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Sample records for neptunium oxide processing

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

    International Nuclear Information System (INIS)

    Squires, Leah N.; Lessing, Paul

    2016-01-01

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

  2. Process for neptunium analysis by absorption spectrophotometry

    International Nuclear Information System (INIS)

    Wagner, J.F.

    1987-01-01

    An aqueous solution of a neptunium compounds is treated by a reagent, preferentially a vanadyl sulfate oxidized by cerium IV ions, to obtain neptunium V by oxidation of neptunium IV and reduction of neptunium VI. The reagent is chosen for a negligible absorption at the wavelength used for neptunium V absorption spectrophotometry for instance 981 nm [fr

  3. Process chemistry of neptunium

    Energy Technology Data Exchange (ETDEWEB)

    Srinivasan, N.; Ramaniah, M. V.; Nadkarni, M. N.; Kumar, S. V.; Patil, S. K.; Ramakrishna, V. V.; Swarup, R.; Avadhany, G. V.N.; Sonawane, R. R.; Kartha, P. K.S.

    1973-07-01

    Research progress is reported on the recovery of neptunium from reprocessing of irradiated uranium. Areas considered are: use of vanadium(V) for oxidation of Np(V) to Np(VI); path of neptunium under partitioning column conditions; co-stability of Np(IV) and Pu(IV); and extraction of Np(IV) by tricaprylmethylammonium nitrate. (DHM)

  4. Sorption of neptunium under oxidizing and reducing groundwater conditions

    International Nuclear Information System (INIS)

    Hakanen, M.

    1991-01-01

    Sorption of neptunium was studied under aerobic, anoxic and reducing groundwater conditions using solutions with initial Np concentrations of 10 -14 to 10 -8 mol/l. Under aerobic conditions the sorption was the same for all concentrations. Under anoxic conditions the same proportion of neptunium (70-80%) was removed from the water. The neptunium sorbed on rock surfaces was of mixed oxidation states. Only Np(V) was found in waters. Under reducing groundwater conditions, nearly all the neptunium was removed from water. The sorbed neptunium was at first almost completely in the form of Np(IV). The submicrogram amounts of neptunium were partly oxidized with time, but Np(V) did not dissolve in reducing water. The holding oxidant character of the tonalite to Np(V) and, the holding reductant character of rocks to small amounts of Np(IV), was demonstrated under anaerobic and reducing groundwater conditions, respectively. (orig.)

  5. Neptunium determination in PUREX process

    International Nuclear Information System (INIS)

    Rawat, Neetika; Kar, Aishwarya S.; Tomar, B.S.; Pandey, M.P.; Umadevi, K.

    2016-10-01

    237 Np is one of the most important minor actinides present in nuclear spent fuel both from environmental and application point of view. The routing of neptunium to the particular stream of PUREX process is necessary for its separation and purification as 237 Np is the target nuclide for production of 238 Pu. The routing of neptunium to a particular PUREX stream will also help in better nuclear waste management, which in turn, will impart less bearing on the environment considering its long half life, alpha emitting properties and mobile nature. In order to route Neptunium to a particular stream of PUREX process, it is imperative to understand the distribution of neptunium in various process streams. Owing to high dose of actual samples, the neptunium distribution was studied using 239 Np tracer by simulating actual column conditions of PUREX streams in lab scale. The present study deals with neptunium determination in actual PUREX streams samples also. (author)

  6. Process chemistry of neptunium. Part II

    Energy Technology Data Exchange (ETDEWEB)

    Srinivasan, N.; Ramaniah, M. V.; Patil, S. K.; Ramakrishna, V. V.; Swarup, R.; Chadha, A.; Avadhany, G. V.N.

    1974-07-01

    The oxidation state analysis of neptunium in the aqueous feed solution from the Plutonium Plant at Trombay was carried out and it was found that neptunium existed mainly as Np(V) in the feed solution. Batch extraction data for Np(IV) and Np(VI) into 30% TBP/Shell Sol T at different aqueous nitric acid concentration and uranium saturation of the organic phase were obtained at 45 deg C and 60 deg C and the results are summarized. The distribution coefficients of Np(IV) and Np(VI) were obtained as a function of TBP concentration and the data are reported. The effect of nitrous acid on the extraction of neptunium, present in the aqueous phase as Np(IV) and Np(V), by 30% TBP was studied and the data obtained are given. The data on the rate of reduction of NP(VI) and Np(V) to Np(IV) by U(IV) were obtained for different U(IV) and nitric acid concentrations. Some redox reactions involving Np(IV), Pu(IV) and V(V) were investigated and their possible application in the purex process for neptunium recovery were explored. (auth)

  7. The extraction neptunium by trilaurylamine

    International Nuclear Information System (INIS)

    Champion, J.; Chesne, A.

    1964-01-01

    The extraction by trilaurylamine of neptunium (IV) from nitric acid and sulfuric acid-nitric acid media has been studied with the aim of developing a purification process for this element. Relative to the plutonium-neptunium separation, conditions are given for the oxidation of neptunium (IV) in sulfuric acid-nitric acid medium and data are presented on the stabilisation of the + 4 oxidation state by the organic solvent. Two procedures have been developed for the simultaneous purification of the two actinides. Both are based on the trilaurylamine extraction of the tetravalent nitrate species. The first utilises a constant redox potential fixed by Fe +++ /Fe ++ couple, while in the second, valencies are determined by successive addition of nitrite and ferrous ions. Gram quantities of neptunium 237 has been recovered from plutonium process solution. Alternate procedures are suggested for the chemical processing of irradiated Np 237 . (authors) [fr

  8. Study of an automatic dosing of neptunium in the industrial process of separation neptunium 237-plutonium 238

    International Nuclear Information System (INIS)

    Ros, Pierre

    1973-01-01

    The objective is to study and to adapt a method of automatic dosing of neptunium to the industrial process of separation and purification of plutonium 238, while taking the information quality and economic aspects into account. After a recall of some generalities on the production of plutonium 238, and the process of separation plutonium-neptunium, the author addresses the dosing of neptunium. The adopted measurement technique is spectrophotometry (of neptunium, of neptunium peroxide) which is the most flexible and economic to adapt to automatic control. The author proposes a project of chemical automatic machine, and discusses the complex (stoichiometry, form) and some aspects of neptunium dosing (redox reactions, process control) [fr

  9. Interaction of neptunium (7) with some oxidation products of normal and secondary alcohols

    International Nuclear Information System (INIS)

    Tananaev, I.G.

    1990-01-01

    Interaction of neptunium (7) with formaldehyde and acetone -products of methane and isopropanol oxidation in alkali medium -was studied. With increase in KOH concentration neptunium (7) reduction rate decreases. The reaction order in the range of 0.2-1.0 mol/l KOH equals -1. The reaction order with regard to reducing agent is 0.9 at acetone concentrations 0.07-0.35 mol/l and 1.0 at formaldehyde concentration 2.5-10 mmol/l. Activation energies are equal to 49±2 kJ/mol for neptunium (7) reduction by acetone and 59±4 kJ/mol - by formaldehyde. Formaldehyde is oxidized by neptunium (7) to formic acid

  10. Investigation on neptunium in a borosilicate glass

    International Nuclear Information System (INIS)

    Poirot, I.

    1988-03-01

    The oxidization state and coordination of neptunium, introduced as dopant in borosilicate glasses were studied through optical, Mossbauer spectroscopies and magnetic measurements. The neptunium oxide, introduced previously as NpO 2 is reduced during the melting process of the glass. This leads to an equilibrium in which the ratio of Np 4+ to Np 3+ valences depends on experimental conditions. Spectroscopic analysises conduct to postulate the presence of different sites for each of the oxydation states of neptunium [fr

  11. The extraction neptunium by trilaurylamine; L'extraction du neptunium par le trilaurylamine

    Energy Technology Data Exchange (ETDEWEB)

    Champion, J; Chesne, A [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1964-07-01

    The extraction by trilaurylamine of neptunium (IV) from nitric acid and sulfuric acid-nitric acid media has been studied with the aim of developing a purification process for this element. Relative to the plutonium-neptunium separation, conditions are given for the oxidation of neptunium (IV) in sulfuric acid-nitric acid medium and data are presented on the stabilisation of the + 4 oxidation state by the organic solvent. Two procedures have been developed for the simultaneous purification of the two actinides. Both are based on the trilaurylamine extraction of the tetravalent nitrate species. The first utilises a constant redox potential fixed by Fe{sup +++} /Fe{sup ++} couple, while in the second, valencies are determined by successive addition of nitrite and ferrous ions. Gram quantities of neptunium 237 has been recovered from plutonium process solution. Alternate procedures are suggested for the chemical processing of irradiated Np{sup 237}. (authors) [French] L'extraction du neptunium par le trilaurylamine en milieu nitrique et sulfonitrique a ete etudiee dans le cadre de la recherche des procedes de purification de cet element. En vue d'effectuer la separation neptunium-plutonium on a precise d'une part les conditions d'oxydation du Np{sup 4+} en milieu sulfonitrique, d'autre part l'influence du solvant sur la stabilite des valences de ces deux elements. Deux procedes de purification simultanee des deux actinides ont ete developpes. Ils sont bases sur l'extraction du nitrate des elements tetravalents dans la trilaury lamine. Dans l'un, la solution a extraire a un potentiel redox fixe par un systeme auxiliaire (Fe{sup +++}/Fe{sup ++}), dans l'autre elle subit dans le meme extracteur des additions successives de nitrite et de fer ferreux. On decrit un essai semi-industriel de recuperation de neptunium 237 a partir de solution provenant de l'usine de production de plutonium de Marcoule. Differents schemas utilisables lors du traitement chimique des cibles de

  12. The extraction neptunium by trilaurylamine; L'extraction du neptunium par le trilaurylamine

    Energy Technology Data Exchange (ETDEWEB)

    Champion, J.; Chesne, A. [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1964-07-01

    The extraction by trilaurylamine of neptunium (IV) from nitric acid and sulfuric acid-nitric acid media has been studied with the aim of developing a purification process for this element. Relative to the plutonium-neptunium separation, conditions are given for the oxidation of neptunium (IV) in sulfuric acid-nitric acid medium and data are presented on the stabilisation of the + 4 oxidation state by the organic solvent. Two procedures have been developed for the simultaneous purification of the two actinides. Both are based on the trilaurylamine extraction of the tetravalent nitrate species. The first utilises a constant redox potential fixed by Fe{sup +++} /Fe{sup ++} couple, while in the second, valencies are determined by successive addition of nitrite and ferrous ions. Gram quantities of neptunium 237 has been recovered from plutonium process solution. Alternate procedures are suggested for the chemical processing of irradiated Np{sup 237}. (authors) [French] L'extraction du neptunium par le trilaurylamine en milieu nitrique et sulfonitrique a ete etudiee dans le cadre de la recherche des procedes de purification de cet element. En vue d'effectuer la separation neptunium-plutonium on a precise d'une part les conditions d'oxydation du Np{sup 4+} en milieu sulfonitrique, d'autre part l'influence du solvant sur la stabilite des valences de ces deux elements. Deux procedes de purification simultanee des deux actinides ont ete developpes. Ils sont bases sur l'extraction du nitrate des elements tetravalents dans la trilaury lamine. Dans l'un, la solution a extraire a un potentiel redox fixe par un systeme auxiliaire (Fe{sup +++}/Fe{sup ++}), dans l'autre elle subit dans le meme extracteur des additions successives de nitrite et de fer ferreux. On decrit un essai semi-industriel de recuperation de neptunium 237 a partir de solution provenant de l'usine de production de plutonium de Marcoule. Differents schemas

  13. Experimental thermochemistry of neptunium oxides: Np2O5 and NpO2

    Science.gov (United States)

    Zhang, Lei; Dzik, Ewa A.; Sigmon, Ginger E.; Szymanowski, Jennifer E. S.; Navrotsky, Alexandra; Burns, Peter C.

    2018-04-01

    Neptunium (Np) compounds are important in the nuclear fuel cycle because of the buildup and long half-life (2.14 Ma) of Np-237 in nuclear waste, especially during long-term disposal in a geological repository. Neptunium in environmental conditions exists mainly in two oxidation states (+5 and + 4) and can substitute for uranium and/or rare earths in solid phases. Yet thermochemical data for solid neptunium compounds are scarce, despite being critical for evaluating the environmental transport of this radioactive and toxic element. Although high temperature oxide melt solution calorimetry has proven very useful in obtaining thermodynamic data for the formation of uranium and thorium oxide materials, it has not yet been applied to transuranium compounds. Continuing a program at Notre Dame to study the thermodynamics of transuranium compounds, we report the first determination of the enthalpies of drop solution of well-characterized neptunium oxides (Np2O5 and NpO2) using oxide melt solution calorimetry in molten sodium molybdate solvent at 973 K. The enthalpy of the decomposition reaction, Np2O5(cr) = 2NpO2(cr) + 1/2O2(g) at 298 K, is determined to be 7.70 ± 5.86 kJ/mol, and this direct measurement is consistent with existing thermodynamic data. The calorimetric methodology is straightforward and produces reliable data using milligram quantities of radioactive materials, and can be applied to many other transuranium compounds.

  14. Two-stage precipitation of neptunium (IV) oxalate

    International Nuclear Information System (INIS)

    Luerkens, D.W.

    1983-07-01

    Neptunium (IV) oxalate was precipitated using a two-stage precipitation system. A series of precipitation experiments was used to identify the significant process variables affecting precipitate characteristics. Process variables tested were input concentrations, solubility conditions in the first stage precipitator, precipitation temperatures, and residence time in the first stage precipitator. A procedure has been demonstrated that produces neptunium (IV) oxalate particles that filter well and readily calcine to the oxide

  15. The complex reaction kinetics of neptunium including redox and extraction process in 30% TBP-nitric acid system

    International Nuclear Information System (INIS)

    Hu Zhang; Zhan-yuan Liu; Xian-ming Zhou; Li Li

    2017-01-01

    In order to understand the complex and dynamic neptunium process chemistry in the TBP-HNO_3 system, the kinetics involved reversible redox reaction and extraction mass transfer was investigated. The results indicates that the mass transfer rate of Np(VI) is much faster than the redox reaction in aqueous solution. The concentrations of nitric acid and nitrous acid not only can change the Np(V) oxidation reaction and Np(VI) reduction reaction rate, but also can ultimately determine the distribution of neptunium extraction equilibrium. The variety of temperature can only influence the extraction equilibrium time, but cannot alter the equilibrium state of neptunium. (author)

  16. Determination of milligram amounts of neptunium by potentiometric titration

    International Nuclear Information System (INIS)

    Ryzhinskij, M.V.; Solntseva, L.F.

    1981-01-01

    Two procedures of potentiometric titration of about 1 mg Np are reported which are based on its oxidation to neptunium (6) with silver (2) oxide followed by titration with iron (2) to neptunium (5) in one case and to neptunium (4) in the alternative one. The error is not greater than 0.2% rel. Ten-fold uranium excess does not interfere. Up to 1% of plutonium relative to neptunium does not interfere in the case of the titration to neptunium (5). In the titration to neptunium (4), plutonium is titrated stoichiometrically [ru

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

    Energy Technology Data Exchange (ETDEWEB)

    Duffey, J

    2003-08-29

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

  18. Separation of different valency states of neptunium from processing solutions

    International Nuclear Information System (INIS)

    Shabana, R.; EL-Naggar, H.A.

    1990-01-01

    The three main oxidation states of neptunium (Np(IV),Np(V) and Np(V I)) have been separated from each other by solvent extraction and extraction chromatographic techniques. The separation procedure is based on a systematic study of the extraction behaviour of each oxidation state using TBP as an extractant. The purity of separated species is identified using spectrophotometry

  19. Unusual radiolytic behavior of neptunium ions in aqueous bicarbonate solutions

    International Nuclear Information System (INIS)

    Shilov, V.P.; Gogolev, A.V.; Pikaev, A.K.

    2000-01-01

    Behavior of neptunium ions in carbonate and bicarbonate aqueous solutions saturated with air, oxygen or argon during gamma radiation ( 60 Co) by doses up to 3 kGy at dose rates 10 and 25 Gy/min was studied by the method of spectrophotometry. It is shown that in neptunium (5) bicarbonate solution nearly complete (95%) neptunium ion oxidation occurs under the effect of radiation, whereas no oxidation is observed in carbonate solution. Radiation-chemical yield of neptunium (5) oxidation and stationary concentration of neptunium (6) ions depend on concentration of bicarbonate-ions. Explanation to the results obtained is made from the viewpoint of potential radiolytic reactions [ru

  20. On formation of neptunium(5) and (6) during thermal decomposition of neptunium(4) compounds

    International Nuclear Information System (INIS)

    Bessonov, A.A.; Afonas'eva, T.V.; Krot, N.N.

    1989-01-01

    A study was made on thermal behaviour of neptunium(4) peroxide (1), binary nitrate of neptunium(4) and ammonium (2), as well as neptunium(4) oxalate (3). It was established that 1 decomposed to NpO 2 in three stages with formation of neptunium(5) hydroxide at 80-100 deg C, transformed to Np 2 O 5 during further heating. The compound 2 is stable up to 150 deg C, and then decomposition, accompanied by intramolecular neptunium oxidation with formation of NH 4 NpO 2 (NO 3 ) 3 , takes place. This compound is transformed to Np 2 O 5 at 260-290 deg C. It was revealed that during 3 heating in the air at 270-330 deg C more than 70 % of metal could be transformed to pentavalent form, which was probably related with (NpO 2 ) 2 C 2 O 4 formation

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

    International Nuclear Information System (INIS)

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

    1994-01-01

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

  2. Radiation-chemical behaviour of neptunium ions in nitric acid solutions in the presence of curium-244

    International Nuclear Information System (INIS)

    Frolova, L.M.; Frolov, A.A.; Vasil'ev, V.Ya.

    1984-01-01

    Radiation-chemical behaviour of neptunium ions in nitric acid solutions is studied under the action of intensive internal alpha-irradiation conditioned by curium nuclides. In 0.3-1.1 mol/l solutions of nitric acid radiation-chemical oxidation of neptunium (4) and reduction of neptunium (6) is obeyed to the first order law of reaction rate in respect to neptunium concentration. Effective constants of neptunium (4) oxidation rates and neptuniumi(6) reduction rates are not dependent on neptunium ion in1tial concentration and increase with a growth of a dose rate of alpha-irradiation of solution. In equilibrium only neptunium (5) and neptunium (6) are present in solutions with HNO 3 concentration less than 1 mol/l. In more concentrated solutions equilibrium between sexa-, penta- and tetravalent neptunium forms is established. Equilibrium concentrations of neptunium valent forms are not dependent on neptunium initial oxidation state under the same initial conditions (dose rate, neptunium concentration and acidity. It is shown form experimental data that under the action of alpha-irradiation neptunium (5) both is oxidated to neptunium (6) and is reduced to neptunium (4)

  3. Method of recovering neptunium from spent nuclear fuel

    International Nuclear Information System (INIS)

    Tsuboya, T.; N.

    1976-01-01

    An improved Purex wet recovery process including the step of extracting and separating uranium and plutonium simultaneously from the fission products in the presence of nitric acid and nitrous acid by using a multistage extractor unit having an extracting section and a washing section is provided for separating and recovering neptunium simultaneously with uranium and plutonium contained in spent nuclear fuel. The improved method comprises the steps of maintaining the nitrous acid concentration in said extracting section at a level suited for effecting oxidation of neptunium from (V) to (VI) valence, while lowering the nitrous acid concentration in said washing section so as to suppress reduction of neptunium from (VI) to (V) valence, and maintaining the nitric acid concentration in said washing section at a high level

  4. X-ray photoemission spectroscopy (XPS) study of uranium, neptunium and plutonium oxides in silicate-based glasses

    International Nuclear Information System (INIS)

    Lam, D.J.; Veal, B.W.; Paulikas, A.P.

    1982-11-01

    Using XPS as the principal investigative tool, we are in the process of examining the bonding properties of selected metal oxides added to silicate glass. In this paper, we present results of XPS studies of uranium, neptunium, and plutonium in binary and multicomponent silicate-based glasses. Models are proposed to account for the very diverse bonding properties of 6+ and 4+ actinide ions in the glasses

  5. Uranium/plutonium and uranium/neptunium separation by the Purex process using hydroxyurea

    International Nuclear Information System (INIS)

    Zhu Zhaowu; He Jianyu; Zhang Zefu; Zhang Yu; Zhu Jianmin; Zhen Weifang

    2004-01-01

    Hydroxyurea dissolved in nitric acid can strip plutonium and neptunium from tri-butyl phosphate efficiently and has little influence on the uranium distribution between the two phases. Simulating the 1B contactor of the Purex process by hydroxyurea with nitric acid solution as a stripping agent, the separation factors of uranium/plutonium and uranium/neptunium can reach values as high as 4.7 x 10 4 and 260, respectively. This indicates that hydroxyurea is a promising salt free agent for uranium/plutonium and uranium/neptunium separations. (author)

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

    Energy Technology Data Exchange (ETDEWEB)

    Paulenova, Alena [Principal Investigator; Vandegrift, III, George F. [Collaborator

    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.

  7. Sorption of americium and neptunium by deep-sea sediments

    International Nuclear Information System (INIS)

    Higgo, J.J.W.; Rees, L.V.C.; Cronan, D.S.

    1983-01-01

    The sorption and desorption of americium and neptunium by a wide range of deep-sea sediments from natural sea water at 4 0 C has been studied using a carefully controlled batch technique. All the sediments studied should form an excellent barrier to the migration of americium since distribution coefficients were uniformly greater than 10 5 and the sorption-desorption reaction may not be reversible. The sorption of neptunium was reversible and, except for one red clay, the distribution coefficients were greater than 10 3 for all the sediments investigated. Nevertheless the migration of neptunium should also be effectively retarded by most deep-sea sediments even under relatively oxidizing conditions. The neptunium in solution remained in the V oxidation state throughout the experiments. Under the experimental conditions used colloidal americium was trapped by the sediment and solubility did not seem to be the controlling factor in the desorption of americium. (Auth.)

  8. Corrosion of type 304L stainless steel in boiling dilute neptunium nitrate solution

    International Nuclear Information System (INIS)

    Motooka, Takafumi; Kiuchi, Kiyoshi

    2003-01-01

    Corrosion of type 304L stainless steel in nitric acid solution containing neptunium was studied under immersion and heat-transfer condition. Corrosion rates of stainless steel were obtained by the weight loss measurement and the quantitative analysis of metallic ions dissolved in solution. The surface morphology was observed by scanning electron microscopy. The corrosion acceleration mechanism was investigated by polarization measurement and spectrophotometry. The corrosion rate in boiling 9M nitric acid was accelerated by addition of neptunium. The corrosion of stainless steel was promoted under heat-transfer condition compared to immersion condition. In polarization measurements, the cathodic current was increased by addition of neptunium. Spectrophotometric measurements showed the oxidization of neptunium in boiling nitric acid. It was suggested that the accelerated corrosion in nitric acid solution containing neptunium was caused by re-oxidation of neptunium. (author)

  9. Counter-current extraction studies for the recovery of neptunium by the Purex process. Part II

    Energy Technology Data Exchange (ETDEWEB)

    Srinivasan, N.; Nadkarni, M. N.; Kumar, S. V.; Kartha, P. K.S.; Sonavane, R. R.; Ramaniah, M. V.; Patil, S. K.

    1974-07-01

    Counter-extraction experiments were carried out under the conditions relevant to the partitioning column (IBX) in the purex process to know the path of neptunium present as Np (VI) the organic phase during the partitioning step. The results obtained show that when ferrous sulphamates is used as the reducing agent, most of the neptunium continues to remain with uranium in the organic stream while with hydrazine stabilized uranous nitrate as the reducing agent, a major fraction of neptunium follows the aqueous stream. Mixer-settler experiments were also carried out under the conditions relevant to the uranium purification cycle (2D) to establish the conditions for forcing neptunium to the aqueous raffinate or for partitioning it from uranium if both neptunium and uranium are co-extracted in this cycle and the results obtained are reported here. (auth)

  10. Counter-current extraction studies for the recovery of neptunium by the Purex process. Part I

    Energy Technology Data Exchange (ETDEWEB)

    Srinivasan, N.; Nadkarni, M. N.; Kumar, S. V.; Kartha, P. K.S.; Sonavane, R. R.; Ramaniah, M. V.; Patil, S. K.

    1974-07-01

    It is proposed to recover neptunium-237, along with uranium and plutonium, during the fuel reprocessing in the PREFRE plant at Tarapur. Counter-current extraction studies, relevant to the code contamination (HA) and partitioning (IA) cycles of the purex process, were carried out to arrive at suitable chemical flowsheet conditions which would enable the co-extraction of neptunium along with uranium and plutonium. The results of the studies carried out using a laboratory mixer-settler unit and synthetic mixtures of neptunium and uranium are reported here. Based on these results, the chemical flowsheet conditions are proposed for the co-extraction of neptunium even if it exists as Np(V) in the aqueous feed solution. (auth)

  11. Redox reactions of neptunium in tributyl phosphate-dodecane mixtures

    International Nuclear Information System (INIS)

    Wehrey, F.

    1989-01-01

    In relation with the reprocessing of irradiated fuels, disproportionation and oxidation by nitric acid of pentavalent neptunium in tributyl phosphate-dodecane mixtures have been studied. The experimental part of this work is based on spectrophotometric measurements. The disproportionation of pentavalent neptunium in organic perchloric medium is a second order reaction with respect to neptunium V. The reaction rate is strongly influenced by the perchloric acid concentration and has a higher value than in an aqueous medium. The reverse reaction in nitric media is a first order with respect to tetravalent and hexavalent ions. The reaction rate is a function of the reverse of the square of the nitric acid concentration. The energy of activation is the same than in aqueous medium. The oxidation rate of pentavalent neptunium by nitric acid is increased by nitrous acid. When no nitrous acid is added to the mixture, the reaction revealed to be autocatalytic, possesses an induction period. When nitrous and nitric acids are in excess to neptunium the reaction is first order with respect to neptunium. The reaction rate depends on the concentration of nitric acid and is a linear function of the concentration of nitrous acid. In tributyl phosphate dodecane mixtures the reaction occurs spontaneously. It is not the case in aqueous media. The values of thermodynamical and kinetical constants determined in this work could be used in a modelization of the behavior of neptunium in the reprocessing of irradiated fuels, which has to eliminate this element among its tasks [fr

  12. Surface Complexation of Neptunium(V) with Goethite

    International Nuclear Information System (INIS)

    Jerden, James L.; Kropf, A. Jeremy

    2007-01-01

    Batch adsorption experiments in which neptunium-bearing solutions were reacted with goethite (alpha-FeOOH) have been performed to study uptake mechanisms in sodium chloride and calcium-bearing sodium silicate solutions. This paper presents results identifying and quantifying the mechanisms by which neptunium is adsorbed as a function of pH and reaction time (aging). Also presented are results from tests in which neptunium is reacted with goethite in the presence of other cations (uranyl and calcium) that may compete with neptunium for sorption sites. The desorption of neptunium from goethite has been studied by re-suspending the neptunium-loaded goethite samples in solutions containing no neptunium. Selected reacted sorbent samples were analyzed by x-ray absorption spectroscopy (XAS) to determine the oxidation state and molecular speciation of the adsorbed neptunium. Results have been used to establish the pH adsorption edge of neptunium on goethite in sodium chloride and calcium-bearing sodium silicate solutions. The results indicate that neptunium uptake on goethite reaches 95% at a pH of approximately 7 and begins to decrease at pH values greater than 8.5. Distribution coefficients for neptunium sorption range from less than 1000 (moles/kg) sorbed / (moles/kg) solution at pH less than 5.0 to greater than 10,000 (moles/kg) sorbed / (moles/kg) solution at pH greater than 7.0. Distribution coefficients as high as 100,000 (moles/kg) sorbed / (moles/kg) solution were recorded for the tests done in calcite equilibrated sodium silicate solutions. XAS results show that neptunium complexes with the goethite surface mainly as Np(V) (although Np(IV) is prevalent in some of the longer-duration sorption tests). The neptunium adsorbed to goethite shows Np-O bond length of approximately 1.8 angstroms which is representative of the Np-O axial bond in the neptunyl(V) complex. This neptunyl(V) ion is coordinated to 5 or 6 equatorial oxygens with Np-O bond lengths of 2

  13. The photochemistry of neptunium in aqueous perchloric acid solutions

    International Nuclear Information System (INIS)

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

    1979-01-01

    The photochemistry of neptunium ions in aqueous perchloric acid has been investigated using 254 and 300 nm UV radiation. In the absence of other reagents, Np(IV) and (V) oxidized to Np(VI), in a stepwise fashion, with individual quantum efficiencies for each step that vary from 0.02 to 0.004. Decreasing acid concentration favors the Np(IV) → Np(V) reaction whereas it hinders the Np(V) → Np(VI) photo-oxidation. When ethanol, acetaldehyde and other mild reducing agents are added to neptunium-perchloric acid solutions which are then photolyzed, the Np species are reduced to Np(III) in a stepwise fashion with individual quantum efficiencies that vary from 0.07 to 0.006. The overall photoredox reactions of neptunium are subject to competing secondary product reactions that become significant as the photolysis products accumulate. Absorption spectrophotometry was used to monitor the changes in Np oxidation states and reference spectra of the various Np oxidation states are given for 1.0 N HClO 4 . The Np species have absorption bands in the 300 to 1320 nm region that obey Beer's law only when they were properly resolved. (author)

  14. Transuranium element chalcogenides. Crystallochemistry and Moessbauer spectrometry of neptunium 237 chalcogenides

    International Nuclear Information System (INIS)

    Thevenin, T.; Pages, M.; Damien, D.

    1981-09-01

    To study actinide compounds , neptunium 237 has been studied by Moessbauer resonance. The different oxidation degrees of neptunium (7, 6, 5, 4 and 3) have a very important effect on isomeric displacements. In the study of chalcogenides, the isomeric displacement value of NpS 3 confirms the valency 4+ of neptunium in this compound. Results obtained with Np 3 S 5 show two valency state +3 and +4 in this compound. There is a good agreement with the two crystalline sites determined by crystallography [fr

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

    International Nuclear Information System (INIS)

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

    1996-08-01

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

  16. Metabolism and toxicity of neptunium

    International Nuclear Information System (INIS)

    Nenot, J.C.

    1983-08-01

    The biological behaviour and toxicity of neptunium were studied. Neptunium was administered either intravenously or intramuscularly in rats. In contrast to other transuranium elements the distribution patterns of neptunium in the case of intravenous injection is not dependent on the physico-chemical state. Urinary excretion is high. The distribution after intramuscular injection showed a rather fast migration from the injection site. 237 Neptonium in urine was approximately equal to bone deposit. Neptunium behaviour followed that of alkaline earths rather than that of transplutonium elements

  17. Organometallic neptunium(III) complexes.

    Science.gov (United States)

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

    2016-08-01

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

  18. Organometallic neptunium(III) complexes

    Science.gov (United States)

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

    2016-08-01

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

  19. Photochemical reactions of neptunium in nitric acid solution containing photocatalyst

    International Nuclear Information System (INIS)

    Fukasawa, Tetsuo; Kawamura, Fumio

    1991-01-01

    Photochemical oxidation and reduction behaviors of neptunium were preliminarily investigated in 3 mol/l nitric acid solution. Nitric acid of 3 mol/l simulated the high level waste solution from a spent fuel reprocessing process. Concentrations of Np(V), Np(VI) and nitrous acid were determined with a photospectrometer, and solution potential with an electrode. Without additives, Np(VI) was reduced to Np(V) by nitrous acid which was photolytically generated from nitric acid. With a scavenger for nitrous acid, Np(V) was oxidized to extractable Np(VI) by a photolytically generated oxidizing reagent which were predicted by the solution potential measurement. The reduction rate was higher than the oxidation rate because of the larger quantity and higher reactivity of nitrous acid than an oxidizing reagent. Photocatalyst was proved to be effective for the oxidation of Np(V) to Np(VI). (author)

  20. Fluorescent determination of neptunium in plutonium

    International Nuclear Information System (INIS)

    Alexandruk, V.M.; Babaev, A.S.; Dem'yanova, T.A.; Stepanov, A.V.

    1991-01-01

    This paper describes a new procedure for direct determination of Neptunium in Plutonium using laser induced time resolved fluorescence method. The procedure based on measurement of fluorescence intensity of Neptunium followed its concentration in effective layer of pellet of calcium fluoride. Detection limit of determination of Neptunium is 2 10 -12 g. At the level of Neptunium content in Plutonium more than 5 ppm relative standard deviation is equal 0.08-0.12. For carrying out of single measurement it is necessary neither more nor less 5 mkg Plutonium

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

    International Nuclear Information System (INIS)

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

    2004-01-01

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

  2. Neptunium (IV) oxalate solubility

    International Nuclear Information System (INIS)

    Luerkens, D.W.

    1983-07-01

    The equilibrium solubility of neptunium (IV) oxalate in nitric/oxalic acid solutions was determined at 22 0 C, 45 0 C, and 60 0 C. The concentrations of nitric/oxalic acid solutions represented a wide range of free oxalate ion concentration. A mathematical solubility model was developed which is based on the formation of the known complexes of neptunium (IV) oxalate. the solubility model uses a simplified concentration parameter which is proportional to the free oxalate ion concentration. The solubility model can be used to estimate the equilibrium solubility of neptunium (IV) oxalate over a wide range of oxalic and nitric acid concentrations at each temperature

  3. The metabolism and gastrointestinal absorption of neptunium and protactinium in adult baboons

    International Nuclear Information System (INIS)

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

    1985-01-01

    The metabolism of neptunium and protactinium was studied in adult female baboons following intravenous injection and intragastric intubation. Neptunium-239, Np-237, and Pa-233 were prepared as either citrate-buffer, nitrate, or bicarbonate solutions with oxidation states of (V) and (VI). Samples of blood, urine, feces and autopsy tissues were measured by gamma spectrometry. Retention of neptunium and protactinium was determined in vivo using whole and partial body gamma-scintillation spectrometry with [NaI-CsI(T1)] detectors. Fed and fasted baboons were administered solutions of Np(VI) bicarbonate (10/sup -8/ to 10/sup -1/ mg/kg) and Pa(V) citrate-buffer (10/sup -9/ mg/kg) by gavage. The gastrointestinal absorption value for neptunium in two fasted baboons, sacrificed at 1 day post administration, was determined to be 0.92 +- 0.04%. Of the total amount of neptunium absorbed, 52 +- 3% was retained in bone, 6 + 2% was in liver, and 42 +- 0.1% was excreted in urine. The metabolism of neptunium followed oral and iv administrations was found to be similar. This observation was also true for baboons which had received oral and iv doses of protactinium. A method was developed to estimate GI absorption values for both nuclides in baboons, which were not sacrificed, by comparison of activities present in bioassay samples after injection and gavage. Absorption values calculated by this method for neptunium and protactinium in fasted baboons were 1.8 +- 0.8% and 0.65 +- 0.01%, respectively. Values for fed animals were 1 to 2 orders of magnitude less than those for fasted animals. Further experiments are currently underway to evaluate this assay technique

  4. Action of copper (3) in periodate complex on hexavalent neptunium and plutonium in alkaline medium

    International Nuclear Information System (INIS)

    Shatokhina, O.B.; Alekseeva, D.P.; Peretrukhin, B.F.; Krot, N.N.

    1977-01-01

    A complex of trivalent copper connected with periodate has been studied in order to determine its possible use for oxidizing hexavalent transuranium elements. Proceeding from the dependence of formal potentials of the pairs Cusup((3))-Cusup((2)), Npsup((7))-Npsup((6)), Pusup((7))-Pusup((6)) on alkali concentration, it has been established that beginning with concentration 1M the potential of the pair Cusup((3))-Cusup((2)) is higher than that of the pair Npsup((7))-Npsup((6)) by approximately 50 mV. This means that a rather complete oxidation of hexavalent neptunium to heptavalent is possible by the action of copper (3) excess on neptunium (6) when KOH concentration is 1M and higher. Oxidation close to quantitative is attained in 1M KOH when excess of copper(3) is used and the ratio Npsup((6)): Cusup((3)) is 1:4 and higher. When KOH concentration is more than 1M a sufficiently complete oxidation (96-97%) of neptunium (6) is attained at Npsup((6)):Cusup((3))=1:2 or 1:3. Optimum conditions for oxidizing plutonium are 11M KOH and 2-3-fold excess of copper (3) reagent. At 9M KOH and a ratio Pusup((6)):Cusup((3))=1:2 the yield of Pu (7) is 33 %

  5. Electroanalytical studies of uranium, neptunium, and plutonium ions in solutions

    International Nuclear Information System (INIS)

    Yoshida, Zenko; Aoyagi, Hisao; Kihara, Sorin

    1989-01-01

    Redox behavior of uranium, neptunium, and plutonium ions, whose oxidation states in acid solutions are between (VI) and (III), were investigated by flow-coulometry with a column electrode of glassy carbon fibers as well as ordinary voltammetry with a rotating disc electrode. Based on current-potential curves the electrode processes were elucidated taking their disproportionation and/or complexation reactions into account. The flow-coulometry, which provides rapid and quantitative electrolysis, was applied to such analytical purposes as follows; the determination of uranium and plutonium in the solution or the solid with discerning their oxidation states, the preparation of species in a desired oxidation state, even in an unstable state which cannot be prepared by ordinary procedure, and the separation of trace amount of uranium in solutions by the electrodeposition of its hydroxide

  6. Solvent extraction of irradiated neptunium targets. I. Valence stabilization

    International Nuclear Information System (INIS)

    Thompson, G.H.; Thompson, M.C.

    1977-01-01

    Solvent extraction of 237 Np and 238 Pu from irradiated neptunium is being investigated as a possible replacement for the currently used anion exchange process at the Savannah River Plant. Solvent extraction would reduce separations costs and waste volume and increase the production rate. The major difficulty in solvent extraction processing is maintaining neptunium and plutonium in the extractable IV or VI valence states during initial extraction. This study investigated the stability of these states. Results show that: The extractable M(IV) valence states of neptunium and plutonium are mutually unstable in plant dissolver solution (2 g/l 237 Np, 0.4 g/l 238 Pu, 1.2M Al 3+ , 4.6M NO 3 - , and 1M H + ). The reaction rates producing inextractable species from extractable M(IV) or M(VI) are fast enough that greater than or equal to 99.9 percent extractable species in 237 Np-- 238 Pu mixtures cannot be maintained for a practicable processing period

  7. The measurement of neptunium in fast reactor fuel reprocessing

    International Nuclear Information System (INIS)

    Mair, M.A.; Savage, D.J.; Kyffin, T.W.

    1986-02-01

    Analytical techniques have been developed to measure neptunium in the feed, waste and product streams of a fast reactor fuel reprocessing plant. The estimated level of one microgram per milligram of plutonium in some solutions presented severe separation and measurement problems. An initial separation stage was essential, and both ion exchange and solvent extraction using thenoyltrifluoroacetone were studied. The redox chemistry of neptunium necessary to achieve good separation is considered. Spectrophotometry measurement of the stable neptunium/arsenazo III complex was selected for the final neptunium determination with additional analysis by radiometric methods. Incomplete recovery of neptunium during the separation stages necessitated yield measurements, using either neptunium-237 as an internal standard or the short lived gamma active neptunium-239 isotope as a tracer. The distribution of neptunium between the waste and product streams is discussed, in relation to the chemistry of neptunium in the reprocessing plant. (author)

  8. Investigation on neptunium behavior in electrolytic partitioning process of uranium and plutonium

    International Nuclear Information System (INIS)

    Zhang Qingxuan; Zhang Jiajun; Tian Baosheng; Jiang Dongliang; Li Zhaoyi; He Jianyu

    1988-01-01

    The electrolytic oxidation-raduction of Np(V, VI) in HNO 3 solution was studied. Experimental results showed that the electrode process of Np(V)-Np(VI) couple is reversible, and the half reaction time of the process mentioned above is about 1.5 minutes under given conditions. The overpotential of reduction of Np(V) is high, which makes it difficult to reduce Np(V) into Np(IV) directly at cathode. Owing to a large quantity of U(IV) produced through electrolysis, it is presaged that neptunium will be mainly in tetravalent state in the electrolytic M-S battery. A new type of electrolytic M-S battery was developed, in which anodes were installed in each settling chamber without any specific anode chamber in the battery. Owing to using of the mechanical stirrer driven by a wheel gear, stage efficiency is high. Demonstration campaign was carried out. It follows from the results that the yield of Pu is 99.90 ∼ 99.99%. Separation factor of U from Pu is 3900 ∼ 33000. Material balance of U and Pu is satisfactory. Heavy accumulation of Np in the battery was observed. Np in the battery is mainly in the tetravalent state. It is believed that it is difficult to recover Np quantitatively from single fluent (e.g. 1BP or 1BU) under normal conditions of partitioning step of the PUREX process

  9. Purification process of uranium hexafluoride containing traces of plutonium fluoride and/or neptunium fluoride

    International Nuclear Information System (INIS)

    Aubert, J.; Bethuel, L.; Carles, M.

    1983-01-01

    In this process impure uranium hexafluoride is contacted with a metallic fluoride chosen in the group containing lead fluoride PbF 2 , uranium fluorides UFsub(4+x) (0 3 at a temperature such as plutonium and/or neptunium are reduced and pure uranium hexafluoride is recovered. Application is made to uranium hexafluoride purification in spent fuel reprocessing [fr

  10. Biology of neptunium

    International Nuclear Information System (INIS)

    Wirth, R.E.

    1985-11-01

    This work contains detailed information about fractional absorption of neptunium through gastrointestinal tract in vivo as well as about organ and subcellular distribution in rats. Biochemical investigations have shown, that neptunium is bound to the iron transport protein transferrin in the blood serum. A long-term experiment resulted in osteosarkomincidences of 11% (0.2 mp Np-237/kg) and 36% (1 mg Np-237/kg); simultaneous the whole-body retention was measured during the natural lifespan of the animals of 2.5 years. (orig.) [de

  11. Investigation of Neptunium Precipitator Cleanout Options

    International Nuclear Information System (INIS)

    Hill, B.C.

    2003-01-01

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

  12. Adsorption of neptunium and plutonium on metal phosphites

    International Nuclear Information System (INIS)

    Silver, G.L.

    1979-01-01

    The removal of neptunium and plutonium from water by adsorption on titanium, zirconium, bismuth, thorium, and uranium phosphites was investigated. These phosphites hydrolyze in neutral or alkaline solution producing the hydrous metal oxides that are more effective adsorbents than the original phosphite compounds. Ageing the plutonium-238 polymer changes its adsorption characteristics on commercial bone char. 37 figures, 7 tables

  13. Sorption and direct speciation of neptunium(V) on aluminium oxide and montmorillonite

    International Nuclear Information System (INIS)

    Wendt, Sonja

    2009-01-01

    This study comprised batch experiments, direct speciation studies via EXAFS, and modelling with the 2SPNE SC/CE model to elucidate the mechanisms of Np(V) sorption on montmorillonite and, for reference, on γ-Al 2 O 3 . The sorption of pM 239 Np(V) and μM 237 Np(V) on montmorillonite (STx-1, 4 g/L) and γ-Al 2 O 3 (0.5 g/L) was studied at room temperature in the presence and absence of ambient CO 2 covering a pH-range from 2.5 (STx-1) or 5 (γ-Al 2 O 3 ) to 10.5 with 0.01 or 0.1M NaClO 4 as background electrolyte. The Np(V) uptake was determined by γ spectroscopy of the supernatants and calculated as percentage as well as distribution coefficient K d . Sorption starts from pH ∼6 and, under exclusion of CO 2 , increases continuously, while, in the presence of ambient air, it reaches a maximum at pH ∝8.5 (γ-Al 2 O 3 : logK d max ∼ 4 mL/g; STx-1: logK d max ∼ 2.7 mL/g). Beyond that it decreases again due to the formation of aqueous neptunium carbonate complexes. Furthermore, neptunium sorption on montmorillonite is influenced by ionic strength at pH <6 through ion exchange processes pointing towards the formation of outer-sphere surface complexes there. Isotherms measured at the sorption maximum showed the precipitation of presumably neptunium carbonate complexes above 3.10 -5 M under ambient air conditions. Additionally, they indicated progressive saturation of the sorption sites of γ-Al 2 O 3 . At selected pH (STx-1: 5.0, 7.0, 8.0, 8.5, 9.0, 9.5; γ-Al 2 O 3 : 8.5, 9.5) EXAFS samples were prepared as wet pastes with μM 237 Np and measured at room temperature in fluorescence mode at ANKA and ESRF. Several spectra were averaged and analysed with EXAFSPAK and FEFF 8.20 employing models of NaNpO 2 (CO 3 ) or soddyite, (UO 2 ) 2 SiO 4 .2(H 2 O). The shorter atomic distances of the neptunyl ion at pH 5 compared to the others hinted at the retention of the hydration shell and, thus, at outer-sphere sorption. On average the bond lengths for Np(V) sorbed on STx

  14. Determination of neptunium by redox titration

    International Nuclear Information System (INIS)

    Godbole, A.G.; Patil, S.K.

    1979-01-01

    A simple and quick method for the potentiometric determination of neptunium on the 2 to 5 mg scale has been developed. It consists of oxidation to Np(VI) by AgO or fuming with HClO 4 , destruction of excess of AgO by sulphamic acid, reduction of Np(VI) to Np(IV) with a slight excess of standard Fe(II) in 2M H 2 SO 4 and potentiometric titration of the excess of Fe(II) with standard Ce(IV). The precision is +- 0.5%. (author)

  15. Investigations into the sorption of neptunium by loose rock from the cap rock of the Gorleben salt dome under aerobic and anaerobic conditions

    International Nuclear Information System (INIS)

    Muehlenweg, U.

    1988-01-01

    In the experiments with the natural loose rock the sorption behaviour of neptunium was essentially determined by the chemical form in which the neptunium occurred in the ground waters. Under aerobic conditions with Eh values of 300 mV, neptunium in its oxidation state +5 occurred. At a pH of 2 + , and at pH > 8 as carbonato complex. The found neptunium species were relatively mobile, with sorption values from 1 ml/g to 20 ml/g. The sorption of neptunium is comparable to that of alkali and alkaline earth ions, such as Cs + or Sr 2+ . Cations attached to the rock surface are exchanged for NpO 2 + . Sorption in this case is reversible. (orig.) [de

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

    International Nuclear Information System (INIS)

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

    1986-01-01

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

  17. Neptunium separation in trace levels from uranium solutions by extraction chromatography

    International Nuclear Information System (INIS)

    Figols, M.E.B.

    1991-01-01

    Neptunium and uranium behavior in extraction chromatography system, aiming the separation of microquantities of neptunium from uranyl nitrate solutions is described. Tri-n-octylamina (TOA), tri-n-butylphosphate (TBP), thenoyltrifluoroacetone (TTA) as stationary phase, alumina, Voltalef-UF-300, silica as support material were verified. The impregnation conditions as well as the best stationary phase/support material ratio were established. TBP/alumina, TBP/Voltalef and TOA/alumina system were selected to uranium and neptunium separation studies. In the system using TBP as extractant agent uranium and neptunium separation was reached by selective elution after the retention of both elements on the column. U-Np separation by selective retention of Np was possible with TOA system. The capacity of the column was the 66.6 mg U/mL and 191.6mg U/mL for the TBP/alumina and TBP/Voltalef systems, respectively. An application of extraction chromatography system in the final phase of irradiated uranium treatment process is proposed. (author)

  18. Separation of neptunium from uranium and plutonium in the Purex process

    International Nuclear Information System (INIS)

    Kolarik, Z.; Schuler, R.

    1984-01-01

    The possibility of removing neptunium from the Purex process in the first extraction cycle was investigated. Butyraldehyde was found to reduce Np(VI) to Np(V), but not Pu(IV) to Pu(III). Up to 99.7% Np can be separated from uranium and plutonium in the 1A extractor or, much more favourably, in an additional partitioning extractor. Hydroxylamine nitrate can be used for reducing Np(VI) to Np(V) in a uranium purification cycle at a high U concentration in the feed solution. Here the decontamination factor for Np can be as high as 2300 and is lowered if iron is present in the feed. (author)

  19. The use of neptunium-239 to assess neptunium distribution throughout a nuclear fuel reprocessing plant

    International Nuclear Information System (INIS)

    Mair, M.A.; Savage, D.J.; Prentice, P.C.

    1989-08-01

    A radiometric technique has been devised to use the gamma emission from the neptunium-239 daughter of americium-243 to estimate neptunium distribution in a plant reprocessing irradiated plutonium based fuels. Three trials were undertaken with samples from the Prototype Fast Reactor at Dounreay. The trials have confirmed the previous chemical measurements and the usefulness of this technique to highlight the effect of altered flowsheet conditions. (author)

  20. Preparation procedure and certification of uranous-uranic oxide and nitric acid solution of neptunium as standard specimens of plant

    International Nuclear Information System (INIS)

    Bulyanitsa, L.S.; Lipovskij, A.A.; Ryzhinskij, M.V.; Preobrazhensskaya, L.D.; Aleksandruk, V.M.; Alekseeva, N.A.; Gromova, E.A.; Solntseva, L.F.; Shereshevskaya, I.I.

    1981-01-01

    Two techniques of certification of standard specimens of plant (SSP) are considered. The first technique-comparison with initial SS-metallic uranium NBS-960 - is used for certification of uranium. protoxide-oxide. The mass part of the sum of analyzed impurities in prepared initial SS is (8.4+-0.8)x10 -3 %. For certification according to mass uranium part the method of gravimetric potentiometric titration with semiautomatic titrator is used; the mean quadratic deviation of the method is s=0.0002-0.0003, certified value of uranium mass part in SSP (taking account of the error of initial SS) is (84.80+-0.02)%. The second technigue - a simplified circular experiment - is used for certification of SSP-nitric acid solution of neptunium as to Np mass part. Coulometry at controlled potential and coulometry at controlled current and two variants of potentiometric titration are used as certification methods of analysis. Relative mean quadratic deviations of the methods are ssub(r)=0.0014-0.0023. When calculating total error of certified value of neptunium mass part constituents of both accidental and unremoved systematic errors of the methods were included. The final certification result of SSP is (5.707+-0.018)% [ru

  1. Geomicrobiological redox cycling of the transuranic element neptunium.

    Science.gov (United States)

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

    2010-12-01

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

  2. The organometallic chemistry of neptunium

    International Nuclear Information System (INIS)

    Bohlander, R.

    1986-09-01

    Organometallic compounds of neptunium with carbocyclic ligands (C 5 H 5 - =cp, C 8 H 8 2- =cot) have been prepared and investigated. Starting from tetrakis(cyclopentadienyle)neptunium(IV) (cp 4 Np) and tris(cyclopentadienyle)neptunium(IV) chloride (cp 3 NpCl) a lot of other Np(IV)-compounds can be obtained by ligand-exchange reactions. These have the general formula cp 3 NpL with either inorganic ionic (L=Br - , I - , 1/2SO 4 2- , NCS - , AlCl 4 - ) or organic ligands (L=NC 4 H 4 - , N 2 C 3 H 3 - , C=CH - , 1/2C= 2- , CH 3 - , C 2 H 5 - , C 6 H 5 - ). Produced by reduction, tris(cyclopentadienyle)neptunium(III), cp 3 Np) gives similar structured 1:1-adduct complexes, cp 3 Np * B, with Lewis-bases like THF, diethylether, acetonitrile. Physico-chemical properties and changes in the molecular structure of the complexes have been studied using IR-, FTIR- and optical spectroscopy (in the NIR, VIS and UV region) as well as by magnetic and EPR measurements and Moessbauer spectrometry. The results are discussed as to their classification within the actinide complex chemistry and to the comparison with lanthanide complexes. (orig./RB) [de

  3. Neptunium sorption and co-precipitation of strontium in simulated DWPF salt solution

    International Nuclear Information System (INIS)

    McIntyre, P.F.; Orebaugh, E.G.; King, C.M.

    1988-01-01

    Batch experiments performed using crushed slag saltstone (∼40 mesh) removed >80% of 237 Np from simulated Defense Waste Processing Facility (DWPF) salt solution. The concentration of 237 Np (110 pCi/ml) used was 1000x greater than levels in actual DWPF solutions. Neptunium-239 was used as a tracer and was formed by neutron activation of uranyl nitrate. Results showed that small amounts of crushed saltstone (as little as 0.05 grams), removed >80% of neptunium from 15 ml of simulated DWPF solution after several hours equilibration. The neptunium is sorbed on insoluble carbonates formed in and on the saltstone matrix. Further testing showed that addition of 0.01 and 0.10 ml of 1 molar Ca +2 (ie. Ca (NO 3 ) 2 , CaCl 2 ) into 15 ml of simulated DWPF solution yielded a white carbonate precipitate which also removed >80% of the neptunium after 1 hour equilibration. Further experiments were performed to determine the effectiveness of this procedure to co-precipitate strontium

  4. Neptunium: a bibliographic reference

    International Nuclear Information System (INIS)

    Mosley, R.E.

    1979-06-01

    A comprehensive bibliograhy of the literature on the element neptunium published prior to January 1976 is presented. A short abstract is given for each listed reference, with a few exceptions. The references are divided into sections categorized as General, Man-Made Sources (Reactors), Man-Made Sources (Fuel Reprocessing), Chemistry (Solubility), Chemistry (Compounds), Chemistry (Isotopes), Analyses (Instrumental), Analyses (Chemical), Chemical (Animal), Biological (Effects), Biological (Animal-Metabolism-Retention), Biological (Air Movement), Biological (Human Inhalation), Measurement, and Dosimetry. The bibliography contains author and keyword indexes and was compiled to serve as a quick reference source for neptunium-related work. 184 citations

  5. Cyclopentadienyl uranium, neptunium and plutonium chemistry

    International Nuclear Information System (INIS)

    Plews, M.J.

    1985-01-01

    The thesis presents the preparation and characterisation of a number of mono, bis and tris(cyclopentadienyl) complexes of uranium(IV), neptunium(IV) and plutonium(IV). The work of previous studies on mono(cyclopentadienyl) thorium and uranium complexes has been extended, and a range of isostructural neptunium species isolated. Their mode of formation and stability in tetrahydrofuran and acetonitrile solutions was investigated. (author)

  6. The effect of carbonate on neptunium sorption by hydroxyapatite

    International Nuclear Information System (INIS)

    Moore, R.C.; Holt, K.

    2005-01-01

    Full text of publication follows: Hydroxyapatite, Ca 10 (PO 4 ) 6 (OH) 2 , is a common mineral, the main inorganic compound in bone and exhibits strong sorptive properties for many radionuclides. It has been widely studied and proposed as a backfill material for nuclear waste repositories. Neptunium is one the radionuclides sorbed by hydroxyapatite. Neptunium is of particular importance to nuclear waste repository performance because of its relatively high aqueous solubility, high mobility in the environment and long half-life. In this work, we report on the effects of carbonate on sorption of neptunium by hydroxyapatite. Batch sorption and desorption studies for neptunium were performed as a function of carbonate concentration in water using a synthetic hydroxyapatite. The results indicate even low concentrations of carbonate significantly reduce neptunium sorption and enhance desorption. The data were fit to several simple isotherm equations with the Langmuir equation giving the best results. The results of the work are discussed with respect to nuclear waste repository performance. (authors)

  7. Quaternary ammonium based task specific ionic liquid for the efficient and selective extraction of neptunium

    Energy Technology Data Exchange (ETDEWEB)

    Gupta, Nishesh Kumar [National Institute of Technology, Odisha (India). Dept. of Chemistry; Sengupta, Arijit [Bhabha Atomic Research Centre, Mumbai (India). Radiochemistry Div.; Biswas, Sujoy [Bhabha Atomic Research Centre, Mumbai (India). Uranium Extraction Div.

    2017-07-01

    Liquid-liquid extraction of neptunium from aqueous acidic solution using quaternary ammonium based task specific ionic liquid (TSIL) was investigated. The extraction of Np was predominated by the 'cation exchange' mechanism via [NpO{sub 2}.Hpth]{sup +} species for NpO{sub 2}{sup 2+}, while NpO{sub 2}{sup +} was extracted in ionic liquid as [NpO{sub 2}.H.Hpth]{sup +}. The extraction process was thermodynamically spontaneous while kinetically slower. Na{sub 2}CO{sub 3} as strippant showed quantitative back extraction of neptunium ions from TSIL. TSIL showed excellent radiolytic stability upto 500 kGy gamma exposure. Finally, the TSIL was employed for the processing of simulated high level waste solutions revealing high selectivity of TSIL towards neptunium.

  8. Study of neptunium hexafluoride formation and its adsorption on metallic fluorides

    International Nuclear Information System (INIS)

    Matcheret, Georges

    1970-01-01

    This report involves two parts. The first part deals with the action of elementary fluorine on neptunium compounds by a thermogravimetric method. The mechanism and the kinetics of this reaction vary according to the nature of the compound. 1 - With neptunium tetrafluoride the reaction, proceeds in a single step. The kinetics corresponds to a uniform attack of the entire surface of the sample and follows the kinetics law: (1-α) 1/3 1-k rel t . 2 - The reaction with neptunium dioxyde involves two steps, neptunium tetrafluoride being the intermediate compound. The kinetics of the first step corresponds to a diffusion process and follows the kinetic law: log (1-α) = kt 1/2 . The kinetics of the second step corresponds to an uniform attack of the entire sur face of the sample. The object of the second part is a study of the adsorption of uranium hexafluoride and neptunium hexafluoride on sodium, magnesium and barium fluorides by a volumetric method. The adsorption of UF 6 on MgF 2 has been investigated at 20 deg. C. The isothermal curve obtained is characteristic of a physical one layer monomolecular adsorption. In a way similar to the behaviour of UF 6 the adsorption of NpF 6 involves in addition a chemical reduction with formation of NpF 5 and release of fluorine. The reaction of NpF 6 with BaF 2 permitted to confirm the influence of the polarizing power of the Ba ++ ion on formation and stability of the product of addition. (author) [fr

  9. Neptunium 237 behaviour in subcellular fractions of rat kidneys

    International Nuclear Information System (INIS)

    Kreslov, V.V.; Maksutova, A.Ya.; Mushkacheva, G.S.

    1978-01-01

    Subcellular distribution of intravenously injected (1 and 0.5 μCi/rat) neptunium nitrate (5- and 6-valent) in kidneys of rat males and females has been investigated. It has been shown that the radionuclide was unevenly distributed within the cell. As early as 24 hours after administration, about 50 per cent of neptunium were concentrated in the mitochondrial fraction. The data are presented on variations in neptunium behaviour within subcellular fractions of rat kidneys depending on the sex of animals, valency and dose of the isotope

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

    International Nuclear Information System (INIS)

    Ken Czerwinski; Don Reed

    2000-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Ken Czerwinski; Don Reed

    2000-09-01

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

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

    International Nuclear Information System (INIS)

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

    1999-01-01

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

  13. Neptunium and manganese biocycling in nuclear legacy sediment systems

    International Nuclear Information System (INIS)

    Thorpe, Clare L.; Morris, Katherine; Lloyd, Jonathan R.; Denecke, Melissa A.; Law, Kathleen A.; Dardenne, Kathy; Boothman, Christopher; Bots, Pieter; Law, Gareth T.W.

    2015-01-01

    Understanding the behaviour of the highly radiotoxic, long half-life radionuclide neptunium in the environment is important for the management of radioactively contaminated land and the safe disposal of radioactive wastes. Recent studies have identified that microbial reduction can reduce the mobility of neptunium via reduction of soluble Np(V) to poorly soluble Np(IV), with coupling to both Mn- and Fe(III)- reduction implicated in neptunyl reduction. To further explore these processes Mn(IV) as δMnO 2 was added to sediment microcosms to create a sediment microcosm experiment “poised” under Mn-reducing conditions. Enhanced removal of Np(V) from solution occurred during Mn-reduction, and parallel X-ray absorption spectroscopy (XAS) studies confirmed Np(V) reduction to Np(IV) commensurate with microbially-mediated Mn-reduction. Molecular ecology analysis of the XAS systems, which contained up to 0.2 mM Np showed no significant impact of elevated Np concentrations on the microbial population. These results demonstrate the importance of Mn cycling on Np biogeochemistry, and clearly highlight new pathways to reductive immobilisation for this highly radiotoxic actinide. - Highlights: • Neptunium is a high radiotoxicity, alpha emitting actinide. • Biostimulation of Mn(IV)-enriched sediments leads to reductive removal of soluble Np(V) from groundwater onto sediments as Np(IV). • Np(V) reduction occurs under defined Mn-reducing conditions. • Under Mn-reducing conditions, enzymatic processes may be important for Np(V) reduction.

  14. Sorption behavior of neptunium on bentonite -- Effect of calcium ion on the sorption

    International Nuclear Information System (INIS)

    Kozai, Naofumi; Ohnuki, Toshihiko; Muraoka, Susumu

    1995-01-01

    The sorption behavior of neptunium on bentonite was studied with batch type sorption and desorption experiments over a pH range of 2 to 8. A series of parallel studies using Na-smectite, Ca-smectite and admixtures of Na-smectite and calcite quantified the capacity of Ca 2+ (which occurs in bentonite as an exchangeable cation of smectite and as a component of calcite) to inhibit the sorption of neptunium. The distribution coefficient (K d ) of neptunium for bentonite was constant from pH 2 to 7, while for pure Na-smectite K d increased below pH 5 due to specific sorption of neptunium on Na-smectite. Specific sorption was defined as occurring when neptunium could be desorbed by a strong acid (1 M HCl) but was stable in the presence of 1 M KCl. It was found that the quantity of neptunium sorbed on Na-smectite was inversely proportional to the concentration of Ca 2+ in solution, an effect most pronounced at pH 2+ limits the specific sorption capacity of Na-smectite for neptunium. Similarly, in the mixture of Na-smectite and calcite, sufficient Ca 2+ was solubilized to depress neptunium sorption. This investigation demonstrates that Ca 2+ contained in bentonite as exchangeable cation and released from calcite reduces the specific sorption of neptunium

  15. Precipitaion of neptunium(6) by urotropin from the heated solutions

    International Nuclear Information System (INIS)

    Logvis', A.I.; Krot, N.N.

    1992-01-01

    The composition of precipitate, formed in the course of neptunium(6) nitric acid solution heating with urotropin under different conditions was studied by the methods of X-ray phase analysis, gravimetry and spectrophotometry. The compound studied is determined as NpO 3 ·xH 2 O·yNH 3 , where x <= 2, y <= 0.28. It is shown that not less than 12 % of the initial amount of neptunium remain in solution in the form of neptunium(5)

  16. Rapid and Automated Determination of Plutonium and Neptunium in Environmental Samples

    DEFF Research Database (Denmark)

    Qiao, Jixin

    This thesis presents improved analytical methods for rapid and automated determination of plutonium and neptunium in environmental samples using sequential injection (SI) based chromatography and inductively coupled plasma mass spectrometry (ICP-MS). The progress of methodology development...... and optimization for rapid determination of plutonium in environmental samples using SIextraction chromatography prior to inductively coupled plasma mass spectrometry (Paper III); (3) Development of an SI-chromatographic method for simultaneous determination of plutonium and neptunium in environmental samples...... for rapid and simultaneous determination of plutonium and neptunium within an SI system (Paper VI). The results demonstrate that the developed methods in this study are reliable and efficient for accurate assays of trace levels of plutonium and neptunium as demanded in different situations including...

  17. Neptunium separation in trace levels from uranium solutions by extraction chromatography

    International Nuclear Information System (INIS)

    Cotrim, M.B.; Matsuda, H.T.

    1994-01-01

    Neptunium and uranium behavior in extraction chromatograph system, aiming the separation of micro quantities of neptunium from uranyl solutions is described. Tri-n-octylamine (TOA), Tri-n-butylphosphate (TBP) as stationary phase, alumine, Voltalef UF-300 as support material were verified. The impregnation conditions as well as the best stationary phase/support material ratio were established. TBP/alumine, TBP/Voltalef and TOA/alumine system were selected to uranium and neptunium separation studies. (author) . 12 refs., 03 tabs., 03 figs

  18. Method of neptunium recovery into the product stream of the Purex second codecontamination step for LWR fuel reprocessing

    Energy Technology Data Exchange (ETDEWEB)

    Tsuboya, T; Nemoto, S; Hoshino, T; Segawa, T [Power Reactor and Nuclear Fuel Development Corp., Tokyo (Japan)

    1973-04-01

    The neptunium behavior in the second codecontamination step in Purex process of Power Reactor and Nuclear Fuel Development Corporation was experimentally studied, and the conditions for discharging neptunium in product stream were examined. Improved nitrous acid method was applied to the second codecontamination step. Nitrous acid (NaNO/sub 2/) was supplied to the 1st stage of extraction section at feed rate of 7.5 mM/hr, and hydrazine (hydrazine nitrate) was supplied to some stages near feed point at feed rate of 1.6 mM/hr, by using laboratory scale mixer-settlers having 6 ml of mixing volume and 17 ml of settling volume. Neptunium extraction behavior was analyzed by the code NEPTUN-I simulating neptunium concentration profile and by the code NEPTUN-II for calculating Np (V) and Np (VI) concentration. Batch experiments were performed for explaining the reduction reaction of Np (VI) in organic phase. After shaking the aqueous solution containing Np (VI) in 3 M nitric acid with the various volume ratios of TBP, both phases were separated, and the neptunium concentration was determined. In conclusion, the improved nitrous acid method was effective for the neptunium discharge in product stream when the flow ratio of organic phase to aqueous phase was increased to about three times.

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

    International Nuclear Information System (INIS)

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

    1985-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1985-01-01

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

  1. A method of neptunium recovery into the product stream of the Purex 1st codecontamination step for LWR fuel reprocessing

    International Nuclear Information System (INIS)

    Tsuboya, Takao; Nemoto, Shinichi; Hoshino, Tadaya; Segawa, Takeshi

    1973-01-01

    An improved nitrous acid method was applied for recovering neptunium in spent fuel. Counter-current solvent extraction has been performed to find out its recovery conditions. The nitrous acid in the form of sodium salt solution was fed to the 1st stage of extraction section, and hydrazine nitrate was fed to some stages near feed point. Flow rate and the concentration of additives were altered for finding out optimum condition. Laboratory scale mixer-settlers having 6 ml of mixing volume and 17 ml of settling volume for each stage were used. The nitrous acid method was improved so that the reduction reaction in scrub section can be eliminated by the decomposition of the nitrous acid using a reagent such as sulfamic acid, urea, or hydrazine. In operation, the feed rate of the nitrous acid was about 3 mM/hr, and about 61% of neptunium charged was discharged in the product stream of Purex-1st codecontamination step designed for the LWR fuel reprocessing plant of Power Reactor and Nuclear Fuel Development Corporation. The calculated value of Δx/x for extraction section agreed with the experimental value, where Δx is the quantity of oxidation, and x is the inventory for neptunium in each stage. In conclusion, the improved nitrous acid method is effective for the neptunium discharge in product stream, and the difference of neptunium extraction between estimate and experiment is caused by some of reduction reaction in scrub section. (Iwakiri, K.)

  2. Fate of neptunium in an anaerobic, methanogenic microcosm

    International Nuclear Information System (INIS)

    Banaszak, J.E.; Webb, S.M.; Rittmann, B.E.; Gaillard, J.F.; Reed, D.T.

    1999-01-01

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

  3. Investigation of composition and properties of some neptunium (5) oxalate compounds

    International Nuclear Information System (INIS)

    Zubarev, V.G.; Krot, N.N.

    1981-01-01

    A simple way of neptunium (5) oxalate synthesis is described and its composition is determined: (NpO 2 ) 2 C 2 O 4 xH 2 O. The compound is precipitated from solution during pouring together stoichiometric quantities of neptunium (5) nitrate and ammonium, sodium or potassium oxalate at pH=4-5. An explanation to unusual effect of solubility change with time of neptunium (5) monooxalate complexes and alkali metal or ammonium ion is found taking into account the slow formation of precipitate and low solubility of the compound obtained (0.62 g/l as to metal). Thermal decomposition of the compound is studied. At 180 deg C a water molecule is split off and at 260 deg C decomposition of neptunium oxalate starts. IR spectra and interplane distances (dsub(hkl)) of the compound crystal lattice are determined. New data on the synthesis and properties of complex neptunium (5) oxalates and monovalent cation in second sphere with the ratio ligand: metal=2:1 and 3:1 are presented. On the basis of results of IR spectroscopy and X-ray phase analyses a supposition is made on the existence of such complex compounds [ru

  4. Energy efficiency of neptunium redox battery in comparison with vanadium battery

    International Nuclear Information System (INIS)

    Yamamura, T.; Watanabe, N.; Shiokawa, Y.

    2006-01-01

    A neptunium ion possesses two isostructural and reversible redox couples (Np 3+ /Np 4+ and NpO 2 + /NpO 2 2+ ) and is therefore suitable as an active material for a redox-flow battery. Since the plastic formed carbon (PFC) is known to show the largest k values for Np(IV)/Np(III) and Np(V)/Np(VI) reactions among various carbon electrodes, a cell was constructed by using the PFC, with the circulation induced by bubbling gas through the electrolyte. In discharge experiments with a neptunium and a vanadium battery using the cell, the former showed a lower voltage loss which suggests a smaller reaction overvoltage. Because of the high radioactivity of the neptunium, it was difficult to obtain sufficient circulation required for the redox-flow battery, therefore a model for evaluating the energy efficiency of the redox-flow battery was developed. By using the known k values for neptunium and vanadium electrode reactions at PFC electrodes, the energy efficiency of the neptunium battery was calculated to be 99.1% at 70 mA cm -2 , which exceeds that of the vanadium battery by ca. 16%

  5. Interaction of neptunium with humic acid and anaerobic bacteria

    International Nuclear Information System (INIS)

    Kubota, Takumi; Sasaki, Takayuki; Kudo, Akira

    2002-01-01

    Humic acid and bacteria play an important role in the migration of radionuclides in groundwaters. The interaction of neptunium with humic acid and anaerobic bacteria has been investigated by liquid/liquid and solid/liquid extraction systems. For liquid/liquid extraction, the apparent complex formation constant, β α was obtained from the distribution between two phases of neptunium. For solid/liquid extraction, the ratio of sorption to bacteria, K d , was measured. K d of humic acid can be evaluated from β α . The large value of β α and K d means strong interaction of neptunium with organisms. In order to examine the effect of the nature of organism on interaction, the interaction with humic acid was compared to that with non-sterilized or sterilized mixed anaerobic bacteria. The value of β α of humate depended on neptunium ion concentration as well as pH, which showed the effect of polyelectrolyte properties and heterogeneous composition of humic acid. The comparison of interaction with humic acid and bacteria indicated that the K d value of humic acid was larger than that of bacteria and more strongly depend on pH. (author)

  6. Selective localization of neptunium-237 in the nuclei of mammalian cells. Localisation selective du neptunium-237 au sein des noyaux des cellules de mammiferes

    Energy Technology Data Exchange (ETDEWEB)

    Galle, P.; Boulahdour, H. (Faculte de Medecine, 94 - Creteil (FR)); Metivier, H. (CEA Centre d' Etudes Nucleaires de Fontenay-aux-Roses, 92 (FR). Inst. de Protection et de Surete Nucleaire)

    1992-01-01

    After injection in the rat of soluble neptunium salt, the distribution of this element was studied at the subcellular level by electron microscopy and electron probe microanalysis. Abnormal structures have been observed by electron microscopy in the nuclei of hepatocytes, and the same structures have also been observed in the nuclei of the proximal tubules cells of the kidney. These structures are formed of clusters of very small and dense particles, several nanometers in diameter. The clusters are localized in the central part of the nuclei and they are separate from nucleoli and heterochromatin. Electron probe X-ray analysis of this cluster have shown that they contain neptunium associated with phosphorus. In the cell containing neptunium inclusions, other non specific lesions are also observed (nuclear pycnosis, mitochondrial depletion).

  7. Rapid and automated determination of plutonium and neptunium in environmental samples

    International Nuclear Information System (INIS)

    Qiao, J.

    2011-03-01

    This thesis presents improved analytical methods for rapid and automated determination of plutonium and neptunium in environmental samples using sequential injection (SI) based chromatography and inductively coupled plasma mass spectrometry (ICP-MS). The progress of methodology development in this work consists of 5 subjects stated as follows: 1) Development and optimization of an SI-anion exchange chromatographic method for rapid determination of plutonium in environmental samples in combination of inductively coupled plasma mass spectrometry detection (Paper II); (2) Methodology development and optimization for rapid determination of plutonium in environmental samples using SI-extraction chromatography prior to inductively coupled plasma mass spectrometry (Paper III); (3) Development of an SI-chromatographic method for simultaneous determination of plutonium and neptunium in environmental samples (Paper IV); (4) Investigation of the suitability and applicability of 242 Pu as a tracer for rapid neptunium determination using anion exchange chromatography in an SI-network coupled with inductively coupled plasma mass spectrometry (Paper V); (5) Exploration of macro-porous anion exchange chromatography for rapid and simultaneous determination of plutonium and neptunium within an SI system (Paper VI). The results demonstrate that the developed methods in this study are reliable and efficient for accurate assays of trace levels of plutonium and neptunium as demanded in different situations including environmental risk monitoring and assessment, emergency preparedness and surveillance of contaminated areas. (Author)

  8. Rapid and automated determination of plutonium and neptunium in environmental samples

    Energy Technology Data Exchange (ETDEWEB)

    Qiao, J.

    2011-03-15

    This thesis presents improved analytical methods for rapid and automated determination of plutonium and neptunium in environmental samples using sequential injection (SI) based chromatography and inductively coupled plasma mass spectrometry (ICP-MS). The progress of methodology development in this work consists of 5 subjects stated as follows: 1) Development and optimization of an SI-anion exchange chromatographic method for rapid determination of plutonium in environmental samples in combination of inductively coupled plasma mass spectrometry detection (Paper II); (2) Methodology development and optimization for rapid determination of plutonium in environmental samples using SI-extraction chromatography prior to inductively coupled plasma mass spectrometry (Paper III); (3) Development of an SI-chromatographic method for simultaneous determination of plutonium and neptunium in environmental samples (Paper IV); (4) Investigation of the suitability and applicability of 242Pu as a tracer for rapid neptunium determination using anion exchange chromatography in an SI-network coupled with inductively coupled plasma mass spectrometry (Paper V); (5) Exploration of macro-porous anion exchange chromatography for rapid and simultaneous determination of plutonium and neptunium within an SI system (Paper VI). The results demonstrate that the developed methods in this study are reliable and efficient for accurate assays of trace levels of plutonium and neptunium as demanded in different situations including environmental risk monitoring and assessment, emergency preparedness and surveillance of contaminated areas. (Author)

  9. Application of Moessbauer spectroscopy to the study of neptunium adsorbed on deep-sea sediments

    International Nuclear Information System (INIS)

    Bennett, B.A.; Rees, L.V.C.

    1987-03-01

    A Neptunium Moessbauer spectrometer (the first in Great Britain) was constructed and the Moessbauer spectra of NpAl Laves phase alloy obtained. Neptunium was sorbed onto a calcareous deep-sea sediment from sea water, using a successive-loading technique. Sorption appeared to be by an equilibrium reaction, and because of the low solubility of neptunium in seawater, this meant that the maximum loading that could be achieved was 8mg 237 Np/g sediment. This proved to be an adequate concentration for Moessbauer measurements and a Moessbauer spectrum was obtained. This showed that most of the neptunium was in exchange sites and not present as precipitates of neptunium compounds. It was probably in the 4+ state indicating that reduction had occurred during sorption. This work has demonstrated that Moessbauer Spectroscopy has great potential as an aid to understanding the mechanism of actinide sorption in natural systems. (author)

  10. Study of oxidation-reduction reactions of plutonium and neptunium in sulphuric-phosphoric acid media

    International Nuclear Information System (INIS)

    Moiseev, I.V.; Kuperman, A.Ya.; Borodina, N.N.; Galkina, V.N.; Vinokurov, V.A.

    1976-01-01

    Potentiostatic, coulometric, potentiometric, and amperometric methods have been used for determining the rate constants of disproportionation (ksub(d)) of plutonium(5) and neptunium (5) and normal real redox potentials (Esub(0)sup(p)) of the following ion pairs in sulphur-phosphoric-acid media: PuOsub(2)sup(2)sup(+) (PuO 2 + , Pu 4+ /Pu 3+ , NpO 2 2+ /NpO 2 + , NpO 2 2+ /Np 4+ , NpO 2 + /Np 4+ , and Fe 3+ /Fe 2+ . The regularities have been shown of changing ksub(d) and Esub(o)sup(p) as a function of H 2 SO 4 and H 3 PO 4 concentration. It has been established that for plutonium and neptunium a linear correlation is observed between lg ksub(d) and Esub(o)sup(p) of the ion pairs NpO 2 2+ /NpO 2 + , NpO 2 2 /Np 4+ , NpO 2 + /Np 4+ and PuO 2 2+ /PuO 2 + in a wide range of their values. The correlation coefficient is close to unity in all cases (no less than 0.96). The results of investigations have made it possible to recommend optimum compositions of background electrolytes for performing continuous amperostatic coulometric titration of Pusup((6)) and Npsup((6)) up to four valent state by electrogenerated ions of iron (2)

  11. Radiolytic oxidation

    International Nuclear Information System (INIS)

    Burns, W.G.; Ewart, F.T.; Hobley, J.; Smith, A.J.; Walters, W.S.; Williams, S.J.

    1991-01-01

    Work under the Radiolytic Oxidation Contract from 1986 until April 1989 is reported. The effects of alpha- and gamma-irradiation on the chemistries of plutonium, neptunium and technetium, under conditions representative of the near fields of intermediate and high level waste repositories, were investigated. Gamma-radiolysis of Np (IV) results in oxidation in solutions below pH 12. Solutions of Tc (VII) are reduced to Tc (IV) by gamma-irradiation in contact with blast furnace slag/ordinary Portland cement under an inert atmosphere but not when in contact with pulverized fuel ash/ordinary Portland cement. Tc (IV) is shown to be susceptible to oxidation by the products of the alpha-radiolysis of water. The results of 'overall effects' experiments, which combined representative components of typical ILW or HLW near fields, supported these observations and also showed enhanced plutonium concentrations in alpha-irradiated, HLW simulations. Mathematical models of the behaviour of plutonium and neptunium during gamma-radiolysis have been developed and indicate that oxidation to Pu (VI) is possible at dose rates typical of those expected for HLW. Simulations at ILW dose rates have indicated some effect upon the speciation of neptunium. Laboratory studies of the gamma-irradiation of Np (IV) in bentonite-equilibrated water have also been modelled. Computer code used: PHREEQE, 8 Figs.; 48 Tabs.; 38 refs

  12. Stabilization of neptunium valence states in nitric media for spent nuclear fuel reprocessing

    International Nuclear Information System (INIS)

    Feldhaus, P.

    1996-12-01

    A possibility of standarizing the extraction-behavior of Neptunium during the reprocessing of spent nuclear fuel corresponding to PUREX-Process was investigated. The aim of the work was a qualitative dirigation of the Transuraniumelement (TRUE) into the raffinat of the first extraction cycle by a complete redoxconversion of the Neptunium valence states to unextractable Np(V). In the beginning the theoretical and experimental research focussed on the redoxchemistry of the actinide during the fuel dissolution and the feed preparation. Thereby the nitrous acid, which is produced by a radiological, photochemical and reductive degradation of the nitric acid, revealed an ambivalent influence on the Neptunium valences. By a short-term increase in HNO 2 -concentration the Np(V)-fraction could be obviously risen. The use of some stabilizing reagents inhibited a later reoxidation to Np(VI) also catalyzed by nitrous acid. The urea used for this purpose also led to a further increase in the obtained conversion rates due to a Np(VI)-reduction. The analysis of the valence distribution was performed by an extraction method. This had been compared to chromatographic separation in some preliminary investigations and had turned out to be comparably reliable and easily manageable. (orig.) [de

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

    Science.gov (United States)

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

    2010-12-01

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

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

    International Nuclear Information System (INIS)

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

    2010-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Ams, David A [Los Alamos National Laboratory; Swanson, Juliet S [Los Alamos National Laboratory; Reed, Donald T [Los Alamos National Laboratory; Fein, Jeremy B [UNIV OF NOTRE DAME

    2010-12-08

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

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

    International Nuclear Information System (INIS)

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

    2010-01-01

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

  17. Study on reduction reactions of neptunium(V) on magnetite surface

    International Nuclear Information System (INIS)

    Kitamura, Akira; Kamei, Gento; Nakata, Kotaro; Tanaka, Satoru; Tomura, Tsutomu

    2004-01-01

    Redox reactions between neptunium(V) (Np(V)) and magnetite (Fe(II) 1 Fe(III) 2 O 4 ) surface were investigated in N 2 gas atmosphere. A batch method was applied to the experiment. A magnetite sample and a 0.1 M NaCl solution were mixed in a polypropylene tube, and pH, redox potential and concentration of dissolved neptunium were measured as a function of shaking time, temperature and liquid/solid ratio. The concentration of dissolved neptunium was reduced rapidly within a day, due to the reducing reaction of Np(V) to Np(IV) and the precipitation of Np(IV). The rate constant of the redox reaction and the activation energy for the rate constant were preliminarily obtained. On the other hand, redox reactions between Np(V) and aqueous Fe(II) were hardly observed. Considering the number of transferred electrons, it was suggested that the redox reaction was promoted by not only Fe(II) on the magnetite surface, but also Fe(II) inside the magnetite. (author)

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

    Science.gov (United States)

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

    2013-06-01

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

  19. Neptunium detector using fiber-optic light guides

    International Nuclear Information System (INIS)

    Spencer, W.A.; Killeen, T.E.; Herold, T.R.

    1981-01-01

    A colorimeter has been constructed and installed to detect neptunium (IV) on-line as it elutes from an ion exchange column in a plant process stream. Because of the high radiation and corrosive atmosphere at the monitoring location, the instrument was designed using remote electronics and glass fiber optic cables. The five-foot cables transmit pulsed white light into a glass monitoring window in a containment box and return the transmitted portion to a photosensor. A simple spring clamp was designed to couple the cables to the monitoring window without modifying existing processes. Details of the design, installation, and operational problems are discussed. Other applications and modifications of the present colorimeter for other actinides, as well as preliminary results on a fiber optic spectrophotometer, are presented

  20. Coprecipitation of neptunium and plutonium with iron and zirconium dibutyl phosphates

    International Nuclear Information System (INIS)

    Sokhina, L.P.; Rovnyj, S.I.; Goncharuk, L.V.

    1988-01-01

    Neptunium and plutonium coprecipitation with precipitates of dibutyl phosphates of some elements significant for radiochemical technology is studied. By the ability to coprecipitation of actinides with precipitates of dibutyl phosphates the cations may be arranged in the series Fe > Al > La > ≥ Zr ≥ Th. The composition of neptunium and plutonium mixed precipitates on the basis of iron dibutyl phosphates corresponding to the formula (Me(NO 3 ) 2 Al 2 ) n x · FeA 3 , where Me-neptunium or plutonium, A-anion of dibutyl phosphoric acid, n=1-4, is determined. Solubility of mixed precipitations in nitric acid and carbonate solutions is studied. Mixed precipitations on the basis of iron dibutyl phosphates are found to have the least solubility, their solubility being lower than that of individual compounds of dibutyl phoshates. The mechanism of formation of mixed precipitates is suggested and discussed

  1. Neptunium immobilization and recovery using phase separated glasses

    International Nuclear Information System (INIS)

    Meaker, T.F.

    1997-01-01

    A phase separated (amorphous) glass has been developed which allows very efficient recovery of +4 valence actinides. The total amount of crystal formation in a heat treated vycor-type glass can be controlled with time, temperature and loading. Heat treatments at lower temperatures and for less time inhibit crystal formation while still allowing significant phase separation. If the Thorium loading exceeds 10 weight percent oxide, crystal formation during heat treatment may not be avoided. The total amount of crystal growth has a direct affect on thorium leachability. An increase in crystal formation limits the Th recovery significantly. High thorium loaded glasses (15 weight percent) with heat treatments (increased crystal formation) leach at approximately the same rate as non-heat treated glasses. A phase separated (amorphous) glass has been produced using thorium as a surrogate for neptunium. Two different homogeneous vycor compositions targeting 10 and 15 weight percent thorium oxide have been processed, heat treated and leached with concentrated nitric acid at 110 degrees C. Thorium recovery rates have been shown to be considerably better when the glass has been heat treated inducing phase separation that is relatively crystal free. Non-heat treated and crystalline (due to heat treatment) glasses have similar Th recovery rates with respect to surface area. Phase separated amorphous samples were found to have significantly higher thorium concentrations in the leachate compared to non-heat treated and crystalline glasses for all mesh sizes. All glasses had increased thorium concentration in the leachate as surface area increased

  2. Neptunium-the neglected actinide: a review of the biological and environmental literature

    International Nuclear Information System (INIS)

    Thompson, R.C.

    1982-01-01

    Data from 89 references relating to the biological and environmental behavior of neptunium are reviewed with particular attention to the potential risks from possible releases of neptunium isotopes by the nuclear industry. The behavior of neptunium differs in many significant respects from that of other transuranic elements. It is more mobile environmentally and more readily absorbed by man, although some of the higher reported values for gastrointestinal absorption appear to have been influenced by the very high mass levels of 237 Np required for experimental study. In studies with experimental animals its ratio of deposition in bone/liver is greater than that of other transuranic elements. Its long-term toxicity in experimental animals is similar to that of other transuranics

  3. Investigation of separation factors of neptunium and plutonium in the process of mass transfer through liquid impregnated membranes with di-2-ethylhexylphosphoric acid

    International Nuclear Information System (INIS)

    Novikov, A.P.; Mikheeva, M.N.; Myasoedov, B.F.

    1990-01-01

    Kinetics of joint transfer of neptunium(6) and plutonium(4) through liquid membranes with di-2-ethylhexylphosphoric acid, depending on the concentration of the carrier, nature of reextracting agent and ratio of metal concentrations, was investigated. The optimal conditions for selective isolation of microimpurity of one of the elements from solutions of the other were determined. Solution of ammonium carbonate with carrier concentration of 0.1-0.2 mol/l can be expediently utilized as reextracting phase for neptunium impurity removal

  4. A study of specific sorption of neptunium(V) on smectite in low pH solution

    International Nuclear Information System (INIS)

    Kozai, Naofumi; Ohnuki, Toshihiko; Matsumoto, Junko; Banba, Tsunetaka; Ito, Yoshimoto

    1996-01-01

    The 'specific sorption' of neptunium(V) on smectite, in other words, a strong sorption undesorbable by 1 M KCl, is studied with a combination of batch type sorption and desorption experiments over a pH range of 2 to 5. Six types of homoionic smectite (Li-, Na-, K-, Cs-, Mg-, and Ca-smectite) are used in this study. Distribution coefficients (K d ) of neptunium for smectite vary over a wide pH range; the maximum K d value of ∝300 cm 3 x g -1 at around pH 2 for Li- and Na-smectite and the minimum value of ∝2 cm 3 x g -1 for Cs-smectite. The specific sorption of neptunium depends on pH and on the affinity of the exchangeable cation for smectite; the lower the pH of solution or the affinity, the larger the specific sorption. The neptunium-smectite association varies with the elapse of contact time. Within the first day of the neptunium-smectite contact the neptunium sorbed on na-smectite at low pH is desorbable by 1 M KCl solution, and on the passage of time most of the neuptunium sorbed becomes undesorbable by KCl (the specific sorption). Hydronium ion in solution is sorbed on smectite at low pH and dissociates the exchangeable cation from smectite into solution, and the specific sorption of neuptunium increases with increasing the exchangeable cation that is dissociated from smectite. (orig.)

  5. An assessment of the thermodynamic behaviour of neptunium in water and model groundwaters from 25 to 150 degrees C

    International Nuclear Information System (INIS)

    Lemire, R.J.

    1984-03-01

    Standard molal Gibbs energy of formation and entropy data for simple neptunium solids and aqueous neptunium complexes with OH - , Cl - , F - , CO 3 2- , PO 4 3- , SO-4 2- and Na + have been critically reviewed. Selected values are used with estimated heat capacity values to derive self-consistent analytical expressions for the temperature dependence of the standard molal Gibbs energies of formation of the species from 25 to 150 degrees C. The Gibbs energies have been used to evaluate the effect of different concentrations of ligands on the solubility of neptunium solids as a function of temperature. Potential-pH diagrams are given for neptunium in pure water and in two model groundwaters. Important deficiencies in the available thermodynamic data for neptunium species are discussed

  6. Determination of microamounts of neptunium by differential pulse polarography

    International Nuclear Information System (INIS)

    Cauchetier, Ph.

    1979-01-01

    Neptunium is produced in significant amounts in the ''light-water'' reactors and must be controlled at different steps of fuel reprocessing. For this purpose a method of differential pulse polarography has been developed. A tight cell containing 10 ml solution is set up in a Faraday cage. Adjustment to the tetravalent state, Np(IV), is carried out electrochemically on a mercury layer and the Np(IV) concentration is determined by differential pulse polarography, using a dropping mercury electrode. In 0.5M sulfuric acid medium, the redox potential of the reversible couple Np(IV)/Np(III) is -0.3 V/SCE. Concentrations as low as 5x10 -7 M neptunium can be measured and detection at the 2x10 -7 M level is still possible (0.5 μg in the polarographic cell). Precision is about 2% in the 10 -5 M and 10% in the 10 -6 M range. The method has been applied to aqueous and organic (TBP-dodecane) solutions. Neptunium can be determined without separation in the presence of plutonium or uranium at M/Np ratios of 10 3 and 5x10 4 , respectively. In the presence of fission products a separation is needed. (author)

  7. Determination of microamounts of neptunium by differential pulse polarography

    International Nuclear Information System (INIS)

    Cauchetier, P.

    1978-01-01

    Neptunium is produced in significant amounts in the light water reactors and must be controlled at different steps of the fuel reprocessing. For this purpose, a method of differential pulse polarography was developed. A tight cell containing 10 ml of solution is set up in a Faraday's cage. Adjustment to the tetravalent state, Np (IV), is carried out electrochemically on a mercury layer and the Np (IV) concentration is determined by differential pulse polarography, using a dropping mercury electrode. In 0,5 M sulfuric acid medium, the redox potential of the reversible system Np (IV)/Np (III) is - 0,3 V/SCE. Concentrations as low as 5.10 -7 M of neptunium can be measured and detection at the 2.10 -7 M level is still possible (0,5 μg in the polarographic cell). Precision is about 2% in the 10 -5 M and 10% in 10 -6 M range. The method has been applied to the case of aqueous and organic (TBP dodecane) solutions. Neptunium can be determined without separation in the presence of plutonium or uranium in the M/Np ratios of 10 3 and 5.10 4 respectively. In the presence of fission products a separation is needed

  8. Solubility product of tetravalent neptunium hydrous oxide and its ionic strength dependence

    Energy Technology Data Exchange (ETDEWEB)

    Fujiwara, K.; Mori, T. [Japan Nuclear Cycle Development Institute (JNC), 4-33, Muramatsu, Tokai-mura, Naka-gun, Ibaraki-ken, 319-1194 (Japan); Kohara, Y. [Inspection and Development Company, 4-33, Muramatsu, Tokaimura, Naka-gun, Ibaraki-ken, 319-1112 (Japan)

    2005-07-01

    Full text of publication follows: Solubility products (K{sub sp}) are key parameters in the context of reliable assessment of actinides migration in the repository conditions of high level radioactive waste. Neptunium (Np(IV)) is one of the most important actinide elements in the assessment, because of its inventory and the long half-life. A few previous data for Np(IV) solubility are varied widely due to experimental difficulties related to the extremely low solubility. We carried out batch-type experiments under nitrogen atmosphere using a glovebox. Np(V) was reduced to Np(III) by bubbling 0.5 ppm H{sub 2} / N{sub 2} gas through the solution for 30 days in the presence of platinum black as catalyst. After reducing treatment, the Np(III) converted to Np(IV) by auto-oxidation within approximately three days. The solubilities of the Np(IV) were measured in the pHc ranging from 2 to 4, at room temperature (23 {+-} 2 deg. C), in ionic strength(I) = 0.1, 0.5, 1.0 and 2.0 M NaClO{sub 4}. The equilibrium condition was confirmed by over-saturation and under-saturation method. After the equilibrium, the pH{sub c} and the E{sub h} value of the suspension were measured. The suspension was then filtered using a filter with a NMWL of 3000 (less than 2 nm{phi}). The Np radio activity in the filtrate was determined by alpha spectrometry and absorption spectra of Np(IV). The solubility decreased with increasing pHc and the hydrolysis species are predominantly formed. From the obtained results, the solubility products (K{sub sp}) of Np hydroxide, for the reaction, NpO{sub 2} . xH{sub 2}O {r_reversible} Np{sup 4+} + 4OH{sup -} + (x-2)H{sub 2}O, at I = 0.1, 0.5, 1.0 and 2.0 were determined by using formation constants ({beta}{sub n}(I)), which were determined for the reaction, Np{sup 4+} + nOH{sup -} {r_reversible} Np(OH){sub n}{sup (4-n)+}. By using the specific interaction theory (SIT), the solubility product of tetravalent Np hydrous oxide is calculated to be log K{sub sp}{sup 0

  9. Kinetics of the reaction between plutonium (4) and neptunium (4) in nitric acid solution

    Energy Technology Data Exchange (ETDEWEB)

    Koltunov, V S; Zhuravleva, G I; Marchenko, V I

    1976-01-01

    The kinetics of the oxidation of neptunium(IV) to neptunium(V) by tetravalent plutonium ions in solutions of HNO/sub 3/ + NaNO/sub 3/ at constant (..mu.. = 2) and variable (..mu.. = 0.7-2.0) ionic strengths of the solution was investigated by a spectrophotometric method. It was established that in the range of concentrations (Np(IV)) = (4.25-10.6) x 10/sup 13/; (Pu(IV)) = (2.6-3.9)x10/sup -3/ M; (H/sup +/) 0.37-1.91 M, a first order is observed with respect to the reagents, while the order of the reaction with respect to H/sup +/ ions is equal to -3. The average value of the true rate constant of the reaction is k = 27.9+-1.3 M/sup 2/xmin/sup -1/ at ..mu..=2 and 39/sup 0/C. It was shown that with increasing analytical concentration of HNO/sub 3/ and NO/sub 3//sup -/ ions (in a mixture of HNO/sub 3/ +HClO/sub 4/), the value of K decreases. On the basis of an invetigation of the dependence of the reaction rate on the temperature in the interval 31-44.8/sup 0/, we calculated the values of the energy (E = 34.6 kcal/mole), enthalpy (..delta..H* = 34 kcal/mole), free energy (..delta..F* = 19.6 kcal/mole, entropy (..delta..S* = 49 entropy units) of activation of the reaction and the formal ionic entropy of the activated complex (PuOOHNp/sup 5 +/)*, S* = -87 entropy units. A reaction mechanism including an interaction of hydrolyzed neptunium and plutonium ions as the rate-determining step was proposed and discusses. The results obtained are compared with data for this reaction in perchloric acid wolution and for other similar redox reactions.

  10. Speciation and solubility of neptunium in underground environments by paper electrophoresis

    International Nuclear Information System (INIS)

    Nagasaki, S.; Tanaka, Satoru; Takahashi, Yoichi

    1988-01-01

    Speciation and solubility of neptunium were studied using paper electrophoresis, ion exchange and ultrafiltration. Among these methods, the paper electrophoresis was found to be suitable for measuring speciation and solubility of neptunium of low concentration, if chemical species had opposite charge to each other or dissolved species had a charge. Using paper electrophoresis, hydrolysis constants of NpO 2 OH 0 and NpO 2 - (OH) 2 - and solubility product of NpO 2 were obtained and ionic-strength dependence of speciation was observed. (author) 9 refs.; 3 figs.; 2 tabs

  11. Electrochemical determination of the oxidation potentials and the thermodynamic stability of the valence states of the transuranium elements in aqueous alkaline media

    International Nuclear Information System (INIS)

    Peretrukhin, V.F.; Spitsyn, V.I.

    1982-01-01

    The oxidation potentials of neptunium, plutonium, and americium in the valance states from (III) to (VII) have been determined experimentally in 0.1-15 M NaOH. Heptavalent plutonium and americium are thermodynamically able to oxidize water with the evolution of oxygen in 0.1-15 M NaOH, neptunium(VII) in 0.1-7 M NaOH. All valance states of plutonium resist disproportionation in alkaline solutions; in the case of neptunium and americium only one disproportionation reaction is possible; of the hexavalent state in to penta- and heptavalent states. The degree of completion of the reaction can be calculated accurately from the oxidation potentials determined

  12. Assessment of the thermodynamic behavior of neptunium in water and model groundwaters from 25 to 150/sup 0/C

    Energy Technology Data Exchange (ETDEWEB)

    Lemire, R J

    1984-03-15

    Standard molal Gibbs energy of formation and entropy data for simple neptunium solids and aqueous neptunium complexes with OH/sup -/, Cl/sup -/, F/sup -/, CO/sub 3//sup 2 -/, PO/sub 4//sup 3 -/, SO/sub 4//sup 2 -/ and Na/sup +/ have been critically reviewed. Selected values are used with estimated heat capacity values to derive self-consistent analytical expressions for the temperature dependence of the standard molal Gibbs energies of formation of the species from 25 to 150/sup 0/C. The Gibbs energies have been used to evaluate the effect of different concentrations of ligands on the solubility of neptunium solids as a function of temperature. Potential-pH diagrams are given for neptunium in pure water and in two model groundwaters. Important deficiencies in the available thermodynamic data for neptunium species are discussed. 90 references, 12 figures, 6 tables.

  13. Partitioning and recovery of neptunium from high level waste streams of PUREX origin using 30% TBP

    International Nuclear Information System (INIS)

    Mathur, J.N.; Murali, M.S.; Balarama Krishna, M.V.; Iyer, R.H.; Chitnis, R.R.; Wattal, P.K.; Theyyunni, T.K.; Ramanujam, A.; Dhami, P.S.; Gopalakrishnan, V.

    1995-01-01

    237 Np is one of the longest-lived nuclides among the actinides present in the high level waste solutions of reprocessing origin. Its separation, recovery and transmutation can reduce the problem of long term storage of the vitrified waste to a great extent. With this objective, the present work was initiated to study the extraction of neptunium into TBP under the conditions relevant to high level waste, along with uranium and plutonium by oxidising it to hexavalent state using potassium dichromate and subsequently recovering it by selective stripping. Three types of simulated HLW solutions namely sulphate bearing (SB), with an acidity of ∼ 0.3 M and non-sulphate wastes originating from the reprocessing of fuels from pressurised heavy water reactor (PHWR) and fast breeder reactor (FBR) with acidities of 3.0 M HNO 3 were employed in these studies. The extraction of U(VI), Np(VI) and Pu(VI) was very high for PHWR- and FBR-HLW solutions, whereas for the SB-HLW solution, these values were less but reasonably high. Quantitative recovery of neptunium and plutonium was achieved using a stripping solution containing 0.1 M H 2 O 2 and 0.01 M ascorbic acid at an acidity of 2.0 M. Since, cerium present in the waste solutions is expected to undergo oxidation in presence of K 2 Cr 2 O 7 , its extraction behaviour was also studied under similar conditions. Based on the results, a scheme was formulated for the recovery of neptunium along with plutonium and was successfully applied to actual high level waste solution originating from the reprocessing of research reactor fuels. (author). 19 refs., 2 figs., 17 tabs

  14. Radionuclide sorption in Yucca Mountain tuffs with J-13 well water: Neptunium, uranium, and plutonium. Yucca Mountain site characterization program milestone 3338

    International Nuclear Information System (INIS)

    Triay, I.R.; Cotter, C.R.; Kraus, S.M.; Huddleston, M.H.

    1996-08-01

    We studied the retardation of actinides (neptunium, uranium, and plutonium) by sorption as a function of radionuclide concentration in water from Well J-13 and of tuffs from Yucca Mountain. Three major tuff types were examined: devitrified, vitric, and zeolitic. To identify the sorbing minerals in the tuffs, we conducted batch sorption experiments with pure mineral separates. These experiments were performed with water from Well J-13 (a sodium bicarbonate groundwater) under oxidizing conditions in the pH range from 7 to 8.5. The results indicate that all actinides studied sorb strongly to synthetic hematite and also that Np(V) and U(VI) do not sorb appreciably to devitrified or vitric tuffs, albite, or quartz. The sorption of neptunium onto clinoptilolite-rich tuffs and pure clinoptilolite can be fitted with a sorption distribution coefficient in the concentration range from 1 X 10 -7 to 3 X 10 -5 M. The sorption of uranium onto clinoptilolite-rich tuffs and pure clinoptilolite is not linear in the concentration range from 8 X 10 -8 to 1 X 10 -4 M, and it can be fitted with nonlinear isotherm models (such as the Langmuir or the Freundlich Isotherms). The sorption of neptunium and uranium onto clinoptilolite in J-13 well water increases with decreasing pH in the range from 7 to 8.5. The sorption of plutonium (initially in the Pu(V) oxidation state) onto tuffs and pure mineral separates in J-13 well water at pH 7 is significant. Plutonium sorption decreases as a function of tuff type in the order: zeolitic > vitric > devitrified; and as a function of mineralogy in the order: hematite > clinoptilolite > albite > quartz

  15. Magnetic and electronic properties of Neptunium chalcogenides from GGA + U + SOC and DFT investigations

    Energy Technology Data Exchange (ETDEWEB)

    Khan, Wilayat [New Technologies – Research Center, University of West Bohemia, Univerzitni 8, 306 14 Pilsen (Czech Republic); Goumri-Said, Souraya, E-mail: sosaid@alfaisal.edu [College of Science, Physics Department, Alfaisal University, Riyadh 11533 (Saudi Arabia)

    2017-06-15

    Highlights: • Electronic and magnetic properties of Neptunium chalcogenides were explored theoretically using DFT approach. • Spin orbit coupling and GGA + U approach described successfully the f–f coupling. • Np{sub 2}X{sub 5} ate metallic with high magnetic character due to the Neptunium. • Fermi surfaces of Np{sub 2}Te{sub 5} have shown a greater electrical conductivity compared to Np{sub 2}Se{sub 5} and Np{sub 2}S{sub 5}. - Abstract: First-principles calculations techniques were employed to explore the structural, electronic and magnetic properties of Neptunium chalcogenides (Np{sub 2}X{sub 5}, X = S, Se and Te). No experimental or theoretical studies of their physical properties have been previously reported in the literature. The presence of highly localized f states has requested the employment of the spin orbit coupling and GGA + U approach in order to describe correctly the f–f coupling. Np{sub 2}X{sub 5} was found metallic with high magnetic character due to the Neptunium presence. Fermi surfaces of Np{sub 2}Te{sub 5} have shown a greater electrical conductivity compared to Np{sub 2}Se{sub 5} and Np{sub 2}S{sub 5}. The magnetic moment was found to be between 13.24 and 13.92μ{sub B}, principally induced by Np f and d-orbitals as well as the spin-polarization of the chalcogenes (Te, Se, S) induced by Np. Neptunium chalcogenides have shown interesting magnetic properties and should be manipulated with precaution due to their radioactive properties.

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

    Science.gov (United States)

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

    2015-03-28

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

  17. OXIDATION OF TRANSURANIC ELEMENTS

    Science.gov (United States)

    Moore, R.L.

    1959-02-17

    A method is reported for oxidizing neptunium or plutonium in the presence of cerous values without also oxidizing the cerous values. The method consists in treating an aqueous 1N nitric acid solution, containing such cerous values together with the trivalent transuranic elements, with a quantity of hydrogen peroxide stoichiometrically sufficient to oxidize the transuranic values to the hexavalent state, and digesting the solution at room temperature.

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

    International Nuclear Information System (INIS)

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

    2016-01-01

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

  19. Combined transuranic-strontium extraction process

    Science.gov (United States)

    Horwitz, E. Philip; Dietz, Mark L.

    1992-01-01

    The transuranic (TRU) elements neptunium, plutonium and americium can be separated together with strontium from nitric acid waste solutions in a single process. An extractant solution of a crown ether and an alkyl(phenyl)-N,N-dialkylcarbanylmethylphosphine oxide in an appropriate diluent will extract the TRU's together with strontium, uranium and technetium. The TRU's and the strontium can then be selectively stripped from the extractant for disposal.

  20. Determination of neptunium in soil by ICP-MS

    International Nuclear Information System (INIS)

    Ayranov, M.; Kraehenbuehl, U.

    2005-01-01

    A fast and simple method for the determination of 237 Np in soil is presented. The borate fusion decreases the sample pre-treatment time and a TEVA extraction chromatography separates neptunium from uranium and the interfering matrix components. A comparison of the sensitivities of alpha spectrometry and sector field ICP-MS for determination of 237 Np is presented. (orig.)

  1. Application of extraction chromatography to the recovery of neptunium, plutonium and americium from an industrial waste

    International Nuclear Information System (INIS)

    Madic, C.; Kertesz, C.; Sontag, R.; Koehly, G.

    1980-01-01

    A pilot scale investigation was made to evaluate the possible application of the extraction chromatographic method (LLC) to the partitioning of alpha emitters from liquid wastes containing traces of transuranium elements. A secondary purpose was to obtain pure Am0 2 , which is used to produce alpha, gamma, and neutron sources. The process developed for alpha partitioning consists essentially of the extraction of macro amounts of uranium with 30% TBP in dodecane in mixer-settlers, then coextraction of Np-237, Pu-239, and Am-241 by LLC on a macro column filled with di-n-hexyl-octoxy-methyl-phosphine oxide (POX.11) adsorbed on an inert support. In each run about 200 liters of initial waste are decontaminated of alpha emitters. The loading step is followed by selective elution of americium, neptunium, and plutonium. The americium eluate is then subjected to the following operations: (1) separation of Am from Fe and Cd by LLC on a TBP column and (2) separation of Am from lanthanide traces by LLC on an HD(DiBM)P column after oxidation of Am(III) to Am(VI). The Am in the eluate is subsequently reduced to Am(III) and precipitated as oxalate with oxalic acid. The oxalate is then filtered and calcined to yield pure AmO 2

  2. Study of extraction chromatography methods of separation of neptunium and its radiometric determination

    International Nuclear Information System (INIS)

    Reich, M.

    2009-04-01

    elution solutions for securing the highest recovery of 239 Np were tested. Isolated 239 Np is suitable as a tracer for the determination of recovery of 237 Np after separation from environmental samples. This method is suitable for preparation of 239 Np generator because the radioactive equilibrium of mother radionuclide/daughter radionuclide occurs after relatively short period of time (33.6 d.). 5. The separation procedure was optimized in order to particular steps followed without useless steps like for example evaporation of solvent solution and subsequent change of chemical composition of system. 6. The scheme was optimised for reaching the highest recovery of separation 237 Np from matrix of model solution of known composition. The matrix of soils is complicated and recovery of 237 Np in separation process lower, but in measured alpha spectrum peaks coming from interfering radionuclides were not observed. The mass of soil sample for analyses influence the salinity of solution which caused decreasing the yield of 237 Np due to competing effect in separation process. 7 .The optimal composition of elution solution used in separation procedure was 0.5 mol.dm -3 HCI - 0.02 mol · dm -3 HF. This solution is compatible with solution suitable for preparation of sample for measuring of alpha activity by alpha spectrometry. It was not necessary to change solution for alpha sample preparation. 8. Dependencies of recoveries of neptunium separation from mass of soil sample and mass of present iron in model solution were observed. Increasing mass of soil sample and mass of iron in the model solution causes decreasing of the recoveries of neptunium. (author)

  3. Absorption, distribution, and fate of neptunium in plants

    International Nuclear Information System (INIS)

    Cataldo, D.A.; Garland, T.R.; Wildung, R.E.

    1988-01-01

    Soil-plant concentration ratios (CR) for neptunium (Np) in bushbean, measured over the range of 5.2 /times/ 10/sup /minus/7/ to 4.1 mg of Np/g of soil, are approximately 2 at soil concentrations below 4 /times/ 10/sup /minus/4/ mg/g and increase to 12 at higher soil levels. The CR values determined for soybean, bushbean, barley, and alfalfa range from 0.5 to 4 at a soil concentration of 2.6 /times/ 10/sup /minus/6/ mg/g. Root absorption by soybean seedlings of Np from solutions containing 7 /times/ 10/sup /minus/7/ to 473 mg of Np(V)/mL is generally proportional to concentration but exhibits some saturation in root absorption at higher concentrations. Seed concentrations in bushbean and wheat are a factor of 10 lower than vegetative tissues. Neptunium is transported within the plant in organic complexes containing one or more organic acid residues. Fractionation of plant tissues indicates that Np is substantially more soluble than plutonium, especially in seeds, with approximately 50% of the soluble Np in roots and leaves associated with plant ligands of less than 5000 molecular weight

  4. The XPS study of physical and chemical forms of neptunium group on the surface of minerals

    Directory of Open Access Journals (Sweden)

    Teterin Anton Yu.

    2010-01-01

    Full Text Available The sorption behavior and the physical and chemical forms of neptunium on the surface of minerals of the two chlorate samples, biotite and kaolin, with different contents of Fe(II was studied. The liquid-liquid extraction and the X-ray photoelectron spectroscopy were employed to identify the valence forms of neptunium. On the basis of the obtained data the quantitative elemental composition of the surface of the studied minerals, as well as the ionic composition of the formed neptunium complexes was determined. It was shown that the Np(IV and Np(VI containing compounds did not form, while the complexes Np(VO+ -hydroxyl did form on the surface. The oxygen ions bonded with iron and oxygen belonging to water and/or of carboxyl were suggested to be present in the equatorial plane of the neptunyl group NpO+.

  5. Selective leaching studies of deep-sea sediments loaded with americium, neptunium and plutonium

    International Nuclear Information System (INIS)

    Cole, T.G.; Higgo, J.J.W.; Cronan, D.S.; Rees, L.V.C.

    1984-07-01

    A series of selective leaching experiments were undertaken to investigate the solid phase speciation and distribution of americium, neptunium and plutonium which had been experimentally loaded onto different marine sediment types. The chemical leaches employed showed rather poor selectivity but certain trends were evident. Adsorption was not by ion exchange. Americium showed a preferential affinity for carbonate and plutonium for organic matter. Neptunium appeared to have no preferential affinities. Americium was sorbed by acetic acid residues (CaCO 3 removed) and by unleached carbonate-rich sediments with equal efficiency. This indicates that it is able to diversify its solid phase affinity/distribution depending upon which solid phases are available. (author)

  6. Processing of irradiated, enriched uranium fuels at the Savannah River Plant

    Energy Technology Data Exchange (ETDEWEB)

    Hyder, M L; Perkins, W C; Thompson, M C; Burney, G A; Russell, E R; Holcomb, H P; Landon, L F

    1979-04-01

    Uranium fuels containing /sup 235/U at enrichments from 1.1% to 94% are processed and recovered, along with neptunium and plutonium byproducts. The fuels to be processed are dissolved in nitric acid. Aluminum-clad fuels are disssolved using a mercury catalyst to give a solution rich in aluminum. Fuels clad in more resistant materials are dissolved in an electrolytic dissolver. The resulting solutions are subjected to head-end treatment, including clarification and adjustment of acid and uranium concentration before being fed to solvent extraction. Uranium, neptunium, and plutonium are separated from fission products and from one another by multistage countercurrent solvent extraction with dilute tri-n-butyl phosphate in kerosene. Nitric acid is used as the salting agent in addition to aluminum or other metal nitrates present in the feed solution. Nuclear safety is maintained through conservative process design and the use of monitoring devices as secondary controls. The enriched uranium is recovered as a dilute solution and shipped off-site for further processing. Neptunium is concentrated and sent to HB-Line for recovery from solution. The relatively small quantities of plutonium present are normally discarded in aqueous waste, unless the content of /sup 238/Pu is high enough to make its recovery desirable. Most of the /sup 238/Pu can be recovered by batch extraction of the waste solution, purified by counter-current solvent extraction, and converted to oxide in HB-Line. By modifying the flowsheet, /sup 239/Pu can be recovered from low-enriched uranium in the extraction cycle; neptunium is then not recovered. The solvent is subjected to an alkaline wash before reuse to remove degraded solvent and fission products. The aqueous waste is concentrated and partially deacidified by evaporation before being neutralized and sent to the waste tanks; nitric acid from the overheads is recovered for reuse.

  7. Processing of irradiated, enriched uranium fuels at the Savannah River Plant

    International Nuclear Information System (INIS)

    Hyder, M.L.; Perkins, W.C.; Thompson, M.C.; Burney, G.A.; Russell, E.R.; Holcomb, H.P.; Landon, L.F.

    1979-04-01

    Uranium fuels containing 235 U at enrichments from 1.1% to 94% are processed and recovered, along with neptunium and plutonium byproducts. The fuels to be processed are dissolved in nitric acid. Aluminum-clad fuels are disssolved using a mercury catalyst to give a solution rich in aluminum. Fuels clad in more resistant materials are dissolved in an electrolytic dissolver. The resulting solutions are subjected to head-end treatment, including clarification and adjustment of acid and uranium concentration before being fed to solvent extraction. Uranium, neptunium, and plutonium are separated from fission products and from one another by multistage countercurrent solvent extraction with dilute tri-n-butyl phosphate in kerosene. Nitric acid is used as the salting agent in addition to aluminum or other metal nitrates present in the feed solution. Nuclear safety is maintained through conservative process design and the use of monitoring devices as secondary controls. The enriched uranium is recovered as a dilute solution and shipped off-site for further processing. Neptunium is concentrated and sent to HB-Line for recovery from solution. The relatively small quantities of plutonium present are normally discarded in aqueous waste, unless the content of 238 Pu is high enough to make its recovery desirable. Most of the 238 Pu can be recovered by batch extraction of the waste solution, purified by counter-current solvent extraction, and converted to oxide in HB-Line. By modifying the flowsheet, 239 Pu can be recovered from low-enriched uranium in the extraction cycle; neptunium is then not recovered. The solvent is subjected to an alkaline wash before reuse to remove degraded solvent and fission products. The aqueous waste is concentrated and partially deacidified by evaporation before being neutralized and sent to the waste tanks; nitric acid from the overheads is recovered for reuse

  8. Transport of neptunium through Yucca Mountain tuffs

    International Nuclear Information System (INIS)

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

    1993-01-01

    Neptunium has a high solubility in groundwaters from Yucca Mountain [1]. Uranium in nuclear reactors produces 237 Np which has a half-life of 2.1 4 x 10 6 years. Consequently, the transport of 237 Np through tuffs is of major importance in assessing the performance of a high-level nuclear waste repository at Yucca Mountain. The objective of this work is to determine the amount of Np retardation that is provided by the minerals in Yucca Mountain tuffs as a function of groundwater chemistry

  9. Simulation study of the chemical forms of neptunium and plutonium in groundwater from a borehole in the northwest region

    International Nuclear Information System (INIS)

    Ma Yingming; Jin Yuren; Wang Zhiqiang; Liu Dongxu; Liu Wei; Liu Yan

    2009-01-01

    According to physics-chymistry characteristic of groundwater from a borehole in the northwest region, we performed simulation study of the chemical forms of neptunium and plutonium by the geochemistry modeling program EQ3/6. The main conclusions are as follows: the main chemical form of neptunium in the groundwater is Np(V)'s NpO 2 + , subordination chemical forms are NpO 2 Cl, NpO 2 CO 3 - , NpO 2 OH, NpO 2 SO 4 - ; the main existing form of plutonium in the groundwater is Pu(IV)'s Pu(OH)5-and subordination chemical form is Pu(V)'s PuO 2 + . In addition,the temperature, pH and Eh also have different impacts on the chemical form of neptunium and plutonium. (authors)

  10. Forefront of PUREX system engineering. Chemistry and engineering of ruthenium, technetium and neptunium

    International Nuclear Information System (INIS)

    2004-07-01

    The paper reports the activity of the research committee organized by the Atomic Energy Society of Japan on 'Ruthenium and Technetium Chemistry in the PUREX System', with focusing on basic behaviors of ruthenium, technetium and neptunium in the PUREX process, the principles of plant design, and behaviors during the final waste treatment. The scope of the work includes the following major topics: (1) basic solution and solid-state chemistry; (2) basic solution and solid-state chemistry of minor actinides in particular, Np; (3) partitioning chemistry in the PUREX system and environmental behavior of the components; (4) processes of recovery, purification, and utilization of rare metal fission products; (5) field data on plant design, operation, decontamination, and decommissioning; (6) numerical process simulations and process control technologies; (7) compilation of a data base for process chemistry and plant engineering. (S. Ohno)

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

    International Nuclear Information System (INIS)

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

    1984-01-01

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

  12. Spectrophotometric study of neptunium (VI) complexation by nitrate ions; Etude par spectrophotometrie de la complexation du neptunium au degre d'oxydation (VI) par les ions nitrates

    Energy Technology Data Exchange (ETDEWEB)

    Pochon, P. [CEA/VALRHO - site de Marcoule, Dept. de Recherche en Retraitement et en Vitrification (DRRV), 30 - Marcoule (France)]|[Conservatoire National des Arts et Metiers (CNAM), 75 - Paris (France)]|[Centre Regional Associe de Lyon, 69 (France)

    2000-07-01

    Neptunium(VI) complexation by nitrate ions was investigated by visible and near-infrared spectrophotometry, a technique suitable for observing the appearance and evolution of the species in solution. In the absence of reference spectra for Np(VI) nitrate- complexes, mathematical (factor analysis) tools were used to interpret the spectra. These chemo-metric techniques were first tested and validated on a simpler chemical system: Np(VI)complexation by the SiW{sub 11}O{sub 39}{sup 8-} anion. The test media used to investigate Np(VI) nitrate- complexes generally contain nitrate and perchlorate salts at high concentrations (high ionic strength). Media effects arising from the presence of cations, acidity or the perchlorate ion concentration are therefore significant, and no doubt account for the scattered values of the complexation constants published in the literature. The evolution of the neptunium spectra according to the parameters of the reaction medium illustrated these effects and allowed them to be quantified by a global 'perturbation constant'. In order to minimize the spectrum modifications due to media effects, the neptunium nitrate-complexes were studied at constant ionic strength in weak acidic media (2 mol.kg{sup -1}{sub H2O}) in the presence of sodium salts. The bulk formation constants and the spectrum of the NpO{sub 2}(NO{sub 3}){sup +} complex were determined for ionic strength values of 2.2, 4, 6 and 8 mol.kg{sup -1}{sub H2O}. The constants remained on the same order of magnitude regardless of the ionic strength; the thermodynamic constant {beta}{sub 1}{sup 0} determined from them according to specific interaction theory is thus probably of little significance. Conversely, the bulk constants can be corrected for the effects of the perchlorate ions by taking the global 'perturbation constant' into account. (author)

  13. Gastrointestinal absorption and retention of neptunium by fasted and fed mice

    International Nuclear Information System (INIS)

    Larsen, R.P.; Bhattacharyya, M.H.; Oldham, R.D.; Moretti, E.S.

    1982-01-01

    The retention of neptunium in liver and bone subsequent to its gastrointestinal absorption has been determined in both fasted and fed mice. The values obtained for fractional retention were 3 x 10 - 3 and 1 x 10 - 4 , respectively, and are within a factor of two the same as those for plutonium in fasted and fed mice

  14. Neptunium control in co-decontamination step of purex process

    International Nuclear Information System (INIS)

    Zhang Zefu; He Jianyu; Zhu Zhaowu; Ye Guoan; Zhao Zhiqiang

    2002-01-01

    A new alternative method for separation of Np in the first co-decontamination step is proposed. It comprises two steps, namely, preconditioning of Np valence state in the dissolved solution of spent fuel by NO gas bubbling in HNO 3 medium to produce HNO 2 , which is considered as salt-free process to convert Np(VI) to Np(V) and stabilization of Np(V) with urea, finally, the demonstrative counter current cascade extraction of Np(IV) and Np(V) in a miniature mixer-settler was carried out. The batch experiments show that Np(V) produced after conditioning may be slowly oxidized again to Np(VI) during standing time. Addition of urea in the HNO 3 solution might enhance the stability of Np(V). On the other hand, the solvent extraction by 30% TBP/kerosene could greatly accelerate the oxidation rate of Np(V). The chemical flow sheet study at 25degC shows that, more than 98% of Np could be routed into HLLW if urea is added in the HNO 3 solution. The operating temperature has great influence on the kinetics of Np(V) oxidation. If operation temperature races to 36degC and urea is not added, about 38% of Np will go along with U and Pu into organic phase. The behavior of Np(IV) during extraction shows great accumulation in the middle stages of battery. (author)

  15. Complexation of neptunium(V) by salicylate, phthalate and citrate ligands in a pH 7.5 phosphate buffered system

    International Nuclear Information System (INIS)

    Rees, T.F.; Daniel, S.R.

    1984-01-01

    Conditional stability constants, enthalpies and entropies of complexation at pH 7.5 and ionic strength 0.1 have been determined for neptunium(V) complexes of phosphate, salicylate, phthalate and citrate. Results are given and discussed. At pH 7.5 salicylate does not form a complex with neptunium(V) due to the low charge density of the NpO 2 + ion and incomplete ionization of the salicylate ion. In all cases, only 1:1 complexes were identified. (U.K.)

  16. Radiation-chemical oxidation of neptunium in perchloric acid solutions

    International Nuclear Information System (INIS)

    Shilov, V.P.; Gusev, Yu.K.; Pikaev, A.K.; Stepanova, E.S.; Krot, N.N.

    1979-01-01

    The γ-radiation effect (at a dose rate of 5x10 16 eV/mlxs) on 1x10 -3 Np(6) and Np(5) perchloric acid solutions is studied. The output of Np(6) loss in aerated 0.001-0.005M HClO 4 solutions was 2.4 ions/100 eV. The output of Np(5) loss in solutions saturated with nitrous oxide was 2.1 ions/100 eV at pH-4. In aerated 0.1-1.0 M HClO 4 solutions in presence of XeO 4 the output of Np(5) loss grows from 6.6 to 13.5 ions/100 eV as (XeO 3 ) 0 increases from 1x10 -3 to 2x10 -2 M. Possible process mechanisms have been proposed

  17. Computer modelling of the chemical speciation of caesium, uranium(VI) and neptunium(V) in human duodenal fluids under fasting conditions

    International Nuclear Information System (INIS)

    Jones, P.W.; Taylor, D.M.; Webb, L.M.; Williams, D.R.

    2002-01-01

    A model simulating the human duodenal contents under physiologically realistic, fasting conditions was developed using the joint expert speciation system (JESS) computer program and database and used to investigate the chemical speciation of caesium, uranium(VI) and neptunium(V). Over the pH range 5.0-9.0, and the concentration range 5x10 -15 -5x10 -5 mol dm -3 , caesium was predicted to occur predominantly as the absorbable free monovalent cation Cs + (∼95%) with species such as CsHPO 4 - and CsCl representing the remainder. The presence or absence of sulphate at 2.1x10 -3 mol dm -3 did not influence the predicted speciation. Uranium was predicted to be present entirely as a soluble, highly charged species, both in the absence and in the presence of sulphate. Between pH 5.0 and ∼6.5 the UO 2 H 2 (PO 4 ) 2 2- predominated, above this pH carbonate species, either UO 2 (CO 3 ) 4 6- or, possibly, UO 2 (CO 3 ) 5 8- . At pH 8.0, and in the presence of sulphate, neptunium(V) was predicted to exist solely as the tetrasulphate species, whilst in the absence of sulphate, an array of negatively charged soluble carbonate species predominated. Studies over the pH range 5.0-9.0 predicted the formation of a spectrum of negatively charged carbonate and phosphate species, ∼40% of the total neptunium was predicted to be present as the electrically net-neutral species NpO 2 HCO 3 at pH6.0, ∼20% at pH 7.0, ∼10% at pH 7.5 and ∼1% at pH 8.0. The observed speciation patterns of uranium and neptunium did not change over the concentration range 5x10 -15 -5x10 -5 mol dm -3 and no solid species were predicted to occur under the conditions simulated. Whether the predicted electrically net-neutral neptunium species or the uranium pentacarbonate species do actually occur under true physiological conditions remains to be established. The observed speciation patterns for caesium and uranium are consistent with the observed absorption of these elements by humans; however, the

  18. Relationships among oxidation-reduction and acid-base properties of the actinides in high oxidation states

    International Nuclear Information System (INIS)

    Morss, L.R.

    1992-01-01

    The first chemical identification of plutonium, its subsequent isolation on the macroscopic scale, and more recent chemical separation schemes were achieved by taking advantage of the differences among the oxidation states of uranium, neptunium, and plutonium. Many acid-base properties modify the relative stabilities of oxidation states of the actinides. In the solid state, strongly basic compounds such as Cs 2 O yield complex oxides with oxidation states of Np(VII), Pu(VI), and Am(VI) whereas more acidic compounds such as CsF yield complex fluorides with lower oxidation states. In aqueous solution, high basicity and strongly covalent complexes favor high oxidation states. In nonaqueous solvent systems, high acidity generally favors low oxidation states. This paper elucidates and attempts to interpret the effects of these acid-base properties in a systematic fashion

  19. HF effect on dissociation kinetics of plutonium and neptunium complexes with 1,2-diaminocyclohexanetetraacetic acid in nitric acid solutions

    International Nuclear Information System (INIS)

    Nikitina, S.A.; Stepanov, A.V.

    1982-01-01

    Dissociation kinetics of Pusup((4)) and Np sup((4)) complexes with DCTA were investigated in HNO 3 solutions in the presence of HF and arsenazo 3. It was found that HF or NaF produced a differentiating effect on the reactivity of the complexes at [HNO 3 ]=1-6 mol/l as well as inhibiting effect at [HNO 3 ]=0.01 mol/l. Conditions of the differential kinetic analysis of plutonium and neptunium in the mixture and differential spectrophotometric analysis of uranium (6) during the camouflage of neptunium (4) and plutonium (4) were determined

  20. Rapid and simultaneous determination of neptunium and plutonium isotopes in environmental samples by extraction chromatography using sequential injection analysis and ICP-MS

    DEFF Research Database (Denmark)

    Qiao, Jixin; Hou, Xiaolin; Roos, Per

    2010-01-01

    plutonium and neptunium in three reference materials were in agreement with the recommended or literature values at the 0.05 significance level. The developed method is suitable for the analysis of up to 10 g of soil and 20 g of seaweed samples. The extraction chromatographic separation within the SI system......This paper reports an automated analytical method for rapid and simultaneous determination of plutonium isotopes (239Pu and 240Pu) and neptunium (237Np) in environmental samples. An extraction chromatographic column packed with TrisKem TEVA® resin was incorporated in a sequential injection (SI...... for a single sample takes less than 1.5 h. As compared to batchwise procedures, the developed method significantly improves the analysis efficiency, reduces the labor intensity and expedites the simultaneous determination of plutonium and neptunium as demanded in emergency actions....

  1. Technetium and neptunium reactions in basalt/groundwater systems

    International Nuclear Information System (INIS)

    Meyer, R.E.; Arnold, W.D.; Kelmers, A.D.; Kessler, J.H.; Clark, R.J.; Johnson, J.S. Jr.; Young, G.C.; Case, F.I.; Westmoreland, C.G.

    1985-01-01

    Sorption isotherms and apparent concentration limits for Tc(VII) and Np(V) for a variety of groundwater/basalt systems were determined using Grande Ronde basalt samples representative of the Hanford Site candidate high-level waste repository. Under oxic redox conditions (air present), little or no sorption of technetium was observed; neptunium exhibited low to moderate sorption ratios. Under anoxic redox conditions (oxygen-free), low to moderate sorption of technetium was often observed, but the extent of sorption was highly dependent upon the groundwater composition and the method of pretreatment (if any) of the basalt. Sorption isotherms for technetium under reducing redox conditions (hydrazine added) indicate an apparent concentration limit of approximately 10 -6 mol/l Tc. No apparent concentration limit was found for neptunium for concentrations in groundwater up to 10 -6 mol/l and 8 x 10 -7 mol/l under oxic and reducing (hydrazine added) redox conditions, respectively. Valence control and valence analysis experiments suggest that the sorption or precipitation of Tc and Np from groundwater in the presence of basalt may result from a heterogeneous reaction occurring on the surface of the basalt. One of the critical factors of this reduction reaction appears to be the accessibility of the reactive ferrous iron component of the basalt. The laboratory simulation of groundwater redox conditions representative of the repository environment through the use of solution phase redox reagents is of questionable validity, and information obtained by such experimental methods may not be defensible for site performance assessment calculations. Anoxic experiments conducted in an argon-filled glove box appear better suited for the laboratory simulation of in situ redox conditions. 15 references, 6 figures

  2. Technetium and neptunium reactions in basalt/groundwater systems

    International Nuclear Information System (INIS)

    Meyer, R.E.; Arnold, W.D.; Kelmers, A.D.; Kessler, J.H.; Clark, R.J.; Johnson, J.S. Jr.; Young, G.C.; Case, F.I.; Westmoreland, C.G.; Florida State Univ., Tallahassee)

    1984-01-01

    Sorption isotherms and apparent concentration limits for Tc(VII) and Np(V) for a variety of groundwater/basalt systems were determined using Grande Ronde basalt samples representative of the Hanford Site candidate high-level waste repository. Under oxic redox conditions (air present), little or no sorption of technetium was observed; neptunium exhibited low to moderate sorption ratios. Under anoxic redox conditions (oxygen-free), low to moderate sorption of technetium was often observed, but the extent of sorption was highly dependent upon the groundwater composition and the method of pretreatment (if any) of the basalt. Sorption isotherms for technetium under reducing redox conditions (hydrazine added) indicate an apparent concentration limit of approximately 10 -6 mol/L Tc. No apparent concentration limit was found for neptunium for concentrations in groundwater up to approx. 10 -6 mol/L and 8 x 10 -7 mol/L under oxic and reducing (hydrazine added) redox conditions, respectively. Valence control and valence analysis experiments suggest that the sorption or precipitation of Tc and Np from groundwater in the presence of basalt may result from a heterogeneous reaction occurring on the surface of the basalt. One of the critical factors of this reduction reaction appears to be the accessibility of the reactive ferrous iron component of the basalt. The laboratory simulation of groundwater redox conditions representative of the repository environment through the use of solution phase redox reagents is of questionable validity, and information obtained by such experimental methods may not be defensible for site performance assessment calculations. Anoxic experiments conducted in an argon-filled glove box appear better suited for the laboratory simulation of in situ redox conditions. 15 refs., 6 tabs

  3. HF effect on dissociation kinetics of plutonium and neptunium complexes with 1,2-diaminocyclohexanetetraacetic acid in nitric acid solutions

    Energy Technology Data Exchange (ETDEWEB)

    Nikitina, S.A.; Stepanov, A.V.

    1982-01-01

    Dissociation kinetics of Pusup((4)) and Np sup((4)) complexes with DCTA were investigated in HNO/sub 3/ solutions in the presence of HF and arsenazo 3. It was found that HF or NaF produced a differentiating effect on the reactivity of the complexes at (HNO/sub 3/)=1-6 mol/l as well as inhibiting effect at (HNO/sub 3/)=0.01 mol/l. Conditions of the differential kinetic analysis of plutonium and neptunium in the mixture and differential spectrophotometric analysis of uranium (6) during the camouflage of neptunium (4) and plutonium (4) were determined.

  4. AN ADVANCED OXIDATION PROCESS : FENTON PROCESS

    Directory of Open Access Journals (Sweden)

    Engin GÜRTEKİN

    2008-03-01

    Full Text Available Biological wastewater treatment is not effective treatment method if raw wastewater contains toxic and refractory organics. Advanced oxidation processes are applied before or after biological treatment for the detoxification and reclamation of this kind of wastewaters. The advanced oxidation processes are based on the formation of powerful hydroxyl radicals. Among advanced oxidation processes Fenton process is one of the most promising methods. Because application of Fenton process is simple and cost effective and also reaction occurs in a short time period. Fenton process is applied for many different proposes. In this study, Fenton process was evaluated as an advanced oxidation process in wastewater treatment.

  5. Training Course of Experimental Chemistry in the Nuclear Fuel Cycle: Solid State and Solution Chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Ju hyeong; Park, Kwangheon; Kim, Tae hoon; Park, Hyoung gyu; Kim, Jisu [Kyunghee University, Yongin (Korea, Republic of); Song, Hyuk jin [Dongguk University, Gyeongju (Korea, Republic of); Lee, Chan ki; Kang, Do kyu; Jeong, Hyeon jun [UNIST, Ulsan (Korea, Republic of)

    2016-10-15

    In this experimental study program in Tohoku University, basic experiments were done by the participants. First one is the hydrogen reduction experiment of the mixture of UO{sub 2} and ZrO{sub 2}. Second one is to observe microscopic structure of solid solution of UO{sub 2} and ZrO{sub 2} using SEM/EDX and XRD system, simulated fuel debris. Third one is milking process of {sup 239}Np from {sup 243}Am by solvent extraction using Tri-n-Octylamine (TOA). Last one is solvent extraction in PUREX by the simulated mixed aqueous solution of U, {sup 85}Sr and {sup 239}Np which is represented minor actinide elements included in the spent nuclear fuel. Uranium is separated from aqueous phase to organic phase during solvent extraction procedure using TBP and dodecane. Also, neptunium can be extracted to organic phase as nitric acid concentration change. The extraction behavior of neptunium is different by oxidation state in aqueous phase. The behavior of neptunium is represented as a combined form of these oxidation states in experiment. Therefore, because the oxidation states of neptunium can be controlled by controlling the concentration of nitric acid, the extractability of neptunium can be controlled.

  6. Neptunium speciation (complexation and redox behaviour) in aqueous citrate medium

    International Nuclear Information System (INIS)

    Bonin, L.; Ansoborlo, E.; Moisy, Ph.

    2005-01-01

    Full text of publication follows: In the framework of the French Environmental Nuclear Toxicology programme, additional experiments related to the decorporation of actinides are planned. The lack of information on the neptunium behaviour within blood and the inefficiency of therapeutic treatments, led us to study the complexation of this element with basic anions. Within this purpose, the in vitro behaviour of Np IV and Np V in simple media simulating biological media was studied: blood plasma is one of the media of interest and it can be simulated, from a chemical point of view, by an aqueous solution with pH 7.4, containing ions such as citrate (1.6 10 -4 mol/L), lactate (1.5 10 -3 mol/L), CO 3 2- (2.5 10 -2 mol/L), PO 4 3- (1.1 10 -3 mol/L), SO 4 2- (3.3 10 -4 mol/L) and Cl - (9 10 -2 mol/L). This study was more specifically focused on the behaviour of neptunium with citrate ion, which is also a basic ligand to consider when one wishes to study the migration of actinides in the environment, since it exists in significant amounts in the ground due to its production by the plants. In order to determine the speciation of this system, spectrophotometry was more particularly used. Concerning the complexation phenomenon, the existence of several complexes of Np V with various acid-basic forms of the citrate anion was observed; regarding Np IV , two complexes, with 1:1 and 1:2 stoichiometry, have been respectively observed. The reactivity of Np VI is probably similar to the behaviour of U VI , which is reported in literature to form a complex with a 1:1 stoichiometry with the Cit 3- anion From the quantitative study of these equilibria, it has been possible to determine the values of various equilibrium constants. Concerning the stability of neptunium towards oxido-reduction, it was confirmed that Np VI was very quickly reduced to Np V by the citrate anions, whereas Np IV was stable. In the case of Np V , it was observed that, depending on the pH and the citrate

  7. Development of analytical methods for the separation of plutonium, americium, curium and neptunium from environmental samples

    Energy Technology Data Exchange (ETDEWEB)

    Salminen, S.

    2009-07-01

    In this work, separation methods have been developed for the analysis of anthropogenic transuranium elements plutonium, americium, curium and neptunium from environmental samples contaminated by global nuclear weapons testing and the Chernobyl accident. The analytical methods utilized in this study are based on extraction chromatography. Highly varying atmospheric plutonium isotope concentrations and activity ratios were found at both Kurchatov (Kazakhstan), near the former Semipalatinsk test site, and Sodankylae (Finland). The origin of plutonium is almost impossible to identify at Kurchatov, since hundreds of nuclear tests were performed at the Semipalatinsk test site. In Sodankylae, plutonium in the surface air originated from nuclear weapons testing, conducted mostly by USSR and USA before the sampling year 1963. The variation in americium, curium and neptunium concentrations was great as well in peat samples collected in southern and central Finland in 1986 immediately after the Chernobyl accident. The main source of transuranium contamination in peats was from global nuclear test fallout, although there are wide regional differences in the fraction of Chernobyl-originated activity (of the total activity) for americium, curium and neptunium. The separation methods developed in this study yielded good chemical recovery for the elements investigated and adequately pure fractions for radiometric activity determination. The extraction chromatographic methods were faster compared to older methods based on ion exchange chromatography. In addition, extraction chromatography is a more environmentally friendly separation method than ion exchange, because less acidic waste solutions are produced during the analytical procedures. (orig.)

  8. Neptunium(V) sorption on quartz and albite in aqueous suspension

    International Nuclear Information System (INIS)

    Kohler, M.; Leckie, J.O.

    1991-10-01

    The behavior of neptunium in the subsurface environment is of interest since neptunium isotopes are included in nuclear waste. Previous work investigated the sorption behavior of Np onto α-Fe 2 O 3 (hematite), an accessory mineral of the Yucca Mountain repository. The work reported herein involves the much more abundant silicate minerals quartz and albite, and is a logical continuation of the ongoing task. In previous work increased sorption was observed in systems containing hematite and EDTA, a ligand which acts as a surrogate for organic complexing agents. In addition, increased partial pressures of CO 2 are common in many ground waters and the effects of carbonate on sorption of radionuclides have to be studied as well. At concentration levels of 10 -7 M, Np(V) does not adsorb strongly on quartz and albite up to pH values of approximately 9 at solid/solution ratios of 30 to 40 g/l. Significant adsorption (> 20%) occurs on both minerals only at pH > 9. Pretreatment of albite affects the sorption behavior of this mineral at pH > 9, possibly due to the formation of secondary mineral phases at the albite surface. EDTA does not adsorb on quartz at concentrations of 10 -6 M. In the presence of 50 μM EDTA, Np(V) sorption seems to be restricted. EDTA at the 10 -6 M level adsorbs onto albite to an appreciable degree at pH values 3 - is the predominant solution species

  9. Structural variability in neptunium(V) oxalate compounds: synthesis and structural characterization of Na2NpO2(C2O4)OH.H2O.

    Science.gov (United States)

    Bean, Amanda C; Garcia, Eduardo; Scott, Brian L; Runde, Wolfgang

    2004-10-04

    Reaction of a (237)Np(V) stock solution in the presence of oxalic acid, calcium chloride, and sodium hydroxide under hydrothermal conditions produces single crystals of a neptunium(V) oxalate, Na(2)NpO(2)(C(2)O(4))OH.H(2)O. The structure consists of one-dimensional chains running down the a axis and is the first example of a neptunium(V) oxalate compound containing hydroxide anions.

  10. Sorption and migration of neptunium in porous sedimentary materials

    International Nuclear Information System (INIS)

    Tanaka, Tadao; Mukai, Masayuki; Nakayama, Shinichi

    2005-01-01

    Column migration experiments of neptunium were conducted for porous sedimentary materials: coastal sand, tuffaceous sand, ando soil, reddish soil, yellowish soil and loess, and migration behavior, sorption mechanisms and chemical formation of Np were investigated. The migration behavior of Np in each material was much different each other, due to chemical formation in solution and/or sorption mechanism of Np. Mathematical models of different concepts were applied to the experimental results to interpret the sorption mechanism and the migration behavior. It can be concluded that both of instantaneous equilibrium sorption and sorption-desorption kinetics have to be considered to model the Np migration in sedimentary materials. (author)

  11. Hydrolysis constants of tetravalent neptunium by using solvent extraction method

    International Nuclear Information System (INIS)

    Fujiwara, K.; Kohara, Y.

    2008-01-01

    The hydrolysis constants of tetravalent neptunium (Np(IV)) were determined by solvent extraction method using thenoyltrifluoroacetone(TTA). In order to avoid colloid formation, a stock solution of carrier-free 239 Np(V) was from 243 Am milked. The valence of Np in the solution was then reduced to Np(IV) by using zinc amalgam. The hydrolysis constants (β m ) of the reactions, Np 4+ + mOH - = Np(OH) m (4-m)+ was evaluated by using distribution ratios at ionic strengths (I) = 0.1, 0.5 and 1.0. All experiments were performed in oxygen-free 0.5% H 2 -N 2 atmosphere (below 1.0 ppm of O 2 ) in a glove-box at room temperature (23 ± 2 C) to avoid oxidation of Np(IV). The β m values were extrapolated to the standard state (I = 0) by using the specific ion interaction theory (SIT), and the formation constants at I = 0 were determined to be log β 1 = 13.91 ± 0.23, log β 2 = 27.13 ± 0.15, log β 3 = 37.70 ± 0.30 and log β 4 = 46.16 ± 0.30. The ion interaction coefficients were also evaluated to be ε(NpOH 3+ , ClO 4 - ) = 0.49 ± 0.15, ε(Np(OH) 2 2+ , ClO 4 - ) = 0.35 ± 0.11, and ε(Np(OH) 3 + , ClO 4 - ) = 0.29 ± 0.15. (orig.)

  12. Neptunium speciation (complexation and redox behaviour) in aqueous citrate medium

    Energy Technology Data Exchange (ETDEWEB)

    Bonin, L.; Ansoborlo, E.; Moisy, Ph. [CEA Marcoule (France)

    2005-07-01

    Full text of publication follows: In the framework of the French Environmental Nuclear Toxicology programme, additional experiments related to the decorporation of actinides are planned. The lack of information on the neptunium behaviour within blood and the inefficiency of therapeutic treatments, led us to study the complexation of this element with basic anions. Within this purpose, the in vitro behaviour of Np{sup IV} and Np{sup V} in simple media simulating biological media was studied: blood plasma is one of the media of interest and it can be simulated, from a chemical point of view, by an aqueous solution with pH 7.4, containing ions such as citrate (1.6 10{sup -4} mol/L), lactate (1.5 10{sup -3} mol/L), CO{sub 3}{sup 2-} (2.5 10{sup -2} mol/L), PO{sub 4}{sup 3-} (1.1 10{sup -3} mol/L), SO{sub 4}{sup 2-} (3.3 10{sup -4} mol/L) and Cl{sup -} (9 10{sup -2} mol/L). This study was more specifically focused on the behaviour of neptunium with citrate ion, which is also a basic ligand to consider when one wishes to study the migration of actinides in the environment, since it exists in significant amounts in the ground due to its production by the plants. In order to determine the speciation of this system, spectrophotometry was more particularly used. Concerning the complexation phenomenon, the existence of several complexes of Np{sup V} with various acid-basic forms of the citrate anion was observed; regarding Np{sup IV}, two complexes, with 1:1 and 1:2 stoichiometry, have been respectively observed. The reactivity of Np{sup VI} is probably similar to the behaviour of U{sup VI}, which is reported in literature to form a complex with a 1:1 stoichiometry with the Cit{sup 3-}anion From the quantitative study of these equilibria, it has been possible to determine the values of various equilibrium constants. Concerning the stability of neptunium towards oxido-reduction, it was confirmed that Np{sup VI} was very quickly reduced to Np{sup V} by the citrate anions

  13. Stability constants and solubility of neptunium and plutonium complexes with alkylphosphoric acids in TBP

    International Nuclear Information System (INIS)

    Fedoseev, D.A.; Romanovskaya, I.A.; Artemova, L.A.; Gubina, M.Yu.

    1988-01-01

    Stability concetration constants K and solubility of neptunium and plutonium complexes with di- and monobuthylphosphoric acids (APC) and with orthophosphoric and di-2-ethylhexyl-phosphoric acids in 30% TBP solution-n-dodecane system are determined by spectrophotometric titration and radiometry methods. Posibility of forecasting radiation-chemical behaviour of actinids according to data on K and APC radiation-chemical yield values is demonstrated

  14. Appraisal of available information on uptake by plants of transplutonium elements and neptunium

    International Nuclear Information System (INIS)

    Thomas, R.L.; Healy, J.W.

    1976-07-01

    A critical review was made of reported information from laboratory studies of plant uptake of transplutonic elements plus neptunium. The available data are meager but indicate that the uptake of Np is the greatest followed by Am and Cm. The data are not sufficient to provide recommended values for use in hazard calculations but they do indicate that the actinides other than plutonium will be accumulated in plants to a greater degree than plutonium

  15. Hydrolysis constants of tetravalent neptunium by using solvent extraction method

    Energy Technology Data Exchange (ETDEWEB)

    Fujiwara, K. [Japan Atomic Energy Agency (JAEA), Naka-gun, Ibaraki-ken (Japan); Kohara, Y. [Inspection and Development Co., Naka-gun, Ibaraki-ken (Japan)

    2008-07-01

    The hydrolysis constants of tetravalent neptunium (Np(IV)) were determined by solvent extraction method using thenoyltrifluoroacetone(TTA). In order to avoid colloid formation, a stock solution of carrier-free {sup 239}Np(V) was from {sup 243}Am milked. The valence of Np in the solution was then reduced to Np(IV) by using zinc amalgam. The hydrolysis constants ({beta}{sub m}) of the reactions, Np{sup 4+} + mOH{sup -} = Np(OH){sub m}{sup (4-m)+} was evaluated by using distribution ratios at ionic strengths (I) = 0.1, 0.5 and 1.0. All experiments were performed in oxygen-free 0.5% H{sub 2}-N{sub 2} atmosphere (below 1.0 ppm of O{sub 2}) in a glove-box at room temperature (23 {+-} 2 C) to avoid oxidation of Np(IV). The {beta}{sub m} values were extrapolated to the standard state (I = 0) by using the specific ion interaction theory (SIT), and the formation constants at I = 0 were determined to be log {beta}{sub 1} = 13.91 {+-} 0.23, log {beta}{sub 2} = 27.13 {+-} 0.15, log {beta}{sub 3} = 37.70 {+-} 0.30 and log {beta}{sub 4} = 46.16 {+-} 0.30. The ion interaction coefficients were also evaluated to be {epsilon}(NpOH{sup 3+}, ClO{sub 4}{sup -}) = 0.49 {+-} 0.15, {epsilon}(Np(OH){sub 2}{sup 2+}, ClO{sub 4}{sup -}) = 0.35 {+-} 0.11, and {epsilon}(Np(OH){sub 3}{sup +}, ClO{sub 4}{sup -}) = 0.29 {+-} 0.15. (orig.)

  16. Stability constants and solubility of neptunium and plutonium complexes with alkylphosphoric acids in TBP

    International Nuclear Information System (INIS)

    Fedoseev, D.A.; Romanovskaya, I.A.; Artemova, L.A.; Gibina, M.Yu.

    1989-01-01

    The concentration stability constants (K s ) and solubility of neptunium and plutonium complexes with di- and monobutylphosphoric acids (APA), as well as with orthophosphoric acid in the system composed of 30% TBP + n-dodecane, have been determined by spectrophotometric titration and radiometry. The feasibility of predicting the radiative chemical behavior of actinides based on their K s values and the radiative chemical yield of APA has been demonstrated

  17. Solvent-extraction purification of neptunium

    International Nuclear Information System (INIS)

    Kyser, E.A.; Hudlow, S.L.

    2008-01-01

    The Savannah River Site (SRS) has recovered 237 Np from reactor fuel that is currently being processed into NpO 2 for future production of 238 Pu. Several purification flowsheets have been utilized. An oxidizing solvent-extraction (SX) flowsheet was used to remove Fe, sulfate ion, and Th while simultaneously 237 Np, 238 Pu, u, and nonradioactive Ce(IV) was extracted into the tributyl phosphate (TBP) based organic solvent. A reducing SX flowsheet (second pass) removed the Ce and Pu and recovered both Np and U. The oxidizing flowsheet was necessary for solutions that contained excessive amounts of sulfate ion. Anion exchange was used to perform final purification of Np from Pu, U, and various non-actinide impurities. The Np(IV) in the purified solution was then oxalate-precipitated and calcined to an oxide for shipment to other facilities for storage and future target fabrication. Performance details of the SX purification and process difficulties are discussed. (authors)

  18. Speciation of neptunium during migration in clay rock; Speziation von Neptunium bei der Migration in Tongestein

    Energy Technology Data Exchange (ETDEWEB)

    Froehlich, Daniel

    2011-12-15

    The present work was performed within a fellowship of the interdisciplinary research training group 826 ''trace analysis of elemental species: method development and application'' funded by the German Research Foundation (DFG) and the federal state Rheinland-Pfalz. Aim of this work was to gain new knowledge of the interaction between neptunium and natural clay rock with respect to the disposal of high-level nuclear waste in deep geological formations. The isotope {sup 237}Np with its long half-life of more than two million years will be one of main contributors to the radiotoxicity of the radioactive waste material after storage times of more than 1000 years. In aqueous solution under environmental relevant conditions Np can exist in the oxidation states +IV and +V. Due to its high solubility and higher mobility Np(V) is the much more hazardous species compared to Np(IV). Opalinus Clay (OPA) from Mont Terri, Switzerland, was used as a natural reference material in the migration studies. The focus of this work was on speciation of Np on the mineral surface by synchrotron based X-ray absorption spectroscopy (EXAFS/XANES). The interaction between Np(V) and OPA was studied in batch sorption and diffusion experiments in dependence of various experimental parameters (e.g. pH, temperature, background electrolyte, effect of humic acid, concurrence with U(VI), aerobic/anaerobic conditions). The investigation of Np speciation was performed on two types of samples. Powder samples from batch experiments were prepared under aerobic and anaerobic conditions and measured by EXAFS spectroscopy. Diffusion samples and OPA thin sections contacted with Np(V) were analyzed by locally resolved μ-XANES measurements on enrichments of Np. A combination with μ-XRF (X-ray fluorescence) mapping and μ-XRD (X-ray diffraction) measurements provided further information about the spatial distribution of Np and other elements contained in OPA as well as crystalline mineral

  19. Mechanisms of sorption of neptunium and technetium on argillaceous materials

    International Nuclear Information System (INIS)

    Hooker, P.J.; West, J.M.; Noy, D.J.

    1986-01-01

    It is of pressing concern to understand the behaviour of radionuclides in the environment and in particular long-lived ones (e.g. Np-237 and Te-99) in argillaceous rocks. Clay formations have been chosen as likely candidates for holding low level radioactive waste repositories and in the event of leakage of radionuclides into the geosphere some knowledge of their fate is required in a far-field safety assessment study. The objectives of this present work were to examine the properties of neptunium and technetium in ground-waters associated with clay-rich materials and to ascertain the variations in sorption of these radionuclides under different environmental conditions and to use the information in a forecast of transport through a clay layer

  20. Source-driven noise analysis measurements with neptunium metal reflected by high enriched uranium

    International Nuclear Information System (INIS)

    Valentine, Timothy E.; Mattingly, John K.

    2003-01-01

    Subcritical noise analysis measurements have been performed with neptunium ( 237 Np) sphere reflected by highly enriched uranium. These measurements were performed at the Los Alamos Critical Experiment Facility in December 2002 to provide an estimate of the subcriticality of 237 Np reflected by various amounts of high-enriched uranium. This paper provides a description of the measurements and presents some preliminary results of the analysis of the measurements. The measured and calculated spectral ratios differ by 15% whereas the 'interpreted' and calculated k eff values differ by approximately 1%. (author)

  1. Mathematical modeling of the radiation-chemical behavior of neptunium in HNO3. Equilibrium states

    International Nuclear Information System (INIS)

    Vladimirova, M.V.

    1995-01-01

    A mathematical model of the radiation-chemical behavior of neptunium is presented for a wide range of α-and γ-irradiation doses. Equations determining the equilibrium concentrations of NP(IV), Np(V), and Np(VI) are derived for various concentrations of HNO 3 and dose rates of the ionizing irradiation. The rate constants of the reactions NP(IV) + OH, Np(IV) + NO 3 , Np(V) + NO 2 , Np(V) + H, Np(IV), and Np(V) + Np(V) are obtained by the mathematical modeling

  2. Neptunium(V) sorption onto kaolinite in the absence and presence of CO2

    International Nuclear Information System (INIS)

    Amayri, S.; Reich, Ta.; Reich, T.

    2005-01-01

    Full text of publication follows: The adsorption of heavy metals on clay minerals such as kaolinite is an important process that affects the migration and retardation of neptunium and other actinides in the geosphere. The sorption of Np(V) onto the reference clay mineral kaolinite KGa-1b was investigated both by batch experiments and EXAFS measurements. The aim of our study was to combine macroscopic studies (batch experiments) with microscopic techniques (EXAFS) to study the Np(V) speciation at the kaolinite surface. The batch experiments were done under relevant environmental conditions with Np(V) concentrations of 10 -11 and 10 -12 mol/L. Sorption samples were prepared in 0.1 mol/L NaClO 4 , 4 g/L kaolinite, pH 6.0 to 10.5, presence and absence of ambient CO 2 , and 60-h equilibration. The sorption curves for 10 -11 and 10 -12 mol/L Np(V) obtained in the presence and absence of CO 2 , respectively, show that the adsorption edge occurs at pH 8.5. The uptake of Np(V) by kaolinite strongly increased above pH 7.0 and reached its sorption maximum (70 %) at pH 9.0. Above pH 9.0, the amount of Np(V) sorbed onto kaolinite decreased and reached ca. 30 % at pH 10.5 due to the formation of Np(V) carbonato species in the aqueous solution. In the CO 2 -free system, the sorption of Np(V) increased continuously with pH until the sorption maximum of 100 % was reached at pH 10.5. The same sorption behavior was found in batch experiments in the CO 2 equilibrated system with Np concentrations ranging from 1 μmol/L to 10 μmol/L. EXAFS experiments on some of these batch samples indicated the formation of Np(V) carbonato species at the kaolinite surface at pH 9.0 where the uptake of Np(V) by kaolinite reaches its maximum [1]. [1] T. Reich, S. Amayri, Ta. Reich, J. Drebert, A. Jermolajev, P. Thoerle, N. Trautmann, C. Hennig, S. Sachs, Feasibility of EXAFS experiments at the Np L-edge to investigate neptunium sorption on kaolinite, Institut fuer Kernchemie, Universitaet Mainz, Annual

  3. Diffusion of water, cesium and neptunium in pores of rocks

    International Nuclear Information System (INIS)

    Puukko, E.; Heikkinen, T.; Hakanen, M.

    1993-10-01

    Teollisuuden Voima Oy (TVO) is investigating the feasibility to dispose of spent nuclear fuel within Finland. The present plan calls for the repository to be located in crystalline rock at a depth of several hundred meters. The safety assessment of the repository includes calculations of migration of waste nuclides. The flow of waste elements in groundwater will be retarded through sorption interaction with minerals and through diffusion into rock. Diffusion is the only mechanism retarding the migration of non-sorbing species and, it is expected to be the dominating retardation mechanism of many of the sorbing elements. In the investigation the simultaneous diffusion of tritiated water (HTO), cesium and neptunium in rocks of TVO investigation sites at Kivetty, Olkiluoto and Romuvaara were studied. (11 refs., 33 figs., 9 tabs.)

  4. An evaluation of safeguards approaches for neptunium

    International Nuclear Information System (INIS)

    Burr, Tom; Stanbro, William D.; Charlton, William

    2001-01-01

    The International Atomic Energy Agency has recently drawn attention to the fact that neptunium (Np), a byproduct of the nuclear power industry, can be used to make nuclear weapons. Current monitoring approaches for Np do not rely on material balance accounting as is used for uranium and plutonium. In the future this may change. Although full material balance accounting is not anticipated for Np, it is informative to evaluate the impact and benefit of full material balance accounting when considering other options. Therefore, this paper will apply systems analysis to evaluate ways to convert the current system to full materials balance accounting that will minimize the intrusiveness of the verification system and minimize costs to both the facility operator and the inspection agency. We then compare full material balance accounting to partial material balance accounting and to a ratio-monitoring technique referred to as flow sheet verification. We conclude that sampling approximately 25% of the batches is likely to be adequate and that Pu (or perhaps 137 Cs) will be the most effective surrogate for estimating the Np in the input accountability tank. (author)

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

    DEFF Research Database (Denmark)

    Qiao, Jixin; Xu, Yihong; Hou, Xiaolin

    2014-01-01

    This paper describes improvement and comparison of analytical methods for simultaneous determination of trace-level plutonium and neptunium in urine samples by inductively coupled plasma mass spectrometry (ICP-MS). Four sample pre-concentration techniques, including calcium phosphate, iron......), it endows urinalysis methods with better reliability and repeatability compared with co-precipitation techniques. In view of the applicability of different pre-concentration techniques proposed previously in the literature, the main challenge behind relevant method development is pointed to be the release...

  6. Brief overview of the long-lived radionuclide separation processes developed in France in connection with the SPIN program

    International Nuclear Information System (INIS)

    Madic, C.; Bourges, J.; Dozol, J.F.

    1995-01-01

    To reduce the long-term potential hazards associated with the management of nuclear wastes generated by nuclear fuel reprocessing, one alternative is the transmutation of long-lived radionuclides into short-lived radionuclides by nuclear means (P ampersand T strategy). In this context, according to the law passed by the French Parliament on 30 December 1991, the CEA launched the SPIN program for the design of long-lived radionuclide separation and nuclear incineration processes. The research in progress to define separation processes focused mainly on the minor actinides (neptunium, americium and curium) and some fission products, like cesium and technetium. To separate these long-lived radionuclides, two strategies were developed. The first involves research on new operating conditions for improving the PUREX fuel reprocessing technology. This approach concerns the elements neptunium and technetium (iodine and zirconium can also be considered). The second strategy involves the design of new processes; DIAMEX for the co-extraction of minor actinides from the high-level liquid waste leaving the PUREX process, An(III)/Ln(III) separation using tripyridyltriazine derivatives or picolinamide extracting agents; SESAME for the selective separation of americium after its oxidation to Am(IV) or Am(VI) in the presence of a heteropolytungstate ligand, and Cs extraction using a new class of extracting agents, calixarenes, which exhibit exceptional Cs separation properties, especially in the presence of sodium ion. This lecture focuses on the latest achievements in these research areas

  7. Brief overview of the long-lived radionuclide separation processes developed in france in connection with the spin program

    Science.gov (United States)

    Madic, Charles; Bourges, Jacques; Dozol, Jean-François

    1995-09-01

    To reduce the long-term potential hazards associated with the management of nuclear wastes generated by nuclear fuel reprocessing, one alternative is the transmutation of long-lived radionuclides into short-lived radionuclides by nuclear means (P & T strategy). In this context, according to the law passed by the French Parliament on 30 December 1991, the CEA launched the SPIN program for the design of long-lived radionuclide separation and nuclear incineration processes. The research in progress to define separation processes focused mainly on the minor actinides (neptunium, americium and curium) and some fission products, like cesium and technetium. To separate these long-lived radionuclides, two strategies were developed. The first involves research on new operating conditions for improving the PUREX fuel reprocessing technology. This approach concerns the elements neptunium and technetium (iodine and zirconium can also be considered). The second strategy involves the design of new processes; DIAMEX for the co-extraction of minor actinides from the high-level liquid waste leaving the PUREX process, An(III)/Ln(III) separation using tripyridyltriazine derivatives or picolinamide extracting agents; SESAME for the selective separation of americium after its oxidation to Am(IV) or Am(VI) in the presence of a heteropolytungstate ligand, and Cs extraction using a new class of extracting agents, calixarenes, which exhibit exceptional Cs separation properties, especially in the presence of sodium ion. This lecture focuses on the latest achievements in these research areas.

  8. Brief overview of the long-lived radionuclide separation processes developed in France in connection with the SPIN program

    Energy Technology Data Exchange (ETDEWEB)

    Madic, C.; Bourges, J. [DRDD, Fontenay-aux-Roses (France); Dozol, J.F. [DESD, Cadarache (France)

    1995-10-01

    To reduce the long-term potential hazards associated with the management of nuclear wastes generated by nuclear fuel reprocessing, one alternative is the transmutation of long-lived radionuclides into short-lived radionuclides by nuclear means (P & T strategy). In this context, according to the law passed by the French Parliament on 30 December 1991, the CEA launched the SPIN program for the design of long-lived radionuclide separation and nuclear incineration processes. The research in progress to define separation processes focused mainly on the minor actinides (neptunium, americium and curium) and some fission products, like cesium and technetium. To separate these long-lived radionuclides, two strategies were developed. The first involves research on new operating conditions for improving the PUREX fuel reprocessing technology. This approach concerns the elements neptunium and technetium (iodine and zirconium can also be considered). The second strategy involves the design of new processes; DIAMEX for the co-extraction of minor actinides from the high-level liquid waste leaving the PUREX process, An(III)/Ln(III) separation using tripyridyltriazine derivatives or picolinamide extracting agents; SESAME for the selective separation of americium after its oxidation to Am(IV) or Am(VI) in the presence of a heteropolytungstate ligand, and Cs extraction using a new class of extracting agents, calixarenes, which exhibit exceptional Cs separation properties, especially in the presence of sodium ion. This lecture focuses on the latest achievements in these research areas.

  9. Sorption of cesium, radium, protactinium, uranium, neptunium and plutonium on rapakivi granite

    International Nuclear Information System (INIS)

    Huitti, T.; Hakanen, M.

    1996-12-01

    The aim of the study is to determine the sorption of cesium, radium, protactinium, uranium, neptunium and plutonium on rapakivi granite in the brackish groundwater of Haestholmen (site of the Loviisa-1, Loviisa-2 reactors). The studies were carried out under aerobic (Cs, Ra, Pa, U, Np, Pu) and anaerobic (Np, Pa, Pu, Tc) laboratory conditions. The cation exchange capasity was determined for the rock and the diffusion of tritiated water in the rocks of different degree of alteration. The sorption and diffusion properties of the rocks are briefly compared with those of host rocks at other sites under investigation by the Finnish company Posiva Oy for the final disposal of spent fuel. (29 refs.)

  10. Gamma radiolysis of alkaline aqueous solutions of neptunium and plutonium ions

    International Nuclear Information System (INIS)

    Pikaev, A.K.; Gogolev, A.V.; Shilov, V.P.

    1998-01-01

    Full text: The paper is a brief review of data obtained by the authors from the study on redox reactions of neptunium and plutonium ions upon γ radiolysis of their aerated alkaline aqueous solutions. It includes the information on radiolytic reduction of Np(V), Np(VI) and Pu(VI) ions under various experimental conditions. It was found that the values of Np(VI) and Pu(VI) reduction yields do not depend on alkali concentration. The values considerably increase in the presence of some organic compounds (EDTA and formate were investigated). The formation of the Np(V) peroxo complex was observed in the γ radiolysis of alkaline aqueous solutions of Np(VI) and Np(V) in the presence of nitrate. The mechanism of radiolytic redox reactions of the ions is discussed in some detail

  11. The incorporation of neptunium and plutonium in thorutite (ThTi{sub 2}O{sub 6})

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yingjie, E-mail: yzx@ansto.gov.au; Gregg, Daniel J.; Lumpkin, Gregory R.; Begg, Bruce D.; Jovanovic, Miodrag

    2013-12-25

    Highlights: •The incorporation of neptunium (Np) and plutonium (Pu) in thorutite (ThTi{sub 2}O{sub 6}) has been studied. •The effect of Np/Pu doping on the unit cell parameter changes has been discussed from the structure point of view. •The effect of Y as charge compensator to encourage the formation of higher valences of Np and Pu has been explored. •The resulting Np/Pu doped thorutite samples have been characterised by using XRD, SEM and DRS. -- Abstract: The incorporation of neptunium (Np) and plutonium (Pu) into the brannerite structured lattice was studied using thorutite (ThTi{sub 2}O{sub 6}) as host lattice and sintering in air. The uncompensated Np and Pu doped samples and the low Y-charge compensated Np and Pu doped samples showed main phases as designed together with trace amounts of rutile. Those samples with larger amounts of Y produced yttrium pyrochlores as an additional minor phase. XRD analyses reveal anisotropic changes of the cell parameters; the a-parameter contracts while b- and c-parameters expand with mean cationic radius. This is in reasonable agreement with previous experimental data on ThTi{sub 2}O{sub 6} and Ce{sub 0.975}Ti{sub 2}O{sub 5.95}. Attempts to form Np or Pu valences >4+ by adding Y as a charge compensator were unsuccessful, suggesting that tetravalent Np and Pu ions are favoured in air-fired thorutite.

  12. Uranium Metal to Oxide Conversion by Air Oxidation –Process Development

    Energy Technology Data Exchange (ETDEWEB)

    Duncan, A

    2001-12-31

    Published technical information for the process of metal-to-oxide conversion of uranium components has been reviewed and summarized for the purpose of supporting critical decisions for new processes and facilities for the Y-12 National Security Complex. The science of uranium oxidation under low, intermediate, and high temperature conditions is reviewed. A process and system concept is outlined and process parameters identified for uranium oxide production rates. Recommendations for additional investigations to support a conceptual design of a new facility are outlined.

  13. Pressure effects on magnetism in the uranium and neptunium monopnictides

    International Nuclear Information System (INIS)

    Braithwaite, D.; Demuer, A.; Ichas, V.; Rebizant, J.; Spirlet, J.C.; Zwirner, S.; Vogt, O.

    1998-01-01

    The magnetic properties of the cubic NaCl uranium and neptunium monopnictides (UX, NpX; X=N, P, As, Sb, Bi) have been widely studied at ambient pressure. Properties ranging from itinerant to localized magnetism, and a variety of ordered magnetic structures have been observed. In particular the profusion of non-collinear double-k or triple-k structures is a consequence of strongly anisotropic exchange interactions. The application of pressure is a clean way of continuously varying the lattice parameter, and the exchange interactions, from one compound to another. A number of studies have been performed using different high pressure techniques. Some of the effects of pressure can be understood in a simple picture of a continuous variation of the lattice parameter, but some highly anomalous effects are also found which are discussed in relation to the possible nature of the magnetic interactions. (orig.)

  14. Fundamental studies of uranium and neptunium redox flow batteries (II)

    International Nuclear Information System (INIS)

    Shiokawa, Y.; Yamamura, T.; Watanabe, N.

    2002-01-01

    The atomic power generation entails production of so-called minor actinides and accumulation of depleted uranium. The theoretical and experimental investigations are underway to transmute minor actinides for minimizing the long-term radiotoxicity and reducing the radioactive waste. The utilization, however, would be alternative means. The actinide redox couples, An(VI)/An(V) and An(IV)/An(III), have excellent properties as battery active materials. Here j the uranium and neptunium redox flow batteries for the electric power storage are discussed from the electrochemical properties of U, Np, Pu and Am [1,2]. One of the required properties for the batteries for electric power storage is high energy efficiency, which is defined by the ratio of the discharge energy to the charge energy. These energies are dependent on the rapidness of kinetics in the electrode reactions, namely the standard rate constants and also the internal resistance of the battery

  15. ADVANCED OXIDATION PROCESSES (AOX) TEXTILE WASTEWATER

    OpenAIRE

    Salas C., G.

    2014-01-01

    Advanced Oxidation Processes (AOX) are based on the in situ generation of hydroxyradicals (·OH), which have a high oxidation potential. In the case of Fenton processes !he generation of hydroxy radicals takes place by the combination of an oxidation agent (H202) with a catalyst (Fe(II)). These radicals are not selective and they react very fast with the organic matter,being able to oxidize a high variety of organic compounds. This property allows the degradation of pollutants into more biodeg...

  16. Direct complexonometric determination of thorium (IV), uranium (IV), neptunium (IV), plutonium (IV) by titration of diethylenetriaminepentaacetic acid with xylenol orange as indicator

    International Nuclear Information System (INIS)

    Rykov, A.G.; Piskunov, E.M.; Timofeev, G.A.

    1975-01-01

    The purpose of the present work was to develop a method of determining Th(IV), U(IV), Np(N) and Pu(IV) in acid solutions by titration with diethylenetriamine pentacetic acid, the indicator being xylenol orange. It has been established that Th, U, Np and Pu can be determined to within 0.5-1.5%. Th and U in quantities of tens of milligrams can be determined with greater accuracy, attaining hundredths of one per cent. During titration the determination is not hindered by singly- and doubly-charged metal ions, trivalent lanthanides and actinides, except plutonium. The proposed method can be used to determine U(IV) in the presence of considerable quantities of U(VI) and Np(IV) in the presence of Np(V). Total concentrations of uranium or neptunium are determined by reducing uranium (VI) or neptunium (V) by a standard method (for example, using metallic lead, cadmium or zinc amalgam) to the tetravalent state and applying the method described in the paper. (E.P.)

  17. The redox chemistry of neptunium in gamma-irradiated aqueous nitric acid in the presence of an organic phase

    Czech Academy of Sciences Publication Activity Database

    Mincher, B.J.; Přeček, Martin; Paulenova, A.

    2016-01-01

    Roč. 308, č. 3 (2016), s. 1005-1009 ISSN 0236-5731 R&D Projects: GA MŠk EE2.3.30.0057 Grant - others:OP VK 4 POSTDOK(XE) CZ.1.07/2.3.00/30.0057 Institutional support: RVO:68378271 Keywords : neptunium * redox chemistry * radiation chemistry * solvent extraction Subject RIV: CH - Nuclear ; Quantum Chemistry OBOR OECD: Inorganic and nuclear chemistry Impact factor: 1.282, year: 2016

  18. Osteosarcoma induction by plutonium-239, americium-241 and neptunium-237 : the problem of deriving risk estimates for man

    International Nuclear Information System (INIS)

    Taylor, D.M.

    1988-01-01

    Spontaneous bone cancer (osteosarcoma) represents only about 0.3% of all human cancers, but is well known to be inducible in humans by internal contamination with radium-226 and radium-224. plutonium-239, americium-241 and neptunium-237 form, or will form, the principal long-lived alpha particle emitting components of high activity waste and burnt-up nuclear fuel elements. These three nuclides deposit extensively in human bone and although, fortunately, no case of a human osteosarcoma induced by any of these nuclides is known, evidence from animal studies suggests that all three are more effective than radium-226 in inducing osteosarcoma. The assumption that the ratio of the risk factors, the number of osteosarcoma expected per 10000 person/animal Gy, for radium-226 and any other bone-seeking alpha-emitter will be independent of animal species has formed the basis of all the important studies of the radiotoxicity of actinide nuclides in experimental animals. The aim of this communication is to review the risk factors which may be calculated from the various animal studies carried out over the last thirty years with plutonium-237, americium-241 and neptunium-237 and to consider the problems which may arise in extrapolating these risk factors to homo sapiens

  19. Potential for radionuclide immobilization in the EBS/NFE: solubility limiting phases for neptunium, plutonium, and uranium

    Energy Technology Data Exchange (ETDEWEB)

    Rard, J. A., LLNL

    1997-10-01

    Retardation and dispersion in the far field of radionuclides released from the engineered barrier system/near field environment (EBS/NFE) may not be sufficient to prevent regulatory limits being exceeded at the accessible environment. Hence, a greater emphasis must be placed on retardation and/or immobilization of radionuclides in the EBS/NFE. The present document represents a survey of radionuclide-bearing solid phases that could potentially form in the EBS/NFE and immobilize radionuclides released from the waste package and significantly reduce the source term. A detailed literature search was undertaken for experimental solubilities of the oxides, hydroxides, and various salts of neptunium, plutonium, and uranium in aqueous solutions as functions of pH, temperature, and the concentrations of added electrolytes. Numerous solubility studies and reviews were identified and copies of most of the articles were acquired. However, this project was only two months in duration, and copies of some the identified solubility studies could not be obtained at short notice. The results of this survey are intended to be used to assess whether a more detailed study of identified low- solubility phase(s) is warranted, and not as a data base suitable for predicting radionuclide solubility. The results of this survey may also prove useful in a preliminary evaluation of the efficacy of incorporating chemical additives to the EBS/NFE that will enhance radionuclide immobilization.

  20. PROCESSES OF CHLORINATION OF URANIUM OXIDES

    Science.gov (United States)

    Rosenfeld, S.

    1958-09-16

    An improvement is described in the process fur making UCl/sub 4/ from uranium oxide and carbon tetrachloride. In that process, oxides of uranium are contacted with carbon tetrachloride vapor at an elevated temperature. It has been fuund that the reaction product and yield are improved if the uranlum oxide charge is disposed in flat trays in the reaction zone, to a depth of not more than 1/2 centimeter.

  1. Microwave processing of ceramic oxide filaments

    Energy Technology Data Exchange (ETDEWEB)

    Vogt, G.J.; Katz, J.D. [Los Alamos National Laboratory, NM (United States)

    1995-05-01

    The objective of the microwave filament processing project is to develop microwave techniques at 2.45 GHZ to manufacture continuous ceramic oxide filaments. Microwave processing uses the volumetric absorption of microwave power in oxide filament tows to drive off process solvents, to burn out organic binders, and to sinter the dried fibers to produce flexible, high-strength ceramic filaments. The technical goal is to advance filament processing technology by microwave heating more rapidly with less energy and at a lower cost than conventional processing, but with the same quality as conventional processing. The manufacturing goal is to collaborate with the 3M Company, a US manufacturer of ceramic oxide filaments, to evaluate the technology using a prototype filament system and to transfer the microwave technology to the 3M Company.

  2. Sequential injection approach for simultaneous determination of ultratrace plutonium and neptunium in urine with accelerator mass spectrometry

    DEFF Research Database (Denmark)

    Qiao, Jixin; Hou, Xiaolin; Roos, Per

    2013-01-01

    An analytical method was developed for simultaneous determination of ultratrace level plutonium (Pu) and neptunium (Np) using iron hydroxide coprecipitation in combination with automated sequential injection extraction chromatography separation and accelerator mass spectrometry (AMS) measurement...... show that preboiling and aging are important for obtaining high chemical yields for both Pu and Np, which is possibly related to the aggregation and adsorption behavior of organic substances contained in urine. Although the optimal condition for Np and Pu simultaneous determination requires 5-day aging...

  3. Investigation on leaching of actinide oxides into supercritical fluids

    International Nuclear Information System (INIS)

    Shafikov, D.N.; Kamachev, V.A.; Babain, V.A.; Murzin, A.A.; Shadrin, A.Yu.; Podojnitsin, S.V.

    2006-01-01

    The extraction of actinide oxides into solutions of the TBP-HNO 3 complex in supercritical (SC) CO 2 was investigated. Experiments on the extraction of the TBP-HNO 3 complex into SC CO 2 were first conducted. It was found that a constant concentration of TBP in SC CO 2 of 13.5-14.8 % vol. can be attained using a constant molar ratio of [HNO 3 ]:[TBP] about 2.5 : 1. Joint leaching of uranium, plutonium and neptunium from mixtures of actinide oxides with solutions of TBP-HNO 3 in SC CO 2 was found feasible. If the leaching of uranium is about 95 %, its purification coefficients from major gamma-emitting radionuclides (Cs and Sr) exceed 100, while the purification coefficients of uranium from rare earth elements are 10-20

  4. Desulfurization of AL-Ahdab Crude Oil using Oxidative Processes

    OpenAIRE

    Neran Khalel Ibrahim; Saja Mohsen Jabbar

    2015-01-01

    Two different oxidative desulfurization strategies based on oxidation/adsorption or oxidation/extraction were evaluated for the desulfurization of AL-Ahdab (AHD) sour crude oil (3.9wt% sulfur content). In the oxidation process, a homogenous oxidizing agent comprising of hydrogen peroxide and formic acid was used. Activated carbons were used as sorbent/catalyst in the oxidation/adsorption process while acetonitrile was used as an extraction solvent in the oxidation/extraction process. For the ...

  5. The sorption of uranium(VI) and neptunium(V) onto surfaces of selected metal oxides and alumosilicates studied by in situ vibrational spectroscopy

    International Nuclear Information System (INIS)

    Mueller, Katharina

    2010-05-01

    The migration behavior of actinides and other radioactive contaminants in the environment is controlled by prominent molecular phenomena such as hydrolysis and complexation reactions in aqueous solutions as well as the diffusion and sorption onto minerals present along groundwater flow paths. These reactions significantly influence the mobility and bioavailability of the metal ions in the environment, in particular at liquid-solid interfaces. Hence, for the assessment of migration processes the knowledge of the mechanisms occurring at interfaces is crucial. The required structural information can be obtained using various spectroscopic techniques. In the present study, the speciation of uranium(VI) and neptunium(V) at environmentally relevant mineral-water interfaces of oxides of titania, alumina, silica, zinc, and alumosilicates has been investigated by the application of attenuated total reflection Fouriertransform infrared (ATR FT-IR) spectroscopy. Moreover, the distribution of the hydrolysis products in micromolar aqueous solutions of U(VI) and Np(V/VI) at ambient atmosphere has been characterized for the first time, by a combination of ATR FT-IR spectroscopy, near infrared (NIR) absorption spectroscopy, and speciation modeling applying updated thermodynamic databases. From the infrared spectra, a significant change of the U(VI) speciation is derived upon lowering the U(VI) concentration from the milli- to the micromolar range, strongly suggesting the dominance of monomeric U(VI) hydrolysis products in the micromolar solutions. In contradiction to the predicted speciation, monomeric hydroxo species are already present at pH ≥ 2.5 and become dominant at pH 3. At higher pH levels (> 6), a complex speciation is evidenced including carbonate containing complexes. For the first time, spectroscopic results of Np(VI) hydrolysis reactions are provided in the submillimolar concentration range and at pH values up to 5.3, and they are comparatively discussed with U

  6. Mesoporous metal oxides and processes for preparation thereof

    Energy Technology Data Exchange (ETDEWEB)

    Suib, Steven L.; Poyraz, Altug Suleyman

    2018-03-06

    A process for preparing a mesoporous metal oxide, i.e., transition metal oxide. Lanthanide metal oxide, a post-transition metal oxide and metalloid oxide. The process comprises providing an acidic mixture comprising a metal precursor, an interface modifier, a hydrotropic ion precursor, and a surfactant; and heating the acidic mixture at a temperature and for a period of time sufficient to form the mesoporous metal oxide. A mesoporous metal oxide prepared by the above process. A method of controlling nano-sized wall crystallinity and mesoporosity in mesoporous metal oxides. The method comprises providing an acidic mixture comprising a metal precursor, an interface modifier, a hydrotropic ion precursor, and a surfactant; and heating the acidic mixture at a temperature and for a period of time sufficient to control nano-sized wall crystallinity and mesoporosity in the mesoporous metal oxides. Mesoporous metal oxides and a method of tuning structural properties of mesoporous metal oxides.

  7. Features oxidative processes in sturgeons fish (Acipenseridae (review

    Directory of Open Access Journals (Sweden)

    M. Symon

    2016-12-01

    Full Text Available Purpose. To anayze scientific sources on physiological-biochemical pecularities of reducing-oxidizing processes, including peroxide oxidation of lipids and work of the system of antioxidant protection system in sturgeon species (Acipenseridae. The initiation and process of the oxidative stress have been described. The main products of peroxide oxidation of lipids, antioxidants of natural and artificial origin, organs and tissues for the studies of reducing-oxidizing processes have been examined. Findings. The work generalizes the processes of lipid peroxidation. Briefly outlined the main mechanism of action of antioxidant enzymes. Antioxidant defense system plays one of key role in the life of organism due regulating its series of metabolic processes, use of assessing of its state gives an opportunity obtain quantitative information on the progress of these processes. The products of free radical peroxidation (dien conjugates and malonic dialdehyde can also act as a sort of biomarkers of tissue damage, because their content can judge about the intensity of the flow of free radical processes in the various systems in organism. The review contains a description of the peculiarities of the liver and its involvement in lipid metabolism and antioxidant defense system. It is shown the most common antioxidants used in the feeding of sturgeon. Organs and tissues, which should be used for studying the processes of peroxide oxidation of lipids in sturgeon species, have been examined. Practical value. The systematized data regarding peroxide oxidation of lipids, oxidative stress and antioxidant protection system allow finding a balance between these processes. The data on antioxidants, which are used in feeds for sturgeon species, will be useful for sturgeon culturists. The array of the generalized information will be important for scientists who study the pecularities of the processes of peroxide oxidation of lipids and antioxidant protection system in

  8. Method for Determination of Neptunium in Large-Sized Urine Samples Using Manganese Dioxide Coprecipitation and 242Pu as Yield Tracer

    DEFF Research Database (Denmark)

    Qiao, Jixin; Hou, Xiaolin; Roos, Per

    2013-01-01

    A novel method for bioassay of large volumes of human urine samples using manganese dioxide coprecipitation for preconcentration was developed for rapid determination of 237Np. 242Pu was utilized as a nonisotopic tracer to monitor the chemical yield of 237Np. A sequential injection extraction chr...... and rapid analysis of neptunium contamination level for emergency preparedness....

  9. Uranium bed oxidation vacuum process system

    International Nuclear Information System (INIS)

    McLeland, H.L.

    1977-01-01

    Deuterium and tritium gases are occluded in uranium powder for release into neutron generator tubes. The uranium powder is contained in stainless steel bottles, termed ''beds.'' If these beds become damaged, the gases must be removed and the uranium oxidized in order not to be flammable before shipment to ERDA disposal grounds. This paper describes the system and methods designed for the controlled degassing and oxidation process. The system utilizes sputter-ion, cryo-sorption and bellows pumps for removing the gases from the heated source bed. Removing the tritium gas is complicated by the shielding effect of helium-3, a byproduct of tritium decay. This effect is minimized by incremental pressure changes, or ''batch'' processing. To prevent runaway exothermic reaction, oxidation of the uranium bed is also done incrementally, or by ''batch'' processing, rather than by continuous flow. The paper discusses in detail the helium-3 shielding effect, leak checks that must be made during processing, bed oxidation, degree of gas depletion, purity of gases sorbed from beds, radioactivity of beds, bed disposal and system renovation

  10. Comparison of extraction chromatography and a procedure based on the molecular recognition method as separation methods in the determination of neptunium and plutonium radionuclides

    International Nuclear Information System (INIS)

    Strisovska, Jana; Galanda, Dusan; Drabova, Veronika; Kuruc, Jozef

    2012-01-01

    The potential of various types of sorbents for separation of radionuclides of plutonium and neptunium were examined. Extraction chromatography and a procedure based on the molecular recognition method were used for the separation. The suitability of the various sorbent types and brands for this purpose was determined. (orig.)

  11. Simulation of the selective oxidation process of semiconductors

    International Nuclear Information System (INIS)

    Chahoud, M.

    2012-01-01

    A new approach to simulate the selective oxidation of semiconductors is presented. This approach is based on the so-called b lack box simulation method . This method is usually used to simulate complex processes. The chemical and physical details within the process are not considered. Only the input and output data of the process are relevant for the simulation. A virtual function linking the input and output data has to be found. In the case of selective oxidation the input data are the mask geometry and the oxidation duration whereas the output data are the oxidation thickness distribution. The virtual function is determined as four virtual diffusion processes between the masked und non-masked areas. Each process delivers one part of the oxidation profile. The method is applied successfully on the oxidation system silicon-silicon nitride (Si-Si 3 N 4 ). The fitting parameters are determined through comparison of experimental and simulation results two-dimensionally.(author)

  12. Plutonium Oxide Process Capability Work Plan

    Energy Technology Data Exchange (ETDEWEB)

    Meier, David E. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Tingey, Joel M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    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.

  13. Frequency analysis of pulmonary tumors occurrence at the rat after exposure to actinide oxide aerosols. Risk factors identification by comparing NpO2 and PuO2

    International Nuclear Information System (INIS)

    Dudoignon, N.

    2001-07-01

    Inhalation of actinide oxide particles is potentially one route of contamination of workers, which might induce pulmonary tumours due to aerosol generation during nuclear fuel fabrication process. Dose-effect relationships for lung tumour induction have been well established from epidemiological and experimental studies. However, they do not take into account specific parameters of exposure. The aim of this study was to compare cancer incidence among groups of rats exposed either to NpO 2 or to PuO 2 , two actinide oxides with different specific activity, but with similar aerosol granulometry. During the rat life-span, lung tumour development could occur and the individual follow-up allowed the determination of lung dose at death. Although aerosol particle sizes were similar, the mean number of particles per unit of activity was 2400 times higher for NpO 2 as compared to PuO 2 . This range of variation appeared higher than the variation of specific activity (450). Initial distribution of aerosol was then much more homogeneous for neptunium. In the range of initial lung deposits studied, the only physiological changes observed concerned lung clearance and rat life- span after exposure to the highest levels of Np activity. Pathological examination performed at death showed that carcinogenic power of neptunium was 2 to 3 times higher than that of plutonium. Dose-effect relationships appeared linear and when compared to previous studies, showed an increase of lung cancer risk as the specific activity of the inhaled actinide oxide decreases. The range of risk variation can reach a factor of 10, revealing that the consideration of lung dose at death solely might not be sufficient for an accurate estimate of risk and that specific parameters of exposure, such as nature and granulometry of aerosols, should also be taken into account. (author)

  14. A contribution to the study of thorium and neptunium (IV) complexes in acidic phosphoric media; Contribution a l`etude des complexes de thorium et de neptunium (IV) en milieux phosphoriques acides

    Energy Technology Data Exchange (ETDEWEB)

    Ghafar, M

    1995-11-30

    The thorium and neptunium (IV) phosphate complexes formation in acidic media has been investigated, essentially at the indicator`s level with {sup 227} Th, {sup 234} Th, {sup 235} Np and {sup 239} Np. Solvent extraction, a commonly used method for determining stability constants in solutions, was used with HDEHP in toluene. In order to get a better understanding of inorganic transparent gels formation in phosphoric aqueous solutions, the effect of the thorium concentration is also studied. Specific experimental conditions have been chosen in order to avoid the formation of chelate and hydrolysis in the aqueous solution. The equilibrium constants and stability constants are calculated, and the results are compared with literature. The results show that increasing the thorium concentration does not lead to polymer forms. refs., 42 figs., 19 tabs.

  15. The aqueous solubility and speciation analysis for uranium, neptunium and selenium by the geochemical code(EQ3/6)

    International Nuclear Information System (INIS)

    Takeda, Seiji; Shima, Shigeki; Kimura, Hideo; Matsuzuru, Hideo

    1995-11-01

    The geochemical condition of a geologic disposal system of HLW controls the solubility and physicochemical forms of dominant aqueous species for elements, which are one of essential information required for safety assessment. Based on the measured compositions of groundwater, the compositions of groundwater in the disposal system were calculated. The solubility and speciation analyses for the polyvalent elements, uranium, neptunium, and selenium, were performed by the geochemical code EQ3/6. The results obtained were compared with the data appeared in the literatures on the solubilities and speciations. The geochemical behaviors of the elements with respect to the solubility and speciation could quantitatively be elucidated for the compositions of the interstitial waters in an engineered barrier and ground water in a natural barrier. In the pH range of neutral to alkali, the solubilities of U and Np tend to increase with an increase of the carbonate concentration in groundwater. This carbonate concentration dependence of the solubility was also estimated. In the engineered barrier the predominant aqueous species were specified, and in the natural barrier the change of aqueous species was also predicted while the chemical compositions changed from the reducing to oxidizing conditions. The dominant aqueous species for the elements, which migrate in and through the disposal system, were determined by the speciation analysis. (author)

  16. Effect of mass of neptunium V in intestinal absorption in the monkey and the rat

    International Nuclear Information System (INIS)

    Metivier, H.; Masse, R.; Lafuma, J.

    1983-01-01

    The coefficient of gastrointestinal transfer of neptunium as pentavalent neptunyl nitrate was studied in rats and monkeys as a function of the ingested mass. In both species, the transfer coefficient ranged between 1.10 - 3 - 1.10 - 2 when the administered mass varied from 0.3 ng to 2 mg per kg. At low concentrations, the values obtained in the monkey are about twice as low as thoses obtained in the rat. Considering the strong urinary excretion, the amounts retained at the organ levels represent about 0.1% in the rat and 0.04% in the monkey for low concentrations. The values obtained are usually in good agreement with the few data published on the rat [fr

  17. ADVANCED OXIDATION PROCESSES FOR FOOD INDUSTRIAL WASTEWATER DECONTAMINATION

    Directory of Open Access Journals (Sweden)

    Dorota Krzemińska

    2015-02-01

    Full Text Available High organic matter content is a basic problem in food industry wastewaters. Typically, the amount and composition of the effluent varies considerably. In the article four groups of advanced processes and their combination of food industry wastewater treatment have been reviewed: electrochemical oxidation (EC, Fenton’s process, ozonation of water and photocatalytic processes. All advanced oxidation processes (AOP`s are characterized by a common chemical feature: the capability of exploiting high reactivity of HO• radicals in driving oxidation processes which are suitable for achieving decolonization and odour reduction, and the complete mineralization or increase of bioavailability of recalcitrant organic pollutants.

  18. Elaboration and characterisation of yttrium oxide and hafnium oxide powders by the sol-gel process

    International Nuclear Information System (INIS)

    Hours, T.

    1988-01-01

    The two classical sol-gel processes, colloidal and polymeric are studied for the preparation of yttrium oxide and hafnium oxide high performance powders. In the colloidal process, controlled and reproducible conditions for the preparation of yttrium oxide and hafnium oxide sols from salts or alkoxides are developed and the hydrothermal synthesis monodisperse hafnium oxide colloids is studied. The polymeric process is studied with hafnium ethyl-hexylate, hydrolysis kinetics for controlled preparation of sols and gels is investigated. Each step of preparation is detailed and powders obtained are characterized [fr

  19. The reduction of plutonium (IV) and neptunium (VI) ions by N,N-ethyl (hydroxyethyl) hydroxylamine in nitric acid

    International Nuclear Information System (INIS)

    Koltunov, V.S.; Baranov, S.M.; Mezhov, E.A.; Taylor, R.J.; May, I.

    1999-01-01

    The kinetics of the reduction of neptunium (VI) and plutonium (IV) ions in nitric acid solution by a new rapid salt free reductant, N,N-ethyl (hydroxyethyl) hydroxylamine, have been studied and rate equations determined. Under equivalent conditions, both Np(VI) and Pu(IV) are reduced faster than by the related reagent, N,N-diethyl hydroxylamine, and it is suggested that this is due to the introduction of the hydroxy group into the reductant molecule. Possible reaction mechanisms have been suggested to account for the observed reaction stoichiometry. (orig.)

  20. Actinide partitioning from high level liquid waste using the Diamex process

    International Nuclear Information System (INIS)

    Madic, C.; Blanc, P.; Condamines, N.; Baron, P.; Berthon, L.; Nicol, C.; Pozo, C.; Lecomte, M.; Philippe, M.; Masson, M.; Hequet, C.

    1994-01-01

    The removal of long-lived radionuclides, which belong to the so-called minor actinides elements, neptunium, americium and curium, from the high level nuclear wastes separated during the reprocessing of the irradiated nuclear fuels in order to transmute them into short-lived nuclides, can substantially decrease the potential hazards associated with the management of these nuclear wastes. In order to separate minor actinides from high-level liquid wastes (HLLW), a liquid-liquid extraction process was considered, based on the use of diamide molecules, which display the property of being totally burnable, thus they do not generate secondary solid wastes. The main extracting properties of dimethyldibutyltetradecylmalonamide (DMDBTDMA), the diamide selected for the development of the DIAMEX process, are briefly described in this paper. Hot tests of the DIAMEX process (using DMDBTDMA) related to the treatment of an mixed oxide fuels (MOX) type HLLW, were successfully performed. The minor actinide decontamination factors of the HLLW obtained were encouraging. The main results of these tests are presented and discussed in this paper. (authors). 9 refs., 2 figs., 7 tabs

  1. Processing of effluent salt from the direct oxide reduction process

    International Nuclear Information System (INIS)

    Mishra, B.; Olson, D.L.

    1992-01-01

    The production of reactive metals by Direct Oxide Reduction (DOR) process using calcium in a molten calcium salt system generates significant amount of contaminated waste as calcium oxide saturated calcium chloride salt mix with calcium oxide content of up to 15 wt. pct. Fused salt electrolysis of a simulated salt mix has been carried out to electrowin calcium, which can be recycled to the DOR reactor along with the calcium chloride salt or may be used in-situ in a combined DOR and electrowinning process. Many reactive metal oxides could thus be reduced in a one-step process without generating a significant amount of waste. The process has been optimized in terms of the calcium solubility, cell temperature, current density and the cell design to maximize the current efficiency. Based on the information available regarding the solubility of calcium in calcium chloride salt in the presence of calcium oxide, and the back reactions occurring in-situ between the electrowon calcium and other components present in the cell, e.g. carbon, oxygen, carbon dioxide and calcium oxide, it is difficult to recover elemental calcium within the system. However, a liquid cathode or a rising cathode has been used in the past to recover calcium. The solubility has also been found to depend on the use of graphite as the anode material as evidenced by the presence of calcium carbonate in the final salt. The rate of recovery for metallic calcium has to be enhanced to levels that overcome the back reactions in a system where quick removal of anodic gases is achieved. Calcium has been detected by the hydrogen evolution technique and the amount of calcia has been determined by titration. A porous ceramic sheath has been used in the cell to prevent the chemical reaction of electrowon calcium to produce oxide or carbonate and to prevent the contamination of salt by the anodic carbon

  2. Distribution behavior of uranium, neptunium, rare-earth elements (Y, La, Ce, Nd, Sm, Eu, Gd) and alkaline-earth metals (Sr,Ba) between molten LiCl-KCl eutectic salt and liquid cadmium or bismuth

    International Nuclear Information System (INIS)

    Kurata, M.; Sakamura, Y.; Hijikata, T.; Kinoshita, K.

    1995-01-01

    Distribution coefficients of uranium neptunium, eight rare-earth elements (Y, La, Ce, Pr, Nd, Sm, Eu and Gd) and two alkaline-earth metals (Sr and Ba) between molten LiCl-KCl eutectic salt and either liquid cadmium or bismuth were measured at 773 K. Separation factors of trivalent rare-earth elements to uranium or neptunium in the LiCl-KCl/Bi system were by one or two orders of magnitude larger than those in the LiCl-KCl/Cd system. On the contrary, the separation factors of alkaline-earth metals and divalent rare-earth elements to trivalent rare-earth elements were by one or two orders of magnitude smaller in the LiCl-KCl/Bi system. (orig.)

  3. Study of the oxidation-reduction kinetics involved in the Np(V) + Fe(II) in equilibrium Np(IV) + Fe(III) system in nitric acid solutions

    International Nuclear Information System (INIS)

    Jao, Y.

    1975-08-01

    Ferrous nitrate-hydrazine is one of the more attractive alternate reactants to the currently used reagent, ferrous sulfamate, for partitioning plutonium from neptunium and uranium. An understanding of the kinetics of the reduction of Np(VI) to Np(IV) by ferrous nitrate-hydrazine is needed before a satisfactory evaluation of the feasibility of this reductant in actinide element separations can be made. The purpose of this work was to study the kinetics and mechanisms of the reduction of Np(V) by Fe(II) and the oxidation of Np(IV) by Fe(III) in 1-2 M nitric acid solutions. The acid concentration range was chosen to include that typically used in the separation of plutonium from neptunium and uranium by solvent extraction with tributylphosphate. The forward and reverse rate constants, hydrogen ion dependence, temperature dependence, ionic strength effects and nitrate ion influence were determined. The proposed reaction mechanisms involve protonation of the NpO 2 + ions and hydroxyoxygenation of Np 4 + ions. (LK)

  4. Microscopic Examination of a Corrosion Front in Spent Nuclear Fuel

    International Nuclear Information System (INIS)

    J.A. Fortner; A.J. Kropf; R.J. Finch; J.C. Cunnane

    2006-01-01

    Spent uranium oxide nuclear fuel hosts a variety of trace chemical constituents, many of which must be sequestered from the biosphere during fuel storage and disposal. In this paper we present synchrotron x-ray absorption spectroscopy and microscopy findings that illuminate the resultant local chemistry of neptunium and plutonium within spent uranium oxide nuclear fuel before and after corrosive alteration in an air-saturated aqueous environment. We find the plutonium and neptunium in unaltered spent fuel to have a +4 oxidation state and an environment consistent with solid-solution in the UO 2 matrix. During corrosion in an air-saturated aqueous environment, the uranium matrix is converted to uranyl U(VI)O 2 2+ mineral assemblage that is depleted in plutonium and neptunium relative to the parent fuel. At the corrosion front interface between intact fuel and the uranyl-mineral corrosion layer, we find evidence of a thin (∼20 micrometer) layer that is enriched in plutonium and neptunium within a predominantly U 4+ environment. Available data for the standard reduction potentials for NpO 2+ /Np 4+ and UO 2 2+ /U 4+ couples indicate that Np(IV) may not be effectively oxidized to Np(V) at the corrosion potentials of uranium dioxide spent nuclear fuel in air-saturated aqueous solutions. Neptunium is an important radionuclide in dose contribution according to performance assessment models of the proposed U. S. repository at Yucca Mountain, Nevada. A scientific understanding of how the UO 2 matrix of spent nuclear fuel impacts the oxidative dissolution and reductive precipitation of neptunium is needed to predict its behavior at the fuel surface during aqueous corrosion. Neptunium would most likely be transported as aqueous Np(V) species, but for this to occur it must first be oxidized from the Np(IV) state found within the parent spent nuclear fuel [1]. In the immediate vicinity of the spent fuel's surface the redox and nucleation behavior is likely to promote

  5. Desulfurization of AL-Ahdab Crude Oil using Oxidative Processes

    Directory of Open Access Journals (Sweden)

    Neran Khalel Ibrahim

    2015-07-01

    Full Text Available Two different oxidative desulfurization strategies based on oxidation/adsorption or oxidation/extraction were evaluated for the desulfurization of AL-Ahdab (AHD sour crude oil (3.9wt% sulfur content. In the oxidation process, a homogenous oxidizing agent comprising of hydrogen peroxide and formic acid was used. Activated carbons were used as sorbent/catalyst in the oxidation/adsorption process while acetonitrile was used as an extraction solvent in the oxidation/extraction process. For the oxidation/adsorption scheme, the experimental results indicated that the oxidation desulfurization efficiency was enhanced on using activated carbon as catalyst/sorbent. The effects of the operating conditions (contact time, temperature, mixing speed and sorbent dose on the desulfurization efficiency were examined. The desulfurization efficiency measured at the best operating conditions(optimum conditions: 60 , 500rpm, 60min contact time and sorbent dose of 0.7g AC/100 ml AHD crude, was 32.8% corresponding to a sulfur content of 2.6 wt%. Applying the same optimum operating conditions and at 3:1 solvent/oil ratio, the oxidation/extraction method gave comparable desulfurization efficiency of 31.5%.

  6. Redox stability of neptunium(V) in the presence of humic substances of varying functionality

    Energy Technology Data Exchange (ETDEWEB)

    Schmeide, K.; Geipel, G.; Bernhard, G. [Forschungszentrum Rossendorf e.V., Institute of Radiochemistry, P.O. Box 510 119, D-01314 Dresden (Germany)

    2005-07-01

    be stabilized in lower oxidation states, e.g. in complexation and sorption studies. [1] Sachs, S., Schmeide, K., Brendler, V., Krepelova, A., Mibus, J., Geipel, G., Heise, K.H., Bernhard, G.: Investigation of the Complexation and the Migration of Actinides and Nonradioactive Substances with Humic Acids under Geo-genic Conditions. Complexation of Humic Acids with Actinides in the Oxidation State IV Th, U, Np. FZR-399, Wissenschaftlich- Technische Berichte, Forschungszentrum Rossendorf, Dresden 2004. [2] Schmeide, K., Geipel, G., Bernhard, G.: Study of the Neptunium(V) Reduction by Various Natural and Synthetic Humic Substances. In: FZKA 7070, Wissenschaftliche Berichte (G. Buckau, ed.). Forschungszentrum Karlsruhe, Karlsruhe 2005, in press. (authors)

  7. Oxidation catalysts and process for preparing same

    International Nuclear Information System (INIS)

    1980-01-01

    Compounds particularly suitable as oxidation catalysis are described, comprising specified amounts of uranium, antimony and tin as oxides. Processes for making and using the catalysts are described. (U.K.)

  8. The effect of temperature on the sorption of technetium, uranium, neptunium and curium on bentonite, tuff and granodiorite

    International Nuclear Information System (INIS)

    Baston, G.M.N.; Berry, J.A.; Brownsword, M.; Heath, T.G.; Ilett, D.J.; Tweed, C.J.; Yui, M.

    1997-01-01

    A study of the sorption of the radioelements technetium; uranium; neptunium; and curium onto geological materials has been carried out as part of the PNC program to increase confidence in the performance assessment for a high-level radioactive waste repository in Japan. Batch sorption experiments have been performed in order to study the sorption of the radioelements onto bentonite, tuff and granodiorite from equilibrated de-ionized water under strongly-reducing conditions at both room temperature and at 60 C. Mathematical modelling using the geochemical speciation program HARPHRQ in conjunction with the HATCHES database has been undertaken in order to interpret the experimental results

  9. Method for the recovery of actinide elements from nuclear reactor waste

    International Nuclear Information System (INIS)

    Horwitz, E.P.; Delphin, W.H.; Mason, G.W.

    1979-01-01

    A process is described for partitioning and recovering actinide values from acidic waste solutions resulting from reprocessing of irradiated nuclear fuels by adding hydroxylammonium nitrate and hydrazine to the waste solution to adjust the valence of the neptunium and plutonium values in the solution to the +4 oxidation state, thus forming a feed solution and contacting the feed solution with an extractant of dihexoxyethyl phosphoric acid in an organic diluent whereby the actinide values, most of the rare earth values and some fission product values are taken up by the extractant. Separation is achieved by contacting the loaded extractant with two aqueous strip solutions, a nitric acid solution to selectively strip the americium, curium and rare earth values and an oxalate and oxalic acid or trimethylammonium hydrogen oxalate to selectively strip the neptunium, plutonium and fission product values. Uranium values remain in the extractant and may be recovered with a phosphoric acid strip. The neptunium and plutonium values are recovered from the oxalate by adding sufficient nitric acid to destroy the complexing ability of the oxalate, forming a second feed, and contacting the second feed with a second extractant of tricaprylmethylammonium nitrate in an inert diluent whereby the neptunium and plutonium values are selectively extracted. The values are recovered from the extractant with formic acid

  10. {open_quotes}Transmutation efficiency calculation in the blanket on melted salts with central neptunium target{close_quotes}

    Energy Technology Data Exchange (ETDEWEB)

    Kolesov, V.F.; Shtarev, S.K.; Khoruzhiy, V.K. [Russia Federal Nuclear Center, Arzamas (Russian Federation)] [and others

    1995-10-01

    In the limits of ABC project version of two-sectional reactor system in the form of combination of subcritical blanket on melted salts and multiplying target from threshold fissile material {sup 237}Np is considered. This research is the development of the VNIIEF`s earlier work`s (Russia) investigating of usage possibilities in ABC project the conception of multisectional blankets with single-sided neutron coupling between sections. With the help of Monte-Carlo program the calculations results of system mentioned are given. The possibility of accelerator`s considerable power reduction at the account of thorium target substitution with neptunium-237 multiplying target is shown.

  11. Characterization of oxalate-based 237NpO2 powder

    International Nuclear Information System (INIS)

    Rankin, D.T.; Burney, G.A.; Smith, P.K.; Sisson, R.D.

    1976-01-01

    238 Pu, a radioisotope heat source, is produced by irradiating reactor targets containing 237 NpO 2 . The neptunium oxide is obtained by precipitating and calcining 237 Np(IV) oxalate. The effects of oxalate precipitation parameters on particle morphology and size distribution of 237 NpO 2 powder were established to provide process controls for fabricating reactor targets

  12. Recent Advances of Solution-Processed Metal Oxide Thin-Film Transistors.

    Science.gov (United States)

    Xu, Wangying; Li, Hao; Xu, Jian-Bin; Wang, Lei

    2018-03-06

    Solution-processed metal oxide thin-film transistors (TFTs) are considered as one of the most promising transistor technologies for future large-area flexible electronics. This review surveys the recent advances in solution-based oxide TFTs, including n-type oxide semiconductors, oxide dielectrics and p-type oxide semiconductors. Firstly, we provide an introduction on oxide TFTs and the TFT configurations and operating principles. Secondly, we present the recent progress in solution-processed n-type transistors, with a special focus on low-temperature and large-area solution processed approaches as well as novel non-display applications. Thirdly, we give a detailed analysis of the state-of-the-art solution-processed oxide dielectrics for low-voltage electronics. Fourthly, we discuss the recent progress in solution-based p-type oxide semiconductors, which will enable the highly desirable future low-cost large-area complementary circuits. Finally, we draw the conclusions and outline the perspectives over the research field.

  13. Partial oxidation process

    International Nuclear Information System (INIS)

    Najjar, M.S.

    1987-01-01

    A process is described for the production of gaseous mixtures comprising H/sub 2/+CO by the partial oxidation of a fuel feedstock comprising a heavy liquid hydrocarbonaceous fuel having a nickel, iron, and vanadium-containing ash or petroleum coke having a nickel, iron, and vanadium-containing ash, or mixtures thereof. The feedstock includes a minimum of 0.5 wt. % of sulfur and the ash includes a minimum of 5.0 wt. % vanadium, a minimum of 0.5 ppm nickel, and a minimum of 0.5 ppm iron. The process comprises: (1) mixing together a copper-containing additive with the fuel feedstock; wherein the weight ratio of copper-containing additive to ash in the fuel feedstock is in the range of about 1.0-10.0, and there is at least 10 parts by weight of copper for each part by weight of vanadium; (2) reacting the mixture from (1) at a temperature in the range of 2200 0 F to 2900 0 F and a pressure in the range of about 5 to 250 atmospheres in a free-flow refactory lined partial oxidation reaction zone with a free-oxygen containing gas in the presence of a temperature moderator and in a reducing atmosphere to produce a hot raw effluent gas stream comprising H/sub 2/+CO and entrained molten slag; and where in the reaction zone and the copper-containing additive combines with at least a portion of the nickel and iron constituents and sulfur found in the feedstock to produce a liquid phase washing agent that collects and transports at least a portion of the vanadium-containing oxide laths and spinels and other ash components and refractory out of the reaction zone; and (3) separating nongaseous materials from the hot raw effluent gas stream

  14. Oxidation-extraction of uranium from wet-process phosphoric acid

    International Nuclear Information System (INIS)

    Lawes, B.C.

    1985-01-01

    The invention involves an improvement to the reductive stripping process for recovering uranium values from wet-process phosphoric acid solution, where uranium in the solution is oxidized to uranium (VI) oxidation state and then extracted from the solution by contact with a water immiscible organic solvent, by adding sufficient oxidant, hydrogen peroxide, to obtain greater than 90 percent conversion of the uranium to the uranium (VI) oxidation state to the phosphoric acid solution and simultaneously extracting the uranium (VI)

  15. Oxide nano-rod array structure via a simple metallurgical process

    International Nuclear Information System (INIS)

    Nanko, M; Do, D T M

    2011-01-01

    A simple method for fabricating oxide nano-rod array structure via metallurgical process is reported. Some dilute alloys such as Ni(Al) solid solution shows internal oxidation with rod-like oxide precipices during high-temperature oxidation with low oxygen partial pressure. By removing a metal part in internal oxidation zone, oxide nano-rod array structure can be developed on the surface of metallic components. In this report, Al 2 O 3 or NiAl 2 O 4 nano-rod array structures were prepared by using Ni(Al) solid solution. Effects of Cr addition into Ni(Al) solid solution on internal oxidation were also reported. Pack cementation process for aluminizing of Ni surface was applied to prepare nano-rod array components with desired shape. Near-net shape Ni components with oxide nano-rod array structure on their surface can be prepared by using the pack cementation process and internal oxidation,

  16. Low Temperature Processed Complementary Metal Oxide Semiconductor (CMOS) Device by Oxidation Effect from Capping Layer

    KAUST Repository

    Wang, Zhenwei

    2015-04-20

    In this report, both p- and n-type tin oxide thin-film transistors (TFTs) were simultaneously achieved using single-step deposition of the tin oxide channel layer. The tuning of charge carrier polarity in the tin oxide channel is achieved by selectively depositing a copper oxide capping layer on top of tin oxide, which serves as an oxygen source, providing additional oxygen to form an n-type tin dioxide phase. The oxidation process can be realized by annealing at temperature as low as 190°C in air, which is significantly lower than the temperature generally required to form tin dioxide. Based on this approach, CMOS inverters based entirely on tin oxide TFTs were fabricated. Our method provides a solution to lower the process temperature for tin dioxide phase, which facilitates the application of this transparent oxide semiconductor in emerging electronic devices field.

  17. Influence of the redox state on the neptunium sorption under alkaline conditions. Batch sorption studies on titanium dioxide and calcium silicate hydrates

    International Nuclear Information System (INIS)

    Tits, Jan; Laube, Andreas; Wieland, Erich; Gaona, Xavier

    2014-01-01

    Wet chemistry experiments were carried out to investigate the effect of the redox state and aqueous speciation on the uptake of neptunium by titanium dioxide (TiO 2 ) and by calcium silicate hydrates (C-S-H) under alkaline conditions. TiO 2 was chosen as a reference sorbent to determine the surface complexation behaviour of neptunium under alkaline conditions. C-S-H phases are important constituents of cement and concrete. They may contribute significantly to radionuclide retention due to their high recrystallization rates making incorporation the dominating sorption mechanism for many radionuclides (e.g. the actinides) on these materials. The sorption of neptunium on both solids was found to depend strongly on the degree of hydrolysis. On TiO 2 R d values for Np(IV), Np(V) and Np(VI) are identical at pH = 10 and decrease with progressing hydrolysis in case of Np(V) and Np(VI). On C-S-H phases, R d values for the three redox states are also identical at pH = 10. While the R d values for Np(VI) sorption on C-S-H phases decrease with progressing hydrolysis, the R d values for Np(IV) and Np(V) sorption are not affected by the pH. In addition to the effect of hydrolysis, the presence of Ca is found to promote Np(V) and Np(VI) sorption on TiO 2 whereas on C-S-H phases, the present wet chemistry data do not give unambiguous evidence. Thus, the aqueous speciation appears to have a similar influence on the sorption of the actinides on both types of solids despite the different sorption mechanism. The similar R d values for Np(IV,V,VI) sorption at pH = 10 can be explained qualitatively by invoking inter-ligand electrostatic repulsion between OH groups in the coordination sphere of Np(V) and Np(VI). This mechanism was proposed earlier in the literature for the prediction of actinide complexation constants with inorganic ligands. A limiting coordination number for each Np redox state, resulting from the inter-ligand electrostatic repulsion, allows the weaker sorption of the

  18. Bio-reduction of plutonyl and neptunyl by Shewanella alga

    International Nuclear Information System (INIS)

    Reed, D.T.; Lucchini, J.F; Rittmann, B.E.; Songkasiri, W.

    2005-01-01

    Full text of publication follows: The results of a concurrent experimental and modeling study to investigate the bio-reduction of higher-valent plutonium and neptunium by Shewanella alga strain BrY are presented. S. Alga, as a facultative metal reducer, is representative of bacteria that will be important in defining the mobility of plutonium and neptunium species as they migrate from oxic to anoxic zones. This is also an important consideration in defining the long-term stability of bio-precipitated 'immobilized' plutonium phases under changing redox conditions in biologically active systems and subsequently the effectiveness of remediation/containment approaches used for bio-remediation. Neptunium (VI) is readily reduced in groundwaters by many organics. In biologically active systems, it is unlikely, for this reason, that this oxidation state of neptunium will be important. Under all conditions investigated, neptunium (V) was reduced to neptunium (IV) when anaerobic conditions were established for a wide variety of electron donors. This was evidences by 3-4 orders of magnitude reduction in solution concentration and confirmed by XANES analysis. This led to high bio-association and/or precipitation of the neptunium. Plutonium (VI), as was the case with neptunium (VI) was reduced by the organics typically present in biologically active systems. Analogous bio-reduction experiments with plutonium (V) and plutonium (VI) are in progress and are expected to show that bio-reduction will predominate under anaerobic conditions, as was the case with neptunium. These results for neptunium and plutonium show S. Alga to be an effective microbe for the bio-reduction, and consequently the immobilization, of these important actinide contaminants. (authors)

  19. Computational Study on Mössbauer Isomer Shifts of Some Organic-neptunium (IV Complexes

    Directory of Open Access Journals (Sweden)

    Masashi Kaneko

    2015-12-01

    Full Text Available Relativistic DFT calculations are applied to some organo-neptunium (IV complexes, Cp3NpIVX (Cp = η5-C5H5; X = BH4, Cl, OtBu, Ph, nBu, in order to understand their bonding properties between Np and the ligands. We employ scalar-relativistic ZORA Hamiltonian with all-electron basis set (SARC. The calculated electron densities at Np nucleus position in the complexes at B2PLYP / SARC theory strongly correlate to the experimental Mössbauer isomer shifts of 237Np system. The result of bond overlap population analysis indicates that the bonding strength decreases in order of X = BH4, Cl, OtBu, Ph and nBu. The tendency depends on the degree of the covalent interaction between Np 5f-electron and X ligand. It is suggested that it is important to estimate the bonding contribution of 5f-orbital to understand the electronic state for organo-actinide complexes.

  20. Removal of actinide elements from high level radioactive waste by trialkylphosphine oxide (TRPO)

    International Nuclear Information System (INIS)

    Song Chongli; Yang Dazhu; He Longhai; Xu Jingming; Zhu Yongjun

    1992-03-01

    The modified TRPO process for removing actinide elements from synthetic solution, which was taken from reprocessing of power reactor nuclear fuel, was verified by cascade experiment. Neptunium valence was adjusted in the process for improving neptunium removing efficiency. At 1 mol/L concentration of HNO 3 of feed solution and after a few stages of extraction with 30% t=TRPO kerosene, over 99.9% of Am, Pu, Np and U could be removed from HAW (high level radioactive waste) solution. The stripping of actinides loaded in TRPO are accomplished by high concentration nitric acid, oxalic acid and sodium carbonate instead of amino carboxylic complexing agents used in previous process. The actinides stripped were divided into three groups, which are Am + RE, Np + Pu, and U, and the cross contamination between them is small. Behaviours of F.P. elements are divided into three types which are not extracted, little extracted and extracted elements. The extracted elements are rare earth and Pd, Zr and Mo which are co-extracted with actinides. The separation factor between actinides and other two types of F.P.elements will increase if more scrubbing sections are added in the process. The relative concentration profile of actinide elements and Tc in various stages as well as the distribution of actinides and F.P. elements in the process stream solutions are also presented

  1. Supported versus colloidal zinc oxide for advanced oxidation processes

    Science.gov (United States)

    Laxman, Karthik; Al Rashdi, Manal; Al Sabahi, Jamal; Al Abri, Mohammed; Dutta, Joydeep

    2017-07-01

    Photocatalysis is a green technology which typically utilizes either supported or colloidal catalysts for the mineralization of aqueous organic contaminants. Catalyst surface area and surface energy are the primary factors determining its efficiency, but correlation between the two is still unclear. This work explores their relation and hierarchy in a photocatalytic process involving both supported and colloidal catalysts. In order to do this the active surface areas of supported zinc oxide nanorods (ZnO NR's) and colloidal zinc oxide nanoparticles (having different surface energies) were equalized and their phenol oxidation mechanism and capacity was analyzed. It was observed that while surface energy had subtle effects on the oxidation rate of the catalysts, the degradation efficiency was primarily a function of the surface area; which makes it a better parameter for comparison when studying different catalyst forms of the same material. Thus we build a case for the use of supported catalysts, wherein their catalytic efficiency was tested to be unaltered over several days under both natural and artificial light, suggesting their viability for practical applications.

  2. Anodic oxidation with doped diamond electrodes: a new advanced oxidation process

    International Nuclear Information System (INIS)

    Kraft, Alexander; Stadelmann, Manuela; Blaschke, Manfred

    2003-01-01

    Boron-doped diamond anodes allow to directly produce OH· radicals from water electrolysis with very high current efficiencies. This has been explained by the very high overvoltage for oxygen production and many other anodic electrode processes on diamond anodes. Additionally, the boron-doped diamond electrodes exhibit a high mechanical and chemical stability. Anodic oxidation with diamond anodes is a new advanced oxidation process (AOP) with many advantages compared to other known chemical and photochemical AOPs. The present work reports on the use of diamond anodes for the chemical oxygen demand (COD) removal from several industrial wastewaters and from two synthetic wastewaters with malic acid and ethylenediaminetetraacetic (EDTA) acid. Current efficiencies for the COD removal between 85 and 100% have been found. The formation and subsequent removal of by-products of the COD oxidation has been investigated for the first time. Economical considerations of this new AOP are included

  3. Neptunium(V) sorption on kaolinite

    Energy Technology Data Exchange (ETDEWEB)

    Amayri, S.; Jermolajev, A.; Reich, T. [Mainz Univ. (Germany). Inst. of Nuclear Chemistry

    2011-07-01

    The sorption behavior of neptunium(V) onto the clay mineral kaolinite was studied in batch experiments under different experimental conditions: [Np(V)] = 7 x 10{sup -12}-8 x 10{sup -6} M, solid-to-liquid ratio 2-20 g L{sup -1}, I = 0.1 and 0.01 M NaClO{sub 4}, pH = 6-10, ambient air and Ar atmosphere. The short-lived isotope {sup 239}Np (T{sub 1/2} = 2.36 d) was used instead of {sup 237}Np (T{sub 1/2} = 2.14 x 10{sup 6} a) to study the sorption behavior of Np(V) at environmentally-relevant concentrations, i.e., 7 x 10{sup -12} M Np. In addition, {sup 239}Np(V) served as tracer to measure sorption isotherms over six orders of magnitude in Np concentration (4.8 x 10{sup -12}-1.0 x 10{sup -4} M). The results show that Np(V) sorption on kaolinite is strongly influenced by pH, CO{sub 2}, and ionic strength. The sorption of 8 x 10{sup -6} M Np(V) at pH 9.0, and ionic strength of 0.1 M NaClO{sub 4} was proportional to the solid-to-liquid ratio of kaolinite in the range of 2-10 g L{sup -1}. In the absence of CO{sub 2}, the Np(V) uptake increased continuously with increasing pH value up to 97% at pH 10. Under ambient CO{sub 2}, the sorption of Np decreased above pH 8 up to zero at pH 10. An increase of Np(V) concentration from 7 x 10{sup -12} to 8 x 10{sup -6} M resulted in a shift of the sorption pH edge by up to one pH unit to higher pH values. The ionic strength influenced the Np(V) sorption onto kaolinite only in the presence of ambient CO{sub 2}. Under Ar atmosphere the sorption of Np(V) was independent from ionic strength, indicating the formation of inner-sphere complexes of Np(V) with kaolinite. Time-dependent batch experiments at pH 9.0 under ambient CO{sub 2} showed that the sorption of Np(V) on kaolinite is fast and fully reversible over six orders in Np(V) concentration. (orig.)

  4. Solubility of neptunium and technetium dioxides in a Yucca Mountain simulated groundwaters

    International Nuclear Information System (INIS)

    Kulyako, Yu.; Perevalov, S.; Malikov, D.; Myasoedov, B.; Atkins-Duffin, Cynthia E.

    2005-01-01

    Full text of publication follows: Solubility of NpO 2 and TcO 2 in the Yucca Mountain simulated ground waters J-13 and UE-25p-1 were studied. It is shown that contents of the dissolved neptunium and technetium in simulated groundwater (SGW) depend on solid/liquid phase ratio in these systems under ambient conditions. Average values of NpO 2 solubility in the suspensions of J-13 SGW are equal to (1.1±0.2) x 10 -6 M, (4.7±0.5) x 10 -6 M and (1.3±0.2) x 10 -5 M at solid/liquid ratios (mg/mL) of 0.4, 2.5 and 9.8 respectively. Average solubility values of NpO 2 in the suspensions of UE-25p-1 SGW are equal to (1.6±0.2) x 10 -7 M, (4.3±0.7) x 10 -7 M and (4.2±1.2) x 10 -6 M for solid/liquid ratios (mg/mL) of 1.2, 3.7 and 18.6, respectively. At equal solid/liquid ratios the solubility of NpO 2 in J-13 SGW is higher than that in UE-25p-1 SGW. At equal contents of solid phase in the suspensions solubility of TcO 2 in J-13 SGW are close to those in UE-25p-1 SGW and they are approximately proportional to the solid/liquid ratio. Average values of TcO 2 solubility in the suspensions of J-13 SGW are equal to (3.0±0.2) x 10 -5 M, (1.7±0.2) x 10 -4 , (6.2±0.2) x 10 -4 M at solid/liquid ratios (mg/mL) of 0.6, 4.8 and 15.5 respectively. Average values of TcO 2 solubility in the suspensions of UE-25p-1 SGW are equal to (5.8±0.3) x 10 -5 M, (2.2±0.1) x 10 -4 M and (3.8±0.2) x 10 -4 M at solid/liquid ratios 1.6, 7.0 and 13.6 (mg/mL) respectively. The dependence of solubility of NpO 2 and TcO 2 on solid/liquid ratio may be explained by the fact that transition of the neptunium and technetium from solid phase into the liquid one occurs on phase interface owing to the dissolving of Np(V) and Tc(VII) compounds being formed under ambient conditions. (authors)

  5. Uranium, neptunium and plutonium kinetics of extraction by tributylphosphate and trilaurylamine in a centrifugal contactor

    International Nuclear Information System (INIS)

    Bergeonneau, P.; Jaouen, C.; Germain, M.; Bathellier, A.

    1977-01-01

    Uranium, plutonium and neptunium kinetics of transfer between various aqueous nitric solutions and solvents have been measured at the laboratory scale, using a centrifugal contactor especially developed in the laboratory. The transfer kinetics of nitric acid, hexavalent U, tetravalent U, Np and Pu from nitric acid solutions into 30% TBP in r-dodecane and 10% trilaurylamine in r-dodecane have been studied. The effects of rotation speed, temperature, initial nitric acid concentration, metal concentration on extraction and stripping kinetics have been investigated. The results obtained show that TBP extraction and stripping are more rapid than trilaurylamine ones. The low activation energies of transfer reactions with TBP suggest that both in extraction and stripping, the transfer rate is limited by the diffusion of the species in the aqueous and organic phases. For trilaurylamine, the transfer mechanism appears more complex

  6. Method for the recovery of actinide elements from nuclear reactor waste

    Science.gov (United States)

    Horwitz, E. Philip; Delphin, Walter H.; Mason, George W.

    1979-01-01

    A process for partitioning and recovering actinide values from acidic waste solutions resulting from reprocessing of irradiated nuclear fuels by adding hydroxylammonium nitrate and hydrazine to the waste solution to adjust the valence of the neptunium and plutonium values in the solution to the +4 oxidation state, thus forming a feed solution and contacting the feed solution with an extractant of dihexoxyethyl phosphoric acid in an organic diluent whereby the actinide values, most of the rare earth values and some fission product values are taken up by the extractant. Separation is achieved by contacting the loaded extractant with two aqueous strip solutions, a nitric acid solution to selectively strip the americium, curium and rare earth values and an oxalate solution of tetramethylammonium hydrogen oxalate and oxalic acid or trimethylammonium hydrogen oxalate to selectively strip the neptunium, plutonium and fission product values. Uranium values remain in the extractant and may be recovered with a phosphoric acid strip. The neptunium and plutonium values are recovered from the oxalate by adding sufficient nitric acid to destroy the complexing ability of the oxalate, forming a second feed, and contacting the second feed with a second extractant of tricaprylmethylammonium nitrate in an inert diluent whereby the neptunium and plutonium values are selectively extracted. The values are recovered from the extractant with formic acid.

  7. Recovery actinide values

    International Nuclear Information System (INIS)

    Horwitz, E.P.; Delphin, W.H.; Mason, G.W.

    1979-01-01

    A process is described for partitioning and recovering actinide values from acidic waste solutions resulting from reprocessing of irradiated nuclear fuels by adding hydroxylammonium nitrate and hydrazine to the waste solution to adjust the valence of the neptunium and plutonium values in the solution to the +4 oxidation state, thus forming a feed solution and contacting the feed solution with an extractant of di-hexoxyethyl phosphoric acid in an organic diluent whereby the actinide values, most of the rare earth values and some fission product values are taken up by the extractant. Separation is achieved by contacting the loaded extractant with two aqueous strip solutions, a nitric acid solution to selectively strip the americium, curium and rare earth values and an oxalate solution of tetramethylammonium hydrogen oxalate and oxalic acid or trimethylammonium hydrogen oxalate to selectively strip the neptunium, plutonium and fission product values. Uranium values remain in the extractant and may be recovered with a phosphoric acid strip. The neptunium and plutonium values are recovered from the oxalate by adding sufficient nitric acid to destroy the complexing ability of the oxalate, forming a second feed, and contacting the second feed with a second extractant of tricaprylmethylammonium nitrate in an inert diluent whereby the neptunium and plutonium values are selectively extracted. The values are recovered from the extractant with formic acid. (author)

  8. Measuring oxidation processes: Atomic oxygen flux monitor

    International Nuclear Information System (INIS)

    Anon.

    1991-01-01

    Of the existing 95 high-energy accelerators in the world, the Stanford Linear Collider (SLC) at the Stanford Linear Accelerator Center (SLAC) is the only one of the linear-collider type, where electrons and positrons are smashed together at energies of 50 GeV using linear beams instead of beam rings for achieving interactions. Use of a collider eliminates energy losses in the form of x-rays due to the curved trajectory of the rings, a phenomena known as bremsstrauhlung. Because these losses are eliminated, higher interaction energies are reached. Consequently the SLC produced the first Z particle in quantities large enough to allow measurement of its physical properties with some accuracy. SLAC intends to probe still deeper into the structure of matter by next polarizing the electrons in the beam. The surface of the source for these polarized particles, typically gallium arsenide, must be kept clean of contaminants. One method for accomplishing this task requires the oxidation of the surface, from which the oxidized contaminants are later boiled off. The technique requires careful measurement of the oxidation process. SLAC researchers have developed a technique for measuring the atomic oxygen flux in this process. The method uses a silver film on a quartz-crystal, deposition-rate monitor. Measuring the initial oxidation rate of the silver, which is proportional to the atomic oxygen flux, determines a lower limit on that flux in the range of 10 13 to 10 17 atoms per square centimeter per second. Furthermore, the deposition is reversible by exposing the sensor to atomic hydrogen. This technique has wider applications to processes in solid-state and surface physics as well as surface chemistry. In semiconductor manufacturing where a precise thickness of oxide must be deposited, this technique could be used to monitor the critical flux of atomic oxygen in the process

  9. Electrochemical advanced oxidation processes: today and tomorrow. A review.

    Science.gov (United States)

    Sirés, Ignasi; Brillas, Enric; Oturan, Mehmet A; Rodrigo, Manuel A; Panizza, Marco

    2014-01-01

    In recent years, new advanced oxidation processes based on the electrochemical technology, the so-called electrochemical advanced oxidation processes (EAOPs), have been developed for the prevention and remediation of environmental pollution, especially focusing on water streams. These methods are based on the electrochemical generation of a very powerful oxidizing agent, such as the hydroxyl radical ((•)OH) in solution, which is then able to destroy organics up to their mineralization. EAOPs include heterogeneous processes like anodic oxidation and photoelectrocatalysis methods, in which (•)OH are generated at the anode surface either electrochemically or photochemically, and homogeneous processes like electro-Fenton, photoelectro-Fenton, and sonoelectrolysis, in which (•)OH are produced in the bulk solution. This paper presents a general overview of the application of EAOPs on the removal of aqueous organic pollutants, first reviewing the most recent works and then looking to the future. A global perspective on the fundamentals and experimental setups is offered, and laboratory-scale and pilot-scale experiments are examined and discussed.

  10. Contribution to the study of liquid-liquid extraction dynamics in the case of fast transfers. Extractions of uranium, plutonium and neptunium in a laboratory centrifugal extractor

    International Nuclear Information System (INIS)

    Bergeonneau, Philippe

    1978-01-01

    The liquid-liquid extraction (also named solvent-based extraction) is a very important technique for the reprocessing of irradiated nuclear fuels. This research thesis is based on the use of a laboratory centrifugal extractor which allows interesting conditions to be achieved: fast transfer due to an intense solution mixing, very short duration of contact between solutions. Thus, after a report of a bibliographical study on chemical mechanisms of extraction, on the composition of extracted species, on extraction kinetics, and on centrifugal extractors, this thesis reports the design, fabrication and use of a centrifugal extractor: presentation of fundamental principles, description and characteristics (materials, hydrodynamic operation test and problems, prototype). It reports studies of fast transfer kinetics: mathematical processing, result interpretation, results and discussions of extraction kinetics for nitric acid, uranium VI and IV, plutonium IV, neptunium IV, and comparison of the different extraction kinetics

  11. Creation of a simplified benchmark model for the neptunium sphere experiment

    International Nuclear Information System (INIS)

    Mosteller, Russell D.; Loaiza, David J.; Sanchez, Rene G.

    2004-01-01

    Although neptunium is produced in significant amounts by nuclear power reactors, its critical mass is not well known. In addition, sizeable uncertainties exist for its cross sections. As an important step toward resolution of these issues, a critical experiment was conducted in 2002 at the Los Alamos Critical Experiments Facility. In the experiment, a 6-kg sphere of 237 Np was surrounded by nested hemispherical shells of highly enriched uranium. The shells were required in order to reach a critical condition. Subsequently, a detailed model of the experiment was developed. This model faithfully reproduces the components of the experiment, but it is geometrically complex. Furthermore, the isotopics analysis upon which that model is based omits nearly 1 % of the mass of the sphere. A simplified benchmark model has been constructed that retains all of the neutronically important aspects of the detailed model and substantially reduces the computer resources required for the calculation. The reactivity impact, of each of the simplifications is quantified, including the effect of the missing mass. A complete set of specifications for the benchmark is included in the full paper. Both the detailed and simplified benchmark models underpredict k eff by more than 1% Δk. This discrepancy supports the suspicion that better cross sections are needed for 237 Np.

  12. Microgravity Processing of Oxide Superconductors

    Science.gov (United States)

    Olive, James R.; Hofmeister, William H.; Bayuzick, Robert J.; Vlasse, Marcus

    1999-01-01

    Considerable effort has been concentrated on the synthesis and characterization of high T(sub c) oxide superconducting materials. The YBaCuO system has received the most intense study, as this material has shown promise for the application of both thin film and bulk materials. There are many problems with the application of bulk materials- weak links, poor connectivity, small coherence length, oxygen content and control, environmental reactivity, phase stability, incongruent melting behavior, grain boundary contamination, brittle mechanical behavior, and flux creep. The extent to which these problems are intrinsic or associated with processing is the subject of controversy. This study seeks to understand solidification processing of these materials, and to use this knowledge for alternative processing strategies, which, at the very least, will improve the understanding of bulk material properties and deficiencies. In general, the phase diagram studies of the YBaCuO system have concentrated on solid state reactions and on the Y2BaCuO(x) + liquid yields YBa2Cu3O(7-delta) peritectic reaction. Little information is available on the complete melting relations, undercooling, and solidification behavior of these materials. In addition, rare earth substitutions such as Nd and Gd affect the liquidus and phase relations. These materials have promising applications, but lack of information on the high temperature phase relations has hampered research. In general, the understanding of undercooling and solidification of high temperature oxide systems lags behind the science of these phenomena in metallic systems. Therefore, this research investigates the fundamental melting relations, undercooling, and solidification behavior of oxide superconductors with an emphasis on improving ground based synthesis of these materials.

  13. Processes regulating nitric oxide emissions from soils

    DEFF Research Database (Denmark)

    Pilegaard, Kim

    2013-01-01

    , the net result is complex and dependent on several factors such as nitrogen availability, organic matter content, oxygen status, soil moisture, pH and temperature. This paper reviews recent knowledge on processes forming NO in soils and the factors controlling its emission to the atmosphere. Schemes......Nitric oxide (NO) is a reactive gas that plays an important role in atmospheric chemistry by influencing the production and destruction of ozone and thereby the oxidizing capacity of the atmosphere. NO also contributes by its oxidation products to the formation of acid rain. The major sources...

  14. Alpha self-irradiation effects in ternary oxides of actinides elements: The zircon-like phases AmIIIVO4 and AIINpIV(VO4)2 (A=Sr, Pb)

    International Nuclear Information System (INIS)

    Goubard, F.; Griesmar, P.; Tabuteau, A.

    2005-01-01

    We report the experimental studies of irradiation damage from alpha decay in neptunium and americium vanadates versus cumulative dose. The isotopes used were the transuranium α-emitter 237 Np and the α,γ-emitter 241 Am. Neptunium and americium vanadates self-irradiation was studied by X-ray diffraction method (XRD). The comparison of the powder diffraction patterns reveal that the irradiation has no apparent effect on the neptunium phases while the americium vanadate swells and becomes metamict as a function of cumulative dose

  15. Iron-oxidation processes in an electroflocculation (electrocoagulation) cell

    Energy Technology Data Exchange (ETDEWEB)

    Sasson, Moshe Ben, E-mail: mosheinspain@hotmail.com [Department of Soil and Water Sciences, Robert H. Smith Faculty of Agriculture, Food and Environment, Hebrew University of Jerusalem, Rehovot 76100 (Israel); Calmano, Wolfgang [Institute of Environmental Technology and Energy Economics, Technical University of Hamburg-Harburg, 21073 Hamburg (Germany); Adin, Avner [Department of Soil and Water Sciences, Robert H. Smith Faculty of Agriculture, Food and Environment, Hebrew University of Jerusalem, Rehovot 76100 (Israel)

    2009-11-15

    The processes of iron oxidation in an electroflocculation cell were investigated for a pH range of 5-9 and electric currents of 0.05-0.4 A (equivalent current densities of 8.6-69 A/m{sup 2}). At all pH values and electric currents investigated, it was demonstrated and proven that for all practical purposes, the form of iron that dissolves from the anode is Fe{sup 2+} (ferrous). The difference between the amount of theoretical dissolution as calculated by Faraday's law and the amount of observed dissolved iron ions may indicate two phenomena in electrochemical cells. The first is possible dissolution of the anode even without the operation of an electric current; this led to higher theoretical dissolution rates at lower pH. The second is the participation of some of the electrons of the electric current in reactions other than anode dissolution which led to lower theoretical dissolution rates at higher pH. Those other reactions did not lead to an increase in the local oxidation saturation level near the anode and did not affect iron-oxidation rates in the electroflocculation processes. The oxidation rates of the dissolved Fe{sup 2+} (ferrous) to Fe{sup 3+} (ferric) ions in electroflocculation processes were strongly dependent on the pH and were similar to the known oxidation rates of iron in non-electrochemical cells.

  16. Iron-oxidation processes in an electroflocculation (electrocoagulation) cell

    International Nuclear Information System (INIS)

    Sasson, Moshe Ben; Calmano, Wolfgang; Adin, Avner

    2009-01-01

    The processes of iron oxidation in an electroflocculation cell were investigated for a pH range of 5-9 and electric currents of 0.05-0.4 A (equivalent current densities of 8.6-69 A/m 2 ). At all pH values and electric currents investigated, it was demonstrated and proven that for all practical purposes, the form of iron that dissolves from the anode is Fe 2+ (ferrous). The difference between the amount of theoretical dissolution as calculated by Faraday's law and the amount of observed dissolved iron ions may indicate two phenomena in electrochemical cells. The first is possible dissolution of the anode even without the operation of an electric current; this led to higher theoretical dissolution rates at lower pH. The second is the participation of some of the electrons of the electric current in reactions other than anode dissolution which led to lower theoretical dissolution rates at higher pH. Those other reactions did not lead to an increase in the local oxidation saturation level near the anode and did not affect iron-oxidation rates in the electroflocculation processes. The oxidation rates of the dissolved Fe 2+ (ferrous) to Fe 3+ (ferric) ions in electroflocculation processes were strongly dependent on the pH and were similar to the known oxidation rates of iron in non-electrochemical cells.

  17. Development studies of a novel wet oxidation process

    International Nuclear Information System (INIS)

    Rogers, T.W.; Dhooge, P.M.

    1995-01-01

    Many DOE waste streams and remediates contain complex and variable mixtures of organic compounds, toxic metals, and radionuclides. These materials are often dispersed in organic or inorganic matrices, such as personal protective equipment, various sludges, soils, and water. Incineration and similar combustive processes do not appear to be viable options for treatment of these waste streams due to various considerations. The objective of this project is to develop a novel catalytic wet oxidation process for the treatment of multi-component wastes. The DETOX process uses a unique combination of metal catalysts to increase the rate of oxidation of organic materials

  18. Development studies of a novel wet oxidation process

    Energy Technology Data Exchange (ETDEWEB)

    Rogers, T.W.; Dhooge, P.M. [Delphi Research, Inc., Albuquerque, NM (United States)

    1995-10-01

    Many DOE waste streams and remediates contain complex and variable mixtures of organic compounds, toxic metals, and radionuclides. These materials are often dispersed in organic or inorganic matrices, such as personal protective equipment, various sludges, soils, and water. Incineration and similar combustive processes do not appear to be viable options for treatment of these waste streams due to various considerations. The objective of this project is to develop a novel catalytic wet oxidation process for the treatment of multi-component wastes. The DETOX process uses a unique combination of metal catalysts to increase the rate of oxidation of organic materials.

  19. Delay oil oxidation during frying process

    International Nuclear Information System (INIS)

    Atta, N.M.M.; Shams Eldin, N.M.M.

    2010-01-01

    Blend oil (mixed of refined sunflower and soy beans oils 1:1 w/w) containing add 200 ppm of rosemary leaves methanolic extract (rosemary extract) (RE) and 3% refined rice bran oil (RRBO), were used in frying process at 1800 degree c for 5 hrs/ day, four consecutive days to delay oil oxidation during frying. Therefore, rosemary extract (methanolic extract) was analyzed by HPLC technique for identification of flavonoids compounds (as a specific active compounds; gives high protection to frying oil). Physical and chemical properties, including refractive index(RI). Red color unit (R), viscosity, acidity (FFA), peroxide value (PV), iodine value (IV) oxidized fatty acid (OFA), polymer content (PC), total polar components (TPC) and trans fatty acid (TFA) as eliadic acid were determined. The results indicated that; rosemary extract contained about eight flavonoids compounds (hypersoid, rutin, 3-OH flavon, luleotin, kempferol, sakarutin, querectrin and apeginin). Addition of RE or RRBO to frying oil caused delay oil oxidation during frying process compared with frying oil without any addition. Also, the results indicated that rosemary extract was more effective in reducing formation of PV, FFA, OFA, PC, TPC and TFA in frying oil than refined rice bran oil

  20. Integrative device and process of oxidization, degassing, acidity adjustment of 1BP from APOR process

    Energy Technology Data Exchange (ETDEWEB)

    Zuo, Chen; Zheng, Weifang, E-mail: wfazh@ciae.ac.cn; Yan, Taihong; He, Hui; Li, Gaoliang; Chang, Shangwen; Li, Chuanbo; Yuan, Zhongwei

    2016-02-15

    Graphical abstract: Previous (left) and present (right) device of oxidation, degassing, acidity adjustment of 1BP. - Highlights: • We designed an integrative device and process. • The utilization efficiency of N{sub 2}O{sub 4} is increased significantly. • Our work results in considerable simplification of the device. • Process parameters are determined by experiments. - Abstract: Device and process of oxidization, degassing, acidity adjustment of 1BP (The Pu production feed from U/Pu separation section) from APOR process (Advanced Purex Process based on Organic Reductants) were improved through rational design and experiments. The device was simplified and the process parameters, such as feed position and flow ratio, were determined by experiments. Based on this new device and process, the reductants N,N-dimethylhydroxylamine (DMHAN) and methylhydrazine (MMH) in 1BP solution could be oxidized with much less N{sub 2}O{sub 4} consumption.

  1. Powder processing of high Tc oxide superconductors and their properties

    International Nuclear Information System (INIS)

    Vajpei, A.C.; Upadhyaya, G.S.

    1992-01-01

    Powder processing of ceramics is an established technology and in the area of high T c superconductors, its importance is felt even more significantly. The present monograph is an attempt in this direction to explore the perspectives and practice of powder processing routes towards control and optimization of the microstructure and pertinent properties of high T c oxide superconductors. The monograph consists of 6 chapters. After a very brief introduction (Chapter 1), Chapter 2 describes various classes of high T c oxide superconductors and their phase equilibria. Chapter 3 highlights the preparation of oxide superconductor powders through various routes and details their subtle distinctions. Chapter 4 briefly covers characterisation of the oxide superconductors, laying emphasis on the process-analysis and microstructure. Chapter 5 describes in detail various fabrication techniques for bulk superconductors through the powder routes. The last Chapter (Chapter 6) describing properties of bulk oxide superconductors, discusses the role of subtituents, compositional variations and processing methods on such properties. References are given at the end of each chapter. (orig.)

  2. OXIDATIVE STRESS AND VASCULAR DAMAGE IN HYPOXIA PROCESSES. MALONDIALDEHYDE (MDA AS BIOMARKER FOR OXIDATIVE DAMAGE

    Directory of Open Access Journals (Sweden)

    Muñiz P

    2014-05-01

    Full Text Available Changes in the levels oxidative stress biomarkers are related with different diseases such as ischemia/reperfusion, cardiovascular, renal, aging, etc. One of these biomarkers is the malondialdehyde (MDA generated as resulted of the process of lipid peroxidation. This biomarker is increased under conditions of the oxidative stress. Their levels, have been frequently used to measure plasma oxidative damage to lipids by their atherogenic potential. Its half-life high and their reactivity allows it to act both inside and outside of cells and interaction with proteins and DNA involve their role in different pathophysiological processes. This paper presents an analysis of the use of MDA as a biomarker of oxidative stress and its implications associated pathologies such as cardiovascular diseases ago.

  3. Reactor modeling and process analysis for partial oxidation of natural gas

    NARCIS (Netherlands)

    Albrecht, B.A.

    2004-01-01

    This thesis analyses a novel process of partial oxidation of natural gas and develops a numerical tool for the partial oxidation reactor modeling. The proposed process generates syngas in an integrated plant of a partial oxidation reactor, a syngas turbine and an air separation unit. This is called

  4. Study of the influence of radiolysis on the stability of plutonium III. Application to a heterogeneous medium formed by a nitric solution of ferrous ions and an organic solution of trilauryl-ammonium nitrate

    International Nuclear Information System (INIS)

    Fourmaux, J.M.

    1980-01-01

    The objective of this research thesis is to study the behaviour of plutonium 238 in media which are commonly used to isolate it from other elements such as neptunium and fission products created during the neutron irradiation of the neptunium 237 isotope. As plutonium 238 purification processes are all based on redox reaction, it is essential to know the influence of radiolysis on the redox behaviour, and on the distribution coefficients of this isotope in solutions used during its separation from the neptunium 237 isotope. Therefore, it is necessary to study the influence of radiolysis on the stability of plutonium with an oxidation III level. As this extraction is performed by an organic solvent (trilauryl-ammonium nitrate), this study addresses the behaviour of plutonium in an emulsion formed by this solvent and the nitric aqueous solution previously adjusted in terms of Fe 2+ ions. After a brief recall of bibliographical generalities related to radiolysis, the author presents and comments the Nernst law in the case of a two-phase system (emulsion), and reports the use of this law to obtain the plutonium potential-distribution coefficient relationship. The last part reports experimental data

  5. Measurement of total alpha activity of neptunium, plutonium, and americium in highly radioactive Hanford waste by iron hydroxide precipitation and 2-heptanone solvent extraction

    International Nuclear Information System (INIS)

    Maiti, T.C.; Kaye, J.H.

    1992-06-01

    An improved method has been developed to concentrate the major alpha-emitting actinide elements neptunium, plutonium, and americium from samples with high salt content such as those resulting from efforts to characterize Hanford storage tank waste. Actinide elements are concentrated by coprecipitation of their hydroxides using iron carrier. The iron is removed by extraction from 8M HCI with 2-heptanone. The actinide elements remain in the aqueous phase free from salts, iron, and long-lived fission products. Recoveries averaged 98 percent

  6. Kinetics and mechanism of synthetic CoS oxidation process

    Directory of Open Access Journals (Sweden)

    Štrbac N.

    2006-01-01

    Full Text Available The results of investigation of kinetics and mechanism for synthetic a-CoS oxidation process are presented in this paper. Based on experimental data obtained using DTA and XRD analysis and constructed PSD diagrams for Co-S-O system, mechanism of synthetic a-CoS oxidation process is suggested. Characteristic kinetic parameters were obtained for experimental isothermal investigations of desulfurization degree using Sharp method.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  8. Conceptual Design for the Pilot-Scale Plutonium Oxide Processing Unit in the Radiochemical Processing Laboratory

    Energy Technology Data Exchange (ETDEWEB)

    Lumetta, Gregg J.; Meier, David E.; Tingey, Joel M.; Casella, Amanda J.; Delegard, Calvin H.; Edwards, Matthew K.; Jones, Susan A.; Rapko, Brian M.

    2014-08-05

    This report describes a conceptual design for a pilot-scale capability to produce plutonium oxide for use as exercise and reference materials, and for use in identifying and validating nuclear forensics signatures associated with plutonium production. This capability is referred to as the Pilot-scale Plutonium oxide Processing Unit (P3U), and it will be located in the Radiochemical Processing Laboratory at the Pacific Northwest National Laboratory. The key unit operations are described, including plutonium dioxide (PuO2) dissolution, purification of the Pu by ion exchange, precipitation, and conversion to oxide by calcination.

  9. Process for selected gas oxide removal by radiofrequency catalysts

    Science.gov (United States)

    Cha, Chang Y.

    1993-01-01

    This process to remove gas oxides from flue gas utilizes adsorption on a char bed subsequently followed by radiofrequency catalysis enhancing such removal through selected reactions. Common gas oxides include SO.sub.2 and NO.sub.x.

  10. Predicting the behaviour or neptunium during nuclear fuel reprocessing

    International Nuclear Information System (INIS)

    Drake, V.A.

    1988-01-01

    Behaviour of Np and its distribution over reprocessing flowsheet is studied due to the necessity of improvement of reprocessing methods of wastes formed during purex-process. Valency states of Np in solutions of reprocessing cycles, Np distribution in organic and acid phases, Np(5) oxidation by nitric acid at the stage of extraction, effect of U and Pu presence on Np behaviour, are considered. Calculation and experimental data are compared; the possibility of Np behaviour forecasting in the process of nuclear fuel reprocessing, provided initial data vay, is shown. 7 refs.; 4 figs.; 1 tab

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

    Energy Technology Data Exchange (ETDEWEB)

    Nash, C. A. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    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. Complex formation between neptunium(V) and various thiosemicarbazide derivatives in aqueous solution

    International Nuclear Information System (INIS)

    Chuguryan, D.G.; Dzyubenko, V.I.; Gerbeleu, N.V.

    1987-01-01

    Complex formation between neptunium(V) and various thiosemicarbazide derivatives in solution has been studied spectrophotometrically in the pH range 4-10. Stepwise formation of three types of complexes, with composition NpO 2 HA, NpO 2 A - , and NpOHA 2- , has been demonstrated with salicylaldehyde thiosemicarbazone (H 2 L) and salicylaldehyde S-methyl-isothiosemicarbazone (H 2 Q) at t = 25 +/- 1 0 C and μ = 0.05. The logarithmic stability constants of the first two complexes are 5.14 +/- 0.06, 11.85 +/- 0.04 and 8.42 +/- 0.09, 13.33 +/- 0.015 for H 2 L and H 2 Q, respectively; equilibrium constants for the formation of hydroxo complexes of the form NpO 2 OHL 2- and NpO 2 OHQ 2- were also determined, and found to be equal to (2.23 +/-0.37) x 10 -5 and (5.02 +/- 0.9) x 10 -5 , respectively. In the case of S-methyl-N 1 ,N 4 -bis(salicylidene)isothiosemicarbazide (H 2 Z), only one type of complex is formed under these experimental conditions, namely, NpO 2 Z - , with a logarithmic stability constant of 4.78 +/- 0.03. Dissociation constants for H 2 Q and H 2 Z were also determined

  13. Simulation of atomistic processes during silicon oxidation

    OpenAIRE

    Bongiorno, Angelo

    2003-01-01

    Silicon dioxide (SiO2) films grown on silicon monocrystal (Si) substrates form the gate oxides in current Si-based microelectronics devices. The understanding at the atomic scale of both the silicon oxidation process and the properties of the Si(100)-SiO2 interface is of significant importance in state-of-the-art silicon microelectronics manufacturing. These two topics are intimately coupled and are both addressed in this theoretical investigation mainly through first-principles calculations....

  14. Improved Aeration Process - Catalytic Role Of The Iron Oxides In Arsenic Oxidation And Coprecipitation

    DEFF Research Database (Denmark)

    Kowalski, Krysztof; Søgaard, Erik Gydesen

    2013-01-01

    Demands for a better drinking water quality, especially concerning arsenic, a compound with many adverse health effects, put a pressure on the utilities to ensure the best treatment technologies that meet nowadays and possible future quality standards. The aim of this paper is to introduce...... an improved aeration process that can also help in developing better arsenic removal treatment. The results present advantages of arsenic oxidation in an aeration process in the presence of ferrihydrite surface that have been shown to adsorb arsenic simultaneously to its oxidation. The presence...

  15. Criticality of a 237Np sphere

    International Nuclear Information System (INIS)

    Sanchez, Rene; Loaiza, David; Kimpland, Robert; Hayes, David; Cappiello, Charlene; Chadwick, Mark

    2006-01-01

    For the past five years, scientists at Los Alamos National Laboratory have mounted an unprecedented effort to get a better estimate of the critical mass of 237 Np. To accomplish this task, a 6-kg neptunium sphere was recently cast at the Chemical and Metallurgy Research (CMR) facility, which is part of the Los Alamos National Laboratory. The neptunium sphere was clad with tungsten and nickel to reduce the dose rates from the 310 keV gamma rays from the first daughter of neptunium, namely, 233 Pa. 237 Np is a byproduct of power production in nuclear reactors. It is primarily produced by successive neutron captures in 235 U or through the (n,2n) reaction in 238 U. These nuclear reactions lead to the production of 237 U, which decays by beta emission into 237 Np, namely, 235 U(n,γ) 236 U, 236 U(n,γ) 237 U→β→ 237 Np, 238 U (n,2n) 237 U→β→ 237 Np. It is estimated that a typical 1000 MW(e) produces on the order of 12 to 13 kg of neptunium in a year. Some of this neptunium in irradiated fuel elements has been separated and is presently stored in containers in a liquid form. This method of storage is quite adequate because the fission cross section for 237 Np at thermal energies is quite low and any moderation of the neutron population by diluting the configurations with water would increase the critical mass to infinity. However, for long term storage, the neptunium liquid solutions must be converted into oxides and metals because these form are less movable and less likely to leak out of containers. Metals and oxides made out of neptunium have finite critical masses but there is a great uncertainty about these values because of the lack of experimental criticality data. Knowing precisely the critical mass of neptunium not only will help to validate mass storage limits or optimize storage configurations for safe disposition of these materials, but will also save thousands of dollars in transportation and disposition costs. The experimental results presented in

  16. Simultaneous nitrate reduction and acetaminophen oxidation using the continuous-flow chemical-less VUV process as an integrated advanced oxidation and reduction process

    Energy Technology Data Exchange (ETDEWEB)

    Moussavi, Gholamreza, E-mail: moussavi@modares.ac.ir; Shekoohiyan, Sakine

    2016-11-15

    Highlights: • Simultaneous advanced oxidation and reduction processes were explored in VUV system. • Complete reduction of nitrate to N{sub 2} was achieved at the presence of acetaminophen. • Complete degradation of acetaminophen was achieved at the presence of nitrate. • Over 95% of acetaminophen was mineralized in the VUV photoreactor. • VUV is a chemical-less advanced process for treating water emerging contaminants. - Abstract: This work was aimed at investigating the performance of the continuous-flow VUV photoreactor as a novel chemical-less advanced process for simultaneously oxidizing acetaminophen (ACT) as a model of pharmaceuticals and reducing nitrate in a single reactor. Solution pH was an important parameter affecting the performance of VUV; the highest ACT oxidation and nitrate reduction attained at solution pH between 6 and 8. The ACT was oxidized mainly by HO· while the aqueous electrons were the main working agents in the reduction of nitrate. The performance of VUV photoreactor improved with the increase of hydraulic retention time (HRT); the complete degradation of ACT and ∼99% reduction of nitrate with 100% N{sub 2} selectivity achieved at HRT of 80 min. The VUV effluent concentrations of nitrite and ammonium at HRT of 80 min were below the drinking water standards. The real water sample contaminated with the ACT and nitrate was efficiently treated in the VUV photoreactor. Therefore, the VUV photoreactor is a chemical-less advanced process in which both advanced oxidation and advanced reduction reactions are accomplished. This unique feature possesses VUV photoreactor as a promising method of treating water contaminated with both pharmaceutical and nitrate.

  17. Simultaneous nitrate reduction and acetaminophen oxidation using the continuous-flow chemical-less VUV process as an integrated advanced oxidation and reduction process

    International Nuclear Information System (INIS)

    Moussavi, Gholamreza; Shekoohiyan, Sakine

    2016-01-01

    Highlights: • Simultaneous advanced oxidation and reduction processes were explored in VUV system. • Complete reduction of nitrate to N_2 was achieved at the presence of acetaminophen. • Complete degradation of acetaminophen was achieved at the presence of nitrate. • Over 95% of acetaminophen was mineralized in the VUV photoreactor. • VUV is a chemical-less advanced process for treating water emerging contaminants. - Abstract: This work was aimed at investigating the performance of the continuous-flow VUV photoreactor as a novel chemical-less advanced process for simultaneously oxidizing acetaminophen (ACT) as a model of pharmaceuticals and reducing nitrate in a single reactor. Solution pH was an important parameter affecting the performance of VUV; the highest ACT oxidation and nitrate reduction attained at solution pH between 6 and 8. The ACT was oxidized mainly by HO· while the aqueous electrons were the main working agents in the reduction of nitrate. The performance of VUV photoreactor improved with the increase of hydraulic retention time (HRT); the complete degradation of ACT and ∼99% reduction of nitrate with 100% N_2 selectivity achieved at HRT of 80 min. The VUV effluent concentrations of nitrite and ammonium at HRT of 80 min were below the drinking water standards. The real water sample contaminated with the ACT and nitrate was efficiently treated in the VUV photoreactor. Therefore, the VUV photoreactor is a chemical-less advanced process in which both advanced oxidation and advanced reduction reactions are accomplished. This unique feature possesses VUV photoreactor as a promising method of treating water contaminated with both pharmaceutical and nitrate.

  18. Partitioning of actinides from high level waste of PUREX origin using octylphenyl-N,N'-diisobutylcarbamoylmethyl phosphine oxide (CMPO)-based supported liquid membrane

    International Nuclear Information System (INIS)

    Ramanujam, A.; Dhami, P.S.; Gopalakrishnan, V.; Dudwadkar, N.L.; Chitnis, R.R.; Mathur, J.N.

    1999-01-01

    The present studies deal with the application of the supported liquid membrane (SLM) technique for partitioning of actinides from high level waste of PUREX origin. The process uses a solution of octylphenyl-N,N'-diisobutylcarbamoylmethyl phosphine oxide (CMPO) in n-dodecane as a carrier with a polytetrafluoroethylene support and a mixture of citric acid, formic acid, and hydrazine hydrate as the receiving phase. The studies involve the investigation of such parameters as carrier concentration in SLM, acidity of the feed, and the feed composition. The studies indicated good transport of actinides like neptunium, americium, and plutonium across the membrane from nitric acid medium. A high concentration of uranium in the feed retards the transport of americium, suggesting the need for prior removal of uranium from the waste. The separation of actinides from uranium-lean simulated samples as well as actual high level waste has been found to be feasible using the above technique

  19. Concept and experimental studies on fuel and target for minor actinides and fission products transmutation

    Energy Technology Data Exchange (ETDEWEB)

    Prunier, C; Guerin, Y [CEA Centre d` Etudes de Cadarache, 13 - Saint-Paul-lez-Durance (France). Dept. d` Etudes des Combustibles; Salvatores, M [CEA Centre d` Etudes de Cadarache, 13 - Saint-Paul-lez-Durance (France). Direction des Reacteurs Nucleaires; Zaetta, A [CEA Centre d` Etudes de Cadarache, 13 - Saint-Paul-lez-Durance (France). Dept. d` Etudes des Reacteurs

    1994-12-31

    High activity long-lived radionuclides in nuclear wastes, namely minor actinides (americium and neptunium) are in large amount generated by current nuclear reactive. The destruction of these radionuclides is a part of the French SPIN (Partitioning and Burning) program consistent with the determination to send a minimum amount of harmful products for final storage. Transmutation concepts are defined for neptunium and americium taking into account fuel cycle strategies. Neptunium destruction does not pose any major problems. It`s a by-product of uranium consumption, as plutonium and in despite of a slight gamma activity due to the protactinium 233 it`s quite easy to handle. Diluting neptunium in the mixed oxide fuels (MOX) should not be an obstacle for fabrication, in-pile behaviour and reprocessing either. Consequently we make the proposal of homogeneous mode of neptunium in MOX which should be soon explored in the experimental OSIRIS reactor and in the Phenix and Superphenix reactors. The analysis is more complex for the multi isotope americium. Its destruction is difficult because of gamma radioactivity which complicates fabrication. Experiments in Phenix and calculation showed that Phenix reactor offers a good potential for americium incineration, but similar data do not exist for PWR. It will remain a well known difficulty for fabrication and reprocessing. In this case we have to put a real new face to the fabrication flow-sheet of americium compounds and we propose to develop the heterogeneous mode. Targets choice are defined in term of: -safety, considering fuel reaction with cladding and water sodium, -transmutation rate, limited by target behaviour, in FR`s (Phenix), PWR`s (OSIRIS) and HFR (Petten), -reprocessing, checking the solubility of such targets by Purex process. So, at the beginning of our program the account has been on improving fuel and targets properties related to safety and fuel cycle. (authors). 4 figs.

  20. Partitioning of actinides from high active waste solution of Purex origin counter-current extraction studies using TBP and CMPO

    International Nuclear Information System (INIS)

    Chitnis, R.R.; Dhami, P.S.; Gopalkrishnan, V.; Wattal, P.K.; Ramanujam, A.; Murali, M.S.; Mathur, J.N.; Bauri, A.K.; Chattopadhyay, S.

    2000-10-01

    A solvent extraction scheme has been formulated for the partitioning of actinides from Purex high level waste (HLW). The scheme is based on the results of earlier studies carried out with simulated waste solutions. In the present studies, the scheme was tested with high active waste (HAW) solution generated during the reprocessing of spent fuel from research reactors using laboratory scale mixer-settlers. The proposed process involved two-step extraction using tri-n-butyl phosphate (TBP) and octyl (phenyl)-N,N-diisobutylcarbamolylmethylphosphine oxide (CMPO). In the first step, uranium, neptunium and plutonium were removed from the waste using TBP as extractant. The minor actinides left in the raffinate were extracted using a mixture of CMPO and TBP in the second step. The results showed complete extraction of actinides from the waste solution. Plutonium and neptunium extracted in TBP, were stripped together using a mixture of hydrogen peroxide and ascorbic acid in 2 M nitric acid medium, leaving uranium in the organic phase. Uranium can later be stripped using dilute nitric acid. Actinides extracted in CMPO-TBP phase were stripped using a mixture of formic acid, hydrazine, hydrate and citric acid. The stripping was quantitative in both the stripping runs. An additional extraction step for the preferential recovery of uranium, neptunium and plutonium from the waste solution using TBP is a modification over the conventional Truex process. Selective stripping of neptunium and plutonium from large quantities of uranium. The extraction of uranium using TBP eliminates the possibility of third phase and undesired loading of CMPO-TBP in the following step. Use of citrate-containing strippant allows the recovery of actinides from loaded CMPO-TBP mixture without causing any reflux of the actinides during stripping. The process has been developed with due consideration to minimising the generation of secondary wastes. The proposed strippants are effective even in presence of

  1. The Evonik-Uhde HPPO process for proplene oxide production

    Energy Technology Data Exchange (ETDEWEB)

    Jaeger, B.; Baerz, M. [Evonik Industries, Hanau (Germany); Schemel, J.; Kolbe, B. [Uhde GmbH, Dortmund/Bad Soden (Germany)

    2011-07-01

    In 2008 the HPPO technology has shown up as an economically and environmentally friendly alternative for manufacturing of propylene oxide. The HPPO technology offers the advantage of an on purpose process for manufacturing of propylene oxide without dependency on disposal or marketing of coupling products. (orig.)

  2. The influence of Ac parameters in the process of micro-arc oxidation film electric breakdown

    Directory of Open Access Journals (Sweden)

    Ma Jin

    2016-01-01

    Full Text Available This paper studies the electric breakdown discharge process of micro-arc oxidation film on the surface of aluminum alloy. Based on the analysis of the AC parameters variation in the micro-arc oxidation process, the following conclusions can be drawn: The growth of oxide film can be divided into three stages, and Oxide film breakdown discharge occurs twice in the micro-arc oxidation process. The first stage is the formation and disruptive discharge of amorphous oxide film, producing the ceramic oxide granules, which belong to solid dielectric breakdown. In this stage the membrane voltage of the oxide film plays a key role; the second stage is the formation of ceramic oxide film, the ceramic oxide granules turns into porous structure oxide film in this stage; the third stage is the growth of ceramic oxide film, the gas film that forms in the oxide film’s porous structure is electric broken-down, which is the second breakdown discharge process, the current density on the oxide film surface could affect the breakdown process significantly.

  3. Oxidative treatment characteristics of biotreated textile-dyeing wastewater and chemical agents used in a textile-dyeing process by advanced oxidation process.

    Science.gov (United States)

    Lim, B R; Hu, H Y; Ahn, K H; Fujie, K

    2004-01-01

    The oxidative treatment characteristics of biotreated textile-dyeing wastewater and typical chemicals such as desizing, scouring, dispersing and swelling agents used in the textile-dyeing process by advanced oxidation process were experimentally studied. The refractory organic matters remained in the effluent of biological treatment process without degradation may be suitable for the improvement of biodegradability and mineralized to CO2 by combined ozonation with and without hydrogen peroxide. On the other hand, the refractory chemicals contained in the scouring agent A and swelling agent may not be mineralized and their biodegradability may not be improved by ozonation. However, the BOD/DOC ratio of scouring agent B increased from 0.3 to 0.45 after ozonation. Based on the results described above, advanced treatment process involving the ozonation without and with the addition of hydrogen peroxide, followed by biological treatment was proposed for the treatment of refractory wastewater discharged from the textile-dyeing process.

  4. A nanogravimmetric investigation of the charging processes on ruthenium oxide thin films and their effect on methanol oxidation

    International Nuclear Information System (INIS)

    Santos, M.C.; Cogo, L.; Tanimoto, S.T.; Calegaro, M.L.; Bulhoes, L.O.S

    2006-01-01

    The charging processes and methanol oxidation that occur during the oxidation-reduction cycles in a ruthenium oxide thin film electrode (deposited by the sol-gel method on Pt covered quartz crystals) were investigated by using cyclic voltammetry, chronoamperometry and electrochemical quartz crystal nanobalance techniques. The ruthenium oxide rutile phase structure was determined by X-ray diffraction analysis. The results obtained during the charging of rutile ruthenium oxide films indicate that in the anodic sweep the transition from Ru(II) to Ru(VI) occurs followed by proton de-intercalation. In the cathodic sweep, electron injection occurs followed by proton intercalation, leading to Ru(II). The proton intercalation/de-intercalation processes can be inferred from the mass/charge relationship which gives a slope close to 1 g mol -1 (multiplied by the Faraday constant) corresponding to the molar mass of hydrogen. From the chronoamperometric measurements, charge and mass saturation of the RuO 2 thin films was observed (440 ng cm -2 ) during the charging processes, which is related to the total number of active sites in these films. Using the electrochemical quartz crystal nanobalance technique to study the methanol oxidation reaction at these films was possible to demonstrate that bulk oxidation occurs without the formation of strongly adsorbed intermediates such as CO ads , demonstrating that Pt electrodes modified by ruthenium oxide particles can be promising catalysts for the methanol oxidation as already shown in the literature

  5. Flue gas cleanup using the Moving-Bed Copper Oxide Process

    Energy Technology Data Exchange (ETDEWEB)

    Pennline, Henry W; Hoffman, James S

    2013-10-01

    The use of copper oxide on a support had been envisioned as a gas cleanup technique to remove sulfur dioxide (SO{sub 2}) and nitric oxides (NO{sub x}) from flue gas produced by the combustion of coal for electric power generation. In general, dry, regenerable flue gas cleanup techniques that use a sorbent can have various advantages, such as simultaneous removal of pollutants, production of a salable by-product, and low costs when compared to commercially available wet scrubbing technology. Due to the temperature of reaction, the placement of the process into an advanced power system could actually increase the thermal efficiency of the plant. The Moving-Bed Copper Oxide Process is capable of simultaneously removing sulfur oxides and nitric oxides within the reactor system. In this regenerable sorbent technique, the use of the copper oxide sorbent was originally in a fluidized bed, but the more recent effort developed the use of the sorbent in a moving-bed reactor design. A pilot facility or life-cycle test system was constructed so that an integrated testing of the sorbent over absorption/regeneration cycles could be conducted. A parametric study of the total process was then performed where all process steps, including absorption and regeneration, were continuously operated and experimentally evaluated. The parametric effects, including absorption temperature, sorbent and gas residence times, inlet SO{sub 2} and NO{sub x} concentration, and flyash loadings, on removal efficiencies and overall operational performance were determined. Although some of the research results have not been previously published because of previous collaborative restrictions, a summary of these past findings is presented in this communication. Additionally, the potential use of the process for criteria pollutant removal in oxy-firing of fossil fuel for carbon sequestration purposes is discussed.

  6. Effect of preliminary oxidation on process of steel carburization

    Energy Technology Data Exchange (ETDEWEB)

    Devochkin, O V; Vorontsov, E S; Filonov, V N [Voronezhskij Politekhnicheskij Inst. (USSR)

    1975-01-01

    Effects of preliminary oxidation of the metal surface and its subsequent reduction steel cementation were studied. The samples with interferentionally coloured oxide film on the surface had deeper carbonated layer than those without film. The kinetics of carbonation process and the mechanism proposed for this phenomenon are given.

  7. Processing of LEU targets for 99Mo production--testing and modification of the Cintichem process

    International Nuclear Information System (INIS)

    Wu, D.; Landsberger, S.; Buchholz, B.

    1995-09-01

    Recent experimental results on testing and modification of the Cintichem process to allow substitution of low enriched uranium (LEU) for high enriched uranium (HEU) targets are presented in this report. The main focus is on 99 Mo recovery and purification by its precipitation with α-benzoin oxime. Parameters that were studied include concentrations of nitric and sulfuric acids, partial neutralization of the acids, molybdenum and uranium concentrations, and the ratio of α-benzoin oxime to molybdenum. Decontamination factors for uranium, neptunium, and various fission products were measured. Experiments with tracer levels of irradiated LEU were conducted for testing the 99 Mo recovery and purification during each step of the Cintichem process. Improving the process with additional processing steps was also attempted. The results indicate that the conversion of molybdenum chemical processing from HEU to LEU targets is possible

  8. Developing alternative oxidation processes for the treatment of organic radioactive waste

    International Nuclear Information System (INIS)

    Turc, H.A.; Broudic, J.Ch.; Joussot-Dubien, Ch.

    2000-01-01

    An electro-generated silver (II) mediated oxidation process is currently under development in the Atalante facility of the French Atomic Energy Commission, as an operation of the DELOS unit, with the aim to mineralize α-contaminated solvents with respect to the principles of nuclear safety. This process is a wet oxidation one involving a powerful mediator (Ag(II)/Ag(I): 1.92 V/NHE), but its throughput is mainly limited by technological constraints. Hydrothermal oxidation (HTO) has been investigated and proved by inactive studies as to be a versatile and powerful process, which could help destroying the contaminated solvents (dodecane, TBP, TLA...) produced by the spent nuclear fuel reprocessing research and industry. The current development aims to set up a continuous HTO pilot in a standard glovebox, in order to solve both technological and safety difficulties and to treat small volumes of contaminated solvents. This paper discusses the main results of the silver(II) oxidation and HTO process development works. (authors)

  9. Carbon contaminant in the ion processing of aluminum oxide film

    International Nuclear Information System (INIS)

    Chaug, Y.; Roy, N.

    1989-01-01

    Ion processing can induce contamination on the bombarded surface. However, this process is essential for the microelectronics device fabrication. Auger electron spectroscopy has been used to study the simultaneous deposition of carbon impurity during ion bombardment of magnetron rf-sputtering deposited aluminum oxide film. Ion bombardment on aluminum oxide results in a preferential removal of surface oxygen and a formation of a metastable state of aluminum suboxide. Cosputtered implanted carbon contaminant appears to have formed a new state of stoichiometry on the surface of the ion bombarded aluminum oxide and existed as an aluminum carbide. This phase has formed due to the interaction of the implanted carbon and the aluminum suboxide. The Ar + ion sputter etching rate is reduced for the carbon contaminated oxide. The electrical resistance of the aluminum oxide between two gold strips has been measured. It is found that the electrical resistance is also reduced due to the formation of the new stoichiometry on the surface

  10. Hybrid process for nitrogen oxides reduction

    Energy Technology Data Exchange (ETDEWEB)

    Epperly, W.R.; Sprague, B.N.

    1991-09-10

    This patent describes a process for reducing the nitrogen oxide concentration in the effluent from the combustion of a carbonaceous fuel. It comprises introducing into the effluent a first treatment agent comprising a nitrogenous composition selected from the group consisting of urea, ammonia, hexamethylenetetramine, ammonium salts of organic acids, 5- or 6-membered heterocyclic hydrocarbons having at least one cyclic nitrogen, hydroxy amino hydrocarbons, NH{sub 4}-lignosulfonate, fur-furylamine, tetrahydrofurylamine, hexamethylenediamine, barbituric acid, guanidine, guanidine carbonate, biguanidine, guanylurea sulfate, melamine, dicyandiamide, biuret, 1.1{prime}-azobisformamide, methylol urea, methylol urea-urea condensation product, dimethylol urea, methyl urea, dimethyl urea, calcium cyanamide, and mixtures thereof under conditions effective to reduce the nitrogen oxides concentration and ensure the presence of ammonia in the effluent; introducing into the effluent a second treatment agent comprising an oxygenated hydrocarbon at an effluent temperature of about 500{degrees} F. to about 1600{degrees} F. under conditions effective to oxidize nitric oxide in the effluent to nitrogen dioxide and ensure the presence of ammonia at a weight ratio of ammonia to nitrogen dioxide of about 1:5 to about 5:1; and contacting the effluent with an aqueous scrubbing solution having a pH of 12 or lower under conditions effective to cause nitrogen dioxide to be absorbed therein.

  11. Catalysed electrolytic metal oxide dissolution processes

    International Nuclear Information System (INIS)

    Machuron-Mandard, X.

    1994-01-01

    The hydrometallurgical processes designed for recovering valuable metals from mineral ores as well as industrial wastes usually require preliminary dissolution of inorganic compounds in aqueous media before extraction and purification steps. Unfortunately, most of the minerals concerned hardly or slowly dissolve in acidic or basic solutions. Metallic oxides, sulfides and silicates are among the materials most difficult to dissolve in aqueous solutions. They are also among the main minerals containing valuable metals. The redox properties of such materials sometimes permit to improve their dissolution by adding oxidizing or reducing species to the leaching solution, which leads to an increase in the dissolution rate. Moreover, limited amounts of redox promoters are required if the redox agent is regenerated continuously thanks to an electrochemical device. Nuclear applications of such concepts have been suggested since the dissolution of many actinide compounds (e.g., UO 2 , AmO 2 , PuC, PuN,...) is mainly based on redox reactions. In the 1980s, improvements of the plutonium dioxide dissolution process have been proposed on the basis of oxidation-reduction principles, which led a few years later to the design of industrial facilities (e.g., at Marcoule or at the french reprocessing plant of La Hague). General concepts and well-established results obtained in France at the Atomic Energy Commission (''Commissariat a l'Energie Atomique'') will be presented and will illustrate applications to industrial as well as analytical problems. (author)

  12. Pyrometallurgical process of actinide metal

    International Nuclear Information System (INIS)

    Yoo, Jae Hyung; Kang, Young Ho; Woo, Mun Sik; Hwang, Sung Chan

    1999-06-01

    Major subject on pyrometallurgical partitioning technology is to separate transmutation elements (TRU) from rare earth elements(RE). Distribution coefficients of TRU and RE between molten chloride and liquid cadmium were measured for reductive extraction, and TRU were separated from RE in simplified molten chloride system by electrorefining. And separation efficiency between TRU and RE were estimated by using thermodynamics data. The results indicate that uranium, neptunium and plutonium are easy to separate from RE but some amount of RE accompany americium, and that processes have to be optimized to attain good separation efficiency of TRU. (author)

  13. Retention of redox sensitive waste elements in compacted bentonite

    International Nuclear Information System (INIS)

    Torstenfelt, B.; Allard, B.

    1984-01-01

    The diffusion of technetium, iodine, uranium and neptunium in compacted bentonite has been studied. The possible reduction of the transport rate of these elements (i.e. redoxsensitive elements) by mixing the clay with metallic iron (for technetium, uranium and neptunium) or by adding a chemisorbent (for iodine) to the clay is reported. Technetium has an apparent diffusivity about 5 times higher in the heptavalent state (TcO 4 - ) than in the tetravalent state (TcO(OH) 2 or TcO 2 ), uranium and neptunium in their higher oxidation state (VI and V) have apparent diffusivities about 6 and 50 times higher, respectively, than in the tetravalent state. Iodine, as I - (or IO 3 - ), has a transport rate more than one order of magnitude lower than TcO 4 - . 10 references, 5 figures, 3 tables

  14. Measurement of the oxidation-extraction of uranium from wet-process phosphoric acid

    International Nuclear Information System (INIS)

    Lawes, B.C.

    1985-01-01

    The present invention relates to processes for the recovery of uranium from wet-process phosphoric acid and more particularly to the oxidation-extraction steps in the DEPA-TOPO process for such recovery. A more efficient use of oxidant is obtained by monitoring the redox potential during the extraction step

  15. Neptunium redox behavior and sorption onto goethite and hematite in the presence of humic acids with different hydroquinone content

    International Nuclear Information System (INIS)

    Khasanova, A.B.; Kalmykov, St.N.; Perminova, I.V.; Clark, S.B.

    2007-01-01

    The effect of humic acids (HA) on neptunium redox behavior and sorption onto hematite, α-Fe 2 O 3 , and goethite, α-FeOOH, colloids was established in batch sorption experiments that were carried out in broad pH interval. The sorption isotherms were provided for two samples of HA: commercial sample of leonardite humic acid and its hydroquinone-enriched derivative obtained using formaldehyde copolycondensation. The distribution of Np fitted the distribution of hydroquinone-enriched HA at low pH values in case of both solids while the influence of parent HA on Np sorption was negligible. This is due to Np(V) reduction upon interaction with hydroquinone-enriched derivative having higher reducing capacity compared to the parent HA. The order of components addition was found to be significant for Np retention

  16. Process for fabricating mixed-oxide powders

    International Nuclear Information System (INIS)

    Elmaleh, D.; Giraudel, A.

    1975-01-01

    A physical-chemical process for fabricating homogeneous powders suitable for sintering is described. It can be applied to the synthesis of all mixed oxides having mutually compatible and water soluble salts. As a specific example, the fabrication of lead titanate-zirconate powders used to make hot pressed ceramics is described. These ceramics show improved piezoelectric properties [fr

  17. Diffusion and sorption of neptunium(V) in compacted montmorillonite: effects of carbonate and salinity

    International Nuclear Information System (INIS)

    Tachi, Y.; Yotsuji, K.; Suyama, T.; Seida, Y.; Yui, M.; Nakazawa, T.; Yamada, N.; Ochs, M.

    2010-01-01

    Diffusion and sorption of radionuclides in compacted bentonite/montmorillonite are key processes in the safe geological disposal of radioactive waste. In this study, the effects of carbonate and salinity on neptunium(V) diffusion and sorption in compacted sodium montmorillonite were investigated by experimental and modeling approaches. Effective diffusion coefficients (D e ) and distribution coefficients (K d ) of 237 Np(V) in sodium montmorillonite compacted to a dry density of 800 kg m -3 were measured under four chemical conditions with different salinities (0.05/0.5 M NaCl) and carbonate concentrations (0.0.01 M NaHCO 3 ). D e values for carbonate-free conditions were of the order of 10 -10 -10 -11 m 2 s -1 and decreased as salinity increased, and those for carbonate conditions were of the order of 10 -11 -10 -12 m 2 s -1 and showed the opposite dependence. Diffusion-derived K d values for carbonate-free conditions were higher by one order of magnitude than those for carbonate conditions. Diffusion and sorption behaviors were interpreted based on mechanistic models by coupling thermodynamic aqueous speciation, thermodynamic sorption model (TSM) based on ion exchange, and surface complexation reactions, and a diffusion model based on electrical double layer (EDL) theory in homogeneous narrow pores. The model predicted the experimentally observed tendency of D e and K d qualitatively, as a result of the following mechanisms; 1) the dominant aqueous species are NpO 2 + and NpO 2 CO 3 - for carbonate-free and carbonate conditions, respectively, 2) the effects of cation excess and anion exclusion result in opposite tendencies of D e for salinity, 3) higher carbonate in solution inhibits sorption due to the formation of carbonate complexes. (orig.)

  18. Electrochemistry of actinide on electrochemically reduced graphene oxide: Electrocatalysis of Np(VI)O22+/Np(V)O2+ in nitric acid solution

    International Nuclear Information System (INIS)

    Ambolikar, Arvind S.; Guin, Saurav K.; Kasar, U.M.; Kamat, J.V.

    2015-01-01

    Highlights: • First report of aqueous electrochemistry of neptunium on electrochemically reduced graphene oxide (ERGNO). • First report on the electrochemical impedance spectroscopy of Np (VI) O 2 2+ /Np (V) O 2 + . • The electrochemical reversibility of Np (VI) O 2 2+ /Np (V) O 2 + redox couple improves on ERGNO compared to GC. • ERGNO shows higher sensitivity for the determination of Np compared to bare GC electrode. • The efficiency of detection of Np by ERGNO is improved by virtue of the electrocatalysis. - Abstract: Driven by the academic interest, we have studied the aqueous electrochemistry of neptunium (Np) in 1 M nitric acid solution on the electrochemically reduced graphene oxide (ERGNO) modified glassy carbon (GC) electrode. Similar to our previous experiences on the electrocatalytic action of ERGNO on the electrochemistry of uranium(VI)/uranium(IV) and plutonium(IV)/plutonium(III) redox couples, the present study confirms the robust electrocatalytic ability of ERGNO for the redox reaction of Np (VI) O 2 2+ /Np (V) O 2 + in acidic solution even at high anodic working potentials. The extent of the electrochemical reversibility of Np (VI) O 2 2+ /Np (V) O 2 + redox couple increases on ERGNO compared to the bare GC electrode. For the first time, the electron transfer reaction of Np (VI) O 2 2+ /Np (V) O 2 + redox couple is investigated by electrochemical impedance spectroscopy. The improved sensitivity as well as the lower limit of detection of Np by anodic square wave voltammetry on ERGNO compared to bare GC opens up the application of ERGNO in the nuclear science and technology.

  19. Investigation into formation of nanoparticles of tetravalent neptunium in slightly alkaline aqueous solution

    International Nuclear Information System (INIS)

    Husar, Richard

    2015-01-01

    H range from pH 3 to pH 10 with ζ = (-) 5 to (-) 30 mV. The zeta potentials of all particle systems containing silica are significantly shifted to more negative values below pH 7 where the isoelectrical point shifts from pH = 8.0 to 2.6 effecting negative charge under ambient conditions which supports electrostatic stabilization of Np(IV) particles. Particle surface charge at the slipping plane, particle size and shape necessarily depend on the initial magnitude of Si content in solution during particle formation. Particular changes of the morphology and internal structure of different Np(IV) silica colloids by aging are indicated by TEM and XPS. The composition and the crystallinity state of the initially formed amorphous phases partially changed into well-ordered nanocrystalline units characterized with fcc structure. The presence of silicate under conditions expected in a nuclear waste repository significantly influences the solubility of Np(IV) and provoke the stabilization of waterborne Np(IV) up to concentrations of 10 -3 M, exceeding Np's solubility limit by a factor of up 10.000. Neptunium and silicate significantly interact with each other, and thereby changing their individual hydrolysis and polymerization behavior. Silicate prevents the intrinsic formation of NpO 2 NCs in fcc-structure, and at the same time, Np(IV) prevents the polymerization of silicate. Both processes result in the formation of Np(IV) silica colloids which possibly influence the migration behavior and fate of Np in the waste repositories and surrounding environments. For tetravalent actinides in general, the most significant transport in the environment would occur by colloidal particles. Therefore, Np(IV) silica colloids could have a significant implication in the migration of Np, the important minor actinide in the waste repositories, via colloidal transport.

  20. Volcano Relation for the Deacon Process over Transition-Metal Oxides

    DEFF Research Database (Denmark)

    Studt, Felix; Abild-Pedersen, Frank; Hansen, Heine Anton

    2010-01-01

    We establish an activity relation for the heterogeneous catalytic oxidation of HCI (the Deacon Process) over rutile transition-metal oxide catalysts by combining density functional theory calculations (DFT) with microkinetic modeling. Linear energy relations for the elementary reaction steps...

  1. Screw calciner mechanical direct denitration process for plutonium nitrate to oxide conversion

    International Nuclear Information System (INIS)

    Souply, K.R.; Sperry, W.E.

    1977-01-01

    This report describes a screw calciner direct-denitration process for converting plutonium nitrate to plutonium oxide. The information should be used when making comparisons of alternative plutonium nitrate-to-oxide conversion processes or as a basis for further detailed studies. The report contains process flow sheets with a material balance; a process description; and a discussion of the process including history, advantages and disadvantages, and additional research required

  2. Investigation of the Scanning Microarc Oxidation Process

    Directory of Open Access Journals (Sweden)

    Lingqin Xia

    2017-01-01

    Full Text Available Scanning microarc oxidation (SMAO is a coating process which is based on conventional microarc oxidation (MAO. The key difference is that deposition in SMAO is achieved by using a stainless steel nozzle to spray an electrolyte stream on the substrate surface as opposed to immersing the workpiece in an electrolyzer. In the present study, SMAO discharge characteristics, coating morphology, and properties are analyzed and compared to results obtained from MAO under similar conditions. Results show that MAO and SMAO have comparable spark and microarc lifetimes and sizes, though significant differences in incubation time and discharge distribution were evident. Results also showed that the voltage and current density for MAO and SMAO demonstrate similar behavior but have markedly different transient and steady-state values. Results obtained from coating A356 aluminum sheet show that oxide thickness and growth rate in SMAO are strongly dependent on interelectrode spacing and travel speed. Analysis of the SMAO coating morphology and structure showed that a denser and slightly harder layer was deposited in comparison to MAO and is attributed to reduced porosity and increased formation of α-Al2O3. Preliminary results indicate that SMAO represents a viable process for coating of aluminum surfaces.

  3. Thermal processing and native oxidation of silicon nanoparticles

    International Nuclear Information System (INIS)

    Winters, Brandon J.; Holm, Jason; Roberts, Jeffrey T.

    2011-01-01

    In this study, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and electron energy loss spectroscopy (EELS) were used to investigate in-air oxidation of silicon nanoparticles ca. 11 nm in diameter. Particle samples were prepared first by extracting them from an RF plasma synthesis reactor, and then heating them in an inert carrier gas stream. The resulting particles had varying surface hydrogen coverages and relative amounts of SiH x (x = 1, 2, and 3), depending on the temperature to which they had been heated. The particles were allowed to oxidize in-air for several weeks. FTIR, XPS, and EELS analyses that were performed during this period clearly establish that adsorbed hydrogen retards oxidation, although in complex ways. In particular, particles that have been heated to intermediate hydrogen coverages oxidize more slowly in air than do freshly generated particles that have a much higher hydrogen content. In addition, the loss of surface hydride species at high processing temperatures results in fast initial oxidation and the formation of a self-limiting oxide layer. Analogous measurements made on deuterium-covered particles show broadly similar behavior; i.e., that oxidation is the slowest at some intermediate coverage of adsorbed deuterium.

  4. The Geochemical Behaviour of Tc, Np, and Pu in Spent Nuclear Fuel in an Oxidizing Environment

    Energy Technology Data Exchange (ETDEWEB)

    Buck, Edgar C.; Hanson, Brady D.; McNamara, Bruce K.; R. Giere and P. Stille

    2004-10-01

    Studies at the Nopal and Shinkolowbwe uranium deposits show that the primary uraninite (UO2) altered to a suite of secondary uranyl minerals similar to those observed in corrosion tests with uranium oxide . Although the Nopal I deposit tells us something about the possible fate of uranium, it tells us little about the likely fate of the important long-lived radionuclides; iodine (129I), cesium (135Cs), technetium (99Tc), neptunium (237Np), and plutonium (239Pu). Most performance assessment (PA) models, assume conservatively, that as the UO2 matrix corrodes, the key radionuclides (129I, 99Tc, 237Np, and 239Pu) will be released congruently. In so doing, these PA models force increased reliance on human engineered barriers.

  5. The Geochemical Behavior of Tc, Np, and Pu in Spent Nuclear Fuel in an Oxidizing Environment

    International Nuclear Information System (INIS)

    Buck, Edgar C.; Hanson, Brady D.; McNamara, Bruce K.; R. Giere; P. Stille

    2004-01-01

    Studies at the Nopal and Shinkolowbwe uranium deposits show that the primary uraninite (UO2) altered to a suite of secondary uranyl minerals similar to those observed in corrosion tests with uranium oxide . Although the Nopal I deposit tells us something about the possible fate of uranium, it tells us little about the likely fate of the important long-lived radionuclides; iodine (129I), cesium (135Cs), technetium (99Tc), neptunium (237Np), and plutonium (239Pu). Most performance assessment (PA) models, assume conservatively, that as the UO2 matrix corrodes, the key radionuclides (129I, 99Tc, 237Np, and 239Pu) will be released congruently. In so doing, these PA models force increased reliance on human engineered barriers

  6. Lewis acid catalysis and Green oxidations: sequential tandem oxidation processes induced by Mn-hyperaccumulating plants.

    Science.gov (United States)

    Escande, Vincent; Renard, Brice-Loïc; Grison, Claude

    2015-04-01

    Among the phytotechnologies used for the reclamation of degraded mining sites, phytoextraction aims to diminish the concentration of polluting elements in contaminated soils. However, the biomass resulting from the phytoextraction processes (highly enriched in polluting elements) is too often considered as a problematic waste. The manganese-enriched biomass derived from native Mn-hyperaccumulating plants of New Caledonia was presented here as a valuable source of metallic elements of high interest in chemical catalysis. The preparation of the catalyst Eco-Mn1 and reagent Eco-Mn2 derived from Grevillea exul exul and Grevillea exul rubiginosa was investigated. Their unusual polymetallic compositions allowed to explore new reactivity of low oxidative state of manganese-Mn(II) for Eco-Mn1 and Mn(IV) for Eco-Mn2. Eco-Mn1 was used as a Lewis acid to catalyze the acetalization/elimination of aldehydes into enol ethers with high yields; a new green and stereoselective synthesis of (-)-isopulegol via the carbonyl-ene cyclization of (+)-citronellal was also performed with Eco-Mn1. Eco-Mn2 was used as a mild oxidative reagent and controlled the oxidation of aliphatic alcohols into aldehydes with quantitative yields. Oxidative cleavage was interestingly noticed when Eco-Mn2 was used in the presence of a polyol. Eco-Mn2 allowed direct oxidative iodination of ketones without using iodine, which is strongly discouraged by new environmental legislations. Finally, the combination of the properties in the Eco-Mn catalysts and reagents gave them an unprecedented potential to perform sequential tandem oxidation processes through new green syntheses of p-cymene from (-)-isopulegol and (+)-citronellal; and a new green synthesis of functionalized pyridines by in situ oxidation of 1,4-dihydropyridines.

  7. Recovery of calcium from the effluent of direct oxide reduction process

    International Nuclear Information System (INIS)

    Ferro, P.; Mishra, B.; Olson, D.L.; Moore, J.J.; Averill, W.A.

    1992-01-01

    This paper reports that the production of plutonium by Direct Oxide Reduction [DOR] process using calcium generates significant amount of contaminated waste as calcium oxide saturated calcium chloride salt mix with calcium oxide content of up to 15 wt. pct. Fused salt electrolysis of a simulated slat mix [CaCl 2 + 15 wt. pct. CaO] is being carried out to election calcium, which can be recycled to the DOR rector along with the calcium chloride salt or may be used in-situ in an combined DOR and electrowinning process. The technology will resolve a major contaminated waste disposal problem, besides improving the cost and process efficiency in radioactive metal production. The process is being optimized in terms of the calcium solubility, cell temperature, current density and cell design to maximize the current efficiency. Scattered information is available regarding the solubility of calcium in calcium chloride salt in the present of calcium oxide. The solubility has also been found to depend on the use of graphite as the anode material. A porous ceramic sheath is being used around the anode to prevent the dissolution of electrowon calcium as oxide or carbonate and to prevent the contamination of salt by the anodic carbon. The electrode reactions are affected by the electrolyte composition and its viscosity which varies with time in this process and, therefore, electrochemical impedance is being measured to understand this time-dependent mechanisms

  8. Automation of the micro-arc oxidation process

    Science.gov (United States)

    Golubkov, P. E.; Pecherskaya, E. A.; Karpanin, O. V.; Shepeleva, Y. V.; Zinchenko, T. O.; Artamonov, D. V.

    2017-11-01

    At present the significantly increased interest in micro-arc oxidation (MAO) encourages scientists to look for the solution of the problem of this technological process controllability. To solve this problem an automated technological installation MAO was developed, its structure and control principles are presented in this article. This device will allow to provide the controlled synthesis of MAO coatings and to identify MAO process patterns which contributes to commercialization of this technology.

  9. Solution processed metal oxide thin film hole transport layers for high performance organic solar cells

    Science.gov (United States)

    Steirer, K. Xerxes; Berry, Joseph J.; Chesin, Jordan P.; Lloyd, Matthew T.; Widjonarko, Nicodemus Edwin; Miedaner, Alexander; Curtis, Calvin J.; Ginley, David S.; Olson, Dana C.

    2017-01-10

    A method for the application of solution processed metal oxide hole transport layers in organic photovoltaic devices and related organic electronics devices is disclosed. The metal oxide may be derived from a metal-organic precursor enabling solution processing of an amorphous, p-type metal oxide. An organic photovoltaic device having solution processed, metal oxide, thin-film hole transport layer.

  10. Kinetic studies on the degradation of crystal violet by the Fenton oxidation process.

    Science.gov (United States)

    Wu, H; Fan, M M; Li, C F; Peng, M; Sheng, L J; Pan, Q; Song, G W

    2010-01-01

    The degradation of dye crystal violet (CV) by Fenton oxidation process was investigated. The UV-Vis spectrogram has shown that CV can be degraded effectively by Fenton oxidation process. Different system variables namely initial H(2)O(2) concentration, initial Fe(2 + ) concentration and reaction temperature, which have effect on the degradation of CV by Fenton oxidation process, have been studied systematically. The degradation kinetics of CV was also elucidated based on the experimental data. The degradation of CV obeys the first-order reaction kinetics. The kinetic model can be described as k=1.5 exp(-(7.5)/(RT))[H(2)O(2)](0)(0.8718)[Fe(2+)](0)(0.5062). According to the IR spectrogram, it is concluded that the benzene ring of crystal violet has been destroyed by Fenton oxidation. The result will be useful in treating dyeing wastewater containing CV by Fenton oxidation process.

  11. Study on emission characteristics and reduction strategy of nitrous oxide during wastewater treatment by different processes.

    Science.gov (United States)

    Sun, Shichang; Bao, Zhiyuan; Sun, Dezhi

    2015-03-01

    Given the inexorable increase in global wastewater treatment, increasing amounts of nitrous oxide are expected to be emitted from wastewater treatment plants and released to the atmosphere. It has become imperative to study the emission and control of nitrous oxide in the various wastewater treatment processes currently in use. In the present investigation, the emission characteristics and the factors affecting the release of nitrous oxide were studied via full- and pilot-scale experiments in anoxic-oxic, sequencing batch reactor and oxidation ditch processes. We propose an optimal treatment process and relative strategy for nitrous oxide reduction. Our results show that both the bio-nitrifying and bio-denitrifying treatment units in wastewater treatment plants are the predominant sites for nitrous oxide production in each process, while the aerated treatment units are the critical sources for nitrous oxide emission. Compared with the emission of nitrous oxide from the anoxic-oxic (1.37% of N-influent) and sequencing batch reactor (2.69% of N-influent) processes, much less nitrous oxide (0.25% of N-influent) is emitted from the oxidation ditch process, which we determined as the optimal wastewater treatment process for nitrous oxide reduction, given the current technologies. Nitrous oxide emissions differed with various operating parameters. Controlling the dissolved oxygen concentration at a proper level during nitrification and denitrification and enhancing the utilization rate of organic carbon in the influent for denitrification are the two critical methods for nitrous oxide reduction in the various processes considered.

  12. Generic process for preparing a crystalline oxide upon a group IV semiconductor substrate

    Science.gov (United States)

    McKee, Rodney A.; Walker, Frederick J.; Chisholm, Matthew F.

    2000-01-01

    A process for growing a crystalline oxide epitaxially upon the surface of a Group IV semiconductor, as well as a structure constructed by the process, is described. The semiconductor can be germanium or silicon, and the crystalline oxide can generally be represented by the formula (AO).sub.n (A'BO.sub.3).sub.m in which "n" and "m" are non-negative integer repeats of planes of the alkaline earth oxides or the alkaline earth-containing perovskite oxides. With atomic level control of interfacial thermodynamics in a multicomponent semiconductor/oxide system, a highly perfect interface between a semiconductor and a crystalline oxide can be obtained.

  13. Remediation of a winery wastewater combining aerobic biological oxidation and electrochemical advanced oxidation processes.

    Science.gov (United States)

    Moreira, Francisca C; Boaventura, Rui A R; Brillas, Enric; Vilar, Vítor J P

    2015-05-15

    Apart from a high biodegradable fraction consisting of organic acids, sugars and alcohols, winery wastewaters exhibit a recalcitrant fraction containing high-molecular-weight compounds as polyphenols, tannins and lignins. In this context, a winery wastewater was firstly subjected to a biological oxidation to mineralize the biodegradable fraction and afterwards an electrochemical advanced oxidation process (EAOP) was applied in order to mineralize the refractory molecules or transform them into simpler ones that can be further biodegraded. The biological oxidation led to above 97% removals of dissolved organic carbon (DOC), chemical oxygen demand (COD) and 5-day biochemical oxygen demand (BOD5), but was inefficient on the degradation of a bioresistant fraction corresponding to 130 mg L(-1) of DOC, 380 mg O2 L(-1) of COD and 8.2 mg caffeic acid equivalent L(-1) of total dissolved polyphenols. Various EAOPs such as anodic oxidation with electrogenerated H2O2 (AO-H2O2), electro-Fenton (EF), UVA photoelectro-Fenton (PEF) and solar PEF (SPEF) were then applied to the recalcitrant effluent fraction using a 2.2 L lab-scale flow plant containing an electrochemical cell equipped with a boron-doped diamond (BDD) anode and a carbon-PTFE air-diffusion cathode and coupled to a photoreactor with compound parabolic collectors (CPCs). The influence of initial Fe(2+) concentration and current density on the PEF process was evaluated. The relative oxidative ability of EAOPs increased in the order AO-H2O2 < EF < PEF ≤ SPEF. The SPEF process using an initial Fe(2+) concentration of 35 mg L(-1), current density of 25 mA cm(-2), pH of 2.8 and 25 °C reached removals of 86% on DOC and 68% on COD after 240 min, regarding the biologically treated effluent, along with energy consumptions of 45 kWh (kg DOC)(-1) and 5.1 kWh m(-3). After this coupled treatment, color, odor, COD, BOD5, NH4(+), NO3(-) and SO4(2-) parameters complied with the legislation targets and, in addition, a total

  14. Investigation on the co-precipitation of transuranium elements from alkaline solutions by the method of appearing reagents

    International Nuclear Information System (INIS)

    Krot, N.; Shilov, V.; Bessonov, A.; Budantseva, N.; Charushnikova, I.; Perminov, V.; Astafurova, L.

    1996-06-01

    Highly alkaline radioactive waste solutions originating from production of plutonium for military purposes are stored in underground tanks at the U.S. Department of Energy Hanford Site. The purification of alkaline solutions from neptunium and plutonium is important in the treatment and disposal of these wastes. This report describes scoping tests with sodium hydroxide solutions, where precipitation techniques were investigated to perform the separation. Hydroxides of iron (III), manganese (II), cobalt (II, III), and chromium (III); manganese (IV) oxide, and sodium uranate were investigated as carriers. The report describes the optimum conditions that were identified to precipitate these carriers homogeneously throughout the solution by reductive, hydrolytic, or catalytic decomposition of alkali-soluble precursor compounds by a technique called the Method of Appearing Reagents. The coprecipitation of pentavalent and hexavalent neptunium and plutonium was investigated for the candidate agents under optimum conditions and is described in this report along with the following results. Plutonium coprecipitated well with all tested materials except manganese (IV) oxide. Neptunium only coprecipitated well with uranate. The report presents a hypothesis to explain these behaviors. Further tests with more complex solution matrices must be performed

  15. Investigation on the co-precipitation of transuranium elements from alkaline solutions by the method of appearing reagents

    Energy Technology Data Exchange (ETDEWEB)

    Krot, N.; Shilov, V.; Bessonov, A.; Budantseva, N.; Charushnikova, I.; Perminov, V.; Astafurova, L. [Russian Academy of Science (Russian Federation). Inst. of Physical Chemistry

    1996-06-06

    Highly alkaline radioactive waste solutions originating from production of plutonium for military purposes are stored in underground tanks at the U.S. Department of Energy Hanford Site. The purification of alkaline solutions from neptunium and plutonium is important in the treatment and disposal of these wastes. This report describes scoping tests with sodium hydroxide solutions, where precipitation techniques were investigated to perform the separation. Hydroxides of iron (III), manganese (II), cobalt (II, III), and chromium (III); manganese (IV) oxide, and sodium uranate were investigated as carriers. The report describes the optimum conditions that were identified to precipitate these carriers homogeneously throughout the solution by reductive, hydrolytic, or catalytic decomposition of alkali-soluble precursor compounds by a technique called the Method of Appearing Reagents. The coprecipitation of pentavalent and hexavalent neptunium and plutonium was investigated for the candidate agents under optimum conditions and is described in this report along with the following results. Plutonium coprecipitated well with all tested materials except manganese (IV) oxide. Neptunium only coprecipitated well with uranate. The report presents a hypothesis to explain these behaviors. Further tests with more complex solution matrices must be performed.

  16. Coupling mechanism between wear and oxidation processes of 304 stainless steel in hydrogen peroxide environments.

    Science.gov (United States)

    Dong, Conglin; Yuan, Chengqing; Bai, Xiuqin; Li, Jian; Qin, Honglin; Yan, Xinping

    2017-05-24

    Stainless steel is widely used in strongly oxidizing hydrogen peroxide (H 2 O 2 ) environments. It is crucial to study its wear behaviour and failure mode. The tribological properties and oxidation of 304 stainless steel were investigated using a MMW-1 tribo-tester with a three-electrode setup in H 2 O 2 solutions with different concentrations. Corrosion current densities (CCDs), coefficients of frictions (COFs), wear mass losses, wear surface topographies, and metal oxide films were analysed and compared. The results show that the wear process and oxidation process interacted significantly with each other. Increasing the concentration of H 2 O 2 or the oxidation time was useful to form a layer of integrated, homogeneous, compact and thick metal oxide film. The dense metal oxide films with higher mechanical strengths improved the wear process and also reduced the oxidation reaction. The wear process removed the metal oxide films to increase the oxidation reaction. Theoretical data is provided for the rational design and application of friction pairs in oxidation corrosion conditions.

  17. Optimization of oxidation processes to improve crystalline silicon solar cell emitters

    Directory of Open Access Journals (Sweden)

    L. Shen

    2014-02-01

    Full Text Available Control of the oxidation process is one key issue in producing high-quality emitters for crystalline silicon solar cells. In this paper, the oxidation parameters of pre-oxidation time, oxygen concentration during pre-oxidation and pre-deposition and drive-in time were optimized by using orthogonal experiments. By analyzing experimental measurements of short-circuit current, open circuit voltage, series resistance and solar cell efficiency in solar cells with different sheet resistances which were produced by using different diffusion processes, we inferred that an emitter with a sheet resistance of approximately 70 Ω/□ performed best under the existing standard solar cell process. Further investigations were conducted on emitters with sheet resistances of approximately 70 Ω/□ that were obtained from different preparation processes. The results indicate that emitters with surface phosphorus concentrations between 4.96 × 1020 cm−3 and 7.78 × 1020 cm−3 and with junction depths between 0.46 μm and 0.55 μm possessed the best quality. With no extra processing, the final preparation of the crystalline silicon solar cell efficiency can reach 18.41%, which is an increase of 0.4%abs compared to conventional emitters with 50 Ω/□ sheet resistance.

  18. Radionuclide sorption kinetics and column sorption studies with Columbia River basalts

    International Nuclear Information System (INIS)

    Barney, G.S.

    1983-09-01

    The kinetics of radionuclide sorption and desorption reactions in basalt-groundwater systems were evaluated at 60 degrees C using a batch equilibration method. It was found that many sorption reactions on surfaces of fresh (unaltered) basalt from the Umtanum and Cohassett flows are slow. Some reactions require more than 50 days to reach a steady state. Sorption of neptunium and uranium in oxidizing (air saturated) groundwater appears to be controlled by slow reduction of these elements by the basalt surfaces. The resulting lower oxidation states are more strongly sorbed. Technetium and selenium, which are anionic under oxidizing conditions, are not measurably sorbed on fresh basalt surfaces, but are slightly sorbed on the altered surfaces of flow top basalt. Under reducing conditions, where the groundwater contains dilute hydrazine, sorption is faster for neptunium, uranium, technetium, selenium, and lead. Plutonium sorption rates were not affected by the groundwater Eh. It was shown that radium was precipitated rather than sorbed under the conditions of these experiments. Umtanum flow top material sorbed radionuclides much faster than fresh basalt surfaces due to its greater surface area and cation exchange capacity. Desorption rates for plutonium, uranium, neptunium, technetium, and selenium were generally much less than sorption rates (especially for reducing conditions). These radionuclides are irreversibly sorbed on the basalts. 25 refs., 20 figs., 19 tabs

  19. Iron oxides and their applications in catalytic processes: a review

    OpenAIRE

    Oliveira, Luiz C. A.; Fabris, José D.; Pereira, Márcio C.

    2013-01-01

    A review of most of the reported studies on the use of iron oxides as catalyst in specific processes, namely Haber-Bosch reaction, Fischer-Tropsch synthesis, Fenton oxidation and photolytic molecular splitting of water to produce gaseous hydrogen, was carried out. An essential overview is thus presented, intending to address the fundamental meaning, as well as the corresponding chemical mechanisms, and perspectives on new technological potentialities of natural and synthetic iron oxides, more...

  20. Flexible substrate compatible solution processed P-N heterojunction diodes with indium-gallium-zinc oxide and copper oxide

    Energy Technology Data Exchange (ETDEWEB)

    Choudhary, Ishan; Deepak, E-mail: saboo@iitk.ac.in

    2017-04-15

    Highlights: • Both n and p-type semiconductors are solution processed. • Temperature compatibility with flexible substrates such as polyimide. • Compatibility of p-type film (CuO) on n-type film (IZO). • Diode with rectification ratio of 10{sup 4} and operating voltage <1.5 V. • Construction of band alignment using XPS. - Abstract: Printed electronics on flexible substrates requires low temperature and solution processed active inks. With n-type indium-gallium-zinc oxide (IGZO) based electronics maturing for thin film transistor (TFT), we here demonstrate its heterojunction diode with p-copper oxide, prepared by sol-gel method and processed at temperatures compatible with polyimide substrates. The phase obtained for copper oxide is CuO. When coated on n-type oxide, it is prone to develop morphological features, which are minimized by annealing treatment. Diodes of p-CuO films with IGZO are of poor quality due to its high resistivity while, conducting indium-zinc oxide (IZO) films yielded good diode with rectification ratio of 10{sup 4} and operating voltage <1.5 V. A detailed measurement at the interface by X-ray photoelectron spectroscopy and optical absorption ascertained the band alignment to be of staggered type. Consistently, the current in the diode is established to be due to electrons tunnelling from n-IZO to p-CuO.

  1. Separation method for uranium, plutonium, and neptunium with each other from spent nuclear fuel

    International Nuclear Information System (INIS)

    Uchiyama, Gunzo; Hotoku, Shinobu; Fujine, Sachio; Maeda, Mitsuru.

    1994-01-01

    In a nuclear fuel reprocessing step of the present invention, an Np oxidation step is provided on a high level side of a co-contamination step, and an Np separation step and a U/Pu recovering step provided preceding to a U/Pu distribution step. Np oxidation step uses an oxidizer which is not extracted by an organic solvent such as ammonium vanadate for oxidizing Np from pentavalence to hexavalence. The Np separation step uses n-butylaldehyde for selectively reducing only hexavalent Np into pentavalent Np in a system in which hexavalent Np and tetravalent Pu are present together. In the U/Pu recovering step, pentavalent U and tetravalent Pu which shift by so much as distribution equilibrium are extracted together with pentavalent Np by using an organic solvent. The U/Pu distribution step uses iso-butylaldehyde as a reagent for selectively reducing only tetravalent Pu present together with hexavalent U into trivalent. With such procedures, U, Pu and Np can be separated with each other by more simplified fuel processing process. (T.M.)

  2. Phenol wastewater remediation: advanced oxidation processes coupled to a biological treatment.

    Science.gov (United States)

    Rubalcaba, A; Suárez-Ojeda, M E; Stüber, F; Fortuny, A; Bengoa, C; Metcalfe, I; Font, J; Carrera, J; Fabregat, A

    2007-01-01

    Nowadays, there are increasingly stringent regulations requiring more and more treatment of industrial effluents to generate product waters which could be easily reused or disposed of to the environment without any harmful effects. Therefore, different advanced oxidation processes were investigated as suitable precursors for the biological treatment of industrial effluents containing phenol. Wet air oxidation and Fenton process were tested batch wise, while catalytic wet air oxidation and H2O2-promoted catalytic wet air oxidation processes were studied in a trickle bed reactor, the last two using over activated carbon as catalyst. Effluent characterisation was made by means of substrate conversion (using high liquid performance chromatography), chemical oxygen demand and total organic carbon. Biodegradation parameters (i.e. maximum oxygen uptake rate and oxygen consumption) were obtained from respirometric tests using activated sludge from an urban biological wastewater treatment plant (WWTP). The main goal was to find the proper conditions in terms of biodegradability enhancement, so that these phenolic effluents could be successfully treated in an urban biological WWTP. Results show promising research ways for the development of efficient coupled processes for the treatment of wastewater containing toxic or biologically non-degradable compounds.

  3. Simultaneous nitrate reduction and acetaminophen oxidation using the continuous-flow chemical-less VUV process as an integrated advanced oxidation and reduction process.

    Science.gov (United States)

    Moussavi, Gholamreza; Shekoohiyan, Sakine

    2016-11-15

    This work was aimed at investigating the performance of the continuous-flow VUV photoreactor as a novel chemical-less advanced process for simultaneously oxidizing acetaminophen (ACT) as a model of pharmaceuticals and reducing nitrate in a single reactor. Solution pH was an important parameter affecting the performance of VUV; the highest ACT oxidation and nitrate reduction attained at solution pH between 6 and 8. The ACT was oxidized mainly by HO while the aqueous electrons were the main working agents in the reduction of nitrate. The performance of VUV photoreactor improved with the increase of hydraulic retention time (HRT); the complete degradation of ACT and ∼99% reduction of nitrate with 100% N2 selectivity achieved at HRT of 80min. The VUV effluent concentrations of nitrite and ammonium at HRT of 80min were below the drinking water standards. The real water sample contaminated with the ACT and nitrate was efficiently treated in the VUV photoreactor. Therefore, the VUV photoreactor is a chemical-less advanced process in which both advanced oxidation and advanced reduction reactions are accomplished. This unique feature possesses VUV photoreactor as a promising method of treating water contaminated with both pharmaceutical and nitrate. Copyright © 2016 Elsevier B.V. All rights reserved.

  4. Processing and properties of silver-metal oxide electrical contact materials

    Directory of Open Access Journals (Sweden)

    Nadežda M. Talijan

    2012-12-01

    Full Text Available The presented study gives a brief overview of the experimental results of investigations of different production technologies of silver-metal oxide electrical contact materials in relation: processing method - properties. The two most common routes of production, i.e. internal oxidation/ingot metallurgy and powder metallurgy are demonstrated on the example of Ag-CdO and Ag-ZnO materials. For illustration of alternative processing routes that provide higher dispersion of metal-oxide particles in silver matrix more environmentally friendly Ag-SnO2 contact materials are used. Processing of electrical contact materials by mechanical mixing of starting powders in high energy ball mill is presented. The obtained experimental results of application of different methods of introduction of SnO2 nanoparticles in the silver matrix such as conventional powder metallurgy mixing and template method are given and discussed in terms of their influence on microstructure and physical properties (density, hardness and electrical conductivity of the prepared Ag-SnO2 electrical contact materials.

  5. SIMULTANEOUS DEGRADATION OF SOME PHTHALATE ESTERS UNDER FENTON AND PHOTO-FENTON OXIDATION PROCESSES

    Directory of Open Access Journals (Sweden)

    BELDEAN-GALEA M.S.

    2015-03-01

    Full Text Available In this study the assessment of the degradation efficiency of five phthalates, DEP, BBP, DEHP, DINP and DIDP, found in a mixture in a liquid phase, using the Fenton and Photo Fenton oxidation processes, was conducted. It was observed that the main parameters that influence the Fenton oxidative processes of phthalates were the concentration of the oxidizing agent, H2O2, the concentration of the catalyst used, Fe2+, the pH value, UV irradiation and the reaction time. For the Fenton oxidative process, the highest degradation efficiencies were 19% for DEP, 50% for BBP, 84% for DEHP, 90% for DINP and 48% for DIDP, when the experiments were carried out using concentrations of 20 mg L-1 phthalate mixture, 100 mg L-1 H2O2, 10 mg L-1 Fe2+ at a pH value of 3, with a total reaction time of 30 minutes. For the Photo-Fenton oxidative process carried out in the same conditions as Fenton oxidative process, it was observed that after an irradiation time of 90 minutes under UV radiation the degradation efficiencies of phthalates were improved, being 22% for DEP, 71% for BBP, 97% for DEHP, 97% for DINP and 81% for DIDP.

  6. Process for the fabrication of nuclear fuel oxide pellets

    International Nuclear Information System (INIS)

    Francois, Bernard; Paradis, Yves.

    1977-01-01

    Process for the fabrication of nuclear fuel oxide pellets of the type for which particles charged with an organic binder -selected from the group that includes polyvinyl alcohol, carboxymethyl cellulose, polyvinyl compounds and methyl cellulose- are prepared from a powder of such an oxide, for instance uranium dioxide. These particles are then compressed into pellets which are then sintered. Under this process the binder charged particles are prepared by stirring the powder with a gas, spraying on to the stirred powder a solution or a suspension in a liquid of this organic binder in order to obtain these particles and then drying the particles so obtained with this gas [fr

  7. Process for the removal of sulfur oxides and nitrogen oxides from flue gas

    International Nuclear Information System (INIS)

    Elshout, R.V.

    1992-01-01

    This patent describes a continuous process for removing sulfur oxide and nitrogen oxide contaminants from the flue gas generated by industrial power plants and boiler systems burning sulfur containing fossil fuels and for converting these contaminants, respectively, into recovered elemental liquid sulfur and nitrogen ammonia and mixtures thereof. It comprises removing at least a portion of the flue gas generated by a power plant or boiler system upstream of the stack thereof; passing the cooled and scrubbed flue gas through an adsorption system; combining a first portion of the reducing gas stream leaving the adsorbers of the adsorption system during regeneration thereof and containing sulfur oxide and nitrogen oxide contaminants with a hydrogen sulfide rich gas stream at a temperature of about 400 degrees F to about 600 degrees F and passing the combined gas streams through a Claus reactor-condenser system over a catalyst in the reactor section thereof which is suitable for promoting the equilibrium reaction between the hydrogen sulfide and the sulfur dioxide of the combined streams to form elemental sulfur

  8. Microgravity Processing of Oxide Superconductors

    Science.gov (United States)

    Hofmeister, William H.; Bayuzick, Robert J.; Vlasse, Marcus; McCallum, William; Peters, Palmer (Technical Monitor)

    2000-01-01

    The primary goal is to understand the microstructures which develop under the nonequilibrium solidification conditions achieved by melt processing in copper oxide superconductor systems. More specifically, to define the liquidus at the Y- 1:2:3 composition, the Nd-1:2:3 composition, and several intermediate partial substitution points between pure Y-1:2:3 and Nd-1:2:3. A secondary goal has been to understand resultant solidification morphologies and pathways under a variety of experimental conditions and to use this knowledge to better characterize solidification phenomena in these systems.

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

    Science.gov (United States)

    Kumata, M.; Vandergraaf, T. T.

    1998-12-01

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

  10. Optimization Recovery of Yttrium Oxide in Precipitation, Extraction, and Stripping Process

    Science.gov (United States)

    Perwira, N. I.; Basuki, K. T.; Biyantoro, D.; Effendy, N.

    2018-04-01

    Yttrium oxide can be used as a dopant control rod of nuclear reactors in YSH material and superconductors. Yttrium oxide is obtained in the Xenotime mineral derived from byproduct of tin mining PT Timah Bangka which contain rare earth elements (REE) dominant Y, Dy, and Gd whose content respectively about 29.53%, 7.76%, and 2.58%. Both usage in the field of nuclear and non-nuclear science and technology is need to pure from the impurities. The presence of impurities in the yttrium oxide may affect the characteristic of the material and the efficiency of its use. Thus it needs to be separated by precipitation and extraction-stripping and calcination in the making of the oxide. However, to obtain higher levels of Yttrium oxide, it is necessary to determine the optimum conditions for its separation. The purpose of this research was to determine the optimum pH of precipitation, determine acid media and concentration optimum in extraction and stripping process and determine the efficiency of the separation of Y from REE concentrate. This research was conducted with pH variation in the precipitation process that pHs were 4 - 8, the difference of acid media for the extraction process, i.e., HNO3, HCl and H2SO4 with each concentration of 0,5 M; 1 M; 1,5 M; and 2 M and for stripping process were HNO3, HCl, and H2SO4 with each concentration of 1 M; 2M; and 3 M. Based on the result, the optimum pH of precipitation process was 6,5, the optimumacid media was HNO3 0,5 M, and for stripping process media was HNO3 3 M. The efficiency of precipitation process at pH 6,5 was 69,53 %, extraction process was 96.39% and stripping process was 4,50%. The separation process from precipitation to extraction had increased the purity and the highest efficiency recovery of Y was in the extraction process and obtained Y2O3 purer compared to the feed with the Y2O3 content of 92.87%.

  11. Determination of uranium in plutonium--238 metal and oxide by differential pulse polarography

    International Nuclear Information System (INIS)

    Fawcett, N.C.

    1976-01-01

    A differential pulse polarographic method was developed for the determination of total uranium in 238 Pu metal and oxides. A supporting electrolyte of 0.5 M ascorbic acid in 0.15 N H 2 SO 4 was found satisfactory for the determination of 500 ppM or more of uranium in 10 mg or less of plutonium. A relative standard deviation of 0.27 to 4.3 percent was obtained in the analysis of samples ranging in uranium content from 0.65 to 2.79 percent. The limit of detection was 0.18 μg ml -1 . Peak current was a linear function of uranium concentration up to at least 100 μg ml -1 . Amounts of neptunium equal to the uranium content were tolerated. The possible interference of a number of other cations and anions were investigated

  12. Petroleum Refinery Effluents Treatment by Advanced Oxidation Process with Methanol

    Energy Technology Data Exchange (ETDEWEB)

    Shoucheng, Wen [Yangtze Univ., HuBei Jingzhou (China)

    2014-02-15

    Petroleum refinery effluents are waste originating from industries primarily engaged in refining crude oil. It is a very complex compound of various oily wastes, water, heavy metals and so on. Conventional processes are unable to effectively remove the chemical oxygen demand (COD) of petroleum refinery effluents. Supercritical water oxidation (SCWO) was proposed to treat petroleum refinery effluents. In this paper, methanol was used to investigate co-oxidative effect of methanol on petroleum refinery effluents treatment. The results indicated that supercritical water oxidation is an effective process for petroleum refinery effluents treatment. Adding methanol caused an increase in COD removal. When reaction temperature is 440 .deg. C, residence time is 20 min, OE is 0.5 and initial COD is 40000 mg/L, and COD removal increases 8.5%.

  13. Petroleum Refinery Effluents Treatment by Advanced Oxidation Process with Methanol

    International Nuclear Information System (INIS)

    Shoucheng, Wen

    2014-01-01

    Petroleum refinery effluents are waste originating from industries primarily engaged in refining crude oil. It is a very complex compound of various oily wastes, water, heavy metals and so on. Conventional processes are unable to effectively remove the chemical oxygen demand (COD) of petroleum refinery effluents. Supercritical water oxidation (SCWO) was proposed to treat petroleum refinery effluents. In this paper, methanol was used to investigate co-oxidative effect of methanol on petroleum refinery effluents treatment. The results indicated that supercritical water oxidation is an effective process for petroleum refinery effluents treatment. Adding methanol caused an increase in COD removal. When reaction temperature is 440 .deg. C, residence time is 20 min, OE is 0.5 and initial COD is 40000 mg/L, and COD removal increases 8.5%

  14. A catalytic wet oxidation process for mixed waste volume reduction/recycling

    International Nuclear Information System (INIS)

    Dhooge, Patrick M.

    1992-01-01

    Mixed wastes have presented a challenge to treatment and destruction technologies. A recently developed catalytic wet oxidation method has promising characteristics for volume reduction and recycling of mixed wastes. The process utilizes iron (III) as an oxidant in the presence of homogeneous cocatalysts which increase organics' oxidation rates and the rate of oxidation of iron (II) by oxygen. The reaction is conducted in an aqueous mineral acid solution at temperatures of 373 - 573 deg K. The mineral acid should solvate a number of heavy metals, including U and Pu. Studies of reaction rates show that the process can oxidize a wide range of organic compounds including aromatics and chlorinated hydrocarbons. Rate constants in the range of 10 -7 to 10 -4 sec -1 , depending on the cocatalyst, acidity, type of anions, type of organic, temperature, and time. Activation energies ranged from 25. to 32. KJ/mole. Preliminary measurements of the extent of oxidation which could be obtained ranged from 80% for trichloroethylene to 99.8% for 1,2,4-trimethylbenzene; evidence was obtained that absorption by the fluorocarbon liners of the reaction bombs allowed some of the organics to escape exposure to the catalyst solution. The results indicate that complete oxidation of the organics used here, and presumably many others, can be achieved. (author)

  15. Application of advanced oxidation processes for removing salicylic acid from synthetic wastewaters

    Institute of Scientific and Technical Information of China (English)

    Djalma; Ribeiro; da; Silva; Carlos; A.Martinez-Huítle

    2010-01-01

    In this study,advanced oxidation processes(AOPs) such as anodic oxidation(AO),UV/H_2O_2 and Fenton processes(FP) were investigated for the degradation of salicylic acid(SA) in lab-scale experiments.Boron-doped diamond(BDD) film electrodes using Ta as substrates were employed for AO of SA.In the case of FP and UV/H_2O_2,most favorable experimental conditions were determined for each process and these were used for comparing with AO process.The study showed that the FP was the most effective process under ...

  16. Treatment of aqueous wastes contaminated with Congo Red dye by electrochemical oxidation and ozonation processes

    International Nuclear Information System (INIS)

    Faouzi Elahmadi, Mohammed; Bensalah, Nasr; Gadri, Abdellatif

    2009-01-01

    Synthetic aqueous wastes polluted with Congo Red (CR) have been treated by two advanced oxidation processes: electrochemical oxidation on boron doped diamond anodes (BDD-EO) and ozonation under alkaline conditions. For same concentrations, galvanostatic electrolyses have led to total COD and TOC removals but ozonation process can reach only 85% and 81% of COD and TOC removals, respectively. UV-vis qualitative analyses have shown different behaviors of CR molecules towards ozonation and electrochemical oxidation. Rapid discoloration has been observed during ozonation, whereas color persistence till the end of galvanostatic electrolyses has been seen during BDD-EO process. It seems that the oxidation mechanisms involved in the two processes are different: simultaneous destruction of azoic groups is suggested during ozonation process but consecutive destruction of these groups is proposed during BDD-EO. However, energetic study has evidenced that BDD-EO appears more efficient and more economic than ozonation in terms of TOC removals. These results have been explained by the fact that during BDD-EO, other strong oxidants electrogenerated from the electrolyte oxidation such as persulfates and direct-oxidation of CR and its byproducts on BDD anodes complement the hydroxyl radicals mediated oxidation to accomplish the total mineralization of organics.

  17. On the use of thermal NF3 as the fluorination and oxidation agent in treatment of used nuclear fuels

    Science.gov (United States)

    Scheele, Randall; McNamara, Bruce; Casella, Andrew M.; Kozelisky, Anne

    2012-05-01

    This paper presents results of our investigation on the use of nitrogen trifluoride as a fluorination or fluorination/oxidation agent for separating valuable constituents from used nuclear fuels by exploiting the different volatilities of the constituent fission product and actinide fluorides. Our thermodynamic calculations show that nitrogen trifluoride has the potential to produce volatile fission product and actinide fluorides from oxides and metals that can form volatile fluorides. Simultaneous thermogravimetric and differential thermal analyses show that the oxides of lanthanum, cerium, rhodium, and plutonium are fluorinated but do not form volatile fluorides when treated with nitrogen trifluoride at temperatures up to 550 °C. However, depending on temperature, volatile fluorides or oxyfluorides can form from nitrogen trifluoride treatment of the oxides of niobium, molybdenum, ruthenium, tellurium, uranium, and neptunium. Thermoanalytical studies demonstrate near-quantitative separation of uranium from plutonium in a mixed 80% uranium and 20% plutonium oxide. Our studies of neat oxides and metals suggest that the reactivity of nitrogen trifluoride may be adjusted by temperature to selectively separate the major volatile fuel constituent uranium from minor volatile constituents, such as Mo, Tc, Ru and from the non-volatile fuel constituents based on differences in their reaction temperatures and kinetic behaviors. This reactivity is novel with respect to that reported for other fluorinating reagents F2, BrF5, ClF3.

  18. Iron Oxide Films Prepared by Rapid Thermal Processing for Solar Energy Conversion.

    Science.gov (United States)

    Wickman, B; Bastos Fanta, A; Burrows, A; Hellman, A; Wagner, J B; Iandolo, B

    2017-01-16

    Hematite is a promising and extensively investigated material for various photoelectrochemical (PEC) processes for energy conversion and storage, in particular for oxidation reactions. Thermal treatments during synthesis of hematite are found to affect the performance of hematite electrodes considerably. Herein, we present hematite thin films fabricated via one-step oxidation of Fe by rapid thermal processing (RTP). In particular, we investigate the effect of oxidation temperature on the PEC properties of hematite. Films prepared at 750 °C show the highest activity towards water oxidation. These films show the largest average grain size and the highest charge carrier density, as determined from electron microscopy and impedance spectroscopy analysis. We believe that the fast processing enabled by RTP makes this technique a preferred method for investigation of novel materials and architectures, potentially also on nanostructured electrodes, where retaining high surface area is crucial to maximize performance.

  19. Organic waste processing using molten salt oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Adamson, M. G., LLNL

    1998-03-01

    Molten Salt Oxidation (MSO) is a thermal means of oxidizing (destroying) the organic constituents of mixed wastes, hazardous wastes, and energetic materials while retaining inorganic and radioactive constituents in the salt. For this reason, MSO is considered a promising alternative to incineration for the treatment of a variety of organic wastes. The U. S. Department of Energy`s Office of Environmental Management (DOE/EM) is currently funding research that will identify alternatives to incineration for the treatment of organic-based mixed wastes. (Mixed wastes are defined as waste streams which have both hazardous and radioactive properties.) One such project is Lawrence Livermore National Laboratory`s Expedited Technology Demonstration of Molten Salt Oxidation (MSO). The goal of this project is to conduct an integrated demonstration of MSO, including off-gas and spent salt treatment, and the preparation of robust solid final forms. Livermore National Laboratory (LLNL) has constructed an integrated pilot-scale MSO treatment system in which tests and demonstrations are presently being performed under carefully controlled (experimental) conditions. The system consists of a MSO process vessel with dedicated off-gas treatment, a salt recycle system, feed preparation equipment, and equipment for preparing ceramic final waste forms. In this paper we describe the integrated system and discuss its capabilities as well as preliminary process demonstration data. A primary purpose of these demonstrations is to identify the most suitable waste streams and waste types for MSO treatment.

  20. Report on the scientifical feasibility of advanced separation

    International Nuclear Information System (INIS)

    2001-01-01

    The advanced separation process Purex has been retained for the recovery of neptunium, technetium and iodine from high level and long lived radioactive wastes. Complementary solvent extraction processes will be used for the recovery of americium, curium and cesium from the high activity effluents of the spent fuel reprocessing treatment. This document presents the researches carried out to demonstrate the scientifical feasibility of the advanced separation processes: the adaptation of the Purex process would allow the recovery of 99% of the neptunium, while the association of the Diamex and Sanex (low acidity variant) processes, or the Paladin concept (single cycle with selective de-extraction of actinides) make it possible the recovery of 99.8% of the actinides III (americium and curium) with a high lanthanides decontamination factor (greater than 150). The feasibility of the americium/curium separation is demonstrated with the Sesame process (extraction of americium IV after electrolytic oxidation). Iodine is today recovered at about 99% with the Purex process and the dissolved fraction of technetium is also recovered at 99% using an adaptation of the Purex process. The non-dissolved fraction is retained by intermetallic compounds in dissolution residues. Cesium is separable from other fission products with recovery levels greater than 99.9% thanks to the use of functionalized calixarenes. The scientifical feasibility of advanced separation is thus demonstrated. (J.S.)

  1. Catalytic Oxidation of Lignins into the Aromatic Aldehydes: General Process Trends and Development Prospects

    Science.gov (United States)

    Tarabanko, Valery E.; Tarabanko, Nikolay

    2017-01-01

    This review discusses principal patterns that govern the processes of lignins’ catalytic oxidation into vanillin (3-methoxy-4-hydroxybenzaldehyde) and syringaldehyde (3,5-dimethoxy-4-hydroxybenzaldehyde). It examines the influence of lignin and oxidant nature, temperature, mass transfer, and of other factors on the yield of the aldehydes and the process selectivity. The review reveals that properly organized processes of catalytic oxidation of various lignins are only insignificantly (10–15%) inferior to oxidation by nitrobenzene in terms of yield and selectivity in vanillin and syringaldehyde. Very high consumption of oxygen (and consequentially, of alkali) in the process—over 10 mol per mol of obtained vanillin—is highlighted as an unresolved and unexplored problem: scientific literature reveals almost no studies devoted to the possibilities of decreasing the consumption of oxygen and alkali. Different hypotheses about the mechanism of lignin oxidation into the aromatic aldehydes are discussed, and the mechanism comprising the steps of single-electron oxidation of phenolate anions, and ending with retroaldol reaction of a substituted coniferyl aldehyde was pointed out as the most convincing one. The possibility and development prospects of single-stage oxidative processing of wood into the aromatic aldehydes and cellulose are analyzed. PMID:29140301

  2. Study on coordination characteristics of neptunium and uranium ions in calcium nitrate hydrate melt by Raman spectrometry and UV/Vis/NIR spectrometry

    International Nuclear Information System (INIS)

    Fujii, T; Okude, G; Uehara, A; Yamana, H

    2010-01-01

    Extraction behavior of neptunium (Np) by tri-n-butyl phosphate from calcium nitrate hydrate melt was investigated. Distribution ratio of Np was found to increase with the decrease of water content. Adding nitric acid into the system resulted in an increase of the distribution ratio. In order to understand the extraction trends, Np species in the hydrate melt were analyzed by Raman spectrometry and UV/Vis/NIR spectrometry. Major fraction was assigned to be NpO 2 2+ of Np(VI) and small fraction to be NpO 2 + of Np(V). A shift of the v 1 symmetric vibrational frequency of NpO 2 2+ in nitrate media was found in Raman spectra. This suggests a coordination circumstance change of NpO 2 2+ .

  3. Reduction of antibiotic resistance genes in municipal wastewater effluent by advanced oxidation processes

    International Nuclear Information System (INIS)

    Zhang, Yingying; Zhuang, Yao; Geng, Jinju; Ren, Hongqiang; Xu, Ke; Ding, Lili

    2016-01-01

    This study investigated the reduction of antibiotic resistance genes (ARGs), intI1 and 16S rRNA genes, by advanced oxidation processes (AOPs), namely Fenton oxidation (Fe"2"+/H_2O_2) and UV/H_2O_2 process. The ARGs include sul1, tetX, and tetG from municipal wastewater effluent. The results indicated that the Fenton oxidation and UV/H_2O_2 process could reduce selected ARGs effectively. Oxidation by the Fenton process was slightly better than that of the UV/H_2O_2 method. Particularly, for the Fenton oxidation, under the optimal condition wherein Fe"2"+/H_2O_2 had a molar ratio of 0.1 and a H_2O_2 concentration of 0.01 mol L"−"1 with a pH of 3.0 and reaction time of 2 h, 2.58–3.79 logs of target genes were removed. Under the initial effluent pH condition (pH = 7.0), the removal was 2.26–3.35 logs. For the UV/H_2O_2 process, when the pH was 3.5 with a H_2O_2 concentration of 0.01 mol L"−"1 accompanied by 30 min of UV irradiation, all ARGs could achieve a reduction of 2.8–3.5 logs, and 1.55–2.32 logs at a pH of 7.0. The Fenton oxidation and UV/H_2O_2 process followed the first-order reaction kinetic model. The removal of target genes was affected by many parameters, including initial Fe"2"+/H_2O_2 molar ratios, H_2O_2 concentration, solution pH, and reaction time. Among these factors, reagent concentrations and pH values are the most important factors during AOPs. - Highlights: • AOPs including Fenton oxidation and UV/H_2O_2 process could reduce ARGs effectively. • Fenton oxidation is slightly more effective than UV/H_2O_2 process in ARG reduction. • Removal of ARGs by AOPs follows the first-order reaction kinetic model. • Selected ARGs and 16S rRNA genes exhibit similar change trends during AOPs.

  4. Preliminary comparison of three processes of AlN oxidation: dry, wet and mixed ones

    Directory of Open Access Journals (Sweden)

    Korbutowicz R.

    2016-03-01

    Full Text Available Three methods of AlN layers oxidation: dry, wet and mixed (wet with oxygen were compared. Some physical parameters of oxidized thin films of aluminum nitride (AlN layers grown on silicon Si(1 1 1 were investigated by means Energy-Dispersive X-ray Spectroscopy (EDS and Spectroscopic Ellipsometry (SE. Three series of the thermal oxidations processes were carried out at 1012 °C in pure nitrogen as carrying gas and various gas ambients: (a dry oxidation with oxygen, (b wet oxidation with water steam and (c mixed atmosphere with various process times. All the research methods have shown that along with the rising of the oxidation time, AlN layer across the aluminum oxide nitride transforms to aluminum oxide. The mixed oxidation was a faster method than the dry or wet ones.

  5. Chemical processes for the extreme enrichment of tellurium into marine ferromanganese oxides

    Science.gov (United States)

    Kashiwabara, Teruhiko; Oishi, Yasuko; Sakaguchi, Aya; Sugiyama, Toshiki; Usui, Akira; Takahashi, Yoshio

    2014-04-01

    Tellurium, an element of growing economic importance, is extremely enriched in marine ferromanganese oxides. We investigated the mechanism of this enrichment using a combination of spectroscopic analysis and adsorption/coprecipitation experiments. X-ray Absorption Near-Edge Structure (XANES) analysis showed that in adsorption/coprecipitation systems, Te(IV) was oxidized on δ-MnO2 and not oxidized on ferrihydrite. Extended X-ray Absorption Fine Structure (EXAFS) analysis showed that both Te(IV) and Te(VI) were adsorbed on the surface of δ-MnO2 and ferrihydrite via formation of inner-sphere complexes. In addition, Te(VI) can be structurally incorporated into the linkage of Fe octahedra through a coprecipitation process because of its molecular geometry that is similar to the Fe octahedron. The largest distribution coefficient obtained in the adsorption/coprecipitation experiments was for the Te(VI)/ferrihydrite coprecipitation system, and it was comparable to those calculated from the distribution between natural ferromanganese oxides and seawater. Our XAFS and micro-focused X-ray fluorescence (μ-XRF) mapping of natural ferromanganese oxides showed that Te was structurally incorporated as Te(VI) in Fe (oxyhydr)oxide phases. We conclude that the main process for the enrichment of Te in ferromanganese oxides is structural incorporation of Te(VI) into Fe (oxyhydr)oxide phases through coprecipitation. This mechanism can explain the unique degree of enrichment of Te compared with other oxyanions, which are mainly enriched via adsorption on the surface of the solid structures. In particular, the great contrast in the distributions of Te and Se is caused by their oxidized species: (i) the similar geometry of the Te(VI) molecule to Fe octahedron, and (ii) quite soluble nature of Se(VI). Coexisting Mn oxide phases may promote structural incorporation of Te(VI) by oxidation of Te(IV), although the surface oxidation itself may not work as the critical enrichment process as

  6. A Study on N{sub 2}O Direct Oxidation Process with Re-oxidation Annealing for the Improvement of Interface Properties in 4H-SiC MOS Capacitor

    Energy Technology Data Exchange (ETDEWEB)

    Cho, Doohyung; Park, Kunsik; Yoo, Seongwook; Kim, Sanggi; Lee, Jinhwan; Kim, Kwangsoo [Electronics and Telecommunications Research Institute (ETRI), Daejeon (Korea, Republic of)

    2017-08-15

    The effect of N{sub 2}O direct oxidation processes with re-oxidation on SiC/SiO{sub 2} interface characteristics has been investigated. With different oxidation and post oxidation annealing (POA) processes, the flat-band voltage, effective dielectric charge density, and interface trap density are obtained from the capacitance-voltage curves. For the proposed N{sub 2}O direct oxidation processes with re-oxidation, oxides were grown in N{sub 2}O ambient, diluted in high-purity N{sub 2} to 10% concentration, for 5 h at 1230 ℃. After the growth, some samples were annealed additionally at 1200 ℃ in O{sub 2} or H{sub 2}O for 20 min. N{sub 2}O direct oxidation with re-oxidation processes was confirmed that SiC/SiO{sub 2} interface properties and dielectric stability have better performance than with other conventional oxidation processes. This oxidation technique is expected to improve gate dielectric stability for application to SiC MOS devices; in particular, it can be used to obtain high-quality SiC/SiO{sub 2} interface properties.

  7. Catalytic/non-catalytic combination process for nitrogen oxides reduction

    International Nuclear Information System (INIS)

    Luftglass, B.K.; Sun, W.H.; Hofmann, J.E.

    1992-01-01

    This patent describes a process for the reduction of nitrogen oxides in the effluent from the combustion of a carbonaceous fuel. It comprises introducing a nitrogenous treatment agent comprising urea, one or more of the hydrolysis products of urea, ammonia, compounds which produce ammonia as a by-product, ammonium salts of organic acids, 5- or 6-membered heterocyclic hydrocarbons having at least one cyclic nitrogen, hydroxy amino hydrocarbons, or mixtures thereof into the effluent at an effluent temperature between about 1200 degrees F and about 2100 degrees F; and contacting the treated effluent under conditions effective to reduce the nitrogen oxides in the effluent with a catalyst effective for the reduction of nitrogen oxides in the presence of ammonia

  8. Retention-oxidation-adsorption process for emergent treatment of organic liquid spills.

    Science.gov (United States)

    Liu, Xianjun; Li, Yu; Zhang, Xingwang; Lei, Lecheng

    2011-11-15

    The feasibility and effectiveness of retention-oxidation-adsorption process (ROA) for the elimination of organic contaminants induced by chemical accidents were investigated in this study. Organobentonites (DTMA-, TTA-, CTMA- and OTMA-bentonite), potassium ferrate (Fe(VI)), ozone and granular activated carbon (GAC) were used as rapid and efficient materials in the treatment and recovery of organic liquid spills. Results indicated that the retention capacities of organobentonites (especially CTMA-bentonite) were much higher than that of natural bentonite towards the chosen organic compounds. Additionally, pH, oxidant dosage, initial concentration of contaminant and chemical structure had significant influences on the effectiveness of the oxidation process. In a pilot-scale experiment, the ferrate/GAC (F/G) and ozone/GAC (O/G) processes made a comparatively good performance in the treatment of wastewater containing aniline or nitrobenzene, with the removal efficiencies of the contaminants greater than 80%. Overall, the ROA process showed a high efficiency and steady operation in the removal of hazardous organic liquids and subsequent clean up of the contaminated site. Crown Copyright © 2011. Published by Elsevier B.V. All rights reserved.

  9. Application of simplified desorption method to sorption study. (2) Sorption of neptunium (V) on montmorillonite-based mixtures

    International Nuclear Information System (INIS)

    Kozai, Naofumi; Ohnuki, Toshihiko

    2013-01-01

    To elucidate the sorption behaviors of radionuclides in multi-mineral systems and the mutual effects of minerals on the sorption, this paper carried out the sorption and desorption experiments of neptunium(V) on montmorillonite-based two-mineral mixtures. The Np sorbed on montmorillonite at pH from 4 to 8 was desorbed with 1M KCl solutions, indicating that the sorption was cation exchange. The Np sorbed on apatite and calcite was nondesorbable with 1M KCl solutions, which is in harmony with the knowledge that Np forms strong complexes with the phosphate groups of apatite and the carbonate groups of calcite. This study utilized these clear distinguishes of the desorption behaviors for examining the two-mineral systems. In montmorillonite-apatite mixtures, the sorption on the montmorillonite was decreased and Np was accumulated on the apatite. In montmorillonite-calcite mixtures, the sorption on the montmorillonite was decreased due to the interference by the calcium and carbonate ions dissolved from calcite while no accumulation of Np to calcite was observed. (author)

  10. Catalytic Oxidation of Lignins into the Aromatic Aldehydes: General Process Trends and Development Prospects

    Directory of Open Access Journals (Sweden)

    Valery E. Tarabanko

    2017-11-01

    Full Text Available This review discusses principal patterns that govern the processes of lignins’ catalytic oxidation into vanillin (3-methoxy-4-hydroxybenzaldehyde and syringaldehyde (3,5-dimethoxy-4-hydroxybenzaldehyde. It examines the influence of lignin and oxidant nature, temperature, mass transfer, and of other factors on the yield of the aldehydes and the process selectivity. The review reveals that properly organized processes of catalytic oxidation of various lignins are only insignificantly (10–15% inferior to oxidation by nitrobenzene in terms of yield and selectivity in vanillin and syringaldehyde. Very high consumption of oxygen (and consequentially, of alkali in the process—over 10 mol per mol of obtained vanillin—is highlighted as an unresolved and unexplored problem: scientific literature reveals almost no studies devoted to the possibilities of decreasing the consumption of oxygen and alkali. Different hypotheses about the mechanism of lignin oxidation into the aromatic aldehydes are discussed, and the mechanism comprising the steps of single-electron oxidation of phenolate anions, and ending with retroaldol reaction of a substituted coniferyl aldehyde was pointed out as the most convincing one. The possibility and development prospects of single-stage oxidative processing of wood into the aromatic aldehydes and cellulose are analyzed.

  11. Effect of processing on structural features of anodic aluminum oxides

    Science.gov (United States)

    Erdogan, Pembe; Birol, Yucel

    2012-09-01

    Morphological features of the anodic aluminum oxide (AAO) templates fabricated by electrochemical oxidation under different processing conditions were investigated. The selection of the polishing parameters does not appear to be critical as long as the aluminum substrate is polished adequately prior to the anodization process. AAO layers with a highly ordered pore distribution are obtained after anodizing in 0.6 M oxalic acid at 20 °C under 40 V for 5 minutes suggesting that the desired pore features are attained once an oxide layer develops on the surface. While the pore features are not affected much, the thickness of the AAO template increases with increasing anodization treatment time. Pore features are better and the AAO growth rate is higher at 20 °C than at 5 °C; higher under 45 V than under 40 V; higher with 0.6 M than with 0.3 M oxalic acid.

  12. Investigation of neptunium(V) reduction to neptunium(IV) by semiconductor photocatalysis

    International Nuclear Information System (INIS)

    Takahashi, M.; Nakamura, T.; Ikeda, T.; Karasawa, H.

    1990-01-01

    Np(V) is the dominant Np oxidation state in high level liquid waste from reprocessing plants. Since low extractability of Np(V) makes its separation from other nuclei difficult, valence control is required. When a 1mM Np(V) solution of 3M nitric acid was irradiated by a Xe-lamp, using n-SiC (5g/dm 3 ) as photocatalyst and hydrazine (0.1M) as donor, 100% of the Np(V) was reduced to Np(IV) within 30 min at room temperature. Electrochemical investigations suggested that Np(V) is reduced by the atomic hydrogen adsorbed on the photocatalyst surface. According to this mechanism, platinum group metals can act as reducing catalysts for No(V) reduction due to their low hydrogen overvoltage. The proposed mechanism was experimentally confirmed using platinum black (5g/dm 3 ) as catalyst and hydroxylammonium nitrate (0.9M) as reducing agent

  13. Atlas of Atomic Spectral Lines of Neptunium Emitted by Inductively Coupled Plasma

    Energy Technology Data Exchange (ETDEWEB)

    DeKalb, E.L. and Edelson, M. C.

    1987-08-01

    Optical emission spectra from high-purity Np-237 were generated with a glovebox-enclosed inductively coupled plasma (ICP) source. Spectra covering the 230-700 nm wavelength range are presented along with general commentary on the methodology used in collecting the data. The Ames Laboratory Nuclear Safeguards and Security Program has been charged with the task of developing optical spectroscopic methods to analyze the composition of spent nuclear fuels. Such materials are highly radioactive even after prolonged 'cooling' and are chemically complex. Neptunium (Np) is a highly toxic by-product of nuclear power generation and is found, in low abundance, in spent nuclear fuels. This atlas of the optical emission spectrum of Np, as produced by an inductively coupled plasma (ICP) spectroscopic source, is part of a general survey of the ICP emission spectra of the actinide elements. The ICP emission spectrum of the actinides originates almost exclusively from the electronic relaxation of excited, singly ionized species. Spectral data on the Np ion emission spectrum (i.e., the Np II spectrum) have been reported by Tomkins and Fred [1] and Haaland [2]. Tomkins and Fred excited the Np II spectrum with a Cu spark discharge and identified 114 Np lines in the 265.5 - 436.3 nm spectral range. Haaland, who corrected some spectral line misidentifications in the work of Tomkins and Fred, utilized an enclosed Au spark discharge to excite the Np II spectrum and reported 203 Np lines within the 265.4 - 461.0 nm wavelength range.

  14. Surface morphology study on chromium oxide growth on Cr films by Nd-YAG laser oxidation process

    International Nuclear Information System (INIS)

    Dong Qizhi; Hu Jiandong; Guo Zuoxing; Lian Jianshe; Chen Jiwei; Chen Bo

    2002-01-01

    Grain sized (60-100 nm) Cr 2 O 3 thin films were prepared on Cr thin film surfaces by Nd-YAG laser photothermal oxidation process. Surface morphology study showed crack-free short plateau-like oxide films formed. Increase of dislocation density after pulsed laser irradiation was found. Thin film external surfaces, grain boundaries and dislocations are main paths of laser surface oxidation. Pinning and sealing of grain boundary was the reason that deeper oxidation did not produce. Grain growth and agglomeration of Cr sub-layer yielded tensile stress on the surface Cr 2 O 3 thin film. It was the reason that short plateau-like surface morphology formed and cracks appeared sometimes. In oxygen annealing at 700 deg. C, grain boundaries were considered not to be pinned at the surface, mixture diffusion was main mechanism in growth of oxide. Compression stress development in whole film led to extrusion of grains that was the reason that multiple appearances such as pyramid-like and nutshell-like morphology formed

  15. Unusual nonlinear absorption response of graphene oxide in the presence of a reduction process

    International Nuclear Information System (INIS)

    Karimzadeh, Rouhollah; Arandian, Alireza

    2015-01-01

    The nonlinear absorption responses of graphene, graphene oxide and reduced graphene oxide are investigated using the Z-scan technique and laser beams at 405, 532 and 635 nm in a continuous wave regime. Results show that graphene, graphene oxide and reduced graphene oxide do not show any open Z-scan signals at wavelengths of 532 and 635 nm. At the same time, fresh graphene oxide suspension is found to exhibit a nonlinear absorption process in the case of a laser light at 405 nm. Moreover, it can be observed that the reduction of graphene oxide by 405 nm laser irradiation decreases its nonlinear absorption value significantly. These findings highlight the important role of the reduction process on the nonlinear absorption performance of graphene oxide. (letter)

  16. Reduction of antibiotic resistance genes in municipal wastewater effluent by advanced oxidation processes

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yingying; Zhuang, Yao; Geng, Jinju, E-mail: jjgeng@nju.edu.cn; Ren, Hongqiang; Xu, Ke; Ding, Lili

    2016-04-15

    This study investigated the reduction of antibiotic resistance genes (ARGs), intI1 and 16S rRNA genes, by advanced oxidation processes (AOPs), namely Fenton oxidation (Fe{sup 2+}/H{sub 2}O{sub 2}) and UV/H{sub 2}O{sub 2} process. The ARGs include sul1, tetX, and tetG from municipal wastewater effluent. The results indicated that the Fenton oxidation and UV/H{sub 2}O{sub 2} process could reduce selected ARGs effectively. Oxidation by the Fenton process was slightly better than that of the UV/H{sub 2}O{sub 2} method. Particularly, for the Fenton oxidation, under the optimal condition wherein Fe{sup 2+}/H{sub 2}O{sub 2} had a molar ratio of 0.1 and a H{sub 2}O{sub 2} concentration of 0.01 mol L{sup −1} with a pH of 3.0 and reaction time of 2 h, 2.58–3.79 logs of target genes were removed. Under the initial effluent pH condition (pH = 7.0), the removal was 2.26–3.35 logs. For the UV/H{sub 2}O{sub 2} process, when the pH was 3.5 with a H{sub 2}O{sub 2} concentration of 0.01 mol L{sup −1} accompanied by 30 min of UV irradiation, all ARGs could achieve a reduction of 2.8–3.5 logs, and 1.55–2.32 logs at a pH of 7.0. The Fenton oxidation and UV/H{sub 2}O{sub 2} process followed the first-order reaction kinetic model. The removal of target genes was affected by many parameters, including initial Fe{sup 2+}/H{sub 2}O{sub 2} molar ratios, H{sub 2}O{sub 2} concentration, solution pH, and reaction time. Among these factors, reagent concentrations and pH values are the most important factors during AOPs. - Highlights: • AOPs including Fenton oxidation and UV/H{sub 2}O{sub 2} process could reduce ARGs effectively. • Fenton oxidation is slightly more effective than UV/H{sub 2}O{sub 2} process in ARG reduction. • Removal of ARGs by AOPs follows the first-order reaction kinetic model. • Selected ARGs and 16S rRNA genes exhibit similar change trends during AOPs.

  17. Characterization of depleted uranium oxides fabricated using different processing methods

    International Nuclear Information System (INIS)

    Hastings, E.P.; Lewis, C.; FitzPatrick, J.; Rademacher, D.; Tandon, L.

    2008-01-01

    Identifying both physical and chemical characteristics of Special Nuclear Material (SNM) production processes is the corner stone of nuclear forensics. Typically, processing markers are based on measuring an interdicted sample's bulk chemical properties, such as the elemental or isotopic composition, or focusing on the chemical and physical morphology of only a few particles. Therefore, it is imperative that known SNM processes be fully characterized from bulk to trace level for each particle size range. This report outlines a series of particle size measurements and fractionation techniques that can be applied to a bulk SNM powders, categorizing both chemical and physical properties in discrete particle size fractions. This will be demonstrated by characterizing the process signatures of a series of different depleted uranium oxides prepared at increasing firing temperatures (350-1100 deg C). Results will demonstrate how each oxides' material density, particle size distribution, and morphology varies. (author)

  18. Optimization of leaching process for sum of rare earth and calcium oxides

    International Nuclear Information System (INIS)

    Troyanier, L.S.; Elunkina, Z.A.; Nikonov, V.N.; Lobov, V.I.

    1978-01-01

    Presented are the results of investigation of leaching process for rare earth and calcium oxides by sulfuric acid. The method of planning experiment has been used for this investigation. Mixtures of cerium, yttrium and neodyum oxides, taken in the relation of 1:1:0.5, have been used as rare earth elements. Received are adequate models characterizing dependence of solubility of rare earth and calcium oxides on some factors (H 2 SO 4 concentration, CaO:R 2 O 3 relation, liquid to solid ratio, solution temperature, mixing time). Dependences of solubility of rare earth elements and calcium on the process parameters are received and presented in a form of regression equations. Dependences received can be used for choice of optimum regime of the process as well as for its control

  19. A manufacturing process for a mixed-oxide type superconducting material

    International Nuclear Information System (INIS)

    Gendre, P.; Regnier, P.; Schmirgeld-Mignot, L.; Marquet, A.

    1995-01-01

    In order to produce high temperature superconducting materials such as YBaCuO and Bi 2 Sr 2 Ca Cu 2 O 8 , a process is presented which consists in an electrodeposition on a conductive substrate of successive layers made of the metallic elements composing the superconductor, with only one element in each layer; between each layer deposition, an intermediary oxide-reaction thermal treatment is carried out; a global oxidation thermal treatment is then finally conducted to produce the mixed oxide material. Narrow superconducting transitions and high critical current densities are possible. 3 refs., 4 figs

  20. Oxidizing attack process of uranium ore by a carbonated liquor

    International Nuclear Information System (INIS)

    Maurel, Pierre; Nicolas, Francois.

    1981-01-01

    A continuous process for digesting a uraniferous ore by oxidation with a recycling aqueous liquor containing alkaline carbonates and bicarbonates in solution as well as uranium in a concentration close to its solubility limit at digestion temperature, and of recuperation of the precipitated uranium within the solid phase remaining after digestion. The digestion is carried out by spraying oxygen into the hot reactional medium in order not only to permit oxidation of the uranium and its solubilization but also to ensure that the sulphides of impurities and organic substances present in the ore are oxidized [fr

  1. Development studies for a novel wet oxidation process

    International Nuclear Information System (INIS)

    Dhooge, P.M.; Hakim, L.B.

    1994-01-01

    A catalytic wet oxidation process (DETOX), which uses an acidic iron solution to oxidize organic compounds to carbon dioxide, water, and other simple products, was investigated as a potential method for the treatment of multicomponent hazardous and mixed wastes. The organic compounds picric acid, poly(vinyl chloride), tetrachlorothiophene, pentachloropyridine, Aroclor 1260 (a polychlorinated biphenyl), and hexachlorobenzene were oxidized in 125 ml reaction vessels. The metals arsenic, barium, beryllium, cadmium, cerium (as a surrogate for plutonium), chromium, lead, mercury, neodymium (as a surrogate for uranium), nickel, and vanadium were tested in the DETOX solution. Barium, beryllium, cerium, chromium, mercury, neodymium, nickel, and vanadium were all found to be very soluble (>100 g/l) in the DETOX chloride-based solution. Arsenic, barium, cadmium, and lead solubilities were lower. Lead could be selectively precipitated from the DETOX solution. Chromium(VI) was reduced to relatively non-toxic chromium(III) by the solution. Six soils were contaminated with arsenic, barium, beryllium, chromium, lead, and neodymium oxides at approximately 0.1% by weight, and benzene, trichloroethene, mineral oil, and Aroclor 1260 at approximately 5% by weight total, and 5.g amounts treated with the DETOX solution in unstirred 125. ml reaction bombs. It is felt that soil treatment in a properly designed system is entirely possible despite incomplete oxidation of the less volatile organic materials in these unstirred tests

  2. Process for depositing epitaxial alkaline earth oxide onto a substrate and structures prepared with the process

    Science.gov (United States)

    McKee, Rodney A.; Walker, Frederick J.

    1996-01-01

    A process and structure involving a silicon substrate utilize molecular beam epitaxy (MBE) and/or electron beam evaporation methods and an ultra-high vacuum facility to grow a layup of epitaxial alkaline earth oxide films upon the substrate surface. By selecting metal constituents for the oxides and in the appropriate proportions so that the lattice parameter of each oxide grown closely approximates that of the substrate or base layer upon which oxide is grown, lattice strain at the film/film or film/substrate interface of adjacent films is appreciably reduced or relieved. Moreover, by selecting constituents for the oxides so that the lattice parameters of the materials of adjacent oxide films either increase or decrease in size from one parameter to another parameter, a graded layup of films can be grown (with reduced strain levels therebetween) so that the outer film has a lattice parameter which closely approximates that of, and thus accomodates the epitaxial growth of, a pervoskite chosen to be grown upon the outer film.

  3. Development studies of a novel wet oxidation process

    International Nuclear Information System (INIS)

    Rogers, T.W.; Dhooge, P.M.

    1995-01-01

    Many DOE waste streams and remediates contain complex and variable mixtures of organic compounds, toxic metals, and radionuclides. These materials are often dispersed in organic or inorganic matrices, such as personal protective equipment, various sludges, soils, and water. Incineration and similar combustive processes do not appear to be viable options for treatment of these waste streams due to various considerations. There is a need for non-combustion processes with a wide application range to treat the large majority of these waste forms. The non-combustion process should also be safe, effective, cost-competitive, permit-able, and preferrably mobile. This paper describes the DETOX process of organic waste oxidation

  4. A PROCESS FOR THE CATALYTIC OXIDATION OF HYDROCARBONS

    DEFF Research Database (Denmark)

    1999-01-01

    A process for producing an alcohol from a gaseous hydrocarbon, e.g. a lower alkane such as methane, via oxidative reaction of the hydrocarbon in a concentrated sulfuric acid medium in the presence of a catalyst employs an added catalyst comprising a substance selected from iodine, iodine compounds...

  5. Microstructure and optical appearance of anodized friction stir processed Al - Metal oxide surface composites

    DEFF Research Database (Denmark)

    Gudla, Visweswara Chakravarthy; Jensen, Flemming; Bordo, Kirill

    2014-01-01

    Multiple-pass friction stir processing (FSP) was employed to impregnate Ti, Y and Ce oxide powders into the surface of an Aluminium alloy. The FSP processed surface composite was subsequently anodized with an aim to develop optical effects in the anodized layer owing to the presence of incorporated...... oxide particles which will influence the scattering of light. This paper presents the investigations on relation between microstructure of the FSP zone and optical appearance of the anodized layer due to incorporation of metal oxide particles and modification of the oxide particles due to the anodizing...

  6. Advanced oxidation of hypophosphite and phosphite using a UV/H2O2 process.

    Science.gov (United States)

    Liu, Peng; Li, Chaolin; Liang, Xingang; Xu, Jianhui; Lu, Gang; Ji, Fei

    2013-01-01

    The oxidation of hypophosphite and phosphite in an aqueous solution by an ultraviolet (UV)/H2O2 process was studied in this work. The reactions were performed in a lab-scale batch photoreactor. The effect of different parameters such as H2O2 dosage, H2O2 feeding mode and the initial pH of the solution on the oxidation efficiency of the process was investigated. The results indicated that the UV/H2O2 process could effectively oxidize hypophosphite and phosphite in both synthesized and real wastewater. However, neither H2O2 nor UV alone was able to appreciably oxidize the hypophosphite or phosphite. The best way of feeding H2O2 was found to be 'continuous feeding', which maximized the reaction rate. It was also found that the process presented a wide range of applicable initial pH (5-11). When treating real rinse-wastewater, which was obtained from the electroless nickel plating industry, both hypophosphite and phosphite were completely oxidized within 60 min, and by extending by another 30 min, over 90% of the chemical oxygen demand removal was obtained. Without any additional catalyst, the UV/H2O2 process can oxidize hypophosphite and phosphite to easily removable phosphate. It is really a powerful and environmentally friendly treatment method for the wastewater containing hypophosphite and phosphite.

  7. Effects of processing techniques on oxidative stability of Prunus pedunculatus seed oil

    Directory of Open Access Journals (Sweden)

    J. Yan

    2017-09-01

    Full Text Available This paper investigated the effects of Prunus pedunculatus (P. pedunculatus seed pre-treatment, including microwaving (M, roasting (R, steaming (S and roasting plus steaming (RS on crude oil quality in terms of yield, color change, fatty acid composition, and oxidative stability. The results showed an increase in monounsaturated fatty acid content and oxidative stability of the oils obtained from different processing treatments compared to the oil obtained from raw seeds (RW without processing. The oils, obtained from pretreated seeds, had higher conjugated diene (CD and 2-thiobarbituric acid (2-TBA values, compared to that obtained from RW when stored in a Schaal oven at 65 °C for 168 h. However, polyphenol and tocopherol contents decreased in all oil samples, processed or unprocessed. The effect of pre-treating the seeds was more prominent in the oil sample obtained through the RS technique, and showed higher oxidative stability than the other processed oils and the oil from RW.

  8. Feasibility of electrochemical oxidation process for treatment of saline wastewater

    Directory of Open Access Journals (Sweden)

    Kavoos Dindarloo

    2015-09-01

    Full Text Available Background: High concentration of salt makes biological treatment impossible due to bacterial plasmolysis. The present research studies the process of electrochemical oxidation efficiency and optimal levels as important factors affecting pH, salt concentration, reaction time and applied voltage. Methods: The sample included graphite electrodes with specifications of 2.5 cm diameter and 15 cm height using a reactor with an optimum capacity of 1 L. Sixty samples were obtained with the aid of the experiments carried out in triplicates for each factor at 5 different levels. The entire experiments were performed based on standard methods for water and waste water treatments. Results: Analysis of variance carried out on effect of pH, salt concentration, reaction time and flow intensity in elimination of chemical oxygen demand (COD showed that they are significant factors affecting this process and reduce COD with a coefficient interval of 95% and test power of 80%. Scheffe test showed that at optimal level, a reaction time of 1 hour, 10 g/L concentration, pH = 9 and 15 V electrical potential difference were obtained. Conclusion: Waste waters containing salt may contribute to the electro-oxidation process due to its cations and anions. Therefore, the process of electrochemical oxidation with graphite electrodes could be a proper strategy for the treatment of saline wastewater where biological treatment is not possible.

  9. JAEA thermodynamic database for performance assessment of geological disposal of high-level and TRU wastes. Refinement of thermodynamic data for tetravalent thorium, uranium, neptunium and plutonium

    International Nuclear Information System (INIS)

    Fujiwara, Kenso; Kitamura, Akira; Yui, Mikazu

    2010-03-01

    Within the scope of the JAEA thermodynamic database project for performance assessment of geological disposal of high-level and TRU radioactive wastes, the refinement of the thermodynamic data for the inorganic compounds and complexes of Thorium(IV), Uranium(IV), Neptunium(IV) and Plutonium(IV) was carried out. Refinement of thermodynamic data for the element was performed on a basis of the thermodynamic database for actinide published by the Nuclear Energy Agency in the Organisation for Economic Co-operation and Development (OECD/NEA). Additionally, the latest data after publication of thermodynamic data by OECD/NEA were reevaluated to determine whether the data should be included in the JAEA-TDB. (author)

  10. Accelerated oxidation processes is biodiesel

    Energy Technology Data Exchange (ETDEWEB)

    Canakci, M.; Monyem, A.; Van Gerpen, J.

    1999-12-01

    Biodiesel is an alternative fuel for diesel engines that can be produced from renewable feedstocks such as vegetable oil and animal fats. These feedstocks are reacted with an alcohol to produce alkyl monoesters that can be used in conventional diesel engines with little or no modification. Biodiesel, especially if produced from highly unsaturated oils, oxidizes more rapidly than diesel fuel. This article reports the results of experiments to track the chemical and physical changes that occur in biodiesel as it oxidizes. These results show the impact of time, oxygen flow rate, temperature, metals, and feedstock type on the rate of oxidation. Blending with diesel fuel and the addition of antioxidants are explored also. The data indicate that without antioxidants, biodiesel will oxidize very quickly at temperatures typical of diesel engines. This oxidation results in increases in peroxide value, acid value, and viscosity. While the peroxide value generally reaches a plateau of about 350 meq/kg ester, the acid value and viscosity increase monotonically as oxidation proceeds.

  11. Understanding the behaviour of the actinides under disposal conditions: A comparison between calculated and experimental solubilities

    International Nuclear Information System (INIS)

    Pryke, D.C.; Rees, J.H.

    1986-01-01

    The solubilities of plutonium, americium and neptunium measured in simulated near-field waters have compared with those predicted using the simple thermodynamic model NearSol. The dependence of solubility on pH and redox potential is examined in an effort to understand the behaviour of actinides in disposal. The agreement was variable. Differences could be appreciable, in particular for neptunium under oxidizing conditions; conversly, the model successfully predicted the behaviour of neptunium under reducing conditions. Such comparisons pinpointed deficiences in the thermodynamic data base and showed the sensitivity of solubilities to certain experimental parameters such as Eh and the concentration of carbonate ions. A comparison between NearSol and the reaction pathway program PHREEQE gave generally good agreement. NearSol was quicker and easier to use, requiring only limited preselection of participating species; however it did not account for the behaviour of bulk inactive species in solution; like feature will be built into an updated version. (orig.)

  12. Process for forming a homogeneous oxide solid phase of catalytically active material

    Science.gov (United States)

    Perry, Dale L.; Russo, Richard E.; Mao, Xianglei

    1995-01-01

    A process is disclosed for forming a homogeneous oxide solid phase reaction product of catalytically active material comprising one or more alkali metals, one or more alkaline earth metals, and one or more Group VIII transition metals. The process comprises reacting together one or more alkali metal oxides and/or salts, one or more alkaline earth metal oxides and/or salts, one or more Group VIII transition metal oxides and/or salts, capable of forming a catalytically active reaction product, in the optional presence of an additional source of oxygen, using a laser beam to ablate from a target such metal compound reactants in the form of a vapor in a deposition chamber, resulting in the deposition, on a heated substrate in the chamber, of the desired oxide phase reaction product. The resulting product may be formed in variable, but reproducible, stoichiometric ratios. The homogeneous oxide solid phase product is useful as a catalyst, and can be produced in many physical forms, including thin films, particulate forms, coatings on catalyst support structures, and coatings on structures used in reaction apparatus in which the reaction product of the invention will serve as a catalyst.

  13. Sorption of neptunium(V) on opalinus clay under aerobic/anaerobic conditions

    International Nuclear Information System (INIS)

    Froehlich, D.R.; Amayri, S.; Drebert, J.; Reich, T.

    2011-01-01

    The interaction between neptunium(V) and a natural argillaceous rock (Opalinus Clay (OPA), Mont Terri, Switzerland) has been investigated in batch sorption experiments by varying pH (6-10), Np(V) concentration (10 -12 -10 -4 M), solid-to-liquid ratio (2-20 g/L), and partial pressure of CO 2 (10 -3.5 and 10 -2.3 atm) under aerobic/anaerobic conditions in saturated calcite solution. All batch experiments were carried out using well characterized aerobic and anaerobic dry powders of OPA. The results show a great influence of pH on Np(V) sorption. Under aerobic conditions sorption increases with increasing pH until maximum sorption is reached between pH 8-9. At pH > 9 sorption decreases due to the formation of negatively charged Np(V)-carbonate complexes. By increasing p CO 2 from 10 -3.5 to 10 -2.3 atm, the sorption edge is shifted ∼ 0.5 units to lower pH values. Under anaerobic conditions stronger sorption of 8 x 10 -6 M Np(V) was found, possibly due to partial reduction of Np(V) to Np(IV). The sorption of 8 x 10 -6 M Np(V) under aerobic conditions at pH 8.2 in saturated calcite solution increases continuously with increasing solid-to-liquid ratio of OPA in the range of 2-20 g/L with a constant K d value of 126 ± 13 L/kg. The sorption isotherm was measured over seven orders of magnitude in Np(V) concentration using 239 Np as tracer. The sorption isotherm could be divided in a part of linear sorption behaviour between 10 -13 -10 -9 M Np(V) and non-linear behaviour in the range of 10 -9 -10 -4 M Np(V). (orig.)

  14. Plutonium and neptunium absorption from the gastrointestinal tract of neonatal baboons

    International Nuclear Information System (INIS)

    Lataillade, Ghislaine; Duserre, Claude; Rateau, Gerard; Verry, Monique; Fritsch, Paul; Metivier, Henri

    1992-06-01

    Nineteen baboons aged 1 to 310 days were given oral doses of 238 Pu citrate or 239 Np nitrate. Gastrointestinal (GI) absorption of Pu and Np were higher than those observed in adults. The values of Pu GI absorption were 0.22% at 1 d, 0.17% at 17 d then about 0.10% until 177 d of age. From 195 d onwards, GI absorption was about 0.02% vs adult values (0.008%). GI absorption of neptunium decreased rapidly with age from 1.71% at 4 d to 0.14% at 6 d and remained at this value until 26 d. From 77 d onwards Np GI absorption was decreased to adult value (0.042%). Gastrointestinal retention associated with GI absorption was small, below 0.4% for Pu and 0.2% for Np. Np and Pu was mainly retained in the small intestine. Pu was retained in the ileum wall till 66 d, and afterwards in the duodenum wall. Histological study of Pu retention showed that it was confined to the macrophages under the ileum villi epithelial cells. Np did not seem to have a well-defined retention compartment. Retention occurred first in the ileum wall up to 6 d, afterwards it was divided between the ileum and duodenum walls up to 77 d and finally, between the duodenum and jejunum walls from 132 days of age onwards. The study shows a difference between Np and Pu GI absorption in neonatal baboons. Np GI absorption decreased to adult value in less than 3 months whereas Pu GI absorption decreased to adult value within 195 days. Our Pu results demonstrated that, the tenfold increase of actinides gastrointestinal transfer proposed by ICRP up to 12 months of age in newborn humans seems acceptable. (authors) [fr

  15. Nitric Oxide and ERK mediates regulation of cellular processes by Ecdysterone

    Energy Technology Data Exchange (ETDEWEB)

    Omanakuttan, Athira; Bose, Chinchu; Pandurangan, Nanjan; Kumar, Geetha B.; Banerji, Asoke; Nair, Bipin G., E-mail: bipin@amrita.edu

    2016-08-15

    The complex process of wound healing is a major problem associated with diabetes, venous or arterial disease, old age and infection. A wide range of pharmacological effects including anabolic, anti-diabetic and hepato-protective activities have been attributed to Ecdysterone. In earlier studies, Ecdysterone has been shown to modulate eNOS and iNOS expression in diabetic animals and activate osteogenic differentiation through the Extracellular-signal-Regulated Kinase (ERK) pathway in periodontal ligament stem cells. However, in the wound healing process, Ecdysterone has only been shown to enhance granulation tissue formation in rabbits. There have been no studies to date, which elucidate the molecular mechanism underlying the complex cellular process involved in wound healing. The present study, demonstrates a novel interaction between the phytosteroid Ecdysterone and Nitric Oxide Synthase (NOS), in an Epidermal Growth Factor Receptor (EGFR)-dependent manner, thereby promoting cell proliferation, cell spreading and cell migration. These observations were further supported by the 4-amino-5-methylamino- 2′ ,7′ -difluorofluorescein diacetate (DAF FM) fluorescence assay which indicated that Ecdysterone activates NOS resulting in increased Nitric Oxide (NO) production. Additionally, studies with inhibitors of both the EGFR and ERK, demonstrated that Ecdysterone activates NOS through modulation of EGFR and ERK. These results clearly demonstrate, for the first time, that Ecdysterone enhances Nitric Oxide production and modulates complex cellular processes by activating ERK1/2 through the EGF pathway. - Highlights: • Ecdysterone significantly enhances cell migration in a dose dependent manner. • Ecdysterone augments cell spreading during the initial phase of cell migration through actin cytoskeletal rearrangement. • Ecdysterone enhances cell proliferation in a nitric oxide dependent manner. • Ecdysterone enhances nitric oxide production via activation of EGFR

  16. Characteristics and fate of natural organic matter during UV oxidation processes.

    Science.gov (United States)

    Ahn, Yongtae; Lee, Doorae; Kwon, Minhwan; Choi, Il-Hwan; Nam, Seong-Nam; Kang, Joon-Wun

    2017-10-01

    Advanced oxidation processes (AOPs) are widely used in water treatments. During oxidation processes, natural organic matter (NOM) is modified and broken down into smaller compounds that affect the characteristics of the oxidized NOM by AOPs. In this study, NOM was characterized and monitored in the UV/hydrogen peroxide (H 2 O 2 ) and UV/persulfate (PS) processes using a liquid chromatography-organic carbon detector (LC-OCD) technique, and a combination of excitation-emission matrices (EEM) and parallel factor analysis (PARAFAC). The percentages of mineralization of NOM in the UV/H 2 O 2 and UV/PS processes were 20.5 and 83.3%, respectively, with a 10 mM oxidant dose and a contact time of 174 s (UV dose: approximately 30,000 mJ). Low-pressure, Hg UV lamp (254 nm) was applied in this experiment. The steady-state concentration of SO 4 - was 38-fold higher than that of OH at an oxidant dose of 10 mM. With para-chlorobenzoic acid (pCBA) as a radical probe compound, we experimentally determined the rate constants of Suwannee River NOM (SRNOM) with OH (k OH/NOM  = 3.3 × 10 8  M -1 s -1 ) and SO 4 - (k SO4-/NOM  = 4.55 × 10 6  M -1 s -1 ). The hydroxyl radical and sulfate radical showed different mineralization pathways of NOM, which have been verified by the use of LC-OCD and EEM/PARAFAC. Consequently, higher steady-state concentrations of SO 4 - , and different reaction preferences of OH and SO 4 - with the NOM constituent had an effect on the mineralization efficiency. Copyright © 2017 Elsevier Ltd. All rights reserved.

  17. Nitric Oxide and ERK mediates regulation of cellular processes by Ecdysterone

    International Nuclear Information System (INIS)

    Omanakuttan, Athira; Bose, Chinchu; Pandurangan, Nanjan; Kumar, Geetha B.; Banerji, Asoke; Nair, Bipin G.

    2016-01-01

    The complex process of wound healing is a major problem associated with diabetes, venous or arterial disease, old age and infection. A wide range of pharmacological effects including anabolic, anti-diabetic and hepato-protective activities have been attributed to Ecdysterone. In earlier studies, Ecdysterone has been shown to modulate eNOS and iNOS expression in diabetic animals and activate osteogenic differentiation through the Extracellular-signal-Regulated Kinase (ERK) pathway in periodontal ligament stem cells. However, in the wound healing process, Ecdysterone has only been shown to enhance granulation tissue formation in rabbits. There have been no studies to date, which elucidate the molecular mechanism underlying the complex cellular process involved in wound healing. The present study, demonstrates a novel interaction between the phytosteroid Ecdysterone and Nitric Oxide Synthase (NOS), in an Epidermal Growth Factor Receptor (EGFR)-dependent manner, thereby promoting cell proliferation, cell spreading and cell migration. These observations were further supported by the 4-amino-5-methylamino- 2′ ,7′ -difluorofluorescein diacetate (DAF FM) fluorescence assay which indicated that Ecdysterone activates NOS resulting in increased Nitric Oxide (NO) production. Additionally, studies with inhibitors of both the EGFR and ERK, demonstrated that Ecdysterone activates NOS through modulation of EGFR and ERK. These results clearly demonstrate, for the first time, that Ecdysterone enhances Nitric Oxide production and modulates complex cellular processes by activating ERK1/2 through the EGF pathway. - Highlights: • Ecdysterone significantly enhances cell migration in a dose dependent manner. • Ecdysterone augments cell spreading during the initial phase of cell migration through actin cytoskeletal rearrangement. • Ecdysterone enhances cell proliferation in a nitric oxide dependent manner. • Ecdysterone enhances nitric oxide production via activation of EGFR

  18. Mathematical Modelling to Predict Oxidative Behaviour of Conjugated Linoleic Acid in the Food Processing Industry

    Directory of Open Access Journals (Sweden)

    Aitziber Ojanguren

    2013-06-01

    Full Text Available Industrial processes that apply high temperatures in the presence of oxygen may compromise the stability of conjugated linoleic acid (CLA bioactive isomers. Statistical techniques are used in this study to model and predict, on a laboratory scale, the oxidative behaviour of oil with high CLA content, controlling the limiting factors of food processing. This modelling aims to estimate the impact of an industrial frying process (140 °C, 7 L/h air on the oxidation of CLA oil for use as frying oil instead of sunflower oil. A factorial design was constructed within a temperature (80–200 °C and air flow (7–20 L/h range. Oil stability index (Rancimat method was used as a measure of oxidation. Three-level full factorial design was used to obtain a quadratic model for CLA oil, enabling the oxidative behaviour to be predicted under predetermined process conditions (temperature and air flow. It is deduced that temperatures applied in food processes affect the oxidation of CLA to a greater extent than air flow. As a result, it is estimated that the oxidative stability of CLA oil is less resistant to industrial frying than sunflower oil. In conclusion, thanks to the mathematical model, a good choice of the appropriate industrial food process can be selected to avoid the oxidation of the bioactive isomers of CLA, ensuring its functionality in novel applications.

  19. Process for recovery of plutonium from fabrication residues of mixed fuels consisting of uranium oxide and plutonium oxide

    International Nuclear Information System (INIS)

    Heremanns, R.H.; Vandersteene, J.J.

    1983-01-01

    The invention concerns a process for recovery of plutonium from fabrication residues of mixed fuels consisting of uranium oxide and plutonium oxide in the form of PuO 2 . Mixed fuels consisting of uranium oxide and plutonium oxide are being used more and more. The plants which prepare these mixed fuels have around 5% of the total mass of fuels as fabrication residue, either as waste or scrap. In view of the high cost of plutonium, it has been attempted to recover this plutonium from the fabrication residues by a process having a purchase price lower than the price of plutonium. The problem is essentially to separate the plutonium, the uranium and the impurities. The residues are fluorinated, the UF 6 and PuF 6 obtained are separated by selective absorption of the PuF 6 on NaF at a temperature of at least 400 0 C, the complex obtained by this absorption is dissolved in nitric acid solution, the plutonium is precipitated in the form of plutonium oxalate by adding oxalic acid, and the precipitated plutonium oxalate is calcined

  20. Effects of tunnel oxide process on SONOS flash memory characteristics

    International Nuclear Information System (INIS)

    Li, Dong Hua; Park, Il Han; Yun, Jang-Gn; Park, Byung-Gook

    2010-01-01

    In this paper, various process conditions of tunnel oxides are applied in SONOS flash memory to investigate their effects on charge transport during the program/erase operations. We focus the key point of analysis on Fermi-level (E F ) variation at the interface of silicon substrate and tunnel oxide. The Si-O chemical bonding information which describes the interface oxidation states at the Si/SiO 2 is obtained by the core-level X-ray photoelectron spectroscopy (XPS). Moreover, relative E F position is determined by measuring the Si 2p energy shift from XPS spectrums. Experimental results from memory characteristic measurement show that MTO tunnel oxide structure exhibits faster erase speed, and larger memory window during P/E cycle compared to FTO and RTO tunnel oxide structures. Finally, we examine long-term charge retention characteristic and find that the memory windows of all the capacitors remain wider than 2 V after 10 5 s.

  1. Microwave based oxidation process for recycling the off-specification (U,Pu)O{sub 2} fuel pellets

    Energy Technology Data Exchange (ETDEWEB)

    Singh, G., E-mail: gitendars@barctara.gov.in [Advanced Fuel Fabrication Facility (AFFF), Bhabha Atomic Research Centre, Tarapur, 401 502 (India); Khot, P.M. [Advanced Fuel Fabrication Facility (AFFF), Bhabha Atomic Research Centre, Tarapur, 401 502 (India); Kumar, Pradeep [Integrated Fuel Fabrication Facility (IFFF), Bhabha Atomic Research Centre, Mumbai, 400 085 (India); Bhatt, R.B.; Behere, P.G.; Afzal, Mohd [Advanced Fuel Fabrication Facility (AFFF), Bhabha Atomic Research Centre, Tarapur, 401 502 (India)

    2017-02-15

    This paper reports development of a process named MicroWave Direct Oxidation (MWDO) for recycling the off-specification (U,Pu)O{sub 2} mixed oxide (MOX) fuel pellets generated during fabrication of typical fast reactor fuels. MWDO is a two-stage, single-cycle process based on oxidative pulverisation of pellets using 2450 MHz microwave. The powder sinterability was evaluated by bulk density and BET specific surface area. The oxidised powders were analyzed for phases using XRD and stoichiometry by thermogravimetry. The sinterability was significantly enhanced by carrying out oxidation in higher oxygen partial pressure and by subjecting MOX to multiple micronisation-oxidation cycles. After three cycles, the recycled powder from (U,28%Pu)O{sub 2} resulted surface area >3 m{sup 2}/g and 100% re-used for MOX fabrication. The flow sheet was developed for maximum utilization of recycled powder describable by a parameter called Scrap Recycling Ratio (SRR). The process demonstrates smaller processing cycle, better powder properties and higher oxidative pulverisation over conventional method. - Highlights: • A process for recycling the off-specification (U,Pu)O{sub 2} sintered fuel pellets of fast reactors was demonstrated. • The method is a two-stage, single cycle process based on oxidative pulverization of MOX pellets using 2450 MHz microwave. • The process demonstrated utilization of recycled powder with SRR of 1.

  2. Low Temperature Processed Complementary Metal Oxide Semiconductor (CMOS) Device by Oxidation Effect from Capping Layer

    KAUST Repository

    Wang, Zhenwei; Al-Jawhari, Hala A.; Nayak, Pradipta K.; Caraveo-Frescas, J. A.; Wei, Nini; Hedhili, Mohamed N.; Alshareef, Husam N.

    2015-01-01

    , which is significantly lower than the temperature generally required to form tin dioxide. Based on this approach, CMOS inverters based entirely on tin oxide TFTs were fabricated. Our method provides a solution to lower the process temperature for tin

  3. Aerosol and Photo-Oxidant Processes in the Eastern Mediterranean

    Czech Academy of Sciences Publication Activity Database

    Lazaridis, M.; Spyridaki, A.; Solberg, S.; Smolík, Jiří; Ždímal, Vladimír; Eleftheriadis, K.; Aleksandropoulos, V.; Hov, O.; Georgopoulos, P. G.

    2004-01-01

    Roč. 4, - (2004), s. 5455-5514 ISSN 1680-7367 Grant - others:ENVK2(XE) 1999-00052 Institutional research plan: CEZ:AV0Z4072921 Keywords : aerosol * mesoscale modeling * photo-oxidant processes Subject RIV: CF - Physical ; Theoretical Chemistry

  4. Thermal imaging of solid oxide fuel cell anode processes

    Energy Technology Data Exchange (ETDEWEB)

    Pomfret, Michael B.; Kidwell, David A.; Owrutsky, Jeffrey C. [Chemistry Division, U.S. Naval Research Laboratory, Washington, DC 20375 (United States); Steinhurst, Daniel A. [Nova Research Inc., Alexandria, VA 22308 (United States)

    2010-01-01

    A Si-charge-coupled device (CCD), camera-based, near-infrared imaging system is demonstrated on Ni/yttria-stabilized zirconia (YSZ) fragments and the anodes of working solid oxide fuel cells (SOFCs). NiO reduction to Ni by H{sub 2} and carbon deposition lead to the fragment cooling by 5 {+-} 2 C and 16 {+-} 1 C, respectively. When air is flowed over the fragments, the temperature rises 24 {+-} 1 C as carbon and Ni are oxidized. In an operational SOFC, the decrease in temperature with carbon deposition is only 4.0 {+-} 0.1 C as the process is moderated by the presence of oxides and water. Electrochemical oxidation of carbon deposits results in a {delta}T of +2.2 {+-} 0.2 C, demonstrating that electrochemical oxidation is less vigorous than atmospheric oxidation. While the high temperatures of SOFCs are challenging in many respects, they facilitate thermal imaging because their emission overlaps the spectral response of inexpensive Si-CCD cameras. Using Si-CCD cameras has advantages in terms of cost, resolution, and convenience compared to mid-infrared thermal cameras. High spatial ({proportional_to}0.1 mm) and temperature ({proportional_to}0.1 C) resolutions are achieved in this system. This approach provides a convenient and effective analytical technique for investigating the effects of anode chemistry in operating SOFCs. (author)

  5. Thermal imaging of solid oxide fuel cell anode processes

    Science.gov (United States)

    Pomfret, Michael B.; Steinhurst, Daniel A.; Kidwell, David A.; Owrutsky, Jeffrey C.

    A Si-charge-coupled device (CCD), camera-based, near-infrared imaging system is demonstrated on Ni/yttria-stabilized zirconia (YSZ) fragments and the anodes of working solid oxide fuel cells (SOFCs). NiO reduction to Ni by H 2 and carbon deposition lead to the fragment cooling by 5 ± 2 °C and 16 ± 1 °C, respectively. When air is flowed over the fragments, the temperature rises 24 ± 1 °C as carbon and Ni are oxidized. In an operational SOFC, the decrease in temperature with carbon deposition is only 4.0 ± 0.1 °C as the process is moderated by the presence of oxides and water. Electrochemical oxidation of carbon deposits results in a Δ T of +2.2 ± 0.2 °C, demonstrating that electrochemical oxidation is less vigorous than atmospheric oxidation. While the high temperatures of SOFCs are challenging in many respects, they facilitate thermal imaging because their emission overlaps the spectral response of inexpensive Si-CCD cameras. Using Si-CCD cameras has advantages in terms of cost, resolution, and convenience compared to mid-infrared thermal cameras. High spatial (∼0.1 mm) and temperature (∼0.1 °C) resolutions are achieved in this system. This approach provides a convenient and effective analytical technique for investigating the effects of anode chemistry in operating SOFCs.

  6. Oxidation process of AlOx-based magnetic tunnel junctions studied by photoconductance

    NARCIS (Netherlands)

    Koller, P.H.P.; Vanhelmont, F.W.M.; Boeve, H.; Lumens, P.G.E.; Jonge, de W.J.M.

    2003-01-01

    The oxidation process of Co/AlOx/Co magnetic tunnel junctions has been investigated by photoconductance, in addition to traditional transport measurements. The shape of the photoconductance curves is explained within the framework of a simple qualitative model, assuming an oxidation time dependent

  7. Zinc-oxide-based sorbents and processes for preparing and using same

    Science.gov (United States)

    Gangwal, Santosh Kumar; Turk, Brian Scott; Gupta, Raghubir Prasael

    2010-03-23

    Zinc oxide-based sorbents, and processes for preparing and using them are provided. The sorbents are preferably used to remove one or more reduced sulfur species from gas streams. The sorbents comprise an active zinc component, optionally in combination with one or more promoter components and/or one or more substantially inert components. The active zinc component is a two phase material, consisting essentially of a zinc oxide (ZnO) phase and a zinc aluminate (ZnAl.sub.2O.sub.4) phase. Each of the two phases is characterized by a relatively small crystallite size of typically less than about 500 Angstroms. Preferably the sorbents are prepared by converting a precursor mixture, comprising a precipitated zinc oxide precursor and a precipitated aluminum oxide precursor, to the two-phase, active zinc oxide containing component.

  8. Development and Processing of p-type Oxide Thermoelectric Materials

    DEFF Research Database (Denmark)

    Wu, NingYu; Van Nong, Ngo

    The main aim of this research is to investigate and develop well-performing p-type thermoelectric oxide materials that are sufficiently stable at high temperatures for power generating applications involving industrial processes. Presently, the challenges facing the widespread implementation...

  9. Treatment of uranium turning with the controllable oxidizing process

    International Nuclear Information System (INIS)

    Shen Bingyi; Zhang Yonggang; Zhen Huikuan

    1989-02-01

    The concept, procedure and safety measures of the controllable oxidizing for uranium turning is described. The feasibility study on technological process has been made. The process provided several advantages such as: simplicity of operation, no pollution environment, safety, high efficiency and low energy consumption. The process can yield nuclear pure uranium dioxide under making no use of a great number of chemical reagent. It may supply raw material for fluoration and provide a simply method of treatment for safe store of uranium turning

  10. Investigation of solid organic waste processing by oxidative pyrolysis

    Science.gov (United States)

    Kolibaba, O. B.; Sokolsky, A. I.; Gabitov, R. N.

    2017-11-01

    A thermal analysis of a mixture of municipal solid waste (MSW) of the average morphological composition and its individual components was carried out in order to develop ways to improve the efficiency of its utilization for energy production in thermal reactors. Experimental studies were performed on a synchronous thermal analyzer NETZSCH STA 449 F3 Jupiter combined with a quadrupole mass spectrometer QMC 403. Based on the results of the experiments, the temperature ranges of the pyrolysis process were determined as well as the rate of decrease of the mass of the sample of solid waste during the drying and oxidative pyrolysis processes, the thermal effects accompanying these processes, as well as the composition and volumes of gases produced during oxidative pyrolysis of solid waste and its components in an atmosphere with oxygen content of 1%, 5%, and 10%. On the basis of experimental data the dependences of the yield of gas on the moisture content of MSW were obtained under different pyrolysis conditions under which a gas of various calorific values was produced.

  11. Oxidation of adsorbed ferrous iron: kinetics and influence of process conditions.

    Science.gov (United States)

    Buamah, R; Petrusevski, B; Schippers, J C

    2009-01-01

    For the removal of iron from groundwater, aeration followed with rapid (sand) filtration is frequently applied. Iron removal in this process is achieved through oxidation of Fe(2 + ) in aqueous solution followed by floc formation as well as adsorption of Fe(2 + ) onto the filter media. The rate of oxidation of the adsorbed Fe(2 + ) on the filter media plays an important role in this removal process. This study focuses on investigating the effect of pH on the rate of oxidation of adsorbed Fe(2 + ). Fe(2 + ) has been adsorbed, under anoxic conditions, on iron oxide coated sand (IOCS) in a short filter column and subsequently oxidized by feeding the column with aerated water. Ferrous ions adsorbed at pH 5, 6, 7 and 8 demonstrated consumption of oxygen, when aerated water was fed into the column. The oxygen uptake at pH 7 and 8 was faster than at pH 5 and 6. However the difference was less pronounced than expected. The difference is attributed to the pH buffering effect of the IOCS. At feedwater pH 5, 6 and 7 the pH in the effluent was higher than in the influent, while a pH drop should occur because of oxidation of adsorbed Fe(2 + ). At pH 8, the pH dropped. These phenomena are attributed to the presence of calcium and /or ferrous carbonate in IOCS.

  12. Effect of the method of processing on quality and oxidative stability ...

    African Journals Online (AJOL)

    In this study four samn samples prepared from cow milk using two processing methods (traditional T1, T2 and factory processed T3, T4) were investigated for their physico-chemical properties, fatty acids composition, oxidative stability and sensory properties. The traditionally processed samples showed a significance ...

  13. Treatment of oilfield wastewater by combined process of micro-electrolysis, Fenton oxidation and coagulation.

    Science.gov (United States)

    Zhang, Zhenchao

    2017-12-01

    In this study, a combined process was developed that included micro-electrolysis, Fenton oxidation and coagulation to treat oilfield fracturing wastewater. Micro-electrolysis and Fenton oxidation were applied to reduce chemical oxygen demand (COD) organic load and to enhance organic components gradability, respectively. Orthogonal experiment were employed to investigate the influence factors of micro-electrolysis and Fenton oxidation on COD removal efficiency. For micro-electrolysis, the optimum conditions were: pH, 3; iron-carbon dosage, 50 mg/L; mass ratio of iron-carbon, 2:3; reaction time, 60 min. For Fenton oxidation, a total reaction time of 90 min, a H 2 O 2 dosage of 12 mg/L, with a H 2 O 2 /Fe 2+ mole ratio of 30, pH of 3 were selected to achieve optimum oxidation. The optimum conditions in coagulation process: pH, cationic polyacrylamide dosage, mixing speed and time is 4.3, 2 mg/L, 150 rpm and 30 s, respectively. In the continuous treatment process under optimized conditions, the COD of oily wastewater fell 56.95%, 46.23%, 30.67%, respectively, from last stage and the total COD removal efficiency reached 83.94% (from 4,314 to 693 mg/L). In the overall treatment process under optimized conditions, the COD of oily wastewater was reduced from 4,314 to 637 mg/L, and the COD removal efficiency reached 85.23%. The contribution of each stage is 68.45% (micro-electrolysis), 24.07% (Fenton oxidation), 7.48% (coagulation), respectively. Micro-electrolysis is the uppermost influencing process on COD removal. Compared with the COD removal efficiency of three processes on raw wastewater under optimized conditions: the COD removal efficiency of single micro-electrolysis, single Fenton oxidation, single coagulation is 58.34%, 44.88% and 39.72%, respectively. Experiments proved the effect of combined process is marvelous and the overall water quality of the final effluent could meet the class III national wastewater discharge standard of petrochemical industry of China

  14. Process for removal of sulfur oxides from hot gases

    International Nuclear Information System (INIS)

    Bauerle, G. L.; Kohl, A. L.

    1984-01-01

    A process for the removal of sulfur oxides from two gas streams containing the same. One gas stream is introduced into a spray dryer zone and contacted with a finely dispersed spray of an aqueous medium containing an absorbent for sulfur oxides. The aqueous medium is introduced at a controlled rate so as to provide water to the gas in an amount to produce a cooled product gas having a temperature at least 7 0 C. above its adiabatic saturation temperature and from about 125-300% of the stoichiometric amount of absorbent required to react with the sulfur oxides to be removed from the gas stream. The effluent from the spray dryer zone comprises a gas stream of reduced sulfur oxide content and contains entrained dry particulate reaction products including unreacted absorbent. This gas stream is then introduced into a particulate removal zone from which is withdrawn a gas stream substantially free of particles and having a reduced sulfur oxide content. the dry particulate reaction products are collected and utilized as a source of absorbent for a second aqueous scrubbing medium containing unreacted absorbent for the sulfur oxides. An effluent gas stream is withdrawn from the aqueous scrubbing zone and comprises a water-saturated gas stream of reduced sulfur oxide content and substantially free of particles. The effluent gas streams from the particulate removal zone and the aqueous scrubbing zone are combined in such proportions that the combined gas stream has a temperature above its adiabatic saturation temperature

  15. Process for growing a film epitaxially upon an oxide surface and structures formed with the process

    Science.gov (United States)

    McKee, Rodney A.; Walker, Frederick J.

    1995-01-01

    A process and structure wherein a film comprised of a perovskite or a spinel is built epitaxially upon a surface, such as an alkaline earth oxide surface, involves the epitaxial build up of alternating constituent metal oxide planes of the perovskite or spinel. The first layer of metal oxide built upon the surface includes a metal element which provides a small cation in the crystalline structure of the perovskite or spinel, and the second layer of metal oxide built upon the surface includes a metal element which provides a large cation in the crystalline structure of the perovskite or spinel. The layering sequence involved in the film build up reduces problems which would otherwise result from the interfacial electrostatics at the first atomic layers, and these oxides can be stabilized as commensurate thin films at a unit cell thickness or grown with high crystal quality to thicknesses of 0.5-0.7 .mu.m for optical device applications.

  16. COMPARISON OF DIFFERENT ADVANCED OXIDATION PROCESSES DEGRADING P-CHLOROPHENOL IN AQUEOUS SOLUTION

    Directory of Open Access Journals (Sweden)

    H. Movahedyan ، A. M. Seid Mohammadi ، A. Assadi

    2009-07-01

    Full Text Available In present study, degradation of p-chlorophenol using several oxidation systems involving advanced oxidation processes such as ultraviolet/H2O2, microwave/H2O2 and both in the absence of hydrogen peroxide in batch mode by photolytic pilot plant and modified domestic microwave oven was evaluated. The oxidation rate was influenced by many factors, such as the pH value, the amount of hydrogen peroxide, irradiation time and microwave power. The optimum conditions obtained for the best degradation rate were pH=7 and H2O2 concentration of 0.05 mol/L for ultraviolet/H2O2 system and pH=10.5, H2O2 concentration of about 0.1 mol/L and microwave irradiation power of about 600W for microwave/H2O2 system at constant p-chlorophenol concentration. The degradation of p-chlorophenol by different types of oxidation processes followed first order rate decay kinetics. The rate constants were 0.137, 0.012, 0.02 and 0.004/min1 for ultraviolet/H2O2, microwave/H2O2, ultraviolet and microwave irradiation alone. Finally a comparison of the specific energy consumption showed that ultraviolet/H2O2 process reduced the energy consumption by at least 67% compared with the microwave/H2O2 process.

  17. High performance printed oxide field-effect transistors processed using photonic curing

    Science.gov (United States)

    Garlapati, Suresh Kumar; Cadilha Marques, Gabriel; Gebauer, Julia Susanne; Dehm, Simone; Bruns, Michael; Winterer, Markus; Baradaran Tahoori, Mehdi; Aghassi-Hagmann, Jasmin; Hahn, Horst; Dasgupta, Subho

    2018-06-01

    Oxide semiconductors are highly promising candidates for the most awaited, next-generation electronics, namely, printed electronics. As a fabrication route for the solution-processed/printed oxide semiconductors, photonic curing is becoming increasingly popular, as compared to the conventional thermal curing method; the former offers numerous advantages over the latter, such as low process temperatures and short exposure time and thereby, high throughput compatibility. Here, using dissimilar photonic curing concepts (UV–visible light and UV-laser), we demonstrate facile fabrication of high performance In2O3 field-effect transistors (FETs). Beside the processing related issues (temperature, time etc.), the other known limitation of oxide electronics is the lack of high performance p-type semiconductors, which can be bypassed using unipolar logics from high mobility n-type semiconductors alone. Interestingly, here we have found that our chosen distinct photonic curing methods can offer a large variation in threshold voltage, when they are fabricated from the same precursor ink. Consequently, both depletion and enhancement-mode devices have been achieved which can be used as the pull-up and pull-down transistors in unipolar inverters. The present device fabrication recipe demonstrates fast processing of low operation voltage, high performance FETs with large threshold voltage tunability.

  18. Second-Order Biomimicry: In Situ Oxidative Self-Processing Converts Copper(I)/Diamine Precursor into a Highly Active Aerobic Oxidation Catalyst.

    Science.gov (United States)

    McCann, Scott D; Lumb, Jean-Philip; Arndtsen, Bruce A; Stahl, Shannon S

    2017-04-26

    A homogeneous Cu-based catalyst system consisting of [Cu(MeCN) 4 ]PF 6 , N , N '-di- tert -butylethylenediamine (DBED), and p -( N , N -dimethylamino)pyridine (DMAP) mediates efficient aerobic oxidation of alcohols. Mechanistic study of this reaction shows that the catalyst undergoes an in situ oxidative self-processing step, resulting in conversion of DBED into a nitroxyl that serves as an efficient cocatalyst for aerobic alcohol oxidation. Insights into this behavior are gained from kinetic studies, which reveal an induction period at the beginning of the reaction that correlates with the oxidative self-processing step, EPR spectroscopic analysis of the catalytic reaction mixture, which shows the buildup of the organic nitroxyl species during steady state turnover, and independent synthesis of oxygenated DBED derivatives, which are shown to serve as effective cocatalysts and eliminate the induction period in the reaction. The overall mechanism bears considerable resemblance to enzymatic reactivity. Most notable is the "oxygenase"-type self-processing step that mirrors generation of catalytic cofactors in enzymes via post-translational modification of amino acid side chains. This higher-order function within a synthetic catalyst system presents new opportunities for the discovery and development of biomimetic catalysts.

  19. Atlas of Atomic Spectral Lines of Neptunium Emitted by an Inductively Coupled Plasma

    International Nuclear Information System (INIS)

    DeKalb, E.L.; Edelson, M.C.

    1987-01-01

    Optical emission spectra from high-purity Np-237 were generated with a glovebox-enclosed inductively coupled plasma (ICP) source. Spectra covering the 230-700 nm wavelength range are presented along with general commentary on the methodology used in collecting the data. The Ames Laboratory Nuclear Safeguards and Security Program has been charged with the task of developing optical spectroscopic methods to analyze the composition of spent nuclear fuels. Such materials are highly radioactive even after prolonged 'cooling' and are chemically complex. Neptunium (Np) is a highly toxic by-product of nuclear power generation and is found, in low abundance, in spent nuclear fuels. This atlas of the optical emission spectrum of Np, as produced by an inductively coupled plasma (ICP) spectroscopic source, is part of a general survey of the ICP emission spectra of the actinide elements. The ICP emission spectrum of the actinides originates almost exclusively from the electronic relaxation of excited, singly ionized species. Spectral data on the Np ion emission spectrum (i.e., the Np II spectrum) have been reported by Tomkins and Fred (1) and Haaland (2). Tomkins and Fred excited the Np II spectrum with a Cu spark discharge and identified 114 Np lines in the 265.5 - 436.3 nm spectral range. Haaland, who corrected some spectral line misidentifications in the work of Tomkins and Fred, utilized an enclosed Au spark discharge to excite the Np II spectrum and reported 203 Np lines within the 265.4 - 461.0 nm wavelength range.

  20. Processing and Characterization of Sol-Gel Cerium Oxide Microspheres

    Energy Technology Data Exchange (ETDEWEB)

    McClure, Zachary D. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Padilla Cintron, Cristina [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2016-09-27

    Of interest to space exploration and power generation, Radioisotope Thermoelectric Generators (RTGs) can provide long-term power to remote electronic systems without the need for refueling or replacement. Plutonium-238 (Pu-238) remains one of the more promising materials for thermoelectric power generation due to its high power density, long half-life, and low gamma emissions. Traditional methods for processing Pu-238 include ball milling irregular precipitated powders before pressing and sintering into a dense pellet. The resulting submicron particulates of Pu-238 quickly accumulate and contaminate glove boxes. An alternative and dust-free method for Pu-238 processing is internal gelation via sol-gel techniques. Sol-gel methodology creates monodisperse and uniform microspheres that can be packed and pressed into a pellet. For this study cerium oxide microspheres were produced as a surrogate to Pu-238. The similar electronic orbitals between cerium and plutonium make cerium an ideal choice for non-radioactive work. Before the microspheres can be sintered and pressed they must be washed to remove the processing oil and any unreacted substituents. An investigation was performed on the washing step to find an appropriate wash solution that reduced waste and flammable risk. Cerium oxide microspheres were processed, washed, and characterized to determine the effectiveness of the new wash solution.

  1. Improving technology and setting-up a production line for high quality zinc oxide (99.5%) with a capacity of 150 ton/year by evaporation-oxidation process

    International Nuclear Information System (INIS)

    Phan Dinh Thinh; Pham Minh Tuan; Luong Manh Hung; Tran Ngoc Vuong

    2015-01-01

    This report presents the technology improvement and a production line to produce high quality zinc oxide of purity upper than 99.5% ZnO by evaporation-oxidation method. Secondary zinc metal recovered from galvanizing industrial will undergo a pre-treatment to meet all requirements of standardized feed material for evaporation-oxidation process. Zinc metal is melted at a temperature of about 650"oC, some impurities and metallic oxides are separated preliminary, then zinc metal is converted into liquid in evaporation pot. Here the temperature is maintained around 1050"oC, zinc liquid is evaporated, zinc vapor is oxidized by air in the oxidation chamber naturally by oxygen in the air and then zinc vapor is converted to zinc oxide. Zinc oxide is passed through a product classification systems and then go to a product collection of filtering bag design. The whole process of melting, evaporation, oxidation, particles classification and product collection is a continuous process. The efficiency of the transformation of zinc metal into zinc oxide can reach the value of 1.1 to 1.2. ZnO product quality is higher than 99.5%. (author)

  2. Effect of process parameters on surface oxides on chromium-alloyed steel powder during sintering

    International Nuclear Information System (INIS)

    Chasoglou, D.; Hryha, E.; Nyborg, L.

    2013-01-01

    The use of chromium in the PM steel industry today puts high demands on the choice and control of the atmosphere during the sintering process due to its high affinity to oxygen. Particular attention is required in order to control the surface chemistry of the powder which in turn is the key factor for the successful sintering and production of PM parts. Different atmosphere compositions, heating rates and green densities were employed while performing sintering trials on water atomized steel powder pre-alloyed with 3 wt.% Cr in order to evaluate the effect on surface chemical reactions. Fracture surfaces of sintered samples were examined using high resolution scanning electron microscopy combined with X-ray microanalysis. The investigation was complemented with thermogravimetric (TG) studies. Reaction products in particulate form containing strong-oxide forming elements such as Cr, Si and Mn were formed during sintering for all conditions. Processing in vacuum results in intensive inter-particle neck development during the heating stage and consequently in the excessive enclosure of surface oxide which is reflected in less good final mechanical properties. Enhanced oxide reduction was observed in samples processed in hydrogen-containing atmospheres independent of the actual content in the range of 3–10 vol.%. An optimum heating rate was required for balancing reduction/oxidation processes. A simple model for the enclosure and growth of oxide inclusions during the sinter-neck development is proposed. The obtained results show that significant reduction of the oxygen content can be achieved by adjusting the atmosphere purity/composition. - Highlights: ► A local atmosphere microclimate is very important for sintering of PM steels. ► High risk of surface oxide enclosure between 800 and 1000 °C. ► Coalescence and agglomeration of enclosed oxides take place during sintering. ► The effect of different process parameters on the oxide reduction is examined. ► A

  3. Formation of Poultry Meat Flavor by Heating Process and Lipid Oxidation

    Directory of Open Access Journals (Sweden)

    Maijon Purba

    2014-09-01

    Full Text Available Flavor is an important factor in the acceptance of food. Flavor of poultry meat is naturally formed through a specific process of heating, where various chemical reactions complex occurred among nonvolatile precursors in fatty tissue or in lean tissue. The main flavor in the form of volatile and nonvolatile components play a major influence on the acceptance of various processed meat, especially the taste. Removal of sulfur components decreases meat flavor (meaty, while removal of carbonyl compounds decrease the specific flavor and increases common flavor of the meat. Poultry meat has a fairly high fat content that easily generates lipid oxidation. Lipid oxidation in poultry meat is a sign that the meat was damaged and caused off odor. Addition of antioxidants in the diet can inhibit lipid oxidation in the meat. Lipids interaction with proteins and carbohydrates is unavoidable during the thermal processing of food, causing the appearance of volatile components. The main reaction in meat flavor formation mechanism is Maillard reaction followed by Stecker reaction and degradation of lipids and thiamine. They involve in the reaction between carbonyl and amine components to form flavor compounds, which enhance the flavor of poultry meat.

  4. Study of the Radical Chain Mechanism of Hydrocarbon Oxidation for In Situ Combustion Process

    Directory of Open Access Journals (Sweden)

    Alexandra Ushakova

    2017-01-01

    Full Text Available Despite the abundance of in situ combustion models of oil oxidation, many of the effects are still beyond consideration. For example, until now, initial stages of oxidation were not considered from a position of radical chain process. This is a serious difficulty for the simulation of oil recovery process that involves air injection. To investigate the initial stages of oxidation, the paper considers the sequence of chemical reactions, including intermediate short-living compounds and radicals. We have attempted to correlate the main stages of the reaction with areas of heat release observed in the experiments. The system of differential equations based on the equations of oxidation reactions was solved. Time dependence of peroxides formation and start of heat release is analytically derived for the initial stages. We have considered the inhibition of initial oxidation stages by aromatic oil compounds and have studied the induction time in dependence on temperature. Chain ignition criteria for paraffins and crude oil in presence of core samples were obtained. The calculation results are compared with the stages of oxidation that arise by high-pressure differential scanning calorimetry. According to experimental observations we have determined which reactions are important for the process and which can be omitted or combined into one as insignificant.

  5. REMOVAL OF REMAZOL ROSSO RB DYE FROM AQUEOUS EFFLUENTS BY HOMOGENOUS FENTON OXIDATION PROCESSES

    Directory of Open Access Journals (Sweden)

    Carmen Zaharia

    2014-06-01

    Full Text Available The paper presents some data from our laboratory-setup experiments of homogenous oxidative processes with hydrogen peroxide (i.e. advanced Fenton oxidation processes applied for Remazol Rosso RB dye-containing aqueous systems, especially textile effluents. Therefore, some different operating parameters (including pH, concentration of dye, H2O2 and ferrous ions, oxidation time, temperature, stirring regime, among its were tested for determination of the best performance in effluent decoloration and dye removal, meaning the optimal values of each studied parameters for highest decoloration or dye removal.

  6. Characterization of 10 μm thick porous silicon dioxide obtained by complex oxidation process for RF application

    International Nuclear Information System (INIS)

    Park, Jeong-Yong; Lee, Jong-Hyun

    2003-01-01

    This paper proposes a 10 μm thick oxide layer structure, which can be used as a substrate for RF circuits. The structure has been fabricated by anodic reaction and complex oxidation, which is a combined process of low temperature thermal oxidation (500 deg. C, for 1 h at H 2 O/O 2 ) and a rapid thermal oxidation (RTO) process (1050 deg. C, for 1 min). The electrical characteristics of oxidized porous silicon layer (OPSL) were almost the same as those of standard thermal silicon dioxide. The leakage current through the OPSL of 10 μm was about 100-500 pA in the range of 0-50 V. The average value of breakdown field was about 3.9 MV cm -1 . From the X-ray photo-electron spectroscopy (XPS) analysis, surface and internal oxide films of OPSL, prepared by complex process were confirmed to be completely oxidized and also the role of RTO process was important for the densification of porous silicon layer (PSL) oxidized at a lower temperature. For the RF-test of Si substrate with thick silicon dioxide layer, we have fabricated high performance passive devices such as coplanar waveguide (CPW) on OPSL substrate. The insertion loss of CPW on OPSL prepared by complex oxidation process was -0.39 dB at 4 GHz and similar to that of CPW on OPSL prepared by a temperature of 1050 deg. C (1 h at H 2 O/O 2 ). Also the return loss of CPW on OPSL prepared by complex oxidation process was -23 dB at 10 GHz, which is similar to that of CPW on OPSL prepared by high temperature

  7. Heterocatalytic Fenton oxidation process for the treatment of tannery effluent: kinetic and thermodynamic studies.

    Science.gov (United States)

    Karthikeyan, S; Ezhil Priya, M; Boopathy, R; Velan, M; Mandal, A B; Sekaran, G

    2012-06-01

    BACKGROUND, AIM, SCOPE: Treatment of wastewater has become significant with the declining water resources. The presence of recalcitrant organics is the major issue in meeting the pollution control board norms in India. The theme of the present investigation was on partial or complete removal of pollutants or their transformation into less toxic and more biodegradable products by heterogeneous Fenton oxidation process using mesoporous activated carbon (MAC) as the catalyst. Ferrous sulfate (FeSO(4)·7H(2)O), sulfuric acid (36 N, specific gravity 1.81, 98% purity), hydrogen peroxide (50% v/v) and all other chemicals used in this study were of analytical grade (Merck). Two reactors, each of height 50 cm and diameter 6 cm, were fabricated with PVC while one reactor was packed with MAC of mass 150 g and other without MAC served as control. The oxidation process was presented with kinetic and thermodynamic constants for the removal of COD, BOD, and TOC from the wastewater. The activation energy (Ea) for homogeneous and heterogeneous Fenton oxidation processes were 44.79 and 25.89 kJ/mol, respectively. The thermodynamic parameters ΔG, ΔH, and ΔS were calculated for the oxidation processes using Van't Hoff equation. Furthermore, the degradation of organics was confirmed through FTIR and UV-visible spectroscopy, and cyclic voltammetry. The heterocatalytic Fenton oxidation process efficiently increased the biodegradability index (BOD/COD) of the tannery effluent. The optimized conditions for the heterocatalytic Fenton oxidation of organics in tannery effluent were pH 3.5, reaction time-4 h, and H(2)O(2)/FeSO(4)·7H(2)O in the molar ratio of 2:1.

  8. Advanced oxidation processes of decomposing dichloroacetic acid and trichloroacetic acid in water

    Institute of Scientific and Technical Information of China (English)

    WANG Kun-ping; GUO Jin-song; YANG Min; JUNJI Hirotsuji; DENG Rong-sen; LIU Wei

    2008-01-01

    We studied the decomposition of two haloacetic acids (HAAs), dichloroacetic acid (DCAA) and trichloroacetic acid (TCAA), in water by single oxidants ozone (O3) and ultraviolet radiation (UV) and the advanced oxidation processes (AOPs) constituted by the combinations of O3/UV, H2O2/UV, O3 /H2O2, and O3/H2O2/UV. The concentrations of HAAs were analyzed at specified time intervals to track their decomposition. Except for O3 and UV, the four combined oxidation processes remarkably enhance the decomposition of DCAA and TCAA owing to the generated very reactive hydroxyl radicals. The fastest decomposition process is O3/H2O2/UV, closely followed by O3/UV. DCAA is much easier to decompose than TCAA. The kinetics of HAA decomposition by O3/UV can be described well by a pseudo first-order reaction model under a constant initial dissolved O3 concentration and fixed UV radiation. Humic acids and HCO3- in the reaction system both decrease the decomposition rate constants for DCAA and TCAA. The amount of H2O2 accumulates in the presence of humic acids in the O3/UV process.

  9. Oxidation of organic compounds in wastewater from the humid processing of coffee berries

    International Nuclear Information System (INIS)

    Goncalves, Maraisa; Guerreiro, Mario Cesar; Oliveira, Luiz Carlos Alves; Rocha, Cristian Luciana da

    2008-01-01

    Materials based on pure iron oxide and impregnated with niobia (Nb 2 O 5 ) were prepared. Their catalytic activities were tested on the oxidation of compounds present in the wastewater from the processing of coffee berries. Particularly caffeine and catechol were tested. The oxidation reactions were carried out with the following systems: UV/H 2 O 2 ; photo-Fenton and heterogeneous Fenton. All materials were characterized with X-ray diffraction, Moessbauer and infrared spectroscopy. Iron was mainly in the forms of goethite and maghemite. The oxidation kinetics were monitored by UV-vis and the oxidation products were monitored by mass spectrometry. The photo-Fenton reaction presented highest oxidation efficiency, removing 98% of all caffeine and catechol contents. (author)

  10. Electrochemical activity of heavy metal oxides in the process of ...

    Indian Academy of Sciences (India)

    Unknown

    2002-02-02

    Feb 2, 2002 ... Electrochemical activity of heavy metal oxides in the process of chloride induced .... represents the protective barrier moderating the chloride attack which ... inhibitors and their influence on the physical properties of. Portland ...

  11. Optimization of process and solution parameters in electrospinning polyethylene oxide

    CSIR Research Space (South Africa)

    Jacobs, V

    2011-11-01

    Full Text Available This paper reports the optimization of electrospinning process and solution parameters using factorial design approach to obtain uniform polyethylene oxide (PEO) nanofibers. The parameters studied were distance between nozzle and collector screen...

  12. The flashcal process for the fabrication of fuel-metal oxides using the whiteshell roto-spray calciner

    International Nuclear Information System (INIS)

    Sridhar, T.S.

    1988-01-01

    A one-step, continuous, thermochemical calcination process, called the FLASHCAL (Flash Calcination) process has been developed for the production of single- and mixed-oxide powders of fuel metals (uranium, thorium and plutonium) from the respective nitrate solutions using the Whiteshell Roto-Spray Calciner (RSC). The metal-nitrate feed solution, either by itself or mixed with a suitable chemical reactant or additive, is converted to its oxide powder in the RSC at temperatures between 300 and 600 0 C. Rapid denitration takes place in the calciner, yielding the metal-oxide powders while simultaneously destroying any excess chemical additive and reaction by-products. In the production of precursor oxide powders suitable for fuel fabrication, the FLASHCAL process has advantages over batch calcination and other processes that involve precipitation and filtration steps because fewer processing and handling operations are needed. Results obtained with thorium nitrate and uranium nitrate-thorium nitrate mixtures indicate that some measure of control over the size distribution and morphology of the oxide product powders is possible in this process with the proper selection of chemical additive, as well as the operating parameters of the calciner

  13. Study of cryoprotectors effect on oxidation processes at storage of frozen halffinished products

    Directory of Open Access Journals (Sweden)

    O. Glushkov

    2016-12-01

    Full Text Available The publication presents data on the effect of polysaccharides as cryoprotectants on changes of the lipid fraction of quick-frozen semi-finished products during storage. Since the structure of minced systems is formed as a result of the destruction of the native structure of the meat and the formation of a new secondary structure, it is important to establish the effect of cryoprotectants on the key functional and technological properties of meat systems after freezing, and in the process of storage. Based on studies of the kinetics of the oxidation of fat and accumulation data on the accumulation of the primary and secondary products of oxidation inhibition of oxidative processes has been found.

  14. Electrochemical processing of spent nuclear fuels: An overview of oxide reduction in pyroprocessing technology

    Directory of Open Access Journals (Sweden)

    Eun-Young Choi

    2015-12-01

    Full Text Available The electrochemical reduction process has been used to reduce spent oxide fuel to a metallic form using pyroprocessing technology for a closed fuel cycle in combination with a metal-fuel fast reactor. In the electrochemical reduction process, oxides fuels are loaded at the cathode basket in molten Li2O–LiCl salt and electrochemically reduced to the metal form. Various approaches based on thermodynamic calculations and experimental studies have been used to understand the electrode reaction and efficiently treat spent fuels. The factors that affect the speed of the electrochemical reduction have been determined to optimize the process and scale-up the electrolysis cell. In addition, demonstrations of the integrated series of processes (electrorefining and salt distillation with the electrochemical reduction have been conducted to realize the oxide fuel cycle. This overview provides insight into the current status of and issues related to the electrochemical processing of spent nuclear fuels.

  15. Literature review on the properties of cuprous oxide Cu2O and the process of copper oxidation

    International Nuclear Information System (INIS)

    Korzhavyi, P. A.; Johansson, B.

    2011-10-01

    The purpose of the present review is to provide a reference guide to the most recent data on the properties of copper(I) oxide as well as on the atomic processes involved in the initial stages of oxidation of copper. The data on the structure of surfaces, as obtained from atomic-resolution microscopy studies (for example, STM) or from first-principles calculations, are reviewed. Information of this kind may be useful for understanding the atomic mechanisms of corrosion and stress-corrosion cracking of copper

  16. Process for the preparation of uranium dioxide

    International Nuclear Information System (INIS)

    Watt, G.W.; Baugh, D.W. Jr.

    1981-01-01

    A method for the preparation of actinide dioxides using actinide nitrate hexahydrates as starting materials is described. The actinide nitrate hexahydrate is reacted with sodium dithionite, and the product is heated in the absence of oxygen to obtain the dioxide. Preferably, the actinide is uranium, plutonium or neptunium. (LL)

  17. Reactive nanophase oxide additions to melt-processed high-{Tc} superconductors

    Energy Technology Data Exchange (ETDEWEB)

    Goretta, K.C.; Brandel, B.P.; Lanagan, M.T.; Hu, J.; Miller, D.J.; Sengupta, S. [Argonne National Lab., IL (United States); Parker, J.C.; Ali, M.N. [Nanophase Technologies Corp., Darien, IL (United States); Chen, Nan [Illinois Superconductor Corp., Evanston, IL (United States)

    1994-10-01

    Nanophase TiO{sub 2} and Al{sub 2}O{sub 3} powders were synthesized by a vapor-phase process and mechanically mixed with stoichiometric YBa{sub 2}Cu{sub 3}O{sub x} and TlBa{sub 2}Ca{sub 2}Cu{sub 3}O{sub x} powders in 20 mole % concentrations. Pellets produced from powders with and without nanophase oxides were heated in air or O{sub 2} above the peritectic melt temperature and slow-cooled. At 4.2 K, the intragranular critical current density (J{sub c}) increased dramatically with the oxide additions. At 35--50 K, effects of the oxide additions were positive, but less pronounced. At 77 K, the additions decreased J{sub c}, probably because of inducing a depresion of the transition temperature.

  18. Laser microstructuring and annealing processes for lithium manganese oxide cathodes

    International Nuclear Information System (INIS)

    Proell, J.; Kohler, R.; Torge, M.; Ulrich, S.; Ziebert, C.; Bruns, M.; Seifert, H.J.; Pfleging, W.

    2011-01-01

    It is expected that cathodes for lithium-ion batteries (LIB) composed out of nano-composite materials lead to an increase in power density of the LIB due to large electrochemically active surface areas but cathodes made of lithium manganese oxides (Li-Mn-O) suffer from structural instabilities due to their sensitivity to the average manganese oxidation state. Therefore, thin films in the Li-Mn-O system were synthesized by non-reactive radiofrequency magnetron sputtering of a spinel lithium manganese oxide target. For the enhancement of the power density and cycle stability, large area direct laser patterning using UV-laser radiation with a wavelength of 248 nm was performed. Subsequent laser annealing processes were investigated in a second step in order to set up a spinel-like phase using 940 nm laser radiation at a temperature of 680 deg. C. The interaction processes between UV-laser radiation and the material was investigated using laser ablation inductively coupled plasma mass spectroscopy. The changes in phase, structure and grain shape of the thin films due to the annealing process were recorded using Raman spectroscopy, X-ray diffraction and scanning electron microscopy. The structured cathodes were cycled using standard electrolyte and a metallic lithium anode. Different surface structures were investigated and a significant increase in cycling stability was found. Surface chemistry of an as-deposited as well as an electrochemically cycled thin film was investigated via X-ray photoelectron spectroscopy.

  19. Oxidation processes on conducting carbon additives for lithium-ion batteries

    KAUST Repository

    La Mantia, Fabio; Huggins, Robert A.; Cui, Yi

    2012-01-01

    The oxidation processes at the interface between different types of typical carbon additives for lithium-ion batteries and carbonates electrolyte above 5 V versus Li/Li+ were investigated. Depending on the nature and surface area of the carbon

  20. Plasma Spray and Pack Cementation Process Optimization and Oxidation Behaviour of Novel Multilayered Coatings

    Science.gov (United States)

    Gao, Feng

    The hot section components in gas turbines are subjected to a harsh environment with the temperature being increased continuously. The higher temperature has directly resulted in severe oxidation of these components. Monolithic coatings such as MCrAIY and aluminide have been traditionally used to protect the components from oxidation; however, increased operating temperature quickly deteriorates the coatings due to accelerated diffusion of aluminum in the coatings. To improve the oxidation resistance a group of multilayered coatings are developed in this study. The multilayered coatings consist of a Cr-Si co-deposited layer as the diffusion barrier, a plasma sprayed NiCrA1Y coating as the middle layer and an aluminized top layer. The Cr-Si and aluminized layers are fabricated using pack cementation processes and the NiCrA1Y coatings are produced using the Mettech Axial III(TM) System. All of the coating processes are optimized using the methodology of Design of Experiments (DOE) and the results are analyzed using statistical method. The optimal processes are adopted to fabricate the multilayered coatings for oxidation tests. The coatings are exposed in air at 1050°C and 1150°C for 1000 hr. The results indicate that a Cr layer and a silicon-rich barrier layer have formed on the interface between the Cr-Si coating and the NiCrA1Y coating. This barrier layer not only prevents aluminum and chromium from diffusing into the substrate, but also impedes the diffusion of other elements from the substrate into the coating. The results also reveal that, for optimal oxidation resistance at 1050°C, the top layer in a multilayered coating should have at least Al/Ni ratio of one; whereas the multilayered coating with the All Ni ratio of two in the top layer exhibits the best oxidation resistance at 1150°C. The DOE methodology provides an excellent means for process optimization and the selection of oxidation test matrix, and also offers a more thorough understanding of the

  1. Study of the chemical interactions of actinide cations in solution at macroscopic concentrations

    International Nuclear Information System (INIS)

    Maurice, C.

    1983-01-01

    The aim of this work was to study the interactions of pentavalent neptunium in dodecane-diluted tributyl phosphate with other metallic cations, especially uranium VI and ruthenium present in reprocessing solutions. Pentavalent neptunium on its own was shown to exist in several forms complexed by water and TBP and also to dimerise. In the complex it forms with uranium VI the interaction via the neptunyl oxygen is considerably enhanced in organic solution. Dibutyl phosphoric acid strengthens the interaction between neptunium and uranium. The Np V-ruthenium interaction reveals the existence of a new cation-cation complex; the process takes place in two successive stage and leads to the formation, reinforced and accelerated by HDBP, of a highly to the formation, reinforced and accelerated by HDBP, of a highly stable complex. These results contribute towards a better knowledge of the behaviour of neptunium in the reprocessing operation [fr

  2. Effect of re-oxidation annealing process on the SiO2/SiC interface characteristics

    International Nuclear Information System (INIS)

    Yan Hongli; Jia Renxu; Tang Xiaoyan; Song Qingwen; Zhang Yuming

    2014-01-01

    The effect of the different re-oxidation annealing (ROA) processes on the SiO 2 /SiC interface characteristics has been investigated. With different annealing processes, the flat band voltage, effective dielectric charge density and interface trap density are obtained from the capacitance—voltage curves. It is found that the lowest interface trap density is obtained by the wet-oxidation annealing process at 1050 °C for 30 min, while a large number of effective dielectric charges are generated. The components at the SiO 2 /SiC interface are analyzed by X-ray photoelectron spectroscopy (XPS) testing. It is found that the effective dielectric charges are generated due to the existence of the C and H atoms in the wet-oxidation annealing process. (semiconductor technology)

  3. Rapid thermal processing of nano-crystalline indium tin oxide transparent conductive oxide coatings on glass by flame impingement technology

    International Nuclear Information System (INIS)

    Schoemaker, S.; Willert-Porada, M.

    2009-01-01

    Indium tin oxide (ITO) is still the best suited material for transparent conductive oxides, when high transmission in the visible range, high infrared reflection or high electrical conductivity is needed. Current approaches on powder-based printable ITO coatings aim at minimum consumption of active coating and low processing costs. The paper describes how fast firing by flame impingement is used for effective sintering of ITO-coatings applied on glass. The present study correlates process parameters of fast firing by flame impingement with optoelectronic properties and changes in the microstructure of suspension derived nano-particulate films. With optimum process parameters the heat treated coatings had a sheet resistance below 0.5 kΩ/ □ combined with a transparency higher than 80%. To characterize the influence of the burner type on the process parameters and the coating functionality, two types of methane/oxygen burner were compared: a diffusion burner and a premixed burner

  4. Purex process operation and performance: 1970 thoria campaign

    International Nuclear Information System (INIS)

    Walser, R.L.

    1978-02-01

    The Hanford Purex Plant has demonstrated suitability for reprocessing irradiated thoria (ThO 2 ) target elements on a campaign basis. A 1965 process test and major production campaigns conducted in 1966 and 1970 recovered nitrate solution form products totaling approximately 565 tons of thorium and 820 kilograms of 233 U. The overall recoveries for the 1970 campaign based on reactor input data were 94.9 percent for thorium and 95.2 percent for uranium. The primary function of the Hanford Purex Plant is reprocessing of irradiated uranium fuel elements to separate and purify uranium, plutonium and neptunium. Converting the plant to thoria reprocessing required major process development work and equipment modifications. The operation and performance of the Plant during the 1970 thoria reprocessing campaign is discussed in this report. The discussion includes background information on the process and equipment, problems encountered, and changes recommended for future campaigns

  5. Friction stir processed Al - Metal oxide surface composites: Anodization and optical appearance

    DEFF Research Database (Denmark)

    Gudla, Visweswara Chakravarthy; Jensen, Flemming; Canulescu, Stela

    2014-01-01

    Multiple-pass friction stir processing (FSP) was employed to impregnate metal oxide (TiO2, Y2O3 and CeO2) particles into the surface of an Aluminium alloy. The surface composites were then anodized in a sulphuric acid electrolyte. The effect of anodizing parameters on the resulting optical...... dark to greyish white. This is attributed to the localized microstructural and morphological differences around the metal oxide particles incorporated into the anodic alumina matrix. The metal oxide particles in the FSP zone electrochemically shadowed the underlying Al matrix and modified the local...

  6. Transport of radionuclides by bentonite and silica colloids in a GR-3 synthetic groundwater-interim report

    International Nuclear Information System (INIS)

    Ames, L.L.; McGarrah, J.E.; Walker, B.A.

    1983-08-01

    Radionuclide distributions in groundwater-colloid-basalt systems were measured using GR-3 groundwater and crushed Umtanum basalt at 60 degree C. The objective was to estimate the potential for radionuclide transport from a nuclear waste repository in basalt by colloids suspended in groundwater. Three colloids were studied -- a bentonite colloid representing a potential component of packing or backfill materials in the repository, and two hydrated silica colloids which might represent those generated from a glass waste form. The radioelements studied included isotopes of neptunium, uranium, selenium, technetium, and radium. Measurements of radionuclide distributions in experiments with the bentonite colloid showed that uranium was sorbed strongly on the colloid (under both oxidizing and reducing conditions) but was readily transferred to basalt when it was added to the system. Sorption of neptunium, technetium, and selenium on the colloid was greatly enhanced by using reducing conditions. Only small amounts of neptunium and technetium were transferred to the basalt under reducing conditions, but most of the selenium was readily transferred under these conditions

  7. Industrial waste water treatment by advanced oxidation processes; Tratamiento de aguas residuales industriales mediante procesos de oxidacion avanzada

    Energy Technology Data Exchange (ETDEWEB)

    Gasso, S.; Baldasano, J.M.

    1996-06-01

    Advanced Oxidation Technologies have been defined as processes which involve the generation of highly reactive oxy radicals. These systems show promise for the destruction of non biodegradable and hazardous organic substances in industrial wastewater. Two types of advanced oxidation processes are considered in this paper: (1) systems that use high energy oxidants (O{sub 3}, H{sub 2}O{sub 2}, UV, etc) at ambient temperature to initiate the oxidation reaction, and (2) processes that use molecular oxygen and high temperature and pressure to initiate the reaction (wet oxidation at subcritical and supercritical conditions). The fundamental aspects of these oxidation technologies are discussed, the application framework is defined and the technology development is indicated. (Author) 33 refs.

  8. Thermodynamic analysis of combined Solid Oxide Electrolyzer and Fischer–Tropsch processes

    International Nuclear Information System (INIS)

    Stempien, Jan Pawel; Ni, Meng; Sun, Qiang; Chan, Siew Hwa

    2015-01-01

    In this paper a thermodynamic analysis and simple optimization of a combined Solid Oxide Electrolyzer Cell and Fisher–Tropsch Synthesis processes for sustainable hydrocarbons fuel production is reported. Comprehensive models are employed to describe effects of temperature, pressure, reactant composition and molar flux and flow on the system efficiency and final production distribution. The electrolyzer model was developed in-house and validated with experimental data of a typical Solid Oxide Electrolyzer. The Fischer–Tropsch Synthesis model employed lumped kinetics of syngas utilization, which includes inhibiting effect of water content and kinetics of Water–Gas Shift reaction. Product distribution model incorporated olefin re-adsorption and varying physisorption and solubility of hydrocarbons with their carbon number. The results were compared with those reported by Becker et al. with simplified analysis of such process. In the present study an opposite effect of operation at elevated pressure was observed. Proposed optimized system achieved overall efficiency of 66.67% and almost equal spread of light- (31%wt), mid-(36%wt) and heavy-hydrocarbons (33%wt). Paraffins contributed the majority of the yield. - Highlights: • Analysis of Solid Oxide Electrolyzer combined with Fisher Tropsch process. • Efficiency of converting water and carbon dioxide into synthetic fuels above 66%. • Effects of process temperature, pressure, gas flux and compositions were analyzed

  9. Electrochemical activity of heavy metal oxides in the process of ...

    Indian Academy of Sciences (India)

    Unknown

    2002-02-02

    Feb 2, 2002 ... Electrochemical activity of heavy metal oxides in the process of chloride induced .... decrease of pH value by MeOx, a synergism of acidic and chloride ... inhibitors and their influence on the physical properties of. Portland ...

  10. Alkaline electrochemical advanced oxidation process for chromium oxidation at graphitized multi-walled carbon nanotubes.

    Science.gov (United States)

    Xue, Yudong; Zheng, Shili; Sun, Zhi; Zhang, Yi; Jin, Wei

    2017-09-01

    Alkaline electrochemical advanced oxidation processes for chromium oxidation and Cr-contaminated waste disposal were reported in this study. The highly graphitized multi-walled carbon nanotubes g-MWCNTs modified electrode was prepared for the in-situ electrochemical generation of HO 2 - . RRDE test results illustrated that g-MWCNTs exhibited much higher two-electron oxygen reduction activity than other nanocarbon materials with peak current density of 1.24 mA cm -2 , %HO 2 - of 77.0% and onset potential of -0.15 V (vs. Hg/HgO). It was originated from the highly graphitized structure and good electrical conductivity as illustrated from the Raman, XRD and EIS characterizations, respectively. Large amount of reactive oxygen species (HO 2 - and ·OH) were in-situ electro-generated from the two-electron oxygen reduction and chromium-induced alkaline electro-Fenton-like reaction. The oxidation of Cr(III) was efficiently achieved within 90 min and the conversion ratio maintained more than 95% of the original value after stability test, offering an efficient and green approach for the utilization of Cr-containing wastes. Copyright © 2017 Elsevier Ltd. All rights reserved.

  11. Electrochemical/chemical oxidation of bisphenol A in a four-electron/two-proton process in aprotic organic solvents

    International Nuclear Information System (INIS)

    Chan, Ya Yun; Yue, Yanni; Li, Yongxin; Webster, Richard D.

    2013-01-01

    Graphical abstract: - Highlights: • Bisphenol A undergoes a chemically irreversible voltammetric oxidation process. • Chemical oxidation was performed to overcome adsorption effects that cause electrode fouling. • A new product was isolated from chemical oxidation with 4 mol equiv. of the one-electron oxidant, NO + . • The oxidative mechanism was proposed to be a four-electron/two-proton process. - Abstract: The electrochemical behavior of bisphenol A (BPA) was examined using cyclic voltammetry, bulk electrolysis and chemical oxidation in aprotic organic solvents. It was found that BPA undergoes a chemically irreversible voltammetric oxidation process to form compounds that cannot be electrochemically converted back to the starting materials on the voltammetric timescale. To overcome the effects of electrode fouling during controlled potential electrolysis experiments, NO + was used as a one-electron chemical oxidant. A new product, hydroxylated bisdienone was isolated from the chemical oxidation of BPA with 4 mol equiv of NO + SbF 6 − in low water content CH 3 CN. The structure of the cation intermediate species was deduced and it was proposed that BPA is oxidized in a four-electron/two-proton process to form a relatively unstable dication which reacts quickly in the presence of water in acetonitrile (in a mechanism that is similar to phenols in general). However, as the water content of the solvent increased it was found that the chemical oxidation mechanism produced a nitration product in high yield. The findings from this study provide useful insights into the reactions that can occur during oxidative metabolism of BPA and highlight the possibility of the role of a bisdienone cation as a reactive metabolite in biological systems

  12. Sludge thermal oxidation processes: mineral recycling, energy impact, and greenhouse effect gases release

    Energy Technology Data Exchange (ETDEWEB)

    Guibelin, Eric

    2003-07-01

    Different treatment routes have been studied for a mixed sludge: the conventional agricultural use is compared with the thermal oxidation processes, including incineration (in gaseous phase) and wet air oxidation (in liquid phase). The interest of a sludge digestion prior to the final treatment has been also considered according to the two major criteria, which are the fossil energy utilisation and the greenhouse effect gases (CO{sub 2}, CH{sub 4}, N{sub 2}O) release. Thermal energy has to be recovered on thermal processes to make these processes environmentally friendly, otherwise their main interest is to extract or destroy micropollutants and pathogens from the carbon cycle. In case of continuous energy recovery, incineration can produce more energy than it consumes. Digestion is especially interesting for agriculture: according to these two schemes, the energy final balance can also be in excess. As to wet air oxidation, it is probably one of the best way to minimize greenhouse effect gases emission. (author)

  13. Treatment of plutonium process residues by molten salt oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Stimmel, J.; Wishau, R.; Ramsey, K.B.; Montoya, A.; Brock, J. [Los Alamos National Lab., NM (United States); Heslop, M. [Naval Surface Warfare Center (United States). Indian Head Div.; Wernly, K. [Molten Salt Oxidation Corp. (United States)

    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.

  14. Treatment of plutonium process residues by molten salt oxidation

    International Nuclear Information System (INIS)

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

    1999-01-01

    Molten Salt Oxidation (MSO) is a thermal process that can remove more than 99.999% of the organic matrix from combustible 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 2 SO 4 , Na 3 PO 4 and NaAsO 2 or Na 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 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

  15. A supercritical carbon dioxide plasma process for preparing tungsten oxide nanowires

    International Nuclear Information System (INIS)

    Kawashima, Ayato; Nomura, Shinfuku; Toyota, Hiromichi; Takemori, Toshihiko; Mukasa, Shinobu; Maehara, Tsunehiro

    2007-01-01

    A supercritical carbon dioxide (CO 2 ) plasma process for fabricating one-dimensional tungsten oxide nanowires coated with amorphous carbon is presented. High-frequency plasma was generated in supercritical carbon dioxide at 20 MPa by using tungsten electrodes mounted in a supercritical cell, and subsequently an organic solvent was introduced with supercritical carbon dioxide into the plasma. Electron microscopy and Raman spectroscopy investigations of the deposited materials showed the production of tungsten oxide nanowires with or without an outer layer. The nanowires with an outer layer exhibited a coaxial structure with an outer concentric layer of amorphous carbon and an inner layer of tungsten oxide with a thickness and diameter of 20-30 and 10-20 nm, respectively

  16. A study of hydrogen permeation in aluminum alloy treated by various oxidation processes

    International Nuclear Information System (INIS)

    Song Wenhai; Long Bin

    1997-01-01

    A set of oxide coatings was formed on the surface of an Al alloy (wt%: Fe, 0.24; Si, 1.16; Cu, 0.05-0.2; Zn, 0.1; Al, residual) by means of various oxidation processes. The hydrogen permeability through the aluminum alloy and its coating materials was determined by a vapor phase permeation technique at temperatures ranging from 400 to 500 C using high-purity H 2 (99.9999%) gas with an upstream hydrogen pressure of 10 4 -10 5 Pa. The experimental results show that the hydrogen permeability through aluminum oxide coating is 100-2000 times lower than that through the aluminum alloy substrate. This means that the aluminum oxide is a significant hydrogen permeation barrier. A high hydrogen permeation resistance was observed in an oxide layer prefilmed in 200 C water, while an anodized aluminum oxide film had a less obstructive effect, possibly caused by the porous structure of the anodic oxide. The hydrogen permeability through films of aluminum oxide was not a simple function of the aluminum-oxide phase configuration. (orig.)

  17. Enhanced degradation of paracetamol by UV-C supported photo-Fenton process over Fenton oxidation.

    Science.gov (United States)

    Manu, B; Mahamood, S

    2011-01-01

    For the treatment of paracetamol in water, the UV-C Fenton oxidation process and classic Fenton oxidation have been found to be the most effective. Paracetamol reduction and chemical oxygen demand (COD) removal are measured as the objective functions to be maximized. The experimental conditions of the degradation of paracetamol are optimized by the Fenton process. Influent pH 3, initial H(2)O(2) dosage 60 mg/L, [H(2)O(2)]/[Fe(2+)] ratio 60 : 1 are the optimum conditions observed for 20 mg/L initial paracetamol concentration. At the optimum conditions, for 20 mg/L of initial paracetamol concentration, 82% paracetamol reduction and 68% COD removal by Fenton oxidation, and 91% paracetamol reduction and 82% COD removal by UV-C Fenton process are observed in a 120 min reaction time. By HPLC analysis, 100% removal of paracetamol is observed at the above optimum conditions for the Fenton process in 240 min and for the UV-C photo-Fenton process in 120 min. The methods are effective and they may be used in the paracetamol industry.

  18. Deactivation of iron oxide used in the steam-iron process to produce hydrogen

    NARCIS (Netherlands)

    Bleeker, M.F.; Veringa, H.J.; Kersten, Sascha R.A.

    2009-01-01

    In the steam-iron process pure hydrogen can be produced from any hydrocarbon feedstock by using a redox cycle of iron oxide. One of the main problems connected to the use of the iron oxide is the inherent structural changes that take place during oxygen loading and unloading leading to severe

  19. Reduction of Tc(VII) and Np(V) in solution by ferrous iron. A laboratory study of homogeneous and heterogeneous redox processes

    International Nuclear Information System (INIS)

    Cui, D.; Eriksen, T.E.

    1996-03-01

    The redox chemistry of Technetium and Neptunium in deep groundwater systems has been studied under well controlled conditions in laboratory experiments. The measured redox potentials in anoxic deep groundwater systems are consistent with redox reactions between Fe(II) in solution and hydrous Fe(III)-oxide phases. The fracture filling material and groundwater in transmissive fractures in bedrock constitute two different compartments in the groundwater system and experiments were therefore carried out in homogeneous Fe(II) containing solutions and in heterogeneous mixtures of solution with Fe(II) containing solid mineral phases. Reduction of the strongly sorbing neptunyl cation (NpO 2 + ) and the slightly sorbing pertechnetate anion (TcO 4 - ) by Fe(II) in solution was found to proceed very slowly, if at all, in reaction vessels with hydrophobic inner surfaces. However, in the heterogeneous systems we observed surface mediated reduction to the slightly soluble ( -8 mol*dm -3 ) tetravalent (hydr)oxides TcO 2 *nH 2 O (=Tc(OH) 4 ) and NpO 2 *nH 2 O (=Np(OH) 4 ) by Fe(II) sorbed on quartz,precipitated Fe(OH) 2 (s), Fe(II)CO 3 (s) and Fe(II) bearing minerals such as magnetite, hornblende and Fe(II)-chlorite. It is concluded that surface mediated redox-reactions will be the most effective pathway for the reduction of Tc(VII) and Np(V) in deep groundwater systems. On exposure of the surface-precipitated tetravalent (hydr)oxides to air saturated groundwater solutions the oxidative dissolution was found to be a very slow process and high concentration of hydrogen peroxide was required for oxidative dissolution. The slow rate of oxidative dissolution is most probably due to kinetic suppression of the reactions between dissolved oxygen and the precipitated (hydr)oxides. The kinetic suppression is caused by competing redox reactions at the surface of the Fe(II)-bearing minerals which consumes the dissolved oxygen. 30 refs, 22 figs

  20. Reduction of Tc(VII) and Np(V) in solution by ferrous iron. A laboratory study of homogeneous and heterogeneous redox processes

    Energy Technology Data Exchange (ETDEWEB)

    Cui, D.; Eriksen, T.E. [Royal Inst. of Tech., Stockholm (Sweden). Dept. of Chemistry

    1996-03-01

    The redox chemistry of Technetium and Neptunium in deep groundwater systems has been studied under well controlled conditions in laboratory experiments. The measured redox potentials in anoxic deep groundwater systems are consistent with redox reactions between Fe(II) in solution and hydrous Fe(III)-oxide phases. The fracture filling material and groundwater in transmissive fractures in bedrock constitute two different compartments in the groundwater system and experiments were therefore carried out in homogeneous Fe(II) containing solutions and in heterogeneous mixtures of solution with Fe(II) containing solid mineral phases. Reduction of the strongly sorbing neptunyl cation (NpO{sub 2}{sup +}) and the slightly sorbing pertechnetate anion (TcO{sub 4}{sup -}) by Fe(II) in solution was found to proceed very slowly, if at all, in reaction vessels with hydrophobic inner surfaces. However, in the heterogeneous systems we observed surface mediated reduction to the slightly soluble (<10{sub -8} mol*dm{sup -3}) tetravalent (hydr)oxides TcO{sub 2}*nH{sub 2}O (=Tc(OH){sub 4}) and NpO{sub 2}*nH{sub 2}O (=Np(OH){sub 4}) by Fe(II) sorbed on quartz,precipitated Fe(OH){sub 2}(s), Fe(II)CO{sub 3}(s) and Fe(II) bearing minerals such as magnetite, hornblende and Fe(II)-chlorite. It is concluded that surface mediated redox-reactions will be the most effective pathway for the reduction of Tc(VII) and Np(V) in deep groundwater systems. On exposure of the surface-precipitated tetravalent (hydr)oxides to air saturated groundwater solutions the oxidative dissolution was found to be a very slow process and high concentration of hydrogen peroxide was required for oxidative dissolution. The slow rate of oxidative dissolution is most probably due to kinetic suppression of the reactions between dissolved oxygen and the precipitated (hydr)oxides. The kinetic suppression is caused by competing redox reactions at the surface of the Fe(II)-bearing minerals which consumes the dissolved oxygen.

  1. Removal of ammonia solutions used in catalytic wet oxidation processes.

    Science.gov (United States)

    Hung, Chang Mao; Lou, Jie Chung; Lin, Chia Hua

    2003-08-01

    Ammonia (NH(3)) is an important product used in the chemical industry, and is common place in industrial wastewater. Industrial wastewater containing ammonia is generally either toxic or has concentrations or temperatures such that direct biological treatment is unfeasible. This investigation used aqueous solutions containing more of ammonia for catalytic liquid-phase oxidation in a trickle-bed reactor (TBR) based on Cu/La/Ce composite catalysts, prepared by co-precipitation of Cu(NO(3))(2), La(NO(3))(2), and Ce(NO(3))(3) at 7:2:1 molar concentrations. The experimental results indicated that the ammonia conversion of the wet oxidation in the presence of the Cu/La/Ce composite catalysts was determined by the Cu/La/Ce catalyst. Minimal ammonia was removed from the solution by the wet oxidation in the absence of any catalyst, while approximately 91% ammonia removal was achieved by wet oxidation over the Cu/La/Ce catalyst at 230 degrees C with oxygen partial pressure of 2.0 MPa. Furthermore, the effluent streams were conducted at a liquid hourly space velocity of under 9 h(-1) in the wet catalytic processes, and a reaction pathway was found linking the oxidizing ammonia to nitric oxide, nitrogen and water. The solution contained by-products, including nitrates and nitrites. Nitrite selectivity was minimized and ammonia removal maximized when the feed ammonia solution had a pH of around 12.0.

  2. Detoxifying of high strength textile effluent through chemical and bio-oxidation processes.

    Science.gov (United States)

    Manekar, Pravin; Patkar, Guarav; Aswale, Pawan; Mahure, Manisha; Nandy, Tapas

    2014-04-01

    Small-scale textile industries (SSTIs) in India struggled for the economic and environmental race. A full-scale common treatment plant (CETP) working on the principle of destabilising negative charge colloidal particles and bio-oxidation of dissolved organic failed to comply with Inland Surface Waters (ISW) standards. Thus, presence of intense colour and organics with elevated temperature inhibited the process stability. Bench scale treatability studies were conducted on chemical and biological processes for its full-scale apps to detoxify a high strength textile process effluent. Colour, SS and COD removals from the optimised chemical process were 88%, 70% and 40%, respectively. Heterotrophic bacteria oxidised COD and BOD more than 84% and 90% at a loading rate 0.0108kgm(-3)d(-1) at 3h HRT. The combined chemical and bio-oxidation processes showed a great promise for detoxifying the toxic process effluent, and implemented in full-scale CETP. The post-assessment of the CETP resulted in detoxify the toxic effluent. Copyright © 2014 Elsevier Ltd. All rights reserved.

  3. Oxidative stability of rice bran, corn, canola, sunflower and soybean oils d baking process and storage of bread

    Directory of Open Access Journals (Sweden)

    Najmeh Jahani

    2016-01-01

    Full Text Available Oxidation of bread lipids during baking and storage reduces the nutritional value of the product and leads to the formation of off-flavors and off-odors. In this research, oxidative stability of rice bran, corn, canola, sunflower and soybean oils during Brotchen bread baking process and storage was evaluated. Baking process caused a significant increase in oxidative indices such as peroxide, anisidine, Totox and thiobarbitoric acid values and free fatty acid content. However, storage of breads for 6 days in room temperature did not affect the value of the indices. Generaly, the value of the indices in bread containing rice bran oil was lower than those of the other breads, which indicated the higher oxidative stability of rice bran oil in baking process and storage. Pure oils treated in simulated baking process and storage had an oxidative quality similar to that of breads. This means that bread ingridients may not have an effect on oil oxidative stability. Bread containing rice bran oil gained also higher scores in sensory evaluation, which of course were in agree with its better oxidative status.

  4. High performance solution processed zirconium oxide gate dielectric appropriate for low temperature device application

    Energy Technology Data Exchange (ETDEWEB)

    Hasan, Musarrat; Nguyen, Manh-Cuong; Kim, Hyojin; You, Seung-Won; Jeon, Yoon-Seok; Tong, Duc-Tai; Lee, Dong-Hwi; Jeong, Jae Kyeong; Choi, Rino, E-mail: rino.choi@inha.ac.kr

    2015-08-31

    This paper reports a solution processed electrical device with zirconium oxide gate dielectric that was fabricated at a low enough temperature appropriate for flexible electronics. Both inorganic dielectric and channel materials were synthesized in the same organic solvent. The dielectric constant achieved was 13 at 250 °C with a reasonably low leakage current. The bottom gate transistor devices showed the highest mobility of 75 cm{sup 2}/V s. The device is operated at low voltage with high-k dielectric with excellent transconductance and low threshold voltage. Overall, the results highlight the potential of low temperature solution based deposition in fabricating more complicated circuits for a range of applications. - Highlights: • We develop a low temperature inorganic dielectric deposition process. • We fabricate oxide semiconductor channel devices using all-solution processes. • Same solvent is used for dielectric and oxide semiconductor deposition.

  5. Contribution to the identification of the processes kinetically limiting of the zirconium alloys oxidation; characterization of the oxide films formed at high temperature by solids electrochemistry

    International Nuclear Information System (INIS)

    Vermoyal, J.J.

    2000-06-01

    The corrosion behavior of zirconium alloys used for cladding tubes has been extensively studied under several oxidation conditions (temperature, steam, dry air, oxygen...) in order to clarify the mechanism(s) of oxide growth and breakdown. Oxidation rate is generally assumed to be controlled by oxygen diffusion inwards the oxide layer. Nevertheless, several experimental facts, such as acceleration or inhibition of corrosion rate in coupling conditions, suggest that electrochemical processes are involved as a rate determining step. This work is an attempt to shed light about the rate-limiting-mechanism of two zirconium alloys oxidation: Zircaloy-4 (Zy-4) and Zr-Nb(1%)O(0,13%). Impedance spectroscopy characterizations of oxide films formed in high temperature water and studied in gaseous atmosphere clearly show the difference of electrical properties between the two alloys. The in situ electrochemical and thermogravimetric investigations in gaseous medium, and the polarization effects on oxidation and hydridation of Zr alloys in PWRs conditions indicate that oxygen diffusion can be considered as the limiting kinetic step for Zy-4 oxidation. On the contrary, the acceleration of oxide growth on Zr-Nb(1%)O(0,13%) under anodic polarization in PWRs conditions (360 deg C) suggests that either the electronic conductivity in the oxide or an interfacial process at least partially control the oxidation rate. Catalytic effects observed in gaseous medium when noble metals increase the oxygen reduction rate would tend to corroborate the oxidation control of this alloy by an interfacial mechanism. An electrochemical description and a heterogeneous kinetics approach based on a diffusion-interfacial process as rate determining step are then proposed. (author)

  6. Combustion synthesized indium-tin-oxide (ITO) thin film for source/drain electrodes in all solution-processed oxide thin-film transistors

    International Nuclear Information System (INIS)

    Tue, Phan Trong; Inoue, Satoshi; Takamura, Yuzuru; Shimoda, Tatsuya

    2016-01-01

    We report combustion solution synthesized (SCS) indium-tin-oxide (ITO) thin film, which is a well-known transparent conductive oxide, for source/drain (S/D) electrodes in solution-processed amorphous zirconium-indium-zinc-oxide TFT. A redox-based combustion synthetic approach is applied to ITO thin film using acetylacetone as a fuel and metal nitrate as oxidizer. The structural and electrical properties of SCS-ITO precursor solution and thin films were systematically investigated with changes in tin concentration, indium metal precursors, and annealing conditions such as temperature, time, and ambient. It was found that at optimal conditions the SCS-ITO thin film exhibited high crystalline quality, atomically smooth surface (RMS ∝ 4.1 Aa), and low electrical resistivity (4.2 x 10 -4 Ω cm). The TFT using SCS-ITO film as the S/D electrodes showed excellent electrical properties with negligible hysteresis. The obtained ''on/off'' current ratio, subthreshold swing factor, subthreshold voltage, and field-effect mobility were 5 x 10 7 , 0.43 V/decade, 0.7 V, and 2.1 cm 2 /V s, respectively. The performance and stability of the SCS-ITO TFT are comparable to those of the sputtered-ITO TFT, emphasizing that the SCS-ITO film is a promising candidate for totally solution-processed oxide TFTs. (orig.)

  7. Study of the pelletizing process zirconium oxide and zircon sand

    International Nuclear Information System (INIS)

    Seo, E.S.M.; Paschoal, J.O.A.; Acevedo, M.T.P.

    1990-12-01

    The study of the process to obtain zirconium tetrachloride under development at IPEN, can be divide into two steps: pelletizing and chlorination. Pelletizing is an important step in the overall process as it facilitates greater contact between the particles and permits the production of pellets with dimensional uniformity and mechanical strength. In this paper, the results of the study of pelletizing zirconium oxide and zircon sand are presented. The influence of some variables related to the process and the equipment on the physical characteristics of the pellets are discussed. (author)

  8. Fluid bed direct denitration process for plutonium nitrate to oxide conversion

    International Nuclear Information System (INIS)

    Souply, K.R.; Neal, D.H.

    1977-01-01

    The fluid bed direct-denitration process appears feasible for reprocessing Light Water Reactor fuel. Considerable experience with the fluid bed process exists in the denitration of uranyl nitrate and it shows promise for use in the denitration of plutonium nitrate. The process will require some development work before it can be used in a production-size facility. This report describes a fluid bed direct-denitration process for converting plutonium nitrate to plutonium oxide, and the information should be used when making comparisons of alternative processes or as a basis for further detailed studies

  9. Preliminary design needs for pilot plant of Monazite processing into Thorium Oxide (ThO_2)

    International Nuclear Information System (INIS)

    Hafni Lissa Nuri; Prayitno; Abdul Jami; M-Pancoko

    2014-01-01

    Data and information collection aimed in order to meet the needs of the initial design for pilot plant of monazite processing into thorium oxide (ThO_2). The content of thorium in monazite is high in Indonesia between 2.9 to 4.1% and relatively abundant in Bangka Belitung Islands. Thorium can be used as fuel because of its potential is more abundant instead of uranium. Plant of thorium oxide commercially from monazite established starting from pilot uranium. Plant of thorium oxide commercially from monazite established starting from pilot plant in order to test laboratory data. Pilot plant design started from initial design, basic design, detailed design, procurement and construction. Preliminary design needs includes data feed and products, a block diagram of the process, a description of the process, the determination of process conditions and type of major appliance has been conducted. (author)

  10. Literature review on the properties of cuprous oxide Cu{sub 2}O and the process of copper oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Korzhavyi, P. A.; Johansson, B. (Department of Materials Science and Engineering, Royal Institute of Technology, Stockholm (Sweden))

    2011-10-15

    The purpose of the present review is to provide a reference guide to the most recent data on the properties of copper(I) oxide as well as on the atomic processes involved in the initial stages of oxidation of copper. The data on the structure of surfaces, as obtained from atomic-resolution microscopy studies (for example, STM) or from first-principles calculations, are reviewed. Information of this kind may be useful for understanding the atomic mechanisms of corrosion and stress-corrosion cracking of copper

  11. Assessment of the Dry Processed Oxide Fuel in Liquid Metal Fast Reactors

    Energy Technology Data Exchange (ETDEWEB)

    Roh, Gyu Hong; Choi, Hang Bok

    2005-09-15

    The neutronic feasibility of the dry process oxide fuel was assessed for the sodium-cooled and lead-cooled fast reactors (SFR and LFR, respectively), which were recommended as Generation-IV (Gen-IV) reactor systems by the Gen-IV international forum. The reactor analysis was performed for the equilibrium fuel cycle of two core configurations: Hybrid BN-600 benchmark core with an enlarged lattice pitch and a modified BN-600 core. The dry process technology assumed in this study is the molten-salt process, which was developed by Russian scientists for recycling oxide fuels. The core calculation was performed by the REBUS-3 code and the reactor characteristics such as the transuranic (TRU) enrichment, breeding ratio, peak linear power, burnup reactivity swing, etc. were calculated for the equilibrium core under a fixed fuel management scheme. The results showed that a fissile self-sustainable breakeven core was achievable without blanket fuels when the fuel volume fraction was {approx}50% and most of the fission products were removed. If the design criteria used in this study is proved to be acceptable through a detailed physics design and thermal hydraulic analysis in the future, it is practically possible to construct an equilibrium fuel cycle of the SFR and LFR systems based on the oxide fuel by utilizing the dry process technology.

  12. Assessment of the Dry Processed Oxide Fuel in Liquid Metal Fast Reactors

    International Nuclear Information System (INIS)

    Roh, Gyu Hong; Choi, Hang Bok

    2005-09-01

    The neutronic feasibility of the dry process oxide fuel was assessed for the sodium-cooled and lead-cooled fast reactors (SFR and LFR, respectively), which were recommended as Generation-IV (Gen-IV) reactor systems by the Gen-IV international forum. The reactor analysis was performed for the equilibrium fuel cycle of two core configurations: Hybrid BN-600 benchmark core with an enlarged lattice pitch and a modified BN-600 core. The dry process technology assumed in this study is the molten-salt process, which was developed by Russian scientists for recycling oxide fuels. The core calculation was performed by the REBUS-3 code and the reactor characteristics such as the transuranic (TRU) enrichment, breeding ratio, peak linear power, burnup reactivity swing, etc. were calculated for the equilibrium core under a fixed fuel management scheme. The results showed that a fissile self-sustainable breakeven core was achievable without blanket fuels when the fuel volume fraction was ∼50% and most of the fission products were removed. If the design criteria used in this study is proved to be acceptable through a detailed physics design and thermal hydraulic analysis in the future, it is practically possible to construct an equilibrium fuel cycle of the SFR and LFR systems based on the oxide fuel by utilizing the dry process technology

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

    Science.gov (United States)

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

    2015-01-01

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

  14. Interim glycol flowsheet reduction/oxidation (redox) model for the Defense Waste Processing Facility (DWPF)

    Energy Technology Data Exchange (ETDEWEB)

    Jantzen, C. M. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Williams, M. S. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Zamecnik, J. R. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Missimer, D. M. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2016-03-08

    Control of the REDuction/OXidation (REDOX) state of glasses containing high concentrations of transition metals, such as High Level Waste (HLW) glasses, is critical in order to eliminate processing difficulties caused by overly reduced or overly oxidized melts. Operation of a HLW melter at Fe+2/ΣFe ratios of between 0.09 and 0.33, a range which is not overly oxidizing or overly reducing, helps retain radionuclides in the melt, i.e. long-lived radioactive 99Tc species in the less volatile reduced Tc4+ state, 104Ru in the melt as reduced Ru+4 state as insoluble RuO2, and hazardous volatile Cr6+ in the less soluble and less volatile Cr+3 state in the glass. The melter REDOX control balances the oxidants and reductants from the feed and from processing additives such as antifoam. Currently, the Defense Waste Processing Facility (DWPF) is running a formic acid-nitric acid (FN) flowsheet where formic acid is the main reductant and nitric acid is the main oxidant. During decomposition formate and formic acid releases H2 gas which requires close control of the melter vapor space flammability. A switch to a nitric acid-glycolic acid (GN) flowsheet is desired as the glycolic acid flowsheet releases considerably less H2 gas upon decomposition. This would greatly simplify DWPF processing. Development of an EE term for glycolic acid in the GN flowsheet is documented in this study.

  15. Post-treatment of reclaimed waste water based on an electrochemical advanced oxidation process

    Science.gov (United States)

    Verostko, Charles E.; Murphy, Oliver J.; Hitchens, G. D.; Salinas, Carlos E.; Rogers, Tom D.

    1992-01-01

    The purification of reclaimed water is essential to water reclamation technology life-support systems in lunar/Mars habitats. An electrochemical UV reactor is being developed which generates oxidants, operates at low temperatures, and requires no chemical expendables. The reactor is the basis for an advanced oxidation process in which electrochemically generated ozone and hydrogen peroxide are used in combination with ultraviolet light irradiation to produce hydroxyl radicals. Results from this process are presented which demonstrate concept feasibility for removal of organic impurities and disinfection of water for potable and hygiene reuse. Power, size requirements, Faradaic efficiency, and process reaction kinetics are discussed. At the completion of this development effort the reactor system will be installed in JSC's regenerative water recovery test facility for evaluation to compare this technique with other candidate processes.

  16. Treatment of hazardous waste landfill leachate using Fenton oxidation process

    Science.gov (United States)

    Singa, Pradeep Kumar; Hasnain Isa, Mohamed; Ho, Yeek-Chia; Lim, Jun-Wei

    2018-03-01

    The efficiency of Fenton's oxidation was assessed in this study for hazardous waste landfill leachate treatment. The two major reagents, which are generally employed in Fenton's process are H2O2 as oxidizing agent and Fe2+ as catalyst. Batch experiments were conducted to determine the effect of experimental conditions viz., reaction time, molar ratio, and Fenton reagent dosages, which are significant parameters that influence the degradation efficiencies of Fenton process were examined. It was found that under the favorable experimental conditions, maximum COD removal was 56.49%. The optimum experimental conditions were pH=3, H2O2/Fe2+ molar ratio = 3 and reaction time = 150 minutes. The optimal amount of hydrogen peroxide and iron were 0.12 mol/L and 0.04 mol/L respectively. High dosages of H2O2 and iron resulted in scavenging effects on OH• radicals and lowered degradation efficiency of organic compounds in the hazardous waste landfill leachate.

  17. Organic contaminants degradation from the S(IV) autoxidation process catalyzed by ferrous-manganous ions: A noticeable Mn(III) oxidation process.

    Science.gov (United States)

    Zhang, Jiaming; Ma, Jun; Song, Haoran; Sun, Shaofang; Zhang, Zhongxiang; Yang, Tao

    2018-04-15

    Remarkable atrazine degradation in the S(IV) autoxidation process catalyzed by Fe 2+ -Mn 2+ (Fe 2+ /Mn 2+ /sulfite) was demonstrated in this study. Competitive kinetic experiments, alcohol inhibiting methods and electron spin resonance (ESR) experiments proved that sulfur radicals were not the major oxidation species. Mn(III) was demonstrated to be the primary active species in the Fe 2+ /Mn 2+ /sulfite process based on the comparison of oxidation selectivity. Moreover, the inhibiting effect of the Mn(III) hydrolysis and the S(IV) autoxidation in the presence of organic contaminants indicated the existence of three Mn(III) consumption routes in the Fe 2+ /Mn 2+ /sulfite process. The absence of hydroxyl radical and sulfate radical was interpreted by the competitive dynamics method. The oxidation capacity of the Fe 2+ /Mn 2+ /sulfite was independent of the initial pH (4.0-6.0) because the fast decay of S(IV) decreased initial pH below 4.0 rapidly. The rate of ATZ degradation was independent of the dissolved oxygen (DO) because that the major DO consumption process was not the rate determining step during the production of SO 5 •- . Phosphate and bicarbonate were confirmed to have greater inhibitory effects than other environmental factors because of their strong pH buffering capacity and complexing capacity for Fe 3+ . The proposed acetylation degradation pathway of ATZ showed the application of the Fe 2+ /Mn 2+ /sulfite process in the research of contaminants degradation pathways. This work investigated the characteristics of the Fe 2+ /Mn 2+ /sulfite process in the presence of organic contaminants, which might promote the development of Mn(III) oxidation technology. Copyright © 2018. Published by Elsevier Ltd.

  18. Design of Biochemical Oxidation Process Engineering Unit for Treatment of Organic Radioactive Liquid Waste

    International Nuclear Information System (INIS)

    Zainus Salimin; Endang Nuraeni; Mirawaty; Tarigan, Cerdas

    2010-01-01

    Organic radioactive liquid waste from nuclear industry consist of detergent waste from nuclear laundry, 30% TBP-kerosene solvent waste from purification or recovery of uranium from process failure of nuclear fuel fabrication, and solvent waste containing D 2 EHPA, TOPO, and kerosene from purification of phosphoric acid. The waste is dangerous and toxic matter having low pH, high COD and BOD, and also low radioactivity. Biochemical oxidation process is the effective method for detoxification of organic waste and decontamination of radionuclide by bio sorption. The result process are sludges and non radioactive supernatant. The existing treatment facilities radioactive waste in Serpong can not use for treatment of that’s organics waste. Dio chemical oxidation process engineering unit for continuous treatment of organic radioactive liquid waste on the capacity of 1.6 L/h has been designed and constructed the equipment of process unit consist of storage tank of 100 L capacity for nutrition solution, 2 storage tanks of 100 L capacity per each for liquid waste, reactor oxidation of 120 L, settling tank of 50 L capacity storage tank of 55 L capacity for sludge, storage tank of 50 capacity for supernatant. Solution on the reactor R-01 are added by bacteria, nutrition and aeration using two difference aerators until biochemical oxidation occurs. The sludge from reactor of R-01 are recirculated to the settling tank of R-02 and on the its reverse operation biological sludge will be settled, and supernatant will be overflow. (author)

  19. Cellular Automata Modelling of Photo-Induced Oxidation Processes in Molecularly Doped Polymers

    Directory of Open Access Journals (Sweden)

    David M. Goldie

    2016-11-01

    Full Text Available The possibility of employing cellular automata (CA to model photo-induced oxidation processes in molecularly doped polymers is explored. It is demonstrated that the oxidation dynamics generated using CA models exhibit stretched-exponential behavior. This dynamical characteristic is in general agreement with an alternative analysis conducted using standard rate equations provided the molecular doping levels are sufficiently low to prohibit the presence of safe-sites which are impenetrable to dissolved oxygen. The CA models therefore offer the advantage of exploring the effect of dopant agglomeration which is difficult to assess from standard rate equation solutions. The influence of UV-induced bleaching or darkening upon the resulting oxidation dynamics may also be easily incorporated into the CA models and these optical effects are investigated for various photo-oxidation product scenarios. Output from the CA models is evaluated for experimental photo-oxidation data obtained from a series of hydrazone-doped polymers.

  20. Electrochemical and morphological analyses on the titanium surface modified by shot blasting and anodic oxidation processes

    Energy Technology Data Exchange (ETDEWEB)

    Szesz, Eduardo M., E-mail: eszesz@neoortho.com.br [Neoortho Research Institute, Rua Ângelo Domingos Durigan, 607-Cascatinha, CEP 82025-100 Curitiba, PR (Brazil); Pereira, Bruno L., E-mail: brnl7@hotmail.com [Physics Department, Universidade Federal do Paraná, 81531-980 Curitiba, PR (Brazil); Kuromoto, Neide K., E-mail: kuromoto@fisica.ufpr.br [Physics Department, Universidade Federal do Paraná, 81531-980 Curitiba, PR (Brazil); Marino, Claudia E.B., E-mail: claudiamarino@yahoo.com [Mechanical Engineering Department, Universidade Federal do Paraná, 81531-980 Curitiba, PR (Brazil); Souza, Gelson B. de, E-mail: gelsonbs@uepg.br [Physics Department, Universidade Estadual de Ponta Grossa, 84051-510 Ponta Grossa, PR (Brazil); Soares, Paulo, E-mail: pa.soares@pucpr.br [Mechanical Engineering Department, Pontifícia Universidade Católica do Paraná, 80215-901 Curitiba, PR (Brazil)

    2013-01-01

    In recent years, many surface modification processes have been developed in order to induce the osseointegration on titanium surface and thus to improve the implants' biocompatibility. In this work, Ti surface has been modified by shot blasting followed by anodic oxidation process in order to associate the good surface characteristics of both processes to obtain a rough and porous surface able to promote the titanium surface bioactivity. Commercially pure titanium (grade 2) plates were used on the surface treatments that were as follows: Shot blasting (SB) performed using alumina (Al{sub 2}O{sub 3}) particles, and anodic oxidation (AO) using NaOH electrolyte. The morphology, structural changes and the open-circuit potentials (OCP) of the surfaces were analyzed. It can be observed that an increase on the roughness of the blasted surface and a rough and porous surface happens after the AO process. The anodic film produced is thin and followed the blasted surface topography. It can be observed that there are small pores with regular shape covering the entire surface. X-ray diffraction results showed the presence of the anatase and rutile phases on the blasted and anodized surface after heat treatment at 600 °C/1 h. Concerning electrochemical measurements, when the different samples were submitted to open-circuit conditions in a physiological electrolyte, the protective effect increases with the oxidation process due to the oxide layer. When the surface was blasted, the OCP was more negative when compared with the Ti surface without surface treatments. - Highlights: ► A combination of shot blasting and anodic oxidation surface treatments is proposed. ► Both processes produced an increase in roughness compared to the polished surface. ► The combination of processes produced a rough and porous surface. ► Open circuit results show that the protective effect increases with oxidation process. ► The combination of processes presents the better results in this

  1. Application of advanced oxidation processes for cleaning of industrial water generated in wet dedusting of shaft furnace gases.

    Science.gov (United States)

    Czaplicka, Marianna; Kurowski, Ryszard; Jaworek, Katarzyna; Bratek, Łukasz

    2013-01-01

    The paper presents results of studies into advanced oxidation processes in 03 and 03/UV systems. An advanced oxidation process (AOP) was conducted to reduce the load of impurities in circulating waters from wet de-dusting of shaft furnace gases. Besides inorganic impurities, i.e. mainly arsenic compounds (16 g As L(-1) on average), lead, zinc, chlorides and sulphates, the waters also contain some organic material. The organic material is composed of a complex mixture that contains, amongst others, aliphatic compounds, phenol and its derivatives, pyridine bases, including pyridine, and its derivatives. The test results show degradation of organic and inorganic compounds during ozonation and photo-oxidation processes. Analysis of the solutions from the processes demonstrated that the complex organic material in the industrial water was oxidized in ozonation and in photo-oxidation, which resulted in formation of aldehydes and carboxylic acids. Kinetic degradation of selected pollutants is presented. Obtained results indicated that the O3/UV process is more effective in degradation of organic matter than ozonation. Depending on the process type, precipitation of the solid phase was observed. The efficiency of solid-phase formation was higher in photo-oxidation with ozone. It was found that the precipitated solid phase is composed mainly of arsenic, iron and oxygen.

  2. Study on the oxidation and reduction of tungsten surface for sub-50 nm patterning process

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Jong Kyu; Nam, Seok Woo; Cho, Sung Il; Jhon, Myung S.; Min, Kyung Suk; Kim, Chan Kyu; Jung, Ho Bum; Yeom, Geun Young [Memory Division Semiconductor Business, Samsung Electronics, San No. 16 Banwol-Ri, Taean-Eup, Hwasung-City, Gyeonggi-Do 449-711, South Korea and Department of Advanced Materials Science and Engineering, Sungkyunkwan University, Suwon, Gyeonggi-do 440-746 (Korea, Republic of); Memory Division Semiconductor Business, Samsung Electronics, San No. 16 Banwol-Ri, Taean-Eup, Hwasung-City, Gyeonggi-Do 449-711 (Korea, Republic of); Department of Chemical Engineering and Data Storage Systems Center, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213 (United States); Department of Advanced Materials Science and Engineering, Sungkyunkwan University, Suwon, Gyeonggi-do 440-746 (Korea, Republic of)

    2012-11-15

    The oxidation characteristics of tungsten line pattern during the carbon-based mask-layer removal process using oxygen plasmas have been investigated for sub-50 nm patterning processes, in addition to the reduction characteristics of the WO{sub x} layer formed on the tungsten line surface using hydrogen plasmas. The surface oxidation of tungsten lines during the mask layer removal process could be minimized by using low-temperature (300 K) plasma processing for the removal of the carbon-based material. Using this technique, the thickness of WO{sub x} on the tungsten line could be decreased to 25% compared to results from high-temperature processing. The WO{sub x} layer could also be completely removed at a low temperature of 300 K using a hydrogen plasma by supplying bias power to the tungsten substrate to provide a activation energy for the reduction. When this oxidation and reduction technique was applied to actual 40-nm-CD device processing, the complete removal of WO{sub x} formed on the sidewall of tungsten line could be observed.

  3. Oxidative treatment of a waste water stream from a molasses processing using ozone and advanced oxidation technologies

    International Nuclear Information System (INIS)

    Gehringer, P.; Szinovatz, W.; Eschweiler, H.; Haberl, R.

    1994-08-01

    The discoloration of a biologically pretreated waste water stream from a molasses processing by ozonation and two advanced oxidation processes (O 3 /H 2 O 2 and O 3 /γ-irradiation, respectively) was studied. Colour removal occurred with all three processes with almost the same efficiency. The main difference of the methods applied was reflected by the BOD increase during the discoloration period. By ozonation it was much higher than by AOPs but it also appeared with AOPs. AOPs were, therefore, not apt for an effective BOD control during discoloration. (authors)

  4. Synthesis and crystal kinetics of cerium oxide nanocrystallites prepared by co-precipitation process

    International Nuclear Information System (INIS)

    Shih, C.J.; Chen, Y.J.; Hon, M.H.

    2010-01-01

    Cerium oxide nanocrystallites were synthesized at a relatively low temperature using cerium nitrate as starting materials in a water solution by a co-precipitation process. Effect of calcination temperature on the crystallite growth of cerium oxide nano-powders was investigated by X-ray diffraction, transmission electron microscopy and electron diffraction. The crystallization temperature of the cerium oxide powders was estimated to be about 273 K by XRD analysis. When calcined from 473 to 1273 K, the crystallization of the face-centered cubic phase was observed by XRD. The crystallite size of the cerium oxide increased from 10.0 to 43.8 nm with calcining temperature increasing from 673 to 1273 K. The activation energy for growth of cerium oxide nanoparticles was found to be 16.0 kJ mol -1 .

  5. Synthesis and crystal kinetics of cerium oxide nanocrystallites prepared by co-precipitation process

    Energy Technology Data Exchange (ETDEWEB)

    Shih, C.J., E-mail: cjshih@kmu.edu.tw [Department of Fragrance and Cosmetics Science, Kaohsiung Medical University, 100 Shi-Chuan 1st Road, Kaohsiung 807, Taiwan (China); Chen, Y.J. [Institute of Biomedical Sciences, National Sun Yat-Sen University, Kaohsiung 804, Taiwan (China); Hon, M.H. [Department of Materials Science and Engineering, National Cheng Kung University, Tainan 701, Taiwan (China)

    2010-05-15

    Cerium oxide nanocrystallites were synthesized at a relatively low temperature using cerium nitrate as starting materials in a water solution by a co-precipitation process. Effect of calcination temperature on the crystallite growth of cerium oxide nano-powders was investigated by X-ray diffraction, transmission electron microscopy and electron diffraction. The crystallization temperature of the cerium oxide powders was estimated to be about 273 K by XRD analysis. When calcined from 473 to 1273 K, the crystallization of the face-centered cubic phase was observed by XRD. The crystallite size of the cerium oxide increased from 10.0 to 43.8 nm with calcining temperature increasing from 673 to 1273 K. The activation energy for growth of cerium oxide nanoparticles was found to be 16.0 kJ mol{sup -1}.

  6. The actinides

    International Nuclear Information System (INIS)

    Bagnall, K.W.

    1987-01-01

    This chapter of coordination compound chemistry is devoted to the actinides and starts with a general survey. Most of the chapter relates to thorium and uranium but protactinium, neptunium and plutonium are included. There are sections on nitrogen, phosphorus, sulfur, selenium, tellurium and halogen ligands of the metals in their +3, +4, +5 and +6 oxidation states and of the transplutonium elements in their +2, +3, +4, and +5 oxidation states. (UK)

  7. Demonstration of an N7 integrated fab process for metal oxide EUV photoresist

    Science.gov (United States)

    De Simone, Danilo; Mao, Ming; Kocsis, Michael; De Schepper, Peter; Lazzarino, Frederic; Vandenberghe, Geert; Stowers, Jason; Meyers, Stephen; Clark, Benjamin L.; Grenville, Andrew; Luong, Vinh; Yamashita, Fumiko; Parnell, Doni

    2016-03-01

    Inpria has developed a directly patternable metal oxide hard-mask as a robust, high-resolution photoresist for EUV lithography. In this paper we demonstrate the full integration of a baseline Inpria resist into an imec N7 BEOL block mask process module. We examine in detail both the lithography and etch patterning results. By leveraging the high differential etch resistance of metal oxide photoresists, we explore opportunities for process simplification and cost reduction. We review the imaging results from the imec N7 block mask patterns and its process windows as well as routes to maximize the process latitude, underlayer integration, etch transfer, cross sections, etch equipment integration from cross metal contamination standpoint and selective resist strip process. Finally, initial results from a higher sensitivity Inpria resist are also reported. A dose to size of 19 mJ/cm2 was achieved to print pillars as small as 21nm.

  8. An investigation to adopt zero liquid discharge in textile dyeing using advanced oxidation processes

    International Nuclear Information System (INIS)

    Ahmd, F.

    2015-01-01

    In this study, a novel idea of using ozone oxidation at the end of reactive dyeing process was explored in order to achieve zero discharge dyeing. An advanced oxidative treatment was given during the dyeing process to remove unfixed and hydrolyzed reactive dyes from cotton substrate. Three different shades were dyed using vinylsulphone reactive class of dyes. At the end of fixation step, washing of fabrics was carried out using appropriate quantities of ozone in the process. Ozone oxidation continued until the liquor was decolorized around 95-100% and COD (Chemical Oxygen Demand) was reduced about 80-90%, thus achieving zero liquid discharge dyeing process. The decolouration efficiency of wastewater was regarded as an indicative of removal of dyes from the textile materials because fabric was being washed continuously in the same liquor. Fabric samples dyed with conventional and new methods were compared in terms of change in shade, colourfastness properties, colour stripping, and fabric appearance. Overall results showed that the use of ozone during reactive dyeing can result in less water consumption, reduced process time, and zero discharge of coloured effluents from textile dyeing factories. (author)

  9. Removal of the antiviral agent oseltamivir and its biological activity by oxidative processes

    International Nuclear Information System (INIS)

    Mestankova, Hana; Schirmer, Kristin; Escher, Beate I.; Gunten, Urs von

    2012-01-01

    The antiviral agent oseltamivir acid (OA, the active metabolite of Tamiflu ® ) may occur at high concentrations in wastewater during pandemic influenza events. To eliminate OA and its antiviral activity from wastewater, ozonation and advanced oxidation processes were investigated. For circumneutral pH, kinetic measurements yielded second-order rate constants of 1.7 ± 0.1 × 10 5 and 4.7 ± 0.2 × 10 9 M −1 s −1 for the reaction of OA with ozone and hydroxyl radical, respectively. During the degradation of OA by both oxidants, the antiviral activity of the treated aqueous solutions was measured by inhibition of neuraminidase activity of two different viral strains. A transient, moderate (two-fold) increase in antiviral activity was observed in solutions treated up to a level of 50% OA transformation, while for higher degrees of transformation the activity corresponded to that caused exclusively by OA. OA was efficiently removed by ozonation in a wastewater treatment plant effluent, suggesting that ozonation can be applied to remove OA from wastewater. - Highlights: ► Oseltamivir acid (OA) is oxidized by ozone and hydroxyl radical. ► Kinetics: We determined rate constants for the reaction with these oxidants. ► The specific activity of OA as neuraminidase inhibitor disappeared during oxidation. ► Ozonation and advanced oxidation can effectively remove OA from wastewaters. - Ozone and hydroxyl radical treatment processes can degrade aqueous oseltamivir acid and remove its antiviral activity.

  10. Development of a novel wet oxidation process for hazardous and mixed wastes

    International Nuclear Information System (INIS)

    Dhooge, P.M.

    1994-01-01

    Many DOE waste streams and remediates contain complex and variable mixtures of organic compounds, toxic metals, and radionuclides. These materials are often dispersed in organic or inorganic matrices, such as personal protective equipment, various sludges, soils, and water. The over all objective of the effort described here is to develop a novel catalytic wet oxidation process for the treatment of these multi-component wastes, with the aim of providing a versatile, non-thermal method which will destroy hazardous organic compounds while simultaneously containing and concentrating toxic and radioactive metals for recovery or disposal in a readily stabilized matrix. The DETOX process uses a unique combination of metal catalysts to increase the rate of oxidation of organic materials. The metal catalysts are in the form of salts dissolved in a dilute acid solution. A typical catalyst composition is 60% ferric chloride, 3--4% hydrochloric acid, 0.13% platinum ions, and 0.13% ruthenium ions in a water solution. The catalyst solution is maintained at 423--473 K. Wastes are introduced into contact with the solution, where their organic portion is oxidized to carbon dioxide and water. If the organic portion is chlorinated, hydrogen chloride will be produced as a product. The process is a viable alternative to incineration for the treatment of organic mixed wastes. Estimated costs for waste treatment using the process are from $2.50/kg to $25.00/kg, depending on the size of the unit and the amount of waste processed. Process units can be mobile for on-site treatment of wastes. Results from phase 1 and 2, design and engineering studies, are described

  11. Microbial methane oxidation processes and technologies for mitigation of landfill gas emissions

    DEFF Research Database (Denmark)

    Scheutz, Charlotte; Kjeldsen, Peter; Bogner, J.E.

    2009-01-01

    Landfill gas containing methane is produced by anaerobic degradation of organic waste. Methane is a strong greenhouse gas and landfills are one of the major anthropogenic sources of atmospheric methane. Landfill methane may be oxidized by methanotrophic microorganisms in soils or waste materials...... to predict methane emissions from landfills. Additional research and technology development is needed before methane mitigation technologies utilizing microbial methane oxidation processes can become commercially viable and widely deployed....

  12. High-temperature Raman spectroscopy of solid oxide fuel cell materials and processes.

    Science.gov (United States)

    Pomfret, Michael B; Owrutsky, Jeffrey C; Walker, Robert A

    2006-09-07

    Chemical and material processes occurring in high temperature environments are difficult to quantify due to a lack of experimental methods that can probe directly the species present. In this letter, Raman spectroscopy is shown to be capable of identifying in-situ and noninvasively changes in material properties as well as the formation and disappearance of molecular species on surfaces at temperatures of 715 degrees C. The material, yttria-stabilized zirconia or YSZ, and the molecular species, Ni/NiO and nanocrystalline graphite, factor prominently in the chemistry of solid oxide fuel cells (SOFCs). Experiments demonstrate the ability of Raman spectroscopy to follow reversible oxidation/reduction kinetics of Ni/NiO as well as the rate of carbon disappearance when graphite, formed in-situ, is exposed to a weakly oxidizing atmosphere. In addition, the Raman active phonon mode of YSZ shows a temperature dependent shift that correlates closely with the expansion of the lattice parameter, thus providing a convenient internal diagnostic for identifying thermal gradients in high temperature systems. These findings provide direct insight into processes likely to occur in operational SOFCs and motivate the use of in-situ Raman spectroscopy to follow chemical processes in these high-temperature, electrochemically active environments.

  13. Biomembrane oxidizing tank used in the process of bacterial heap leaching of uranium ore

    International Nuclear Information System (INIS)

    Meng Yunsheng; Fan Baotuan; Liu Jian; Zheng Ying; Liu Chao

    2004-01-01

    The construction characteristic of biomembrane oxidizing tank and specialty of packing material used in the process of bacterial heap leaching of uranium ore are introduced in this paper. Method for designing biomembrane oxidizing tank, layout principle of aeration system and measurements on running management are summarized

  14. Single-column extraction chromatographic separation of U, Pu, Np and Am

    Energy Technology Data Exchange (ETDEWEB)

    Morgenstern, A.; Apostolidis, C.; Carlos-Marquez, R.; Mayer, K.; Molinet, R. [Commission of the European Communities, Karlsruhe (Germany). European Inst. for Transuranium Elements

    2002-07-01

    A rapid, single-column extraction chromatographic method using commercially available UTEVA resin has been developed for the separation of uranium, plutonium, neptunium and americium. The method yields recoveries superior to 90% and allows direct loading of separated fractions on filaments for subsequent analysis by thermal ionization mass spectrometry. The use of reagents compatible with robotized equipment allows automation of the separation process for routine analysis of nuclear materials. The redox reactions between plutonium, neptunium and hydrogen peroxide involved in the separation process were studied by UV/Vis/NIR absorption spectroscopy. (orig.)

  15. Synthesis of yttrium oxide nanoparticles via a facile microplasma-assisted process

    NARCIS (Netherlands)

    Lin, Liangliang; Starostin, Sergey A.; Li, Sirui; Khan, Saif A.; Hessel, Volker

    2018-01-01

    Plasma electrochemistry is an emerging technique for nanomaterial synthesis. The present study reports the preparation of yttrium oxide nanoparticles via a simple, environmentally benign, microplasma-assisted process operated in pin-to-liquid configuration under ambient atmospheric conditions using

  16. Trace metal pyritization variability in response to mangrove soil aerobic and anaerobic oxidation processes.

    Science.gov (United States)

    Machado, W; Borrelli, N L; Ferreira, T O; Marques, A G B; Osterrieth, M; Guizan, C

    2014-02-15

    The degree of iron pyritization (DOP) and degree of trace metal pyritization (DTMP) were evaluated in mangrove soil profiles from an estuarine area located in Rio de Janeiro (SE Brazil). The soil pH was negatively correlated with redox potential (Eh) and positively correlated with DOP and DTMP of some elements (Mn, Cu and Pb), suggesting that pyrite oxidation generated acidity and can affect the importance of pyrite as a trace metal-binding phase, mainly in response to spatial variability in tidal flooding. Besides these aerobic oxidation effects, results from a sequential extraction analyses of reactive phases evidenced that Mn oxidized phase consumption in reaction with pyrite can be also important to determine the pyritization of trace elements. Cumulative effects of these aerobic and anaerobic oxidation processes were evidenced as factors affecting the capacity of mangrove soils to act as a sink for trace metals through pyritization processes. Copyright © 2013 Elsevier Ltd. All rights reserved.

  17. Electrochemical and spectroscopic studies of neptunium in the aluminum chloride-1-n-butylpyridinium chloride melt at 400C

    International Nuclear Information System (INIS)

    Schoebrechts, J.P.; Gilbert, B.

    1985-01-01

    The chemistry of neptunium in acidic and basic AlCl 3 -1-n-butylpyridinium chloride melts at 40 0 C has been investigated by means of electrochemical and spectral techniques. In acidic as well as in basic melts, the reduction of Np(IV) to Np(III) at glassy-carbon electrodes is quasi-reversible. Indirect measurements of the formal potential and spectroscopic results on the Np(IV)-Np(III) system as a function of the acidity indicate that Np(III) and Np(IV) exist as NpCl 6 3- and NpCl 6 2- and solvated Np 3+ and NpCl/sub x//sup (4-x)+/ (with 3 greater than or equal to x greater than or equal to 1), respectively, in basic and acidic melts. The apparent rate constant K 0 ' has been measured on the basic and acidic sites. It depends on the melt acidity only in the latter melts. The Nugent linearization method has been applied to the standard potentials of Np(IV)-Np(III) and U(IV)-U(III) in 2:1 melts. A comparison with the results obtained from other room-temperature solvents shows, as already found with lanthanides, that the acidic melt is a very weak solvating medium

  18. Simultaneous application of chemical oxidation and extraction processes is effective at remediating soil Co-contaminated with petroleum and heavy metals.

    Science.gov (United States)

    Yoo, Jong-Chan; Lee, Chadol; Lee, Jeung-Sun; Baek, Kitae

    2017-01-15

    Chemical extraction and oxidation processes to clean up heavy metals and hydrocarbon from soil have a higher remediation efficiency and take less time than other remediation processes. In batch extraction/oxidation process, 3% hydrogen peroxide (H 2 O 2 ) and 0.1 M ethylenediaminetetraacetic acid (EDTA) could remove approximately 70% of the petroleum and 60% of the Cu and Pb in the soil, respectively. In particular, petroleum was effectively oxidized by H 2 O 2 without addition of any catalysts through dissolution of Fe oxides in natural soils. Furthermore, heavy metals bound to Fe-Mn oxyhydroxides could be extracted by metal-EDTA as well as Fe-EDTA complexation due to the high affinity of EDTA for metals. However, the strong binding of Fe-EDTA inhibited the oxidation of petroleum in the extraction-oxidation sequential process because Fe was removed during the extraction process with EDTA. The oxidation-extraction sequential process did not significantly enhance the extraction of heavy metals from soil, because a small portion of heavy metals remained bound to organic matter. Overall, simultaneous application of oxidation and extraction processes resulted in highly efficient removal of both contaminants; this approach can be used to remove co-contaminants from soil in a short amount of time at a reasonable cost. Copyright © 2016 Elsevier Ltd. All rights reserved.

  19. Lipolysis and lipid oxidation in fermented sausages depending on different processing conditions and different antioxidants.

    Science.gov (United States)

    Zanardi, Emanuela; Ghidini, Sergio; Battaglia, Alessandra; Chizzolini, Roberto

    2004-02-01

    Lipolysis and lipid oxidation in Mediterranean and North Europe type sausages were studied in relation to raw material, processing conditions and additives. In particular the effect of ascorbic acid, nitrites and spices was evaluated. Lipolysis was measured by the determination of total and free fatty acids of fresh minces and matured products and lipid oxidation was evaluated by thiobarbituric acid reactive substances and cholesterol oxidation products. The increase of free fatty acids during maturation appears to be independent from processing conditions and the differences in polyunsaturated fatty acids increment found among the formulations appear to be due to inherent variations of raw materials. The presence of ascorbic acid and/or nitrite seems important for cholesterol protection and, as a consequence, for the safety of fermented meat products while spices at doses up to 0.1% do not seem to have a remarkable effect. The effect on fatty acid oxidation of the same additives and of the different processing technologies is not significantly different and the variations linked to raw material may play the greatest role.

  20. Process for depositing an oxide epitaxially onto a silicon substrate and structures prepared with the process

    Science.gov (United States)

    McKee, Rodney A.; Walker, Frederick J.

    1993-01-01

    A process and structure involving a silicon substrate utilizes an ultra high vacuum and molecular beam epitaxy (MBE) methods to grow an epitaxial oxide film upon a surface of the substrate. As the film is grown, the lattice of the compound formed at the silicon interface becomes stabilized, and a base layer comprised of an oxide having a sodium chloride-type lattice structure grows epitaxially upon the compound so as to cover the substrate surface. A perovskite may then be grown epitaxially upon the base layer to render a product which incorporates silicon, with its electronic capabilities, with a perovskite having technologically-significant properties of its own.

  1. An overview on the removal of synthetic dyes from water by electrochemical advanced oxidation processes.

    Science.gov (United States)

    Nidheesh, P V; Zhou, Minghua; Oturan, Mehmet A

    2018-04-01

    Wastewater containing dyes are one of the major threats to our environment. Conventional methods are insufficient for the removal of these persistent organic pollutants. Recently much attention has been received for the oxidative removal of various organic pollutants by electrochemically generated hydroxyl radical. This review article aims to provide the recent trends in the field of various Electrochemical Advanced Oxidation Processes (EAOPs) used for removing dyes from water medium. The characteristics, fundamentals and recent advances in each processes namely anodic oxidation, electro-Fenton, peroxicoagulation, fered Fenton, anodic Fenton, photoelectro-Fenton, sonoelectro-Fenton, bioelectro-Fenton etc. have been examined in detail. These processes have great potential to destroy persistent organic pollutants in aqueous medium and most of the studies reported complete removal of dyes from water. The great capacity of these processes indicates that EAOPs constitute a promising technology for the treatment of the dye contaminated effluents. Copyright © 2018 Elsevier Ltd. All rights reserved.

  2. Beyond Diabetes: Does Obesity-Induced Oxidative Stress Drive the Aging Process?

    Directory of Open Access Journals (Sweden)

    Adam B. Salmon

    2016-07-01

    Full Text Available Despite numerous correlative data, a causative role for oxidative stress in mammalian longevity has remained elusive. However, there is strong evidence that increased oxidative stress is associated with exacerbation of many diseases and pathologies that are also strongly related to advanced age. Obesity, or increased fat accumulation, is one of the most common chronic conditions worldwide and is associated with not only metabolic dysfunction but also increased levels of oxidative stress in vivo. Moreover, obesity is also associated with significantly increased risks of cardiovascular disease, neurological decline and cancer among many other diseases as well as a significantly increased risk of mortality. In this review, we investigate the possible interpretation that the increased incidence of these diseases in obesity may be due to chronic oxidative stress mediating segmental acceleration of the aging process. Understanding how obesity can alter cellular physiology beyond that directly related to metabolic function could open new therapeutic areas of approach to extend the period of healthy aging among people of all body composition.

  3. Inherent health and environmental risk assessment of nanostructured metal oxide production processes.

    Science.gov (United States)

    Torabifard, Mina; Arjmandi, Reza; Rashidi, Alimorad; Nouri, Jafar; Mohammadfam, Iraj

    2018-01-10

    The health and environmental effects of chemical processes can be assessed during the initial stage of their production. In this paper, the Chemical Screening Tool for Exposure and Environmental Release (ChemSTEER) software was used to compare the health and environmental risks of spray pyrolysis and wet chemical techniques for the fabrication of nanostructured metal oxide on a semi-industrial scale with a capacity of 300 kg/day in Iran. The pollution sources identified in each production process were pairwise compared in Expert Choice software using indicators including respiratory damage, skin damage, and environmental damages including air, water, and soil pollution. The synthesis of nanostructured zinc oxide using the wet chemical technique (with 0.523 wt%) leads to lower health and environmental risks compared to when spray pyrolysis is used (with 0.477 wt%). The health and environmental risk assessment of nanomaterial production processes can help select safer processes, modify the operation conditions, and select or modify raw materials that can help eliminate the risks.

  4. Treatment of toxic and hazardous organic wastes by wet oxidation process with oxygenated water at low temperature

    International Nuclear Information System (INIS)

    Piccinno, T.; Salluzzo, A.; Nardi, L.; Gili, M.; Luce, A.; Troiani, F.; Cornacchia, G.

    1989-11-01

    The wet oxidation process using air or molecular oxygen is a well-known process from long time. It is suitable to oxidize several types of waste refractory to the usual biological, thermal and chemical treatments. The drastic operating conditions (high pressures and temperatures) prevented its industrial development. In the last years a new interest was assigned to the process for the treatment of nuclear wastes (organic resins and exhaust organic wastes); the treatment is carried out at widely reduced operating conditions (atmospheric pressure and boiling temperature) by means of metallic catalysts and hydrogen peroxide. With some limits, the wet oxidation with hydrogen peroxide at low temperature can be applied to conventional waste waters containing toxic organic compounds. In the present report are summarized the activities developed at ENEA Fuel Cycle Department by the task force 'Deox' constituted by laboratory and plant specialists in order to verify the application of the wet oxidation process to the treatment of the toxic wastes. (author)

  5. Review of the literature for dry reprocessing oxide, metal, and carbide fuel: The AIROX, RAHYD, and CARBOX pyrochemical processes

    Energy Technology Data Exchange (ETDEWEB)

    Hoyt, R.C.; Rhee, B.W. [Rockwell International Corp., Canoga Park, CA (United States). Energy Systems Group

    1979-09-30

    The state of the art of dry processing oxide, carbide, and metal fuel has been determined through an extensive literature review. Dry processing in one of the most proliferation resistant fuel reprocessing technologies available to date, and is one of the few which can be exported to other countries. Feasibility has been established for oxide, carbide, and metal fuel on a laboratory scale, and large-scale experiments on oxide and carbide fuel have shown viability of the dry processing concept. A complete dry processing cycle has been demonstrated by multicycle processing-refabrication-reirradiation experiments on oxide fuel. Additional experimental work is necessary to: (1) demonstrate the complete fuel cycle for carbide and metal fuel, (2) optimize dry processing conditions, and (3) establish fission product behavior. Dry process waste management is easier than for an aqueous processing facility since wastes are primarily solids and gases. Waste treatment can be accomplished by techniques which have been, or are being, developed for aqueous plants.

  6. Process for producing metal oxide kernels and kernels so obtained

    International Nuclear Information System (INIS)

    Lelievre, Bernard; Feugier, Andre.

    1974-01-01

    The process desbribed is for producing fissile or fertile metal oxide kernels used in the fabrication of fuels for high temperature nuclear reactors. This process consists in adding to an aqueous solution of at least one metallic salt, particularly actinide nitrates, at least one chemical compound capable of releasing ammonia, in dispersing drop by drop the solution thus obtained into a hot organic phase to gel the drops and transform them into solid particles. These particles are then washed, dried and treated to turn them into oxide kernels. The organic phase used for the gel reaction is formed of a mixture composed of two organic liquids, one acting as solvent and the other being a product capable of extracting the anions from the metallic salt of the drop at the time of gelling. Preferably an amine is used as product capable of extracting the anions. Additionally, an alcohol that causes a part dehydration of the drops can be employed as solvent, thus helping to increase the resistance of the particles [fr

  7. Modification in oxidative processes in muscle tissues exposed to laser- and light-emitting diode radiation.

    Science.gov (United States)

    Monich, Victor A; Bavrina, Anna P; Malinovskaya, Svetlana L

    2018-01-01

    Exposure of living tissues to high-intensity red or near-infrared light can produce the oxidative stress effects both in the target zone and adjacent ones. The protein oxidative modification (POM) products can be used as reliable and early markers of oxidative stress. The contents of modified proteins in the investigated specimens can be evaluated by the 2,4-dinitrophenylhydrazine assay (the DNPH assay). Low-intensity red light is able to decrease the activity of oxidative processes and the DNPH assay data about the POM products in the biological tissues could show both an oxidative stress level and an efficiency of physical agent protection against the oxidative processes. Two control groups of white rats were irradiated by laser light, the first control group by red light and the second one by near-infrared radiation (NIR).Two experimental groups were consequently treated with laser and red low-level light-emitting diode radiation (LED). One of them was exposed to red laser light + LED and the other to NIR + LED. The fifth group was intact. Each group included ten animals. The effect of laser light was studied by methods of protein oxidative modifications. We measured levels of both induced and spontaneous POM products by the DNPH assay. The dramatic increase in levels of POM products in the control group samples when compared with the intact group data as well as the sharp decrease in the POM products in the experimental groups treated with LED low-level light were statistically significant (p ≤ 0.05). Exposure of skeletal muscles to high-intensity red and near-infrared laser light causes oxidative stress that continues not less than 3 days. The method of measurement of POM product contents by the DNPH assay is a reliable test of an oxidative process rate. Red low-intensity LED radiation can provide rehabilitation of skeletal muscle tissues treated with high-intensity laser light.

  8. Fingerprinting DNA oxidation processes: IR characterization of the 5-methyl-2'-deoxycytidine radical cation.

    Science.gov (United States)

    Bucher, Dominik B; Pilles, Bert M; Pfaffeneder, Toni; Carell, Thomas; Zinth, Wolfgang

    2014-02-24

    Methylated cytidine plays an important role as an epigenetic signal in gene regulation. Its oxidation products are assumed to be involved in active demethylation processes but also in damaging DNA. Here, we report the photochemical production of the 5-methyl-2'-deoxycytidine radical cation via a two-photon ionization process. The radical cation is detected by time-resolved IR spectroscopy and identified by band assignment using density functional theory calculations. Two final oxidation products are characterized with liquid chromatography coupled to mass spectrometry. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Contribution to the study of the redox couple Np(VI)/Np(V) in the presence of uranium(VI) in solutions of nitric acid and nitrous acid; Contribution a l'etude du comportement redox du couple Np(VI)/Np(V) en presence d'uranium VI dans les solutions constituees d'acide nitrique et d'acide nitreux

    Energy Technology Data Exchange (ETDEWEB)

    Arpigny, S. [CEA Marcoule, Dept. de Radiochimie et Procedes, DRP, 30 (France)

    2001-07-01

    The redox behavior of the Np(VI)/Np(V) couple was the subject of a spectrometric study of the Np(VI) reduction reaction in nitric acid solutions (4 to 5 M) containing variable concentrations (1.5 to 3.5 x 10{sup -3} M) of nitrous acid. A low nitrous acid concentration and a high nitric acid concentration were found to favor the stabilization of Np(VI). The stoichiometric coefficients of nitrous acid and nitric acid in the Np(VI) reduction reaction were determined thermodynamically, although only the reaction order with respect to HNO{sub 2} could be calculated from a kinetic analysis. Adding nitrate ions to a HNO{sub 3}/HNO{sub 2} solution enhanced the stability of neptunium at oxidation state +VI, but also increased the reduction rate. When uranium(VI) was added to the HNO{sub 3}/HNO{sub 2} solutions, the total quantity of neptunium at oxidation state +V (either free or as a Np(V)-U(VI) complex) remained practically unchanged, as did the Np(VI) reduction rate. The electrochemical behavior of the Np(VI)/Np(V) couple was investigated in a weak acidic medium by voltammetry with an ultra-micro-electrode (UME). The oxidation wave limiting current variation was a linear function of the Np(V) concentration when a gold UME was used, but not with a platinum UME; the reduction wave limiting current variation versus the Np(V) concentration was linear with either gold or platinum UMEs. The presence of the Np(V)-U(VI) complex in the neptunium solutions was characterized by a shift in the normal apparent potential of the Np(VI)/Np(V) couple toward anodic potentials consistent with the previously determined values of the complexation constants. (author)

  10. Periodic Table of Elements: Los Alamos National Laboratory

    Science.gov (United States)

    metal buttons (photo courtesy Lawrence Berkeley National Laboratory) Neptunium metal buttons (photo Configuration: [Rn]7s25f46d1 Oxidation States: 7, 6, 5, 4, 3, 2 History Named for the planet Neptune (named bombarding uranium with neutrons followed by beta decay would lead to the formation of element 93. In 1934

  11. Engineering application of anaerobic ammonium oxidation process in wastewater treatment.

    Science.gov (United States)

    Mao, Nianjia; Ren, Hongqiang; Geng, Jinju; Ding, Lili; Xu, Ke

    2017-08-01

    Anaerobic ammonium oxidation (Anammox), a promising biological nitrogen removal process, has been verified as an efficient, sustainable and cost-effective alternative to conventional nitrification and denitrification processes. To date, more than 110 full-scale anammox plants have been installed and are in operation, treating industrial NH 4 + -rich wastewater worldwide, and anammox-based technologies are flourishing. This review the current state of the art for engineering applications of the anammox process, including various anammox-based technologies, reactor selection and attempts to apply it at different wastewater plants. Process control and implementation for stable performance are discussed as well as some remaining issues concerning engineering application are exposed, including the start-up period, process disturbances, greenhouse gas emissions and especially mainstream anammox applications. Finally, further development of the anammox engineering application is proposed in this review.

  12. Thorium/uranium mixed oxide nano-crystals: Synthesis, structural characterization and magnetic properties

    International Nuclear Information System (INIS)

    Hudry, Damien; Griveau, Jean-Christophe; Apostolidis, Christos; Colineau, Eric; Rasmussen, Gert; Walter, Olaf; Wang, Di; Venkata Sai Kiran Chakravadhaluna; Courtois, Eglantine; Kubel, Christian

    2014-01-01

    One of the primary aims of the actinide community within nano-science is to develop a good understanding similar to what is currently the case for stable elements. As a consequence, efficient, reliable and versatile synthesis techniques dedicated to the formation of new actinide-based nano-objects (e.g., nano-crystals) are necessary. Hence, a 'library' dedicated to the preparation of various actinide based nano-scale building blocks is currently being developed. Nano-scale building blocks with tunable sizes, shapes and compositions are of prime importance. So far, the non-aqueous synthesis method in highly coordinating organic media is the only approach which has demonstrated the capability to provide size and shape control of actinide-based nano-crystals (both for thorium and uranium, and recently extended to neptunium and plutonium). In this paper, we demonstrate that the non-aqueous approach is also well adapted to control the chemical composition of the nano-crystals obtained when mixing two different actinides. Indeed, the controlled hot co-injection of thorium acetylacetonate and uranyl acetate (together with additional capping agents) into benzyl ether can be used to synthesize thorium/uranium mixed oxide nano-crystals covering the full compositional spectrum. Additionally, we found that both size and shape are modified as a function of the thorium/uranium ratio. Finally, the magnetic properties of the different thorium/uranium mixed oxide nano-crystals were investigated. Contrary to several reports, we did not observe any ferromagnetic behavior. As a consequence, ferromagnetism cannot be described as a universal feature of nano-crystals of non-magnetic oxides as recently claimed in the literature. (authors)

  13. Contribution to the study of diffusion in rare earth metals and actinides

    International Nuclear Information System (INIS)

    Marbach, Gabriel.

    1978-07-01

    This work describes several experiments carried out in order to understand the process of self diffusion in rare earth and actinides (self diffusion of body centered cubic γ neptunium, diffusion of gadolinium in body centered delta cerium, measurement of the activation volume of face centered cubic γ cerium). The unstable electronic structure of some elements cannot be correlate with anomalous diffusion properties. In fact the diffusion parameters of neptunium and plutonium are similar (high diffusivity and low activation energy) whereas the electronic structure of neptunium is stable and that of plutonium is temperature dependent. The negative activation volume of the body centered cubic phases of plutonium and cerium does not indicate a particular diffusion mechanism since self diffusion is faster under pressure in face centered cubic γ cerium where a vacancy mechanism is assumed according to earlier results. The vacancy mechanism is the most probable diffusion process in the body centered cubic and compact phases of rare earths and actinides [fr

  14. IMPACTS OF ANTIFOAM ADDITIONS AND ARGON BUBBLING ON DEFENSE WASTE PROCESSING FACILITY REDUCTION/OXIDATION

    Energy Technology Data Exchange (ETDEWEB)

    Jantzen, C.; Johnson, F.

    2012-06-05

    During melting of HLW glass, the REDOX of the melt pool cannot be measured. Therefore, the Fe{sup +2}/{Sigma}Fe ratio in the glass poured from the melter must be related to melter feed organic and oxidant concentrations to ensure production of a high quality glass without impacting production rate (e.g., foaming) or melter life (e.g., metal formation and accumulation). A production facility such as the Defense Waste Processing Facility (DWPF) cannot wait until the melt or waste glass has been made to assess its acceptability, since by then no further changes to the glass composition and acceptability are possible. therefore, the acceptability decision is made on the upstream process, rather than on the downstream melt or glass product. That is, it is based on 'feed foward' statistical process control (SPC) rather than statistical quality control (SQC). In SPC, the feed composition to the melter is controlled prior to vitrification. Use of the DWPF REDOX model has controlled the balanjce of feed reductants and oxidants in the Sludge Receipt and Adjustment Tank (SRAT). Once the alkali/alkaline earth salts (both reduced and oxidized) are formed during reflux in the SRAT, the REDOX can only change if (1) additional reductants or oxidants are added to the SRAT, the Slurry Mix Evaporator (SME), or the Melter Feed Tank (MFT) or (2) if the melt pool is bubble dwith an oxidizing gas or sparging gas that imposes a different REDOX target than the chemical balance set during reflux in the SRAT.

  15. The discrimination of the oxidation states of neptunium in sodium hydroxide solutions by means of chromatography on alumina

    International Nuclear Information System (INIS)

    Shiokawa, Yoshinobu; Yamana, Hajimu; Sato, Akiko; Suzuki, Shin

    1982-01-01

    A method of discriminating the oxidation states of Np in a NaOH solution by means of chromatography on alumina is proposed. In a NaOH solution of 0.5 - 1.7 M (1 M = 1 mol dm - 3 ), the separation of Np (VI) from Np (VII) can be made effectively by means of chromatography on alumina. Only a little Np (VI) is adsorbed on alumina the Np (VII) adsorbed to some extent, and the Np (V), strongly, under the same conditions. By applying this chromatographic method, the method of preparing Np (VI) and Np (VII) of a tracer quantity in 1 M NaOH is established. (author)

  16. Reaction Mechanism for m- Xylene Oxidation in the Claus Process by Sulfur Dioxide

    KAUST Repository

    Sinha, Sourab

    2015-09-24

    In the Claus process, the presence of aromatic contaminants such benzene, toluene, and xylenes (BTX), in the H2S feed stream has a detrimental effect on catalytic reactors, where BTX form soot particles and clog and deactivate the catalysts. Among BTX, xylenes are proven to be most damaging contaminant for catalysts. BTX oxidation in the Claus furnace, before they enter catalyst beds, provides a solution to this problem. A reaction kinetics study on m-xylene oxidation by SO2, an oxidant present in Claus furnace, is presented. The density functional theory is used to study the formation of m-xylene radicals (3-methylbenzyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, and 3,5-dimethylphenyl) through H-abstraction and their oxidation by SO2. The mechanism begins with SO2 addition on the radicals through an O-atom rather than the S-atom with the release of 180.0-183.1 kJ/mol of reaction energies. This exothermic reaction involves energy barriers in the range 3.9-5.2 kJ/mol for several m-xylene radicals. Thereafter, O-S bond scission takes place to release SO, and the O-atom remaining on aromatics leads to CO formation. Among four m-xylene radicals, the resonantly stabilized 3-methylbenzyl exhibited the lowest SO2 addition and SO elimination rates. The reaction rate constants are provided to facilitate Claus process simulations to find conditions suitable for BTX oxidation. © 2015 American Chemical Society.

  17. Reaction Mechanism for m- Xylene Oxidation in the Claus Process by Sulfur Dioxide

    KAUST Repository

    Sinha, Sourab; Raj, Abhijeet; Al Shoaibi, Ahmed S.; Chung, Suk-Ho

    2015-01-01

    In the Claus process, the presence of aromatic contaminants such benzene, toluene, and xylenes (BTX), in the H2S feed stream has a detrimental effect on catalytic reactors, where BTX form soot particles and clog and deactivate the catalysts. Among BTX, xylenes are proven to be most damaging contaminant for catalysts. BTX oxidation in the Claus furnace, before they enter catalyst beds, provides a solution to this problem. A reaction kinetics study on m-xylene oxidation by SO2, an oxidant present in Claus furnace, is presented. The density functional theory is used to study the formation of m-xylene radicals (3-methylbenzyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, and 3,5-dimethylphenyl) through H-abstraction and their oxidation by SO2. The mechanism begins with SO2 addition on the radicals through an O-atom rather than the S-atom with the release of 180.0-183.1 kJ/mol of reaction energies. This exothermic reaction involves energy barriers in the range 3.9-5.2 kJ/mol for several m-xylene radicals. Thereafter, O-S bond scission takes place to release SO, and the O-atom remaining on aromatics leads to CO formation. Among four m-xylene radicals, the resonantly stabilized 3-methylbenzyl exhibited the lowest SO2 addition and SO elimination rates. The reaction rate constants are provided to facilitate Claus process simulations to find conditions suitable for BTX oxidation. © 2015 American Chemical Society.

  18. Disintegration and dissolution of spent radioactive cationic exchange resins using Fenton-like oxidation process

    International Nuclear Information System (INIS)

    Wan, Zhong; Xu, Lejin; Wang, Jianlong

    2015-01-01

    Highlights: • The spent radioactive resins could be oxidized by Fenton-like process. • The influencing factors on resin oxidation were evaluated. • Chemical oxygen demand (COD) reduction rate was more than 99%. • SEM and Raman spectrum were used to analyze the resins morphological change. - Abstract: The treatment and disposal of the spent radioactive resins is essential for the sustainable development of the nuclear industry. In this paper, the disintegration and dissolution of spent cationic resins were studied by Fenton-like process. The influencing factors on resin dissolution, such as pH, temperature, type and concentration of catalysts were evaluated. The results showed that the spent resins could be effectively dissolved at pH < 1, [Fe 2+ ] = 0.2 M and T = 97 ± 2 °C. Chemical oxygen demand (COD) reduction rate was more than 99%. The scanning electron microscopy and the Raman spectrum were used to observe the morphological changes of the spent resins during the dissolution process. Fenton-like oxidation is an efficient method for the volume reduction and stabilization of the spent resins before further immobilization

  19. Disintegration and dissolution of spent radioactive cationic exchange resins using Fenton-like oxidation process

    Energy Technology Data Exchange (ETDEWEB)

    Wan, Zhong; Xu, Lejin [Collaborative Innovation Center for Advanced Nuclear Energy Technology, INET, Tsinghua University, Beijing 100084 (China); Wang, Jianlong, E-mail: wangjl@tsinghua.edu.cn [Collaborative Innovation Center for Advanced Nuclear Energy Technology, INET, Tsinghua University, Beijing 100084 (China); Beijing Key Laboratory of Radioactive Wastes Treatment, Tsinghua University, Beijing 100084 (China)

    2015-09-15

    Highlights: • The spent radioactive resins could be oxidized by Fenton-like process. • The influencing factors on resin oxidation were evaluated. • Chemical oxygen demand (COD) reduction rate was more than 99%. • SEM and Raman spectrum were used to analyze the resins morphological change. - Abstract: The treatment and disposal of the spent radioactive resins is essential for the sustainable development of the nuclear industry. In this paper, the disintegration and dissolution of spent cationic resins were studied by Fenton-like process. The influencing factors on resin dissolution, such as pH, temperature, type and concentration of catalysts were evaluated. The results showed that the spent resins could be effectively dissolved at pH < 1, [Fe{sup 2+}] = 0.2 M and T = 97 ± 2 °C. Chemical oxygen demand (COD) reduction rate was more than 99%. The scanning electron microscopy and the Raman spectrum were used to observe the morphological changes of the spent resins during the dissolution process. Fenton-like oxidation is an efficient method for the volume reduction and stabilization of the spent resins before further immobilization.

  20. Electrodeposition of Actinide and Lanthanide Elements

    International Nuclear Information System (INIS)

    Baerring, N.E.

    1966-02-01

    Some deposition parameters for the quantitative electrodeposition of hydrolysis products of plutonium were qualitatively studied at trace concentrations of plutonium. The hydrogen ion concentration, the current and the electrolysis time proved to be the determining factors in the quantitative electrolytic precipitation of plutonium, while other factors such as cathode material, the pretreatment of the cathode surface, the nature of the electrolytic anion, and the oxidation state of plutonium in the starting solution were found to be of less importance. The conditions selected for quantitative electrodeposition of plutonium from slightly acid nitrate solutions on a stainless steel cathode were successfully tried also with uranium, neptunium, americium, cerium and thulium. Details of a procedure used for plating mg amounts of plutonium and neptunium on small stainless steel cylinders are also given

  1. Electrodeposition of Actinide and Lanthanide Elements

    Energy Technology Data Exchange (ETDEWEB)

    Baerring, N E

    1966-02-15

    Some deposition parameters for the quantitative electrodeposition of hydrolysis products of plutonium were qualitatively studied at trace concentrations of plutonium. The hydrogen ion concentration, the current and the electrolysis time proved to be the determining factors in the quantitative electrolytic precipitation of plutonium, while other factors such as cathode material, the pretreatment of the cathode surface, the nature of the electrolytic anion, and the oxidation state of plutonium in the starting solution were found to be of less importance. The conditions selected for quantitative electrodeposition of plutonium from slightly acid nitrate solutions on a stainless steel cathode were successfully tried also with uranium, neptunium, americium, cerium and thulium. Details of a procedure used for plating mg amounts of plutonium and neptunium on small stainless steel cylinders are also given.

  2. Rapid deposition process for zinc oxide film applications in pyroelectric devices

    International Nuclear Information System (INIS)

    Hsiao, Chun-Ching; Yu, Shih-Yuan

    2012-01-01

    Aerosol deposition (AD) is a rapid process for the deposition of films. Zinc oxide is a low toxicity and environmentally friendly material, and it possesses properties such as semiconductivity, pyroelectricity and piezoelectricity without the poling process. Therefore, AD is used to accelerate the manufacturing process for applications of ZnO films in pyroelectric devices. Increasing the temperature variation rate in pyroelectric films is a useful method for enhancing the responsivity of pyroelectric devices. In the present study, a porous ZnO film possessing the properties of large heat absorption and high temperature variation rate is successfully produced by the AD rapid process and laser annealing for application in pyroelectric devices. (paper)

  3. Dose dependent oxidation kinetics of lipids in fish during irradiation processing

    International Nuclear Information System (INIS)

    Tukenmez, I.; Ersen, M.S.; Bakioglu, A.T.; Bicer, A.; Pamuk, V.

    1997-01-01

    Kinetic aspects of the development of lipid oxidation in complex foods as fish in the course of irradiation were analyzed with respect to the associated formation of malonaldehyde (MA) through the reactions modified so as to be consistent with those in complex foods as fish. Air-packed anchovy (Engraulis encrasicholus) samples in polyethylene pouches were irradiated at the doses of 1, 2, 5, 10, 15,20 and 25 kGy at 20 o C in a Cs-137 gamma irradiator of 1.806 kGy/h dose rate. Immediately after each irradiation, MA contents of irradiated and unirradiated samples were determined by thiobarbituric acid test. Based on the MA formation, a kinetic model to simulate the apparent oxidation of lipid in fish as a function of irradiation dose was derived from the rate equations consistent with modified reactions. Kinetic parameters and simulation were related to conditions of lipid oxidation, and associated rancidity state of fish with respect to the doses applied in different irradiation-preservation processes. Numerical values of kinetic parameters based on the MA formation were found as a threshold dose of 0.375 kGy, an apparent yield of 1.871 μmol/kg kGy, and a maximum attainable concentration of 15.853 μmol/kg which may be used for process control and dosimetry. (author)

  4. Graphene oxide for acid catalyzed-reactions: Effect of drying process

    Science.gov (United States)

    Gong, H. P.; Hua, W. M.; Yue, Y. H.; Gao, Z.

    2017-03-01

    Graphene oxides (GOs) were prepared by Hummers method through various drying processes, and characterized by XRD, SEM, FTIR, XPS and N2 adsorption. Their acidities were measured using potentiometric titration and acid-base titration. The catalytic properties were investigated in the alkylation of anisole with benzyl alcohol and transesterification of triacetin with methanol. GOs are active catalysts for both reaction, whose activity is greatly affected by their drying processes. Vacuum drying GO exhibits the best performance in transesterification while freezing drying GO is most active for alkylation. The excellent catalytic behavior comes from abundant surface acid sites as well as proper surface functional groups, which can be obtained by selecting appropriate drying process.

  5. Cosmetic wastewater treatment by coagulation and advanced oxidation processes.

    Science.gov (United States)

    Naumczyk, Jeremi; Bogacki, Jan; Marcinowski, Piotr; Kowalik, Paweł

    2014-01-01

    In this study, the treatment process of three cosmetic wastewater types has been investigated. Coagulation allowed to achieve chemical oxygen demand (COD) removal of 74.6%, 37.7% and 74.0% for samples A (Al2(SO4)3), B (Brentafloc F3) and C (PAX 16), respectively. The Fenton process proved to be effective as well - COD removal was equal to 75.1%, 44.7% and 68.1%, respectively. Coagulation with FeCl3 and the subsequent photo-Fenton process resulted in the best values of final COD removal equal to 92.4%, 62.8% and 90.2%. In case of the Fenton process, after coagulation these values were equal to 74.9%, 50.1% and 84.8%, while in case of the H2O2/UV process, the obtained COD removal was 83.8%, 36.2% and 80.9%. High value of COD removal in the Fenton process carried out for A and C wastewater samples was caused by a significant contribution of the final neutralization/coagulation. Very small effect of the oxidation reaction in the Fenton process in case of sample A resulting from the presence of antioxidants, 'OH radical scavengers' in the wastewater.

  6. Experimental Methodology for Determining Optimum Process Parameters for Production of Hydrous Metal Oxides by Internal Gelation

    Energy Technology Data Exchange (ETDEWEB)

    Collins, J.L.

    2005-10-28

    The objective of this report is to describe a simple but very useful experimental methodology that was used to determine optimum process parameters for preparing several hydrous metal-oxide gel spheres by the internal gelation process. The method is inexpensive and very effective in collection of key gel-forming data that are needed to prepare the hydrous metal-oxide microspheres of the best quality for a number of elements.

  7. Oxidation kinetics of Si and SiGe by dry rapid thermal oxidation, in-situ steam generation oxidation and dry furnace oxidation

    Science.gov (United States)

    Rozé, Fabien; Gourhant, Olivier; Blanquet, Elisabeth; Bertin, François; Juhel, Marc; Abbate, Francesco; Pribat, Clément; Duru, Romain

    2017-06-01

    The fabrication of ultrathin compressively strained SiGe-On-Insulator layers by the condensation technique is likely a key milestone towards low-power and high performances FD-SOI logic devices. However, the SiGe condensation technique still requires challenges to be solved for an optimized use in an industrial environment. SiGe oxidation kinetics, upon which the condensation technique is founded, has still not reached a consensus in spite of various studies which gave insights into the matter. This paper aims to bridge the gaps between these studies by covering various oxidation processes relevant to today's technological needs with a new and quantitative analysis methodology. We thus address oxidation kinetics of SiGe with three Ge concentrations (0%, 10%, and 30%) by means of dry rapid thermal oxidation, in-situ steam generation oxidation, and dry furnace oxidation. Oxide thicknesses in the 50 Å to 150 Å range grown with oxidation temperatures between 850 and 1100 °C were targeted. The present work shows first that for all investigated processes, oxidation follows a parabolic regime even for thin oxides, which indicates a diffusion-limited oxidation regime. We also observe that, for all investigated processes, the SiGe oxidation rate is systematically higher than that of Si. The amplitude of the variation of oxidation kinetics of SiGe with respect to Si is found to be strongly dependent on the process type. Second, a new quantitative analysis methodology of oxidation kinetics is introduced. This methodology allows us to highlight the dependence of oxidation kinetics on the Ge concentration at the oxidation interface, which is modulated by the pile-up mechanism. Our results show that the oxidation rate increases with the Ge concentration at the oxidation interface.

  8. Iron Oxide Films Prepared by Rapid Thermal Processing for Solar Energy Conversion

    DEFF Research Database (Denmark)

    Wickman, B.; da Silva Fanta, Alice Bastos; Burrows, Andrew

    2017-01-01

    Hematite is a promising and extensively investigated material for various photoelectrochemical (PEC) processes for energy conversion and storage, in particular for oxidation reactions. Thermal treatments during synthesis of hematite are found to affect the performance of hematite electrodes...

  9. Mathematical Modeling of Nitrous Oxide Production during Denitrifying Phosphorus Removal Process.

    Science.gov (United States)

    Liu, Yiwen; Peng, Lai; Chen, Xueming; Ni, Bing-Jie

    2015-07-21

    A denitrifying phosphorus removal process undergoes frequent alternating anaerobic/anoxic conditions to achieve phosphate release and uptake, during which microbial internal storage polymers (e.g., Polyhydroxyalkanoate (PHA)) could be produced and consumed dynamically. The PHA turnovers play important roles in nitrous oxide (N2O) accumulation during the denitrifying phosphorus removal process. In this work, a mathematical model is developed to describe N2O dynamics and the key role of PHA consumption on N2O accumulation during the denitrifying phosphorus removal process for the first time. In this model, the four-step anoxic storage of polyphosphate and four-step anoxic growth on PHA using nitrate, nitrite, nitric oxide (NO), and N2O consecutively by denitrifying polyphosphate accumulating organisms (DPAOs) are taken into account for describing all potential N2O accumulation steps in the denitrifying phosphorus removal process. The developed model is successfully applied to reproduce experimental data on N2O production obtained from four independent denitrifying phosphorus removal study reports with different experimental conditions. The model satisfactorily describes the N2O accumulation, nitrogen reduction, phosphate release and uptake, and PHA dynamics for all systems, suggesting the validity and applicability of the model. The results indicated a substantial role of PHA consumption in N2O accumulation due to the relatively low N2O reduction rate by using PHA during denitrifying phosphorus removal.

  10. Application of secondary ion mass spectrometry to the study of a corrosion process: oxidation of uranium by water

    International Nuclear Information System (INIS)

    Cristy, S.S.; Condon, J.B.

    1985-01-01

    Corrosion of metals is an extremely important field with great economic and engineering implications at the Oak Ridge Y-12 Plant. To effectively combat corrosion, one must understand the processes occurring. This paper shows the utility of Secondary Ion Mass Spectrometry (SIMS) data for elucidating the processes occurring in one particular corrosion process - the oxidation of uranium by water - and for validating a theoretical model. It had long been known that the oxidation of uranium by water is retarded by the presence of oxygen gas and the retardation has been assumed to occur by site blocking at the surface. However, when alternate isotopic exposures were made, followed by exposure to a mixture of 16 O 2 and 18 OH 2 , the rapid exchange of 16 O and 18 O occurred in the oxide layer, but the further oxidation by water in this and subsequent exposures was retarded for up to 21 hours. This shows graphically that OH 2 is not held up at the surface and that the retarding mechanism is effective at the oxide/metal interface rather than at the surface. The effectiveness of the O 2 to retard the further water oxidation was much reduced if no water-formed oxide layer were present. The effectiveness was also crystallite related. 12 refs., 5 figs

  11. High Dielectric Performance of Solution-Processed Aluminum Oxide-Boron Nitride Composite Films

    Science.gov (United States)

    Yu, Byoung-Soo; Ha, Tae-Jun

    2018-04-01

    The material compositions of oxide films have been extensively investigated in an effort to improve the electrical characteristics of dielectrics which have been utilized in various electronic devices such as field-effect transistors, and storage capacitors. Significantly, solution-based compositions have attracted considerable attention as a highly effective and practical technique to replace vacuum-based process in large-area. Here, we demonstrate solution-processed composite films consisting of aluminum oxide (Al2O3) and boron nitride (BN), which exhibit remarkable dielectric properties through the optimization process. The leakage current of the optimized Al2O3-BN thin films was decreased by a factor of 100 at 3V, compared to pristine Al2O3 thin film without a loss of the dielectric constant or degradation of the morphological roughness. The characterization by X-ray photoelectron spectroscopy measurements revealed that the incorporation of BN with an optimized concentration into the Al2O3 dielectric film reduced the density of oxygen vacancies which act as defect states, thereby improving the dielectric characteristics.

  12. Analysis of the laser oxidation kinetics process of In-In(2)O(3) MTMO photomasks by laser direct writing.

    Science.gov (United States)

    Xia, Feng; Zhang, Xinzheng; Wang, Meng; Liu, Qian; Xu, Jingjun

    2015-11-02

    One kind of novel grayscale photomask based on Metal-transparent-metallic-oxides (MTMOs) system fabricated by laser direct writing was demonstrated recently. Here, a multilayer oxidation model of In-In(2)O(3) film with a glass substrate was proposed to study the pulsed laser-induced oxidation mechanism. The distribution of the electromagnetic field in the film is calculated by the transfer matrix method. Temperature fields of the model are simulated based on the heat transfer equations with the Finite-Difference Time-Domain method. The oxidation kinetics process is studied based on the laser-induced Cabrera-Mott theory. The simulated oxidation processes are consistent with the experimental results, which mean that our laser-induced oxidation model can successfully interpret the fabrication mechanism of MTMO grayscale photomasks.

  13. Effect of gamma radiation and storage on cholesterol oxidative stability of raw and processed eggs

    International Nuclear Information System (INIS)

    Medina, Marliz Klaumann Julca

    2005-01-01

    The egg have being studied due its nutritional wealth, for show industrial interest as a raw material, e due its higher cholesterol content. At the same time, due its susceptibility to contamination mainly with salmonella, it is being proposed the ionizing radiation as a hygienic measure. Cholesterol is subject to oxidation, that it is facilitated by several factors, among them ionizing radiation. Formed cholesterol oxides, by its turn, show harmful biological properties to human health, as atherogenicity, cytotoxicity, carcinogenicity and mutagenicity, among others. The objectives of this work were evaluate the effect of ionizing radiation over pH, viscosity and color, besides the oxidative stability of cholesterol, in stored and processed crude eggs. With the increase of used doses (1, 2 and 3 KGy), there was an reduction in the viscosity of the egg white and in the color yolk egg, besides the increase in lipidic oxidation, measured through tiobarbituric acid-reactive substances (TBARS). Specifications as humidity, total lipids and egg yolk cholesterol were not influenced. In the subject of humidity and of cholesterol, there was an meaningful alteration due storage (30 days in 4 deg C). The sum of the analyzed oxides didn't variate with the irradiation, only individually, although it did vary with storage. The thermal processing caused an meaningful increase of TBARS, but despite this, the oxides sum didn't differed between treatments. (author)

  14. The role of saliva in the process of oxidative stress – review of literature

    Directory of Open Access Journals (Sweden)

    Anna Krysińska

    2016-12-01

    Full Text Available Background: Saliva constitutes a first line of defence against free radical-mediated oxidative stress, since the process of mastication and digestion promotes lipid peroxidation. During gingival inflammation, gingival crevicular fluid flow increases the change of saliva composition with products from the inflammatory response, modulating oxidative damages in the oral cavity. Authors review the current literature concerning the reactive oxygen species, oxidants, pro-oxidants and antioxidants in saliva, and methods for assessing the antioxidant capacity of saliva. Comparison of salivary antioxidant status in male and female subjects reveales a significant gender-related difference in saliva composition. The current data demonstrate a significant enhancement of the salivary antioxidant system in juvenile idiopathic arthritis patients. Also patients with chronic renal failure, diabetes and on hemodialysis show increase oxidative stress burden in both serum and saliva. The finding of reduced oral peroxidase levels in smoking subjects may represent a contributory mechanism for initiation and progression of cigarette smoke-related oral diseases such as oral cancer. The results of recent studies indicate that the total antioxidant capacity of saliva decreased in children with HIV infection. Conclusion: Whole saliva may contain simply measured indicators of oxidative processes. This may provide a tool for the development and monitoring of new treatment strategies. A non-invasive determination of the salivary concentrations of antioxidants such as superoxide dismutase (SOD and uric acid (UR allows the evaluation of the defensive capacity of the oral mucosa. Still, there is a need for standardization of methods for saliva sampling and testing protocol.

  15. Sequential application of Fenton and ozone-based oxidation process for the abatement of Ni-EDTA containing nickel plating effluents.

    Science.gov (United States)

    Zhao, Zilong; Liu, Zekun; Wang, Hongjie; Dong, Wenyi; Wang, Wei

    2018-07-01

    Treatment of Ni-EDTA in industrial nickel plating effluents was investigated by integrated application of Fenton and ozone-based oxidation processes. Determination of integrated sequence found that Fenton oxidation presented higher apparent kinetic rate constant of Ni-EDTA oxidation and capacity for contamination load than ozone-based oxidation process, the latter, however, was favorable to guarantee the further mineralization of organic substances, especially at a low concentration. Serial-connection mode of two oxidation processes was appraised, Fenton effluent after treated by hydroxide precipitation and filtration negatively affected the overall performance of the sequential system, as evidenced by the removal efficiencies of Ni 2+ and TOC dropping from 99.8% to 98.7%, and from 74.8% to 66.6%, respectively. As a comparison, O 3 /Fe 2+ oxidation process was proved to be more effective than other processes (e.g. O 3 -Fe 2+ , O 3 /H 2 O 2 /Fe 2+ , O 3 /H 2 O 2 -Fe 2+ ), and the final effluent Ni 2+ concentration could satisfied the discharge standard (Fenton reaction, initial influent pH of 3.0, O 3 dosage of 252 mg L -1 , Fe 2+ of 150 mg L -1 , and reaction time of 30 min for O 3 /Fe 2+ oxidation). Furthermore, pilot-scale test was carried out to study the practical treatability towards the real nickel plating effluent, revealing the effective removal of some other co-existence contaminations. And Fenton reaction has contributed most, with the percentage ranging from 72.41% to 93.76%. The economic cost advantage made it a promising alternative to the continuous Fenton oxidation. Copyright © 2018 Elsevier Ltd. All rights reserved.

  16. Development of chemical and biological processes for production of bioethanol. Optimization of the wet oxidation process and characterization of products

    Energy Technology Data Exchange (ETDEWEB)

    Bjerre, A B; Skammelsen Schmidt, A

    1997-02-01

    The combination of the wet oxidation pretreatment process and alkaline hydrolysis was investigated in order to efficiently solubilize the hemicellulose, degrade the lignin, and open the solid crystalline cellulose structure of wheat straw lignocellulose without generating fermentation inhibitors. The effects of temperature, oxygen pressure, reaction time, and concentration of straw were evaluated. The degree of lignin degradation and hemicellulose solubilization increased with the reaction temperature and time. The optimum conditions were 15 minutes at 185 deg. C, producing 9.8 g/L hemicellulose. For quantification of the solubilized hemicellulose the best overall acid hydrolysis was obtained by treatment with 4 %w/v sulfuric acid for 10 minutes. The Aminex HPX-87H column was less sensitive towards impurities than the Aminex HPX-87P column. HPX-87H gave improved recovery and reproducibility, and was chosen for routine quantification of hydrolyzed hemicellulose sugars. The purity of the solid cellulose fraction also improved with higher temperature. The optimum condition for obtaining enzymatic convertible cellulose (90%) was 10 minutes at 170 deg. C using a high carbonate concentration. The hemicellulose yield and recovery were significantly reduced under these conditions indicating that a simultaneous optimal utilization of the hemicellulose and cellulose was difficult. The oxygen pressure and sodium carbonate concentration had little effect on the solubilization of hemicellulose, however, by combining wet oxidation with alkaline hydrolysis the formation of 2-furfural, a known microbial inhibitor, was minimal. Much more hemicellulose and lignin were solubilized from the straw by wet oxidation than by steaming(an alternative process). More cellulose was solubilized (and degraded) by steaming than by wet oxidation. Overall carbohydrates `losses` of 20.1% for steaming and 16.2% for wet oxidation were found. More 2-furfural was formed by steaming than by wet oxidation.

  17. Development of chemical and biological processes for production of bioethanol. Optimization of the wet oxidation process and characterization of products

    International Nuclear Information System (INIS)

    Bjerre, A.B.; Skammelsen Schmidt, A.

    1997-02-01

    The combination of the wet oxidation pretreatment process and alkaline hydrolysis was investigated in order to efficiently solubilize the hemicellulose, degrade the lignin, and open the solid crystalline cellulose structure of wheat straw lignocellulose without generating fermentation inhibitors. The effects of temperature, oxygen pressure, reaction time, and concentration of straw were evaluated. The degree of lignin degradation and hemicellulose solubilization increased with the reaction temperature and time. The optimum conditions were 15 minutes at 185 deg. C, producing 9.8 g/L hemicellulose. For quantification of the solubilized hemicellulose the best overall acid hydrolysis was obtained by treatment with 4 %w/v sulfuric acid for 10 minutes. The Aminex HPX-87H column was less sensitive towards impurities than the Aminex HPX-87P column. HPX-87H gave improved recovery and reproducibility, and was chosen for routine quantification of hydrolyzed hemicellulose sugars. The purity of the solid cellulose fraction also improved with higher temperature. The optimum condition for obtaining enzymatic convertible cellulose (90%) was 10 minutes at 170 deg. C using a high carbonate concentration. The hemicellulose yield and recovery were significantly reduced under these conditions indicating that a simultaneous optimal utilization of the hemicellulose and cellulose was difficult. The oxygen pressure and sodium carbonate concentration had little effect on the solubilization of hemicellulose, however, by combining wet oxidation with alkaline hydrolysis the formation of 2-furfural, a known microbial inhibitor, was minimal. Much more hemicellulose and lignin were solubilized from the straw by wet oxidation than by steaming(an alternative process). More cellulose was solubilized (and degraded) by steaming than by wet oxidation. Overall carbohydrates 'losses' of 20.1% for steaming and 16.2% for wet oxidation were found. More 2-furfural was formed by steaming than by wet oxidation

  18. Mathematical modeling of nitrous oxide production in an anaerobic/oxic/anoxic process.

    Science.gov (United States)

    Ding, Xiaoqian; Zhao, Jianqiang; Hu, Bo; Chen, Ying; Ge, Guanghuan; Li, Xiaoling; Wang, Sha; Gao, Kun; Tian, Xiaolei

    2016-12-01

    This study incorporates three currently known nitrous oxide (N 2 O) production pathways: ammonium-oxidizing bacteria (AOB) denitrification, incomplete hydroxylamine (NH 2 OH) oxidation, and heterotrophic denitrification on intracellular polymers, into a mathematical model to describe N 2 O production in an anaerobic/oxic/anoxic (AOA) process for the first time. The developed model was calibrated and validated by four experimental cases, then evaluated by two independent anaerobic/aerobic (AO) studies from literature. The modeling results displayed good agreement with the measured data. N 2 O was primarily generated in the aerobic stage by AOB denitrification (67.84-81.64%) in the AOA system. Smaller amounts of N 2 O were produced via incomplete NH 2 OH oxidation (15.61-32.17%) and heterotrophic denitrification on intracellular polymers (0-12.47%). The high nitrite inhibition on N 2 O reductase led to the increased N 2 O accumulation in heterotrophic denitrification on intracellular polymers. The new model was capable of modeling nitrification-denitrification dynamics and heterotrophic denitrification on intracellular polymers in the AOA system. Copyright © 2016 Elsevier Ltd. All rights reserved.

  19. Improvements in or relating to processes for reducing the oxygen content of metal oxides

    International Nuclear Information System (INIS)

    James, R.H.; Spooner, J.A.

    1980-01-01

    A process is described for reducing the oxygen content of a metal oxide material (such as an intimate mixture of uranium and plutonium oxides or a mixed oxide of uranium and plutonium) by contacting the material with a hydrogen-containing gas at an elevated temperature, wherein the material is contained in a plurality of carbon crucibles, each crucible having apertured ends and being otherwise a closed vessel, the crucibles being moved through a heated zone in end-to-end contact and thereby forming a duct through which the gas is passed counter-current to the direction of movement of the crucibles. (author)

  20. Solar photoassisted advanced oxidation process of azo dyes.

    Science.gov (United States)

    Prato-Garcia, D; Buitrón, G

    2009-01-01

    Advanced oxidation processes assisted with natural solar radiation in CPC type reactors (parabolic collector compound), was applied for the degradation of three azo dyes: acid orange (AO7), acid red 151 (AR151) and acid blue 113 (AB113). Fenton, Fenton like and ferrioxalate-type complexes showed to be effective for degrade the azo linkage and moieties in different extensions. Initially, the best dose of reagents (Fe(3 + )-H(2)O(2)) was determined through a factorial experimental design, next, using response surface methodologies, the reagent consumption was reduced up to 40%, maintaining in all cases high decolourisation percentages (>98%) after 60 min. of phototreatment. In this work, it was also studied the effect of concentration changes of the influent between 100-300 mg/L and the operation of the photocatalytic process near neutral conditions (pH 6.0-6.5) by using ferrioxalate type complex (FeOx).