.

    1959-01-01

    An alloy is presented for use as a reactor fuel. The binary alloy consists essentially of from about 5 to 90 atomic per cent cerium and the balance being plutonium. A complete phase diagram for the cerium--plutonium system is given.

  2. Adsorption and diffusion of plutonium in soil

    SciTech Connect

    Brown, D A

    1980-01-01

    The behavior of plutonium (Pu) was studied in three soils that varied in texture, CEC, pH, organic matter content and mineralogy (Fuquay, Muscatine, Burbank). Two isotopes, /sup 238/Pu and /sup 239/Pu, were used in order to detect Pu over a range of several orders of magnitude. Unless added in a chelated form, Pu was added to the soil as a nitrate in .01 N HNO/sub 3/ to simulate the release of acidic waste on the soil and to prevent rapid Pu hydrolysis or polymerization.

  3. Plutonium Finishing Plant (PFP) Final Safety Analysis Report (FSAR) [SEC 1 THRU 11

    SciTech Connect

    ULLAH, M K

    2001-02-26

    The Plutonium Finishing Plant (PFP) is located on the US Department of Energy (DOE) Hanford Site in south central Washington State. The DOE Richland Operations (DOE-RL) Project Hanford Management Contract (PHMC) is with Fluor Hanford Inc. (FH). Westinghouse Safety Management Systems (WSMS) provides management support to the PFP facility. Since 1991, the mission of the PFP has changed from plutonium material processing to preparation for decontamination and decommissioning (D and D). The PFP is in transition between its previous mission and the proposed D and D mission. The objective of the transition is to place the facility into a stable state for long-term storage of plutonium materials before final disposition of the facility. Accordingly, this update of the Final Safety Analysis Report (FSAR) reflects the current status of the buildings, equipment, and operations during this transition. The primary product of the PFP was plutonium metal in the form of 2.2-kg, cylindrical ingots called buttoms. Plutonium nitrate was one of several chemical compounds containing plutonium that were produced as an intermediate processing product. Plutonium recovery was performed at the Plutonium Reclamation Facility (PRF) and plutonium conversion (from a nitrate form to a metal form) was performed at the Remote Mechanical C (RMC) Line as the primary processes. Plutonium oxide was also produced at the Remote Mechanical A (RMA) Line. Plutonium processed at the PFP contained both weapons-grade and fuels-grade plutonium materials. The capability existed to process both weapons-grade and fuels-grade material through the PRF and only weapons-grade material through the RMC Line although fuels-grade material was processed through the line before 1984. Amounts of these materials exist in storage throughout the facility in various residual forms left from previous years of operations.

  4. 31. VIEW OF A WORKER HOLDING A PLUTONIUM 'BUTTON.' PLUTONIUM, ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    31. VIEW OF A WORKER HOLDING A PLUTONIUM 'BUTTON.' PLUTONIUM, A MAN-MADE SUBSTANCE, WAS RARE. SCRAPS RESULTING FROM PRODUCTION AND PLUTONIUM RECOVERED FROM RETIRED NUCLEAR WEAPONS WERE REPROCESSED INTO VALUABLE PURE-PLUTONIUM METAL (9/19/73). - Rocky Flats Plant, Bounded by Indiana Street & Routes 93, 128 & 72, Golden, Jefferson County, CO

  5. PLUTONIUM-CERIUM-COBALT AND PLUTONIUM-CERIUM-NICKEL ALLOYS

    DOEpatents

    Coffinberry, A.S.

    1959-08-25

    >New plutonium-base teroary alloys useful as liquid reactor fuels are described. The alloys consist of 10 to 20 atomic percent cobalt with the remainder plutonium and cerium in any desired proportion, with the plutonium not in excess of 88 atomic percent; or, of from 10 to 25 atomic percent nickel (or mixture of nickel and cobalt) with the remainder plutonium and cerium in any desired proportion, with the plutonium not in excess of 86 atomic percent. The stated advantages of these alloys over unalloyed plutonium for reactor fuel use are a lower melting point and a wide range of permissible plutonium dilution.

  6. Effects of various moderators on the critical mass of plutonium

    SciTech Connect

    Doherty, A.L.

    1986-01-01

    The fissile material storage tanks in the Hanford Plutonium Critical Mass Laboratory (CML) in Richland, Washington, are presently being upgraded. During the design and planning phase of this modification, criticality analysis was necessary to compare potential moderator/absorber materials used as isolators between tanks. A parameter study was performed to assist in determining the appropriate moderator material to be used in the plutonium nitrate storage tank system in the mix room at the CML. Four moderator/absorber materials were identified as providing adequate isolation between the tanks.

  7. Method for dissolving plutonium dioxide

    DOEpatents

    Tallent, Othar K.

    1978-01-01

    The fluoride-catalyzed, non-oxidative dissolution of plutonium dioxide in HNO.sub.3 is significantly enhanced in rate by oxidizing dissolved plutonium ions. It is believed that the oxidation of dissolved plutonium releases fluoride ions from a soluble plutonium-fluoride complex for further catalytic action.

  8. PLUTONIUM PURIFICATION PROCESS EMPLOYING THORIUM PYROPHOSPHATE CARRIER

    DOEpatents

    King, E.L.

    1959-04-28

    The separation and purification of plutonium from the radioactive elements of lower atomic weight is described. The process of this invention comprises forming a 0.5 to 2 M aqueous acidffc solution containing plutonium fons in the tetravalent state and elements with which it is normally contaminated in neutron irradiated uranium, treating the solution with a double thorium compound and a soluble pyrophosphate compound (Na/sub 4/P/sub 2/O/sub 7/) whereby a carrier precipitate of thorium A method is presented of reducing neptunium and - trite is advantageous since it destroys any hydrazine f so that they can be removed from solutions in which they are contained is described. In the carrier precipitation process for the separation of plutonium from uranium and fission products including zirconium and columbium, the precipitated blsmuth phosphate carries some zirconium, columbium, and uranium impurities. According to the invention such impurities can be complexed and removed by dissolving the contaminated carrier precipitate in 10M nitric acid, followed by addition of fluosilicic acid to about 1M, diluting the solution to about 1M in nitric acid, and then adding phosphoric acid to re-precipitate bismuth phosphate carrying plutonium.

  9. SEPARATION OF PLUTONIUM FROM FISSION PRODUCTS BY A COLLOID REMOVAL PROCESS

    DOEpatents

    Schubert, J.

    1960-05-24

    A method is given for separating plutonium from uranium fission products. An acidic aqueous solution containing plutonium and uranium fission products is subjected to a process for separating ionic values from colloidal matter suspended therein while the pH of the solution is maintained between 0 and 4. Certain of the fission products, and in particular, zirconium, niobium, lanthanum, and barium are in a colloidal state within this pH range, while plutonium remains in an ionic form, Dialysis, ultracontrifugation, and ultrafiltration are suitable methods of separating plutonium ions from the colloids.

  10. METHOD OF SEPARATING TETRAVALENT PLUTONIUM VALUES FROM CERIUM SUB-GROUP RARE EARTH VALUES

    DOEpatents

    Duffield, R.B.; Stoughton, R.W.

    1959-02-01

    A method is presented for separating plutonium from the cerium sub-group of rare earths when both are present in an aqueous solution. The method consists in adding an excess of alkali metal carbonate to the solution, which causes the formation of a soluble plutonium carbonate precipitate and at the same time forms an insoluble cerium-group rare earth carbonate. The pH value must be adjusted to bctween 5.5 and 7.5, and prior to the precipitation step the plutonium must be reduced to the tetravalent state since only tetravalent plutonium will form the soluble carbonate complex.

  11. Plutonium radiation surrogate

    DOEpatents

    Frank, Michael I.

    2010-02-02

    A self-contained source of gamma-ray and neutron radiation suitable for use as a radiation surrogate for weapons-grade plutonium is described. The source generates a radiation spectrum similar to that of weapons-grade plutonium at 5% energy resolution between 59 and 2614 keV, but contains no special nuclear material and emits little .alpha.-particle radiation. The weapons-grade plutonium radiation surrogate also emits neutrons having fluxes commensurate with the gamma-radiation intensities employed.

  12. PLUTONIUM ELECTROREFINING CELLS

    DOEpatents

    Mullins, L.J. Jr.; Leary, J.A.; Bjorklund, C.W.; Maraman, W.J.

    1963-07-16

    Electrorefining cells for obtaining 99.98% plutonium are described. The cells consist of an impure liquid plutonium anode, a molten PuCl/sub 3/-- alkali or alkaline earth metal chloanode, a molten PuCl/sub 3/-alkali or alkaline earth metal chloride electrolyte, and a nonreactive cathode, all being contained in nonreactive ceramic containers which separate anode from cathode by a short distance and define a gap for the collection of the purified liquid plutonium deposited on the cathode. Important features of these cells are the addition of stirrer blades on the anode lead and a large cathode surface to insure a low current density. (AEC)

  13. Plutonium Vulnerability Management Plan

    SciTech Connect

    1995-03-01

    This Plutonium Vulnerability Management Plan describes the Department of Energy`s response to the vulnerabilities identified in the Plutonium Working Group Report which are a result of the cessation of nuclear weapons production. The responses contained in this document are only part of an overall, coordinated approach designed to enable the Department to accelerate conversion of all nuclear materials, including plutonium, to forms suitable for safe, interim storage. The overall actions being taken are discussed in detail in the Department`s Implementation Plan in response to the Defense Nuclear Facilities Safety Board (DNFSB) Recommendation 94-1. This is included as Attachment B.

  14. Ultra-small plutonium oxide nanocrystals: an innovative material in plutonium science.

    PubMed

    Hudry, Damien; Apostolidis, Christos; Walter, Olaf; Janssen, Arne; Manara, Dario; Griveau, Jean-Christophe; Colineau, Eric; Vitova, Tonya; Prüssmann, Tim; Wang, Di; Kübel, Christian; Meyer, Daniel

    2014-08-11

    Apart from its technological importance, plutonium (Pu) is also one of the most intriguing elements because of its non-conventional physical properties and fascinating chemistry. Those fundamental aspects are particularly interesting when dealing with the challenging study of plutonium-based nanomaterials. Here we show that ultra-small (3.2±0.9 nm) and highly crystalline plutonium oxide (PuO2 ) nanocrystals (NCs) can be synthesized by the thermal decomposition of plutonyl nitrate ([PuO2 (NO3 )2 ]⋅3 H2 O) in a highly coordinating organic medium. This is the first example reporting on the preparation of significant quantities (several tens of milligrams) of PuO2 NCs, in a controllable and reproducible manner. The structure and magnetic properties of PuO2 NCs have been characterized by a wide variety of techniques (powder X-ray diffraction (PXRD), X-ray absorption fine structure (XAFS), X-ray absorption near edge structure (XANES), TEM, IR, Raman, UV/Vis spectroscopies, and superconducting quantum interference device (SQUID) magnetometry). The current PuO2 NCs constitute an innovative material for the study of challenging problems as diverse as the transport behavior of plutonium in the environment or size and shape effects on the physics of transuranium elements. PMID:25042621

  15. PREPARATION OF DIBASIC ALUMINUM NITRATE

    DOEpatents

    Gresky, A.T.; Nurmi, E.O.; Foster, D.L.; Wischow, R.P.; Savolainen, J.E.

    1960-04-01

    A method is given for the preparation and recovery of basic aluminum nltrates having an OH: Al ratio of at least two, comprising two steps. First, metallic aluminum is dissolved in aqueous Al(NO/sub 3/)/sub 3/, in the presence of a small quantity of elemental or ionic mercury, to increase its Al: NO/sub 3/ ratio into the range 1 to 1.2. The resulting aqueous solution is then added to an excess of a special organic solvent, typically a mixture of five parts methanol and six parts diethyl ether, whereupon the basic aluminum nitrate, e.g. Al/sub 6/(OH)/sub 13/-(NO/sub 3/)/sub 5/, recoverably precipitates.

  16. Plutonium dissolution process

    DOEpatents

    Vest, Michael A.; Fink, Samuel D.; Karraker, David G.; Moore, Edwin N.; Holcomb, H. Perry

    1996-01-01

    A two-step process for dissolving plutonium metal, which two steps can be carried out sequentially or simultaneously. Plutonium metal is exposed to a first mixture containing approximately 1.0M-1.67M sulfamic acid and 0.0025M-0.1M fluoride, the mixture having been heated to a temperature between 45.degree. C. and 70.degree. C. The mixture will dissolve a first portion of the plutonium metal but leave a portion of the plutonium in an oxide residue. Then, a mineral acid and additional fluoride are added to dissolve the residue. Alteratively, nitric acid in a concentration between approximately 0.05M and 0.067M is added to the first mixture to dissolve the residue as it is produced. Hydrogen released during the dissolution process is diluted with nitrogen.

  17. Plutonium: Requiem or reprieve

    SciTech Connect

    Pillay, K.K.S.

    1996-01-01

    Many scientific discoveries have had profound effects on humanity and its future. However, the discovery of fissionable characteristics of a man-made element, plutonium, discovered in 1941 by Glenn Seaborg and associates, has probably had the greatest impact on world affairs. Although about 20 new elements have been synthesized since 1940, element 94 unarguably had the most dramatic impact when it was introduced to the world as the core of the nuclear bomb dropped on Nagasaki. Ever since, large quantities of this element have been produced, and it has had a major role in maintaining peace during the past 50 years. in addition, the rapid spread of nuclear power technology worldwide contributed to major growth in the production of plutonium as a by-product. This article discusses the following issues related to plutonium: plutonium from Nuclear Power Generation; environmental safety and health issues; health effects; safeguards issues; extended storage; disposal options.

  18. Spectroscopy of plutonium-organic complexes

    SciTech Connect

    Richmann, M.K.; Reed, D.T.

    1995-12-31

    Information on the spectroscopy of plutonium-organic complexes is needed to help establish the speciation of these complexes under environmentally relevant conditions. Laser photoacoustic spectroscopy (LPAS) and absorption spectrometry were used to characterize the Pu(IV)-citrate and Pu(IV)-nitrilotriacetic acid (NTA) complexes at concentrations of 10{sup {minus}3}--10{sup {minus}7} M in aqueous solution. Good agreement was observed between the band shape of the LPAS and absorption spectra for the Pu(IV)-NTA complex. Agreement for the Pu(IV)-citrate complex was not quite as good. In both cases, a linear dependence of the LPAS signal on laser power and total concentration of the complexes was noted. This work is part of an ongoing research effort to study key subsurface interactions of plutonium-organic complexes.

  19. COGEMA Experience in Uranous Nitrate Preparation

    SciTech Connect

    Tison, E.; Bretault, Ph.

    2006-07-01

    Separation and purification of plutonium by PUREX process is based on a sequence of extraction and back extraction which requires reducing plutonium Pu IV (extractable form) into Pu III (inextractable form) Different reducers can be used to reduce Pu IV into Pu III. Early plants such as that for Magnox fuel at Sellafield used ferrous sulfamate while UP 1 at Marcoule used uranous sulfamate. These reducers are efficient and easy to prepare but generates ferric and/or sulphate ions and so complicates management of the wastes from the plutonium purification cycle. Recent plants such as UP3 and UP2 800 at La Hague, THORP at Sellafield, and RRP at Rokkasho Mura (currently under tests) use uranous nitrate (U IV) stabilized by hydrazinium nitrate (N{sub 2}H{sub 5}NO{sub 3}) and hydroxyl ammonium nitrate (HAN). In the French plants, uranous nitrate is used in U-Pu separation and alpha barrier and HAN is used in Pu purification. Compared to sulfamate, U IV does not generate extraneous chemical species and uranyl nitrate (U VI) generated by reducing Pu IV follows the main uranium stream. More over uranous nitrate is prepared from reprocessed purified uranyl nitrate taken at the outlet of the reprocessing plant. Hydrazine and HAN offer the advantage to be salt-free reagents. Uranous nitrate can be generated either by electrolysis or by catalytic hydrogenation process. Electrolytic process has been implemented in early plant UP 1 at Marcoule (when changing reducer from uranous sulfamate to uranous nitrate) and was used again in UP2 plant at La Hague. However, the electrolytic process presented several disadvantages such as a low conversion rate and problems associated with the use of mercury. Electrolysis cells with no mercury were developed for the Eurochemic plant in Belgium and then implemented in the first Japanese reprocessing plant in Tokai-Mura. But finally, in 1975, the electrolytic process was abandoned in favor of the catalytic hydrogenation process developed at La Hague. The yield of the operation and its simplicity were the main reasons for this choice. Nowadays, our catalytic hydrogenation process is used in all the commercial reprocessing plants worldwide: THORP at Sellafield, UP3 and UP2 800 at La Hague, and RRP at Rokkasho-Mura. In this process, uranyl nitrate is reduced to uranous nitrate by hydrogen in presence of a platinum based catalyst. Most of the plants implement the reaction in the same kind of reactor: 'co-current, up-flow and fixed-bed reactor'. For UP2 800 at La Hague, started in 1994, a new kind of reactor allowing a higher capacity has been developed. In this reactor, the catalyst bed is not fixed but circulating (fluidized bed). The aim of the paper is to describe both reactor technology implemented in La Hague (fixed bed and fluidized bed), to show their performance in terms of capacity and yield and to compare their operating and maintenance principles. (authors)

  20. Plutonium microstructures, part 1

    NASA Astrophysics Data System (ADS)

    Cramer, E. M.; Bergin, J. B.

    1981-09-01

    Illustrations of inclusions that are seen in plutonium metal as a consequence of inherent and tramp impurities, alloy additions, and thermal or mechanical treatments are presented. This part includes illustrations of nonmetallic and intermetallic inclusions characteristic of major impurity elements as an aid to identifying unknowns are included. Historical aspects of the increased purity of laboratory plutonium samples are described and the composition of the etchant solutions are given. The etching procedure used in the preparation of each illustrated sample is described.

  1. Alkali metal nitrate purification

    DOEpatents

    Fiorucci, Louis C. (Hamden, CT); Morgan, Michael J. (Guilford, CT)

    1986-02-04

    A process is disclosed for removing contaminants from impure alkali metal nitrates containing them. The process comprises heating the impure alkali metal nitrates in solution form or molten form at a temperature and for a time sufficient to effect precipitation of solid impurities and separating the solid impurities from the resulting purified alkali metal nitrates. The resulting purified alkali metal nitrates in solution form may be heated to evaporate water therefrom to produce purified molten alkali metal nitrates suitable for use as a heat transfer medium. If desired, the purified molten form may be granulated and cooled to form discrete solid particles of purified alkali metal nitrates.

  2. Low-level detection and quantification of Plutonium(III, IV, V,and VI) using a liquid core waveguide

    SciTech Connect

    Wilson, Richard E.; Hu, Yung-Jin; Nitsche, Heino

    2003-06-28

    Understanding the aqueous chemistry of plutonium, in particular in environmental conditions, is often complicated by plutonium's complex redox chemistry. Because plutonium possesses four oxidation states, all of which can coexist in solution, a reliable method for the identification of these oxidation states is needed. The identification of plutonium oxidation states at low levels in aqueous solution is often accomplished through an indirect determination using series of liquid-liquid extraction procedures using oxidation state specific reagents such as HDEHP and TTA. While these methods, coupled with radioactive counting techniques provide superior limits of detection they may influence the plutonium redox equilibrium, are time consuming, waste intensive and costly. Other analytical methods such as mass spectrometry and radioactive counting as stand alone methods provide excellent detection limits but lack the ability to discriminate between the oxidation states of the plutonium ions in solution.

  3. Enzyme catalytic nitration of aromatic compounds.

    PubMed

    Kong, Mingming; Wang, Kun; Dong, Runan; Gao, Haijun

    2015-06-01

    Nitroaromatic compounds are important intermediates in organic synthesis. The classic method used to synthesize them is chemical nitration, which involves the use of nitric acid diluted in water or acetic acid, both harmful to the environment. With the development of green chemistry, environmental friendly enzyme catalysis is increasingly employed in chemical processes. In this work, we adopted a non-aqueous horseradish peroxidase (HRP)/NaNO2/H2O2 reaction system to study the structural characteristics of aromatic compounds potentially nitrated by enzyme catalysis, as well as the relationship between the charges on carbon atoms in benzene ring and the nitro product distribution. Investigation of various reaction parameters showed that mild reaction conditions (ambient temperature and neutral pH), plus appropriate use of H2O2 and NaNO2 could prevent inactivation of HRP and polymerization of the substrates. Compared to aqueous-organic co-solvent reaction media, the aqueous-organic two-liquid phase system had great advantages in increasing the dissolved concentration of substrate and alleviating substrate inhibition. Analysis of the aromatic compounds' structural characteristics indicated that substrates containing substituents of NH2 or OH were readily catalyzed. Furthermore, analysis of the relationship between natural bond orbital (NBO) charges on carbon atoms in benzene ring, as calculated by the density functional method, and the nitro product distribution characteristics, demonstrated that the favored nitration sites were the ortho and para positions of substituents in benzene ring, similar to the selectivity of chemical nitration. PMID:26002502

  4. SEPARATION OF RUTHENIUM FROM AQUEOUS SOLUTIONS

    DOEpatents

    Beederman, M.; Vogler, S.; Hyman, H.H.

    1959-07-14

    The separation of rathenium from a rathenium containing aqueous solution is described. The separation is accomplished by adding sodium nitrite, silver nitrate and ozone to the ruthenium containing aqueous solution to form ruthenium tetroxide and ihen volatilizing off the ruthenium tetroxide.

  5. CESIUM RECOVERY FROM AQUEOUS SOLUTIONS

    DOEpatents

    Goodall, C.A.

    1960-09-13

    A process is given for precipitating cesium on zinc ferricyanide (at least 0.0004 M) from aqueous solutions containing mineral acid in a concentration of from 0.2 N acidity to 0.61 N acid-deficiency and advantageously, but not necessarily, also aluminum nitrate in a concentration of from l to 2.5 M.

  6. Tracing nitrate in watersheds

    NASA Astrophysics Data System (ADS)

    Balcerak, Ernie

    2013-05-01

    Plants need nitrogen to grow, and nitrate is a common fertilizer ingredient, but high levels of nitrate contamination in drinking water sources can cause health problems. It is generally known that nitrogen flows through watersheds from upslope areas down to streams, but the relationships between upslope soil solution or groundwater nitrate concentrations and stream water nitrate levels—and the ways in which land use changes may alter this relationship—are not fully understood.

  7. 21 CFR 181.33 - Sodium nitrate and potassium nitrate.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Sodium nitrate and potassium nitrate. 181.33... nitrate and potassium nitrate. Sodium nitrate and potassium nitrate are subject to prior sanctions issued... potassium nitrite, in the production of cured red meat products and cured poultry products....

  8. 21 CFR 181.33 - Sodium nitrate and potassium nitrate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Sodium nitrate and potassium nitrate. 181.33...-Sanctioned Food Ingredients § 181.33 Sodium nitrate and potassium nitrate. Sodium nitrate and potassium nitrate are subject to prior sanctions issued by the U.S. Department of Agriculture for use as sources...

  9. Plutonium Disposition Now!

    SciTech Connect

    Buckner, M.R.

    1995-05-24

    A means for use of existing processing facilities and reactors for plutonium disposition is described which requires a minimum capital investment and allows rapid implementation. The scenario includes interim storage and processing under IAEA control, and fabrication into MOX fuel in existing or planned facilities in Europe for use in operating reactors in the two home countries. Conceptual studies indicate that existing Westinghouse four-loop designs can safety dispose of 0.94 MT of plutonium per calendar year. Thus, it would be possible to consume the expected US excess stockpile of about 50 MT in two to three units of this type, and it is highly likely that a comparable amount of the FSU excess plutonium could be deposed of in a few VVER-1000`s. The only major capital project for this mode of plutonium disposition would be the weapons-grade plutonium processing which could be done in a dedicated international facility or using existing facilities in the US and FSU under IAEA control. This option offers the potential for quick implementation at a very low cost to the governments of the two countries.

  10. INTERCOMPARISON OF PLUTONIUM-239 MEASUREMENTS

    EPA Science Inventory

    In 1977 the U.S. Environmental Protection Agency distributed calibrated solutions of plutonium-239 to laboratories interested in participating in an intercomparison study of plutonium analysis. Participants were asked to perform a quantitative radioactivity analysis of the soluti...

  11. RECOVERY OF TETRAVALENT CATIONS FROM AQUEOUS SOLUTIONS

    DOEpatents

    Moore, R.L.

    1958-05-01

    The recovery of plutonium, zirconium, and tetravalent cerium values from aqueous solutions is described. It consists of adding an alkyl phosphate to a nnineral acid aqueous solution containing the metal to be recovered, whereby a precipitate forms with the tetravalent values, and separating the precipitate from the solution. All alkyl phosphates, if water-soluble, are suitable for the process; however, monobutyl phosphate has been found best.

  12. Evidence for a plasma-membrane-bound nitrate reductase involved in nitrate uptake of Chlorella sorokiniana

    NASA Technical Reports Server (NTRS)

    Tischner, R.; Ward, M. R.; Huffaker, R. C.

    1989-01-01

    Anti-nitrate-reductase (NR) immunoglobulin-G (IgG) fragments inhibited nitrate uptake into Chlorella cells but had no affect on nitrate uptake. Intact anti-NR serum and preimmune IgG fragments had no affect on nitrate uptake. Membrane-associated NR was detected in plasma-membrane (PM) fractions isolated by aqueous two-phase partitioning. The PM-associated NR was not removed by sonicating PM vesicles in 500 mM NaCl and 1 mM ethylenediaminetetraacetic acid and represented up to 0.8% of the total Chlorella NR activity. The PM NR was solubilized by Triton X-100 and inactivated by Chlorella NR antiserum. Plasma-membrane NR was present in ammonium-grown Chlorella cells that completely lacked soluble NR activity. The subunit sizes of the PM and soluble NRs were 60 and 95 kDa, respectively, as determined by sodium-dodecyl-sulfate electrophoresis and western blotting.

  13. METHOD OF PRODUCING PLUTONIUM TETRAFLUORIDE

    DOEpatents

    Tolley, W.B.; Smith, R.C.

    1959-12-15

    A process is presented for preparing plutonium tetrafluoride from plutonium(IV) oxalate. The oxalate is dried and decomposed at about 300 deg C to the dioxide, mixed with ammonium bifluoride, and the mixture is heated to between 50 and 150 deg C whereby ammonium plutonium fluoride is formed. The ammonium plutonium fluoride is then heated to about 300 deg C for volatilization of ammonium fluoride. Both heating steps are preferably carried out in an inert atmosphere.

  14. METHOD OF MAKING PLUTONIUM DIOXIDE

    DOEpatents

    Garner, C.S.

    1959-01-13

    A process is presented For converting both trivalent and tetravalent plutonium oxalate to substantially pure plutonium dioxide. The plutonium oxalate is carefully dried in the temperature range of 130 to300DEC by raising the temperature gnadually throughout this range. The temperature is then raised to 600 C in the period of about 0.3 of an hour and held at this level for about the same length of time to obtain the plutonium dioxide.

  15. Plutonium 239 Equivalency Calculations

    SciTech Connect

    Wen, J

    2011-05-31

    This document provides the basis for converting actual weapons grade plutonium mass to a plutonium equivalency (PuE) mass of Plutonium 239. The conversion can be accomplished by performing calculations utilizing either: (1) Isotopic conversions factors (CF{sub isotope}), or (2) 30-year-old weapons grade conversion factor (CF{sub 30 yr}) Both of these methods are provided in this document. Material mass and isotopic data are needed to calculate PuE using the isotopic conversion factors, which will provide the actual PuE value at the time of calculation. PuE is the summation of the isotopic masses times their associated isotopic conversion factors for plutonium 239. Isotopic conversion factors are calculated by a normalized equation, relative to Plutonium 239, of specific activity (SA) and cumulated dose inhalation affects based on 50-yr committed effective dose equivalent (CEDE). The isotopic conversion factors for converting weapons grade plutonium to PuE are provided in Table-1. The unit for specific activity (SA) is curies per gram (Ci/g) and the isotopic SA values come from reference [1]. The cumulated dose inhalation effect values in units of rem/Ci are based on 50-yr committed effective dose equivalent (CEDE). A person irradiated by gamma radiation outside the body will receive a dose only during the period of irradiation. However, following an intake by inhalation, some radionuclides persist in the body and irradiate the various tissues for many years. There are three groups CEDE data representing lengths of time of 0.5 (D), 50 (W) and 500 (Y) days, which are in reference [2]. The CEDE values in the (W) group demonstrates the highest dose equivalent value; therefore they are used for the calculation.

  16. Lithium metal reduction of plutonium oxide to produce plutonium metal

    DOEpatents

    Coops, Melvin S.

    1992-01-01

    A method is described for the chemical reduction of plutonium oxides to plutonium metal by the use of pure lithium metal. Lithium metal is used to reduce plutonium oxide to alpha plutonium metal (alpha-Pu). The lithium oxide by-product is reclaimed by sublimation and converted to the chloride salt, and after electrolysis, is removed as lithium metal. Zinc may be used as a solvent metal to improve thermodynamics of the reduction reaction at lower temperatures. Lithium metal reduction enables plutonium oxide reduction without the production of huge quantities of CaO--CaCl.sub.2 residues normally produced in conventional direct oxide reduction processes.

  17. Plutonium microstructures. Part 1

    SciTech Connect

    Cramer, E.M.; Bergin, J.B.

    1981-09-01

    This report is the first of three parts in which Los Alamos and Lawrence Livermore National Laboratory metallographers exhibit a consolidated set of illustrations of inclusions that are seen in plutonium metal as a consequence of inherent and tramp impurities, alloy additions, and thermal or mechanical treatments. This part includes illustrations of nonmetallic and intermetallic inclusions characteristic of major impurity elements as an aid to identifying unknowns. It also describes historical aspects of the increased purity of laboratory plutonium samples, and it gives the composition of the etchant solutions and describes the etching procedure used in the preparation of each illustrated sample. 25 figures.

  18. Plutonium-DTPA Model Application with USTUR Case 0269.

    PubMed

    Konzen, Kevin; Brey, Richard; Miller, Scott

    2016-01-01

    A plutonium-DTPA (Pu-DTPA) biokinetic model was introduced that had originated from the study of a plutonium-contaminated wound. This work evaluated the extension of the Pu-DTPA model to United States Transuranium and Uranium Registry (USTUR) Case 0269 involving an acute inhalation of a plutonium nitrate aerosol. Chelation was administered intermittently for the first 7 mo as Ca-EDTA, mostly through intravenous injection, with Ca-DTPA treatments administered approximately 2.5 y post intake. Urine and fecal bioassays were collected following intake for several years. Tissues were collected and analyzed for plutonium content approximately 38 y post intake. This work employed the Pu-DTPA model for predicting the urine and fecal bioassay and final tissue quantity at autopsy. The Pu-DTPA model was integrated with two separate plutonium systemic models (i.e., ICRP Publication 67 and its proposed modification). This work illustrated that the Pu-DTPA model was useful for predicting urine and fecal bioassay, including final tissue quantity, 38 y post intake. PMID:26606066

  19. PLUTONIUM LOADING CAPACITY OF REILLEX HPQ ANION EXCHANGE COLUMN - AFS-2 PLUTONIUM FLOWSHEET FOR MOX

    SciTech Connect

    Kyser, E.; King, W.; O'Rourke, P.

    2012-07-26

    Radioactive plutonium (Pu) anion exchange column experiments using scaled HB-Line designs were performed to investigate the dependence of column loading performance on the feed composition in the H-Canyon dissolution process for plutonium oxide (PuO{sub 2}) product shipped to the Mixed Oxide (MOX) Fuel Fabrication Facility (MFFF). These loading experiments show that a representative feed solution containing {approx}5 g Pu/L can be loaded onto Reillex{trademark} HPQ resin from solutions containing 8 M total nitrate and 0.1 M KF provided that the F is complexed with Al to an [Al]/[F] molar ratio range of 1.5-2.0. Lower concentrations of total nitrate and [Al]/[F] molar ratios may still have acceptable performance but were not tested in this study. Loading and washing Pu losses should be relatively low (<1%) for resin loading of up to 60 g Pu/L. Loading above 60 g Pu/L resin is possible, but Pu wash losses will increase such that 10-20% of the additional Pu fed may not be retained by the resin as the resin loading approaches 80 g Pu/L resin.

  20. Atomic spectrum of plutonium

    SciTech Connect

    Blaise, J.; Fred, M.; Gutmacher, R.G.

    1984-08-01

    This report contains plutonium wavelengths, energy level classifications, and other spectroscopic data accumulated over the past twenty years at Laboratoire Aime Cotton (LAC) Argonne National Laboratory (ANL), and Lawrence Livermore National Laboratory (LLNL). The primary purpose was term analysis: deriving the energy levels in terms of quantum numbers and electron configurations, and evaluating the Slater-Condon and other parameters from the levels.

  1. Plutonium: An introduction

    SciTech Connect

    Condit, R.H.

    1993-10-01

    This report is a summary of the history and properties of plutonium. It presents information on the atoms, comparing chemical and nuclear properties. It looks at the history of the atom, including its discovery and production methods. It summarizes the metallurgy and chemistry of the element. It also describes means of detecting and measuring the presence and quantity of the element.

  2. Collector for recovering gallium from weapons plutonium

    SciTech Connect

    Philip, C.V.; Anthony, R.G.; Chokkaram, S.

    1998-09-01

    Currently, the separation of gallium from weapons plutonium involves the use of aqueous processing using either solvent extraction of ion exchange. However, this process generates significant quantities of liquid radioactive wastes. A Thermally Induced Gallium Removal process, or TIGR, developed by researchers at Los Alamos National Laboratories, is a simpler alternative to aqueous processing. This research examined this process, and the behavior of gallium suboxide, a vapor that is swept away by passing hydrogen/argon over gallium trioxide/plutonium oxide heated at 1100 C during the TIGR process. Through experimental procedures, efforts were made to prevent the deposition of corrosive gallium onto furnace and vent surfaces. Experimental procedures included three options for gallium removal and collection: (1) collection of gallium suboxide through use of a cold finger; (2) collection by in situ air oxidation; and (3) collection of gallium on copper. Results conclude all three collection mechanisms are feasible. In addition, gallium trioxide exists in three crystalline forms, and each form was encountered during each experiment, and that each form will have a different reactivity.

  3. NITRATE CONVERSION OF HB-LINE REILLEXTM HPQ RESIN

    SciTech Connect

    Steimke, J.; Williams, M.; Steeper, T.; Leishear, R.

    2012-05-29

    Reillex{trademark} HPQ ion exchange resin is used by HB Line to remove plutonium from aqueous streams. Reillex{trademark} HPQ resin currently available from Vertellus Specialties LLC is a chloride ionic form, which can cause stress corrosion cracking in stainless steels. Therefore, HB Line Engineering requested that Savannah River National Laboratory (SRNL) convert resin from chloride form to nitrate form in the Engineering Development Laboratory (EDL). To perform this task, SRNL treated two batches of resin in 2012. The first batch of resin from Reilly Industries Batch 80302MA was initially treated at SRNL in 2001 to remove chloride. This batch of resin, nominally 30 liters, has been stored wet in carboys since that time until being retreated in 2012. The second batch of resin from Batch 23408 consisted of 50 kg of new resin purchased from Vertellus Specialties in 2012. Both batches were treated in a column designed to convert resin using downflow of 1.0 M sodium nitrate solution through the resin bed followed by rinsing with deionized water. Both batches were analyzed for chloride concentration, before and after treatment, using Neutron Activation Analysis (NAA). The resin specification [Werling, 2003] states the total chlorine and chloride concentration shall be less than 250 ppm. The resin condition for measuring this concentration is not specified; however, in service the resin would always be fully wet. Measurements in SRNL showed that changing from oven dry resin to fully wet resin, with liquid in the particle interstices but no supernatant, increases the total weight by a factor of at least three. Therefore, concentration of chlorine or chloride expressed as parts per million (ppm) decreases by a factor of three. Therefore, SRNL recommends measuring chlorine concentration on an oven dry basis, then dividing by three to estimate chloride concentration in the fully wet condition. Chloride concentration in the first batch (No.80302MA) was nearly the same before the current treatment (759 ppm dry) and after treatment (745 ppm dry or {approx}248 ppm wet). Treatment of the second batch of resin (No.23408) was very successful. Chloride concentration decreased from 120,000 ppm dry to an average of 44 ppm dry or {approx}15ppm wet, which easily passes the 250 ppm wet criterion. Per guidance from HB Line Engineering, SRNL blended Batch 80302 resin with Batch P9059 resin which had been treated previously by ResinTech to remove chloride. The chloride concentrations for the two drums of Batch P9059 were 248 ppm dry ({approx}83 ppm wet) {+-}22.8% and 583 ppm dry ({approx}194 ppm wet) {+-} 11.8%. The blended resin was packaged in five gallon buckets.

  4. 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.

  5. Recovery of plutonium from electrorefining anode heels at Savannah River

    SciTech Connect

    Gray, J H; Gray, L W; Karraker, D G

    1987-03-01

    In a joint effort, the Savannah River Laboratory (SRL), Savannah River Plant (SRP), and the Rocky Flats Plant (RFP) have developed two processes to recover plutonium from electrorefining anode heel residues. Aqueous dissolution of anode heel metal was demonstrated at SRL on a laboratory scale and on a larger pilot scale using either sulfamic acid or nitric acid-hydrazine-fluoride solutions. This direct anode heel metal dissolution requires the use of a geometrically favorable dissolver. The second process developed involves first diluting the plutonium in the anode heel residues by alloying with aluminum. The alloyed anode heel plutonium can then be dissolved using a nitric acid-fluoride-mercury(II) solution in large non-geometrically favorable equipment where nuclear safety is ensured by concentration control.

  6. 21 CFR 181.33 - Sodium nitrate and potassium nitrate.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Sodium nitrate and potassium nitrate. 181.33...-Sanctioned Food Ingredients § 181.33 Sodium nitrate and potassium nitrate. Sodium nitrate and potassium... nitrite, with or without sodium or potassium nitrite, in the production of cured red meat products...

  7. 21 CFR 181.33 - Sodium nitrate and potassium nitrate.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Sodium nitrate and potassium nitrate. 181.33...-Sanctioned Food Ingredients § 181.33 Sodium nitrate and potassium nitrate. Sodium nitrate and potassium... nitrite, with or without sodium or potassium nitrite, in the production of cured red meat products...

  8. 21 CFR 181.33 - Sodium nitrate and potassium nitrate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Sodium nitrate and potassium nitrate. 181.33...-Sanctioned Food Ingredients § 181.33 Sodium nitrate and potassium nitrate. Sodium nitrate and potassium... nitrite, with or without sodium or potassium nitrite, in the production of cured red meat products...

  9. Cylodextrin Polymer Nitrate

    NASA Technical Reports Server (NTRS)

    Kosowski, Bernard; Ruebner, Anja; Statton, Gary; Robitelle, Danielle; Meyers, Curtis

    2000-01-01

    The development of the use of cyclodextrin nitrates as possible components of insensitive, high-energy energetics is outlined over a time period of 12 years. Four different types of cyclodextrin polymers were synthesized, nitrated, and evaluated regarding their potential use for the military and aerospace community. The synthesis of these novel cyclodextrin polymers and different nitration techniques are shown and the potential of these new materials is discussed.

  10. Report of scouting study on precipitation of strontium, plutonium, and americium from Hanford complexant concentrate waste

    SciTech Connect

    Herting, D.L.

    1995-09-05

    A laboratory scouting test was conducted of precipitation methods for reducing the solubility of radionuclides in complexant concentrate (CC) waste solution. The results show that addition of strontium nitrate solution is effective in reducing the liquid phase activity of 90Sr (Strontium) in CC waste from tank 107-AN by 94% when the total strontium concentration is adjusted to 0.1 M. Addition of ferric nitrate solution effective in reducing the 241Am (Americium) activity in CC waste by 96% under the conditions described in the report. Ferric nitrate was also marginally effective in reducing the solubility of 239/240Pu (Plutonium) in CC waste

  11. Separation of Plutonium from Irradiated Fuels and Targets

    SciTech Connect

    Gray, Leonard W.; Holliday, Kiel S.; Murray, Alice; Thompson, Major; Thorp, Donald T.; Yarbro, Stephen; Venetz, Theodore J.

    2015-09-30

    Spent nuclear fuel from power production reactors contains moderate amounts of transuranium (TRU) actinides and fission products in addition to the still slightly enriched uranium. Originally, nuclear technology was developed to chemically separate and recover fissionable plutonium from irradiated nuclear fuel for military purposes. Military plutonium separations had essentially ceased by the mid-1990s. Reprocessing, however, can serve multiple purposes, and the relative importance has changed over time. In the 1960’s the vision of the introduction of plutonium-fueled fast-neutron breeder reactors drove the civilian separation of plutonium. More recently, reprocessing has been regarded as a means to facilitate the disposal of high-level nuclear waste, and thus requires development of radically different technical approaches. In the last decade or so, the principal reason for reprocessing has shifted to spent power reactor fuel being reprocessed (1) so that unused uranium and plutonium being recycled reduce the volume, gaining some 25% to 30% more energy from the original uranium in the process and thus contributing to energy security and (2) to reduce the volume and radioactivity of the waste by recovering all long-lived actinides and fission products followed by recycling them in fast reactors where they are transmuted to short-lived fission products; this reduces the volume to about 20%, reduces the long-term radioactivity level in the high-level waste, and complicates the possibility of the plutonium being diverted from civil use – thereby increasing the proliferation resistance of the fuel cycle. In general, reprocessing schemes can be divided into two large categories: aqueous/hydrometallurgical systems, and pyrochemical/pyrometallurgical systems. Worldwide processing schemes are dominated by the aqueous (hydrometallurgical) systems. This document provides a historical review of both categories of reprocessing.

  12. Field determination of nitrate using nitrate reductase

    SciTech Connect

    Campbell, E.R.; Corrigan, J.S.; Campbell, W.H.

    1997-12-31

    Nitrate is routinely measured in a variety of substrates - water, tissues, soils, and foods - both in the field and in laboratory settings. The most commonly used nitrate test methods involve the reduction of nitrate to nitrite via a copper-cadmium reagent, followed by reaction of the nitrite with the Griess dye reagents. The resulting color is translated into a nitrate concentration by comparison with a calibrated color chart or comparator, or by reading the absorbance in a spectrophotometer. This basic method is reliable and sufficiently sensitive for many applications. However, the cadmium reagent is quite toxic. The trend today is for continued increase in concern for worker health and safety; in addition, there are increasing costs and logistical problems associated with regulatory constraints on transport and disposal of hazardous materials. Some suppliers have substituted a zinc-based reagent powder for the cadmium in an effort to reduce toxicity. We describe here an enzyme-based nitrate detection method as an improvement on the basic Griess method that demonstrates equal or superior sensitivity, superior selectivity, and is more environmentally benign. Comparisons between the enzyme-based method and some standard field test kits being used today are made.

  13. REDUCTION OF PLUTONIUM TO Pu$sup +3$ BY SODIUM DITHIONITE IN POTASSIUM CARBONATE

    DOEpatents

    Miller, D.R.; Hoekstra, H.R.

    1958-12-16

    Plutonium values are reduced in an alkaline aqueous medlum to the trlvalent state by means of sodium dlthionite. Plutonlum values are also separated from normally assoclated contaminants by metathesizing a lanthanum fluoride carrier precipitate containing plutonium with a hydroxide solution, performing the metathesis in the presence of about 0.2 M sodium dithionite at a temperature of between 40 and 90 icient laborato C.

  14. Plutonium Finishing Plant. Interim plutonium stabilization engineering study

    SciTech Connect

    Sevigny, G.J.; Gallucci, R.H.; Garrett, S.M.K.; Geeting, J.G.H.; Goheen, R.S.; Molton, P.M.; Templeton, K.J.; Villegas, A.J.; Nass, R.

    1995-08-01

    This report provides the results of an engineering study that evaluated the available technologies for stabilizing the plutonium stored at the Plutonium Finishing Plant located at the hanford Site in southeastern Washington. Further processing of the plutonium may be required to prepare the plutonium for interim (<50 years) storage. Specifically this document provides the current plutonium inventory and characterization, the initial screening process, and the process descriptions and flowsheets of the technologies that passed the initial screening. The conclusions and recommendations also are provided. The information contained in this report will be used to assist in the preparation of the environmental impact statement and to help decision makers determine which is the preferred technology to process the plutonium for interim storage.

  15. Complexation of Plutonium (IV) With Sulfate At Variable Temperatures

    SciTech Connect

    Y. Xia; J.I. Friese; D.A> Moore; P.P. Bachelor; L. Rao

    2006-10-05

    The complexation of plutonium(IV) with sulfate at variable temperatures has been investigated by solvent extraction method. A NaBrO{sub 3} solution was used as holding oxidant to maintain the plutonium(IV) oxidation state throughout the experiments. The distribution ratio of Pu(IV) between the organic and aqueous phases was found to decrease as the concentrations of sulfate were increased. Stability constants of the 1:1 and 1:2 Pu(IV)-HSO{sub 4}{sup -} complexes, dominant in the aqueous phase, were calculated from the effect of [HSO{sub 4}{sup -}] on the distribution ratio. The enthalpy and entropy of complexation were calculated from the stability constants at different temperatures using the Van't Hoff equation.

  16. 4. VIEW OF PLUTONIUM CANISTER ON CHAINVEYOR. SCRAP PLUTONIUM WAS ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    4. VIEW OF PLUTONIUM CANISTER ON CHAINVEYOR. SCRAP PLUTONIUM WAS COLLECTED INTO CANS AT INDIVIDUAL WORKSTATIONS. THE CANS WERE TRANSFERRED VIA THE CHAIN CONVEYOR TO A WORKSTATION IN MODULE C WHERE THE MATERIAL WAS COMPRESSED INTO BRIQUETTES FOR LATER USE. (6/20/93) - Rocky Flats Plant, Plutonium Manufacturing Facility, North-central section of Plant, just south of Building 776/777, Golden, Jefferson County, CO

  17. Recovery of americium-241 from aged plutonium metal

    SciTech Connect

    Gray, L.W.; Burney, G.A.; Reilly, T.A.; Wilson, T.W.; McKibben, J.M.

    1980-12-01

    About 5 kg of ingrown /sup 241/Am was recovered from 850 kg of aged plutonium using a process developed specifically for Savannah River Plant application. The aged plutonium metal was first dissolved in sulfamic acid. Sodium nitrite was added to oxidize the plutonium to Pu(IV) and the residual sulfamate ion was oxidized to nitrogen gas and sulfate. The plutonium and americium were separated by one cycle of solvent extraction. The recovered products were subsequently purified by cation exchange chromatography, precipitated as oxalates, and calcined to the oxides. Plutonium processng was routine. Before cation exchange purification, the aqueous americium solution from solvent extraction was concentrated and stripped of nitric acid. More than 98% of the /sup 241/Am was then recovered from the cation exchange column where it was effectively decontaminated from all major impurities except nickel and chromium. This partially purified product solution was concentrated further by evaporation and then denitrated by reaction with formic acid. Individual batches of americium oxalate were then precipitated, filtered, washed, and calcined. About 98.5% of the americium was recovered. The final product purity averaged 98% /sup 241/AmO/sub 2/; residual impurities were primarily lead and nickel.

  18. Surprising Coordination for Plutonium in the First Plutonium (III) Borate

    SciTech Connect

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

    2011-02-22

    The first plutonium(III) borate, Pu2[B12O18(OH)4Br2(H2O)3]·0.5H2O, has been prepared by reacting plutonium(III) with molten boric acid under strictly anaerobic conditions. This compound contains a three-dimensional polyborate network with triangular holes that house the plutonium(III) sites. The plutonium sites in this compound are 9- and 10-coordinate and display atypical geometries.

  19. Molecular Characterization of Actinide Oxocations from Protactinium to Plutonium

    SciTech Connect

    Den Auwer, C.; Guilbaud, P.; Guillaumont, D.; Moisy, P.; Hennig, C.; Scheinost, A.; Conradson, S. D.

    2007-02-02

    This presentation addresses the structural characterization by EXAFS of actinide cations at oxidation states (V) and (VI) as one walks across the periodic table from Z = 91 (protactinium) to Z = 94 (plutonium). A structural comparison between Pa, U, Np and Pu oxocations in aqueous solution at formal oxidation states (V) and (VI) is carried out. These results are corroborated by quantum chemical and molecular dynamics calculations.

  20. PLUTONIUM-URANIUM ALLOY

    DOEpatents

    Coffinberry, A.S.; Schonfeld, F.W.

    1959-09-01

    Pu-U-Fe and Pu-U-Co alloys suitable for use as fuel elements tn fast breeder reactors are described. The advantages of these alloys are ease of fabrication without microcracks, good corrosion restatance, and good resistance to radiation damage. These advantages are secured by limitation of the zeta phase of plutonium in favor of a tetragonal crystal structure of the U/sub 6/Mn type.

  1. MOLDS FOR CASTING PLUTONIUM

    DOEpatents

    Anderson, J.W.; Miley, F.; Pritchard, W.C.

    1962-02-27

    A coated mold for casting plutonium comprises a mold base portion of a material which remains solid and stable at temperatures as high as the pouring temperature of the metal to be cast and having a thin coating of the order of 0.005 inch thick on the interior thereof. The coating is composed of finely divided calcium fluoride having a particle size of about 149 microns. (AEC)

  2. Welding Plutonium Storage Containers

    SciTech Connect

    HUDLOW, SL

    2004-04-20

    The outer can welder (OCW) in the FB-Line Facility at the Savannah River Site (SRS) is a Gas Tungsten Arc Weld (GTAW) system used to create outer canisters compliant with the Department of Energy 3013 Standard, DOE-STD-3013-2000, Stabilization, Packaging, and Storage of Plutonium-Bearing Materials. The key welding parameters controlled and monitored on the outer can welder Data Acquisition System (DAS) are weld amperage, weld voltage, and weld rotational speed. Inner 3013 canisters from the Bagless Transfer System that contain plutonium metal or plutonium oxide are placed inside an outer 3013 canister. The canister is back-filled with helium and welded using the outer can welder. The completed weld is screened to determine if it is satisfactory by reviewing the OCW DAS key welding parameters, performing a helium leak check, performing a visual examination by a qualified weld inspector, and performing digital radiography of the completed weld. Canisters with unsatisfactory welds are cut open and repackaged. Canisters with satisfactory welds are deemed compliant with the 3013 standard for long-term storage.

  3. PROCESS OF PRODUCING SHAPED PLUTONIUM

    DOEpatents

    Anicetti, R.J.

    1959-08-11

    A process is presented for producing and casting high purity plutonium metal in one step from plutonium tetrafluoride. The process comprises heating a mixture of the plutonium tetrafluoride with calcium while the mixture is in contact with and defined as to shape by a material obtained by firing a mixture consisting of calcium oxide and from 2 to 10% by its weight of calcium fluoride at from 1260 to 1370 deg C.

  4. Manufacturing of Plutonium Tensile Specimens

    SciTech Connect

    Knapp, Cameron M

    2012-08-01

    Details workflow conducted to manufacture high density alpha Plutonium tensile specimens to support Los Alamos National Laboratory's science campaigns. Introduces topics including the metallurgical challenge of Plutonium and the use of high performance super-computing to drive design. Addresses the utilization of Abaqus finite element analysis, programmable computer numerical controlled (CNC) machining, as well as glove box ergonomics and safety in order to design a process that will yield high quality Plutonium tensile specimens.

  5. Plutonium recovery from organic materials

    DOEpatents

    Deaton, R.L.; Silver, G.L.

    1973-12-11

    A method is described for removing plutonium or the like from organic material wherein the organic material is leached with a solution containing a strong reducing agent such as titanium (III) (Ti/sup +3None)/, chromium (II) (Cr/ sup +2/), vanadium (II) (V/sup +2/) ions, or ferrous ethylenediaminetetraacetate (EDTA), the leaching yielding a plutonium-containing solution that is further processed to recover plutonium. The leach solution may also contain citrate or tartrate ion. (Official Gazette)

  6. Gamma radiation characteristics of plutonium dioxide fuel

    NASA Technical Reports Server (NTRS)

    Gingo, P. J.

    1969-01-01

    Investigation of plutonium dioxide as an isotopic fuel for Radioisotope Thermoelectric Generators yielded the isotopic composition of production-grade plutonium dioxide fuel, sources of gamma radiation produced by plutonium isotopes, and the gamma flux at the surface.

  7. CSER 00-003 Criticality Safety Evaluation report for PFP Magnesium Hydroxide Precipitation Process for Plutonium Stabilization Glovebox 3

    SciTech Connect

    LAN, J.S.

    2000-07-13

    This Criticality Safety Evaluation Report analyzes the stabilization of plutonium/uranium solutions in Glovebox 3 using the magnesium hydroxide precipitation process at PFP. The process covered are the receipt of diluted plutonium solutions into three precipitation tanks, the precipitation of plutonium from the solution, the filtering of the plutonium precipitate from the solution, the scraping of the precipitate from the filter into boats, and the initial drying of the precipitated slurry on a hot plate. A batch (up to 2.5 kg) is brought into the glovebox as plutonium nitrate, processed, and is then removed in boats for further processing. This CSER establishes limits for the magnesium hydroxide precipitation process in Glovebox 3 to maintain criticality safety while handling fissionable material.

  8. Cesium recovery from aqueous solutions

    DOEpatents

    Goodhall, C. A.

    1960-09-13

    A process for recovering cesium from aqueous solutions is given in which precipitation on zinc ferricyanide is used. The precipitation is preferably carried out in solutions containing at least 0.0004M zinc ferricyanide, an acidity ranging from 0.2N mineral acid to 0.61N acid deficiency, and 1 to 2.5M aluminum nitrate. (D.L.C.)

  9. Application of ICP-QMS for the determination of plutonium in environmental samples for safeguards purposes.

    PubMed

    Godoy, Maria Luiza D P; Godoy, José Marcus; Roldão, Luiz Alfredo

    2007-01-01

    Aiming to determine the plutonium amount as well as its isotopic composition, in particular, in swipe samples for safeguards purposes, an analytical method was developed with a plutonium separation step based on extraction chromatography using 2 cm TEVA columns and detection with quadrupole ICP-MS applying an ultra-sonic nebulizer coupled with membrane desolvation system. The method was successfully applied to New Brunswick plutonium certified reference materials as well as to Lawrence Livermore National Laboratory round robin samples, based on the round robin samples provided by the Institute for Reference Materials and Measurements (Belgium), as part of the Regular European Interlaboratory Measurement Evaluation Programme (REIMEP), campaign 16 (isotopic abundances of plutonium in plutonium nitrate samples), with a total plutonium amount between 1 and 0.25 ng per sample. After the introduction of an additional separation step, it was also possible to carry out precise and accurate total plutonium, (240)Pu/(239)Pu, (241)Pu/(239)Pu and (242)Pu/(239)Pu atom ratios determination in sediment sample showing its applicability to environmental samples in general, reaching a detection limit equivalent to 5 mBq(239)Pu kg(-1). PMID:17543430

  10. On the existence of 'bis (L-glutamine) potassium nitrate' crystal

    NASA Astrophysics Data System (ADS)

    Srinivasan, Bikshandarkoil R.; Shyama, Soorambail K.; Naik, Suvidha G.; Jyai, Rita N.

    2015-02-01

    The slow evaporation of an aqueous solution containing L-glutamine and potassium nitrate in 2:1 mol ratio results in the fractional crystallization of L-glutamine and not the formation of a so called bis (L-glutamine) potassium nitrate as reported recently by Hanumantharao and Kalainathan (2012).

  11. Literature review for oxalate oxidation processes and plutonium oxalate solubility

    SciTech Connect

    Nash, C. A.

    2015-10-01

    A literature review of oxalate oxidation processes finds that manganese(II)-catalyzed nitric acid oxidation of oxalate in precipitate filtrate is a viable and well-documented process. The process has been operated on the large scale at Savannah River in the past, including oxidation of 20 tons of oxalic acid in F-Canyon. Research data under a variety of conditions show the process to be robust. This process is recommended for oxalate destruction in H-Canyon in the upcoming program to produce feed for the MOX facility. Prevention of plutonium oxalate precipitation in filtrate can be achieved by concentrated nitric acid/ferric nitrate sequestration of oxalate. Organic complexants do not appear practical to sequester plutonium. Testing is proposed to confirm the literature and calculation findings of this review at projected operating conditions for the upcoming campaign.

  12. METHOD FOR OBTAINING PLUTONIUM METAL AND ALLOYS OF PLUTONIUM FROM PLUTONIUM TRICHLORIDE

    DOEpatents

    Reavis, J.G.; Leary, J.A.; Maraman, W.J.

    1962-11-13

    A process is given for both reducing plutonium trichloride to plutonium metal using cerium as the reductant and simultaneously alloying such plutonium metal with an excess of cerium or cerium and cobalt sufficient to yield the desired nuclear reactor fuel composition. The process is conducted at a temperature from about 550 to 775 deg C, at atmospheric pressure, without the use of booster reactants, and a substantial decontamination is effected in the product alloy of any rare earths which may be associated with the source of the plutonium. (AEC)

  13. The Chilean nitrate deposits.

    USGS Publications Warehouse

    Ericksen, G.E.

    1983-01-01

    The nitrate deposits in the arid Atacama desert of northern Chile consist of saline-cemented surficial material, apparently formed in and near a playa lake that formerly covered the area. Many features of their distribution and chemical composition are unique. The author believes the principal sources of the saline constituents were the volcanic rocks of late Tertiary and Quaternary age in the Andes and that the nitrate is of organic origin. Possible sources of the nitrate, iodate, perchlorate and chromate are discussed. -J.J.Robertson

  14. Probing Phonons in Plutonium

    NASA Astrophysics Data System (ADS)

    Wong, Joe

    2004-03-01

    The phonon spectra of plutonium and its alloys have been sought after in the past few decades following the discovery of this actinide element in 1941, but with no success. This was due to a combination of the high neutron absorption cross section of 239Pu, the common isotope, and non-availability of large single crystals of any Pu-bearing materials. We have recent designed a high resolution inelastic x-ray scattering experiment using a bright synchrotron x-ray beam at the European Sychrotron Radiation Facility (ESRF), Grenoble and mapped the full phonon dispersion curves of an fcc delta-phase polycrystalline Pu-Ga alloy (1). Several unusual features including, a large elastic anisotropy, a small shear elastic modulus C', a Kohn-like anomaly in the T1[011] branch, and a pronounced softening of the [111] transverse modes are found. These features can be related to the phase transitions of plutonium and to strong coupling between the lattice structure and the 5f valence instabilities. Our results also provide a critical test for theoretical treatments of highly correlated 5f electron systems as exemplified by recent dynamical mean field theory (DMFT) calculations for d-plutonium.(2) This work was performed in collaboration with Dr. M. Krisch (ESRF)) and Prof. T.-C. Chiang (UIU), and under the auspices of the U. S. Department of Energy by the University of California, Lawrence Livermore National Laboratory under Contract No. W-7405-Eng-48. 1. Joe Wong et al. Science, vol.301, 1078 (2003) 2. X. Dai et al. Science, vol.300, 953 (2003)

  15. PLUTONIUM-URANIUM-TITANIUM ALLOYS

    DOEpatents

    Coffinberry, A.S.

    1959-07-28

    A plutonium-uranium alloy suitable for use as the fuel element in a fast breeder reactor is described. The alloy contains from 15 to 60 at.% titanium with the remainder uranium and plutonium in a specific ratio, thereby limiting the undesirable zeta phase and rendering the alloy relatively resistant to corrosion and giving it the essential characteristic of good mechanical workability.

  16. Photochemical preparation of plutonium pentafluoride

    DOEpatents

    Rabideau, Sherman W. (Los Alamos, NM); Campbell, George M. (Los Alamos, NM)

    1987-01-01

    The novel compound plutonium pentafluoride may be prepared by the photodissociation of gaseous plutonium hexafluoride. It is a white solid of low vapor pressure, which consists predominantly of a face-centered cubic structure with a.sub.o =4.2709.+-.0.0005 .ANG..

  17. SEPARATION OF PLUTONIUM FROM URANIUM

    DOEpatents

    Feder, H.M.; Nuttall, R.L.

    1959-12-15

    A process is described for extracting plutonium from powdered neutron- irradiated urarium metal by contacting the latter, while maintaining it in the solid form, with molten magnesium which takes up the plutonium and separating the molten magnesium from the solid uranium.

  18. PLUTONIUM-CERIUM-COPPER ALLOYS

    DOEpatents

    Coffinberry, A.S.

    1959-05-12

    A low melting point plutonium alloy useful as fuel is a homogeneous liquid metal fueled nuclear reactor is described. Vessels of tungsten or tantalum are useful to contain the alloy which consists essentially of from 10 to 30 atomic per cent copper and the balance plutonium and cerium. with the plutontum not in excess of 50 atomic per cent.

  19. Plutonium Multiple Recycling In PWRs

    SciTech Connect

    Nigon, Jean-Louis; Lenain, Richard; Zaetta, Alain

    2002-07-01

    Reprocessing and recycling open the road to a sustainable management of nuclear materials and an environment friendly management of nuclear waste. However, long or very long term recycling implies fast neutron reactors. High burn-ups of irradiated standard UO{sub 2} fuel as well as recycling of plutonium fuel in thermal reactors lead to a 'degradation' of plutonium that means a low fissile content, which is hardly compatible with recycling in LWRs. Thus the question of plutonium management has been raised; although there are some limitations, a truly large variety of options do exist; no one of the presently selected ways of plutonium management is a dead end road. Among these various options, some are fully compatible with the existing reactors and may be considered for the mid term future; they offer a competitive management of plutonium during the transition from thermal to fast reactors. (authors)

  20. Thermal decomposition hazard evaluation of hydroxylamine nitrate.

    PubMed

    Wei, Chunyang; Rogers, William J; Mannan, M Sam

    2006-03-17

    Hydroxylamine nitrate (HAN) is an important member of the hydroxylamine family and it is a liquid propellant when combined with alkylammonium nitrate fuel in an aqueous solution. Low concentrations of HAN are used primarily in the nuclear industry as a reductant in nuclear material processing and for decontamination of equipment. Also, HAN has been involved in several incidents because of its instability and autocatalytic decomposition behavior. This paper presents calorimetric measurement for the thermal decomposition of 24 mass% HAN/water. Gas phase enthalpy of formation of HAN is calculated using both semi-empirical methods with MOPAC and high-level quantum chemical methods of Gaussian 03. CHETAH is used to estimate the energy release potential of HAN. A Reactive System Screening Tool (RSST) and an Automatic Pressure Tracking Adiabatic Calorimeter (APTAC) are used to characterize thermal decomposition of HAN and to provide guidance about safe conditions for handling and storing of HAN. PMID:16154263

  1. Plutonium oxide dissolution

    SciTech Connect

    Gray, J.H.

    1992-09-30

    Several processing options for dissolving plutonium oxide (PuO[sub 2]) from high-fired materials have been studied. The scoping studies performed on these options were focused on PuO[sub 2] typically generated by burning plutonium metal and PuO[sub 2] produced during incineration of alpha contaminated waste. At least two processing options remain applicable for dissolving high-fired PuO[sub 2] in canyon dissolvers. The options involve solid solution formation of PuO[sub 2] With uranium oxide (UO[sub 2]) and alloying incinerator ash with aluminum. An oxidative dissolution process involving nitric acid solutions containing a strong oxidizing agent, such as cerium (IV), was neither proven nor rejected. This uncertainty was due to difficulty in regenerating cerium (IV) ions during dissolution. However, recent work on silver-catalyzed dissolution of PuO[sub 2] with persulfate has demonstrated that persulfate ions regenerate silver (II). Use of persulfate to regenerate cerium (IV) or bismuth (V) ions during dissolution of PuO[sub 2] materials may warrant further study.

  2. Plutonium oxide dissolution

    SciTech Connect

    Gray, J.H.

    1992-09-30

    Several processing options for dissolving plutonium oxide (PuO{sub 2}) from high-fired materials have been studied. The scoping studies performed on these options were focused on PuO{sub 2} typically generated by burning plutonium metal and PuO{sub 2} produced during incineration of alpha contaminated waste. At least two processing options remain applicable for dissolving high-fired PuO{sub 2} in canyon dissolvers. The options involve solid solution formation of PuO{sub 2} With uranium oxide (UO{sub 2}) and alloying incinerator ash with aluminum. An oxidative dissolution process involving nitric acid solutions containing a strong oxidizing agent, such as cerium (IV), was neither proven nor rejected. This uncertainty was due to difficulty in regenerating cerium (IV) ions during dissolution. However, recent work on silver-catalyzed dissolution of PuO{sub 2} with persulfate has demonstrated that persulfate ions regenerate silver (II). Use of persulfate to regenerate cerium (IV) or bismuth (V) ions during dissolution of PuO{sub 2} materials may warrant further study.

  3. Increase of the transdermal penetration of testosterone by miconazole nitrate.

    PubMed

    Baert, Bram; Roche, Nathalie; Burvenich, Christian; De Spiegeleer, Bart

    2012-12-01

    Miconazole nitrate is an imidazole derivative used to treat skin disorders caused by fungi. The aim of this study was to investigate in a systematic way whether miconazole nitrate can have skin penetration enhancing properties. Using Franz diffusion cells, three representative model compounds (caffeine, testosterone and ibuprofen) were applied to human skin as 10 mM aqueous-ethanolic solutions with or without 1 mM of miconazole nitrate. The apparent permeability coefficient K(p) for each of the model compounds was determined with and without miconazole nitrate. While a statistically significant penetration enhancement effect of 33% was found for testosterone, no overall statistically significant effect could be demonstrated for caffeine and ibuprofen. The increase in skin permeability of testosterone is mainly due to an improved partitioning from the dose solution into the skin, thereby resulting in a higher delivery through the human skin. Our results indicate that miconazole can act as a penetration enhancer. PMID:23263811

  4. Fluorescence-based measurement of water-dissolved nitrate ions

    NASA Astrophysics Data System (ADS)

    Sharma, Ashutosh; Street, Nicolas J.

    1999-02-01

    A novel method for measuring ion concentration is reported based on a photochemical reaction between reduced nitrate ions and 2-amino-1-napthalene sulphonic acid. Reduced nitrate ions, in the form of nitrite, react with phot excited 2-amino-1- naphthalene sulphonic acid in acidic media resulting in the formation of a fluorescent product. The photochemical reaction was found selective to nitrite ions, with interference only from sulphide, sulphite, thiosulphate and iron (III) among various water dissolved ionic species investigated. The reported reaction offers a method to measure both nitrate and nitrite ion concentrations. The calibration plot was linear over the investigated range of 0 1 - 12 (mu) M and a detection limit of 24 nM plus or minus 2.4 nM. The method which was used to investigate nitrite ion concentrations in North London tap water and commercially available bottled water was found to be suitable for nitrate and nitrite ion measurement in such aqueous media.

  5. Probing phonons in plutonium

    SciTech Connect

    Wong, Joe; Krisch, M.; Farber, D.; Occelli, F.; Schwartz, A.; Chiang, T.C.; Wall, M.; Boro, C.; Xu, Ruqing

    2010-11-16

    Plutonium (Pu) is well known to have complex and unique physico-chemical properties. Notably, the pure metal exhibits six solid-state phase transformations with large volume expansions and contractions along the way to the liquid state: {alpha} {yields} {beta} {yields} {gamma} {yields} {delta} {yields} {delta}{prime} {yields} {var_epsilon} {yields} liquid. Unalloyed Pu melts at a relatively low temperature {approx}640 C to yield a higher density liquid than that of the solid from which it melts, (Figure 1). Detailed understanding of the properties of plutonium and plutonium-based alloys is critical for the safe handling, utilization, and long-term storage of these important, but highly toxic materials. However, both technical and and safety issues have made experimental observations extremely difficult. Phonon dispersion curves (PDCs) are key experimenta l data to the understanding of the basic properties of Pu materials such as: force constants, sound velocities, elastic constants, thermodynamics, phase stability, electron-phonon coupling, structural relaxation, etc. However, phonon dispersion curves (PDCs) in plutonium (Pu) and its alloys have defied measurement for the past few decades since the discovery of this element in 1941. This is due to a combination of the high thermal-neutron absorption cross section of plutonium and the inability to grow the large single crystals (with dimensions of a few millimeters) necessary for inelastic neutron scattering. Theoretical simulations of the Pu PDC continue to be hampered by the lack of suitable inter -atomic potentials. Thus, until recently the PDCs for Pu and its alloys have remained unknown experimentally and theoretically. The experimental limitations have recently been overcome by using a tightly focused undulator x-ray micro-beam scattered from single -grain domains in polycrystalline specimens. This experimental approach has been applied successfully to map the complete PDCs of an fcc d-Pu-Ga alloy using the high resolution inelastic x-ray scattering (HRIXS) capability on ID28. The complete PDCs for an fcc Pu-0.6 wt% Ga alloy are plotted in Figure 2, and represent the first full set of phonon dispersions ever determined for any Pu-bearing materials. The solid curves (red) are calculated using a standard Born-von Karman (B-vK) force constant model. An adequate fit to the experimental data is obtained if interactions up to the fourth-nearest neighbours are included. The dashed curves (blue) are recent dynamical mean field theory (DMFT) results by Dai et al. The elastic moduli calculated from the slopes of the experimental phonon dispersion curves near the {Lambda} point are: C{sub 11} = 35.3 {+-} 1.4 GPa, C{sub 12} = 25.5 {+-} 1.5 GPa and C{sub 44} = 30.53 {+-} 1.1 GPa. These values are in excellent agreement with those of the only other measurement on a similar alloy (1 wt % Ga) using ultrasonic techniques as well as with those recently calculated from a combined DMFT and linear response theory for pure {delta}-Pu. Several unusual features, including a large elastic anisotropy, a small shear elastic modulus C{prime}, a Kohn-like anomaly in the T{sub 1}[011] branch, and a pronounced softening of the [111] transverse modes are found. These features can be related to the phase transitions of plutonium and to strong coupling between the lattice structure and the 5f valence instabilities. The HRIXS results also provide a critical test for theoretical treatments of highly correlated 5f electron systems as exemplified by recent dynamical mean field theory (DMFT) calculations for {delta}-plutonium. The experimental-theoretical agreements shown in Figure 2 in terms of a low shear elastic modulus C{prime}, a Kohn-like anomaly in the T{sub 1}[011] branch, and a large softening of the T[111] modes give credence to the DMFT approach for the theoretical treatment of 5f electron systems of which {delta}-Pu is a classic example. However, quantitative differences remain. These are the position of the Kohn anomaly along the T{sub 1}[011] branch, the energy maximum of the T[111] mode s and the softening of the calculated T[100] branch near the X point, which is not observed experimentally. These differences are significant and thus provide a framework for refined theoretical treatments. Systematic HRIXS experiments as a function of temperature and concentration in the fcc Pu-Ga alloys are underway.

  6. Dissolution Behavior of Plutonium Containing Zirconia-Magnesia Ceramics

    SciTech Connect

    Kiel Holliday; Thomas Hartmann; Gary Cerefice; Ken Czerwinski

    2012-03-01

    This study explores the dissolution properties of zirconia-magnesia ceramics containing plutonium as the basis of an inert atrix nuclear fuel. The magnesium oxide phase remains pure MgO, while the zirconia incorporates a small amount of magnesium oxide along with all of the plutonium oxide and erbium oxide. The performance of the material under reactor and repository environments was examined. Reactor conditions are examined using a pressure vessel to expose the material to 300 degrees C water. To assess the performance of the material as a waste form it was submerged in 90 degrees C water for 1000 h. In both aqueous dissolution studies there was minimal release of less than 0.8 wt.% of plutonium from the material. To examine the potential for recycling, the dissolution behavior of the fuel matrix was examined in acidic solutions: pure nitric acid and a nitric acid-hydrofluoric acid-peroxide solution. Both acidic media exhibit potential for dissolving plutonium from the zirconia matrix. The experiments performed in this study are meant to lay a foundation for the chemical performance of zirconia-magnesia inert matrix fuel containing fissile material and burnable poison.

  7. Vitrified magnesia dissolution and its impact on plutonium residue processing

    SciTech Connect

    Keith W. Fife; Jennifer L. Alwin; Coleman A. Smith; Michael D. Mayne; David A. Rockstraw

    2000-03-01

    Aqueous chloride operations at the Los Alamos Plutonium Facility cannot directly dispose of acidic waste solutions because of compatibility problems with existing disposal lines. Consequently, all hydrochloric acid must be neutralized and filtered prior to exiting the facility. From a waste minimization standpoint, the use of spent magnesia pyrochemical crucibles as the acid neutralization agent is attractive since this process would take a stream destined for transuranic waste and use it as a reagent in routine plutonium residue processing. Since Los Alamos National Laboratory has several years of experience using magnesium hydroxide as a neutralizing agent for waste acid from plutonium processing activities, the use of spent magnesia pyrochemical crucibles appeared to be an attractive extension of this activity. In order to be competitive with magnesium hydroxide, however, size reduction of crucible shards had to be performed effectively within the constraints of glovebox operations, and acid neutralization time using crucible shards had to be comparable to neutralization times observed when using reagent-grade magnesium hydroxide. The study utilized non-plutonium-contaminated crucibles for equipment evaluation and selection and used nonradioactive acid solutions for completing the neutralization experiments. This paper discusses experience in defining appropriate size reduction equipment and presents results from using the magnesia crucibles for hydrochloric acid neutralization, a logical precursor to introduction into glovebox enclosures.

  8. Dissolution behavior of plutonium containing zirconia-magnesia ceramics

    NASA Astrophysics Data System (ADS)

    Holliday, Kiel; Hartmann, Thomas; Cerefice, Gary; Czerwinski, Ken

    2012-03-01

    This study explores the dissolution properties of zirconia-magnesia ceramics containing plutonium as the basis of an inert matrix nuclear fuel. The magnesium oxide phase remains pure MgO, while the zirconia incorporates a small amount of magnesium oxide along with all of the plutonium oxide and erbium oxide. The performance of the material under reactor and repository environments was examined. Reactor conditions are examined using a pressure vessel to expose the material to 300 °C water. To assess the performance of the material as a waste form it was submerged in 90 °C water for 1000 h. In both aqueous dissolution studies there was minimal release of less than 0.8 wt.% of plutonium from the material. To examine the potential for recycling, the dissolution behavior of the fuel matrix was examined in acidic solutions: pure nitric acid and a nitric acid-hydrofluoric acid-peroxide solution. Both acidic media exhibit potential for dissolving plutonium from the zirconia matrix. The experiments performed in this study are meant to lay a foundation for the chemical performance of zirconia-magnesia inert matrix fuel containing fissile material and burnable poison.

  9. Low temperature oxidation of plutonium

    SciTech Connect

    Nelson, Art J.; Roussel, Paul

    2013-05-15

    The initial oxidation of gallium stabilized {delta}-plutonium metal at 193 K has been followed using x-ray photoelectron spectroscopy. On exposure to Langmuir quantities of oxygen, plutonium rapidly forms a trivalent oxide followed by a tetravalent plutonium oxide. The growth modes of both oxides have been determined. Warming the sample in vacuum, the tetravalent oxide reduces to the trivalent oxide. The kinetics of this reduction reaction have followed and the activation energy has been determined to be 38.8 kJ mol{sup -1}.

  10. Long term plutonium solubility and speciation studies in a synthetic brine

    SciTech Connect

    Nitsche, Heino; Roberts, K.; Xi, Ruihua

    1993-12-31

    The rate at which elements can be transported in groundwater systems is governed in part by the solubility of the element in the groundwater. This report documents plutonium solubility experiments in a brine simulant relevant to the Waste Isolation Pilot Plant. Approximately 1 to 2.5 mL of five stock solutions containing single oxidation states of plutonium (Pu(IV)-polymer, Pu{sup 3+}, Pu{sup 4+}, PuO{sub 2}{sup +}, and PuO{sub 2}{sup 2+}) were added to {approximately}75 mL of synthetic H-17 Brine in five reaction vessels. Initial plutonium concentrations ranged from 1.3 {times} l0{sup {minus}4} to 5.l {times} l0{sup {minus}4} M (moles per liter) total plutonium. Because these initial concentrations were far above the plutonium solubility limit in H-17 Brine, plutonium-containing solids precipitated. Aqueous plutonium concentrations were measured over time until steady-state was reached, requiring over 300 days in H-17 Brine.

  11. METHOD FOR SEPARATION OF PLUTONIUM FROM URANIUM AND FISSION PRODUCTS BY SOLVENT EXTRACTION

    DOEpatents

    Seaborg, G.T.; Blaedel, W.J.; Walling, M.T. Jr.

    1960-08-23

    A process is given for separating from each other uranium, plutonium, and fission products in an aqueous nitric acid solution by the so-called Redox process. The plutonium is first oxidized to the hexavalent state, e.g., with a water-soluble dichromate or sodium bismuthate, preferably together with a holding oxidant such as potassium bromate. potassium permanganate, or an excess of the oxidizing agent. The solution is then contacted with a water-immiscible organic solvent, preferably hexone. whereby uranium and plutonium are extracted while the fission products remain in the aqueous solution. The separated organic phase is then contacted with an aqueous solution of a reducing agent, with or without a holding reductant (e.g., with a ferrous salt plus hydrazine or with ferrous sulfamate), whereby plutonium is reduced to the trivalent state and back- extracted into the aqueous solution. The uranium may finally be back-extracted from the organic solvent (e.g., with a 0.1 N nitric acid).

  12. Hydroxylamine Nitrate Decomposition under Non-radiological Conditions

    SciTech Connect

    McFarlane, Joanna; Delmau, Laetitia Helene; DePaoli, David W.; Mattus, Catherine H.; Phelps, Clarice E.; Roach, Benjamin D.

    2015-07-01

    Hydroxylamine nitrate (HAN) is used to reduce Pu(IV) to Pu(III) in the separation of plutonium from uranium. HAN becomes unstable under certain conditions and has been known to explode, causing injury to humans including death. Hence, it is necessary to deactivate HAN once the reduction of plutonium is finished. This report reviews what is known about the chemistry of HAN and various methods to achieve a safe decomposition. However, there are areas where more information is needed to make a decision about the handling of HAN in reprocessing of nuclear fuel. Experiments have demonstrated a number of non-radiolytic ways to safely decompose HAN, including heating in HNO3, photolytic oxidation in the presence of H2O2, and the addition of a metal such as Fe(III) that will oxidize the HAN.

  13. Solubility of plutonium and waste evaporation

    SciTech Connect

    Karraker, D.G.

    1993-10-22

    Chemical processing of irradiated reactor elements at the Savannah River Site separates uranium, plutonium and fission products; fission products and process-added chemicals are mixed with an excess of NaOH and discharged as a basic slurry into large underground tanks for temporary storage. The slurry is composed of base-insoluble solids that settle to the bottom of the tank; the liquid supemate contains a mixture of base-soluble chemicals--nitrates, nitrites aluminate, sulfate, etc. To conserve space in the waste tanks, the supemate is concentrated by evaporation. As the evaporation proceeds, the solubilities of some components are exceeded, and these species crystallize from solution. Normally, these components are soluble in the hot solution discharged from the waste tank evaporator and do not crystallize until the solution cools. However, concern was aroused at West Valley over the possibility that plutonium would precipitate and accumulate in the evaporator, conceivably to the point that a nuclear accident was possible. There is also a concern at SRS from evaporation of sludge washes, which arise from washing the base-insoluble solids ({open_quote}sludge{close_quote}) with ca. 1M NaOH to reduce the Al and S0{sub 4}{sup {minus}2} content. The sludge washes of necessity extract a low level of Pu from the sludge and are evaporated to reduce their volume, presenting the possibility of precipitating Pu. Measurements of the solubility of Pu in synthetic solutions of similar composition to waste supernate and sludge washes are described in this report.

  14. Crystallization of sodium nitrate from radioactive waste

    SciTech Connect

    Krapukhin, V.B.; Krasavina, E.P. Pikaev, A.K.

    1997-07-01

    From the 1940s to the 1980s, the Institute of Physical Chemistry of the Russian Academy of Sciences (IPC/RAS) conducted research and development on processes to separate acetate and nitrate salts and acetic acid from radioactive wastes by crystallization. The research objective was to decrease waste volumes and produce the separated decontaminated materials for recycle. This report presents an account of the IPC/RAS experience in this field. Details on operating conditions, waste and product compositions, decontamination factors, and process equipment are described. The research and development was generally related to the management of intermediate-level radioactive wastes. The waste solutions resulted from recovery and processing of uranium, plutonium, and other products from irradiated nuclear fuel, neutralization of nuclear process solutions after extractant recovery, regeneration of process nitric acid, equipment decontamination, and other radiochemical processes. Waste components include nitric acid, metal nitrate and acetate salts, organic impurities, and surfactants. Waste management operations generally consist of two stages: volume reduction and processing of the concentrates for storage, solidification, and disposal. Filtration, coprecipitation, coagulation, evaporation, and sorption were used to reduce waste volume. 28 figs., 40 tabs.

  15. Electrospun cellulose nitrate nanofibers.

    PubMed

    Nartker, Steven; Drzal, Lawrence T

    2010-09-01

    Cellulose nitrate nonwoven mats of submicron-sized fibers (100-1200 nm in diameter) were obtained by electrospinning cellulose nitrate solutions. Two solvent systems were evaluated. A 70:30 (wt) ratio of ethanol to acetone and a 60:40 (wt) ratio of tetrahydrofuran (THF) to N,N-dimethylformamide (DMF) were studied. The effects of the two solvent systems, and type two different collectors; void gap, and steel drum coated with polyvinylidene dichloride (PVDC), were investigated. The PVDC layer applied to the rotating drum aided in fiber harvesting. Electron microscopy (FESEM and ESEM) studies of as-spun fibers revealed that the morphology of cellulose nitrate fibers depended on the collector type and solution viscosity. When a rotating steel drum was employed a random morphology was observed, while the void gap collector produced aligned fiber mats. Increases in viscosity lead to larger diameter fibers. PMID:21133109

  16. TERNARY ALLOY-CONTAINING PLUTONIUM

    DOEpatents

    Waber, J.T.

    1960-02-23

    Ternary alloys of uranium and plutonium containing as the third element either molybdenum or zirconium are reported. Such alloys are particularly useful as reactor fuels in fast breeder reactors. The alloy contains from 2 to 25 at.% of molybdenum or zirconium, the balance being a combination of uranium and plutonium in the ratio of from 1 to 9 atoms of uranlum for each atom of plutonium. These alloys are prepared by melting the constituent elements, treating them at an elevated temperature for homogenization, and cooling them to room temperature, the rate of cooling varying with the oomposition and the desired phase structure. The preferred embodiment contains 12 to 25 at.% of molybdenum and is treated by quenching to obtain a body centered cubic crystal structure. The most important advantage of these alloys over prior binary alloys of both plutonium and uranium is the lack of cracking during casting and their ready machinability.

  17. Mechanism study of nitrate reduction by nano zero valent iron.

    PubMed

    Hwang, Yu-Hoon; Kim, Do-Gun; Shin, Hang-Sik

    2011-01-30

    This study investigates the fate of nitrogen species during nitrate reduction by nano-scale zero valent iron (NZVI) and related reaction mechanisms. The NZVI used for the experiments was prepared by chemical reduction without a stabilizing agent. NZVI has great ability to reduce nitrate. However, the question of what end-product results from nitrate reduction by NZVI has sparked controversy. Establishing nitrogen mass balance by quantitative analysis of aqueous phase and gas-phase nitrogen species, this study clearly determines that nitrate was converted to ammonium ion followed by ammonia stripping under a strong alkaline condition, which leads to a decrease in the total aqueous nitrogen amount. Moreover, some of the major reactions, which consisted of nitrate reduction, ammonia production, and ammonia stripping were modelled by pseudo first-order kinetics. According to the model estimation results, additional reaction mechanisms would exist in an early stage of reaction. This might be due to the adsorption and desorption reaction which could be explained by the core-shell structure model. PMID:21093984

  18. Solvent extraction of uranium(VI) into toluene by dicyclohexano-18-crown-6 from mixed aqueous-organic solutions.

    PubMed

    Shukla, J P; Kumar, A; Singh, R K

    1993-08-01

    Extraction behaviour of uranium(VI) from mixed organo-aqueous solutions containing water-miscible protic aliphatic alcohols and several aprotic solvents was investigated by using dicyclohexano-18-crown-6(DC18C6) as an extractant. The organic phase was a binary solution of DC18C6 and toluene while the polar phase was a three component solution of uranyl nitrate, polar additive and aqueous nitric acid. Methanol, ethanol, isobutanol, dioxane, acetone, propylene carbonate and acetonitrile were used as the organic components of the mixed (polar) phase. Propylene carbonate, acetone, acetonitrile and dioxane increased the extractability of U(VI), whereas alcoholic additives showed only an antagonistic effect. The relative increase in extraction was found to be more at lower nitric acid concentrations. Possible reasons for such behaviour are briefly discussed. Recovery of U(VI) from loaded organic phase was easily accomplished using dilute perchloric acid and sulphuric acid. A sample method was standardized for the separation of plutonium(IV) from uranium(VI) based on its reductive stripping. PMID:18965777

  19. Nitrated phenols in the atmosphere: a review

    NASA Astrophysics Data System (ADS)

    Harrison, Mark A. J.; Barra, Silvia; Borghesi, Daniele; Vione, Davide; Arsene, Cecilia; Iulian Olariu, Romeo

    2005-01-01

    This paper reviews the data concerning the atmospheric occurrence of nitrophenols, both in the gas and in the condensed phase (rainwater, cloud, fog and snow). Data obtained from field campaigns are reported, together with a description of the analytical techniques employed for the identification and quantification of nitrophenols. Analysis is usually performed using techniques such as High Performance Liquid Chromatography (HPLC) or Gas Chromatography-Mass Spectrometry (GC-MS), with the sampling method largely determined according to the matrix under investigation. The sources of atmospheric nitrophenols include direct emissions resulting from combustion processes, hydrolysis of pesticides (e.g. parathion) and the secondary formation of nitrophenols in the atmosphere. Atmospheric nitration of phenol can take place both in the gas and liquid phases, but the relative importance of these processes is still under discussion. The gas-phase nitration involves reaction between phenol and radOH+radNO2 during the day or radNO3+radNO2 during the night. Gas-phase nitration during the day yields only 2-nitrophenol (2-NP); while during the night it is thought that both 2-NP and 4-nitrophenol (4-NP) may be formed. Because of many gaps in the experimental evidence it is apparent that more research is required to indicate whether the 4-NP present in the environment can be accounted for by this nighttime process. Nitration in the condensed phase can be initiated by electrophilic nitration agents such as N2O5 and ClNO2. Other liquid-phase processes can also take place, in the presence of radNO3, nitrate and nitrite, in the dark and under irradiation. Condensed-phase processes have been shown to yield 2- and 4-NP in similar amounts. It is also important to consider the atmospheric sinks of nitrophenols. The rate constant for the reaction between 2-NP and radOH in the gas phase is rather low (9.010-13 cm3 molecule-1 s-1), while incomplete data are available for the reaction with radNO3. In addition, condensed-phase processes might also represent an important nitrophenol sink. Potential loss routes include the reaction with radicals such as radOH and radNO3 in aqueous solution as well as the nitration to form the dinitrophenols.

  20. On NO3-H2O interactions in aqueous solutions and at interfaces

    SciTech Connect

    Dang, Liem X.; Chang, Tsun-Mei; Roeselova, Martina; Garrett, Bruce C.; Tobias, Douglas J.

    2006-02-14

    Constrained molecular dynamics technique was employed to investigate the transport of a nitrate ion across the water liquid/vapor interface. We developed the nitrate ion-water polarizable potential capable of describing well the solvation properties of the hydrated nitrate ion. The computed free energy profile for the transfer of the nitrate ion across the air/water interface increases monotonically as the nitrate ion approaches the Gibbs dividing surface from the bulk liquid side. The computed density profiles of 1M KNO3 salt solution slab indicate that the nitrate and potassium ions are both found below the aqueous interface. Upon analyzing the results, we can conclude that the probability of finding the nitrate anion at the aqueous interface is quite small.

  1. Actinide recovery using aqueous biphasic extraction: Initial developmental studies

    SciTech Connect

    Chaiko, D.J.; Mensah-Biney, R.; Mertz, C.J.; Rollins, A.N.

    1992-08-01

    Aqueous biphasic extraction systems are being developed to treat radioactive wastes. The separation technique involves the selective partitioning of either solutes or colloid-size particles between two scible aqueous phases. Wet grinding of plutonium residues to an average particle size of one micron will be used to liberate the plutonium from the bulk of the particle matrix. The goal is to produce a plutonium concentrate that will integrate with existing and developing chemical recovery processes. Ideally, the process would produce a nonTRU waste stream. Coupling physical beneficiation with chemical processing will result in a substantial reduction in the volume of mixed wastes generated from dissolution recovery processes. As part of this program, we will also explore applications of aqueous biphasic extraction that include the separation and recovery of dissolved species such as metal ions and water-soluble organics. The expertise and data generated in this work will form the basis for developing more cost-effective processes for handling waste streams from environmental restoration and waste management activities within the DOE community. This report summarizes the experimental results obtained during the first year of this effort. Experimental efforts were focused on elucidating the surface and solution chemistry variables which govern partitioning behavior of plutonium and silica in aqueous biphasic extraction systems. Additional efforts were directed toward the development of wet grinding methods for producing ultrafine particles with diameters of one micron or less.

  2. Electrochemical reduction of nitrate in the presence of an amide

    DOEpatents

    Dziewinski, Jacek J.; Marczak, Stanislaw

    2002-01-01

    The electrochemical reduction of nitrates in aqueous solutions thereof in the presence of amides to gaseous nitrogen (N.sub.2) is described. Generally, electrochemical reduction of NO.sub.3 proceeds stepwise, from NO.sub.3 to N.sub.2, and subsequently in several consecutive steps to ammonia (NH.sub.3) as a final product. Addition of at least one amide to the solution being electrolyzed suppresses ammonia generation, since suitable amides react with NO.sub.2 to generate N.sub.2. This permits nitrate reduction to gaseous nitrogen to proceed by electrolysis. Suitable amides include urea, sulfamic acid, formamide, and acetamide.

  3. Sonochemical Synthesis of Layered Copper Hydroxy Nitrate Nanosheets.

    PubMed

    Anandan, Sambandam; Wu, Jerry J; Ashokkumar, Muthupandian

    2015-11-01

    Sonochemical reduction of copper nitrate, using 20 kHz ultrasound in aqueous solutions in the presence of urea, led to the formation of layered copper hydroxy nitrate nanosheets, as evidenced by scanning and transmission electron microscopy images. Fourier-transform infrared, X-ray diffraction, and X-ray photoelectron spectroscopy analyses were used to characterize layered Cu2 (OH)3 NO3 nanosheets. The ultrasound-assisted progressive hydrolysis of urea and in situ formation of Cu(0) through the sonochemical reduction process induced homogeneous nucleation and crystallization of layered Cu2 (OH)3 NO3 nanosheets. PMID:26314269

  4. Multiple Oxygen Isotope Photochemistry of Nitrate in Ice

    NASA Astrophysics Data System (ADS)

    McCabe, J. R.; Boxe, C. S.; Colussi, A.; Hoffman, M. R.; Thiemens, M. H.

    2004-12-01

    Nitrate (NO3 -) is a major anion in polar ice [de Angelis and Legrand, 1995;Dibb et al., 1998;Silvente and Legrand, 1995]. As the primary sink for atmospheric NOx, nitrate's chemical history is a link to understanding the nitrogen budget and oxidation capacity of the polar atmosphere over time. Our understanding of variations in ice core nitrate concentrations has been limited by depositional and post-depositional loss processes, associated with temperature, accumulation rate, diffusion, photochemistry and volatilization [Wolff, 1995]. The first report of multiple oxygen isotope composition of nitrate in ice cores (Alexander et al., 2004) demonstrates the ability to observe changes in the oxidation capacity of past atmospheres. To accurately interpret this and future isotopic data, we need to ascertain the oxygen isotope fractionation (δ 17O, δ ^{18}O) associated with the photolysis of nitrate in ice. Post-depositional processes, such as nitrate photolysis and volatilization may alter the initial isotopic signal of nitrate in the snowpack. A series of nitrate photolysis experiments were conducted on 10 mM solutions of Fisher KNO_{3} and USGS-35 NaNO_{3} at 313 ± 20 nm over 12 to 48 hours and between -30 and 25 ° C. With initial mass-dependent nitrate, a strict mass-dependent fractionation was observed in the residual irradiated nitrate. However, after 12 and 24 hours of irradiation, mass-independent USGS-35 NaNO3 (Δ 17O = 21.0 \\pm 0.4 ‰ ) displayed a decrease of 1.6 ± 0.4 and 2.0 \\pm 0.4 % at 25 \\degC, 1.2 ± 0.4 and 1.3 \\pm 0.4 ‰ at -5\\degC, 0.2 ± 0.4 \\permil and 1.1 \\pm 0.4 ‰ at -30\\degC, respectively. The greater isotope effect at higher temperatures may be due to a thicker quasi-liquid layer (QLL) allowing faster rates for secondary nitrate producing reactions between H_{2}O and photoproducts NO, NO_{2}, NO_{2}$-. In the aqueous phase this effect is even greater. Hence, we infer that the production of nitrate via these 'secondary processes' has positive temperature dependence, causing a noticeable but minor decrease in Δ 17O. The potential application of utilizing Δ 17O -NO3- as a new technique to interpret the nitrate ice record to increase our understanding of the polar paleoatmosphere is evaluated in the context of the present measurements.

  5. The chemistry of tributyl phosphate at elevated temperatures in the Plutonium Finishing Plant Process Vessels

    SciTech Connect

    Barney, G.S.; Cooper, T.D.

    1994-06-01

    Potentially violent chemical reactions of the tributyl phosphate solvent used by the Plutonium Finishing Plant at the Hanford Site were investigated. There is a small probability that a significant quantity of this solvent could be accidental transferred to heated process vessels and react there with nitric acid or plutonium nitrate also present in the solvent extraction process. The results of laboratory studies of the reactions show that exothermic oxidation of tributyl phosphate by either nitric acid or actinide nitrates is slow at temperatures expected in the heated vessels. Less than four percent of the tributyl phosphate will be oxidized in these vented vessels at temperatures between 125{degrees}C and 250{degrees}C because the oxidant will be lost from the vessels by vaporization or decomposition before the tributyl phosphate can be extensively oxidized. The net amounts of heat generated by oxidation with concentrated nitric acid and with thorium nitrate (a stand-in for plutonium nitrate) were determined to be about -150 and -220 joules per gram of tributyl phosphate initially present, respectively. This is not enough heat to cause violent reactions in the vessels. Pyrolysis of the tributyl phosphate occurred in these mixtures at temperatures of 110{degrees}C to 270{degrees}C and produced mainly 1-butene gas, water, and pyrophosphoric acid. Butene gas generation is slow at expected process vessel temperatures, but the rate is faster at higher temperatures. At 252{degrees}C the rate of butene gas generated was 0.33 g butene/min/g of tributyl phosphate present. The measured heat absorbed by the pyrolysis reaction was 228 J/g of tributyl phosphate initially present (or 14.5 kcal/mole of tributyl phosphate). Release of flammable butene gas into process areas where it could ignite appears to be the most serious safety consideration for the Plutonium Finishing Plant.

  6. Factor analysis applied to Raman spectra for quantitative speciation in thorium nitrate solutions

    SciTech Connect

    Delgado-Lopez, M.; Niemczyk, T.M.; Haaland, D.M.

    1996-10-01

    Nitrate anion exchange is a very important industrial process in nuclear fuel processing systems. The parameters that must be controlled for optimum ion exchange operation are the concentrations of the individual chemical species present in the metal-nitrate solutions. A multichannel fiber-optic Raman instrumentation is used to remotely collect the spectral data from the aqueous thorium nitrate solutions. By applying factor analysis to the spectra, the amount of nitrate bound to thorium and the formation constant has been estimated. From this quantitative factor analysis, it is possible to monitor bound and free nitrate concentrations in an anion exchange process. Thus, Raman spectroscopy is an excellent candidate for rapid and remote quantitative on-line monitoring required for controlling the nitrate anion exchange process.

  7. Plutonium focus area

    SciTech Connect

    1996-08-01

    To ensure research and development programs focus on the most pressing environmental restoration and waste management problems at the U.S. Department of Energy (DOE), the Assistant Secretary for the Office of Environmental Management (EM) established a working group in August 1993 to implement a new approach to research and technology development. As part of this new approach, EM developed a management structure and principles that led to the creation of specific Focus Areas. These organizations were designed to focus the scientific and technical talent throughout DOE and the national scientific community on the major environmental restoration and waste management problems facing DOE. The Focus Area approach provides the framework for intersite cooperation and leveraging of resources on common problems. After the original establishment of five major Focus Areas within the Office of Technology Development (EM-50, now called the Office of Science and Technology), the Nuclear Materials Stabilization Task Group (EM-66) followed the structure already in place in EM-50 and chartered the Plutonium Focus Area (PFA). The following information outlines the scope and mission of the EM, EM-60, and EM-66 organizations as related to the PFA organizational structure.

  8. Plutonium solution analyzer

    SciTech Connect

    Burns, D.A.

    1994-09-01

    A fully automated analyzer has been developed for plutonium solutions. It was assembled from several commercially available modules, is based upon segmented flow analysis, and exhibits precision about an order of magnitude better than commercial units (0.5%-O.05% RSD). The system was designed to accept unmeasured, untreated liquid samples in the concentration range 40-240 g/L and produce a report with sample identification, sample concentrations, and an abundance of statistics. Optional hydraulics can accommodate samples in the concentration range 0.4-4.0 g/L. Operating at a typical rate of 30 to 40 samples per hour, it consumes only 0.074 mL of each sample and standard, and generates waste at the rate of about 1.5 mL per minute. No radioactive material passes through its multichannel peristaltic pump (which remains outside the glovebox, uncontaminated) but rather is handled by a 6-port, 2-position chromatography-type loop valve. An accompanying computer is programmed in QuickBASIC 4.5 to provide both instrument control and data reduction. The program is truly user-friendly and communication between operator and instrument is via computer screen displays and keyboard. Two important issues which have been addressed are waste minimization and operator safety (the analyzer can run in the absence of an operator, once its autosampler has been loaded).

  9. Microdistribution and Long-Term Retention of 239Pu (NO3)4 in the Respiratory Tracts of an Acutely Exposed Plutonium Worker and Experimental Beagle Dogs

    SciTech Connect

    Nielsen, Christopher E.; Wilson, Dulaney A.; Brooks, Antone L.; McCord, Stacey; Dagle, Gerald E.; James, Anthony C.; Tolmachev, Sergei Y.; Thrall, Brian D.; Morgan, William F.

    2012-11-01

    The long-term retention of inhaled soluble forms of plutonium raises concerns as to the potential health effects in persons working in nuclear energy or the nuclear weapons program. The distributions of long-term retained inhaled plutonium-nitrate [239Pu (NO3)4] deposited in the lungs of an accidentally exposed nuclear worker (Human Case 0269) and in the lungs of experimentally exposed beagle dogs with varying initial lung depositions were determined via autoradiographs of selected histological lung, lymph node, trachea, and nasal turbinate tissue sections. These studies showed that both the human and dogs had a non-uniform distribution of plutonium throughout the lung tissue. Fibrotic scar tissue effectively encapsulated a portion of the plutonium and prevented its clearance from the body or translocation to other tissues and diminished dose to organ parenchyma. Alpha radiation activity from deposited plutonium in Human Case 0269 was observed primarily along the sub-pleural regions while no alpha activity was seen in the tracheobronchial lymph nodes of this individual. However, relatively high activity levels in the tracheobronchial lymph nodes of the beagles indicated the lymphatic system was effective in clearing deposited plutonium from the lung tissues. In both the human case and beagle dogs, the appearance of retained plutonium within the respiratory tract was inconsistent with current biokinetic models of clearance for soluble forms of plutonium. Bound plutonium can have a marked effect on the dose to the lungs and subsequent radiation exposure has the potential increase in cancer risk.

  10. Microdistribution and long-term retention of 239Pu (NO3)4 in the respiratory tracts of an acutely exposed plutonium worker and experimental beagle dogs.

    PubMed

    Nielsen, Christopher E; Wilson, Dulaney A; Brooks, Antone L; McCord, Stacey L; Dagle, Gerald E; James, Anthony C; Tolmachev, Sergei Y; Thrall, Brian D; Morgan, William F

    2012-11-01

    The long-term retention of inhaled soluble forms of plutonium raises concerns as to the potential health effects in persons working in nuclear energy or the nuclear weapons program. The distributions of long-term retained inhaled plutonium-nitrate [(239)Pu (NO(3))(4)] deposited in the lungs of an accidentally exposed nuclear worker (Human Case 0269) and in the lungs of experimentally exposed beagle dogs with varying initial lung depositions were determined via autoradiographs of selected histologic lung, lymph node, trachea, and nasal turbinate tissue sections. These studies showed that both the human and dogs had a nonuniform distribution of plutonium throughout the lung tissue. Fibrotic scar tissue effectively encapsulated a portion of the plutonium and prevented its clearance from the body or translocation to other tissues and diminished dose to organ parenchyma. Alpha radiation activity from deposited plutonium in Human Case 0269 was observed primarily along the subpleural regions while no alpha activity was seen in the tracheobronchial lymph nodes of this individual. However, relatively high activity levels in the tracheobronchial lymph nodes of the beagles indicated the lymphatic system was effective in clearing deposited plutonium from the lung tissues. In both the human case and beagle dogs, the appearance of retained plutonium within the respiratory tract was inconsistent with current biokinetic models of clearance for soluble forms of plutonium. Bound plutonium can have a marked effect on the dose to the lungs and subsequent radiation exposure has the potential to increase cancer risk. PMID:22962267

  11. Influence of chemical form, feeding regimen, and animal species on the gastrointestinal absorption of plutonium

    SciTech Connect

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

    1985-01-01

    We evaluated the effect of chemical form and feeding regimen on the gastrointestinal (GI) absorption of plutonium in adult mice at plutonium concentrations relevant to the establishment of drinking water standards. Mean fractional GI absorption values in fasted adult mice were: Pu(VI) bicarbonate, 15 x 10/sup -4/; Pu(IV) bicarbonate, 20 x 10/sup -4/; Pu(IV) nitrate (pH2), 17 x 10/sup -4/; Pu(IV) citrate, 24 x 10/sup -4/; and Pu(IV) polymer, 3 x 10/sup -4/. Values in fed adult mice were: Pu(VI) bicarbonate, 1.4 x 10/sup -4/; Pu(IV) polymer, 0.3 x 10/sup -4/. Pu(VI) is the oxidation state in chlorinated drinking waters and Pu(IV) is the oxidation state in many untreated natural waters. To assess the validity of extrapolating data from mice to humans, we also determined the GI absorption of Pu(VI) bicarbonate in adult baboons with a dual-isotope method that does not require animal sacrifice. Fractional GI absorption values obtained by this method were 23 +- 10 x 10/sup -4/ for fasted baboons (n=5) and 1.4 +- 0.9 x 10/sup -4/ for fed baboons (n=3). We have so far validated this method in one baboon and are currently completing validation in two additional animals. At low plutonium concentrations, plutonium oxidation state (Pu(VI) vs Pu(IV)) and administration medium (bicarbonate vs nitrate vs citrate) had little effect on the GI absorption of plutonium in mice. Formation of Pu(IV) polymers and animal feeding decreased the GI absorption of plutonium 5- to 10-fold. The GI absorption of Pu(VI) bicarbonate in both fed and fasted adult baboons appeared to be the same as in fed and fasted adult mice, respectively. 17 refs., 2 tabs.

  12. IUPAC-NIST Solubility Data Series. 89. Alkali Metal Nitrates. Part 1. Lithium Nitrate

    NASA Astrophysics Data System (ADS)

    Eysseltová, Jitka

    2010-09-01

    This paper is the first part in the nitrate solubility volume. The solubility data for lithium nitrate are reviewed. Where appropriate, binary, ternary, and multicomponent systems are critically evaluated. Most of the solubility results were obtained in water or aqueous solutions. The solubility in ethanol and in alcohol+water solvent mixtures is also included. All data were critically examined for their reliability. The best values were selected on the basis of critical evaluations and presented in tabular form. Fitting equations and plots are also provided. The quantities, units, and symbols used are in accord with IUPAC recommendations. The original data have been reported and, if necessary, transferred into the units and symbols recommended by IUPAC. The literature on solubility data was researched through 2007.

  13. DEVELOPMENT OF GLASS AND CRYSTALLINE CERAMIC FORMS FOR DISPOSITION OF EXCESS PLUTONIUM

    SciTech Connect

    Marra, James; Cozzi, A; Crawford, C.; Herman, C.; Marra, John; Peeler, D.

    2009-09-10

    In the aftermath of the Cold War, the United States Department of Energy (DOE) has identified up to 50 metric tons of excess plutonium that needs to be dispositioned. The bulk of the material is slated to be blended with uranium and fabricated into a Mixed Oxide (MOX) fuel for subsequent burning in commercial nuclear reactors. Excess plutonium-containing impurity materials making it unsuitable for fabrication into MOX fuel will need to be dispositioned via other means. Glass and crystalline ceramics have been developed and studied as candidate forms to immobilize these impure plutonium feeds. A titanate-based ceramic was identified as an excellent actinide material host. This composition was based on Synroc compositions previously developed for nuclear waste immobilization. These titanate ceramics were found to be able to accommodate extremely high quantities of fissile material and exhibit excellent aqueous durability. A lanthanide borosilicate (LaBS) glass was developed to accommodate high concentrations of plutonium and to be very tolerant of impurities yet still maintain good aqueous durability. Recent testing of alkali borosilicate compositions showed promise of using these compositions to disposition lower concentrations of plutonium using existing high level waste vitrification processes. The developed waste forms all appear to be suitable for Pu disposition. Depending on the actual types and concentrations of the Pu residue streams slated for disposition, each waste form offers unique advantages.

  14. 33 CFR 126.28 - Ammonium nitrate, ammonium nitrate fertilizers, fertilizer mixtures, or nitro carbo nitrate...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ..., described and defined as an oxidizer by the regulations of 49 CFR part 173 is handled, stored, stowed...) must be eliminated or plugged. Note: See 49 CFR 176.415 for permit requirements for nitro carbo nitrate... nitrate fertilizers, fertilizer mixtures, or nitro carbo nitrate; general provisions. 126.28 Section...

  15. 33 CFR 126.28 - Ammonium nitrate, ammonium nitrate fertilizers, fertilizer mixtures, or nitro carbo nitrate...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ..., described and defined as an oxidizer by the regulations of 49 CFR part 173 is handled, stored, stowed...) must be eliminated or plugged. Note: See 49 CFR 176.415 for permit requirements for nitro carbo nitrate... nitrate fertilizers, fertilizer mixtures, or nitro carbo nitrate; general provisions. 126.28 Section...

  16. 33 CFR 126.28 - Ammonium nitrate, ammonium nitrate fertilizers, fertilizer mixtures, or nitro carbo nitrate...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ..., described and defined as an oxidizer by the regulations of 49 CFR part 173 is handled, stored, stowed...) must be eliminated or plugged. Note: See 49 CFR 176.415 for permit requirements for nitro carbo nitrate... nitrate fertilizers, fertilizer mixtures, or nitro carbo nitrate; general provisions. 126.28 Section...

  17. 33 CFR 126.28 - Ammonium nitrate, ammonium nitrate fertilizers, fertilizer mixtures, or nitro carbo nitrate...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ..., described and defined as an oxidizer by the regulations of 49 CFR part 173 is handled, stored, stowed...) must be eliminated or plugged. Note: See 49 CFR 176.415 for permit requirements for nitro carbo nitrate... nitrate fertilizers, fertilizer mixtures, or nitro carbo nitrate; general provisions. 126.28 Section...

  18. 33 CFR 126.28 - Ammonium nitrate, ammonium nitrate fertilizers, fertilizer mixtures, or nitro carbo nitrate...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., described and defined as an oxidizer by the regulations of 49 CFR part 173 is handled, stored, stowed...) must be eliminated or plugged. Note: See 49 CFR 176.415 for permit requirements for nitro carbo nitrate... nitrate fertilizers, fertilizer mixtures, or nitro carbo nitrate; general provisions. 126.28 Section...

  19. Zone refining of plutonium metal

    SciTech Connect

    1997-05-01

    The purpose of this study was to investigate zone refining techniques for the purification of plutonium metal. The redistribution of 10 impurity elements from zone melting was examined. Four tantalum boats were loaded with plutonium impurity alloy, placed in a vacuum furnace, heated to 700{degrees}C, and held at temperature for one hour. Ten passes were made with each boat. Metallographic and chemical analyses performed on the plutonium rods showed that, after 10 passes, moderate movement of certain elements were achieved. Molten zone speeds of 1 or 2 inches per hour had no effect on impurity element movement. Likewise, the application of constant or variable power had no effect on impurity movement. The study implies that development of a zone refining process to purify plutonium is feasible. Development of a process will be hampered by two factors: (1) the effect on impurity element redistribution of the oxide layer formed on the exposed surface of the material is not understood, and (2) the tantalum container material is not inert in the presence of plutonium. Cold boat studies are planned, with higher temperature and vacuum levels, to determine the effect on these factors. 5 refs., 1 tab., 5 figs.

  20. Ammonium nitrate explosive systems

    DOEpatents

    Stinecipher, Mary M.; Coburn, Michael D.

    1981-01-01

    Novel explosives which comprise mixtures of ammonium nitrate and an ammonium salt of a nitroazole in desired ratios are disclosed. A preferred nitroazole is 3,5-dinitro-1,2,4-triazole. The explosive and physical properties of these explosives may readily be varied by the addition of other explosives and oxidizers. Certain of these mixtures have been found to act as ideal explosives.

  1. Nitrate Storage and Dissimilatory Nitrate Reduction by Eukaryotic Microbes

    PubMed Central

    Kamp, Anja; Høgslund, Signe; Risgaard-Petersen, Nils; Stief, Peter

    2015-01-01

    The microbial nitrogen cycle is one of the most complex and environmentally important element cycles on Earth and has long been thought to be mediated exclusively by prokaryotic microbes. Rather recently, it was discovered that certain eukaryotic microbes are able to store nitrate intracellularly and use it for dissimilatory nitrate reduction in the absence of oxygen. The paradigm shift that this entailed is ecologically significant because the eukaryotes in question comprise global players like diatoms, foraminifers, and fungi. This review article provides an unprecedented overview of nitrate storage and dissimilatory nitrate reduction by diverse marine eukaryotes placed into an eco-physiological context. The advantage of intracellular nitrate storage for anaerobic energy conservation in oxygen-depleted habitats is explained and the life style enabled by this metabolic trait is described. A first compilation of intracellular nitrate inventories in various marine sediments is presented, indicating that intracellular nitrate pools vastly exceed porewater nitrate pools. The relative contribution by foraminifers to total sedimentary denitrification is estimated for different marine settings, suggesting that eukaryotes may rival prokaryotes in terms of dissimilatory nitrate reduction. Finally, this review article sketches some evolutionary perspectives of eukaryotic nitrate metabolism and identifies open questions that need to be addressed in future investigations. PMID:26734001

  2. Structure and spectroscopy of hydrated neptunyl(VI) nitrate complexes.

    PubMed

    Lindqvist-Reis, Patric; Apostolidis, Christos; Walter, Olaf; Marsac, Remi; Banik, Nidhu Lal; Skripkin, Mikhail Yu; Rothe, Jörg; Morgenstern, Alfred

    2013-11-21

    Complexation between hexavalent neptunium and nitrate was studied in aqueous nitric acid solution using optical absorption, vibrational and X-ray absorption spectroscopies. Distributions of aqueous [NpO2](2+), [NpO2(NO3)](+) and [NpO2(NO3)2] species were obtained as a function of nitric acid concentration between 0 and 14 M. The crystal structure of [NpO2(NO3)2(H2O)2]·H2O was determined. PMID:24042456

  3. 49 CFR 175.704 - Plutonium shipments.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... Regulations Applicable According to Classification of Material § 175.704 Plutonium shipments. Shipments of plutonium which are subject to 10 CFR 71.88(a)(4) must comply with the following: (a) Each package... 49 Transportation 2 2012-10-01 2012-10-01 false Plutonium shipments. 175.704 Section...

  4. 49 CFR 175.704 - Plutonium shipments.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... Regulations Applicable According to Classification of Material § 175.704 Plutonium shipments. Shipments of plutonium which are subject to 10 CFR 71.88(a)(4) must comply with the following: (a) Each package... 49 Transportation 2 2014-10-01 2014-10-01 false Plutonium shipments. 175.704 Section...

  5. 49 CFR 175.704 - Plutonium shipments.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... Regulations Applicable According to Classification of Material § 175.704 Plutonium shipments. Shipments of plutonium which are subject to 10 CFR 71.88(a)(4) must comply with the following: (a) Each package... 49 Transportation 2 2013-10-01 2013-10-01 false Plutonium shipments. 175.704 Section...

  6. Plutonium Oxide Process Capability Work Plan

    SciTech Connect

    Meier, David E.; Tingey, Joel M.

    2014-02-28

    Pacific Northwest National Laboratory (PNNL) has been tasked to develop a Pilot-scale Plutonium-oxide Processing Unit (P3U) providing a flexible capability to produce 200g (Pu basis) samples of plutonium oxide using different chemical processes for use in identifying and validating nuclear forensics signatures associated with plutonium production. Materials produced can also be used as exercise and reference materials.

  7. 49 CFR 175.704 - Plutonium shipments.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... Regulations Applicable According to Classification of Material § 175.704 Plutonium shipments. Shipments of plutonium which are subject to 10 CFR 71.88(a)(4) must comply with the following: (a) Each package... 49 Transportation 2 2010-10-01 2010-10-01 false Plutonium shipments. 175.704 Section...

  8. 49 CFR 175.704 - Plutonium shipments.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... Regulations Applicable According to Classification of Material § 175.704 Plutonium shipments. Shipments of plutonium which are subject to 10 CFR 71.88(a)(4) must comply with the following: (a) Each package... 49 Transportation 2 2011-10-01 2011-10-01 false Plutonium shipments. 175.704 Section...

  9. Reduction of nitrate and nitrite salts under hydrothermal conditions

    SciTech Connect

    Foy, B.R.; Dell`Orco, P.C.; Wilmanns, E.; McInroy, R.; Ely, J.; Robinson, J.M.; Buelow, S.J.

    1994-10-01

    The feasibility of reducing nitrate/nitrite salts under hydrothermal conditions for the treatment of aqueous mixed wastes stored in the underground tanks at the Department of Energy site at Hanford, Washington was studied. The reduction of nitrate and nitrite salts by reaction with EDTA using a tank waste simulant was examined at temperatures between 623K and 800K and pressures between 0.6 and 1.2 kbar. Continuous flow reactors were used to determine kinetics and products of reactions. All reactions were studied under pressures high enough to produce single phase conditions. The reactions are rapid, go to completion in less than a minute, and produce simple products, such as carbonate, nitrogen, and nitrous oxide gases. The experimental results demonstrate the ability of chemical reactions under hydrothermal conditions to reduce the nitrate and nitrite salts and destroy organic compounds in the waste mixtures.

  10. Plutonium stabilization and packaging system

    SciTech Connect

    1996-05-01

    This document describes the functional design of the Plutonium Stabilization and Packaging System (Pu SPS). The objective of this system is to stabilize and package plutonium metals and oxides of greater than 50% wt, as well as other selected isotopes, in accordance with the requirements of the DOE standard for safe storage of these materials for 50 years. This system will support completion of stabilization and packaging campaigns of the inventory at a number of affected sites before the year 2002. The package will be standard for all sites and will provide a minimum of two uncontaminated, organics free confinement barriers for the packaged material.

  11. Complexation of Plutonium (IV) with Fluoride at Variable Temperatures

    SciTech Connect

    Xia, Yuanxian; Rao, Linfeng; Friese, Judah I.; Moore, Dean A.; Bachelor, Paula P.

    2010-02-02

    The complexation of Pu(IV) with fluoride at elevated temperatures was studied by solvent extraction technique. A solution of NaBrO3 was used as holding oxidant to maintain the oxidation state of plutonium throughout the experiments. The distribution ratio of Pu(IV) between the organic and aqueous phases was found to decrease as the concentrations of fluoride were increased. Stability constants of the 1:1 and 1:2 Pu(IV)-F- complexes, dominant in the aqueous phase under the experimental conditions, were calculated from the effect of fluoride ions on the distribution ratio. The thermodynamic parameters, including enthalpy and entropy of complexation between Pu(IV) and fluoride at 25 degrees C - 55 degrees C were calculated from the stability constants at different temperatures by using the Van’t Hoff equation.

  12. Plutonium immobilization form evaluation

    SciTech Connect

    Gray, L. W., LLNL

    1998-02-13

    The 1994 National Academy of Sciences study and the 1997 assessment by DOE`s Office of Nonproliferation and National Security have emphasized the importance of the overall objectives of the Plutonium Disposition Program of beginning disposition rapidly. President Clinton and other leaders of the G-7 plus one (`Political Eight`) group of states, at the Moscow Nuclear Safety And Security Summit in April 1996, agreed on the objectives of accomplishing disposition of excess fissile material as soon as practicable. To meet these objectives, DOE has laid out an aggressive schedule in which large-scale immobilization operations would begin in 2005. Lawrence Livermore National Laboratory (LLNL), the lead laboratory for the development of Pu immobilization technologies for the Department of Energy`s Office of Fissile Materials Disposition (MD), was requested by MD to recommend the preferred immobilization form and technology for the disposition of excess weapons-usable Pu. In a series of three separate evaluations, the technologies for the candidate glass and ceramic forms were compared against criteria and metrics that reflect programmatic and technical objectives: (1) Evaluation of the R&D and engineering data for the two forms against the decision criteria/metrics by a technical evaluation panel comprising experts from within the immobilization program. (2) Integrated assessment by LLNL immobilization management of the candidate technologies with respect to the weighted criteria and other programmatic objectives, leading to a recommendation to DOE/MD on the preferred technology based on technical factors. (3) Assessment of the decision process, evaluation, and recommendation by a peer review panel of independent experts. Criteria used to assess the relative merits of the immobilization technologies were a subset of the criteria previously used by MD to choose among disposition options leading to the Programmatic Environmental Impact Statement and Record of Decision for the Storage and Disposition of Weapons-Usable Fissile Materials, January 1997. Criteria were: (1) resistance to Pu theft, diversion, and recovery by a terrorist organization or rogue nation; (2) resistance to recovery and reuse by host nation; (3) technical viability, including technical maturity, development risk, and acceptability for repository disposal; (4) environmental, safety, and health factors; (5) cost effectiveness; and (6) timeliness. On the basis of the technical evaluation and assessments, in September, 1997, LLNL recommended to DOE/MD that ceramic technologies be developed for deployment in the planned Pu immobilization plant.

  13. Nitrate biosensors and biological methods for nitrate determination.

    PubMed

    Sohail, Manzar; Adeloju, Samuel B

    2016-06-01

    The inorganic nitrate (NO3‾) anion is present under a variety of both natural and artificial environmental conditions. Nitrate is ubiquitous within the environment, food, industrial and physiological systems and is mostly present as hydrated anion of a corresponding dissolved salt. Due to the significant environmental and toxicological effects of nitrate, its determination and monitoring in environmental and industrial waters are often necessary. A wide range of analytical techniques are available for nitrate determination in various sample matrices. This review discusses biosensors available for nitrate determination using the enzyme nitrate reductase (NaR). We conclude that nitrate determination using biosensors is an excellent non-toxic alternative to all other available analytical methods. Over the last fifteen years biosensing technology for nitrate analysis has progressed very well, however, there is a need to expedite the development of nitrate biosensors as a suitable alternative to non-enzymatic techniques through the use of different polymers, nanostructures, mediators and strategies to overcome oxygen interference. PMID:27130094

  14. Plutonium recovery from carbonate wash solutions

    SciTech Connect

    Gray, J.H.; Reif, D.J.; Chostner, D.F.; Holcomb, H.P.

    1991-12-31

    Periodically higher than expected levels of plutonium are found in carbonate solutions used to wash second plutonium cycle solvent. The recent accumulation of plutonium in carbonate wash solutions has led to studies to determine the cause of that plutonium accumulation, to evaluate the quality of all canyon solvents, and to develop additional criteria needed to establish when solvent quality is acceptable. Solvent from three canyon solvent extraction cycles was used to evaluate technology required to measure tributyl phosphate (TBP) degradation products and was used to evaluate solvent quality criteria during the development of plutonium recovery processes. 1 fig.

  15. Plutonium inventory characterization technical evaluation report

    SciTech Connect

    Wittman, G.R., Westinghouse Hanford

    1996-07-10

    This is a technical report on the data, gathered to date, under WHC- SD-CP-TP-086, Rev. 1, on the integrity of the food pack cans currently being used to store plutonium or plutonium compounds at the Plutonium Finishing Plant. Workplan PFP-96-VO-009, `Inspection of Special Nuclear Material Using X-ray`, was used to gather data on material and containment conditions using real time radiography. Some of those images are included herein. A matrix found in the `Plutonium Inventory Characterization Implementation Plan` was used to categorize different plutonium items based upon the type of material being stored and the life expectancy of the containers.

  16. The chemistry, waste form development, and properties of the Nitrate to Ammonia and Ceramic (NAC) process

    SciTech Connect

    Mattus, A.J.; Lee, D.D.; Youngblood, E.L.; Walker, J.F. Jr.; Tiegs, T.N.

    1994-06-01

    A process for the conversion of alkaline, aqueous nitrate wastes to ammonia gas at low temperature, based upon the use of the active metal reductant aluminum, has been developed at the Oak Ridge National Laboratory (ORNL). The process is also well suited for the removal of low-level waste (LLW) radioelements and hazardous metals which report to the solid, alumina-based by-product. ne chemistry of the interaction of aluminum powders with nitrate, and other waste stream metals is presented.

  17. Assimilation of nitrate by yeasts.

    PubMed

    Siverio, José M

    2002-08-01

    Nitrate assimilation has received much attention in filamentous fungi and plants but not so much in yeasts. Recently the availability of classical genetic and molecular biology tools for the yeast Hansenula polymorpha has allowed the advance of the study of this metabolic pathway in yeasts. The genes YNT1, YNR1 and YNI1, encoding respectively nitrate transport, nitrate reductase and nitrite reductase, have been cloned, as well as two other genes encoding transcriptional regulatory factors. All these genes lie closely together in a cluster. Transcriptional regulation is the main regulatory mechanism that controls the levels of the enzymes involved in nitrate metabolism although other mechanisms may also be operative. The process involved in the sensing and signalling of the presence of nitrate in the medium is not well understood. In this article the current state of the studies of nitrate assimilation in yeasts as well as possible venues for future research are reviewed. PMID:12165428

  18. Plutonium Recycle: The Fateful Step

    ERIC Educational Resources Information Center

    Speth, J. Gustave; And Others

    1974-01-01

    Calls attention to the fact that if the Atomic Energy Commission proceeds with its plans to authorize the nuclear power industry to use plutonium as a fuel in commercial nuclear reactors around the country, this will result in a dramatic escalation in the risks posed by nuclear power. (PEB)

  19. Plutonium waste incineration using pyrohydrolysis

    SciTech Connect

    Meyer, M.L.

    1991-12-31

    Waste generated by Savannah River Site (SRS) plutonium operations includes a contaminated organic waste stream. A conventional method for disposing of the organic waste stream and recovering the nuclear material is by incineration. When the organic material is burned, the plutonium remains in the incinerator ash. Plutonium recovery from incinerator ash is highly dependent on the maximum temperature to which the oxide is exposed. Recovery via acid leaching is reduced for a high fired ash (>800{degree}C), while plutonium oxides fired at lower decomposition temperatures (400--800{degrees}C) are more soluble at any given acid concentration. To determine the feasibility of using a lower temperature process, tests were conducted using an electrically heated, controlled-air incinerator. Nine nonradioactive, solid, waste materials were batch-fed and processed in a top-heated cylindrical furnace. Waste material processing was completed using a 19-liter batch over a nominal 8-hour cycle. A processing cycle consisted of 1 hour for heating, 4 hours for reacting, and 3 hours for chamber cooling. The water gas shift reaction was used to hydrolyze waste materials in an atmosphere of 336% steam and 4.4% oxygen. Throughput ranged from 0.14 to 0.27 kg/hr depending on the variability in the waste material composition and density.

  20. Plutonium waste incineration using pyrohydrolysis

    SciTech Connect

    Meyer, M.L.

    1991-01-01

    Waste generated by Savannah River Site (SRS) plutonium operations includes a contaminated organic waste stream. A conventional method for disposing of the organic waste stream and recovering the nuclear material is by incineration. When the organic material is burned, the plutonium remains in the incinerator ash. Plutonium recovery from incinerator ash is highly dependent on the maximum temperature to which the oxide is exposed. Recovery via acid leaching is reduced for a high fired ash (>800{degree}C), while plutonium oxides fired at lower decomposition temperatures (400--800{degrees}C) are more soluble at any given acid concentration. To determine the feasibility of using a lower temperature process, tests were conducted using an electrically heated, controlled-air incinerator. Nine nonradioactive, solid, waste materials were batch-fed and processed in a top-heated cylindrical furnace. Waste material processing was completed using a 19-liter batch over a nominal 8-hour cycle. A processing cycle consisted of 1 hour for heating, 4 hours for reacting, and 3 hours for chamber cooling. The water gas shift reaction was used to hydrolyze waste materials in an atmosphere of 336% steam and 4.4% oxygen. Throughput ranged from 0.14 to 0.27 kg/hr depending on the variability in the waste material composition and density.

  1. The First Weighing of Plutonium

    DOE R&D Accomplishments Database

    Seaborg, Glenn T.

    1967-09-10

    Recollections and reminiscences at the 25th Anniversary of the First Weighing of Plutonium, Chicago, IL, September 10, 1967, tell an important part of the story of this fascinating new element that is destined to play an increasingly significant role in the future of man.

  2. Safe disposal of surplus plutonium

    NASA Astrophysics Data System (ADS)

    Gong, W. L.; Naz, S.; Lutze, W.; Busch, R.; Prinja, A.; Stoll, W.

    2001-06-01

    About 150 tons of weapons grade and weapons usable plutonium (metal, oxide, and in residues) have been declared surplus in the USA and Russia. Both countries plan to convert the metal and oxide into mixed oxide fuel for nuclear power reactors. Russia has not yet decided what to do with the residues. The US will convert residues into a ceramic, which will then be over-poured with highly radioactive borosilicate glass. The radioactive glass is meant to provide a deterrent to recovery of plutonium, as required by a US standard. Here we show a waste form for plutonium residues, zirconia/boron carbide (ZrO 2/B 4C), with an unprecedented combination of properties: a single, radiation-resistant, and chemically durable phase contains the residues; billion-year-old natural analogs are available; and criticality safety is given under all conceivable disposal conditions. ZrO 2/B 4C can be disposed of directly, without further processing, making it attractive to all countries facing the task of plutonium disposal. The US standard for protection against recovery can be met by disposal of the waste form together with used reactor fuel.

  3. Glutarimidedioxime: A Complexing and Reducing Reagent for Plutonium Recovery from Spent Nuclear Fuel Reprocessing.

    PubMed

    Xian, Liang; Tian, Guoxin; Beavers, Christine M; Teat, Simon J; Shuh, David K

    2016-04-01

    Efficient separation processes for recovering uranium and plutonium from spent nuclear fuel are essential to the development of advanced nuclear fuel cycles. The performance characteristics of a new salt-free complexing and reducing reagent, glutarimidedioxime (H2 A), are reported for recovering plutonium in a PUREX process. With a phase ratio of organic to aqueous of up to 10:1, plutonium can be effectively stripped from 30 % tributyl phosphate (TBP) in kerosene into 1 m HNO3 with H2 A. The complexation-reduction mechanism is illustrated with the combination of UV/Vis absorption spectra and the crystal structure of a Pu(IV) complex with the reagent. The fast stripping rate and the high efficiency for stripping Pu(IV) , through the complexation-reduction mechanism, is suitable for use in centrifugal contactors with very short contact/resident times, thereby offering significant advantages over conventional processes. PMID:26970221

  4. PLUTONIUM SOLUBILITY IN SIMULATED SAVANNAH RIVER SITE WASTE SOLUTIONS

    SciTech Connect

    Rudisill, T.; Hobbs, D.; Edwards, T.

    2010-09-27

    To address the accelerated disposition of the supernate and salt portions of Savannah River Site (SRS) high level waste (HLW), solubility experiments were performed to develop a predictive capability for plutonium (Pu) solubility. A statistically designed experiment was used to measure the solubility of Pu in simulated solutions with salt concentrations and temperatures which bounded those observed in SRS HLW solutions. Constituents of the simulated waste solutions included: hydroxide (OH{sup -}), aluminate (Al(OH){sub 4}{sup -}), sulfate (SO{sub 4}{sup 2-}), carbonate (CO{sub 3}{sup 2-}), nitrate (NO{sub 3}{sup -}), and nitrite (NO{sub 2}{sup -}) anions. Each anion was added to the waste solution in the sodium form. The solubilities were measured at 25 and 80 C. Five sets of samples were analyzed over a six month period and a partial sample set was analyzed after nominally fifteen months of equilibration. No discernable time dependence of the measured Pu concentrations was observed except for two salt solutions equilibrated at 80 C which contained OH{sup -} concentrations >5 mol/L. In these solutions, the Pu solubility increased with time. This observation was attributed to the air oxidation of a portion of the Pu from Pu(IV) to the more soluble Pu(V) or Pu(VI) valence states. A data driven approach was subsequently used to develop a modified response surface model for Pu solubility. Solubility data from this study and historical data from the literature were used to fit the model. The model predicted the Pu solubility of the solutions from this study within the 95% confidence interval for individual predictions and the analysis of variance indicated no statistically significant lack of fit. The Savannah River National Laboratory (SRNL) model was compared with predicted values from the Aqueous Electrolyte (AQ) model developed by OLI Systems, Inc. and a solubility prediction equation developed by Delegard and Gallagher for Hanford tank waste. The agreement between measured or values predicted by the SRNL model and values predicted by the OLI AG model was very poor. The much higher predicted concentrations by the OLI AQ model appears to be the result of the model predicting the predominate Pu oxidation state is Pu(V) which is reported as unstable below sodium hydroxide (NaOH) concentrations of 6 M. There was very good agreement between the predicted Pu concentrations using the SRNL model and the model developed by Delegard and Gallagher with the exception of solutions that had very high OH{sup -} (15 M) concentrations. The lower Pu solubilities in these solutions were attributed to the presence of NO{sub 3}{sup -} and NO{sub 2}{sup -} which limit the oxidation of Pu(IV) to Pu(V).

  5. dl-Asparaginium nitrate.

    PubMed

    Moussa Slimane, Nabila; Cherouana, Aouatef; Bendjeddou, Lamia; Dahaoui, Slimane; Lecomte, Claude

    2009-01-01

    In the title compound, C(4)H(9)N(2)O(3) (+)·NO(3) (-), alternatively called (1RS)-2-carbamoyl-1-carboxy-ethanaminium nitrate, the asymmetric unit comprises one asparaginium cation and one nitrate anion. The strongest cation-cation O-H⋯O hydrogen bond in the structure, together with other strong cation-cation N-H⋯O hydrogen bonds, generates a succession of infinite chains of R(2) (2)(8) rings along the b axis. Additional cation-cation C-H⋯O hydrogen bonds link these chains into two-dimensional layers formed by alternating R(4) (4)(24) and R(4) (2)(12) rings. Connections between these layers are provided by the strong cation-anion N-H⋯O hydrogen bonds, as well as by one weak C-H⋯O inter-action, thus forming a three-dimensional network. Some of the cation-anion N-H⋯O hydrogen bonds are bifurcated of the type D-H⋯(A(1),A(2)). PMID:21577586

  6. dl-Asparaginium nitrate

    PubMed Central

    Moussa Slimane, Nabila; Cherouana, Aouatef; Bendjeddou, Lamia; Dahaoui, Slimane; Lecomte, Claude

    2009-01-01

    In the title compound, C4H9N2O3 +·NO3 −, alternatively called (1RS)-2-carbamoyl-1-carboxy­ethanaminium nitrate, the asymmetric unit comprises one asparaginium cation and one nitrate anion. The strongest cation–cation O—H⋯O hydrogen bond in the structure, together with other strong cation–cation N—H⋯O hydrogen bonds, generates a succession of infinite chains of R 2 2(8) rings along the b axis. Additional cation–cation C—H⋯O hydrogen bonds link these chains into two-dimensional layers formed by alternating R 4 4(24) and R 4 2(12) rings. Connections between these layers are provided by the strong cation–anion N—H⋯O hydrogen bonds, as well as by one weak C—H⋯O inter­action, thus forming a three-dimensional network. Some of the cation–anion N—H⋯O hydrogen bonds are bifurcated of the type D—H⋯(A 1,A 2). PMID:21577586

  7. LOW TEMPERATURE PROCESS FOR THE REMOVAL AND RECOVERY OF CHLORIDES AND NITRATES FROM AQUEOUS NITRATE SOLUTIONS

    DOEpatents

    Savolainen, J.E.

    1963-01-29

    A method is described for reducing the chloride content of a solution derived from the dissolution of a stainless steel clad nuclear fuel element with an aqua regia dissolution medium. The solutlon is adjusted to a nitric acid concentration in the range 5 to 10 M and is countercurrently contacted at room temperature with a gaseous oxide of nitrogen selected from NO, NO/sub 2/, N/sub 2/ O/sub 3/, and N/sub 2/O/sub 4/. Chlo ride is recovered from the contacted solution as nitrosyl chloride. After reduction of the chloride content, the solution is then contacted with gaseous NO to reduce the nitric acid molarity to a desired level. (AEC)

  8. Effects of nitrate on the treatment of lead contaminated groundwater by nanoscale zerovalent iron.

    PubMed

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

    2014-09-15

    Nanoscale zerovalent iron (nZVI) is efficient for removing Pb(2+) and nitrate from water. However, the influence of nitrate, a common groundwater anion, on Pb(2+) removal by nZVI is not well understood. In this study, we showed that under excess Fe(0) conditions (molar ratio of Fe(0)/nitrate>4), Pb(2+) ions were immobilized more quickly (<5 min) than in nitrate-free systems (∼ 15 min) due to increasing pH. With nitrate in excess (molar ratio of Fe(0)/nitrate<4), nitrate stimulated the formation of crystal PbxFe3-xO4 (ferrite), which provided additional Pb(2+) removal. However, ∼ 7% of immobilized Pb(2+) ions were released into aqueous phase within 2h due to ferrite deformation. Oxidation-reduction potential (ORP) values below -600 mV correlated with excess Fe(0) conditions (complete Pb(2+) immobilization), while ORP values ≥-475 mV characterized excess nitrate conditions (ferrite process and Pb(2+) release occurrence). This study indicates that ORP monitoring is important for proper management of nZVI-based remediation in the subsurface to avoid lead remobilization in the presence of nitrate. PMID:25209830

  9. Thermal Decomposition of Nitrated Tributyl Phosphate

    SciTech Connect

    Paddleford, D.F.; Hou, Y.; Barefield, E.K.; Tedder, D.W.; Abdel-Khalik, S.I.

    1995-01-01

    Contact between tributyl phosphate and aqueous solutions of nitric acid and/or heavy metal nitrate salts at elevated temperatures can lead to exothermic reactions of explosive violence. Even though such operations have been routinely performed safely for decades as an intrinsic part of the Purex separation processes, several so-called ``red oil`` explosions are known to have occurred in the United States, Canada, and the former Soviet Union. The most recent red oil explosion occurred at the Tomsk-7 separations facility in Siberia, in April 1993. That explosion destroyed part of the unreinforced masonry walls of the canyon-type building in which the process was housed, and allowed the release of a significant quantity of radioactive material.

  10. Collaborative study of the colorimetric determination of nitrate and nitrite in cheese.

    PubMed

    Hamilton, J E

    1976-03-01

    A quantitative colorimetric method for the determination of nitrate and nitrite in cheese has been subjected to collaborative study. The method includes clarification of an aqueous extract of cheese with zinc hydroxide, reduction of nitrate to nitrite via a spongy cadmium collumn (the nitrite originally present is unaltered), diazotization of sulfanilic acid with the nitrite, and coupling with 1-naphthylamine hydrochloride to form a pink azo dye whose absorbance is measured at 522 nm. The spectrophotometric responses are compared to a standard curve. In samples containing both nitrate and nitrite, nitrate is determined by difference. A standard deviation of 5.5 was obtained (5 of 6 collaborators) when a cheese sample spiked with 276 ppm sodium nitrate was analyzed by the method. The method has been adopted as official first action. PMID:1254548

  11. Processes for extraction of uranium and radium from uranium-containing ores using ferric nitrate

    SciTech Connect

    Nirdosh, I.

    1987-03-10

    A process is described for the extraction of both uranium and radium from uranium ores in the presence of an interfering sulfate ion resulting from the presence of sulfide therein by use of an aqueous ferric nitrate leachant including the steps of: (a) mechanically treating the finely ground ore for the removal of sulfide therefrom; (b) leaching the mechanically treated finely ground ore with aqueous acidic ferric nitrate solution in a concentration from 0.01 to 0.1M for the removal of uranium and radium therefrom to result in a liquid ferric nitrate leachate containing radium and uranium and a wet cake containing radium, uranium and ferric nitrate; (c) treating the ferric nitrate leachate to separate uranium and radium therefrom; (d) separately treating the wet cake for removal of retained ferric nitrate and the residual radium and uranium therefrom; and (e) recirculating a major portion of the ferric nitrate leachate from step (c) for the leaching of more of the mechanically treated finely ground ore.

  12. Comparison of plasma generated nitrogen fertilizer to conventional fertilizers ammonium nitrate and sodium nitrate for pre-emergent and seedling growth

    NASA Astrophysics Data System (ADS)

    Andhavarapu, A.; King, W.; Lindsay, A.; Byrns, B.; Knappe, D.; Fonteno, W.; Shannon, S.

    2014-10-01

    Plasma source generated nitrogen fertilizer is compared to conventional nitrogen fertilizers in water for plant growth. Root, shoot sizes, and weights are used to examine differences between plant treatment groups. With a simple coaxial structure creating a large-volume atmospheric glow discharge, a 162 MHz generator drives the air plasma. The VHF plasma source emits a steady state glow; the high drive frequency is believed to inhibit the glow-to-arc transition for non-thermal discharge generation. To create the plasma activated water (PAW) solutions used for plant treatment, the discharge is held over distilled water until a 100 ppm nitrate aqueous concentration is achieved. The discharge is used to incorporate nitrogen species into aqueous solution, which is used to fertilize radishes, marigolds, and tomatoes. In a four week experiment, these plants are watered with four different solutions: tap water, dissolved ammonium nitrate DI water, dissolved sodium nitrate DI water, and PAW. Ammonium nitrate solution has the same amount of total nitrogen as PAW; sodium nitrate solution has the same amount of nitrate as PAW. T-tests are used to determine statistical significance in plant group growth differences. PAW fertilization chemical mechanisms are presented.

  13. Protein nitration in cardiovascular diseases.

    PubMed

    Turko, Illarion V; Murad, Ferid

    2002-12-01

    There is growing evidence that cardiovascular disease is associated with progressive changes in the production of free radicals and radical-derived reactive species. These intermediates react with all major cellular constituents and may serve several physiological and pathophysiological functions. The nitration of protein tyrosine residues has been used as a footprint for in vivo production of radical and nonradical reactive species. Tyrosine nitration may alter protein function and metabolism and therefore, provides for further dysfunctional changes. This review focuses on an appearance of tyrosine nitrated proteins in cardiovascular tissues under different settings of cardiovascular disease. Sources of reactive species, putative mechanisms of protein nitration in vivo, as well as protein nitration under normal physiological conditions, are also described. The goal of this review is to attract more attention to identification of specific proteins, which undergo tyrosine nitration and to study a correlation between their altered function and pathology. Understanding how protein nitration affects disease progression may offer a unique option for design of antioxidant therapy for the treatment of cardiovascular complications. At the same time, protein nitration can be a biological marker of efficiency of antioxidant therapy. PMID:12429871

  14. Some History of Nitrates

    NASA Astrophysics Data System (ADS)

    Barnum, Dennis W.

    2003-12-01

    The history of saltpeter is an interesting combination of chemistry, world trade, technology, politics, and warfare. Originally it was obtained from the dirt floors of stables, sheep pens, pigeon houses, caverns, and even peasants' cottages; any place manure and refuse accumulated in soil under dry conditions. When these sources became inadequate to meet demand it was manufactured on saltpeter plantations, located in dry climates, where piles of dirt, limestone, and manure were allowed to stand for three to five years while soil microbes oxidized the nitrogen to nitrate—an example of early bioengineering. Extensive deposits of sodium nitrate were mined in the Atacama Desert in northern Chile from 1830 until the mid 1920s when the mines were displaced by the Haber Ostwald process.

  15. Nitrate reductase from Rhodopseudomonas sphaeroides.

    PubMed Central

    Kerber, N L; Cardenas, J

    1982-01-01

    The facultative phototroph Rhodopseudomonas sphaeroides DSM158 was incapable of either assimilating or dissimilating nitrate, although the organism could reduce it enzymatically to nitrite either anaerobically in the light or aerobically in the dark. Reduction of nitrate was mediated by a nitrate reductase bound to chromatophores that could be easily solubilized and functioned with chemically reduced viologens or photochemically reduced flavins as electron donors. The enzyme was solubilized, and some of its kinetic and molecular parameters were determined. It seemed to be nonadaptive, ammonia did not repress its synthesis, and its activity underwent a rapid decline when the cells entered the stationary growth phase. Studies with inhibitors and with metal antagonists indicated that molybdenum and possibly iron participate in the enzymatic reduction of nitrate. The conjectural significance of this nitrate reductase in phototrophic bacteria is discussed. PMID:6978883

  16. TREATMENT OF AMMONIUM NITRATE SOLUTIONS

    DOEpatents

    Boyer, T.W.; MacHutchin, J.G.; Yaffe, L.

    1958-06-10

    The treatment of waste solutions obtained in the processing of neutron- irradiated uranium containing fission products and ammonium nitrate is described. The object of this process is to provide a method whereby the ammonium nitrate is destroyed and removed from the solution so as to permit subsequent concentration of the solution.. In accordance with the process the residual nitrate solutions are treated with an excess of alkyl acid anhydride, such as acetic anhydride. Preferably, the residual nitrate solution is added to an excess of the acetic anhydride at such a rate that external heat is not required. The result of this operation is that the ammonium nitrate and acetic anhydride react to form N/sub 2/ O and acetic acid.

  17. Enhanced Surface Photochemistry in Chloride-Nitrate Ion Aerosol Mixtures

    NASA Astrophysics Data System (ADS)

    Wingen, L. M.; Moskun, A. C.; Thomas, J. L.; Roeselova, M.; Tobias, D. J.; Finlayson-Pitts, B. J.

    2007-12-01

    Heterogeneous reactions of sea salt aerosol with various oxides of nitrogen often lead to replacement of chloride ion by nitrate ion. Photolysis of aqueous nitrate at wavelengths > 290 nm leads to the production of nitrogen dioxide, hydroxyl radicals and other oxidants. The photochemistry of aerosols containing NO3- and Cl-, however, has not been investigated. Aerosols containing mixtures of NaCl and NaNO3 were used as a model system for processed sea salt aerosol. Photolysis experiments (λmax = 306 nm) were performed in 55 L Teflon chambers that contained deliquesced aerosols and production of gas phase NO2 was measured as a function of time using chemiluminescence detection. Simple alkanes were added in some experiments to probe OH radical and Cl atom production. Molecular dynamics simulations were also carried out on mixed aqueous NaCl and NaNO3 slabs to help understand ion solvation in these mixed salt systems. The simulations showed that as the Cl- to NO3- ratio increases, nitrate ions are drawn toward the interface due to the large double layer of interfacial Cl- and subsurface Na+. The systems explored both experimentally and computationally included pure NaNO3 and mixtures of Cl- and NO3- in molar ratios of 1:9, 1:1, and 9:1. The photolysis experiments showed an enhanced yield of gas phase NO2 as the chloride to nitrate ratio increased. We attribute the observed enhanced NO2 yields to an increased interfacial concentration of under-coordinated nitrate ion as the ratio of Cl- to NO3- increases. The implications of these enhanced NO2 yields as sea salt aerosols become processed in the atmosphere will also be discussed.

  18. Provenance of unknown plutonium material.

    PubMed

    Nicolaou, G

    2008-10-01

    The determination of the provenance of 'unknown' plutonium material is demonstrated through a simulation study based on an isotopic fingerprinting approach. Plutonium of known provenance was considered as the 'unknown' nuclear material in order to evaluate the potential of the approach and verify its predictive capabilities. Factor analysis was used to compare the Pu isotopic composition of the 'unknown' material with Pu isotopic compositions simulating well known spent fuels from a range of commercial nuclear power stations. The provenance of the 'unknown material' is assigned to the commercial fuel with which exhibits the highest degree of similarity with respect to the Pu composition. The approach appears promising since it accurately predicted the provenance of the one 'unknown' sample considered; nevertheless, the approach is still at the development stage. Important challenging issues related to the simulation uncertainties and its testing on real laboratory samples have to be explored prior to evaluating the potential of the approach. PMID:18639370

  19. Plutonium Immobilization Can Loading Concepts

    SciTech Connect

    Kriikku, E.; Ward, C.; Stokes, M.; Randall, B.; Steed, J.; Jones, R.; Hamilton, L.; Rogers, L.; Fiscus, J.; Dyches, G.

    1998-05-01

    The Plutonium Immobilization Facility will encapsulate plutonium in ceramic pucks and seal the pucks inside welded cans. Remote equipment will place these cans in magazines and the magazines in a Defense Waste Processing Facility (DWPF) canister. The DWPF will fill the canister with glass for permanent storage. This report discusses five can loading conceptual designs and the lists the advantages and disadvantages for each concept. This report identifies loading pucks into cans and backfilling cans with helium as the top priority can loading development areas. The can loading welder and cutter are very similar to the existing Savannah River Site (SRS) FB-Line bagless transfer welder and cutter and thus they are a low priority development item.

  20. PROCESS FOR SEGREGATING URANIUM FROM PLUTONIUM AND FISSION-PRODUCT CONTAMINATION

    DOEpatents

    Ellison, C.V.; Runion, T.C.

    1961-06-27

    An aqueous nitric acid solution containing uranium, plutonium, and fission product values is contacted with an organic extractant comprised of a trialkyl phosphate and an organic diluent. The relative amounts of trialkyl phosphate and uranium values are controlled to achieve a concentration of uranium values in the organic extractant of at least 0.35 moles uranium per mole of trialkyl phosphate, thereby preferentially extracting uranium values into the organic extractant.

  1. A review of the corrosion and pyrophoricity behavior of uranium and plutonium

    SciTech Connect

    Totemeier, T.C.

    1995-06-01

    This report presents a review of the corrosion and pyrophoricity behavior of uranium and plutonium. For each element, the reactions with oxygen, water vapor, and aqueous solutions are described in terms of reaction rates, products, and mechanisms. Their pyrophoric tendencies in terms of measured ignition temperatures are discussed, and the effects of the important variables specific area, gas composition, and prior storage rare stated. The implications of the observed behavior for current storage issues are considered.

  2. SEPARATION OF PLUTONIUM HYDROXIDE FROM BISMUTH HYDROXIDE

    DOEpatents

    Watt, G.W.

    1958-08-19

    An tmproved method is described for separating plutonium hydroxide from bismuth hydroxide. The end product of the bismuth phosphate processes for the separation amd concentration of plutonium is a inixture of bismuth hydroxide amd plutonium hydroxide. It has been found that these compounds can be advantageously separated by treatment with a reducing agent having a potential sufficient to reduce bismuth hydroxide to metalltc bisinuth but not sufficient to reduce the plutonium present. The resulting mixture of metallic bismuth and plutonium hydroxide can then be separated by treatment with a material which will dissolve plutonium hydroxide but not metallic bismuth. Sodiunn stannite is mentioned as a preferred reducing agent, and dilute nitric acid may be used as the separatory solvent.

  3. Zone refining of plutonium metal

    SciTech Connect

    Blau, M.S.

    1994-08-01

    The zone refining process was applied to Pu metal containing known amounts of impurities. Rod specimens of plutonium metal were melted into and contained in tantalum boats, each of which was passed horizontally through a three-turn, high-frequency coil in such a manner as to cause a narrow molten zone to pass through the Pu metal rod 10 times. The impurity elements Co, Cr, Fe, Ni, Np, U were found to move in the same direction as the molten zone as predicted by binary phase diagrams. The elements Al, Am, and Ga moved in the opposite direction of the molten zone as predicted by binary phase diagrams. As the impurity alloy was zone refined, {delta}-phase plutonium metal crystals were produced. The first few zone refining passes were more effective than each later pass because an oxide layer formed on the rod surface. There was no clear evidence of better impurity movement at the slower zone refining speed. Also, constant or variable coil power appeared to have no effect on impurity movement during a single run (10 passes). This experiment was the first step to developing a zone refining process for plutonium metal.

  4. Proceedings of the Plutonium Futures ? The Science 2006 Conference

    SciTech Connect

    Fluss, M; Hobart, D; Allan, P; Jarvinen, G

    2007-07-12

    Plutonium Futures--The Science 2006 provided opportunities to examine present knowledge of the chemical and physical properties of plutonium and other actinides in complex media and materials; to discuss the current and emerging science (chemistry, physics, materials science, nuclear science, and environmental effects) of plutonium and actinides relevant to enhancing global nuclear security; and to exchange ideas. This international conference also provided a forum for illustrating and enhancing capabilities and interests, and assessing issues in these areas. U.S. and international scientists, engineers, faculty, and students from universities, national laboratories, and DOE's nuclear complex were encouraged to participate and make technical contributions. The Conference ran from Sunday, July 9th through Thursday, July 13th. A popular aspect of the conference was the opening tutorial session on Sunday afternoon intended for students and scientists new to the area of plutonium research. The tutorial was well attended by novices and veterans alike, and featured such diverse topics as; plutonium metallurgy, plutonium in the environment, and international arms control and nonproliferation. Two plenary lectures began each morning and each afternoon session and highlighted the breakout sessions on coordination/organometallic chemistry, solid-state physics, environmental chemistry, materials science, separations and reprocessing, advanced fuels and waste forms, phase transformations, solution and gas-phase chemistry, compounds and complexes, electronic structure and physical properties, and more. Chemistry Highlights--Among the many chemistry highlights presented in this proceedings are the overview of concepts and philosophies on inert nuclear fuel matrices and concerns about the ever-increasing amounts of minor actinides and plutonium generated in the fuel cycle. The various ideas involve multiple reduction schemes for these materials, suggesting fuels for 'burning' or 'cradle-to-grave' accountability for various reactor types. Related work is presented on identification of the unique reaction mechanisms and identification of the intermediate products, including Pu(III), at the end of the PUREX process. In the important area of nuclear forensics, actual scenarios of nuclear materials confiscation and the successes of applying forensics protocols to determine attribution and possible intention are provided. In the area of reactor incidents, there is no other place on Earth like the Chernobyl Site Object Shelter and radioactive aerosol particle characterization studies reflect an important effort described herein. An additional report from another unique environmental site presents results on radionuclide monitoring, fate, and transport in the ecosystem of the Yenisei River in the Krasoyarsk region. In the area of nuclear waste disposal, a study of the ion irradiation damage to pyrochlore compounds with varying amounts of host elements and actinide dopants is presented. Papers on both the aqueous and nonaqueous chemistry of plutonium and other actinides are presented including anhydrous coordination chemistry and redox behavior in the presence of humic materials and the their sorption on common minerals in the environment. Also published herein are reports on the field of anhydrous coordination chemistry of the transuranic elements where there is scarce information. Solid-State and Materials Highlights--Plutonium solid-state and materials research is represented in these proceedings by a wealth of leading edge discovery class research. The breadth of this research is reflected in the topics covered: solid-state; materials science; superconductivity; phase changes, phonons, and entropy; electronic structure and physical properties; surface science and corrosion; and radiation effects, defects, impurities, and property changes. Indeed the scientific challenge and excitement of plutonium can best be highlighted by quoting the tutorial prospectus of Drs. Sarrao and Schwartz. 'Plutonium has long been recognized as a complex and scientifically rich metal. The challenge of Pu derives from the fact that its 5f electrons are neither fully localized nor fully itinerant. The resulting low energy scales lead to competing interactions and important entropic and lattice considerations as well. As a consequence, plutonium is on the verge of magnetic order and can be stabilized in a variety of crystal structures. The past several years have seen a renaissance in plutonium materials research. Despite significant progress and important breakthroughs, metallic plutonium remains a mystery at the frontier of materials research'. As we hope you will discover, much progress is being made that is reflected in these proceedings. More importantly however, is that the papers herein also inspire new experiments and theoretical approaches that we trust will not go unnoticed by the reader.

  5. Air transport of plutonium metal: content expansion initiative for the plutonium air transportable (PAT01) packaging

    SciTech Connect

    Caviness, Michael L; Mann, Paul T

    2010-01-01

    The National Nuclear Security Administration (NNSA) has submitted an application to the Nuclear Regulatory Commission (NRC) for the air shipment of plutonium metal within the Plutonium Air Transportable (PAT-1) packaging. The PAT-1 packaging is currently authorized for the air transport of plutonium oxide in solid form only. The INMM presentation will provide a limited overview of the scope of the plutonium metal initiative and provide a status of the NNSA application to the NRC.

  6. Air transport of plutonium metal : content expansion initiative for the Plutonium Air Transportable (PAT-1) packaging.

    SciTech Connect

    Mann, Paul T.; Caviness, Michael L.; Yoshimura, Richard Hiroyuki

    2010-06-01

    The National Nuclear Security Administration (NNSA) has submitted an application to the Nuclear Regulatory Commission (NRC) for the air shipment of plutonium metal within the Plutonium Air Transportable (PAT-1) packaging. The PAT-1 packaging is currently authorized for the air transport of plutonium oxide in solid form only. The INMM presentation will provide a limited overview of the scope of the plutonium metal initiative and provide a status of the NNSA application to the NRC.

  7. Influence of Iron Redox Transformations on Plutonium Sorption to Sediments

    SciTech Connect

    Hixon, Amy E.; Hu, Yung-Jin; Kaplan, Daniel I.; Kukkadapu, Ravi K.; Nitsche, Heino; Qafoku, Odeta; Powell, Brian A.

    2010-10-01

    Plutonium subsurface mobility is primarily controlled by its oxidation state, which in turn is loosely coupled to the oxidation state of iron in the system. Experiments were conducted to examine the effect of sediment iron mineral composition and oxidation state on plutonium sorption and oxidation state. A pH 6.3 vadose zone sediment containing iron oxides and iron-containing phyllosilicates was treated with various complexants (ammonium oxalate) and reductants (dithionite-citrate-bicarbonate) to selectively leach and/or reduce iron oxide and phyllosilicate phases. Mössbauer spectroscopy was used to identify initial iron mineral composition of the sediment and monitor dissolution and reduction of iron oxides. Sorption of Pu(V) was monitored over one week for each of six treated sediment fractions. Plutonium oxidation state speciation in the aqueous and solid phases was monitored using solvent extraction, coprecipitation, and XANES. Mössbauer spectroscopy showed that the sediment contained 25-30% hematite, 60-65% Al-goethite, and <10%Fe(III) in phyllosilicate; there was no detectable Fe(II). Upon reduction with a strong chemical reductant (dithionite-citrate buffer, DCB), much of the hematite and goethite disappeared and the Fe in the phyllosilicate reduced to Fe(II). The rate of sorption was found to correlate with the 1 fraction of Fe(II) remaining within each treated sediment phase. Pu(V) was the only oxidation state measured in the aqueous phase, irrespective of treatment, whereas Pu(IV) and much smaller amounts of Pu(V) and Pu(VI) were measured in the solid phase. Surface-mediated reduction of Pu(V) to Pu(IV) occurred in treated and untreated sediment samples; Pu(V) remained on untreated sediment surface for two days before reducing to Pu(IV). Similar to the sorption kinetics, the reduction rate was correlated with sediment Fe(II) concentration. The correlation between Fe(II) concentrations and Pu(V) reduction demonstrates the potential impact of changing iron mineralogy on plutonium subsurface transport through redox transition areas. These findings should influence the conceptual models of long-term stewardship of Pu contaminated sites that have fluctuating redox conditions, such as vadose zones or riparian zones.

  8. PLUTONIUM METAL: OXIDATION CONSIDERATIONS AND APPROACH

    SciTech Connect

    Estochen, E.

    2013-03-20

    Plutonium is arguably the most unique of all metals when considered in the combined context of metallurgical, chemical, and nuclear behavior. Much of the research in understanding behavior and characteristics of plutonium materials has its genesis in work associated with nuclear weapons systems. However, with the advent of applications in fuel materials, the focus in plutonium science has been more towards nuclear fuel applications, as well as long term storage and disposition. The focus of discussion included herein is related to preparing plutonium materials to meet goals consistent with non-proliferation. More specifically, the emphasis is on the treatment of legacy plutonium, in primarily metallic form, and safe handling, packaging, and transport to meet non-proliferation goals of safe/secure storage. Elevated temperature oxidation of plutonium metal is the treatment of choice, due to extensive experiential data related to the method, as the oxide form of plutonium is one of only a few compounds that is relatively simple to produce, and stable over a large temperature range. Despite the simplicity of the steps required to oxidize plutonium metal, it is important to understand the behavior of plutonium to ensure that oxidation is conducted in a safe and effective manner. It is important to understand the effect of changes in environmental variables on the oxidation characteristics of plutonium. The primary purpose of this report is to present a brief summary of information related to plutonium metal attributes, behavior, methods for conversion to oxide, and the ancillary considerations related to processing and facility safety. The information provided is based on data available in the public domain and from experience in oxidation of such materials at various facilities in the United States. The report is provided as a general reference for implementation of a simple and safe plutonium metal oxidation technique.

  9. Addressing mixed waste in plutonium processing

    SciTech Connect

    Christensen, D.C.; Sohn, C.L. ); Reid, R.A. . Anderson Schools of Management)

    1991-01-01

    The overall goal is the minimization of all waste generated in actinide processing facilities. Current emphasis is directed toward reducing and managing mixed waste in plutonium processing facilities. More specifically, the focus is on prioritizing plutonium processing technologies for development that will address major problems in mixed waste management. A five step methodological approach to identify, analyze, solve, and initiate corrective action for mixed waste problems in plutonium processing facilities has been developed.

  10. PROCESS FOR THE RECOVERY OF PLUTONIUM

    DOEpatents

    Potratz, H.A.

    1958-12-16

    A process for the separation of plutonium from uranlum and other associated radioactlve fission products ls descrlbed conslstlng of contacting an acid solution containing plutonium in the tetravalent state and uranium in the hexavalent state with enough ammonium carbonate to form an alkaline solution, adding cupferron to selectlvely form plutonlum cupferrlde, then recoverlng the plutonium cupferride by extraction with a water lmmiscible organic solvent such as chloroform.

  11. PLUTONIUM-CUPFERRON COMPLEX AND METHOD OF REMOVING PLUTONIUM FROM SOLUTION

    DOEpatents

    Potratz, H.A.

    1959-01-13

    A method is presented for separating plutonium from fission products present in solutions of neutronirradiated uranium. The process consists in treating such acidic solutions with cupferron so that the cupferron reacts with the plutonium present to form an insoluble complex. This plutonium cupferride precipitates and may then be separated from the solution.

  12. Nitrate concentrations under irrigated agriculture

    USGS Publications Warehouse

    Zaporozec, A.

    1983-01-01

    In recent years, considerable interest has been expressed in the nitrate content of water supplies. The most notable toxic effect of nitrate is infant methemoglobinemia. The risk of this disease increases significantly at nitrate-nitrogen levels exceeding 10 mg/l. For this reason, this concentration has been established as a limit for drinking water in many countries. In natural waters, nitrate is a minor ionic constituent and seldom accounts for more than a few percent of the total anions. However, nitrate in a significant concentration may occur in the vicinity of some point sources such as septic tanks, manure pits, and waste-disposal sites. Non-point sources contributing to groundwater pollution are numerous and a majority of them are related to agricultural activities. The largest single anthropogenic input of nitrate into the groundwater is fertilizer. Even though it has not been proven that nitrogen fertilizers are responsible for much of nitrate pollution, they are generally recognized as the main threat to groundwater quality, especially when inefficiently applied to irrigated fields on sandy soils. The biggest challenge facing today's agriculture is to maintain the balance between the enhancement of crop productivity and the risk of groundwater pollution. ?? 1982 Springer-Verlag New York Inc.

  13. PRECIPITATION METHOD FOR THE SEPARATION OF PLUTONIUM AND RARE EARTHS

    DOEpatents

    Thompson, S.G.

    1960-04-26

    A method of purifying plutonium is given. Tetravalent plutonium is precipitated with thorium pyrophosphate, the plutonium is oxidized to the tetravalent state, and then impurities are precipitated with thorium pyrophosphate.

  14. METHOD OF REDUCING PLUTONIUM WITH FERROUS IONS

    DOEpatents

    Dreher, J.L.; Koshland, D.E.; Thompson, S.G.; Willard, J.E.

    1959-10-01

    A process is presented for separating hexavalent plutonium from fission product values. To a nitric acid solution containing the values, ferrous ions are added and the solution is heated and held at elevated temperature to convert the plutonium to the tetravalent state via the trivalent state and the plutonium is then selectively precipitated on a BiPO/sub 4/ or LaF/sub 3/ carrier. The tetravalent plutonium formed is optionally complexed with fluoride, oxalate, or phosphate anion prior to carrier precipitation.

  15. Plutonium transmutation in thorium fuel cycle

    SciTech Connect

    Necas, Vladimir; Breza, Juraj |; Darilek, Petr

    2007-07-01

    The HELIOS spectral code was used to study the application of the thorium fuel cycle with plutonium as a supporting fissile material in a once-through scenario of the light water reactors PWR and VVER-440 (Russian design). Our analysis was focused on the plutonium transmutation potential and the plutonium radiotoxicity course of hypothetical thorium-based cycles for current nuclear power reactors. The paper shows a possibility to transmute about 50% of plutonium in analysed reactors. Positive influence on radiotoxicity after 300 years and later was pointed out. (authors)

  16. The effect of mass on the gastrointestinal absorption of plutonium and neptunium

    SciTech Connect

    Sullivan, M.F.; Miller, B.M.; Ryan, J.L.

    1983-04-01

    Absorption and retention of plutonium were determined in mice after intragastric administration of either 6 x 10/sup -4/ or 1.5 mg/kg in bicarbonate, citrate, or nitrate media. At the higher concentration, absorption of the citrate was greater than that of the nitrate; at the lower concentration, chemical form was not an important factor in absorption. Concentration and chemical form had much less influence on absorption by the neonatal (versus the adult) rat. The transfer factor (f/sub 1/) for neonates was between one and two orders of magnitude higher than for adults. Absorption and retention of neptunium were determined in rats and/or mice after intragastric administration at doses ranging from 2.2 x 10/sup -7/ to 43 mg/kg in nitrate solutions of pH 1.5. At the higher concentrations, absorption was 1.5 to 2.7%. For lower concentrations, absorption was 25 to 65 times less. In contrast to results obtained in adult animals, absorption of neptunium by neonates decreased with increasing dose. The data obtained in adult animals suggest that the f/sub 1/ factor recommended by the ICRP for plutonium should be increased by a factor of 10, but the neptunium f/sub 1/ factor, in contrast, should be decreased by a factor of 10.

  17. A pulse radiolysis investigation of the reactions of tributyl phosphate with the radical products of aqueous nitric acid irradiation.

    PubMed

    Mincher, Bruce J; Mezyk, Stephen P; Martin, Leigh R

    2008-07-17

    Tributyl phosphate (TBP) is the most common organic compound used in liquid-liquid separations for the recovery of uranium, neptunium, and plutonium from acidic nuclear fuel dissolutions. The goal of these processes is to extract the actinides while leaving fission products in the acidic, aqueous phase. However, the radiolytic degradation of TBP has been shown to reduce separation factors of the actinides from fission products and to impede the back-extraction of the actinides during stripping. As most previous investigations of the radiation chemistry of TBP have focused on steady state radiolysis and stable product identification, with dibutylphosphoric acid (HDBP) invariably being the major product, here we have determined room temperature rate constants for the reactions of TBP and HDBP with the hydroxyl radical [(5.00 +/- 0.05) x 10(9), (4.40 +/- 0.13) x 10(9) M(-1) s(-1)], hydrogen atom [(1.8 +/-0.2) x 10(8), (1.1 +/- 0.1) x 10(8) M(-1) s(-1)], nitrate radical [(4.3 +/- 0.7) x 10(6), (2.9 +/- 0.2) x 10(6) M(-1) s(-1)], and nitrite radical (<2 x 10 (5), <2 x 10(5) M(-1) s(-1)), respectively. These data are used to discuss the mechanism of TBP radical-induced degradation. PMID:18572898

  18. EXPERIENCES IN DECONTAMINATION & DEMOLITION OF A FORMER PLUTONIUM CONCENTRATION FACILITY HANFORD RESERVATION

    SciTech Connect

    BISHOP, G.E.

    2002-06-01

    The 233-S Plutonium Concentration Facility received plutonium nitrate paste from the nearby Reduction-Oxidation (REDOX) Facility and concentrated the plutonium for shipment to Hanford's Plutonium Finishing Plant. Operations ceased in 1967 and the Facility languished in a state of minimal maintenance until the mid-1990's when a decision was made to decontaminate and demolish (D&D) it. This work is being performed as a pilot project that integrates DOE nuclear safety analysis and worker safety requirements with Environmental Protection Agency (EPA) requirements under CERCLA (Comprehensive Environmental Response, Compensation, and Liability Act, 1980). The pilot project is a CERCLA non-time critical removal action. Difficulties were encountered during D&D. These included conflict between the development of the safety basis as an EPA pilot project and DOE requirements for safety analysis reports, updating the safety analysis to keep it current with field conditions, and major difficulties with nondestructive assays (NDA) of the contaminated waste. No demonstrable benefit has been obtained by integrating the EPA and DOE safety methodologies.

  19. Microbially Enhanced Oil Recovery by Sequential Injection of Light Hydrocarbon and Nitrate in Low- And High-Pressure Bioreactors.

    PubMed

    Gassara, Fatma; Suri, Navreet; Stanislav, Paul; Voordouw, Gerrit

    2015-10-20

    Microbially enhanced oil recovery (MEOR) often involves injection of aqueous molasses and nitrate to stimulate resident or introduced bacteria. Use of light oil components like toluene, as electron donor for nitrate-reducing bacteria (NRB), offers advantages but at 1-2 mM toluene is limiting in many heavy oils. Because addition of toluene to the oil increased reduction of nitrate by NRB, we propose an MEOR technology, in which water amended with light hydrocarbon below the solubility limit (5.6 mM for toluene) is injected to improve the nitrate reduction capacity of the oil along the water flow path, followed by injection of nitrate, other nutrients (e.g., phosphate) and a consortium of NRB, if necessary. Hydrocarbon- and nitrate-mediated MEOR was tested in low- and high-pressure, water-wet sandpack bioreactors with 0.5 pore volumes of residual oil in place (ROIP). Compared to control bioreactors, those with 11-12 mM of toluene in the oil (gained by direct addition or by aqueous injection) and 80 mM of nitrate in the aqueous phase produced 16.5 ± 4.4% of additional ROIP (N = 10). Because toluene is a cheap commodity chemical, HN-MEOR has the potential to be a cost-effective method for additional oil production even in the current low oil price environment. PMID:26406569

  20. Adsorption of uranium from aqueous solutions using activated carbon

    SciTech Connect

    Abbasi, W.A. ); Streat, M. )

    1994-06-01

    The adsorption of uranium from aqueous solution has been investigated using conventional commercially available activated carbons. It was found that treatment with hot nitric acid oxidized the surface of activated carbon and significantly increased the adsorption capacity for uranium in near-neutral and slightly acidic nitrate solutions. Equilibrium data were fitted to a simplified Freundlich isotherm for the purpose of comparison of oxidized and as-received samples. The decontamination of aqueous solutions was investigated in small column experiments. An ion-exchange mechanism of uranium sorption from aqueous solution is discussed. 43 refs., 11 figs., 1 tab.

  1. Using Nitrogen and Oxygen Isotope Compositions of Nitrate to Distinguish Contaminant Sources in Hanford Soil and Groundwater

    SciTech Connect

    Conrad, Mark; Bill, Markus

    2008-08-01

    The nitrogen ({delta}{sup 15}N) and oxygen ({delta}{sup 18}O) isotopic compositions of nitrate in the environment are primarily a function of the source of the nitrate. The ranges of isotopic compositions for nitrate resulting from common sources are outlined in Figure 1 from Kendall (1998). As noted on Figure 1, processes such as microbial metabolism can modify the isotopic compositions of the nitrate, but the effects of these processes are generally predictable. At Hanford, nitrate and other nitrogenous compounds were significant components of most of the chemical processes used at the site. Most of the oxygen in nitrate chemicals (e.g., nitric acid) is derived from atmospheric oxygen, giving it a significantly higher {delta}{sup 18}O value (+23.5{per_thousand}) than naturally occurring nitrate that obtains most of its oxygen from water (the {delta}{sup 18}O of Hanford groundwater ranges from -14{per_thousand} to -18{per_thousand}). This makes it possible to differentiate nitrate from Hanford site activities from background nitrate at the site (including most fertilizers that might have been used prior to the Department of Energy plutonium production activities at the site). In addition, the extreme thermal and chemical conditions that occurred during some of the waste processing procedures and subsequent waste storage in select single-shell tanks resulted in unique nitrate isotopic compositions that can be used to identify those waste streams in soil and groundwater at the site (Singleton et al., 2005; Christensen et al., 2007). This report presents nitrate isotope data for soil and groundwater samples from the Hanford 200 Areas and discusses the implications of that data for potential sources of groundwater contamination.

  2. Modeling of distribution and speciation of plutonium in the Urex extraction system

    SciTech Connect

    Paulenova, A.; Tkac, P.; Vandegrift, G.F.; Krebs, J.F.

    2008-07-01

    The PUREX extraction process is used worldwide to recover uranium and plutonium from dissolved spent nuclear fuel using the tributylphosphate-nitric acid extraction system. In the recent decade, significant research progress was achieved with the aim to modify this system by addition of a salt-free agent to optimize stripping of plutonium from the tributylphosphate (TBP) extraction product (UREX). Experimental results on the extraction of Pu(IV) with and without acetohydroxamic acid in the HNO{sub 3}/TBP (30 vol %) were used for the development of a thermodynamic model of distribution and speciation of Pu(IV) in this separation process. Extraction constants for several sets of nitric acid, nitrate, and acetohydroxamic acid concentrations were used to model the obtained data. The extraction model AMUSE (Argonne Model for Universal Solvent Extraction) was employed in our calculations. (authors)

  3. Winter Wheat and Maize Response to Urea Ammonium Nitrate and a New Urea Formaldehyde Polymer Fertilizer

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Slow release nitrogen (N) fertilizers have potential to improve yield and nitrogen use efficiency (NUE) in winter wheat (Triticum aestivum L.) and maize (Zea mays L.). A slow release urea formaldehyde polymer (UFP) was compared with conventional aqueous urea-ammonium nitrate (UAN) [(NH2)2CO, NH4NO3]...

  4. Enhanced removal of nitrate from water using nZVI@MWCNTs composite: synthesis, kinetics and mechanism of reduction.

    PubMed

    Babaei, Ali Akbar; Azari, Ali; Kalantary, Roshanak Rezaei; Kakavandi, Babak

    2015-01-01

    Herein, multi-wall carbon nanotubes (MWCNTs) were used as the carrier of nano-zero valent iron (nZVI) particles to fabricate a composite known as nZVI@MWCNTs. The composite was then characterized and applied in the nitrate removal process in a batch system under anoxic conditions. The influential parameters such as pH, various concentrations of nitrate and composite were investigated within 240 min of the reaction. The mechanism, kinetics and end-products of nitrate reduction were also evaluated. Results revealed that the removal nitrate percentage for nZVI@MWCNTs composite was higher than that of nZVI and MWCNTs alone. Experimental data from nitrate reduction were fitted to the Langmuir-Hinshelwood kinetic model. The values of observed rate constant (kobs) decreased with increasing the initial concentration of nitrate. Our experiments proved that the nitrate removal efficiency was favorable once both high amounts of nZVI@MWCNTs and low concentrations of nitrate were applied. The predominant end-products of the nitrate reduction were ammonium (84%) and nitrogen gas (15%). Our findings also revealed that ZVI@MWCNTs is potentially a good composite for removal/reduction of nitrate from aqueous solutions. PMID:26606093

  5. Destruction of nitrates, organics, and ferrocyanides by hydrothermal processing

    SciTech Connect

    Robinson, J.M.; Foy, B.R.; Dell'Orco, P.C.; Anderson, G.; Archuleta, F.; Atencio, J.; Breshears, D.; Brewer, R.; Eaton, H.; McFarland, R.; McInroy, R.; Reynolds, T.; Sedillo, M.; Wilmanns, E.; Buelow, S.J.

    1993-01-01

    This work targets the remediation of the aqueous mixed wastes stored in the underground tanks at the Department of Energy site in Hanford, Washington via hydrothermal processing. The feasibility of destroying the nitrate, organic, and ferrocyanide components of the wastes under supercritical and near critical conditions (623 [degree]K to 873[degree]K, 22.1 MPa to 103.4 MPa) is addressed. A novel method was developed for determining the solubility of nitrate salts in supercritical water solutions at pressures ranging from 24.8 MPa to 30.3 MPa (3600 psi to 4400 psi) and temperatures from 723 [degree]K to 798 [degree]K. Sodium nitrate solubilities ranged from 293 mg/kg at 24.8 MPa and 798 [degree]K to 1963 mg/kg at 30.3 MPa and 723[degree]K. Solubility was found to vary directly with pressure, and inversely with temperature. An empirical relationship was developed for the estimation of sodium nitrate solubility at water densities between 0.08 and 0.16 kg/L and temperatures between 723[degree]K and 798[degree]K. A small volume batch reactor equipped with optical diagnostics was used to monitor the phase behavior of a diluted variant of a tank 101-SY simulant. Preliminary results suggest that a single phase is formed at 83 MPa at 773 [degree]K.

  6. Destruction of nitrates, organics, and ferrocyanides by hydrothermal processing

    SciTech Connect

    Robinson, J.M.; Foy, B.R.; Dell`Orco, P.C.; Anderson, G.; Archuleta, F.; Atencio, J.; Breshears, D.; Brewer, R.; Eaton, H.; McFarland, R.; McInroy, R.; Reynolds, T.; Sedillo, M.; Wilmanns, E.; Buelow, S.J.

    1993-03-01

    This work targets the remediation of the aqueous mixed wastes stored in the underground tanks at the Department of Energy site in Hanford, Washington via hydrothermal processing. The feasibility of destroying the nitrate, organic, and ferrocyanide components of the wastes under supercritical and near critical conditions (623 {degree}K to 873{degree}K, 22.1 MPa to 103.4 MPa) is addressed. A novel method was developed for determining the solubility of nitrate salts in supercritical water solutions at pressures ranging from 24.8 MPa to 30.3 MPa (3600 psi to 4400 psi) and temperatures from 723 {degree}K to 798 {degree}K. Sodium nitrate solubilities ranged from 293 mg/kg at 24.8 MPa and 798 {degree}K to 1963 mg/kg at 30.3 MPa and 723{degree}K. Solubility was found to vary directly with pressure, and inversely with temperature. An empirical relationship was developed for the estimation of sodium nitrate solubility at water densities between 0.08 and 0.16 kg/L and temperatures between 723{degree}K and 798{degree}K. A small volume batch reactor equipped with optical diagnostics was used to monitor the phase behavior of a diluted variant of a tank 101-SY simulant. Preliminary results suggest that a single phase is formed at 83 MPa at 773 {degree}K.

  7. Development program to recycle and purify plutonium-238 oxide fuel from scrap

    SciTech Connect

    Schulte, L.D.; Silver, G.L.; Avens, L.R.; Jarvinen, G.D.; Espinoza, J.; Foltyn, E.M.; Rinehart, G.H.

    1996-12-31

    Nuclear Materials Technology (NMT) Division has initiated a development program to recover and purify plutonium-238 oxide from impure sources. A glove box line has been designed and a process flowsheet developed to perform this task on a large scale. The initial effort has focused on purification of {sup 238}PuO{sub 2} fuel that fails to meet General Purpose Heat Source (GPHS) specifications because of impurities. The notable non-actinide impurities were silicon and phosphorus, but aluminum, chromium, iron and nickel were also near or in excess of limits specified by GPHS fuel powder specifications. Among actinide impurities, uranium is of paramount concern because {sup 234}U is the daughter of {sup 2238}Pu by alpha decay, and is the largest actinide impurity. An aqueous method based on nitric acid was selected for purification of the {sup 238}PuO{sub 2} fuel. All aqueous processing used high purity reagents, and was performed in PTFE apparatus to minimize introduction of new contaminants. Impure {sup 238}PuO{sub 2} was first dissolved in refluxing HNO{sub 3}/HF and then the solution was filtered. The dissolved {sup 238}Pu was adjusted to the trivalent state by an excess of reducing reagents to compensate for radiolytic effects, precipitated as plutonium(III) oxalate, and recovered by filtration. The plutonium(III) oxalate was subsequently calcined to convert the plutonium to the oxide. Decontamination factors for silicon, phosphorus and uranium were excellent. Decontamination factors for aluminum, chromium, iron and nickel were very good. The purity of the {sup 238}PuO{sub 2} recovered from this operation was significantly better than specifications. Efforts continue to develop the capability for efficient, safe, cost-effective, and environmentally acceptable methods to recover and purify {sup 238}PuO{sub 2} fuel in a glovebox environment. Plutonium-238 materials targeted for recovery includes impure oxide and scrap items that are lean in {sup 238}Pu values.

  8. Development program to recycle and purify plutonium-238 oxide fuel from scrap

    NASA Astrophysics Data System (ADS)

    Schulte, Louis D.; Silver, Gary L.; Avens, Larry R.; Jarvinen, Gordon D.; Espinoza, Jacob; Foltyn, Elizabeth M.; Rinehart, Gary H.

    1997-01-01

    Nuclear Materials Technology (NMT) Division of Los Alamos National Laboratory (LANL) has initiated a development program to recover & purify plutonium-238 oxide from impure sources. A glove box line has been designed and a process flowsheet developed to perform this task on a large scale. Our initial effort has focused on purification of 238PuO2 fuel that fails to meet General Purpose Heat Source (GPHS) specifications because of impurities. The most notable non-actinide impurity was silicon, but aluminum, chromium, iron and nickel were also near or in excess of limits specified by GPHS fuel powder specifications. 234U was by far the largest actinide impurity observed in the feed material because it is the daughter product of 238Pu by alpha decay. An aqueous method based on nitric acid was selected for purification of the 238PuO2 fuel. All aqueous processing used high purity reagents, and was performed in PTFE apparatus to minimize introduction of new contaminants. Impure 238PuO2 was finely milled, then dissolved in refluxing HNO3/HF and the solution filtered. The dissolved 238Pu was adjusted to the trivalent state by an excess of reducing reagents to compensate for radiolytic effects, precipitated as plutonium(III) oxalate, and recovered by filtration. The plutonium(III) oxalate was subsequently calcined to convert the plutonium to the oxide. Decontamination factors for silicon, phosphorus and uranium were excellent. Decontamination factors for aluminum, chromium, iron and nickel were very good. The purity of the 238PuO2 recovered from this operation was significantly better than specifications. Efforts continue to develop the capability for efficient, safe, cost-effective, and environmentally acceptable methods to recover and purify 238PuO2 fuel in a glove box environment. Plutonium-238 materials targeted for recovery includes impure oxide and scrap items that are lean in 238Pu values.

  9. Nitrate assimilation in Lotus japonicus.

    PubMed

    Márquez, Antonio J; Betti, Marco; García-Calderón, Margarita; Pal'ove-Balang, Peter; Díaz, Pedro; Monza, Jorge

    2005-07-01

    This paper summarizes some recent advances in the understanding of nitrate assimilation in the model legume Lotus japonicus. First, different types of experimental evidence are presented that emphasize the importance of the root in the nitrate-reducing assimilatory processes in this plant. Secondly, the main results from an ethyl methanesulphonate mutagenesis programme are presented. In this programme, chlorate-resistant and photorespiratory mutants were produced and characterized. The phenotype of one particular chlorate-resistant mutant suggested the importance of a low-affinity nitrate transport system for growth of L. japonicus plants under nitrate nutrition. The phenotype of photorespiratory mutants, affected in all forms of plastid glutamine synthetase in leaves, roots, and nodules, indicated that plastid glutamine synthetase was not required for primary nitrate assimilation nor for the symbiotic associations of the plant (nodulation, mycorrhization), provided photorespiration was suppressed. However, the phenotype of these mutants confirmed that plastid glutamine synthetase was required for the reassimilation of ammonium released by photorespiration. Finally, different aspects of the relationship between nitrate assimilation and osmotic stress in L. japonicus are also discussed, with specific reference to the biosynthesis of proline as an osmolyte. PMID:15911564

  10. Chemical and Radiochemical Composition of Thermally Stabilized Plutonium Oxide from the Plutonium Finishing Plant Considered as Alternate Feedstock for the Mixed Oxide Fuel Fabrication Facility

    SciTech Connect

    Tingey, Joel M.; Jones, Susan A.

    2005-07-01

    Eighteen plutonium oxide samples originating from the Plutonium Finishing Plant (PFP) on the Hanford Site were analyzed to provide additional data on the suitability of PFP thermally stabilized plutonium oxides and Rocky Flats oxides as alternate feedstock to the Mixed Oxide Fuel Fabrication Facility (MFFF). Radiochemical and chemical analyses were performed on fusions, acid leaches, and water leaches of these 18 samples. The results from these destructive analyses were compared with nondestructive analyses (NDA) performed at PFP and the acceptance criteria for the alternate feedstock. The plutonium oxide materials considered as alternate feedstock at Hanford originated from several different sources including Rocky Flats oxide, scrap from the Remote Mechanical C-Line (RMC) and the Plutonium Reclamation Facility (PRF), and materials from other plutonium conversion processes at Hanford. These materials were received at PFP as metals, oxides, and solutions. All of the material considered as alternate feedstock was converted to PuO2 and thermally stabilized by heating the PuO2 powder at 950 C in an oxidizing environment. The two samples from solutions were converted to PuO2 by precipitation with Mg(OH)2. The 18 plutonium oxide samples were grouped into four categories based on their origin. The Rocky Flats oxide was divided into two categories, low- and high-chloride Rocky Flats oxides. The other two categories were PRF/RMC scrap oxides, which included scrap from both process lines and oxides produced from solutions. The two solution samples came from samples that were being tested at Pacific Northwest National Laboratory because all of the plutonium oxide from solutions at PFP had already been processed and placed in 3013 containers. These samples originated at the PFP and are from plutonium nitrate product and double-pass filtrate solutions after they had been thermally stabilized. The other 16 samples originated from thermal stabilization batches before canning at PFP. Samples varied in appearance depending on the original source of material. Rocky Flats items were mostly dark olive green with clumps that crushed easily with a mortar and pestle. PRF/RMC items showed more variability. These items were mostly rust colored. One sample contained white particles that were difficult to crush, and another sample was a dark grey with a mixture of fines and large, hard fragments. The appearance and feel of the fragments indicated they might be an alloy. The color of the solution samples was indicative of the impurities in the sample. The double-pass filtrate solution was a brown color indicative of the iron impurities in the sample. The other solution sample was light gray in color. Radiochemical analyses, including thermal ionization mass spectrometry (TIMS), alpha and gamma energy analysis (AEA and GEA), and kinetic phosphorescence analysis (KPA), indicate that these materials are all weapons-grade plutonium with consistent plutonium isotopics. A small amount of uranium (<0.14 wt%) is also present in these samples. The isotopic composition of the uranium varied widely but was consistent among each category of material. The primary water-soluble anions in these samples were Cl-, NO3-, SO42-, and PO43-. The only major anion observed in the Rocky Flats materials was Cl-, but the PRF/RMC samples had significant quantities of all of the primary anions observed. Prompt gamma measurements provide a representative analysis of the Cl- concentration in the bulk material. The primary anions observed in the solution samples were NO3-, and PO43-. The concentration of these anions did not exceed the mixed oxide (MOX) specification limits. Cations that exceeded the MOX specification limits included Cr, Fe, Ni, Al, Cu, and Si. All of the samples exceeded at least the 75% specification limit in one element.

  11. MOLTEN PLUTONIUM FUELED FAST BREEDER REACTOR

    DOEpatents

    Kiehn, R.M.; King, L.D.P.; Peterson, R.E.; Swickard, E.O. Jr.

    1962-06-26

    A description is given of a nuclear fast reactor fueled with molten plutonium containing about 20 kg of plutonium in a tantalum container, cooled by circulating liquid sodium at about 600 to 650 deg C, having a large negative temperature coefficient of reactivity, and control rods and movable reflector for criticality control. (AEC)

  12. Plutonium Immobilization Project -- Robotic canister loading

    SciTech Connect

    Hamilton, L.

    2000-04-28

    The Plutonium Immobilization Program (PIP) is a joint venture between the Savannah River Site, Lawrence Livermore National Laboratory, Argonne National Laboratory, and Pacific Northwest National Laboratory. When operational in 2008, the PIP will fulfill the nation's nonproliferation commitment by placing surplus weapons-grade plutonium in a permanently stable ceramic form.

  13. Uses for plutonium: Weapons, reactors, and other

    SciTech Connect

    Condit, R.H.

    1994-05-01

    This document begins with a introduction on criticality and supercriticality. Then, types and components, design and engineering, yields, and disassembly of nuclear weapons are discussed. Plutonium is evaluated as a reactor fuel, including neutronics and chemistry considerations. Finally, other uses of plutonium are analyzed.

  14. Surplus Plutonium Disposition Final Environmental Impact Statement

    SciTech Connect

    N /A

    1999-11-19

    In December 1996, the U.S. Department of Energy (DOE) published the ''Storage and Disposition of Weapons-Usable Fissile Materials Final Programmatic Environmental Impact Statement (Storage and Disposition PEIS)'' (DOE 1996a). That PEIS analyzes the potential environmental consequences of alternative strategies for the long-term storage of weapons-usable plutonium and highly enriched uranium (HEU) and the disposition of weapons-usable plutonium that has been or may be declared surplus to national security needs. The Record of Decision (ROD) for the ''Storage and Disposition PEIS'', issued on January 14, 1997 (DOE 1997a), outlines DOE's decision to pursue an approach to plutonium disposition that would make surplus weapons-usable plutonium inaccessible and unattractive for weapons use. DOE's disposition strategy, consistent with the Preferred Alternative analyzed in the ''Storage and Disposition PEIS'', allows for both the immobilization of some (and potentially all) of the surplus plutonium and use of some of the surplus plutonium as mixed oxide (MOX) fuel in existing domestic, commercial reactors. The disposition of surplus plutonium would also involve disposal of both the immobilized plutonium and the MOX fuel (as spent nuclear fuel) in a potential geologic repository.

  15. Reactive sintering of plutonium-bearing titanates.

    SciTech Connect

    Hash, M. C.

    1999-06-24

    Titanate ceramics are being developed for the immobilization of weapons-grade plutonium. These multi-phase ceramics are intended to be both corrosion and proliferation resistant. Reactive sintering techniques were refined to reproducibly provide titanate ceramics for further characterization and testing. Plutonium-bearing pyrochlore-rich composites were consolidated to greater than 90% of their theoretical density.

  16. Pyrochemical process for extracting plutonium from an electrolyte salt

    DOEpatents

    Mullins, Lawrence J.; Christensen, Dana C.

    1984-01-01

    A pyrochemical process for extracting plutonium from a plutonium-bearing salt is disclosed. The process is particularly useful in the recovery of plutonium from electrolyte salts which are left over from the electrorefining of plutonium. In accordance with the process, the plutonium-bearing salt is melted and mixed with metallic calcium. The calcium reduces ionized plutonium in the salt to plutonium metal, and also causes metallic plutonium in the salt, which is typically present as finely dispersed metallic shot, to coalesce. The reduced and coalesced plutonium separates out on the bottom of the reaction vessel as a separate metallic phase which is readily separable from the overlying salt upon cooling of the mixture. Yields of plutonium are typically on the order of 95%. The stripped salt is virtually free of plutonium and may be discarded to low-level waste storage.

  17. Pyrochemical process for extracting plutonium from an electrolyte salt

    DOEpatents

    Mullins, L.J.; Christensen, D.C.

    1982-09-20

    A pyrochemical process for extracting plutonium from a plutonium-bearing salt is disclosed. The process is particularly useful in the recovery of plutonium for electrolyte salts which are left over from the electrorefining of plutonium. In accordance with the process, the plutonium-bearing salt is melted and mixed with metallic calcium. The calcium reduces ionized plutonium in the salt to plutonium metal, and also causes metallic plutonium in the salt, which is typically present as finely dispersed metallic shot, to coalesce. The reduced and coalesced plutonium separates out on the bottom of the reaction vessel as a separate metallic phase which is readily separable from the overlying salt upon cooling of the mixture. Yields of plutonium are typically on the order of 95%. The stripped salt is virtually free of plutonium and may be discarded to low-level waste storage.

  18. Hydroxylamine nitrate self-catalytic kinetics study with adiabatic calorimetry.

    PubMed

    Liu, Lijun; Wei, Chunyang; Guo, Yuyan; Rogers, William J; Sam Mannan, M

    2009-03-15

    Hydroxylamine nitrate (HAN) is an important member of the hydroxylamine compound family with applications that include equipment decontamination in the nuclear industry and aqueous or solid propellants. Due to its instability and autocatalytic behavior, HAN has been involved in several incidents at the Hanford and Savannah River Site (SRS) [Technical Report on Hydroxylamine Nitrate, US Department of Energy, 1998]. Much research has been conducted on HAN in different areas, such as combustion mechanism, decomposition mechanism, and runaway behavior. However, the autocatalytic decomposition behavior of HAN at runaway stage has not been fully addressed due to its highly exothermic and rapid decomposition behavior. This work is focused on extracting HAN autocatalytic kinetics and analyzing HAN critical behavior from adiabatic calorimetry measurements. A lumped autocatalytic kinetic model for HAN and associated model parameters are determined. Also the storage and handling critical conditions of diluted HAN solution without metal presence are quantified. PMID:18639378

  19. 46 CFR 148.205 - Ammonium nitrate and ammonium nitrate fertilizers.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... total combustible material; (3) Ammonium nitrate with ammonium sulfate containing more than 45 percent... 46 Shipping 5 2011-10-01 2011-10-01 false Ammonium nitrate and ammonium nitrate fertilizers. 148... Materials § 148.205 Ammonium nitrate and ammonium nitrate fertilizers. (a) This section applies to...

  20. 46 CFR 148.205 - Ammonium nitrate and ammonium nitrate fertilizers.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 46 Shipping 5 2013-10-01 2013-10-01 false Ammonium nitrate and ammonium nitrate fertilizers. 148... Materials § 148.205 Ammonium nitrate and ammonium nitrate fertilizers. (a) This section applies to the stowage and transportation in bulk of ammonium nitrate and the following fertilizers composed of...

  1. 46 CFR 148.205 - Ammonium nitrate and ammonium nitrate fertilizers.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 46 Shipping 5 2012-10-01 2012-10-01 false Ammonium nitrate and ammonium nitrate fertilizers. 148... Materials § 148.205 Ammonium nitrate and ammonium nitrate fertilizers. (a) This section applies to the stowage and transportation in bulk of ammonium nitrate and the following fertilizers composed of...

  2. 46 CFR 148.205 - Ammonium nitrate and ammonium nitrate fertilizers.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 46 Shipping 5 2014-10-01 2014-10-01 false Ammonium nitrate and ammonium nitrate fertilizers. 148... Materials § 148.205 Ammonium nitrate and ammonium nitrate fertilizers. (a) This section applies to the stowage and transportation in bulk of ammonium nitrate and the following fertilizers composed of...

  3. PROCESS FOR THE RECOVERY OF PLUTONIUM

    DOEpatents

    Ritter, D.M.

    1959-01-13

    An improvement is presented in the process for recovery and decontamination of plutonium. The carrier precipitate containing plutonium is dissolved and treated with an oxidizing agent to place the plutonium in a hexavalent oxidation state. A lanthanum fluoride precipitate is then formed in and removed from the solution to carry undesired fission products. The fluoride ions in the reniaining solution are complexed by addition of a borate sueh as boric acid, sodium metaborate or the like. The plutonium is then reduced and carried from the solution by the formation of a bismuth phosphate precipitate. This process effects a better separation from unwanted flssion products along with conccntration of the plutonium by using a smaller amount of carrier.

  4. Nondestructive assay methods for solids containing plutonium

    SciTech Connect

    Macmurdo, K.W.; Gray, L.W.; Gibbs, A.

    1984-06-01

    Specific nondestructive assay (NDA) methods, e.g. calorimetry, coincidence neutron counting, singles neutron counting, and gamma ray spectrometry, were studied to provide the Savannah River Plant with an NDA method to measure the plutonium content of solid scrap (slag and crucible) generated in the JB-Line plutonium metal production process. Results indicate that calorimetry can be used to measure the plutonium content to within about 3% in 4 to 6 hours by using computerized equilibrium sample power predictive models. Calorimetry results confirm that a bias exists in the present indirect measurement method used to estimate the plutonium content of slag and crucible. Singles neutron counting of slag and crucible can measure plutonium to only +-30%, but coincidence neutron counting methods improve measurement precision to better than +-10% in less than ten minutes. Only four portions of a single slag and crucible sample were assayed, and further study is recommended.

  5. 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.

  6. Treatment of plutonium process residues by molten salt oxidation

    SciTech Connect

    Stimmel, J.; Wishau, R.; Ramsey, K.B.; Montoya, A.; Brock, J.; Heslop, M.; Wernly, K.

    1999-04-01

    Molten Salt Oxidation (MSO) is a thermal process that can remove more than 99.999% of the organic matrix from combustible {sup 238}Pu material. Plutonium processing residues are injected into a molten salt bed with an excess of air. The salt (sodium carbonate) functions as a catalyst for the conversion of the organic material to carbon dioxide and water. Reactive species such as fluorine, chlorine, bromine, iodine, sulfur, phosphorous and arsenic in the organic waste react with the molten salt to form the corresponding neutralized salts, NaF, NaCl, NaBr, NaI, Na{sub 2}SO{sub 4}, Na{sub 3}PO{sub 4} and NaAsO{sub 2} or Na{sub 3}AsO4. Plutonium and other metals react with the molten salt and air to form metal salts or oxides. Saturated salt will be recycled and aqueous chemical separation will be used to recover the {sup 238}Pu. The Los Alamos National Laboratory system, which is currently in the conceptual design stage, will be scaled down from current systems for use inside a glovebox.

  7. The geochemistry of plutonium in fresh and marine water environments

    NASA Astrophysics Data System (ADS)

    Sholkovitz, Edward R.

    1983-04-01

    The chemical behaviour of plutonium in the hydrosphere is a subject of both great practical and intrinsic importance. The production and eventual disposal of Pu and other artificial radionuclides dictates that this be the case. The main objective of this paper is to provide a synthesis and critical examination of currently published data and interpretations on the geochemistry of Pu in natural waters and sediments. Where appropriate, an attempt is made to reinterpret published data with the aim of establishing the relationships between geochemical and biological processes and the distribution, concentration and speciation of Pu. Particular attention is paid to the question of the potential for the chemical remobilization of Pu from the solid to the aqueous phase. Approximately one third of the text deals with freshwaters (mostly lakes) while two thirds discusses the estuarine, coastal and open ocean environments.

  8. REMOVAL OF LEGACY PLUTONIUM MATERIALS FROM SWEDEN

    SciTech Connect

    Dunn, Kerry A.; Bellamy, J. Steve; Chandler, Greg T.; Iyer, Natraj C.; Koenig, Rich E.; Leduc, D.; Hackney, B.; Leduc, Dan R.

    2013-08-18

    U.S. Department of Energy’s National Nuclear Security Administration (NNSA) Office of Global Threat Reduction (GTRI) recently removed legacy plutonium materials from Sweden in collaboration with AB SVAFO, Sweden. This paper details the activities undertaken through the U.S. receiving site (Savannah River Site (SRS)) to support the characterization, stabilization, packaging and removal of legacy plutonium materials from Sweden in 2012. This effort was undertaken as part of GTRI’s Gap Materials Program and culminated with the successful removal of plutonium from Sweden as announced at the 2012 Nuclear Security Summit. The removal and shipment of plutonium materials to the United States was the first of its kind under NNSA’s Global Threat Reduction Initiative. The Environmental Assessment for the U.S. receipt of gap plutonium material was approved in May 2010. Since then, the multi-year process yielded many first time accomplishments associated with plutonium packaging and transport activities including the application of the of DOE-STD-3013 stabilization requirements to treat plutonium materials outside the U.S., the development of an acceptance criteria for receipt of plutonium from a foreign country, the development and application of a versatile process flow sheet for the packaging of legacy plutonium materials, the identification of a plutonium container configuration, the first international certificate validation of the 9975 shipping package and the first intercontinental shipment using the 9975 shipping package. This paper will detail the technical considerations in developing the packaging process flow sheet, defining the key elements of the flow sheet and its implementation, determining the criteria used in the selection of the transport package, developing the technical basis for the package certificate amendment and the reviews with multiple licensing authorities and most importantly integrating the technical activities with the Swedish partners.

  9. Surface Nanobubbles in Nonaqueous Media: Looking for Nanobubbles in DMSO, Formamide, Propylene Carbonate, Ethylammonium Nitrate, and Propylammonium Nitrate.

    PubMed

    An, Hongjie; Liu, Guangming; Atkin, Rob; Craig, Vincent S J

    2015-07-28

    Surface nanobubbles produced by supersaturation during the exchange of ethanol for water are routinely observed on hydrophobic surfaces, are stable for days, and have contact angles that are very much greater than observed macroscopically. Here, we test the hypothesis that nanobubbles can also be observed in nonaqueous solvents in order to ascertain if their anomalous lifetimes and contact angles are related to properties of the solvent. Nanobubbles were seen in the protic solvents formamide, ethylammonium nitrate, and propylammonium nitrate, but not in propylene carbonate or dimethyl sulfoxide. Solvents in which nanobubbles were observed exhibit a three-dimensional hydrogen-bonding network. Like in aqueous systems, the nanobubbles were stable for days and exhibited high contact angles (∼165°). PMID:26153620

  10. Synthesis of nano-structured polypyrrole/copper electrodes for nitrate and nitrite electroreduction

    NASA Astrophysics Data System (ADS)

    Phuong Thoa Nguyen, Thi; Thinh Nguyen, Viet; Nguyen Bui, Nhat; Do, Duong Kim Bao; Pham, Anh Minh

    2010-09-01

    Nanostructured polypyrrole film was synthesized onto a copper electrode in solutions of oxalic and salicylic acids and their buffers. The electrooxidation of pyrrole to form polypyrrole film and the electroreduction of nitrate and nitrite ions at synthesized Ppy modified copper electrodes (Ppy/Cu) in potassium chloride aqueous solutions were studied using chronoamperometry. The nanoporous structure of the synthesized Ppy films was characterized by scanning electron microscopy (SEM). Nitrate and nitrite reduction were performed by an electrochemical method under potentiostatic conditions. The Ppy/Cu electrodes prepared in the oxalate buffer and salicylic acid solutions perform more stable catalytic activity for nitrate reduction; their service life is about ten times longer than that for the electrodes prepared in oxalic acid solution. After 20?h of electrolysis, the nitrite was reduced completely with 100% efficiency and the nitrate was reduced with 35% efficiency. Report submitted to the 5th International Workshop on Advanced Materials Science and Nanotechnology IWAMSN, Hanoi, 9-12 November 2010.

  11. Automated amperometric plutonium assay system

    SciTech Connect

    Burt, M.C.

    1985-01-01

    The amperometric titration for plutonium assay has been used in the nuclear industry for over twenty years and has been in routine use at the Hanford Engineering Development Laboratory since 1976 for the analysis of plutonium oxide and mixed oxide fuel material for the Fast Flux Test Facility. It has proven itself to be an accurate and reliable method. The method may be used as a direct end point titration or an excess of titrant may be added and a back titration performed to aid in determination of the end point. Due to the slowness of the PuVI-FeII reaction it is difficult to recognize when the end point is being approached and is very time consuming if the current is allowed to decay to the residual value after each titrant addition. For this reason the back titration in which the rapid FeII-CrVI reaction occurs is used by most laboratories. The back titration is performed by the addition of excess ferrous solution followed by two measured aliquots of standard dichromate with measurement of cell current after each addition.

  12. Plutonium focus area. Technology summary

    SciTech Connect

    1997-09-01

    The Assistant Secretary for the Office of Environmental Management (EM) at the U.S. Department of Energy (DOE) chartered the Plutonium Focus Area (PFA) in October 1995. The PFA {open_quotes}...provides for peer and technical reviews of research and development in plutonium stabilization activities...{close_quotes} In addition, the PFA identifies and develops relevant research and technology. The purpose of this document is to focus attention on the requirements used to develop research and technology for stabilization, storage, and preparation for disposition of nuclear materials. The PFA Technology Summary presents the approach the PFA uses to identify, recommend, and review research. It lists research requirements, research being conducted, and gaps where research is needed. It also summarizes research performed by the PFA in the traditional research summary format. This document encourages researchers and commercial enterprises to do business with PFA by submitting research proposals or {open_quotes}white papers.{close_quotes} In addition, it suggests ways to increase the likelihood that PFA will recommend proposed research to the Nuclear Materials Stabilization Task Group (NMSTG) of DOE.

  13. Nitrate transport is independent of NADH and NAD(P)H nitrate reductases in barley seedlings

    NASA Technical Reports Server (NTRS)

    Warner, R. L.; Huffaker, R. C.

    1989-01-01

    Barley (Hordeum vulgare L.) has NADH-specific and NAD(P)H-bispecific nitrate reductase isozymes. Four isogenic lines with different nitrate reductase isozyme combinations were used to determine the role of NADH and NAD(P)H nitrate reductases on nitrate transport and assimilation in barley seedlings. Both nitrate reductase isozymes were induced by nitrate and were required for maximum nitrate assimilation in barley seedlings. Genotypes lacking the NADH isozyme (Az12) or the NAD(P)H isozyme (Az70) assimilated 65 or 85%, respectively, as much nitrate as the wild type. Nitrate assimilation by genotype (Az12;Az70) which is deficient in both nitrate reductases, was only 13% of the wild type indicating that the NADH and NAD(P)H nitrate reductase isozymes are responsible for most of the nitrate reduction in barley seedlings. For all genotypes, nitrate assimilation rates in the dark were about 55% of the rates in light. Hypotheses that nitrate reductase has direct or indirect roles in nitrate uptake were not supported by this study. Induction of nitrate transporters and the kinetics of net nitrate uptake were the same for all four genotypes indicating that neither nitrate reductase isozyme has a direct role in nitrate uptake in barley seedlings.

  14. Plutonium Uptake and Distribution in Mammalian Cells: Molecular vs Polymeric Plutonium

    PubMed Central

    ARYAL, BAIKUNTHA P.; GORMAN-LEWIS, DREW; PAUNESKU, TATJANA; WILSON, RICHARD E.; LAI, BARRY; VOGT, STEFAN; WOLOSCHAK, GAYLE E.; JENSEN, MARK P.

    2013-01-01

    Purpose To study the cellular responses to molecular and polymeric forms of plutonium using PC12 cells derived from rat adrenal glands. Materials and methods Serum starved PC12 cells were exposed to polymeric and molecular forms of plutonium for three hours. Cells were washed with 10 mM EGTA, 100 mM NaCl at pH 7.4 to remove surface sorbed plutonium. Localization of plutonium in individual cell was quantitatively analyzed by synchrotron X-ray fluorescence (XRF) microscopy. Results Molecular plutonium complexes introduced to cell growth media in the form of NTA, citrate, or transferrin complexes were taken up by PC12 cells, and mostly co-localized with iron within the cells. Polymeric plutonium prepared separately was not internalized by PC12 cells but it was always found on the cell surface as big agglomerates; however polymeric plutonium formed in situ was mostly found within the cells as agglomerates. Conclusions PC12 cells can differentiate molecular and polymeric forms of plutonium. Molecular plutonium is taken up by PC12 cells and mostly co-localized with iron but aged polymeric plutonium is not internalized by the cells. PMID:21770702

  15. Laboratory study of nitrate photolysis in Antarctic snow. I. Observed quantum yield, domain of photolysis, and secondary chemistry

    NASA Astrophysics Data System (ADS)

    Meusinger, Carl; Berhanu, Tesfaye A.; Erbland, Joseph; Savarino, Joel; Johnson, Matthew S.

    2014-06-01

    Post-depositional processes alter nitrate concentration and nitrate isotopic composition in the top layers of snow at sites with low snow accumulation rates, such as Dome C, Antarctica. Available nitrate ice core records can provide input for studying past atmospheres and climate if such processes are understood. It has been shown that photolysis of nitrate in the snowpack plays a major role in nitrate loss and that the photolysis products have a significant influence on the local troposphere as well as on other species in the snow. Reported quantum yields for the main reaction spans orders of magnitude - apparently a result of whether nitrate is located at the air-ice interface or in the ice matrix - constituting the largest uncertainty in models of snowpack NOx emissions. Here, a laboratory study is presented that uses snow from Dome C and minimizes effects of desorption and recombination by flushing the snow during irradiation with UV light. A selection of UV filters allowed examination of the effects of the 200 and 305 nm absorption bands of nitrate. Nitrate concentration and photon flux were measured in the snow. The quantum yield for loss of nitrate was observed to decrease from 0.44 to 0.003 within what corresponds to days of UV exposure in Antarctica. The superposition of photolysis in two photochemical domains of nitrate in snow is proposed: one of photolabile nitrate, and one of buried nitrate. The difference lies in the ability of reaction products to escape the snow crystal, versus undergoing secondary (recombination) chemistry. Modeled NOx emissions may increase significantly above measured values due to the observed quantum yield in this study. The apparent quantum yield in the 200 nm band was found to be ˜1%, much lower than reported for aqueous chemistry. A companion paper presents an analysis of the change in isotopic composition of snowpack nitrate based on the same samples as in this study.

  16. Laboratory study of nitrate photolysis in Antarctic snow. I. Observed quantum yield, domain of photolysis, and secondary chemistry.

    PubMed

    Meusinger, Carl; Berhanu, Tesfaye A; Erbland, Joseph; Savarino, Joel; Johnson, Matthew S

    2014-06-28

    Post-depositional processes alter nitrate concentration and nitrate isotopic composition in the top layers of snow at sites with low snow accumulation rates, such as Dome C, Antarctica. Available nitrate ice core records can provide input for studying past atmospheres and climate if such processes are understood. It has been shown that photolysis of nitrate in the snowpack plays a major role in nitrate loss and that the photolysis products have a significant influence on the local troposphere as well as on other species in the snow. Reported quantum yields for the main reaction spans orders of magnitude - apparently a result of whether nitrate is located at the air-ice interface or in the ice matrix - constituting the largest uncertainty in models of snowpack NOx emissions. Here, a laboratory study is presented that uses snow from Dome C and minimizes effects of desorption and recombination by flushing the snow during irradiation with UV light. A selection of UV filters allowed examination of the effects of the 200 and 305 nm absorption bands of nitrate. Nitrate concentration and photon flux were measured in the snow. The quantum yield for loss of nitrate was observed to decrease from 0.44 to 0.003 within what corresponds to days of UV exposure in Antarctica. The superposition of photolysis in two photochemical domains of nitrate in snow is proposed: one of photolabile nitrate, and one of buried nitrate. The difference lies in the ability of reaction products to escape the snow crystal, versus undergoing secondary (recombination) chemistry. Modeled NOx emissions may increase significantly above measured values due to the observed quantum yield in this study. The apparent quantum yield in the 200 nm band was found to be ∼1%, much lower than reported for aqueous chemistry. A companion paper presents an analysis of the change in isotopic composition of snowpack nitrate based on the same samples as in this study. PMID:24985636

  17. Laboratory study of nitrate photolysis in Antarctic snow. I. Observed quantum yield, domain of photolysis, and secondary chemistry

    SciTech Connect

    Meusinger, Carl; Johnson, Matthew S.; Berhanu, Tesfaye A.; Erbland, Joseph; Savarino, Joel

    2014-06-28

    Post-depositional processes alter nitrate concentration and nitrate isotopic composition in the top layers of snow at sites with low snow accumulation rates, such as Dome C, Antarctica. Available nitrate ice core records can provide input for studying past atmospheres and climate if such processes are understood. It has been shown that photolysis of nitrate in the snowpack plays a major role in nitrate loss and that the photolysis products have a significant influence on the local troposphere as well as on other species in the snow. Reported quantum yields for the main reaction spans orders of magnitude – apparently a result of whether nitrate is located at the air-ice interface or in the ice matrix – constituting the largest uncertainty in models of snowpack NO{sub x} emissions. Here, a laboratory study is presented that uses snow from Dome C and minimizes effects of desorption and recombination by flushing the snow during irradiation with UV light. A selection of UV filters allowed examination of the effects of the 200 and 305 nm absorption bands of nitrate. Nitrate concentration and photon flux were measured in the snow. The quantum yield for loss of nitrate was observed to decrease from 0.44 to 0.003 within what corresponds to days of UV exposure in Antarctica. The superposition of photolysis in two photochemical domains of nitrate in snow is proposed: one of photolabile nitrate, and one of buried nitrate. The difference lies in the ability of reaction products to escape the snow crystal, versus undergoing secondary (recombination) chemistry. Modeled NO{sub x} emissions may increase significantly above measured values due to the observed quantum yield in this study. The apparent quantum yield in the 200 nm band was found to be ∼1%, much lower than reported for aqueous chemistry. A companion paper presents an analysis of the change in isotopic composition of snowpack nitrate based on the same samples as in this study.

  18. Alpaca plant poisonings: nitrate-nitrite and possible cyanide.

    PubMed

    McKenzie, Ra; Gordon, An; Burren, Bg; Gibson, Ja; Gardner, Mp

    2009-03-01

    Nitrate-nitrite poisoning killed four adult alpacas and induced the abortion of a full-term fetus after access to oaten hay (Avena sativa) containing 3.2% KNO(3) equivalent in dry matter. Necropsy findings were cyanosis, dark-coloured blood, and pulmonary congestion and oedema. Aqueous humour from two adults contained 25 mg NO(3)/L and that from the fetus contained 10 mg NO(3)/L. Cyanide poisoning possibly killed two adult wether alpacas that ate a garden-cultivated variety of Osteospermum ecklonis (South African daisy, bietou) with a cyanide potential of 6800 mg HCN/kg dry matter. PMID:19245625

  19. Uranyl Nitrate Flow Loop

    SciTech Connect

    Ladd-Lively, Jennifer L

    2008-10-01

    The objectives of the work discussed in this report were to: (1) develop a flow loop that would simulate the purified uranium-bearing aqueous stream exiting the solvent extraction process in a natural uranium conversion plant (NUCP); (2) develop a test plan that would simulate normal operation and disturbances that could be anticipated in an NUCP; (3) use the flow loop to test commercially available flowmeters for use as safeguards monitors; and (4) recommend a flowmeter for production-scale testing at an NUCP. There has been interest in safeguarding conversion plants because the intermediate products [uranium dioxide (UO{sub 2}), uranium tetrafluoride (UF{sub 4}), and uranium hexafluoride (UF{sub 6})] are all suitable uranium feedstocks for producing special nuclear materials. Furthermore, if safeguards are not applied virtually any nuclear weapons program can obtain these feedstocks without detection by the International Atomic Energy Agency (IAEA). Historically, IAEA had not implemented safeguards until the purified UF{sub 6} product was declared as feedstock for enrichment plants. H. A. Elayat et al. provide a basic definition of a safeguards system: 'The function of a safeguards system on a chemical conversion plant is in general terms to verify that no useful nuclear material is being diverted to use in a nuclear weapons program'. The IAEA now considers all highly purified uranium compounds as candidates for safeguarding. DOE is currently interested in 'developing instruments, tools, strategies, and methods that could be of use to the IAEA in the application of safeguards' for materials found in the front end of the nuclear fuel cycle-prior to the production of the uranium hexafluoride or oxides that have been the traditional starting point for IAEA safeguards. Several national laboratories, including Oak Ridge, Los Alamos, Lawrence Livermore, and Brookhaven, have been involved in developing tools or techniques for safeguarding conversion plants. This study was sponsored by the U.S. Department of Energy (DOE) NA-241, Office of Dismantlement and Transparency.

  20. ADSORPTION-BISMUTH PHOSPHATE METHOD FOR SEPARATING PLUTONIUM

    DOEpatents

    Russell, E.R.; Adamson, A.W.; Boyd, G.E.

    1960-06-28

    A process is given for separating plutonium from uranium and fission products. Plutonium and uranium are adsorbed by a cation exchange resin, plutonium is eluted from the adsorbent, and then, after oxidation to the hexavalent state, the plutonium is contacted with a bismuth phosphate carrier precipitate.

  1. Reduction of nitrate in Shewanella

    SciTech Connect

    Gao, Haichun; Yang, Zamin Koo; Barua, Sumitra; Reed, SB; Nealson, Kenneth H.; Fredrikson, JK; Tiedje, James; Zhou, Jizhong

    2009-01-01

    In the genome of Shewanella oneidensis, a napDAGHB gene cluster encoding periplasmic nitrate reductase (NapA) and accessory proteins and an nrfA gene encoding periplasmic nitrite reductase (NrfA) have been identified. These two systems seem to be atypical because the genome lacks genes encoding cytoplasmic membrane electron transport proteins, NapC for NAP and NrfBCD/NrfH for NRF, respectively. Here, we present evidence that reduction of nitrate to ammonium in S. oneidensis is carried out by these atypical systems in a two-step manner. Transcriptional and mutational analyses suggest that CymA, a cytoplasmic membrane electron transport protein, is likely to be the functional replacement of both NapC and NrfH in S. oneidensis. Surprisingly, a strain devoid of napB encoding the small subunit of nitrate reductase exhibited the maximum cell density sooner than the wild type. Further characterization of this strain showed that nitrite was not detected as a free intermediate in its culture and NapB provides a fitness gain for S. oneidensis to compete for nitrate in the environments. On the basis results from mutational analyses of napA, napB, nrfA and napBnrfA in-frame deletion mutants, we propose that NapB is able to favor nitrate reduction by routing electrons to NapA exclusively.

  2. Crevice Repassivation Potential of Alloy 22 in High-Nitrate Dust Deliquescence Type Environments

    SciTech Connect

    Lian, T; Gdowski, G E; Hailey, P D; Rebak, R B

    2007-02-08

    The nitrate ion (NO{sub 3}{sup -}) is an inhibitor for crevice corrosion of Alloy 22 (N06022) in chloride (Cl{sup -}) aqueous solutions. Naturally formed electrolytes may contain both chloride and nitrate ions. The higher the ratio R = [NO{sub 3}{sup -}]/[Cl{sup -}] in the solution the stronger the inhibition of crevice corrosion. Atmospheric desert dust contains both chloride and nitrate salts, generally based on sodium (Na{sup +}) and potassium (K{sup +}). Some of these salts may deliquescence at relatively low humidity at temperatures on the order of 150 C and higher. The resulting deliquescent brines are highly concentrated and especially rich in nitrate. Electrochemical tests have been performed to explore the anodic behavior of Alloy 22 in high chloride high nitrate electrolytes at temperatures as high as 150 C at ambient atmospheres. Naturally formed brines at temperatures higher than 120 C do not induce crevice corrosion in Alloy 22 because they contain high levels of nitrate. The inhibitive effect of nitrate on crevice corrosion is still active for temperatures higher than 100 C.

  3. Effect of surface property of activated carbon on adsorption of nitrate ion.

    PubMed

    Iida, Tatsuya; Amano, Yoshimasa; Machida, Motoi; Imazeki, Fumio

    2013-01-01

    In this study, the removal of acidic functional groups and introduction of basic groups/sites on activated carbons (ACs) by outgassing and ammonia gas treatment were respectively carried out to enhance the nitrate ion adsorption in aqueous solution. Then, the relationships between nitrate ion adsorption and solution pH as well as surface charge of AC were investigated to understand the basic mechanisms of nitrate ion adsorption by AC. The result showed that the nitrate ion adsorption depended on the equilibrium solution pH (pHe) and the adsorption amount was promoted with decreasing pHe. The ACs treated by outgassing and ammonia gas treatment showed larger amount of nitrate ion adsorption than that by untreated AC. These results indicated that, since basic groups/sites could adsorb protons in the solution, the AC surface would be charged positively, and that the nitrate ion would be electrically interacted with positively charged carbon surface. Accordingly, it was concluded that basic groups/sites on the surface of AC could promote nitrate ion adsorption. PMID:24189304

  4. Oxidant supply and aqueous photochemical SOA formation in cloud droplets and aqueous aerosol

    NASA Astrophysics Data System (ADS)

    Turpin, B. J.; Ervens, B.; Lim, Y. B.

    2012-12-01

    Many recent laboratory, field and model studies point to significant contributions to the total secondary organic aerosol (SOA) budget from aqueous phase reactions in cloud droplets and aqueous aerosol particles. Laboratory studies of the photochemical oxidation of glyoxal and methylglyoxal in the aqueous phase show a strong dependence on the initial concentration of dissolved organics, with preferential formation of large molecules (dimers, oligomers) at the high concentrations found in ambient deliquesced aerosol particles. In such experimental studies OH radicals are produced in the aqueous phase (via hydrogen peroxide photolysis) and OH radical is assumed to be the major oxidant. An explicit aqueous photooxidation mechanism has been validated, in part, based on the observed temporal evolution of organic intermediates and products in these experiments. In this work, this mechanism was incorporated into multiphase process models (box, cloud parcel) in order to further explore aqueous SOA formation in dilute cloud droplets and concentrated aerosol particles. We found that the predicted SOA mass in both aqueous phases can be comparable despite the much lower liquid water content in aerosols, where oligomer formation is favored. Direct uptake from the gas phase was the largest source of OH radicals in the aqueous phase. In-situ production through the Fenton reaction (Fe), hydrogen peroxide and nitrate photolysis were minor sources. Since phase transfer is slower than the OH(aq) consumption by organics, modeled OH(aq) concentrations were smaller by 1-2 orders of magnitude than predicted based on thermodynamic equilibrium. Our model studies suggest that, unless there are substantial additional sources of OH radical in the aqueous phase, aqueous SOA formation will be oxidant limited. Since the phase transfer rate is a function of the drop (or particle) surface area, aqueous SOA formation may occur preferentially at or near the drop/particle surface (e.g., be surface-limited) and thus add SOA mass preferentially to particle populations with higher surface/volume ratios. These model results will be compared and contrasted with aqueous sulfate formation. We will discuss our findings in the context of ambient data that might suggest a preferential aqueous SOA formation in smaller (high surface/volume) particles. We will also highlight current gaps in our understanding of oxidant production and cycling in the aqueous phase that might influence our results and change dependencies on bulk water volume versus surface area.

  5. How much plutonium does North Korea have?

    SciTech Connect

    Albright, D.

    1994-09-01

    U.S. intelligence discovered in the 1980s that North Korea was building a small nuclear reactor. The reactor was described as a gas-cooled, graphite-moderated model similar to those Britian and France used to produce electric power as well as plutonium for nuclear weapons. When Western nations expressed concern about the reactor Russia pressed North Korea to sign the Non-Proliferation Treaty (NPT) which it did on December 12, 1985. However, North Korea stalled on signing the required safeguards agreement that allows the International Atomic Energy Agency (IAEA) to inspect nuclear facilities until January 1992. Inspections by the IAEA revealed discrepancies with the amounts of plutonium separated as declared by the North Koreans. The IAEA also received reports that two North Korean waste sites were hidden. By February 1993 the IAEA and the North Koreans has reached an impasse: North Koreas initial declarations of plutonium inventory could not be confirmed and North Korea refused to cooperate. At the least, North Korea admits to having separated 100 grams of plutonium. At the most, worst case estimate, they could have a total of 6 - 13 kilograms of separated plutonium. A first nuclear weapon can require up to 10 kilograms of weapon-grade plutonium. Any settlement needs to include a way to insure that the IAEA can verify North Korea`s past nuclear activities and determine the amount of plutonium that may have been separated in the past. 2 refs.

  6. Mechanism of enhanced nitrate reduction via micro-electrolysis at the powdered zero-valent iron/activated carbon interface.

    PubMed

    Luo, Jinghuan; Song, Guangyu; Liu, Jianyong; Qian, Guangren; Xu, Zhi Ping

    2014-12-01

    Nitrate reduction by zero-valent iron (Fe(0)) powder always works well only at controlled pH lower than 4 due to the formation of iron (hydr)oxides on its surface. Fe(0) powder combined with activated carbon (AC), i.e., Fe(0)/AC micro-electrolysis system, was first introduced to enhance nitrate reduction in aqueous solution. Comparative study was carried out to investigate nitrate reduction by Fe(0)/AC system and Fe(0) under near-neutral conditions, showing that the Fe(0)/AC system successfully reduced nitrate even at initial pH 6 with the reduction efficiency of up to 73%, whereas for Fe(0) only ∼10%. The effect of Fe(0) to AC mass ratio on nitrate reduction efficiency was examined. Easier nitrate reduction was achieved with more contact between Fe(0) and AC as the result of decreasing Fe(0) to AC mass ratio. Ferrous ion and oxidation-reduction potential were measured to understand the mechanism of enhanced nitrate reduction by Fe(0)/AC micro-electrolysis. The results suggest that a relative potential difference drives much more electrons from Fe(0) to AC, thus generating adsorbed atomic hydrogen which makes it possible for nitrate to be reduced at near-neural pH. Fe(0)/AC micro-electrolysis thus presents a great potential for practical application in nitrate wastewater treatment without excessive pH adjustment. PMID:25217726

  7. Immobilization of excess weapons plutonium in Russia

    SciTech Connect

    Borisov, G B; Jardine, L J; Mansourov, O A

    1999-01-25

    In this paper, we examine the logic and framework for the development of a capability to immobilize excess Russian weapons plutonium by the year 2004. The initial activities underway in Russia, summarized here, include engineering feasibility studies of the immobilization of plutonium-containing materials at the Krasnoyarsk and Mayak industrial sites. In addition, research and development (R&D) studies are underway at Russian institutes to develop glass and ceramic forms suitable for the immobilization of plutonium-containing materials, residues, and wastes and for their geologic disposal.

  8. Plutonium Immobilization Can Loading Conceptual Design

    SciTech Connect

    Kriikku, E.

    1999-05-13

    'The Plutonium Immobilization Facility will encapsulate plutonium in ceramic pucks and seal the pucks inside welded cans. Remote equipment will place these cans in magazines and the magazines in a Defense Waste Processing Facility (DWPF) canister. The DWPF will fill the canister with glass for permanent storage. This report discusses the Plutonium Immobilization can loading conceptual design and includes a process block diagram, process description, preliminary equipment specifications, and several can loading issues. This report identifies loading pucks into cans and backfilling cans with helium as the top priority can loading development areas.'

  9. The metabolism of plutonium and related elements

    SciTech Connect

    Not Available

    1986-01-01

    This report reviews, updates and extends the information on the metabolism of plutonium, neptunium and the trivalent actinides, previously reviewed in ICRP Publication 19, with special reference to the absorption from the gastro-intestinal tract, the retention times in liver and skeleton, the influence of bone re-modelling on the microdistribution within the skeleton and the relation of actinide metabolism to that of other radionuclides. Contents (partial): Introduction; The chemistry of plutonium and related elements; Entry of actinides by inhalation; Entry of actinide elements via the gastro-intestinal tract; The penetration of plutonium and other actinides through the intact skin; Distribution and retention of systemically absorbed actinides; General conclusions.

  10. NON-CORROSIVE PLUTONIUM FUEL SYSTEMS

    DOEpatents

    Coffinberry, A.S.; Waber, J.T.

    1962-10-23

    An improved plutonium reactor liquid fuel is described for utilization in a nuclear reactor having a tantalum fuel containment vessel. The fuel consists of plutonium and a diluent such as iron, cobalt, nickel, cerium, cerium-- iron, cerium--cobalt, cerium--nickel, and cerium--copper, and an additive of carbon and silicon. The carbon and silicon react with the tantalum container surface to form a coating that is self-healing and prevents the corrosive action of liquid plutonium on the said tantalum container. (AEC)

  11. Removal of plutonium from hepatic tissue

    DOEpatents

    Lindenbaum, Arthur; Rosenthal, Marcia W.

    1979-01-01

    A method is provided for removing plutonium from hepatic tissues by introducing into the body and blood stream a solution of the complexing agent DTPA and an adjunct thereto. The adjunct material induces aberrations in the hepatic tissue cells and removes intracellularly deposited plutonium which is normally unavailable for complexation with the DTPA. Once the intracellularly deposited plutonium has been removed from the cell by action of the adjunct material, it can be complexed with the DTPA present in the blood stream and subsequently removed from the body by normal excretory processes.

  12. A Study of the Stability and Characterization Plutonium Dioxide and Chemical Characterization [of] Rocky Flats and Los Alamos Plutonium-Containing Incinerator Ash

    SciTech Connect

    Ray, A.K.; Boettger, J.C.; Behrens, Robert G.

    1999-11-29

    In the presentation ''A Study of the Stability and Characterization of Plutonium Dioxide'', the authors discuss their recent work on actinide stabilities and characterization, in particular, plutonium dioxide PuO{sub 2}. Earlier studies have indicated that PuO{sub 2} has the fluorite structure of CaF{sub 2} and typical oxide semiconductor properties. However, detailed results on the bulk electronic structure of this important actinide oxide have not been available. The authors have used all-electron, full potential linear combinations Gaussian type orbitals fitting function (LCGTO-FF) method to study PuO{sub 2}. The LCGTO-FF technique characterized by its use of three independent GTO basis sets to expand the orbitals, charge density, and exchange-correlation integral kernels. Results will be presented on zero pressure using both the Hedin-Lundquist local density approximation (LDA) model or the Perdew-Wang generalized gradient approximation (GGA) model. Possibilities of different characterizations of PuO{sub 2} will be explored. The paper ''Chemical Characterization Rocky Flats and Los Alamos Plutonium-Containing Incinerator Ash'' describes the results of a comprehensive study of the chemical characteristics of virgin, calcined and fluorinated incinerator ash produced at the Rocky Flats Plant and at the Los Alamos National Laboratory prior to 1988. The Rocky Flats and Los Alamos virgin, calcined, and fluorinated ashes were also dissolved using standard nitrate dissolution chemistry. Corresponding chemical evaluations were preformed on the resultant ash heel and the results compared with those of the virgin ash. Fluorination studies using FT spectroscopy as a diagnostic tool were also performed to evaluate the chemistry of phosphorus, sulfur, carbon, and silicon containing species in the ash. The distribution of plutonium and other chemical elements with the virgin ash, ash heel, fluorinated ash, and fluorinated ash heel particulates were studied in detail using microprobe analysis. Some of the more interesting results of these investigations are presented.

  13. VOLATILE FLUORIDE PROCESS FOR SEPARATING PLUTONIUM FROM OTHER MATERIALS

    DOEpatents

    Spedding, F.H.; Newton, A.S.

    1959-04-14

    The separation of plutonium from uranium and/or tission products by formation of the higher fluorides of uranium and/or plutonium is discussed. Neutronirradiated uranium metal is first convcrted to the hydride. This hydrided product is then treatced with fluorine at about 315 deg C to form and volatilize UF/sup 6/ leaving plutonium behind. The plutonium may then be separated by reacting the residue with fluorine at about 500 deg C and collecting the volatile plutonium fluoride thus formed.

  14. Volatile fluoride process for separating plutonium from other materials

    DOEpatents

    Spedding, F. H.; Newton, A. S.

    1959-04-14

    The separation of plutonium from uranium and/or fission products by formation of the higher fluorides off uranium and/or plutonium is described. Neutronirradiated uranium metal is first converted to the hydride. This hydrided product is then treated with fluorine at about 315 deg C to form and volatilize UF/sub 6/ leaving plutonium behind. Thc plutonium may then be separated by reacting the residue with fluorine at about 5004DEC and collecting the volatile plutonium fluoride thus formed.

  15. Nitrate Trends in Minnesota Rivers

    USGS Publications Warehouse

    Wall, Dave; Christopherson, Dave; Lorenz, Dave; Martin, Gary

    2013-01-01

    The objective of this study was to assess long-term trends (30 to 35 years) of flow-adjusted concentrations of nitrite+nitrate-N (hereinafter referred to as nitrate) in a way that would allow us to discern changing trends. Recognizing that these trends are commonly different from one river to another river and from one part of the state to another, our objective was to examine as many river monitoring sites across the state as possible for which sufficient long term streamflow and concentration data were available.

  16. Opportunities in Plutonium Metallurgical Research

    SciTech Connect

    Schwartz, Adam J.

    2007-07-01

    This is an exciting time to be involved in plutonium metallurgical research. Over the past few years, there have been significant advances in our understanding of the fundamental materials science of this unusual metal, particularly in the areas of self-irradiation induced aging of Pu, the equilibrium phase diagram, the homogenization of {delta}-phase alloys, the crystallography and morphology of the {alpha}'-phase resulting from the isothermal martensitic phase transformation, and the phonon dispersion curves, among many others. In addition, tremendous progress has been made, both experimentally and theoretically, in our understanding of the condensed matter physics and chemistry of the actinides, particularly in the area of electronic structure. Although these communities have made substantial progress, many challenges still remain. This brief overview will address a number of important challenges that we face in fully comprehending the metallurgy of Pu with a specific focus on aging and phase transformations. (author)

  17. PLUTONIUM METALLOGRAPHY AT LOS ALAMOS

    SciTech Connect

    PEREYRA, RAMIRO A.; LOVATO, DARRYL

    2007-01-08

    From early days of the Manhattan program to today, scientists and engineers have continued to investigate the metallurgical properties of plutonium (Pu). Although issues like aging was not a concern to the early pioneers, today the reliability of our aging stockpile is of major focus. And as the country moves toward a new generation of weapons similar problems that the early pioneers faced such as compatibility, homogeneity and malleability have come to the forefront. And metallography will continue to be a principle tool for the resolution of old and new issues. Standard metallographic techniques are used for the preparation of plutonium samples. The samples are first cut with a slow speed idamond saw. After mounting in Epon 815 epoxy resin, the samples are ground through 600 grit silicon carbide paper. PF 5070 (a Freon substitute) is used as a coolant, lubricant, and solvent for most operations. Rough mechanical polished is done with 9-{mu} diamond using a nap less cloth, for example nylon or cotton. Final polish is done with 1-{mu} diamond on a nappy cloth such as sylvet. Ethyl alcohol is then used ultrasonically to clean the samples before electro polishing. The sample is then electro-polished and etched in an electrolyte containing 10% nitric acid, and 90% dimethyleneformalmide. Ethyl alcohol is used as a final cleaning agent. Although standard metallographic preparation techniques are used, there are several reasons why metallography of Pu is difficult and challenging. Firstly, because of the health hazards associated with its radioactive properties, sample preparation is conducted in glove boxes. Figure 1 shows the metallography line, in an R and D facility. Since they are designed to be negative in pressure to the laboratory, cross-contamination of abrasives is a major problem. In addition, because of safety concerns and waste issues, there is a limit to the amount of solvent that can be used. Secondly, Pu will readily hydride or oxidize when in contact with metallographic polishing lubricants, solvents, or chemicals. And water being one of the most reactive solutions, is not used in the preparation. Figure 2 shows an example of a plutonium sample in which an oxide film has formed on the surface due to overexposure to solutions. it has been noted that nucleation of the hydride/oxide begins around inclusions and samples with a higher concentration of impurities seem to be more susceptible to this reaction. Figure 3 shows examples of small oxide rings, forming around inclusions. Lastly, during the cutting, grinding, or polishing process there is enough stress induced in the sample that the surface can transform from the soft face-centered-cubic delta phase (30 HV) to the strain-induced monoclinic alpha{prime} phase (300 HV). Figure 4 and 5 shows cross-sectional views of samples in which one was cut using a diamond saw and the other was processed through 600 grit. The white layers on the edges is the strain induced alpha{prime} phase. The 'V' shape indentation in Figure 5 was caused by a coarser abrasive which resulted in transformations to a depth of approximately 20 {micro}m. Another example of the transformation sensitivity of plutonium can be seen in Figure 6, in which the delta phase has partly transformed to alpha{prime} during micro hardness indentation.

  18. Weapons-grade plutonium dispositioning. Volume 4. Plutonium dispositioning in light water reactors

    SciTech Connect

    Sterbentz, J.W.; Olsen, C.S.; Sinha, U.P.

    1993-06-01

    This study is in response to a request by the Reactor Panel Subcommittee of the National Academy of Sciences (NAS) Committee on International Security and Arms Control (CISAC) to evaluate the feasibility of using plutonium fuels (without uranium) for disposal in existing conventional or advanced light water reactor (LWR) designs and in low temperature/pressure LWR designs that might be developed for plutonium disposal. Three plutonium-based fuel forms (oxides, aluminum metallics, and carbides) are evaluated for neutronic performance, fabrication technology, and material and compatibility issues. For the carbides, only the fabrication technologies are addressed. Viable plutonium oxide fuels for conventional or advanced LWRs include plutonium-zirconium-calcium oxide (PuO{sub 2}-ZrO{sub 2}-CaO) with the addition of thorium oxide (ThO{sub 2}) or a burnable poison such as erbium oxide (Er{sub 2}O{sub 3}) or europium oxide (Eu{sub 2}O{sub 3}) to achieve acceptable neutronic performance. Thorium will breed fissile uranium that may be unacceptable from a proliferation standpoint. Fabrication of uranium and mixed uranium-plutonium oxide fuels is well established; however, fabrication of plutonium-based oxide fuels will require further development. Viable aluminum-plutonium metallic fuels for a low temperature/pressure LWR include plutonium aluminide in an aluminum matrix (PuAl{sub 4}-Al) with the addition of a burnable poison such as erbium (Er) or europium (Eu). Fabrication of low-enriched plutonium in aluminum-plutonium metallic fuel rods was initially established 30 years ago and will require development to recapture and adapt the technology to meet current environmental and safety regulations. Fabrication of high-enriched uranium plate fuel by the picture-frame process is a well established process, but the use of plutonium would require the process to be upgraded in the United States to conform with current regulations and minimize the waste streams.

  19. Plutonium focus area: Technology summary

    SciTech Connect

    1996-03-01

    To ensure research and development programs focus on the most pressing environmental restoration and waste management problems at the U.S. Department of Energy (DOE), the Assistant Secretary for the Office of Environmental Management (EM) established a working group in August 1993 to implement a new approach to research and technology development. As part of this approach, EM developed a management structure and principles that led to creation of specific focus areas. These organizations were designed to focus scientific and technical talent throughout DOE and the national scientific community on major environmental restoration and waste management problems facing DOE. The focus area approach provides the framework for inter-site cooperation and leveraging of resources on common problems. After the original establishment of five major focus areas within the Office of Technology Development (EM-50), the Nuclear Materials Stabilization Task Group (NMSTG, EM-66) followed EM-50`s structure and chartered the Plutonium Focus Area (PFA). NMSTG`s charter to the PFA, described in detail later in this book, plays a major role in meeting the EM-66 commitments to the Defense Nuclear Facilities Safety Board (DNFSB). The PFA is a new program for FY96 and as such, the primary focus of revision 0 of this Technology Summary is an introduction to the Focus Area; its history, development, and management structure, including summaries of selected technologies being developed. Revision 1 to the Plutonium Focus Area Technology Summary is slated to include details on all technologies being developed, and is currently planned for release in August 1996. The following report outlines the scope and mission of the Office of Environmental Management, EM-60, and EM-66 organizations as related to the PFA organizational structure.

  20. Spectrophotometric determination of plutonium-239 based on the spectrum of plutonium(III) chloride

    SciTech Connect

    Temer, D.J.; Walker, L.F.

    1994-07-01

    This report describes a spectrophotometric method for determining plutonium-239 (Pu-239) based on the spectrum of Pu(III) chloride. The authors used the sealed-reflux technique for the dissolution of plutonium oxide with hydrochloric acid (HCl) and small amounts of nitric and hydrofluoric acids. To complex the fluoride, they added zirconium, and to reduce plutonium to Pu(III), they added ascorbic acid. They then adjusted the solution to a concentration of 2 M HCl and measured the absorbances at five wavelengths of the Pu(III) chloride spectrum. This spectrophotometric determination can also be applied to samples of plutonium metal dissolved in HCl.

  1. PRODUCTION OF PLUTONIUM FLUORIDE FROM BISMUTH PHOSPHATE PRECIPITATE CONTAINING PLUTONIUM VALUES

    DOEpatents

    Brown, H.S.; Bohlmann, E.G.

    1961-05-01

    A process is given for separating plutonium from fission products present on a bismuth phosphate carrier. The dried carrier is first treated with hydrogen fluoride at between 500 and 600 deg C whereby some fission product fluorides volatilize away from plutonium tetrafluoride, and nonvolatile fission product fluorides are formed then with anhydrous fluorine at between 400 and 500 deg C. Bismuth and plutonium distill in the form of volatile fluorides away from the nonvolatile fission product fluorides. The bismuth and plutonium fluorides are condensed at below 290 deg C.

  2. What is plutonium stabilization, and what is safe storage of plutonium?

    SciTech Connect

    Forsberg, C.W.

    1995-06-29

    The end of the cold war has resulted in the shutdown of nuclear weapons production and the start of dismantlement of significant numbers of nuclear weapons. This, in turn, is creating an inventory of plutonium requiring interim and long-term storage. A key question is, ``What is required for safe, multidecade, plutonium storage?`` The requirements for storage, in turn, define what is needed to stabilize the plutonium from its current condition into a form acceptable for interim and long-term storage. Storage requirements determine if research is required to (1) define required technical conditions for interim and long-term storage and (2) develop or improve current stabilization technologies. Storage requirements depend upon technical, policy, and economic factors. The technical issues are complicated by several factors. Plutonium in aerosol form is highly hazardous. Plutonium in water is hazardous. The plutonium inventory is in multiple chemical forms--some of which are chemically reactive. Also, some of the existing storage forms are clearly unsuitable for storage periods over a few years. Gas generation by plutonium compounds complicates storage: (1) all plutonium slowly decays creating gaseous helium and (2) the radiation from plutonium decay can initiate many chemical reactions-some of which generate significant quantities of gases. Gas generation can pressurize sealed storage packages. Last nuclear criticality must be avoided.

  3. Method for dissolving plutonium oxide with HI and separating plutonium

    DOEpatents

    Vondra, Benedict L.; Tallent, Othar K.; Mailen, James C.

    1979-01-01

    PuO.sub.2 -containing solids, particularly residues from incomplete HNO.sub.3 dissolution of irradiated nuclear fuels, are dissolved in aqueous HI. The resulting solution is evaporated to dryness and the solids are dissolved in HNO.sub.3 for further chemical reprocessing. Alternatively, the HI solution containing dissolved Pu values, can be contacted with a cation exchange resin causing the Pu values to load the resin. The Pu values are selectively eluted from the resin with more concentrated HI.

  4. Sorption/Desorption Interactions of Plutonium with Montmorillonite

    NASA Astrophysics Data System (ADS)

    Begg, J.; Zavarin, M.; Zhao, P.; Kersting, A. B.

    2012-12-01

    Plutonium (Pu) release to the environment through nuclear weapon development and the nuclear fuel cycle is an unfortunate legacy of the nuclear age. In part due to public health concerns over the risk of Pu contamination of drinking water, predicting the behavior of Pu in both surface and sub-surface water is a topic of continued interest. Typically it was assumed that Pu mobility in groundwater would be severely restricted, as laboratory adsorption studies commonly show that naturally occurring minerals can effectively remove plutonium from solution. However, evidence for the transport of Pu over significant distances at field sites highlights a relative lack of understanding of the fundamental processes controlling plutonium behavior in natural systems. At several field locations, enhanced mobility is due to Pu association with colloidal particles that serve to increase the transport of sorbed contaminants (Kersting et al., 1999; Santschi et al., 2002, Novikov et al., 2006). The ability for mineral colloids to transport Pu is in part controlled by its oxidation state and the rate of plutonium adsorption to, and desorption from, the mineral surface. Previously we have investigated the adsorption affinity of Pu for montmorillonite colloids, finding affinities to be similar over a wide range of Pu concentrations. In the present study we examine the stability of adsorbed Pu on the mineral surface. Pu(IV) at an initial concentration of 10-10 M was pre-equilibrated with montmorillonite in a background electrolyte at pH values of 4, 6 and 8. Following equilibration, aliquots of the suspensions were placed in a flow cell and Pu-free background electrolyte at the relevant pH was passed through the system. Flow rates were varied in order to investigate the kinetics of desorption and hence gain a mechanistic understanding of the desorption process. The flow cell experiments demonstrate that desorption of Pu from the montmorillonite surface cannot be modeled as a simple first order process. Furthermore, a pH dependence was observed, with less desorbed at pH 4 compared to pH 8. We suggest the pH dependence is likely controlled by reoxidation of Pu(IV) to Pu(V) and aqueous speciation. We will present models used to describe desorption behavior and discuss the implications for Pu transport. References: Kersting, A.B.; Efurd, D.W.; Finnegan, D.L.; Rokop, D.J.; Smith, D.K.; Thompson J.L. (1999) Migration of plutonium in groundwater at the Nevada Test Site, Nature, 397, 56-59. Novikov A.P.; Kalmykov, S.N.; Utsunomiya, S.; Ewing, R.C.; Horreard, F.; Merkulov, A.; Clark, S.B.; Tkachev, V.V.; Myasoedov, B.F. (2006) Colloid transport of plutonium in the far-field of the Mayak Production Association, Russia, Science, 314, 638-641. Santschi, P.H.; Roberts, K.; Guo, L. (2002) The organic nature of colloidal actinides transported in surface water environments. Environ. Sci. Technol., 36, 3711-3719. This work was funded by U. S. DOE Office of Biological & Environmental Sciences, Subsurface Biogeochemistry Research Program, and performed under the auspices of the U. S. Department of Energy by Lawrence Livermore National Security, LLC under Contract DE-AC52-07NA27344. LLNL-ABS-570161

  5. Preparation of thin ceramic films via an aqueous solution route

    DOEpatents

    Pederson, Larry R.; Chick, Lawrence A.; Exarhos, Gregory J.

    1989-01-01

    A new chemical method of forming thin ceramic films has been developed. An aqueous solution of metal nitrates or other soluble metal salts and a low molecular weight amino acid is coated onto a substrate and pyrolyzed. The amino acid serves to prevent precipitation of individual solution components, forming a very viscous, glass-like material as excess water is evaporated. Using metal nitrates and glycine, the method has been demonstrated for zirconia with various levels of yttria stabilization, for lanthanum-strontium chromites, and for yttrium-barium-copper oxide superconductors on various substrates.

  6. Interaction between stainless steel and plutonium metal

    SciTech Connect

    Dunwoody, John T; Mason, Richard E; Freibert, Franz J; Willson, Stephen P; Veirs, Douglas K; Worl, Laura A; Archuleta, Alonso; Conger, Donald J

    2010-01-01

    Long-term storage of excess plutonium is of great concern in the U.S. as well as abroad. The current accepted configuration involves intimate contact between the stored material and an iron-bearing container such as stainless steel. While many safety scenario studies have been conducted and used in the acceptance of stainless steel containers, little information is available on the physical interaction at elevated temperatures between certain forms of stored material and the container itself. The bulk of the safety studies has focused on the ability of a package to keep the primary stainless steel containment below the plutonium-iron eutectic temperature of approximately 410 C. However, the interactions of plutonium metal with stainless steel have been of continuing interest. This paper reports on a scoping study investigating the interaction between stainless steel and plutonium metal in a pseudo diffusion couple at temperatures above the eutectic melt-point.

  7. Recommendations for plutonium colloid size determination

    SciTech Connect

    Kosiewicz, S.T.

    1984-02-01

    This report presents recommendations for plutonium colloid size determination and summarizes a literature review, discussions with other researchers, and comments from equipment manufacturers. Four techniques suitable for plutonium colloid size characterization are filtration and ultrafiltration, gel permeation chromatography, diffusion methods, and high-pressure liquid chromatography (conditionally). Our findings include the following: (1) Filtration and ultrafiltration should be the first methods used for plutonium colloid size determination because they can provide the most rapid results with the least complicated experimental arrangement. (2) After expertise has been obtained with filtering, gel permeation chromatography should be incorporated into the colloid size determination program. (3) Diffusion methods can be used next. (4) High-pressure liquid chromatography will be suitable after appropriate columns are available. A plutonium colloid size characterization program with filtration/ultrafiltration and gel permeation chromatography has been initiated.

  8. Pulmonary carcinogenesis from plutonium-containing particles

    SciTech Connect

    Thomas, R.G.; Smith, D.M.; Anderson, E.C.

    1980-01-01

    Plutonium administered as an alpha radiation source to the respiratory tracts of Syrian hamsters has resulted in various incidences of neoplasia. Adenomas are the primary lung tumor observed, but adenocarcinomas are also prevalent.

  9. Plutonium finishing plant dangerous waste training plan

    SciTech Connect

    ENTROP, G.E.

    1999-05-24

    This training plan describes general requirements, worker categories, and provides course descriptions for operation of the Plutonium Finish Plant (PFP) waste generation facilities, permitted treatment, storage and disposal (TSD) units, and the 90-Day Accumulation Areas.

  10. International shipment of plutonium by air

    SciTech Connect

    Mercado, J.E.; McGrogan, J.P.

    1995-05-01

    In support of the United States (US) Government`s decision to place excess plutonium oxide at the US Department of Energy`s (DOE) Hanford Site under International Atomic Energy Agency (IAEA) safeguards, the Department of State notified the Congress that a plutonium storage vault at the Plutonium Finishing Plant at the Hanford Site would be added to the eligible facilities list. As part of the preparations to transfer the plutonium oxide under IAEA safeguards, samples of the powder were taken from the inventory to be shipped to the IAEA headquarters in Vienna, Austria, for laboratory analysis. The analysis of these samples was of high priority, and the IAEA requested that the material be shipped by aircraft, the most expeditious method.

  11. Development of a plutonium solution-assay instrument with isotopic capability

    SciTech Connect

    Hsue, S.T.; Marks, T.

    1992-09-01

    A new generation of solution-assay instrument has been developed to satisfy all the assay requirements of an aqueous plutonium-recovery operation. The assay is based on a transmission-corrected passive assay technique. We have demonstrated that the system can cover a concentration range of 0.5--300 g/{ell} with simultaneous isotopic determination. The system can be used to assay input and eluate streams of the recovery operation. The system can be modified to measure low-concentration effluent solutions from the recovery operation covering 0.01--40 g/{ell}. The same system has also been modified to assay plutonium solutions enriched in {sup 242}Pu. 6 refs.

  12. Plutonium-238 processing at Savannah River Plant

    SciTech Connect

    Burney, G.A.

    1983-01-01

    Plutonium-238 is produced by irradiating NpO/sub 2/-Al cermet slugs or tubes with neutrons. The neptunium-237 is produced as a by-product when natural or enriched uranium is irradiated with neutrons. The neptunium is separated by solvent extraction and ion exchange and precipitated as neptunium oxalate. Neptunium oxalate is calcined to neptunium oxide and fabricated into targets for irradiation. The irradiation conditions are controlled to produce plutonium with 80 to 90 wt % /sup 238/Pu.

  13. Biological denitrification of high concentration nitrate waste

    DOEpatents

    Francis, Chester W.; Brinkley, Frank S.

    1977-01-01

    Biological denitrification of nitrate solutions at concentrations of greater than one kilogram nitrate per cubic meter is accomplished anaerobically in an upflow column having as a packing material a support for denitrifying bacteria.

  14. Complementary technologies for verification of excess plutonium

    SciTech Connect

    Langner, , D.G.; Nicholas, N.J.; Ensslin, N.; Fearey, B.L.; Mitchell, D.J.; Marlow, K.W.; Luke, S.J.; Gosnell, T.B.

    1998-12-31

    Three complementary measurement technologies have been identified as candidates for use in the verification of excess plutonium of weapons origin. These technologies: high-resolution gamma-ray spectroscopy, neutron multiplicity counting, and low-resolution gamma-ray spectroscopy, are mature, robust technologies. The high-resolution gamma-ray system, Pu-600, uses the 630--670 keV region of the emitted gamma-ray spectrum to determine the ratio of {sup 240}Pu to {sup 239}Pu. It is useful in verifying the presence of plutonium and the presence of weapons-grade plutonium. Neutron multiplicity counting is well suited for verifying that the plutonium is of a safeguardable quantity and is weapons-quality material, as opposed to residue or waste. In addition, multiplicity counting can independently verify the presence of plutonium by virtue of a measured neutron self-multiplication and can detect the presence of non-plutonium neutron sources. The low-resolution gamma-ray spectroscopic technique is a template method that can provide continuity of knowledge that an item that enters the a verification regime remains under the regime. In the initial verification of an item, multiple regions of the measured low-resolution spectrum form a unique, gamma-radiation-based template for the item that can be used for comparison in subsequent verifications. In this paper the authors discuss these technologies as they relate to the different attributes that could be used in a verification regime.

  15. PLUTONIUM FINISHING PLANT (PFP) STABILIZATION & PACKAGING PROJECT

    SciTech Connect

    GERBER, M.S.

    2004-01-14

    Fluor Hanford is pleased to submit the Plutonium Finishing Plant (PFP) Stabilization and Packaging Project (SPP) for consideration by the Project Management Institute as Project of the Year for 2004. The SPP thermally stabilized and/or packaged nearly 18 metric tons (MT) of plutonium and plutonium-bearing materials left in PFP facilities from 40 years of nuclear weapons production and experimentation. The stabilization of the plutonium-bearing materials substantially reduced the radiological risk to the environment and security concerns regarding the potential for terrorists to acquire the non-stabilized plutonium products for nefarious purposes. The work was done In older facilities which were never designed for the long-term storage of plutonium, and required working with materials that were extremely radioactive, hazardous, pyrophoric, and In some cases completely unique. I n some Instances, one-of-a-kind processes and equipment were designed, installed, and started up. The SPP was completed ahead of schedule, substantially beating all Interim progress milestone dates set by the Defense Nuclear Facilities Safety Board (DNFSB) and in the Hanford Site's Federal Facility Agreement and Consent Order (Tri-Party Agreement or TPA), and finished $1-million under budget.

  16. Plutonium Finishing Plant safety evaluation report

    SciTech Connect

    Not Available

    1995-01-01

    The Plutonium Finishing Plant (PFP) previously known as the Plutonium Process and Storage Facility, or Z-Plant, was built and put into operation in 1949. Since 1949 PFP has been used for various processing missions, including plutonium purification, oxide production, metal production, parts fabrication, plutonium recovery, and the recovery of americium (Am-241). The PFP has also been used for receipt and large scale storage of plutonium scrap and product materials. The PFP Final Safety Analysis Report (FSAR) was prepared by WHC to document the hazards associated with the facility, present safety analyses of potential accident scenarios, and demonstrate the adequacy of safety class structures, systems, and components (SSCs) and operational safety requirements (OSRs) necessary to eliminate, control, or mitigate the identified hazards. Documented in this Safety Evaluation Report (SER) is DOE`s independent review and evaluation of the PFP FSAR and the basis for approval of the PFP FSAR. The evaluation is presented in a format that parallels the format of the PFP FSAR. As an aid to the reactor, a list of acronyms has been included at the beginning of this report. The DOE review concluded that the risks associated with conducting plutonium handling, processing, and storage operations within PFP facilities, as described in the PFP FSAR, are acceptable, since the accident safety analyses associated with these activities meet the WHC risk acceptance guidelines and DOE safety goals in SEN-35-91.

  17. Plutonium: The first 50 years. United States plutonium production, acquisition, and utilization from 1944 through 1994

    SciTech Connect

    1996-02-01

    The report contains important newly declassified information regarding the US production, acquisition, and removals of plutonium. This new information, when combined with previously declassified data, has allowed the DOE to issue, for the first time, a truly comprehensive report on the total DOE plutonium inventory. At the December 7, 1993, Openness Press Conference, the DOE declassified the plutonium inventories at eight locations totaling 33.5 metric tons (MT). This report declassifies the remainder of the DOE plutonium inventory. Newly declassified in this report is the quantity of plutonium at the Pantex Site, near Amarillo, Texas, and in the US nuclear weapons stockpile of 66.1 MT, which, when added to the previously released inventory of 33.5 MT, yields a total plutonium inventory of 99.5 MT. This report will document the sources which built up the plutonium inventory as well as the transactions which have removed plutonium from that inventory. This report identifies four sources that add plutonium to the DOE/DoD inventory, and seven types of transactions which remove plutonium from the DOE/DoD inventory. This report also discusses the nuclear material control and accountability system which records all nuclear material transactions, compares records with inventory and calculates material balances, and analyzes differences to verify that nuclear materials are in quantities as reported. The DOE believes that this report will aid in discussions in plutonium storage, safety, and security with stakeholders as well as encourage other nations to declassify and release similar data. These data will also be available for formulating policies with respect to disposition of excess nuclear materials. The information in this report is based on the evaluation of available records. The information contained in this report may be updated or revised in the future should additional or more detailed data become available.

  18. A Novel Chemical Nitrate Destruction Process

    SciTech Connect

    Dziewinski, J.; Marczak, S.

    1999-03-01

    Nitrates represent one of the most significant pollutant discharged to the Baltic Sea by the Sliiamae hydrometallurgical plant. This article contains a brief overview of the existing nitrate destruction technologies followed by the description of a new process developed by the authors. The new chemical process for nitrate destruction is cost effective and simple to operate. It converts the nitrate to nitrogen gas which goes to the atmosphere.

  19. Plutonium Mobility Through Vadose Zone Lysimeters: Influence of Oxidation State

    NASA Astrophysics Data System (ADS)

    Kaplan, D.; Demirkanli, D. I.; Gumapas, L.; Powell, B. A.; Fjeld, R. A.; Molz, F. I.; Serkiz, S. M.

    2005-12-01

    Understanding the processes controlling plutonium (Pu) mobility in the subsurface environment is important for estimating the amount of Pu waste that can be safely disposed in vadose zone burial sites. To study long-term Pu mobility, four 52-L lysimeters filled with sediment collected from the Savannah River Site near Aiken South Carolina were amended with well characterized solid Pu sources (Pu(III)-chloride, Pu(IV)-nitrate, Pu(IV)-oxalate, and Pu(VI)-nitrate and left exposed to natural precipitation for 2 to 11 years. Pu oxidation state distribution in the Pu(III) and Pu(IV) lysimeters sediments (a red clayey sediment, pH = 6.3) were similar, consisting of 0% Pu(III), >92% Pu(IV), 1% Pu(V), 1% Pu(VI), and the remainder was a Pu polymer. These three lysimeters also had near identical sediment Pu concentration profiles, where >95% of the Pu remained within 1.25 cm of the source after 11 years; moving at an overall rate of 0.9 cm/yr. As expected, Pu moved more rapidly through the Pu(VI) lysimeter, at an overall rate of 12.5 cm/yr. Solute transport modeling of the sediment Pu concentration profile data in the Pu(VI) lysimeter indicated that some transformation of Pu into a much less mobile form, presumably Pu(IV), had occurred during the course of the two year study. This modeling also supported previous laboratory measurements showing that Pu(V) or Pu(VI) reduction was five orders of magnitude faster than corresponding Pu(III) or Pu(IV) oxidation. The slow oxidation rate (1e-8 1/hr; half-life = 8,000 yr) was not discernable from the Pu(VI) lysimeter data that reflected only two years of transport but was readily discernable from the Pu(III) and Pu(IV) lysimeter data that reflected 11 yr of transport.

  20. Plasma nitrate and nitrite are increased by a high nitrate supplement, but not by high nitrate foods in older adults

    PubMed Central

    Miller, Gary D.; Marsh, Anthony P.; Dove, Robin W.; Beavers, Daniel; Presley, Tennille; Helms, Christine; Bechtold, Erika; King, S. Bruce; Kim-Shapiro, Daniel

    2012-01-01

    Little is known about the effect of dietary nitrate on the nitrate/nitrite/NO (nitric oxide) cycle in older adults. We examined the effect of a 3-day control diet vs. high nitrate diet, with and without a high nitrate supplement (beetroot juice), on plasma nitrate and nitrite kinetics, and blood pressure using a randomized four period cross-over controlled design. We hypothesized that the high nitrate diet would show higher levels of plasma nitrate/nitrite and blood pressure compared to the control diet, which would be potentiated by the supplement. Participants were eight normotensive older men and women (5 female, 3 male, 72.5±4.7 yrs) with no overt disease or medications that affect NO metabolism. Plasma nitrate and nitrite levels and blood pressure were measured prior to and hourly for 3 hours after each meal. The mean daily changes in plasma nitrate and nitrite were significantly different from baseline for both control diet+supplement (p<0.001 and =0.017 for nitrate and nitrite, respectively) and high nitrate diet+supplement (p=0.001 and 0.002), but not for control diet (p=0.713 and 0.741) or high nitrate diet (p=0.852 and 0.500). Blood pressure decreased from the morning baseline measure to the three 2 hr post-meal follow-up time-points for all treatments, but there was no main effect for treatment. In healthy older adults, a high nitrate supplement consumed at breakfast elevated plasma nitrate and nitrite levels throughout the day. This observation may have practical utility for the timing of intake of a nitrate supplement with physical activity for older adults with vascular dysfunction. PMID:22464802

  1. CHEMOX: An integrated facility for the conversion of Russian weapon-grade plutonium into oxide for MOX fuel fabrication

    NASA Astrophysics Data System (ADS)

    Glagovski, E.; Kolotilov, Y.; Sicard, B.; Josso, F.; Fraize, G.; Herlet, N.; Villa, A.; Brossard, P.

    2000-07-01

    In the frame of the trilateral agreement between Russia, Germany and France, the CHEMOX (chemistry from metal into oxide) facility is proposed for the conversion of the alloyed plutonium coming from the dismantling of nuclear pits into an oxide suitable for MOX fuel fabrication and irradiation in VVER- or BN-type reactors. For the CHEMOX facility an aqueous conversion process has been chosen for its versatility, and compatibility with known technologies and with existing on-site treatment facilities.

  2. Guidelines for international plutonium management: Overview and implications

    SciTech Connect

    Bryson, M.C.; Fitzgerald, C.P.; Kincaid, C.

    1998-12-31

    In September, 1997, nine of the world`s plutonium-using countries agreed to a set of guidelines for international plutonium management, with acceptances to be submitted to the International Atomic Energy Agency on December 1. Following three years of discussion, the guidelines provide a unified package of accepted rules for the storage, handling, and transportation of civil plutonium as well as military plutonium that has been declared as no longer required for defense purposes. New requirements include a formal declaration of national plutonium strategies, which will recognize the environmental, economic, and proliferation concerns and the consequent importance of balancing plutonium supply and demand. Nations will also make annual declaration of their non-military stockpiles of unirradiated plutonium, together with estimates of the plutonium content in spent reactor fuel. These guidelines represent the first formally accepted recognition of the need for plutonium management of this scope and could thus provide a partial basis for future monitoring and policy regimes.

  3. 49 CFR 176.410 - Division 1.5 materials, ammonium nitrate and ammonium nitrate mixtures.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 49 Transportation 2 2011-10-01 2011-10-01 false Division 1.5 materials, ammonium nitrate and ammonium nitrate mixtures. 176.410 Section 176.410 Transportation Other Regulations Relating to... nitrate and ammonium nitrate mixtures. (a) This section prescribes requirements to be observed...

  4. 49 CFR 176.410 - Division 1.5 materials, ammonium nitrate and ammonium nitrate mixtures.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 49 Transportation 2 2010-10-01 2010-10-01 false Division 1.5 materials, ammonium nitrate and ammonium nitrate mixtures. 176.410 Section 176.410 Transportation Other Regulations Relating to... nitrate and ammonium nitrate mixtures. (a) This section prescribes requirements to be observed...

  5. 21 CFR 172.170 - Sodium nitrate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Sodium nitrate. 172.170 Section 172.170 Food and... Preservatives § 172.170 Sodium nitrate. The food additive sodium nitrate may be safely used in or on specified... follows: (1) As a preservative and color fixative, with or without sodium nitrite, in smoked,...

  6. 21 CFR 172.170 - Sodium nitrate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Sodium nitrate. 172.170 Section 172.170 Food and... Preservatives § 172.170 Sodium nitrate. The food additive sodium nitrate may be safely used in or on specified... follows: (1) As a preservative and color fixative, with or without sodium nitrite, in smoked,...

  7. Nitration of Naphthol: A Laboratory Experiment.

    ERIC Educational Resources Information Center

    Mowery, Dwight F.

    1982-01-01

    Products of nitrations, upon distillation or steam distillation, may produce dermatitis in some students. A procedure for nitration of beta-naphthol producing a relatively non-volatile product not purified by steam distillation is described. Nitration of alpha-naphthol by the same procedure yields Martius Yellow dye which dyes wool yellow or

  8. Modeling nitrate removal in a denitrification bed

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Denitrification beds are being promoted to reduce nitrate concentrations in agricultural drainage water to alleviate the adverse environmental effects associated with nitrate pollution in surface water. In this system, water flows through a trench filled with a carbon media where nitrate is transfor...

  9. 21 CFR 172.160 - Potassium nitrate.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Potassium nitrate. 172.160 Section 172.160 Food... ADDITIVES PERMITTED FOR DIRECT ADDITION TO FOOD FOR HUMAN CONSUMPTION Food Preservatives § 172.160 Potassium nitrate. The food additive potassium nitrate may be safely used as a curing agent in the processing of...

  10. 21 CFR 172.160 - Potassium nitrate.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Potassium nitrate. 172.160 Section 172.160 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR... Food Preservatives § 172.160 Potassium nitrate. The food additive potassium nitrate may be safely...

  11. 21 CFR 172.160 - Potassium nitrate.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Potassium nitrate. 172.160 Section 172.160 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR... Food Preservatives § 172.160 Potassium nitrate. The food additive potassium nitrate may be safely...

  12. Post-translational Regulation of Nitrate Reductase

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Nitrate reductase (NR) catalyzes the reduction of nitrate to nitrite, which is the first step in the nitrate assimilation pathway, but can also reduce nitrite to nitric oxide (NO), an important signaling molecule that is thought to mediate a wide array of of developmental and physiological processes...

  13. 21 CFR 172.160 - Potassium nitrate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Potassium nitrate. 172.160 Section 172.160 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN... Preservatives § 172.160 Potassium nitrate. The food additive potassium nitrate may be safely used as a...

  14. 21 CFR 172.160 - Potassium nitrate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Potassium nitrate. 172.160 Section 172.160 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR... Food Preservatives § 172.160 Potassium nitrate. The food additive potassium nitrate may be safely...

  15. 21 CFR 172.170 - Sodium nitrate.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Sodium nitrate. 172.170 Section 172.170 Food and... Preservatives § 172.170 Sodium nitrate. The food additive sodium nitrate may be safely used in or on specified... follows: (1) As a preservative and color fixative, with or without sodium nitrite, in smoked,...

  16. 21 CFR 172.170 - Sodium nitrate.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Sodium nitrate. 172.170 Section 172.170 Food and... PERMITTED FOR DIRECT ADDITION TO FOOD FOR HUMAN CONSUMPTION Food Preservatives § 172.170 Sodium nitrate. The food additive sodium nitrate may be safely used in or on specified foods in accordance with...

  17. 21 CFR 172.170 - Sodium nitrate.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Sodium nitrate. 172.170 Section 172.170 Food and... Preservatives § 172.170 Sodium nitrate. The food additive sodium nitrate may be safely used in or on specified... follows: (1) As a preservative and color fixative, with or without sodium nitrite, in smoked,...

  18. Method of producing thin cellulose nitrate film

    DOEpatents

    Lupica, S.B.

    1975-12-23

    An improved method for forming a thin nitrocellulose film of reproducible thickness is described. The film is a cellulose nitrate film, 10 to 20 microns in thickness, cast from a solution of cellulose nitrate in tetrahydrofuran, said solution containing from 7 to 15 percent, by weight, of dioctyl phthalate, said cellulose nitrate having a nitrogen content of from 10 to 13 percent.

  19. Nitration of Naphthol: A Laboratory Experiment.

    ERIC Educational Resources Information Center

    Mowery, Dwight F.

    1982-01-01

    Products of nitrations, upon distillation or steam distillation, may produce dermatitis in some students. A procedure for nitration of beta-naphthol producing a relatively non-volatile product not purified by steam distillation is described. Nitration of alpha-naphthol by the same procedure yields Martius Yellow dye which dyes wool yellow or…

  20. Efflux Of Nitrate From Hydroponically Grown Wheat

    NASA Technical Reports Server (NTRS)

    Huffaker, R. C.; Aslam, M.; Ward, M. R.

    1992-01-01

    Report describes experiments to measure influx, and efflux of nitrate from hydroponically grown wheat seedlings. Ratio between efflux and influx greater in darkness than in light; increased with concentration of nitrate in nutrient solution. On basis of experiments, authors suggest nutrient solution optimized at lowest possible concentration of nitrate.

  1. Dosimetric and spectrometric neutron measurements around an annular vessel containing a plutonium nitrate fissile solution

    NASA Astrophysics Data System (ADS)

    Tournier, B.; Itié, C.; Médioni, R.; Rich, C.; Mussoni, F.; Camus, L.; Pichenot, G.; Crovisier, Ph.; Cutarella, D.; Asselineau, B.; Groetz, J. E.

    2002-01-01

    The new ICPR60 recommendations and the consideration of the ALARA principle have led the operators of nuclear facilities to evaluate with a higher care, the doses received by workers. The aim of this paper is to present a recent study concerning mixed field characterisation at a workplace located in a reprocessing laboratory. As a first step, neutron spectrum determination was achieved by two ways: simulation using MCNP code and experimental measurements with Bonner spheres and recoil proton counters. Neutron spectrum allowed the evaluation of dosimetric quantities. Measurements were then performed with different devices routinely used in radioprotection. The authors describe the measurement techniques, present the results obtained, and finally compare and discuss them.

  2. Recycle of scrap plutonium-238 oxide fuel to support future radioisotope applications

    SciTech Connect

    Schulte, L.D.; Purdy, G.M.; Jarvinen, G.D.; Ramsey, K.; Silver, G.L.; Espinoza, J.; Rinehart, G.H.

    1998-01-01

    The Nuclear Materials Technology (NMT) Division of Los Alamos National Laboratory has initiated a development program to recover & purify plutonium-238 oxide from impure feed sources in a glove box environment. A glove box line has been designed and a chemistry flowsheet developed to perform this recovery task at large scale. The initial demonstration effort focused on purification of {sup 238}PuO{sub 2} fuel by HNO{sub 3}/HF dissolution, followed by plutonium(III) oxalate precipitation and calcination to an oxide. Decontamination factors for most impurities of concern in the fuel were very good, producing {sup 238}PuO{sub 2} fuel significantly better in purity than specified by General Purpose Heat Source (GPHS) fuel powder specifications. A sufficient quantity of purified {sup 238}PuO{sub 2} fuel was recovered from the process to allow fabrication of a GPHS unit for testing. The results are encouraging for recycle of relatively impure plutonium-238 oxide and scrap residue items into fuel for useful applications. The high specific activity of plutonium-238 magnifies the consequences and concerns of radioactive waste generation. This work places an emphasis on development of waste minimization technologies to complement the aqueous processing operation. Results from experiments on neutralized solutions of plutonium-238 resulted in decontamination to about 1 millicurie/L. Combining ultrafiltration treatment with addition of a water-soluble polymer designed to coordinate Pu, allowed solutions to be decontaminated to about 1 microcurie/L. Efforts continue to develop a capability for efficient, safe, cost-effective, and environmentally acceptable methods to recover and purify {sup 238}PuO{sub 2} fuel. {copyright} {ital 1998 American Institute of Physics.}

  3. Recycle of scrap plutonium-238 oxide fuel to support future radioisotope applications

    NASA Astrophysics Data System (ADS)

    Schulte, Louis D.; Purdy, Geraldine M.; Jarvinen, Gordon D.; Ramsey, Kevin; Silver, Gary L.; Espinoza, Jacob; Rinehart, Gary H.

    1998-01-01

    The Nuclear Materials Technology (NMT) Division of Los Alamos National Laboratory has initiated a development program to recover & purify plutonium-238 oxide from impure feed sources in a glove box environment. A glove box line has been designed and a chemistry flowsheet developed to perform this recovery task at large scale. The initial demonstration effort focused on purification of 238PuO2 fuel by HNO3/HF dissolution, followed by plutonium(III) oxalate precipitation and calcination to an oxide. Decontamination factors for most impurities of concern in the fuel were very good, producing 238PuO2 fuel significantly better in purity than specified by General Purpose Heat Source (GPHS) fuel powder specifications. A sufficient quantity of purified 238PuO2 fuel was recovered from the process to allow fabrication of a GPHS unit for testing. The results are encouraging for recycle of relatively impure plutonium-238 oxide and scrap residue items into fuel for useful applications. The high specific activity of plutonium-238 magnifies the consequences and concerns of radioactive waste generation. This work places an emphasis on development of waste minimization technologies to complement the aqueous processing operation. Results from experiments on neutralized solutions of plutonium-238 resulted in decontamination to about 1 millicurie/L. Combining ultrafiltration treatment with addition of a water-soluble polymer designed to coordinate Pu, allowed solutions to be decontaminated to about 1 microcurie/L. Efforts continue to develop a capability for efficient, safe, cost-effective, and environmentally acceptable methods to recover and purify 238PuO2 fuel.

  4. SEPARATION OF PLUTONIUM FROM URANIUM AND FISSION PRODUCTS

    DOEpatents

    Boyd, G.E.; Adamson, A.W.; Schubert, J.; Russell, E.R.

    1958-10-01

    A chromatographic adsorption process is presented for the separation of plutonium from other fission products formed by the irradiation of uranium. The plutonium and the lighter element fission products are adsorbed on a sulfonated phenol-formaldehyde resin bed from a nitric acid solution containing the dissolved uranium. Successive washes of sulfuric, phosphoric, and nitric acids remove the bulk of the fission products, then an eluate of dilute phosphoric and nitric acids removes the remaining plutonium and fission products. The plutonium is selectively removed by passing this solution through zirconium phosphate, from which the plutonium is dissolved with nitric acid. This process provides a convenient and efficient means for isolating plutonium.

  5. Method for Plutonium-Gallium Separation by Anodic Dissolution of a Solid Plutonium-Gallium Alloy

    SciTech Connect

    Miller, William E.; Tomczuk, Zygmunt

    1998-12-08

    Purified plutonium and gallium are efficiently recovered from a solid plutonium-gallium (Pu-Ga) alloy by using an electrorefining process. The solid Pu-Ga alloy is the cell anode, preferably placed in a moving basket within the electrolyte. As the surface of the Pu-Ga anode is depleted in plutonium by the electrotransport of the plutonium to a cathode, the temperature of the electrolyte is sufficient to liquify the surface, preferably at about 500 C, resulting in a liquid anode layer substantially comprised of gallium. The gallium drips from the liquified surface and is collected below the anode within the electrochemical cell. The transported plutonium is collected on the cathode surface and is recovered.

  6. Nitrated fatty acids: Synthesis and measurement

    PubMed Central

    Woodcock, Steven R.; Bonacci, Gustavo; Gelhaus, Stacy L.; Schopfer, Francisco J.

    2012-01-01

    Nitrated fatty acids are the product of nitrogen dioxide reaction with unsaturated fatty acids. The discovery of peroxynitrite and peroxidase-induced nitration of biomolecules led to the initial reports of endogenous nitrated fatty acids. These species increase during ischemia reperfusion, but concentrations are often at or near the limits of detection. Here, we describe multiple methods for nitrated fatty acid synthesis, sample extraction from complex biological matrices, and a rigorous method of qualitative and quantitative detection of nitrated fatty acids by LC-MS. In addition, optimized instrument conditions and caveats regarding data interpretation are discussed. PMID:23200809

  7. Continuous flow nitration in miniaturized devices

    PubMed Central

    2014-01-01

    Summary This review highlights the state of the art in the field of continuous flow nitration with miniaturized devices. Although nitration has been one of the oldest and most important unit reactions, the advent of miniaturized devices has paved the way for new opportunities to reconsider the conventional approach for exothermic and selectivity sensitive nitration reactions. Four different approaches to flow nitration with microreactors are presented herein and discussed in view of their advantages, limitations and applicability of the information towards scale-up. Selected recent patents that disclose scale-up methodologies for continuous flow nitration are also briefly reviewed. PMID:24605161

  8. Phytochrome, Nitrate Movement, and Induction of Nitrate Reductase in Etiolated Pea Terminal Buds 1

    PubMed Central

    Jones, Richard W.; Sheard, Robert W.

    1975-01-01

    The role of phytochrome in the induction of nitrate reductase of etiolated field peas (Pisum arvense L.) was examined. Terminal bud nitrate concentration increased in darkness, and the increase correlated with induction of nitrate reductase following brief exposure of intact plants to red, blue, far red, and white lights. Brief light exposure of intact plants stimulated nitrate uptake and induction of nitrate reductase by terminal buds subsequently excised and incubated on nitrate solution in darkness; exposure of excised buds in contact with nitrate led to less uptake but more induction. Nitrate and nitrate reductase activity both declined during incubation with water, irrespective of light treatment. Nitrate enrichment of intact terminal buds and uptake into excised buds and increases in nitrate reductase activity were all red/far red reversible. Dimethyl sulfoxide (1%, v/v) and sugars (sucrose 0.5%, glucose 1, w/v), although stimulating nitrate uptake into excised tissue in darkness, failed to enhance nitrate reductase activity over dark controls. Phytochrome may regulate nitrate reductase via both nitrate movement and a general mechanism such as enhancement of protein synthesis. PMID:16659226

  9. Thermodynamic quantities of surface formation of aqueous electrolyte solutions VIII. Aqueous solutions of sulfates salts.

    PubMed

    Matubayasi, Norihiro; Tsuchihashi, Susumu; Yoshikawa, Ryuji

    2009-01-15

    In this work the surface tension of the aqueous solutions of alkali metal sulfate, magnesium sulfate, and magnesium nitrate have been measured with an expectation that the effect of sulfate salts on the air/water surface differs from that of typical electrolyte because of their peculiar results of surface potential data. The results show that the slope of surface tension-concentration curves of sulfate salts depends to some extent upon cations while that of alkali metal nitrate gives almost the same magnitude. In order to make comparison with salts of different valence types, we used the ratio of surface excess density to bulk concentration of a salt as an index of surface activity of the salt. It was shown that the surface activity of a salt largely dependent upon its valence type as well as its specific property of anion. PMID:18930247

  10. Deconstructing nitrate isotope dynamics in aquifers

    NASA Astrophysics Data System (ADS)

    Granger, J.

    2012-12-01

    The natural abundance N and O stable isotope ratios of nitrate provide an invaluable tool to differentiate N sources to the environment, track their dispersal, and monitor their attenuation by biological transformations. The interpretation of patterns in isotope abundances relies on knowledge of the isotope ratios of the source end-members, as well as on constraints on the isotope discrimination imposed on nitrate by respective biological processes. Emergent observations from mono-culture experiments of denitrifying bacteria reveal nitrate fractionation trends that appear at odds with trends ascribed to denitrification in soils and aquifers. This discrepancy raises the possibility that additional biological N transformations may be acting in tandem with denitrification. Here, the N and O isotope enrichments associated with nitrate removal by denitrification in aquifers are posited to bear evidence of coincident biological nitrate production - from nitrification and/or from anammox. Simulations are presented from a simple time-dependent one-box model of a groundwater mass ageing that is subject to net nitrate loss by denitrification with coincident nitrate production by nitrification or anammox. Within boundary conditions characteristic of freshwater aquifers, the apparent slope of the parallel enrichments in nitrate N and O isotopes associated with net N loss to denitrification can vary in proportion to the nitrate added simultaneous by oxidative processes. Pertinent observations from nitrate plumes in suboxic to anoxic aquifers are examined to validate this premise. In this perspective, nitrate isotope distributions suggest that we may be missing important N fluxes inherent to most aquifers.

  11. Sulfide-induced nitrate reduction in the sludge of an anaerobic digester of a zero-discharge recirculating mariculture system.

    PubMed

    Sher, Yonatan; Schneider, Kenneth; Schwermer, Carsten U; van Rijn, Jaap

    2008-10-01

    The anaerobic digester is a vital component in a zero-discharge mariculture system as therein most of the organic matter is mineralized and nitrogen-containing compounds are converted to gaseous N(2). Although denitrification is a major respiratory process in this nitrate-rich treatment stage, also sulfate respiration takes place and may cause undesirable high sulfide concentrations in the effluent water. To examine the effect of sulfide on nitrate reduction, in situ depth profiles of inorganic nitrogen and sulfur compounds were determined. Additionally, nitrate reduction was examined as a function of ambient sulfide concentrations in sludge collected from different locations in the anaerobic reactor. Depth profiles showed high concentrations of nitrate and low concentrations of sulfide and ammonia in the aqueous layer of the reactor. A sharp decrease of nitrate and an increase in sulfide and ammonia concentrations was measured at the water-sludge interface. Nitrate reduction was highest in this interface zone with rates of up to 8.05+/-0.57 micromol NO(3)(-)h(-1)g((sludge))(-1). Addition of sulfide increased the nitrate reduction rate at all sludge depths, pointing to the important role of autotrophic denitrification in the anaerobic reactor. Dissimilatory nitrate reduction to ammonia (DNRA) was found to be low in all sludge layers but was enhanced when sludge was incubated at high sulfide concentrations. Although nitrate reduction rates increased as a result of sulfide addition to sludge samples, no differences in nitrate reduction rates were observed between the samples incubated with different initial sulfide concentrations. This as opposed to sulfide oxidation rates, which followed Michaelis-Menten enzymatic kinetics. Partial oxidation of sulfide to elemental sulfur instead of a complete oxidation to sulfate, could explain the observed patterns of nitrate reduction and sulfide oxidation in sludge incubated with different initial sulfide concentrations. PMID:18718629

  12. Nitrate Utilization by the Diatom Skeletonema costatum

    PubMed Central

    Serra, Juan L.; Llama, Maria J.; Cadenas, Eduardo

    1978-01-01

    Nitrate uptake has been studied in nitrogen-deficient cells of the marine diatom Skeletonema costatum. When these cells are incubated in the presence of nitrate, this ion is quickly taken up from the medium, and nitrite is excreted by the cells. Nitrite is excreted following classical saturation kinetics, its rate being independent of nitrate concentration in the incubation medium for nitrate concentration values higher than 3 micromolar. Nitrate uptake shows mixed-transfer kinetics, which can be attributed to the simultaneous contributions of mediated and diffusion transfer. Cycloheximide and p-hydroxymercuribenzoate inhibit the carrier-mediated contribution to nitrate uptake, without affecting the diffusion component. When cells are preincubated with nitrate, the net nitrogen uptake is increased. PMID:16660652

  13. High performance ammonium nitrate propellant

    NASA Technical Reports Server (NTRS)

    Anderson, F. A. (Inventor)

    1979-01-01

    A high performance propellant having greatly reduced hydrogen chloride emission is presented. It is comprised of: (1) a minor amount of hydrocarbon binder (10-15%), (2) at least 85% solids including ammonium nitrate as the primary oxidizer (about 40% to 70%), (3) a significant amount (5-25%) powdered metal fuel, such as aluminum, (4) a small amount (5-25%) of ammonium perchlorate as a supplementary oxidizer, and (5) optionally a small amount (0-20%) of a nitramine.

  14. 49 CFR 176.415 - Permit requirements for Division 1.5, ammonium nitrates, and certain ammonium nitrate fertilizers.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... nitrates, and certain ammonium nitrate fertilizers. 176.415 Section 176.415 Transportation Other... requirements for Division 1.5, ammonium nitrates, and certain ammonium nitrate fertilizers. (a) Except as... Captain of the Port (COTP). (1) Ammonium nitrate UN1942, ammonium nitrate fertilizers containing more...

  15. 49 CFR 176.415 - Permit requirements for Division 1.5, ammonium nitrates, and certain ammonium nitrate fertilizers.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... nitrates, and certain ammonium nitrate fertilizers. 176.415 Section 176.415 Transportation Other... requirements for Division 1.5, ammonium nitrates, and certain ammonium nitrate fertilizers. (a) Except as... Captain of the Port (COTP). (1) Ammonium nitrate UN1942, ammonium nitrate fertilizers containing more...

  16. 49 CFR 176.415 - Permit requirements for Division 1.5, ammonium nitrates, and certain ammonium nitrate fertilizers.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... nitrates, and certain ammonium nitrate fertilizers. 176.415 Section 176.415 Transportation Other... requirements for Division 1.5, ammonium nitrates, and certain ammonium nitrate fertilizers. (a) Except as... Captain of the Port (COTP). (1) Ammonium nitrate UN1942, ammonium nitrate fertilizers containing more...

  17. 49 CFR 176.415 - Permit requirements for Division 1.5, ammonium nitrates, and certain ammonium nitrate fertilizers.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... nitrates, and certain ammonium nitrate fertilizers. 176.415 Section 176.415 Transportation Other... requirements for Division 1.5, ammonium nitrates, and certain ammonium nitrate fertilizers. (a) Except as... Captain of the Port (COTP). (1) Ammonium nitrate UN1942, ammonium nitrate fertilizers containing more...

  18. 49 CFR 176.415 - Permit requirements for Division 1.5, ammonium nitrates, and certain ammonium nitrate fertilizers.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... nitrates, and certain ammonium nitrate fertilizers. 176.415 Section 176.415 Transportation Other... requirements for Division 1.5, ammonium nitrates, and certain ammonium nitrate fertilizers. (a) Except as... Captain of the Port (COTP). (1) Ammonium nitrate UN1942, ammonium nitrate fertilizers containing more...

  19. Preserving Plutonium-244 as a National Asset

    SciTech Connect

    Patton, Bradley D; Alexander, Charles W; Benker, Dennis; Collins, Emory D; Romano, Catherine E; Wham, Robert M

    2011-01-01

    Plutonium-244 (244 Pu) is an extremely rare and long-lived isotope of plutonium with a half-life of 80 million years. Measureable amounts of 244 Pu are found in neither reactor-grade nor weapons-grade plutonium. Production of this isotope requires a very high thermal flux to permit the two successive neutron captures that convert 242 Pu to 243 Pu to 244 Pu, particularly given the short (about 5 hour) half-life of 243 Pu. Such conditions simply do not exist in plutonium production processes. Therefore, 244 Pu is ideal for precise radiochemical analyses measuring plutonium material properties and isotopic concentrations in items containing plutonium. Isotope dilution mass spectrometry is about ten times more sensitive when using 244 Pu rather than 242 Pu for determining plutonium isotopic content. The isotope can also be irradiated in small quantities to produce superheavy elements. The majority of the existing global inventory of 244 Pu is contained in the outer housing of Mark-18A targets at the Savannah River Site (SRS). The total inventory is about 20 grams of 244 Pu in about 400 grams of plutonium distributed among the 65 targets. Currently, there are no specific plans to preserve these targets. Although the cost of separating and preserving this material would be considerable, it is trivial in comparison to new production costs. For all practical purposes, the material is irreplaceable, because new production would cost billions of dollars and require a series of irradiation and chemical separation cycles spanning up to 50 years. This paper will discuss a set of options for overcoming the significant challenges to preserve the 244 Pu as a National Asset: (1) the need to relocate the material from SRS in a timely manner, (2) the need to reduce the volume of material to the extent possible for storage, and (3) the need to establish an operational capability to enrich the 244 Pu in significant quantities. This paper suggests that if all the Mark-18A plutonium is separated, it would occupy a small volume and would be inexpensive to store while an enrichment capability is developed. Very small quantities could be enriched in existing mass separators to support critical needs.

  20. Photoemission Spectroscopy of Delta- Plutonium: Experimental Review

    NASA Astrophysics Data System (ADS)

    Tobin, J. G.

    2002-03-01

    The electronic structure of Plutonium, particularly delta- Plutonium, remains ill defined and without direct experimental verification. Recently, we have embarked upon a program of study of alpha- and delta- Plutonium, using synchrotron radiation from the Advanced Light Source in Berkeley, CA, USA [1]. This work is set within the context of Plutonium Aging [2] and the complexities of Plutonium Science [3]. The resonant photoemission of delta-plutonium is in partial agreement with an atomic, localized model of resonant photoemission, which would be consistent with a correlated electronic structure. The results of our synchrotron- based studies will be compared with those of recent laboratory- based works [4,5,6]. The talk will conclude with a brief discussion of our plans for the future, such as the performance of spin-resolving and dichroic photoemission measurements of Plutonium [7] and the development of single crystal ultrathin films of Plutonium. This work was performed under the auspices of the U.S. Department of Energy by the University of California, Lawrence Livermore National Laboratory under Contract No. W-7405-Eng-48. 1. J. Terry, R.K. Schulze, J.D. Farr, T. Zocco, K. Heinzelman, E. Rotenberg, D.K. Shuh, G. van der Laan, D.A. Arena, and J.G. Tobin, “5f Resonant Photoemission from Plutonium”, UCRL-JC-140782, Surf. Sci. Lett., accepted October 2001. 2. B.D. Wirth, A.J. Schwartz, M.J. Fluss, M.J. Caturla, M.A. Wall, and W.G. Wolfer, MRS Bulletin 26, 679 (2001). 3. S.S. Hecker, MRS Bulletin 26, 667 (2001). 4. T. Gouder, L. Havela, F. Wastin, and J. Rebizant, Europhys. Lett. 55, 705 (2001); MRS Bulletin 26, 684 (2001); Phys. Rev. Lett. 84, 3378 (2000). 5. A.J. Arko, J.J. Joyce, L. Morales, J. Wills, J. Lashley, F. Wastin, and J. Rebizant, Phys. Rev. B 62, 1773 (2000). 6. L.E. Cox, O. Eriksson, and B.R. Cooper, Phys. Rev. B 46, 13571 (1992). 7. J. Tobin, D.A. Arena, B. Chung, P. Roussel, J. Terry, R.K. Schulze, J.D. Farr, T. Zocco, K. Heinzelman, E. Rotenberg, and D.K. Shuh, “Photoelectron Spectroscopy of Plutonium at the Advanced Light Source”, UCRL-JC-145703, J. Nucl. Sci. Tech./ Proc. of Actinides 2001, submitted November 2001.

  1. Unraveling Pathways of Guaiacol Nitration in Atmospheric Waters: Nitrite, A Source of Reactive Nitronium Ion in the Atmosphere.

    PubMed

    Kroflič, Ana; Grilc, Miha; Grgić, Irena

    2015-08-01

    The tropospheric aqueous-phase aging of guaiacol (2-methoxyphenol, GUA), a lignocellulosic biomass burning pollutant, is addressed in this work. Pathways of GUA nitration in aqueous solution under atmospherically relevant conditions are proposed and critically discussed. The influence of NaNO2 and H2O2, hydroxyl radical scavenger, and sunlight was assessed by an experimental-modeling approach. In the presence of the urban pollutant, nitrite, GUA is preferentially nitrated to yield 4- and 6-nitroguaiacol. After a short lag-time, 4,6-dinitroguaiacol is also formed. Its production accelerates after guaiacol is completely consumed, which is nicely described by the model function accounting for NO2(•) and NO2(+) as nitrating agents. Although the estimated second-order kinetic rate constants of methoxyphenol nitration with NO2(•) are substantially higher than the corresponding rate constants of nitration with NO2(+), nitration rates are competitive under nighttime and liquid atmospheric aerosol-like conditions. In contrast to concentrations of radicals, which are governed by the interplay between diffusion-controlled reactions and are therefore mostly constant, concentrations of electrophiles are very much dependent on the ratio of NO2(-) to activated aromatics in solution. These results contribute substantially to the understanding of methoxyphenol aging in the atmospheric waters and underscore the importance of including electrophilic aromatic substitution reactions in atmospheric models. PMID:26162010

  2. Fate of nitrogen species in nitrate reduction by nanoscale zero valent iron and characterization of the reaction kinetics.

    PubMed

    Hwang, Y H; Kim, D G; Ahn, Y T; Moon, C M; Shin, H S

    2010-01-01

    This study investigates the fate of nitrogen species during nitrate reduction by nanoscale zero valent iron (NZVI) as well as the related kinetics. The NZVI used for the experiments was prepared by chemical reduction without a stabilizing agent. The pseudo first order kinetic constant of nitrate reduction at 30 degrees C with an NZVI/nitrate ratio of 1.25:1, which were the reference conditions of this study, was 4.08 h(-1) (R(2)=0.955). A nitrogen mass balance was established by quantitative analysis of aqueous-phase and gas-phase nitrogen species. The results confirm that the nitrate was converted to ammonium ion, that ammonia stripping subsequently occurred under a strong alkaline condition, and that the total amount of aqueous nitrogen was consequently reduced. The nitrate reduction rate also increased with a lower pH and a higher temperature when microscale ZVI was used. However, in contrast to the reaction by microscale ZVI, the nitrate reduction rate by NZVI was higher for an unbuffered condition, possibly due to the abundance of surface atoms and the smaller size. PMID:20150707

  3. Sensitivity of nitrate aerosols to ammonia emissions and to nitrate chemistry: implications for present and future nitrate optical depth

    NASA Astrophysics Data System (ADS)

    Paulot, F.; Ginoux, P.; Cooke, W. F.; Donner, L. J.; Fan, S.; Lin, M.; Mao, J.; Naik, V.; Horowitz, L. W.

    2015-09-01

    We update and evaluate the treatment of nitrate aerosols in the Geophysical Fluid Dynamics Laboratory (GFDL) atmospheric model (AM3). Accounting for the radiative effects of nitrate aerosols generally improves the simulated aerosol optical depth, although nitrate concentrations at the surface are biased high. This bias can be reduced by increasing the deposition of nitrate to account for the near-surface volatilization of ammonium nitrate or by neglecting the heterogeneous production of nitric acid to account for the inhibition of N2O5 reactive uptake at high nitrate concentrations. Globally, uncertainties in these processes can impact the simulated nitrate optical depth by up to 25 %, much more than the impact of uncertainties in the seasonality of ammonia emissions (6 %) or in the uptake of nitric acid on dust (13 %). Our best estimate for present-day fine nitrate optical depth at 550 nm is 0.006 (0.005-0.008). We only find a modest increase of nitrate optical depth (< 30 %) in response to the projected changes in the emissions of SO2 (-40 %) and ammonia (+38 %) from 2010 to 2050. Nitrate burden is projected to increase in the tropics and in the free troposphere, but to decrease at the surface in the midlatitudes because of lower nitric acid concentrations. Our results suggest that better constraints on the heterogeneous chemistry of nitric acid on dust, on tropical ammonia emissions, and on the transport of ammonia to the free troposphere are needed to improve projections of aerosol optical depth.

  4. Sensitivity of nitrate aerosols to ammonia emissions and to nitrate chemistry: implications for present and future nitrate optical depth

    NASA Astrophysics Data System (ADS)

    Paulot, F.; Ginoux, P.; Cooke, W. F.; Donner, L. J.; Fan, S.; Lin, M.-Y.; Mao, J.; Naik, V.; Horowitz, L. W.

    2016-02-01

    We update and evaluate the treatment of nitrate aerosols in the Geophysical Fluid Dynamics Laboratory (GFDL) atmospheric model (AM3). Accounting for the radiative effects of nitrate aerosols generally improves the simulated aerosol optical depth, although nitrate concentrations at the surface are biased high. This bias can be reduced by increasing the deposition of nitrate to account for the near-surface volatilization of ammonium nitrate or by neglecting the heterogeneous production of nitric acid to account for the inhibition of N2O5 reactive uptake at high nitrate concentrations. Globally, uncertainties in these processes can impact the simulated nitrate optical depth by up to 25 %, much more than the impact of uncertainties in the seasonality of ammonia emissions (6 %) or in the uptake of nitric acid on dust (13 %). Our best estimate for fine nitrate optical depth at 550 nm in 2010 is 0.006 (0.005-0.008). In wintertime, nitrate aerosols are simulated to account for over 30 % of the aerosol optical depth over western Europe and North America. Simulated nitrate optical depth increases by less than 30 % (0.0061-0.010) in response to projected changes in anthropogenic emissions from 2010 to 2050 (e.g., -40 % for SO2 and +38 % for ammonia). This increase is primarily driven by greater concentrations of nitrate in the free troposphere, while surface nitrate concentrations decrease in the midlatitudes following lower concentrations of nitric acid. With the projected increase of ammonia emissions, we show that better constraints on the vertical distribution of ammonia (e.g., convective transport and biomass burning injection) and on the sources and sinks of nitric acid (e.g., heterogeneous reaction on dust) are needed to improve estimates of future nitrate optical depth.

  5. Dispersion of plutonium from contaminated pond sediments

    USGS Publications Warehouse

    Rees, T.F.; Cleveland, J.M.; Carl, Gottschall W.

    1978-01-01

    Sediment-water distributions of plutonium as a function of pH and contact time are investigated in a holding pond at the Rocky Flats plant of the Department of Energy. Although plutonium has been shown to sorb from natural waters onto sediments, the results of this study indicate that under the proper conditions it can be redispersed at pH 9 and above. Concentrations greater than 900 pCi Pu/L result after 34 h contact at pH 11 or 12 and the distribution coefficient, defined as the ratio of concentration in the sediment to that in the liquid, decreases from 1.1 ?? 105 at pH 7 to 1.2 ?? 103 at pH 11. The plutonium is probably dispersed as discrete colloids or as hydrolytic species adsorbed onto colloidal sediment particles whose average size decreases with increasing pH above pH 9. About 5% of the total plutonium is dispersed at pH 12, and the dispersion seems to readsorb on the sediment with time. Consequently, migration of plutonium from the pond should be slow, and it would be difficult to remove this element completely from pond sediment by leaching with high pH solutions. ?? 1978 American Chemical Society.

  6. Long-term plutonium storage: Design concepts

    SciTech Connect

    Wilkey, D.D.; Wood, W.T.; Guenther, C.D.

    1994-08-01

    An important part of the Department of Energy (DOE) Weapons Complex Reconfiguration (WCR) Program is the development of facilities for long-term storage of plutonium. The WCR design goals are to provide storage for metals, oxides, pits, and fuel-grade plutonium, including material being held as part of the Strategic Reserve and excess material. Major activities associated with plutonium storage are sorting the plutonium inventory, material handling and storage support, shipping and receiving, and surveillance of material in storage for both safety evaluations and safeguards and security. A variety of methods for plutonium storage have been used, both within the DOE weapons complex and by external organizations. This paper discusses the advantages and disadvantages of proposed storage concepts based upon functional criteria. The concepts discussed include floor wells, vertical and horizontal sleeves, warehouse storage on vertical racks, and modular storage units. Issues/factors considered in determining a preferred design include operational efficiency, maintenance and repair, environmental impact, radiation and criticality safety, safeguards and security, heat removal, waste minimization, international inspection requirements, and construction and operational costs.

  7. Behaviors of acrylamide/itaconic acid hydrogels in uptake of uranyl ions from aqueous solutions

    SciTech Connect

    Karadag, E.; Saraydin, D.; Gueven, O.

    1995-12-01

    In this study, adsorptions of uranyl ions from two different aqueous uranyl solutions by acrylamide-itaconic acid hydrogels were investigated by a spectroscopic method. The hydrogels were prepared by irradiating with {gamma}-radiation. In the experiment of uranyl ions adsorption, Type II adsorption was found. One gram of acrylamide-itaconic acid hydrogels sorbed 178-219 mg uranyl ions from the solutions of uranyl acetate, 42-76 mg uranyl ions from the aqueous solutions of uranyl nitrate, while acrylamide hydrogel did not sorb any uranyl ion. For the hydrogel containing 40 mg of itaconic acid and irradiated to 3.73 kGy, swelling of the hydrogels was observed in water (1660%), in the aqueous solution of uranyl acetate (730%), and in the aqueous solution of uranyl nitrate (580%). Diffusions of water onto hydrogels were a non-Fickian type of diffusion, whereas diffusions of uranyl ions were a Fickian type of diffusion.

  8. Effects of nitrate on the stability of uranium in a bioreduced region of the subsurface

    SciTech Connect

    Wu, Weimin; Carley, Jack M; Green, Stefan; Luo, Jian; Kelly, Shelly D; Van Nostrand, Joy; Lowe, Kenneth Alan; Mehlhorn, Tonia L; Carroll, Sue L; Boonchayanant, Dr. Benjaporn; Loeffler, Frank E; Jardine, Philip M; Criddle, Craig

    2010-06-01

    The effects of nitrate on the stability of reduced, immobilized uranium were evaluated in field experiments at a U.S. Department of Energy site in Oak Ridge, TN. Nitrate (2.0 mM) was injected into a reduced region of the subsurface containing high levels of previously immobilized U(IV). The nitrate was reduced to nitrite, ammonium, and nitrogen gas; sulfide levels decreased; and Fe(II) levels increased then deceased. Uranium remobilization occurred concomitant with nitrite formation, suggesting nitrate-dependent, iron-accelerated oxidation of U(IV). Bromide tracer results indicated changes in subsurface flowpaths likely due to gas formation and/or precipitate. Desorption-adsorption of uranium by the iron-rich sediment impacted uranium mobilization and sequestration. After rereduction of the subsurface through ethanol additions, background groundwater containing high levels of nitrate was allowed to enter the reduced test zone. Aqueous uranium concentrations increased then decreased. Clone library analyses of sediment samples revealed the presence of denitrifying bacteria that can oxidize elemental sulfur, H{sub 2}S, Fe(II), and U(IV) (e.g., Thiobacillus spp.), and a decrease in relative abundance of bacteria that can reduce Fe(III) and sulfate. XANES analyses of sediment samples confirmed changes in uranium oxidation state. Addition of ethanol restored reduced conditions and triggered a short-term increase in Fe(II) and aqueous uranium, likely due to reductive dissolution of Fe(III) oxides and release of sorbed U(VI). After two months of intermittent ethanol addition, sulfide levels increased, and aqueous uranium concentrations gradually decreased to <0.1 {mu}M.

  9. Complexation of Lanthanides with Nitrate at Variable Temperatures: Thermodynamics and Coordination Modes

    SciTech Connect

    Rao, Linfeng; Tian, Guoxin

    2008-12-10

    Complexation of neodymium(III) with nitrate was studied at variable temperatures (25, 40, 55 and 70 C) by spectrophotometry and microcalorimetry. The NdNO{sub 3}{sup 2+} complex is weak and becomes slightly stronger as the temperature is increased. The enthalpy of complexation at 25 C was determined by microcalorimetry to be small and positive, (1.5 {+-} 0.2) kJ {center_dot} mol{sup -1}, in good agreement with the trend of the stability constant at variable temperatures. Luminescence emission spectra and lifetime of Eu(III) in nitrate solutions suggest that inner-sphere and bidentate complexes form between trivalent lanthanides (Nd{sup 3+} and Eu{sup 3+}) and nitrate in aqueous solutions. Specific Ion Interaction approach (SIT) was used to obtain the stability constants of NdNO{sub 3}{sup 2+} at infinite dilution and variable temperatures.

  10. Analysis of nitrate in environmental samples by reversed-phase HPLC

    SciTech Connect

    Schroeder, D.C.

    1987-09-01

    A method is presented for the analysis of nitrate in natural waters and waste water by high-performance liquid chromatography (HPLC) with a reversed-phase octadecyl column, aqueous phosphoric acid/dihydrogen phosphate mobile phase, and UV detector. The optimum nitrate concentration is 0.3 to 3 mg/L as N with linear detector response below 3 mg/L. The detection limit is 0.007 mg/L. Relative standard deviations in the optimum range are consistently less than one percent. Several potential interferences have been investigated; nitrite and organic chromophores are resolved from nitrate and do not interfere. Hexavalent chromium and sulfate are slight positive interferences, negligible at typical environmental concentrations. The method produces results in agreement with the accepted chromotropic acid method except in samples from eutrophic lakes, for which evidence is presented indicating that the chromotropic acid is inaccurate.

  11. REVIEW OF PLUTONIUM OXIDATION LITERATURE

    SciTech Connect

    Korinko, P.

    2009-11-12

    A brief review of plutonium oxidation literature was conducted. The purpose of the review was to ascertain the effect of oxidation conditions on oxide morphology to support the design and operation of the PDCF direct metal oxidation (DMO) furnace. The interest in the review was due to a new furnace design that resulted in oxide characteristics that are different than those of the original furnace. Very little of the published literature is directly relevant to the DMO furnace operation, which makes assimilation of the literature data with operating conditions and data a convoluted task. The oxidation behavior can be distilled into three regimes, a low temperature regime (RT to 350 C) with a relatively slow oxidation rate that is influenced by moisture, a moderate temperature regime (350-450 C) that is temperature dependent and relies on more or less conventional oxidation growth of a partially protective oxide scale, and high temperature oxidation (> 500 C) where the metal autocatalytically combusts and oxidizes. The particle sizes obtained from these three regimes vary with the finest being from the lowest temperature. It is surmised that the slow growth rate permits significant stress levels to be achieved that help break up the oxides. The intermediate temperatures result in a fairly compact scale that is partially protective and that grows to critical thickness prior to fracturing. The growth rate in this regime may be parabolic or paralinear, depending on the oxidation time and consequently the oxide thickness. The high temperature oxidation is invariant in quiescent or nearly quiescent conditions due to gas blanketing while it accelerates with temperature under flowing conditions. The oxide morphology will generally consist of fine particles (<15 {micro}m), moderately sized particles (15 < x < 250 {micro}m) and large particles (> 250 {micro}m). The particle size ratio is expected to be < 5%, 25%, and 70% for fine, medium and large particles, respectively, for metal temperatures in the 500-600 C range.

  12. Fused salt processing of impure plutonium dioxide to high-purity plutonium metal

    SciTech Connect

    Mullins, L.J.; Christensen, D.C.; Babcock, B.R.

    1982-01-01

    A process for converting impure plutonium dioxide (approx. 96% pure) to high-purity plutonium metal (>99.9%) was developed. The process consists of reducing the oxide to an impure plutonium metal intermediate with calcium metal in molten calcium chloride. The impure intermediate metal is cast into an anode and electrorefined to produce high-purity plutonium metal. The oxide reduction step is being done now on a 0.6-kg scale with the resulting yield being >99.5%. The electrorefining is being done on a 4.0-kg scale with the resulting yield being 80 to 85%. The purity of the product, which averages 99.98%, is essentially insensitive to the purity of the feed metal. The yield, however, is directly dependent on the chemical composition of the feed. To date, approximately 250 kg of impure oxide has been converted to pure metal by this processing sequence. The availability of impure plutonium dioxide, together with the need for pure plutonium metal, makes this sequence a valuable plutonium processing tool.

  13. Effect of nitrate on microbial perchlorate reduction

    NASA Astrophysics Data System (ADS)

    Sun, Y.; Coates, J. D.

    2007-12-01

    Over the last decade perchlorate has been recognized as an important emerging water contaminant that poses a significant public health threat. Because of its chemical stability, low ionic charge density, and significant water solubility microbial remediation has been identified as the most feasible method for its in situ attenuation. Our previous studies have demonstrated that dissimilatory perchlorate reducing bacteria (DPRB) capable of the respiratory reduction of perchlorate into innocuous chloride are ubiquitous in soil and sedimentary environments. As part of their metabolism these organisms reduce perchlorate to chlorite which is subsequently dismutated into chloride and molecular oxygen. These initial steps are mediated by the perchlorate reductase and chlorite dismutase enzymes respectively. Previously we found that the activity of these organisms is dependent on the presence of molybdenum and is inhibited by the presence of oxygen and to different extents nitrate. However, to date, there is little understanding of the mechanisms involved in the regulation of perchlorate reduction by oxygen and nitrate. As a continuation of our studies into the factors that control DPRB activity we investigated these regulatory mechanisms in more detail as a model organism, Dechloromonas aromatica strain RCB, transitions from aerobic metabolism through nitrate reduction to perchlorate reduction. In series of growth transition studies where both nitrate and perchlorate were present, preference for nitrate to perchlorate was observed regardless of the nitrate to perchlorate ratio. Even when the organism was pre-grown anaerobically in perchlorate, nitrate was reduced prior to perchlorate. Using non-growth washed cell suspension, perchlorate- grown D. aromatica was capable of reducing both perchlorate and nitrate concomitantly suggesting the preferentially utilization of nitrate was not a result of enzyme functionality. To elucidate the mechanism for preferential utilization of nitrate, transcripts of perchlorate reductase and chlorite dismutase were analyzed to determine possible transcriptional regulation from nitrate. During growth transition studies, increase in the level of transcripts necessary for nitrate reduction and perchlorate reduction was observed concomitantly with decrease in the concentration of nitrate and perchlorate respectively suggesting transcriptional regulation was involved in the preferential utilization of nitrate and that nitrate might be a transcriptional inhibitor of perchlorate reduction. Again, using non-growth washed cell suspensions of perchlorate grown D. aromatica, a decrease of transcript level of the perchlorate reductase but not the chlorite dismutase was observed after incubation with nitrate. In conclusion, from physiological and molecular evidence, nitrate negatively regulates transcription of perchlorate reductase thus inhibiting perchlorate reduction. This result is unexpected as it is in contrast to the accepted dogma that microorganisms regulate their metabolisms to utilize electron acceptors in a sequential manner based on thermodynamic optimization which would imply that perchlorate should be used preferentially to nitrate.

  14. COLUMBIC OXIDE ADSORPTION PROCESS FOR SEPARATING URANIUM AND PLUTONIUM IONS

    DOEpatents

    Beaton, R.H.

    1959-07-14

    A process is described for separating plutonium ions from a solution of neutron irradiated uranium in which columbic oxide is used as an adsorbert. According to the invention the plutonium ion is selectively adsorbed by Passing a solution containing the plutonium in a valence state not higher than 4 through a porous bed or column of granules of hydrated columbic oxide. The adsorbed plutonium is then desorbed by elution with 3 N nitric acid.

  15. Nitrate deposition and impact on Adirondack streams

    SciTech Connect

    Simonin, H.A.; Kretser, W.A.

    1997-12-31

    Acidic deposition has a great impact on water chemistry and fish populations in the Adirondack region. Although the Clean Air Act Amendments of 1990 have resulted in some reductions of sulfate deposition, nitrate deposition has not yet been well controlled, and continues to impact aquatic resources. As part of the USEPA funded Episodic Response Project four Adirondack headwater streams were intensively monitored over an 18 month period. Atmospheric deposition was also monitored at a centrally located station. The quantity of nitrate being deposited on the study watersheds was calculated based on monthly net deposition data which ranged from 0.6 kg/ha/month to 3.6 kg/ha/month. These data were then compared to the monthly export of nitrate from the watershed in these streams. Nitrate concentrations were highest in the streamwater during the spring snowmelt period prior to the time when forest vegetation actively utilizes nitrate. On an annual basis the amount of nitrate which left the watershed via stream water exceeded the amount which fell as nitrate deposition. These data are important in documenting the impact of nitrate in the acidification of Adirondack streams during the spring, which coincides with brook trout hatching. Control programs for nitrous oxide emissions are presently aimed at reducing ozone levels during the May-September period. These emissions control programs need to be expanded to also reduce nitrate deposition in the sensitive Adirondack region during the winter and spring periods when nitrate deposition has its greatest impact on aquatic resources.

  16. Nitrate deposition and impact of Adirondack streams

    SciTech Connect

    Simonin, H.A.; Kretser, W.

    1995-12-31

    Acidic deposition has a great impact on water chemistry and fish populations in the Adirondack region. Although the Clean Air Act Amendments of 1990 have resulted in some reductions of sulfur deposition, nitrate deposition has not yet been well controlled, and continues to impact aquatic resources. As part of the USEPA funded Episodic Response Project, four Adirondack headwater streams were intensively monitored over an 18 month period. Atmospheric deposition was also monitored at a centrally located station. The quantity of nitrate being deposited on the study watersheds was calculated based on monthly net deposition data, which ranged from 0.6 kg/ha/month to 3.6 kg/ha/month. These data were then compared to the monthly export of nitrate from the watershed in these streams. Nitrate concentrations were highest in the stream water during the spring snowmelt period prior to the time when forest vegetation actively utilizes nitrate. On an annual basis, the amount of nitrate that left the watershed via stream water was approximately equal to the amount that fell as nitrate deposition. These data are important in documenting the impact that nitrate has in acidifying Adirondack streams during the spring, which coincides with brook trout hatching. Control programs for nitrous oxide emissions are presently aimed at reducing ozone levels during the May--September period. These emissions control programs need to be expanded to also reduce nitrate deposition in the sensitive Adirondack region during the water and spring periods when nitrate deposition has its greatest impact on aquatic resources.

  17. Excess plutonium disposition using ALWR technology

    SciTech Connect

    Phillips, A.; Buckner, M.R.; Radder, J.A.; Angelos, J.G.; Inhaber, H.

    1993-02-01

    The Office of Nuclear Energy of the Department of Energy chartered the Plutonium Disposition Task Force in August 1992. The Task Force was created to assess the range of practicable means of disposition of excess weapons-grade plutonium. Within the Task Force, working groups were formed to consider: (1) storage, (2) disposal,and(3) fission options for this disposition,and a separate group to evaluate nonproliferation concerns of each of the alternatives. As a member of the Fission Working Group, the Savannah River Technology Center acted as a sponsor for light water reactor (LWR) technology. The information contained in this report details the submittal that was made to the Fission Working Group of the technical assessment of LWR technology for plutonium disposition. The following aspects were considered: (1) proliferation issues, (2) technical feasibility, (3) technical availability, (4) economics, (5) regulatory issues, and (6) political acceptance.

  18. Plutonium(VI) sorption to manganese dioxide.

    SciTech Connect

    Reilly, S. D.; Myers, W. K.; Stout, S. A.; Smith, D. M.; Ginder-Vogel, M. A.; Neu, M. P.

    2003-01-01

    Redox-active metal oxides may strongly affect the environmental behavior and mobility of actinides . Manganese oxides are relatively common redox-active soil components, which have a high surface area and which some studies show sorb plutonium selectively over other mineral phases .' For plutonium, oxidation states that could exist in the environment include +111 to +VI, with Pu(IV) being predominant in the insoluble phase. Plutonium(V), and to a lesser extent Pu(VI), are the stable Pu oxidation states in solution under environmental conditions .Z We are using synthetic 6-Mn02 because it is most similar to the common natural manganese oxide mineral birnessite . Previously, we have shown that Pu(V) is oxidized to Pu(VI) in solution by 8-Mn02, then very effectively sorbed to the mineral . We are now studying Pu(VI) sorption to synthetic 8-Mn02 in detail to determine its sorption mechanisms and sorption capacity .

  19. Interaction of divalent plutonium and curium

    SciTech Connect

    Mikheev, N.B.; Kazakevich, M.Z.; Rumer, I.A.

    1988-11-01

    It has been established that at plutonium concentrations ranging from 10/sup -5/ to 10/sup -4/ mole % the oxidation potentials of the Pu/sup 3 +//Pu/sup 2 +/ and Cm/sup 3 +//Cm/sup 2 +/ pairs increased by 0.15-0.2 V due to the dimerization of Pu/sup 2 +/ and the formation of mixed dimers of plutonium and curium. Promethium(2+) does not have a similar ability to form mixed dimers owing to the fact that Pm/sup 2 +/ does not have a free d electron. The oxidation potential of the Pm/sup 3 +//Pm/sup 2 +/ pair does not vary in the presence of massive quantities of plutonium

  20. ESTIMATING IMPURITIES IN SURPLUS PLUTONIUM FOR DISPOSITION

    SciTech Connect

    Allender, J.; Moore, E.

    2013-07-17

    The United States holds at least 61.5 metric tons (MT) of plutonium that is permanently excess to use in nuclear weapons programs, including 47.2 MT of weapons-grade plutonium. Surplus inventories will be stored safely by the Department of Energy (DOE) and then transferred to facilities that will prepare the plutonium for permanent disposition. The Savannah River National Laboratory (SRNL) operates a Feed Characterization program for the Office of Fissile Materials Disposition of the National Nuclear Security Administration and the DOE Office of Environmental Management. Many of the items that require disposition are only partially characterized, and SRNL uses a variety of techniques to predict the isotopic and chemical properties that are important for processing through the Mixed Oxide Fuel Fabrication Facility and alternative disposition paths. Recent advances in laboratory tools, including Prompt Gamma Analysis and Peroxide Fusion treatment, provide data on the existing inventories that will enable disposition without additional, costly sampling and destructive analysis.