WorldWideScience

Sample records for uranium reaction pathways

  1. Competing retention pathways of uranium upon reaction with Fe(II)

    Science.gov (United States)

    Massey, Michael S.; Lezama-Pacheco, Juan S.; Jones, Morris E.; Ilton, Eugene S.; Cerrato, José M.; Bargar, John R.; Fendorf, Scott

    2014-10-01

    Biogeochemical retention processes, including adsorption, reductive precipitation, and incorporation into host minerals, are important in contaminant transport, remediation, and geologic deposition of uranium. Recent work has shown that U can become incorporated into iron (hydr)oxide minerals, with a key pathway arising from Fe(II)-induced transformation of ferrihydrite, (Fe(OH)3·nH2O) to goethite (α-FeO(OH)); this is a possible U retention mechanism in soils and sediments. Several key questions, however, remain unanswered regarding U incorporation into iron (hydr)oxides and this pathway's contribution to U retention, including: (i) the competitiveness of U incorporation versus reduction to U(IV) and subsequent precipitation of UO2; (ii) the oxidation state of incorporated U; (iii) the effects of uranyl aqueous speciation on U incorporation; and, (iv) the mechanism of U incorporation. Here we use a series of batch reactions conducted at pH ∼7, [U(VI)] from 1 to 170 μM, [Fe(II)] from 0 to 3 mM, and [Ca] at 0 or 4 mM coupled with spectroscopic examination of reaction products of Fe(II)-induced ferrihydrite transformation to address these outstanding questions. Uranium retention pathways were identified and quantified using extended X-ray absorption fine structure (EXAFS) spectroscopy, X-ray powder diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy. Analysis of EXAFS spectra showed that 14-89% of total U was incorporated into goethite, upon reaction with Fe(II) and ferrihydrite. Uranium incorporation was a particularly dominant retention pathway at U concentrations ⩽50 μM when either uranyl-carbonato or calcium-uranyl-carbonato complexes were dominant, accounting for 64-89% of total U. With increasing U(VI) and Fe(II) concentrations, U(VI) reduction to U(IV) became more prevalent, but U incorporation remained a functioning retention pathway. These findings highlight the potential importance of U(V) incorporation within iron

  2. TRIMOLECULAR REACTIONS OF URANIUM HEXAFLUORIDE WITH WATER

    Energy Technology Data Exchange (ETDEWEB)

    Westbrook, M.; Becnel, J.; Garrison, S.

    2010-02-25

    The hydrolysis reaction of uranium hexafluoride (UF{sub 6}) is a key step in the synthesis of uranium dioxide (UO{sub 2}) powder for nuclear fuels. Mechanisms for the hydrolysis reactions are studied here with density functional theory and the Stuttgart small-core scalar relativistic pseudopotential and associated basis set for uranium. The reaction of a single UF{sub 6} molecule with a water molecule in the gas phase has been previously predicted to proceed over a relatively sizeable barrier of 78.2 kJ {center_dot} mol{sup -1}, indicating this reaction is only feasible at elevated temperatures. Given the observed formation of a second morphology for the UO{sub 2} product coupled with the observations of rapid, spontaneous hydrolysis at ambient conditions, an alternate reaction pathway must exist. In the present work, two trimolecular hydrolysis mechanisms are studied with density functional theory: (1) the reaction between two UF{sub 6} molecules and one water molecule, and (2) the reaction of two water molecules with a single UF{sub 6} molecule. The predicted reaction of two UF{sub 6} molecules with one water molecule displays an interesting 'fluorine-shuttle' mechanism, a significant energy barrier of 69.0 kJ {center_dot} mol{sup -1} to the formation of UF{sub 5}OH, and an enthalpy of reaction ({Delta}H{sub 298}) of +17.9 kJ {center_dot} mol{sup -1}. The reaction of a single UF{sub 6} molecule with two water molecules displays a 'proton-shuttle' mechanism, and is more favorable, having a slightly lower computed energy barrier of 58.9 kJ {center_dot} mol{sup -1} and an exothermic enthalpy of reaction ({Delta}H{sub 298}) of -13.9 kJ {center_dot} mol{sup -1}. The exothermic nature of the overall UF{sub 6} + 2 {center_dot} H{sub 2}O trimolecular reaction and the lowering of the barrier height with respect to the bimolecular reaction are encouraging; however, the sizable energy barrier indicates further study of the UF{sub 6} hydrolysis reaction

  3. Separation of uranium isotopes by accelerated isotope exchange reactions

    International Nuclear Information System (INIS)

    Seko, M.; Miyake, T.; Inada, K.; Ochi, K.; Sakamoto, T.

    1977-01-01

    A novel catalyst for isotope exchange reaction between uranium(IV) and uranium(VI) compounds enables acceleration of the reaction rate as much as 3000 times to make industrial separation of uranium isotopes economically possible

  4. Uranium fluoride chemistry. Part 1. The gas phase reaction of uranium hexafluoride with alcohols

    International Nuclear Information System (INIS)

    Schnautz, N.G.; Venter, P.J.

    1992-01-01

    The reaction between uranium hexafluoride (UF 6 ) and simple alcohols in the gas phase was observed to proceed by way of three possible reaction pathways involving dehydration, deoxygenative fluorination, and ether formation. These reactions can best be explained by assuming that alcohols first react with UF 6 to afford the alkoxy uranium pentafluoride intermediate ROUF 5 , which reacts further to give the dehydration, deoxygenative fluorination, and ether products. In each of the above three reaction pathways, UF 6 is transformed to UOF 4 , which being as reactive toward alcohols as UF 6 , reacts further with the alcohol in question to finally afford the unreactive uranyl fluoride (UO 2 F 2 ). 6 refs., 2 tabs

  5. Reaction between uranium hexafluoride and trimethylsilylhalides

    Energy Technology Data Exchange (ETDEWEB)

    Brown, D; Berry, J A [UKAEA Atomic Energy Research Establishment, Harwell. Chemistry Div.; Holloway, J H; Staunton, G M [Leicester Univ. (UK). Dept. of Chemistry

    1938-07-01

    Reactions involving 1.1:1 molar ratios of uranium hexafluoride to either trimethylsilylchloride or trimethylsilylbromide in halocarbon solutions yield ..beta..-UF/sub 5/ at room temperature. With 2 mol equivalents of trimethylsilylchloride the product is UF/sub 4/. The reactions appear to proceed via the intermediate formation of unstable brown uranium(VI) chloride and bromide fluorides. Calculations show that UClF/sub 5/ and UCl/sub 2/F/sub 4/ are thermodynamically unstable with respect to the loss of chlorine at room temperature.

  6. The reaction of uranium with moist hydrogen

    International Nuclear Information System (INIS)

    Pearce, R.J.; Kay, P.

    1987-10-01

    The reaction of uranium in moist hydrogen at a total pressure of 101 kPa over the temperature range 105 0 -200 0 C and water vapour pressures in the range 5-100 kPa has been examined in a limited thermogravimetric study. It has been shown that initially there is a period during which only linear kinetics are observed with a rate similar to that exhibited in similarly moist argon, i.e. hydrogen has no apparent effect on the reaction. At water vapour pressures of and above 49 kPa, corresponding to hydrogen:water vapour pressure ratios in the range 1:1 to 1:100, over the exposure times studied (not > 20h) only such linear kinetics are observed. Below this water vapour pressure and after an initial period of linear kinetics a continuously increasing reaction rate was observed in some instances resulting from rapid attach on localised areas. The localised reaction rates were approximately 2-3 orders of magnitude faster than the original linear reaction kinetics and the interaction rates in either moist argon or moist air. Comparison with a single experiment carried out at 150 0 C indicated that breakaway rates were approaching that in dry hydrogen. During breakaway attack there was a significant increase in the relative amounts of uranium hydride formed. The duration of the linear kinetics phase was extended by pre-oxidation of the uranium surface, decreasing temperature at a constant water vapour pressure, or increasing water vapour pressure (or water vapour: hydrogen pressure ratio) at a constant temperature. (author)

  7. Fluorination reaction uranium dioxide by fluorine

    International Nuclear Information System (INIS)

    Ogata, Shinji; Homma, Shunji; Koga, Jiro; Matsumoto, Shiro; Sasahira, Akira; Kawamura, Fumio

    2004-01-01

    Kinetics of the fluorination reaction of uranium dioxide is studied using un-reacted core model with shrinking particles. The model includes the film mass transfer of fluorine gas and its diffusion in the particle. The rate constants of the model are determined by fitting the experimental data for 370-450degC. The model successfully represents the fluorination in this temperature range. The rate control step is identified by examining the rate constants of the model for 300-1,800degC. For temperature range up to 900degC, the fluorination reaction is rate controlling. For over 900degC, both mechanisms of the mass transfer of fluorine and the fluorination reaction control the rate of the fluorination. With further increase of the temperature, however, the fluorination reaction becomes so fast that the mass transfer of fluorine eventually controls the rate of the fluorination. (author)

  8. Combustion kinetics and reaction pathways

    Energy Technology Data Exchange (ETDEWEB)

    Klemm, R.B.; Sutherland, J.W. [Brookhaven National Laboratory, Upton, NY (United States)

    1993-12-01

    This project is focused on the fundamental chemistry of combustion. The overall objectives are to determine rate constants for elementary reactions and to elucidate the pathways of multichannel reactions. A multitechnique approach that features three independent experiments provides unique capabilities in performing reliable kinetic measurements over an exceptionally wide range in temperature, 300 to 2500 K. Recent kinetic work has focused on experimental studies and theoretical calculations of the methane dissociation system (CH{sub 4} + Ar {yields} CH{sub 3} + H + Ar and H + CH{sub 4} {yields} CH{sub 3} + H{sub 2}). Additionally, a discharge flow-photoionization mass spectrometer (DF-PIMS) experiment is used to determine branching fractions for multichannel reactions and to measure ionization thresholds of free radicals. Thus, these photoionization experiments generate data that are relevant to both reaction pathways studies (reaction dynamics) and fundamental thermochemical research. Two distinct advantages of performing PIMS with high intensity, tunable vacuum ultraviolet light at the National Synchrotron Light Source are high detection sensitivity and exceptional selectivity in monitoring radical species.

  9. Some reactions of uranium chloride pentafluoride

    International Nuclear Information System (INIS)

    Downs, A.J.; Gardner, C.J.

    1986-01-01

    The molecule UF 5 Cl has been isolated, together with an excess of UF 6 , in a solid matrix of Ar, N 2 , or CO and characterised by its i.r. spectrum. Under these conditions it dissociates under the action of radiation having wavelengths close to 500 nm to give UF 5 ; OCCl and OCClF are also formed on photolysis in a solid CO matrix, whereas a species believed to be U 2 F 11 is formed on photolysis in a solid N 2 matrix. CCl 3 F solutions of fluoride-rich mixtures of uranium(VI) chloride fluorides have been shown to function as chlorinating, fluorinating, or chlorofluorinating reagents in their reactions with various unsaturated molecules at temperatures low enough to preclude thermal decomposition of the mixed halides ( 0 C). (author)

  10. Reaction of nickel with uranium mononitride

    International Nuclear Information System (INIS)

    Anselin, F.; Calais, D.; Lorenzelli, N.; Passefort, J.C.

    1965-01-01

    UN-Ni system has been investigated in solid phase by diffusion couples UN-Ni or by mixed powders pressed and sintered. Studies have been carried out by micrography, X-rays and microanalysis with a CASTAING microprobe. UN-Ni compatibility is quite good up to 600 C; beyond this temperature diffusion zones corresponding to UNi 5 and U 2 N 3 appear in the couples either reaction : 3 U N + 5 Ni → U 2 N 3 + UNi 5 ; UN + 5 Ni → UNi 5 + 1/2 N 2 takes place from 700 C according to nitrogen pressure involved. For temperatures between 800 and 1000 C nickel solubility in uranium nitride is 1500 ± 500 wt ppm. (authors) [fr

  11. Applying reaction condition index to predict sandstone type uranium deposit

    International Nuclear Information System (INIS)

    Chen Gongxin; Liu Jinhui; Cheng Hai

    2002-01-01

    On the basic of the explanation of reaction condition index, the deduction of reaction condition index calculation principle, the hydrogeological setting in Gongpoquan basin in Baishan, Gansu province and the study of reaction condition index of its water source point, the north Luotuoquan area in Gongpoquan basin seems to be a favourable place for sandstone type uranium deposit, and the prospect area for sandstone type uranium deposit is delimitated

  12. Uranium redox transition pathways in acetate-amended sediments

    Science.gov (United States)

    Bargar, John R.; Williams, Kenneth H.; Campbell, Kate M.; Long, Philip E.; Stubbs, Joanne E.; Suvorova, Elenal I.; Lezama-Pacheco, Juan S.; Alessi, Daniel S.; Stylo, Malgorzata; Webb, Samuel M.; Davis, James A.; Giammar, Daniel E.; Blue, Lisa Y.; Bernier-Latmani, Rizlan

    2013-01-01

    Redox transitions of uranium [from U(VI) to U(IV)] in low-temperature sediments govern the mobility of uranium in the environment and the accumulation of uranium in ore bodies, and inform our understanding of Earth’s geochemical history. The molecular-scale mechanistic pathways of these transitions determine the U(IV) products formed, thus influencing uranium isotope fractionation, reoxidation, and transport in sediments. Studies that improve our understanding of these pathways have the potential to substantially advance process understanding across a number of earth sciences disciplines. Detailed mechanistic information regarding uranium redox transitions in field sediments is largely nonexistent, owing to the difficulty of directly observing molecular-scale processes in the subsurface and the compositional/physical complexity of subsurface systems. Here, we present results from an in situ study of uranium redox transitions occurring in aquifer sediments under sulfate-reducing conditions. Based on molecular-scale spectroscopic, pore-scale geochemical, and macroscale aqueous evidence, we propose a biotic–abiotic transition pathway in which biomass-hosted mackinawite (FeS) is an electron source to reduce U(VI) to U(IV), which subsequently reacts with biomass to produce monomeric U(IV) species. A species resembling nanoscale uraninite is also present, implying the operation of at least two redox transition pathways. The presence of multiple pathways in low-temperature sediments unifies apparently contrasting prior observations and helps to explain sustained uranium reduction under disparate biogeochemical conditions. These findings have direct implications for our understanding of uranium bioremediation, ore formation, and global geochemical processes.

  13. Uranium oxidation: characterization of oxides formed by reaction with water

    International Nuclear Information System (INIS)

    Fuller, E.L. Jr.; Smyrl, N.R.; Condon, J.B.; Eager, M.H.

    1983-01-01

    Three different uranium oxide samples have been characterized with respect to the different preparation techniques. Results show that the water reaction with uranium metal occurs cyclically forming laminar layers of oxide which spall off due to the strain at the oxide/metal interface. Single laminae are released if liquid water is present due to the prizing penetration at the reaction zone. The rate of reaction of water with uranium is directly proportional to the amount of adsorbed water on the oxide product. Rapid transport is effected through the open hydrous oxide product. Dehydration of the hydrous oxide irreversibly forms a more inert oxide which cannot be rehydrated to the degree that prevails in the original hydrous product of uranium oxidation with water. 27 figures

  14. Reaction of uranium and the fluorocarbon FC-75

    Science.gov (United States)

    Young, R. H.

    1985-04-01

    Because of criticality concerns with water cooling in enriched uranium upgrading, a fluorocarbon has been evaluated as a replacement coolant for internal module components in the Plasma Separation Process (PSP). The interaction of bulk uranium and of powdered uranium with FC-75 has been investigated at temperatures between 200 and 700 C. The gas pressure and the metal temperature were monitored as a function of time. Modest temperature changes of 50 to 100 C were observed for the bulk uranium/fluorocarbon reaction. Much larger changes (up to 1000 C) were noted for the reaction involving high surface area uranium powder. These temperature transients, particularly for the powdered uranium reaction, were short-lived ( 10 seconds) and indicative of the formation of a protective layer of reaction products. Analysis of residual gas products by infrared spectroscopy indicated that one potentially serious hazard, UF6, was not present; however, several small toxic fluorocarbons were produced by thermolysis and/or reaction. X-ray diffraction analysis of the residual solids indicated UF4 and UO2 were the major solid products.

  15. Reaction of nickel with uranium mononitride; Reaction du nickel avec le nitrure d'uranium

    Energy Technology Data Exchange (ETDEWEB)

    Anselin, F; Calais, D; Lorenzelli, N; Passefort, J C [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1965-07-01

    UN-Ni system has been investigated in solid phase by diffusion couples UN-Ni or by mixed powders pressed and sintered. Studies have been carried out by micrography, X-rays and microanalysis with a CASTAING microprobe. UN-Ni compatibility is quite good up to 600 C; beyond this temperature diffusion zones corresponding to UNi{sub 5} and U{sub 2}N{sub 3} appear in the couples either reaction : 3 U N + 5 Ni {yields} U{sub 2}N{sub 3} + UNi{sub 5}; UN + 5 Ni {yields} UNi{sub 5}+ 1/2 N{sub 2} takes place from 700 C according to nitrogen pressure involved. For temperatures between 800 and 1000 C nickel solubility in uranium nitride is 1500 {+-} 500 wt ppm. (authors) [French] Le systeme UN-Ni a ete etudie par diffusion en phase solide a partir de couples (UN-Ni) ou de melanges pulverulents presses et frittes. Les techniques utilisees sont la micrographie, les rayons X et l'analyse ponctuelle a la microsonde de CASTAING. La compatibilite UN-Ni est bonne jusqu'a 600 C; au-dela il apparait dans les couples de diffusion des zones correspondant a UNi{sub 5} et U{sub 2}N{sub 3}. L'une ou l'autre des deux reactions: 3UN + 5 Ni {yields} U{sub 2}N{sub 3} + UNi{sub 5}; UN + 5 Ni {yields} UNi{sub 5} + 1/2 N{sub 2} se produisant des 700 C suivant la pression d'azote exercee. La solubilite du nickel dans le nitrure d'uranium pour des temperatures comprises entre 800 et 1000 C est de 1500 {+-} 500 ppm en poids. (auteurs)

  16. Study of reactions for the production of uranium titrafluoride and uranium hexafluoride

    International Nuclear Information System (INIS)

    Guzella, M.F.R.

    1985-01-01

    The main production processes of uranium hexafluoride in pilot plants and industrial facilities are described. The known reactions confirmed in laboratory experiments that lead to Uf 6 or other intermediate fluorides are discussed. For the purpose of determining a thermodinamically feasible reaction involving the sulfur hexafluoride as fluorinating agent, a mock-up facility was designed and constructed as a part of the R and D work planned at the CDTN (Nuclebras Center for Nuclear Technology Development). IN the uranium tatrafluoride synthesis employing U 3 O 8 and SF 6 several experimental parameters are studied. The reaction time, gasflow, temperature and stoechiometic relations among reagents are described in detail. (Author) [pt

  17. Literature information applicable to the reaction of uranium oxides with chlorine to prepare uranium tetrachloride

    Energy Technology Data Exchange (ETDEWEB)

    Haas, P.A.

    1992-02-01

    The reaction of uranium oxides and chlorine to prepare anhydrous uranium tetrachloride (UCl{sub 4}) are important to more economical preparation of uranium metal. The most practical reactions require carbon or carbon monoxide (CO) to give CO or carbon dioxide (CO{sub 2}) as waste gases. The chemistry of U-O-Cl compounds is very complex with valances of 3, 4, 5, and 6 and with stable oxychlorides. Literature was reviewed to collect thermochemical data, phase equilibrium information, and results of experimental studies. Calculations using thermodynamic data can identify the probable reactions, but the results are uncertain. All the U-O-Cl compounds have large free energies of formation and the calculations give uncertain small differences of large numbers. The phase diagram for UCl{sub 4}-UO{sub 2} shows a reaction to form uranium oxychloride (UOCl{sub 2}) that has a good solubility in molten UCl{sub 4}. This appears more favorable to good rates of reaction than reaction of solids and gases. There is limited information on U-O-Cl salt properties. Information on the preparation of titanium, zirconium, silicon, and thorium tetrachlorides (TiCl{sub 4}, ZrCl{sub 4}, SiCl{sub 4}, ThCl{sub 4}) by reaction of oxides with chlorine (Cl{sub 2}) and carbon has application to the preparation of UCl{sub 4}.

  18. Literature information applicable to the reaction of uranium oxides with chlorine to prepare uranium tetrachloride

    International Nuclear Information System (INIS)

    Haas, P.A.

    1992-02-01

    The reaction of uranium oxides and chlorine to prepare anhydrous uranium tetrachloride (UCl 4 ) are important to more economical preparation of uranium metal. The most practical reactions require carbon or carbon monoxide (CO) to give CO or carbon dioxide (CO 2 ) as waste gases. The chemistry of U-O-Cl compounds is very complex with valances of 3, 4, 5, and 6 and with stable oxychlorides. Literature was reviewed to collect thermochemical data, phase equilibrium information, and results of experimental studies. Calculations using thermodynamic data can identify the probable reactions, but the results are uncertain. All the U-O-Cl compounds have large free energies of formation and the calculations give uncertain small differences of large numbers. The phase diagram for UCl 4 -UO 2 shows a reaction to form uranium oxychloride (UOCl 2 ) that has a good solubility in molten UCl 4 . This appears more favorable to good rates of reaction than reaction of solids and gases. There is limited information on U-O-Cl salt properties. Information on the preparation of titanium, zirconium, silicon, and thorium tetrachlorides (TiCl 4 , ZrCl 4 , SiCl 4 , ThCl 4 ) by reaction of oxides with chlorine (Cl 2 ) and carbon has application to the preparation of UCl 4

  19. Explorations into Chemical Reactions and Biochemical Pathways.

    Science.gov (United States)

    Gasteiger, Johann

    2016-12-01

    A brief overview of the work in the research group of the present author on extracting knowledge from chemical reaction data is presented. Methods have been developed to calculate physicochemical effects at the reaction site. It is shown that these physicochemical effects can quite favourably be used to derive equations for the calculation of data on gas phase reactions and on reactions in solution such as aqueous acidity of alcohols or carboxylic acids or the hydrolysis of amides. Furthermore, it is shown that these physicochemical effects are quite effective for assigning reactions into reaction classes that correspond to chemical knowledge. Biochemical reactions constitute a particularly interesting and challenging task for increasing our understanding of living species. The BioPath.Database is a rich source of information on biochemical reactions and has been used for a variety of applications of chemical, biological, or medicinal interests. Thus, it was shown that biochemical reactions can be assigned by the physicochemical effects into classes that correspond to the classification of enzymes by the EC numbers. Furthermore, 3D models of reaction intermediates can be used for searching for novel enzyme inhibitors. It was shown in a combined application of chemoinformatics and bioinformatics that essential pathways of diseases can be uncovered. Furthermore, a study showed that bacterial flavor-forming pathways can be discovered. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Uranium Metal Reaction Behavior in Water, Sludge, and Grout Matrices

    Energy Technology Data Exchange (ETDEWEB)

    Delegard, Calvin H.; Schmidt, Andrew J.

    2009-05-27

    This report summarizes information and data on the reaction behavior of uranium metal in water, in water-saturated simulated and genuine K Basin sludge, and in grout matrices. This information and data are used to establish the technical basis for metallic uranium reaction behavior for the K Basin Sludge Treatment Project (STP). The specific objective of this report is to consolidate the various sources of information into a concise document to serve as a high-level reference and road map for customers, regulators, and interested parties outside the STP (e.g., external reviewers, other DOE sites) to clearly understand the current basis for the corrosion of uranium metal in water, sludge, and grout.

  1. Uranium Metal Reaction Behavior in Water, Sludge, and Grout Matrices

    Energy Technology Data Exchange (ETDEWEB)

    Delegard, Calvin H.; Schmidt, Andrew J.

    2008-09-25

    This report summarizes information and data on the reaction behavior of uranium metal in water, in water-saturated simulated and genuine K Basin sludge, and in grout matrices. This information and data are used to establish the technical basis for metallic uranium reaction behavior for the K Basin Sludge Treatment Project (STP). The specific objective of this report is to consolidate the various sources of information into a concise document to serve as a high-level reference and road map for customers, regulators, and interested parties outside the STP (e.g., external reviewers, other DOE sites) to clearly understand the current basis for the corrosion of uranium metal in water, sludge, and grout.

  2. Reaction rate constant for uranium in water and water vapor

    Energy Technology Data Exchange (ETDEWEB)

    TRIMBLE, D.J.

    1998-11-09

    The literature on uranium oxidation in water and oxygen free water vapor was reviewed. Arrhenius rate equations were developed from the review data. These data and equations will be used as a baseline from which to compare reaction rates measured for K Basin fuel.

  3. Kinetics of gaseous uranium hexafluoride reaction with hydrogen chloride

    International Nuclear Information System (INIS)

    Ezubchenko, A.N.; Ilyukhin, A.I.; Merzlyakov, A.V.

    1993-01-01

    Kinetics of decrease of concentration of gaseous uranium hexafluoride in reaction with hydrogen chloride at temperatures close to room ones, was investigated by the method of IR spectroscopy. It was established that the process represented the first order reaction by both UF 6 and HCl. Activation energy of the reaction was determined: 7.6 ± 0.7 kcal/mol. Specific feature of reaction kinetics was noted: inversely proportional dependence of effective constant on UF 6 initial pressure. 5 refs., 3 figs

  4. Chemometric approach for prediction of uranium pathways in the soil

    International Nuclear Information System (INIS)

    Stojanovic, Mirjana; Nihajlovic, Marija; Petrovic, Jelena; Petrovic, Marija; Sostaric, Tanja; Milojkovic, Jelena; Pezo, Lato

    2014-01-01

    Understanding the effect of soil parameters (pH, Eh and organic and inorganic ligands availability) on uranium mobility under different geochemical conditions is fundamental for reliable prediction of its behaviour and fate in the environment. In this study, the impact of total and available phosphorus content, humus and acidity of Serbian agricultural soils on the content of total and available uranium were evaluated by Response Surface Methodology (RSM), second order polynomial regression models (SOPs) and artificial neural networks (ANNs). The performance of ANNs was compared with the performance of SOPs and experimental results. SOPs showed high coefficients of determination (0.785-0.956), while ANN model performed high prediction accuracy: 0.8893-0.904. According to the results, total and available uranium content in the soil were mostly affected by pH, statistically significant at p < 0.05 level. For the same responses the total phosphorus was found to be also very influential, statistically significant at p < 0.05 and p < 0.10 levels. The impact of available phosphorus and humus was much more influential on total and available uranium content, compared to total phosphorus content. Proposed chemometric approach will be very helpful in preserving the natural resources and practical application for risk assessment modeling of uranium environmental pathways.

  5. Serpentinization reaction pathways: implications for modeling approach

    Energy Technology Data Exchange (ETDEWEB)

    Janecky, D.R.

    1986-01-01

    Experimental seawater-peridotite reaction pathways to form serpentinites at 300/sup 0/C, 500 bars, can be accurately modeled using the EQ3/6 codes in conjunction with thermodynamic and kinetic data from the literature and unpublished compilations. These models provide both confirmation of experimental interpretations and more detailed insight into hydrothermal reaction processes within the oceanic crust. The accuracy of these models depends on careful evaluation of the aqueous speciation model, use of mineral compositions that closely reproduce compositions in the experiments, and definition of realistic reactive components in terms of composition, thermodynamic data, and reaction rates.

  6. Uranium/water vapor reactions in gaseous atmospheres

    International Nuclear Information System (INIS)

    Jackson, R.L.; Condon, J.B.; Steckel, L.M.

    1977-07-01

    Experiments have been performed to determine the effect of varying humidities, gaseous atmospheres, and temperatures on the uranium/water vapor reaction. A balance, which allowed continuous in-system weighings, was used to determine the rates of the uranium/water vapor reactions at water vapor pressures of 383, 1586, and 2853 Pa and at temperatures of 80, 100, and 150 0 C in atmospheres of hydrogen, argon, or argon/oxygen mixtures. Based on rate data, the reactions were characterized as hydriding or nonhydriding. Hydriding reactions were found to be preferred in moist hydrogen systems at the higher temperatures and the lower humidities. The presence of hydrogen in hydriding systems was found to initially inhibit the reaction, but causes an acceleration of the rate in the final stages. In general, reaction rates of hydriding systems approached the hydriding rates calculated and observed in dry hydrogen. Hydriding and nonhydriding reaction rates showed a positive correlation to temperature and water vapor pressure. Final reaction rates in moist argon/oxygen mixtures of 1.93, 4.57, and 9.08 mole percent oxygen were greater than the rates observed in moist hydrogen or argon. Final reaction rates were negatively correlated to the oxygen concentration

  7. Reaction of water vapor with a clean liquid uranium surface

    International Nuclear Information System (INIS)

    Siekhaus, W.

    1985-01-01

    To study the reaction of water vapor with uranium, we have exposed clean liquid uranium surfaces to H 2 O under UHV conditions. We have measured the surface concentration of oxygen as a function of exposure, and determined the maximum attainable surface oxygen concentration X 0 /sup s/ as a function of temperature. We have used these measurements to estimate, close to the melting point, the solubility of oxygen (X 0 /sup b/, -4 ) and its surface segregation coefficient β/sup s/(> 10 3 ). 8 refs., 5 figs., 1 tab

  8. Reaction of uranium oxides with chlorine and carbon or carbon monoxide to prepare uranium chlorides

    Energy Technology Data Exchange (ETDEWEB)

    Haas, P.A.; Lee, D.D.; Mailen, J.C.

    1991-11-01

    The preferred preparation concept of uranium metal for feed to an AVLIS uranium enrichment process requires preparation of uranium tetrachloride (UCI{sub 4}) by reacting uranium oxides (UO{sub 2}/UO{sub 3}) and chlorine (Cl{sub 2}) in a molten chloride salt medium. UO{sub 2} is a very stable metal oxide; thus, the chemical conversion requires both a chlorinating agent and a reducing agent that gives an oxide product which is much more stable than the corresponding chloride. Experimental studies in a quartz reactor of 4-cm ID have demonstrated the practically of some chemical flow sheets. Experimentation has illustrated a sequence of results concerning the chemical flow sheets. Tests with a graphite block at 850{degrees}C demonstrated rapid reactions of Cl{sub 2} and evolution of carbon dioxide (CO{sub 2}) as a product. Use of carbon monoxide (CO) as the reducing agent also gave rapid reactions of Cl{sub 2} and formation of CO{sub 2} at lower temperatures, but the reduction reactions were slower than the chlorinations. Carbon powder in the molten salt melt gave higher rates of reduction and better steady state utilization of Cl{sub 2}. Addition of UO{sub 2} feed while chlorination was in progress greatly improved the operation by avoiding the plugging effects from high UO{sub 2} concentrations and the poor Cl{sub 2} utilizations from low UO{sub 2} concentrations. An UO{sub 3} feed gave undesirable effects while a feed of UO{sub 2}-C spheres was excellent. The UO{sub 2}-C spheres also gave good rates of reaction as a fixed bed without any molten chloride salt. Results with a larger reactor and a bottom condenser for volatilized uranium show collection of condensed uranium chlorides as a loose powder and chlorine utilizations of 95--98% at high feed rates. 14 refs., 7 figs., 14 tabs.

  9. Reactions of uranium hexafluoride photolysis products

    Science.gov (United States)

    Lyman, John L.; Laguna, Glenn; Greiner, N. R.

    1985-01-01

    This paper confirms that the ultraviolet photolysis reactions of UF6 in the B band spectral region is simple bond cleavage to UF5 and F. The photolysis products may either recombine to UF6 or the UF5 may dimerize, and ultimately polymerize, to solid UF5 particles. We use four methods to set an upper limit for the rate constant for recombination of krUF6 and UF5 after laser photolysis of the UF6 gas sample.

  10. Multistage reaction pathways in detonating high explosives

    International Nuclear Information System (INIS)

    Li, Ying; Kalia, Rajiv K.; Nakano, Aiichiro; Nomura, Ken-ichi; Vashishta, Priya

    2014-01-01

    Atomistic mechanisms underlying the reaction time and intermediate reaction products of detonating high explosives far from equilibrium have been elusive. This is because detonation is one of the hardest multiscale physics problems, in which diverse length and time scales play important roles. Here, large spatiotemporal-scale reactive molecular dynamics simulations validated by quantum molecular dynamics simulations reveal a two-stage reaction mechanism during the detonation of cyclotrimethylenetrinitramine crystal. Rapid production of N 2 and H 2 O within ∼10 ps is followed by delayed production of CO molecules beyond ns. We found that further decomposition towards the final products is inhibited by the formation of large metastable carbon- and oxygen-rich clusters with fractal geometry. In addition, we found distinct unimolecular and intermolecular reaction pathways, respectively, for the rapid N 2 and H 2 O productions

  11. Identifying Reaction Pathways and their Environments

    DEFF Research Database (Denmark)

    Maronsson, Jon Bergmann

    Finding the mechanisms and estimating the rate of chemical reactions is an essential part of modern research of atomic scale systems. In this thesis, the application of well established methods for reaction rates and paths to important systems for hydrogen storage is considered before developing...... extensions to further identify the reaction environment for a more accurate rate. Complex borohydrides are materials of high hydrogen storage capacity and high thermodynamic stability (too high for hydrogen storage). In an effort to gain insight into the structural transitions of two such materials, Ca(BH4......-interstitial defects. In good agreement with the experiments, C3-type rotations activate at lower temperature than C2-type rotations. In order to investigate the environment of reaction pathways, a method for finding the ridge between first order saddle points on a multidimensional surface was developed...

  12. Multistage reaction pathways in detonating high explosives

    Energy Technology Data Exchange (ETDEWEB)

    Li, Ying [Collaboratory for Advanced Computing and Simulations, Department of Physics and Astronomy, Department of Computer Science, and Department of Chemical Engineering and Materials Science, University of Southern California, Los Angeles, California 90089-0242 (United States); Argonne Leadership Computing Facility, Argonne National Laboratory, Argonne, Illinois 60439 (United States); Kalia, Rajiv K.; Nakano, Aiichiro; Nomura, Ken-ichi; Vashishta, Priya [Collaboratory for Advanced Computing and Simulations, Department of Physics and Astronomy, Department of Computer Science, and Department of Chemical Engineering and Materials Science, University of Southern California, Los Angeles, California 90089-0242 (United States)

    2014-11-17

    Atomistic mechanisms underlying the reaction time and intermediate reaction products of detonating high explosives far from equilibrium have been elusive. This is because detonation is one of the hardest multiscale physics problems, in which diverse length and time scales play important roles. Here, large spatiotemporal-scale reactive molecular dynamics simulations validated by quantum molecular dynamics simulations reveal a two-stage reaction mechanism during the detonation of cyclotrimethylenetrinitramine crystal. Rapid production of N{sub 2} and H{sub 2}O within ∼10 ps is followed by delayed production of CO molecules beyond ns. We found that further decomposition towards the final products is inhibited by the formation of large metastable carbon- and oxygen-rich clusters with fractal geometry. In addition, we found distinct unimolecular and intermolecular reaction pathways, respectively, for the rapid N{sub 2} and H{sub 2}O productions.

  13. Study of reactions between uranium-plutonium mixed oxide and uranium nitride and between uranium oxide and uranium nitride; Etude des reactions entre l`oxyde mixte d`uranium-plutonium et le nitrure d`uranium et entre l`oxyde d`uranium et le nitrure d`uranium

    Energy Technology Data Exchange (ETDEWEB)

    Lecraz, C

    1993-06-11

    A new type of combustible elements which is a mixture of uranium nitride and uranium-plutonium oxide could be used for Quick Neutrons Reactors. Three different studies have been made on the one hand on the reactions between uranium nitride (UN) and uranium-plutonium mixed oxide (U,Pu)O{sub 2}, on the other hand on these between UN and uranium oxide UO{sub 2}. They show a sizeable reaction between nitride and oxide for the studied temperatures range (1573 K to 1973 K). This reaction forms a oxynitride compound, MO{sub x} N{sub y} with M=U or M=(U,Pu), whose crystalline structure is similar to oxide`s. Solubility of nitride in both oxides is studied, as the reaction kinetics. (TEC). 32 refs., 48 figs., 22 tabs.

  14. Minimum Energy Pathways for Chemical Reactions

    Science.gov (United States)

    Walch, S. P.; Langhoff, S. R. (Technical Monitor)

    1995-01-01

    Computed potential energy surfaces are often required for computation of such parameters as rate constants as a function of temperature, product branching ratios, and other detailed properties. We have found that computation of the stationary points/reaction pathways using CASSCF/derivative methods, followed by use of the internally contracted CI method to obtain accurate energetics, gives useful results for a number of chemically important systems. The talk will focus on a number of applications to reactions leading to NOx and soot formation in hydrocarbon combustion.

  15. Sintering with a chemical reaction as applied to uranium monocarbide

    International Nuclear Information System (INIS)

    Accary, A.; Caillat, R.

    1960-01-01

    The present paper provides a survey of different investigations whose aim was the preparation and fabrication of uranium monocarbide for nuclear use. If a chemical reaction takes place in the sample during the sintering operation, it may be expected that the atom rearrangements involved in this reaction should favour the sintering process and thereby lower the temperature needed to yield a body of a given density. With this hypothesis in mind, the following methods have been studied: - Sintering of U-C mixtures; - Sintering of UO 2 -C mixtures; - Hot pressing of U-C mixtures; - Extrusion of U-C mixtures. To generalize our result, it could be said that a chemical reaction does not lead to high densification, if one depends on a simple contact between discrete particles. On the contrary, a chemical reaction can help sintering if, as our hot pressing experiments shows, the densification can be achieved prior to the reaction. (author) [fr

  16. Advances in heterogeneous autocatalytic reactions applied to uranium dissolution - 5317

    International Nuclear Information System (INIS)

    Marc, P.; Magnaldo, A.; Godard, J.; Schaer, E.

    2015-01-01

    Dissolution and the solubilization of the chemical elements is a milestone of the head-end of hydrometallurgical processes. When dissolving spent nuclear fuels, additional constraints are added due to the permanent need to strictly control and limit the hold-up. Thus the need for kinetic modeling concerning the dissolution of spent nuclear fuels in nitric acid. This study aims at better understanding the chemical and physical-chemical phenomena of uranium dioxide dissolution reactions in nitric medium. It has been documented that the nitric acid attack of sintering-manufactured uranium dioxide solids occurs through preferential attack sites. This non uniform attack leads to the development of cracks in the solids. Optical microscopy observations show that in some cases, the development of these cracks can lead to the solid cleavage. In this case, we show that the dissolution of the detached fragments is much slower than the time required for the complete cleavage of the solid. These points motivated the measurements of dissolution kinetics using optical microscopy and image processing. A comparison of the measured kinetics with the diffusion kinetics by the mean of the external resistance fraction allows discriminating between measured kinetics corresponding to the chemical reaction or mass-transport limitation. This capability to measure, for the very first time, the 'true' chemical kinetics of the reaction has enabled the confirmation of the highly autocatalytic nature of the reaction, and first evaluation of the constants of the chemical reactions kinetic laws. These data are fundamental to set the kinetic parameters of the chemical reactions in a future model of the dissolution of uranium dioxide sintered pellets. (authors)

  17. Uranium reactions with water vapor. Final progress report

    International Nuclear Information System (INIS)

    Condon, J.B.; Cristy, S.S.; Kirkpatrick, J.R.

    1983-01-01

    The reaction kinetics and ion microprobe mass analyzer (IMMA) depth-profile data for water-oxygen-uranium reaction is explained in terms of the perfusive-precipitation model. This model is reviewed extensively enough to deal with this interacting, 3-element reaction system. The model, based on simultaneous diffusion and product precipitation, can be applied to several systems in a parameterless fashion. It is applied to the uranium-water reaction in the absence and presence of the oxygen inhibitor. The results of the calculations of the model are compared to the experimental rates and the IMMA depth profiles obtained when 18 O-labeled water is used. The predictions are excellent for the pressure dependence of the rates, the activation energies for both the oxygen-poisoned and oxygen-free reactions, the absolute rates for the oxygen-poisoned case, and the IMMA depth profiles. The prediction of the absolute rate for the oxygen-free case is only within a factor of five due to the approximations made for the thermodynamics of the product layer that fixes the oxygen activity. Comparison of the model to experimental data for other metal-oxidation systems such as iron, silicon, copper, zirconium with oxygen, and thorium with water, is also presented to lend credibility to the modeling technique

  18. Compound Nucleus Reactions in LENR, Analogy to Uranium Fission

    Science.gov (United States)

    Hora, Heinrich; Miley, George; Philberth, Karl

    2008-03-01

    The discovery of nuclear fission by Hahn and Strassmann was based on a very rare microanalytical result that could not initially indicate the very complicated details of this most important process. A similarity is discussed for the low energy nuclear reactions (LENRs) with analogies to the yield structure found in measurements of uranium fission. The LENR product distribution measured earlier in a reproducible way in experiments with thin film electrodes and a high density deuteron concentration in palladium has several striking similarities with the uranium fission fragment yield curve.ootnotetextG.H. Miley and J.A. Patterson, J. New Energy 1, 11 (1996); G.H. Miley et al, Proc ICCF6, p. 629 (1997).This comparison is specifically focussed to the Maruhn-Greiner local maximum of the distribution within the large-scale minimum when the fission nuclei are excited. Implications for uranium fission are discussed in comparison with LENR relative to the identification of fission a hypothetical compound nuclear reaction via a element ^306X126 with double magic numbers.

  19. Compact reaction cell for homogenizing and down-blending highly enriched uranium metal

    Science.gov (United States)

    McLean, W. II; Miller, P.E.; Horton, J.A.

    1995-05-02

    The invention is a specialized reaction cell for converting uranium metal to uranium oxide. In a preferred form, the reaction cell comprises a reaction chamber with increasing diameter along its length (e.g. a cylindrical chamber having a diameter of about 2 inches in a lower portion and having a diameter of from about 4 to about 12 inches in an upper portion). Such dimensions are important to achieve the necessary conversion while at the same time affording criticality control and transportability of the cell and product. The reaction chamber further comprises an upper port and a lower port, the lower port allowing for the entry of reactant gases into the reaction chamber, the upper port allowing for the exit of gases from the reaction chamber. A diffuser plate is attached to the lower port of the reaction chamber and serves to shape the flow of gas into the reaction chamber. The reaction cell further comprises means for introducing gases into the reaction chamber and a heating means capable of heating the contents of the reaction chamber. The present invention also relates to a method for converting uranium metal to uranium oxide in the reaction cell of the present invention. The invention is useful for down-blending highly enriched uranium metal by the simultaneous conversion of highly enriched uranium metal and natural or depleted uranium metal to uranium oxide within the reaction cell. 4 figs.

  20. Compact reaction cell for homogenizing and down-blanding highly enriched uranium metal

    Science.gov (United States)

    McLean, II, William; Miller, Philip E.; Horton, James A.

    1995-01-01

    The invention is a specialized reaction cell for converting uranium metal to uranium oxide. In a preferred form, the reaction cell comprises a reaction chamber with increasing diameter along its length (e.g. a cylindrical chamber having a diameter of about 2 inches in a lower portion and having a diameter of from about 4 to about 12 inches in an upper portion). Such dimensions are important to achieve the necessary conversion while at the same time affording criticality control and transportability of the cell and product. The reaction chamber further comprises an upper port and a lower port, the lower port allowing for the entry of reactant gasses into the reaction chamber, the upper port allowing for the exit of gasses from the reaction chamber. A diffuser plate is attached to the lower port of the reaction chamber and serves to shape the flow of gas into the reaction chamber. The reaction cell further comprises means for introducing gasses into the reaction chamber and a heating means capable of heating the contents of the reaction chamber. The present invention also relates to a method for converting uranium metal to uranium oxide in the reaction cell of the present invention. The invention is useful for down-blending highly enriched uranium metal by the simultaneous conversion of highly enriched uranium metal and natural or depleted uranium metal to uranium oxide within the reaction cell.

  1. Reactions of aluminum with uranium fluorides and oxyfluorides

    Energy Technology Data Exchange (ETDEWEB)

    Leitnaker, J.M.; Nichols, R.W.; Lankford, B.S. [Martin Marietta Energy Systems, Inc., Oak Ridge, TN (United States)

    1991-12-31

    Every 30 to 40 million operating hours a destructive reaction is observed in one of the {approximately}4000 large compressors that move UF{sub 6} through the gaseous diffusion plants. Despite its infrequency, such a reaction can be costly in terms of equipment and time. Laboratory experiments reveal that the presence of moderate pressures of UF{sub 6} actually cools heated aluminum, although thermodynamic calculations indicate the potential for a 3000-4000{degrees}C temperature rise. Within a narrow and rather low (<100 torr; 1 torr = 133.322 Pa) pressure range, however, the aluminum is seen to react with sufficient heat release to soften an alumina boat. Three things must occur in order for aluminum to react vigorously with either UF{sub 6} or UO{sub 2}F{sub 2}. 1. An initiating source of heat must be provided. In the compressors, this source can be friction, permitted by disruption of the balance of the large rotating part or by creep of the aluminum during a high-temperature treatment. In the absence of this heat source, compressors have operated for 40 years in UF{sub 6} without significant reaction. 2. The film protecting the aluminum must be breached. Melting (of UF{sub 5} at 620 K or aluminum at 930 K) can cause such a breach in laboratory experiments. In contrast, holding Al samples in UF{sub 6} at 870 K for several hours produces only moderate reaction. Rubbing in the cascade can undoubtedly breach the protective film. 3. Reaction products must not build up and smother the reaction. While uranium products tend to dissolve or dissipate in molten aluminum, AIF{sub 3} shows a remarkable tendency to surround and hence protect even molten aluminum. Hence the initial temperature rise must be rapid and sufficient to move reactants into a temperature region in which products are removed from the reaction site.

  2. Thermogravimetric study of the reaction of uranium oxides with fluorine

    International Nuclear Information System (INIS)

    Komura, Motohiro; Sato, Nobuaki; Kirishima, Akira; Tochiyama, Osamu

    2008-01-01

    Thermogravimetric study of the reaction of uranium oxides with fluorine was conducted by TG-DTA method using anti-corrosion type differential thermobalance. When UO 2 was heated from R.T. to 500 deg. C in 5% F 2 /He atmosphere, the weight increase appeared at ca. 250 deg. C with an exothermic peak. Then the weight decreased slightly with a small exothermic peak followed by the complete volatilization with a large exothermic peak at ca. 350 deg. C. At a flow rate of 15, 30, 60 ml min -1 , there seemed to be no significant change for the fluorination of UO 2 . With the different heating rates of 1, 2, 5 and 10 deg. C min -1 , the fluorination peak shifted to higher temperature with increasing heating rates. For the comparison with thermogravimetric results, phase analysis by XRD method was conducted for the products obtained at different temperatures. At 260 deg. C, the product was UO 2 with a small amount of the intermediate compound, UO 2 F. The amount of this compound increased with increasing temperature up to 320 deg. C. Then another phase of UO 2 F 2 appeared at 340 deg. C but it was immediately fluorinated to the volatile fluoride. When U 3 O 8 was used as a starting material, it was found that the steep weight decrease peak appeared at ca. 350 deg. C and the uranium volatilized completely. This result suggests that fluorination of U 3 O 8 occurs at this temperature forming UF 6 . Uranium trioxide showed the similar fluorination behavior to that of U 3 O 8

  3. Reaction of hydrogen peroxide with uranium zirconium oxide solid solution - Zirconium hinders oxidative uranium dissolution

    Science.gov (United States)

    Kumagai, Yuta; Takano, Masahide; Watanabe, Masayuki

    2017-12-01

    We studied oxidative dissolution of uranium and zirconium oxide [(U,Zr)O2] in aqueous H2O2 solution to estimate (U,Zr)O2 stability to interfacial reactions with H2O2. Studies on the interfacial reactions are essential for anticipating how a (U,Zr)O2-based molten fuel may chemically degrade after a severe accident. The fuel's high radioactivity induces water radiolysis and continuous H2O2 generation. Subsequent reaction of the fuel with H2O2 may oxidize the fuel surface and facilitate U dissolution. We conducted our experiments with (U,Zr)O2 powder (comprising Zr:U mole ratios of 25:75, 40:60, and 50:50) and quantitated the H2O2 reaction via dissolved U and H2O2 concentrations. Although (U,Zr)O2 reacted more quickly than UO2, the dissolution yield relative to H2O2 consumption was far less for (U,Zr)O2 compared to that of UO2. The reaction kinetics indicates that most of the H2O2 catalytically decomposed to O2 at the surface of (U,Zr)O2. We confirmed the H2O2 catalytic decomposition via O2 production (quantitative stoichiometric agreement). In addition, post-reaction Raman scattering spectra of the undissolved (U,Zr)O2 showed no additional peaks (indicating a lack of secondary phase formation). The (U,Zr)O2 matrix is much more stable than UO2 against H2O2-induced oxidative dissolution. Our findings will improve understanding on the molten fuels and provide an insight into decommissioning activities after a severe accident.

  4. Reaction of uranium and plutonium carbides with austenitic steels

    International Nuclear Information System (INIS)

    Mouchnino, M.

    1967-01-01

    The reaction of uranium and plutonium carbides with austenitic steels has been studied between 650 and 1050 deg. C using UC, steel and (UPu)C, steel diffusion couples. The steels are of the type CN 18.10 with or without addition of molybdenum. The carbides used are hyper-stoichiometric. Tests were also carried out with UCTi, UCMo, UPuCTi and UPuCMo. Up to 800 deg. C no marked diffusion of carbon into stainless steel is observed. Between 800 and 900 deg. C the carbon produced by the decomposition of the higher carbides diffuses into the steel. Above 900 deg. C, decomposition of the monocarbide occurs according to a reaction which can be written schematically as: (U,PuC) + (Fe,Ni,Cr) → (U,Pu) Fe 2 + Cr 23 C 6 . Above 950 deg. C the behaviour of UPuCMo and that of the titanium (CN 18.12) and nickel (NC 38. 18) steels is observed to be very satisfactory. (author) [fr

  5. Reactions of laser ablated uranium with nitrogen studied using matrix isolation spectroscopy

    International Nuclear Information System (INIS)

    Sankaran, K.; Sundararajan, K.; Viswanathan, K.S.

    1999-01-01

    Unusual reactions were found to occur when uranium was laser ablated in the presence of nitrogen. The reaction products were trapped in a rigid inert gas matrix and studied using infrared spectroscopy. The species formed were strongly dependent on the partial pressure of nitrogen in the matrix gas used during the ablation process; at low nitrogen partial pressures uranium dinitride (NUN) was the major reaction product, while at high partial pressures of nitrogen the mononitride, UN, was the predominant product. (author)

  6. Radiation pathways and potential health impacts from inactive uranium mill tailings

    International Nuclear Information System (INIS)

    1978-07-01

    Radiation exposure pathways and potential health impacts were estimated as part of the evaluation of radioactive uranium mill tailings at the sites of inactive mills in eight western states. The purpose of this report is to describe in detail the methodology used in performing the pathway analysis and health effects estimations. In addition, specific parameters are presented for each of the 22 uranium mill sites that were evaluated. A computer program, RADAD, developed as part of this program, is described and listed

  7. Aligning Metabolic Pathways Exploiting Binary Relation of Reactions.

    Directory of Open Access Journals (Sweden)

    Yiran Huang

    Full Text Available Metabolic pathway alignment has been widely used to find one-to-one and/or one-to-many reaction mappings to identify the alternative pathways that have similar functions through different sets of reactions, which has important applications in reconstructing phylogeny and understanding metabolic functions. The existing alignment methods exhaustively search reaction sets, which may become infeasible for large pathways. To address this problem, we present an effective alignment method for accurately extracting reaction mappings between two metabolic pathways. We show that connected relation between reactions can be formalized as binary relation of reactions in metabolic pathways, and the multiplications of zero-one matrices for binary relations of reactions can be accomplished in finite steps. By utilizing the multiplications of zero-one matrices for binary relation of reactions, we efficiently obtain reaction sets in a small number of steps without exhaustive search, and accurately uncover biologically relevant reaction mappings. Furthermore, we introduce a measure of topological similarity of nodes (reactions by comparing the structural similarity of the k-neighborhood subgraphs of the nodes in aligning metabolic pathways. We employ this similarity metric to improve the accuracy of the alignments. The experimental results on the KEGG database show that when compared with other state-of-the-art methods, in most cases, our method obtains better performance in the node correctness and edge correctness, and the number of the edges of the largest common connected subgraph for one-to-one reaction mappings, and the number of correct one-to-many reaction mappings. Our method is scalable in finding more reaction mappings with better biological relevance in large metabolic pathways.

  8. A kinetic study of the reaction of water vapor and carbon dioxide on uranium

    International Nuclear Information System (INIS)

    Santon, J.P.

    1964-09-01

    The kinetic study of the reaction of water vapour and carbon dioxide with uranium has been performed by thermogravimetric methods at temperatures between 160 and 410 deg G in the first case, 350 and 1050 deg C in the second: Three sorts of uranium specimens were used: uranium powder, thin evaporated films, and small spheres obtained from a plasma furnace. The experimental results led in the case of water vapour, to a linear rate of reaction controlled by diffusion at the lower temperatures, and by a surface reaction at the upper ones. In the case of carbon dioxide, a parabolic law has been found, controlled by diffusional processes. (author) [fr

  9. Tris(Cyclopentadienyl)Uranium-t-Butyl: Synthesis, reactions, and mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Weydert, M.

    1993-04-01

    Compounds (RC[sub 5]H[sub 4])[sub 3]U(t-Bu) were prepared for R = H, Me, Et. Their decomposition products in aromatic solvents are consistent with a radical decomposition pathway induced by solvent-assisted U-C bond homolysis. NMR was used to study the reactions of (RC[sub 5]H[sub 4])[sub 3]UCl with t-BuLi (R = t-Bu, Me[sub 3]Si). Reactions of (MeC[sub 5]H[sub 4])[sub 3]U(t-Bu) with Lewis bases and fluorocarbons were studied. Analogous reaction chemistry between (RC[sub 5]H[sub 4])[sub 3]ThX systems and t-BuLi was also studied, and reactivity differences between U and Th are discussed. Synthesis of sterically crowded (RC[sub 5]H[sub 4])[sub 4]U compounds is next considered. Reaction of the trivalent (RC[sub 5]H[sub 4])[sub 3]U with (RC[sub 5]H[sub 4])[sub 2]Hg results in formation of (RC[sub 5]H[sub 4])[sub 4]U. Steric congestion, cyclopentadienyl ligand exchange, and electron transfer are discussed. (DLC)

  10. Tris(Cyclopentadienyl)Uranium-t-Butyl: Synthesis, reactions, and mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Weydert, Marc [Univ. of California, Berkeley, CA (United States)

    1993-04-01

    Compounds (RC5H4)3U(t-Bu) were prepared for R = H, Me, Et. Their decomposition products in aromatic solvents are consistent with a radical decomposition pathway induced by solvent-assisted U-C bond homolysis. NMR was used to study the reactions of (RC5H4)3UCl with t-BuLi (R = t-Bu, Me3Si). Reactions of (MeC5H4)3U(t-Bu) with Lewis bases and fluorocarbons were studied. Analogous reaction chemistry between (RC5H4)3ThX systems and t-BuLi was also studied, and reactivity differences between U and Th are discussed. Synthesis of sterically crowded (RC5H4)4U compounds is next considered. Reaction of the trivalent (RC5H4)3U with (RC5H4)2Hg results in formation of (RC5H4)4U. Steric congestion, cyclopentadienyl ligand exchange, and electron transfer are discussed. (DLC)

  11. Filtration and Hydrogen Reaction Modeling in a Depleted Uranium Bed

    Energy Technology Data Exchange (ETDEWEB)

    Jung, Kwang Jin; Kim, Yean Jin; Ahn, Do Hee; Chung, Hong Suk [UST, Daejeon (Korea, Republic of); Kang, Hee Seok [KAERI, Daejeon (Korea, Republic of); Yun, Sei Hun [NFRI, Daejeon (Korea, Republic of)

    2016-05-15

    The storage and delivery system (SDS) stores the hydrogen isotopes and delivers them to the fuel injection system. Depleted uranium (DU) was chosen as a hydrogen isotope storage material. The hydrogen isotopes stored in the SDS are in the form of DU hydride confined in the primary and secondary containment within a glove box with an argon atmosphere. In this study, we performed a modeling study of the SDS. A modeling study is practically important because an experimental study requires comparatively more money and time. We estimated the hydrogen atomic ratio in DU hydride by two empirical equations we formulated. Two empirical equations are used to determine Pressure-Composition-Temperature (PCT) curves and the hydrogen atomic ratio in DU hydride. In addition, we present the effect of pressure and temperature in the hydriding and dehydriding. A modeling study of the SDS was performed in this study. It is practically important to save more money and time. The hydrogen atomic ratio in the DU hydride was estimated using two empirical equations. The two empirical equations are modified and reformulated to determine PCT curves and the hydrogen atomic ratio in DU hydride. All parameters that are required to solve two empirical equations are obtained from the experimental data. The derived parameters are utilized for the numerical simulations. In the numerical simulations, the effects of pressure and temperature on both the hydriding and dehydriding reaction rates are confirmed.

  12. A review of the rates of reaction of unirradiated uranium in gaseous atmospheres

    International Nuclear Information System (INIS)

    Pearce, R.J.

    1989-10-01

    The review collates available quantitative rate data for the reaction of unirradiated uranium in dry and moist air, steam and carbon dioxide based atmospheres at temperatures ranging from room temperature to above the melting point of uranium. Reactions in nitrogen and carbon monoxide are also considered. The aim of the review is to provide a compilation of base data for the hazard analysis of fault conditions relating to Magnox fuel. (author)

  13. Uranium

    International Nuclear Information System (INIS)

    Anon.

    1983-01-01

    Recent decisions by the Australian Government will ensure a significant expansion of the uranium industry. Development at Roxby Downs may proceed and Ranger may fulfil two new contracts but the decision specifies that apart from Roxby Downs, no new mines should be approved. The ACTU maintains an anti-uranium policy but reaction to the decision from the trade union movement has been muted. The Australian Science and Technology Council (ASTEC) has been asked by the Government to conduct an inquiry into a number of issues relating to Australia's role in the nuclear fuel cycle. The inquiry will examine in particular Australia's nuclear safeguards arrangements and the adequacy of existing waste management technology. In two additional decisions the Government has dissociated itself from a study into the feasibility of establishing an enrichment operation and has abolished the Uranium Advisory Council. Although Australian reserves account for 20% of the total in the Western World, Australia accounts for a relatively minor proportion of the world's uranium production

  14. Uranium oxidation: Characterization of oxides formed by reaction with water by infrared and sorption analyses

    Science.gov (United States)

    Fuller, E. L.; Smyrl, N. R.; Condon, J. B.; Eager, M. H.

    1984-04-01

    Three different uranium oxide samples have been characterized with respect to the different preparation techniques. The results show that the water reaction with uranium metal occurs cyclically forming laminar layers of oxide which spall off due to the strain at the oxide/metal interface. Single laminae are released if liquid water is present due to the prizing penetration at the reaction zone. The rate of reaction of water with uranium is directly proportional to the amount of adsorbed water on the oxide product. Rapid transport is effected through the open hydrous oxide product. Dehydration of the hydrous oxide irreversibly forms a more inert oxide which cannot be rehydrated to the degree that prevails in the original hydrous product of uranium oxidation with water. Inert gas sorption analyses and diffuse reflectance infrared studies combined with electron microscopy prove valuable in defining the chemistry and morphology of the oxidic products and hydrated intermediates.

  15. Study on the surface reaction of uranium metal in hydrogen atmosphere with XPS

    International Nuclear Information System (INIS)

    Wang Xiaolin; Fu Yibei; Xie Renshou; Zuo Changming; Zhao Chunpei; Chen Hong

    1998-01-01

    The surface reactions of uranium metal in hydrogen atmosphere at 25 degree C and 200 degree C and effects of temperature and carbon monoxide to the hydriding reaction have been studied by X-ray photoelectron spectroscopy (XPS). The reaction between H 2 and uranium metal at 25 degree C leads to the further oxidation of surface layer of metal due to traces of water vapor. At 200 degree C, it may lead to the hydriding reaction of uranium and the hydriding increases with increasing exposure to H 2 in the initial stages. The U4f 7/2 binding energy of UH 3 has been found to be 378.6 eV. Investigation indicates carbon monoxide inhibits both the hydriding reaction and oxidation on the condition of H 2 -CO atmosphere

  16. Experimental Observation of Nuclear Reactions in Palladium and Uranium

    International Nuclear Information System (INIS)

    J. Dufour; D. Murat; X. Dufour; J. Foos

    2001-01-01

    By submitting various metals (Pd, U) containing hydrogen (from 2000 to 700 000 atoms of hydrogen for 1 000 000 atoms of the host metal) to the combined action of electrical currents and magnetic fields, we have observed a sizeable exothermal effect (from 0.1 to 8 W for 500 mg of metal used). This effect is beyond experimental errors, the energy output being typically 130 to 250% of the energy input and not of chemical origin (exothermal effect in the range of 7000 MJ/mol of metal in the case of palladium and of 60 MJ/mol in the case of uranium). New chemical species also appear in the processes metals. It has been shown by a QED calculation that resonances of long lifetime (s), nuclear dimensions (fm), and low energy of formation (eV) could exist. This concept seems to look like the 'shrunken hydrogen atoms' proposed by various authors. It is indeed very different in two ways (a) being a metastable state, it needs energy to be formed (a few eV) and reverts to normal hydrogen after a few seconds, liberating back its energy of formation (it is thus not the source of the energy observed); (b) its formation can be described as the electron spin/proton nuclear spin interaction becoming first order in the lattice environment (whereas it is third order in a normal hydrogen atom). Moreover, we consider that the hydrex cannot yield a neutron because this reaction is strongly endothermic. To explain our results, we put forward the following working hypothesis: In a metal lattice and under proper conditions, the formation of such resonances (metastable state) could be favored. We propose to call them HYDREX, and we assume that they are actually formed in cold fusion (CF) and low-energy nuclear reaction (LENR) experiments. Once formed, a number of HYDREX could gather around a nucleus of the lattice to form a cluster of nuclear size and of very long life time compared to nuclear time (10 -22 s). In this cluster, nuclear rearrangements could take place, yielding mainly 4 He

  17. Stepwise radical cation Diels-Alder reaction via multiple pathways.

    Science.gov (United States)

    Shimizu, Ryo; Okada, Yohei; Chiba, Kazuhiro

    2018-01-01

    Herein we disclose the radical cation Diels-Alder reaction of aryl vinyl ethers by electrocatalysis, which is triggered by an oxidative SET process. The reaction clearly proceeds in a stepwise fashion, which is a rare mechanism in this class. We also found that two distinctive pathways, including "direct" and "indirect", are possible to construct the Diels-Alder adduct.

  18. A density functional theory study on redox reaction of uranium

    International Nuclear Information System (INIS)

    Toraishi, T.; Kawaguchi, M.; Tsuneda, T.; Tanaka, S.; Nagasaki, S.

    2005-01-01

    Full text of publication follows: Redox reactions are key issues for predicting the migration behavior of actinides in the geosphere, and therefore the chemical processes have to be profoundly understood. However, redox reactions basically involve several elemental processes, and in many cases only limited chemical information can be obtained experimentally. A theoretical approach gives further information which never can be obtained by experiments, such as precise thermodynamic data or reaction pathways of very rapid charge transfer reactions. For this reason, ab initio MO calculations have been applied in the last 5-6 years to the elucidation of redox processes in the U(VI)-Fe(II) or U(VI)-U(IV) system [1- 3]. Those studies provided extremely important chemical information. Nevertheless, the 'huge' calculation costs of ab initio MO techniques now interfere with the extension of the calculation to the 'real' size system: In order to deal with the practically important chemical reactions such as the reduction of actinides at solid surfaces, a large chemical system involving many atoms (electrons) has to be treated. Present ab initio MO techniques at CASSCF, CASPT2 or MRCI level, however, do not allow to handle such a large systems because of the high calculation costs. Density functional theory (DFT) calculations should be also feasible for such systems. Nevertheless, there are very few reports on redox processes of actinides calculated by DFT. This fact was based on the argument that DFT could not treat charge transfer phenomena accurately since the two-electron exchange integral term is not explicitly involved [1-3]. However this is no longer correct: the long-range corrected (LC) energy function was recently developed, and now the charge transfer reaction can safely be calculated by DFT [4]. In the present work, we employ the DFT technique to treat the reduction of U(VI) to U(V) by Fe(II) via the bi-nuclear complex system, and confirm the applicability of the

  19. Uranium

    International Nuclear Information System (INIS)

    Hamdoun, N.A.

    2007-01-01

    The article includes a historical preface about uranium, discovery of portability of sequential fission of uranium, uranium existence, basic raw materials, secondary raw materials, uranium's physical and chemical properties, uranium extraction, nuclear fuel cycle, logistics and estimation of the amount of uranium reserves, producing countries of concentrated uranium oxides and percentage of the world's total production, civilian and military uses of uranium. The use of depleted uranium in the Gulf War, the Balkans and Iraq has caused political and environmental effects which are complex, raising problems and questions about the effects that nuclear compounds left on human health and environment.

  20. redox reactions of uranium in the presence of potassium 2-phospho-17-tungstate

    International Nuclear Information System (INIS)

    Maslov, L.P.; Rykov, A.G.; Sirotinkina, L.V.

    1986-01-01

    The redox reactions of uranium in the presence of potassium 2-phospho-17-tungstate (17W2P) - K 10 P 2 W 17 O 61 - were studied by the methods of spectrophotometry and potentiometry. It was established that in the presence of 17W2P the UO /SUP 2/2/ + ion is reduced by iron(II) to uranium(IV) as a result of the binding of U(IV) into a strong complex with composition (U(p 2 W 17 O 61 ) 2 ) 16- . The peculiarities of the coordination of uranium(IV) by voluminous 17W2P ligands are the cause of the different nature of its interaction with various types of oxidizing agents. It was established that under the action of oxidizing agents (K 2 Cr 2 O 7 , KMnO 4 ), the reduced form of which is a complex with 17W2P, there is a conversion of the complex of uranium(IV) to the corresponding complex of uranium(V), evidently with conservation of a structure analogous to that for uranium(IV). It was also shown that uranium(IV) in complex with 17W2P is practically not oxidized in the cold by persulfate ions which react according to a radical mechanism, whereas weaker oxidizing agents, for example, H 2 O 2 , oxidize it to the UO /SUP 2/2/ + ion. Hypotheses are advanced on the possible mechanisms of the occurrence of the corresponding reactions

  1. Purification of free hydrogen or hydrogen combined in a gaseous mixture by chemical reactions with uranium

    International Nuclear Information System (INIS)

    Caron-Charles, M.; Gilot, B.

    1989-01-01

    Within the framework of the European fusion program, the authors are dealing with the tritium technology aspect. Hydrogen, free or under a combined form within a H 2 , N 2 , NH 3 , O 2 , gaseous mixture, can be purified by chemical reactions with uranium metal. The resulting reactions consist in absorbing the impurities without holding back H 2 . Working conditions have been defined according to two main goals: the formation of stable solid products, especially under hydrogenated atmosphere and the optimization of the material quantities to be used. Thermodynamical considerations have shown that the 950-1300 K temperature range should be suitable for this chemical process. Experiments performed with massive uranium set in a closed reactor at 973 K, have produced hydrogen according to the predicted reactions rates. But they have also pointed out the importance of interferences that might occur in the uranium-gas system, on the gases conversion rates. The comparison between the chemical kinetic ratings of the reactions of pure gases and the chemical kinetic ratings of the reactions of the same gases in mixture, has been set up. It proves that simultaneous reactions can modify the working conditions of the solid products formation, and particularly modify their structure. In this case, chemical kinetic ratings are increased up to their maximal value; that means surface phenomena are favoured as with uranium powder gases reactions. (orig.)

  2. Kynurenine pathway metabolites and enzymes involved in redox reactions.

    Science.gov (United States)

    González Esquivel, D; Ramírez-Ortega, D; Pineda, B; Castro, N; Ríos, C; Pérez de la Cruz, V

    2017-01-01

    Oxido-reduction reactions are a fundamental part of the life due to support many vital biological processes as cellular respiration and glucose oxidation. In the redox reactions, one substance transfers one or more electrons to another substance. An important electron carrier is the coenzyme NAD + , which is involved in many metabolic pathways. De novo biosynthesis of NAD + is through the kynurenine pathway, the major route of tryptophan catabolism, which is sensitive to redox environment and produces metabolites with redox capacity, able to alter biological functions that are controlled by redox-responsive signaling pathways. Kynurenine pathway metabolites have been implicated in the physiology process and in the physiopathology of many diseases; processes that also share others factors as dysregulation of calcium homeostasis, mitochondrial dysfunction, oxidative stress, inflammation and cell death, which impact the redox environment. This review examines in detail the available evidence in which kynurenine pathway metabolites participate in redox reactions and their effect on cellular redox homeostasis, since the knowledge of the main factors and mechanisms that lead to cell death in many neurodegenative disorders and other pathologies, such as mitochondrial dysfunction, oxidative stress and kynurenines imbalance, will allow to develop therapies using them as targets. This article is part of the Special Issue entitled 'The Kynurenine Pathway in Health and Disease'. Copyright © 2016 Elsevier Ltd. All rights reserved.

  3. Studies of the reactions of uranium pentabromide and hexabromouranate(V) in non-aqueous solvents

    International Nuclear Information System (INIS)

    Dehos, R.F.

    1984-01-01

    With the help of IR and electron spectra, the behaviour of uranium pentabromide and hexabromo uranate in non-aqueous nitromethane, nitroethane, bromine, dichlormethane, dibromomethane and acetonitrile was studied. By comparison of the spectra of the solutions in nitromethane with the solutions using other solvents on one side, and on the other side with the solids spectra of the end products, the redox reactions of the uranium V in nitromethane solutions could be more than clarified. Studies were also carried out on the time-dependency of the uranium IV and uranium V contents of the solutions at room temperature and at -20 0 C. The existence of the HUBr 6 which probably appears as an intermediate product was tested in another experiment. First evidence for the existence of UBr 6 as a disproportionation product of UBr 5 were achieved by tests in solutions of acetonitrile at -47 0 C. (RB) [de

  4. Kinetic study of the reaction of uranium with various carbon-containing gases

    International Nuclear Information System (INIS)

    Feron, G.

    1963-09-01

    The kinetic study of the reaction U + CO 2 and U + CO has been performed by a thermogravimetric method on a spherical uranium powder, in temperature ranges respectively from 460 to 690 deg. C and from 570 to 850 deg. C. The reaction with carbon dioxide leads to uranium dioxide. A carbon deposition takes place at the same time. The global reactions is the result of two reactions: U + 2 CO 2 → UO 2 + 2 CO U + CO 2 → UO 2 + C The reaction with carbon monoxide leads to a mixture of dioxide UO 2 , dicarbide UC 2 and free carbon. The main reaction can be written. U + CO → 1/2 UO 2 + 1/2 UC 2 The free carbon results of the disproportionation of the carbon monoxide. A remarkable separation of the two phases UO 2 and UC 2 can be observed. A mechanism accounting for the phenomenon has been proposed. The two reactions U + CO 2 and U + CO begin with a long germination period, after which, the reaction velocity seems to be limited in both cases by the ionic diffusion of oxygen through the uranium dioxide. (author) [fr

  5. Uranium

    International Nuclear Information System (INIS)

    Cuney, M.; Pagel, M.; Leroy, J.

    1992-01-01

    First, this book presents the physico-chemical properties of Uranium and the consequences which can be deduced from the study of numerous geological process. The authors describe natural distribution of Uranium at different scales and on different supports, and main Uranium minerals. A great place in the book is assigned to description and classification of uranium deposits. The book gives also notions on prospection and exploitation of uranium deposits. Historical aspects of Uranium economical development (Uranium resources, production, supply and demand, operating costs) are given in the last chapter. 7 refs., 17 figs

  6. Kinetic study of the reaction of uranium with various carbon-containing gases; Etude cinetique de la reaction sur l'uranium de differents gaz carbones

    Energy Technology Data Exchange (ETDEWEB)

    Feron, G [Commissariat a l' Energie Atomique, Grenoble (France). Centre d' Etudes Nucleaires

    1963-09-15

    The kinetic study of the reaction U + CO{sub 2} and U + CO has been performed by a thermogravimetric method on a spherical uranium powder, in temperature ranges respectively from 460 to 690 deg. C and from 570 to 850 deg. C. The reaction with carbon dioxide leads to uranium dioxide. A carbon deposition takes place at the same time. The global reactions is the result of two reactions: U + 2 CO{sub 2} {yields} UO{sub 2} + 2 CO U + CO{sub 2} {yields} UO{sub 2} + C The reaction with carbon monoxide leads to a mixture of dioxide UO{sub 2}, dicarbide UC{sub 2} and free carbon. The main reaction can be written. U + CO {yields} 1/2 UO{sub 2} + 1/2 UC{sub 2} The free carbon results of the disproportionation of the carbon monoxide. A remarkable separation of the two phases UO{sub 2} and UC{sub 2} can be observed. A mechanism accounting for the phenomenon has been proposed. The two reactions U + CO{sub 2} and U + CO begin with a long germination period, after which, the reaction velocity seems to be limited in both cases by the ionic diffusion of oxygen through the uranium dioxide. (author) [French] L'etude cinetique des reactions U sol + CO{sub 2} gaz et U sol + CO gaz a ete effectuee par thermogravirnetrie sur une poudre d'uranium a grains spheriques, les domaines de temperature etudies s'etendant respectivement de 460 a 690 deg. C et de 570 a 850 deg. C. L'action du dioxyde de carbone conduit au dioxyde d'uranium UO{sub 2}; il se produit en meme temps un depot de carbone. La reaction globale resulte des deux reactions: U + 2 CO{sub 2} {yields} UO{sub 2} + 2 CO U + CO{sub 2} {yields} UO{sub 2} + C Le mono-oxyde de carbone conduit a un melange de dioxyde UO{sub 2}, de dicarbure UC{sub 2} et de carbone libre. La reaction principale s'ecrit: U + CO {yields} 1/2 UO{sub 2} + 1/2 UC{sub 2} Le carbone libre provient de la dismutation du mono-oxyde de carbone. On observe une separation remarquable des deux phases UO{sub 2} et UC{sub 2}; un mecanisme rendant compte de ce phenomene a

  7. Reactions of plutonium and uranium with water: Kinetics and potential hazards

    International Nuclear Information System (INIS)

    Haschke, J.M.

    1995-12-01

    The chemistry and kinetics of reactions between water and the metals and hydrides of plutonium and uranium are described in an effort to consolidate information for assessing potential hazards associated with handling and storage. New experimental results and data from literature sources are presented. Kinetic dependencies on pH, salt concentration, temperature and other parameters are reviewed. Corrosion reactions of the metals in near-neutral solutions produce a fine hydridic powder plus hydrogen. The corrosion rate for plutonium in sea water is a thousand-fold faster than for the metal in distilled water and more than a thousand-fold faster than for uranium in sea water. Reaction rates for immersed hydrides of plutonium and uranium are comparable and slower than the corrosion rates for the respective metals. However, uranium trihydride is reported to react violently if a quantity greater than twenty-five grams is rapidly immersed in water. The possibility of a similar autothermic reaction for large quantities of plutonium hydride cannot be excluded. In addition to producing hydrogen, corrosion reactions convert the massive metals into material forms that are readily suspended in water and that are aerosolizable and potentially pyrophoric when dry. Potential hazards associated with criticality, environmental dispersal, spontaneous ignition and explosive gas mixtures are outlined

  8. XPS study on the surface reaction of uranium metal in H2 and H2-CO atmospheres

    International Nuclear Information System (INIS)

    Wang Xiaolin; Fu Yibei; Xie Renshou

    1996-04-01

    The surface reactions of uranium metal in H 2 and H 2 -CO atmospheres and the effects of temperature and CO on the hydriding reaction have been studied by X-ray photoelectron spectroscopy (XPS). The reaction between commercial H 2 and uranium metal at 25 degree C leads mainly to the further oxidation of surface layer of metal due to traces of water vapour. At 200 degree C, it may lead to the hydriding reaction of uranium and the hydriding increases with increasing the exposure of H 2 . Investigation indicates CO inhibits both the hydriding reaction and oxidation on the condition of H 2 -CO atmospheres. (13 refs., 10 figs.)

  9. Sintering with a chemical reaction as applied to uranium monocarbide; Frittage-reaction dans le cas du monocarbure d'uranium

    Energy Technology Data Exchange (ETDEWEB)

    Accary, A; Caillat, R [Commissariat a l' Energie Atomique, Saclay (France).Centre d' Etudes Nucleaires

    1960-07-01

    The present paper provides a survey of different investigations whose aim was the preparation and fabrication of uranium monocarbide for nuclear use. If a chemical reaction takes place in the sample during the sintering operation, it may be expected that the atom rearrangements involved in this reaction should favour the sintering process and thereby lower the temperature needed to yield a body of a given density. With this hypothesis in mind, the following methods have been studied: - Sintering of U-C mixtures; - Sintering of UO{sub 2}-C mixtures; - Hot pressing of U-C mixtures; - Extrusion of U-C mixtures. To generalize our result, it could be said that a chemical reaction does not lead to high densification, if one depends on a simple contact between discrete particles. On the contrary, a chemical reaction can help sintering if, as our hot pressing experiments shows, the densification can be achieved prior to the reaction. (author) [French] Le present article resume les etudes faites pour le compte du Commissariat a l'Energie Atomique dans le but de preparer du monocarbure d'uranium pour usage nucleaire. Si, en meme temps que l'on fritte une poudre, celle-ci est le siege d'une reaction chimique, on peut s'attendre a ce que le rearrangement atomique d'une reaction chimique favorise le frittage et, ainsi abaisse la temperature de travail necessaire pour obtenir une densite donnee. Nous avons etudie les methodes suivantes: - frittage des melanges U-C; - frittage des melanges UO{sub 2}-C; - frittage sous charge des melanges U-C; - filage des melanges U-C. Nos resultats montrent qu'une reaction chimique en cours de frittage ne conduit pas a un produit de haute densite si on opere sur un melange de poudres. Par contre, elle permet d'atteindre de hautes densites si la densification peut etre obtenue avant la reaction chimique. (auteur)

  10. Oxidation kinetics of reaction products formed in uranium metal corrosion

    International Nuclear Information System (INIS)

    Totemeier, T. C.

    1998-01-01

    The oxidation behavior of uranium metal ZPPR fuel corrosion products in environments of Ar-4%O 2 and Ar-20%O 2 were studied using thermo-gravimetric analysis (TGA). These tests were performed to extend earlier work in this area specifically, to assess plate-to-plate variations in corrosion product properties and the effect of oxygen concentration on oxidation behavior. The corrosion products from two relatively severely corroded plates were similar, while the products from a relatively intact plate were not reactive. Oxygen concentration strongly affected the burning rate of reactive products, but had little effect on low-temperature oxidation rates

  11. Oxidation kinetics of reaction products formed in uranium metal corrosion.

    Energy Technology Data Exchange (ETDEWEB)

    Totemeier, T. C.

    1998-04-22

    The oxidation behavior of uranium metal ZPPR fuel corrosion products in environments of Ar-4%O{sub 2} and Ar-20%O{sub 2} were studied using thermo-gravimetric analysis (TGA). These tests were performed to extend earlier work in this area specifically, to assess plate-to-plate variations in corrosion product properties and the effect of oxygen concentration on oxidation behavior. The corrosion products from two relatively severely corroded plates were similar, while the products from a relatively intact plate were not reactive. Oxygen concentration strongly affected the burning rate of reactive products, but had little effect on low-temperature oxidation rates.

  12. Interest of uranium complexes for the mechanism study of the McMurry reaction

    International Nuclear Information System (INIS)

    Maury, O.

    1997-01-01

    The reducing coupling reactions of ketones in diols and olefins are generally carried out with titanium or samarium compounds. In this work uranium complexes have been used. They have allowed to study the chemical reaction mechanism. This thesis is divided into three parts: 1) the reduction mechanism of uranium tetrachloride by cyclic voltametry has been studied at first. It has been shown that this reduction is followed by a transfer reaction of chlorides between the reduced specie of the higher electronic density and UCl . 2) In the second part is described: the synthesis, the crystal structure, the reactivity of the chemical agents, the stereochemistry of diols and alkenes formation and the pinacolisation reaction catalysis. 3) In the last part, the limits of the McMurry reaction are given by the study of the aromatic ketones pinacolisation reaction by-products. The obtained results show that the complexes of the metals which present a high reducing and oxo-philic (Ti, Sm, U..) character react in a similar way with the carbonyl compounds. If the uranium compounds are less used than those of the titanium in the field of the organic synthesis applications, they are precious auxiliaries and excellent models for reactions mechanisms study and for the synthesis methods optimization. (O.M.)

  13. Estimated dose to man from uranium milling via the terrestrial food-chain pathway

    Energy Technology Data Exchange (ETDEWEB)

    Rayno, D.R.

    1982-01-01

    One of the major pathways of radiological exposure to man from uranium milling operations is through the terrestrial food chain. Studies by various investigators have shown the extent of uptake and distribution of U-238, U-234, Th-230, Ra-226, Pb-210, and Po-210 in plants and animals. These long-lived natural radioisotopes, all nuclides of the uranium decay series, are found in concentrated amounts in uranium mill tailings. Data from these investigations are used to estimate the dose to man from consumption of beef and milk contaminated by the tailings. This dose estimate from this technologically enhanced source is compared with that from average normal dietary intake of these radionuclides from natural sources.

  14. Estimated dose to man from uranium milling via the terrestrial food-chain pathway

    International Nuclear Information System (INIS)

    Rayno, D.R.

    1982-01-01

    One of the major pathways of radiological exposure to man from uranium milling operations is through the terrestrial food chain. Studies by various investigators have shown the extent of uptake and distribution of U-238, U-234, Th-230, Ra-226, Pb-210, and Po-210 in plants and animals. These long-lived natural radioisotopes, all nuclides of the uranium decay series, are found in concentrated amounts in uranium mill tailings. Data from these investigations are used to estimate the dose to man from consumption of beef and milk contaminated by the tailings. This dose estimate from this technologically enhanced source is compared with that from average normal dietary intake of these radionuclides from natural sources

  15. Estimated dose to man from uranium milling via the beef/milk food-chain pathway

    Energy Technology Data Exchange (ETDEWEB)

    Rayno, D R

    1983-12-01

    One of the major pathways of radiological exposure to man from uranium milling operations is through the beef/milk food chain. Studies by various investigators have shown the extent of uptake and distribution of 238U, 234U, 230Th, 226Ra, 210Pb, and 210Po in plants and cattle. These long-lived natural radioisotopes, all nuclides of the uranium decay series, are found in concentrated amounts in uranium mill tailings. In this paper, data from these investigations are used to estimate the dose to man from consumption of beef and milk from cattle that have fed on forage contaminated with the tailings. The estimated doses from this technologically enhanced source are compared with those resulting from average dietary intake of these radionuclides from natural sources.

  16. A multi-pathway model for photosynthetic reaction center

    International Nuclear Information System (INIS)

    Qin, M.; Shen, H. Z.; Yi, X. X.

    2016-01-01

    Charge separation occurs in a pair of tightly coupled chlorophylls at the heart of photosynthetic reaction centers of both plants and bacteria. Recently it has been shown that quantum coherence can, in principle, enhance the efficiency of a solar cell, working like a quantum heat engine. Here, we propose a biological quantum heat engine (BQHE) motivated by Photosystem II reaction center (PSII RC) to describe the charge separation. Our model mainly considers two charge-separation pathways which is more than that typically considered in the published literature. We explore how these cross-couplings increase the current and power of the charge separation and discuss the effects of multiple pathways in terms of current and power. The robustness of the BQHE against the charge recombination in natural PSII RC and dephasing induced by environments is also explored, and extension from two pathways to multiple pathways is made. These results suggest that noise-induced quantum coherence helps to suppress the influence of acceptor-to-donor charge recombination, and besides, nature-mimicking architectures with engineered multiple pathways for charge separations might be better for artificial solar energy devices considering the influence of environments.

  17. Reaction of Tris(cyclopentadienyl)uranium compounds with amines, azides, and related ligands

    International Nuclear Information System (INIS)

    Rosen, R.K.

    1989-12-01

    The trivalent uranium compound, (MeC 5 H 4 ) 3 U(thf), serves as a one- or two-electron reducing agent towards azides, RN 3 . These reactions produce either the uranium(IV) azide, (MeC 5 H 4 ) 3 UN 3 , or uranium(V) imides, (MeC 5 H 4 ) 3 UNR. The role of steric and electronic effects upon this reaction has been investigated using several series of azides. For Me 3 XN 3 , the imides are produced when X = C or Si, both products are formed when X = Ge, and the azide is produced when X = Sn. For Ph 3 XN 3 , the azide is produced when X = C or Sn. For Ph 3-x CH 3 N 3 , the imide is produced when x = 2 and both compounds are produced when x = 1. For substituted phenylazides, RC 6 H 4 N 3 , only the imides are produced. The magnetic properties of uranium diimides, [(MeC 5 H 4 ) 3 U] 2 (μ-NRN), were investigated. Several uranium(III) amines, (MeC 5 H 4 ) 3 U(NH 2 R), were produced from (MeC 5 H 4 ) 3 U(thf) and RNH 2 , and NH 3 was found to be a better ligand towards (MeC 5 H 4 ) 3 U than is PMe 3

  18. The reaction of sintered aluminium products with uranium dioxide and monocarbide

    DEFF Research Database (Denmark)

    Lauritzen, T.; Knudsen, Per

    1965-01-01

    The compatibility of SAP 930 with uranium dioxide and uranium monocarbide was investigated in the temperature range 450–600° C. The results indicate that a severe reaction occurs between SAP 930 and UO2 within 8000 hours at 600° C, a slight reaction at 600° C for 1000 hours and after 11 900 hours...... at 525° C, and no reaction in 14 300 hours at 450° C. Of the three grades of UC tested (hot pressed, arc cast, cold pressed and sintered) the slightly substoichiometric, hot-pressed UC is judged to be least compatible with SAP 930, reaction occurring after 7300 hours at 450° C. No reaction was observed...... between SAP 930 and the other carbides at this temperature. All SAP−UC combinations are incompatible at 600° C for as little as 100 hours of heat treatment. Tests designed to study the effect of a diffusion barrier on the SAP−UC reaction have shown that anodized SAP 930 and the three uranium carbides...

  19. Reaction pathways of the dissociation of methylal: A DFT study

    Energy Technology Data Exchange (ETDEWEB)

    Frey, H -M; Beaud, P; Gerber, T; Mischler, B; Radi, P P; Tzannis, A -P [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1999-08-01

    Schemata for modelling combustion processes do not yet include reaction rates for oxygenated fuels like methylal (DMM) which is considered as an additive or replacement for diesel due to its low sooting propensity. Density functional theory (DFT) studies of the possible reaction pathways for different dissociation steps of methylal are presented. Cleavage of a hydrogen bond to the methoxy group or the central carbon atom were simulated at the BLYP/6-311++G{sup **} level of theory. The results are compared to the experiment when dissociating and/or ionising DMM with femtosecond pulses. (author) 1 fig., 1 tab., 1 ref.

  20. Uranium

    International Nuclear Information System (INIS)

    Anon.

    1984-01-01

    The article briefly discusses the Australian government policy and the attitude of political party factions towards the mining and exporting of the uranium resources in Australia. Australia has a third of the Western World's low-cost uranium resources

  1. Uranium

    International Nuclear Information System (INIS)

    Poty, B.; Cuney, M.; Bruneton, P.; Virlogeux, D.; Capus, G.

    2010-01-01

    With the worldwide revival of nuclear energy comes the question of uranium reserves. For more than 20 years, nuclear energy has been neglected and uranium prospecting has been practically abandoned. Therefore, present day production covers only 70% of needs and stocks are decreasing. Production is to double by 2030 which represents a huge industrial challenge. The FBR-type reactors technology, which allows to consume the whole uranium content of the fuel, is developing in several countries and will ensure the long-term development of nuclear fission. However, the implementation of these reactors (the generation 4) will be progressive during the second half of the 21. century. For this reason an active search for uranium ores will be necessary during the whole 21. century to ensure the fueling of light water reactors which are huge uranium consumers. This dossier covers all the aspects of natural uranium production: mineralogy, geochemistry, types of deposits, world distribution of deposits with a particular attention given to French deposits, the exploitation of which is abandoned today. Finally, exploitation, ore processing and the economical aspects are presented. Contents: 1 - the uranium element and its minerals: from uranium discovery to its industrial utilization, the main uranium minerals (minerals with tetravalent uranium, minerals with hexavalent uranium); 2 - uranium in the Earth's crust and its geochemical properties: distribution (in sedimentary rocks, in magmatic rocks, in metamorphic rocks, in soils and vegetation), geochemistry (uranium solubility and valence in magmas, uranium speciation in aqueous solution, solubility of the main uranium minerals in aqueous solution, uranium mobilization and precipitation); 3 - geology of the main types of uranium deposits: economical criteria for a deposit, structural diversity of deposits, classification, world distribution of deposits, distribution of deposits with time, superficial deposits, uranium

  2. Uranium

    International Nuclear Information System (INIS)

    Mackay, G.A.

    1978-01-01

    The author discusses the contribution made by various energy sources in the production of electricity. Estimates are made of the future nuclear contribution, the future demand for uranium and future sales of Australian uranium. Nuclear power growth in the United States, Japan and Western Europe is discussed. The present status of the six major Australian uranium deposits (Ranger, Jabiluka, Nabarlek, Koongarra, Yeelerrie and Beverley) is given. Australian legislation relevant to the uranium mining industry is also outlined

  3. Uranium

    International Nuclear Information System (INIS)

    1982-01-01

    The development, prospecting, research, processing and marketing of South Africa's uranium industry and the national policies surrounding this industry form the headlines of this work. The geology of South Africa's uranium occurences and their positions, the processes used in the extraction of South Africa's uranium and the utilisation of uranium for power production as represented by the Koeberg nuclear power station near Cape Town are included in this publication

  4. XPS study on the surface reaction of uranium metal with carbon monoxide at 200 degree C

    International Nuclear Information System (INIS)

    Wang Xiaoling; Fu Yibei; Xie Renshou; Huang Ruiliang

    1996-12-01

    The surface reaction of uranium metal with carbon monoxide at 200 degree C has been studied by X-ray photoelectron spectroscopy (XPS). The carbon monoxide adsorption on the surface oxide layer resulted in U4f peak shifting to the lower binding energy and the content of oxygen in the oxide is decreased. O/U radio decreases with increasing the exposure of carbon monoxide to the surface layer. The investigation indicated the surface layer of uranium metal was further reduced in the atmosphere of carbon monoxide at high temperature. (3 refs., 5 figs.)

  5. Reaction of Antimony-Uranium Composite Oxide in the Chlorination Treatment of Waste Catalyst - 13521

    International Nuclear Information System (INIS)

    Sawada, Kayo; Hirabayashi, Daisuke; Enokida, Youichi

    2013-01-01

    The effect of oxygen gas concentration on the chlorination treatment of antimony-uranium composite oxide catalyst waste was investigated by adding different concentrations of oxygen at 0-6 vol% to its chlorination agent of 0.6 or 6 vol% hydrogen chloride gas at 1173 K. The addition of oxygen tended to prevent the chlorination of antimony in the oxide. When 6 vol% hydrogen chloride gas was used, the addition of oxygen up to 0.1 vol% could convert the uranium contained in the catalyst to U 3 O 8 without any significant decrease in the reaction rate compared to that of the treatment without oxygen. (authors)

  6. Uranium

    International Nuclear Information System (INIS)

    Stewart, E.D.J.

    1974-01-01

    A discussion is given of uranium as an energy source in The Australian economy. Figures and predictions are presented on the world supply-demand position and also figures are given on the added value that can be achieved by the processing of uranium. Conclusions are drawn about Australia's future policy with regard to uranium (R.L.)

  7. Uranium

    International Nuclear Information System (INIS)

    Toens, P.D.

    1981-03-01

    The geological setting of uranium resources in the world can be divided in two basic categories of resources and are defined as reasonably assured resources, estimated additional resources and speculative resources. Tables are given to illustrate these definitions. The increasing world production of uranium despite the cutback in the nuclear industry and the uranium requirements of the future concluded these lecture notes

  8. Reaction of uranium and plutonium carbides with nitrogen; Reaction avec l'azote des carbures d'uranium et de plutonium

    Energy Technology Data Exchange (ETDEWEB)

    Lorenzelli, R; Martin, A; Schickel, R [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1966-03-01

    Uranium and plutonium carbides react with nitrogen during the grinding process preceding the final sintering. The reaction occurs even in argon atmospheres containing a few percent of residual nitrogen. The resulting contamination is responsible for the appearance of an equivalent quantity of higher carbide in the sintered products; nitrogen remains quantitatively in the monocarbide phase. UC can be transformed completely into nitride under a nitrogen pressure, at a temperature as low as 400 C. The reaction is more sluggish with PuC. The following reactions take places: UC + 0,8 N{sub 2} {yields}> UN{sub 1.60} + C and PuC + 0,5 N{sub 2} {yields} PuN + C. (authors) [French] Les carbures d'uranium et de plutonium reagissent avec l'azote au cours du broyage qui precede le frittage final. Cette reaction est sensible meme sous des atmospheres d'argon ne contenant que quelques pour cent d'azote. Cette contamination se traduit sur les produits frittes par l'apparition d'une quantite equivalente de carbure superieur, l'azote restant fixe quantitativement dans la phase monocarbure. On peut transformer entierement UC en nitrure par action de l'azote sous pression des 400 C. La reaction est plus difficile avec PuC. Les reactions sont les suivantes: UC + 0,8 N{sub 2} {yields} UN{sub 1.60} + C et PuC + 0,5 N{sub 2} {yields} PuN + C.

  9. Ab initio study on the reaction between uranium and O2

    International Nuclear Information System (INIS)

    Shuai Maobing; Zhao Pengji; Tian Anmin

    2000-08-01

    Optimized geometries, total energies and electronic structures of some gaseous atoms and molecules of uranium-oxygen system are calculated with harmonic vibration analysis using ab initio method. The potential energy surfaces (PESs) of the uranium oxidation process are also constructed. The calculated optimized geometries, infrared vibrational frequencies and the first ionized potential energies are in well accordance with available experimental data. Although U6p, U7s and U6d valence orbital electrons take part in the formation of U - O bond, the U5f electrons play an dominant role in this process and because the energies of U5f, U6d, U7s and Uds atomic orbitals are close to each other, these orbitals may hybrid and interact with O2p orbital, simultaneously, to form molecular orbitals of uranium oxides. The PESs show that different reaction modes result in different product geometries

  10. Terminal uranium(V/VI) nitride activation of carbon dioxide and carbon disulfide. Factors governing diverse and well-defined cleavage and redox reactions

    International Nuclear Information System (INIS)

    Cleaves, Peter A.; Gardner, Benedict M.; Liddle, Stephen T.; Kefalidis, Christos E.; Maron, Laurent; Tuna, Floriana; McInnes, Eric J.L.; Lewis, William

    2017-01-01

    The reactivity of terminal uranium(V/VI) nitrides with CE 2 (E=O, S) is presented. Well-defined C=E cleavage followed by zero-, one-, and two-electron redox events is observed. The uranium(V) nitride [U(Tren TIPS )(N)][K(B15C5) 2 ] (1, Tren TIPS =N(CH 2 CH 2 NSiiPr 3 ) 3 ; B15C5=benzo-15-crown-5) reacts with CO 2 to give [U(Tren TIPS )(O)(NCO)][K(B15C5) 2 ] (3), whereas the uranium(VI) nitride [U(Tren TIPS )(N)] (2) reacts with CO 2 to give isolable [U(Tren TIPS )(O)(NCO)] (4); complex 4 rapidly decomposes to known [U(Tren TIPS )(O)] (5) with concomitant formation of N 2 and CO proposed, with the latter trapped as a vanadocene adduct. In contrast, 1 reacts with CS 2 to give [U(Tren TIPS )(κ 2 -CS 3 )][K(B15C5) 2 ] (6), 2, and [K(B15C5) 2 ][NCS] (7), whereas 2 reacts with CS 2 to give [U(Tren TIPS )(NCS)] (8) and ''S'', with the latter trapped as Ph 3 PS. Calculated reaction profiles reveal outer-sphere reactivity for uranium(V) but inner-sphere mechanisms for uranium(VI); despite the wide divergence of products the initial activation of CE 2 follows mechanistically related pathways, providing insight into the factors of uranium oxidation state, chalcogen, and NCE groups that govern the subsequent divergent redox reactions that include common one-electron reactions and a less-common two-electron redox event. Caution, we suggest, is warranted when utilising CS 2 as a reactivity surrogate for CO 2 . (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  11. Fission dynamics of superheavy nuclei formed in uranium induced reactions

    International Nuclear Information System (INIS)

    Gurjit Kaur; Sandhu, Kirandeep; Sharma, Manoj K.

    2017-01-01

    The compound nuclear system follows symmetric fission if the competing processes such as quasi-elastic, deep inelastic, quasi-fission etc are absent. The contribution of quasi fission events towards the fusion-fission mechanism depends on the entrance channel asymmetry of reaction partners, deformations and orientations of colliding nuclei beside the dependence on energy and angular momentum. Usually the 209 Bi and 208 Pb targets are opted for the production of superheavy nuclei with Z CN =104-113. The nuclei in same mass/charge range can also be synthesized using actinide targets + light projectiles (i.e. asymmetric reaction partners) via hot fusion interactions. These actinide targets are prolate deformed which prefer the compact configurations at above barrier energies, indicating the occurrence of symmetric fission events. Here an attempt is made to address the dynamics of light superheavy system (Z CN =104-106), formed via hot fusion interactions involving actinide targets

  12. Experimental study and numerical modelling of geochemical reactions occurring during uranium in situ recovery (ISR) mining

    International Nuclear Information System (INIS)

    Ben Simon, R.

    2011-09-01

    The in situ Recovery (ISR) method consists of ore mining by in situ chemical leaching with acid or alkaline solutions. ISR takes place underground and is therefore limited to the analysis of the pumped solutions, hence ISR mine management is still empirical. Numerical modelling has been considered to achieve more efficient management of this process. Three different phenomena have to be taken into account for numerical simulations of uranium ISR mining: (1) geochemical reactions; (2) the kinetics of these reactions, and (3) hydrodynamic transport with respect to the reaction kinetics. Leaching tests have been conducted on ore samples from an uranium mine in Tortkuduk (Kazakhstan) where ISR is conducted by acid leaching. Two types of leaching experiments were performed: (1) tests in batch reactors; and (2) extraction in flow through columns. The assumptions deduced from the leaching tests were tested and validated by modelling the laboratory experiments with the numerical codes CHESS and HYTEC, both developed at the Geosciences research center of Mines ParisTech. A well-constrained 1D hydrogeochemical transport model of the ISR process at laboratory-scale was proposed. It enables to translate the chemical release sequence that is observed during experiments into a geochemical reaction sequence. It was possible to highlight the controlling factors of uranium dissolution, and the precipitation of secondary mineral phase in the deposit, as well as the determination of the relative importance of these factors. (author)

  13. Some Investigations of the Reaction of Activated Charcoal with Fluorine and Uranium Hexafluoride

    Energy Technology Data Exchange (ETDEWEB)

    Del Cul, G.D.; Fiedor, J.N.; Simmons, D.W.; Toth, L.M.; Trowbridge, L.D.; Williams

    1998-09-01

    The Molten Salt Reactor Experiment (MSRE) at Oak Ridge National Laboratory has been shut down since 1969, when the fuel salt was drained from the core into two Hastelloy N drain tanks at the reactor site. Over time, fluorine (F{sub 2}) and uranium hexafluoride (UF{sub 6}) moved from the salt through the gas piping to a charcoal bed, where they reacted with the activated charcoal. Some of the immediate concerns related to the migration of F{sub 2} and UF{sub 6} to the charcoal bed were the possibility of explosive reactions between the charcoal and F{sub 2}, the existence of conditions that could induce a criticality accident, and the removal and recovery of the fissile uranium from the charcoal. This report addresses the reactions and reactivity of species produced by the reaction of fluorine and activated charcoal and between charcoal and F{sub 2}-UF{sub 6} gas mixtures in order to support remediation of the MSRE auxiliary charcoal bed (ACB) and the recovery of the fissile uranium. The chemical identity, stoichiometry, thermochemistry, and potential for explosive decomposition of the primary reaction product, fluorinated charcoal, was determined.

  14. Some Investigations of the Reaction of Activated Charcoal with Fluorine and Uranium Hexafluoride

    International Nuclear Information System (INIS)

    Del Cul, G.D.; Fiedor, J.N.; Simmons, D.W.; Toth, L.M.; Trowbridge, L.D.; Williams

    1998-01-01

    The Molten Salt Reactor Experiment (MSRE) at Oak Ridge National Laboratory has been shut down since 1969, when the fuel salt was drained from the core into two Hastelloy N drain tanks at the reactor site. Over time, fluorine (F 2 ) and uranium hexafluoride (UF 6 ) moved from the salt through the gas piping to a charcoal bed, where they reacted with the activated charcoal. Some of the immediate concerns related to the migration of F 2 and UF 6 to the charcoal bed were the possibility of explosive reactions between the charcoal and F 2 , the existence of conditions that could induce a criticality accident, and the removal and recovery of the fissile uranium from the charcoal. This report addresses the reactions and reactivity of species produced by the reaction of fluorine and activated charcoal and between charcoal and F 2 -UF 6 gas mixtures in order to support remediation of the MSRE auxiliary charcoal bed (ACB) and the recovery of the fissile uranium. The chemical identity, stoichiometry, thermochemistry, and potential for explosive decomposition of the primary reaction product, fluorinated charcoal, was determined

  15. Investigation of the kinetics of the reactions of oxidation, nitration, and hydrogenation of uranium

    International Nuclear Information System (INIS)

    Adda, Y.

    1955-06-01

    Various physico-chemical methods have been used to investigate the kinetics of the oxidation hydridation and nitridation of uranium. The experimental results show that the kinetics of these reactions are influenced by many factors also the Pilling and Bedworth rule is valid only under very limited conditions. The disagreement between this rule and the experimental results could be explained by the existence of numerous mechanical faults in the compounds obtained by the dry corrosion of the metal. (author) [fr

  16. Pathways of the Maillard reaction under physiological conditions.

    Science.gov (United States)

    Henning, Christian; Glomb, Marcus A

    2016-08-01

    Initially investigated as a color formation process in thermally treated foods, nowadays, the relevance of the Maillard reaction in vivo is generally accepted. Many chronic and age-related diseases such as diabetes, uremia, atherosclerosis, cataractogenesis and Alzheimer's disease are associated with Maillard derived advanced glycation endproducts (AGEs) and α-dicarbonyl compounds as their most important precursors in terms of reactivity and abundance. However, the situation in vivo is very challenging, because Maillard chemistry is paralleled by enzymatic reactions which can lead to both, increases and decreases in certain AGEs. In addition, mechanistic findings established under the harsh conditions of food processing might not be valid under physiological conditions. The present review critically discusses the relevant α-dicarbonyl compounds as central intermediates of AGE formation in vivo with a special focus on fragmentation pathways leading to formation of amide-AGEs.

  17. Reaction of Tris(cyclopentadienyl)uranium compounds with amines, azides, and related ligands

    Energy Technology Data Exchange (ETDEWEB)

    Rosen, R.K.

    1989-12-01

    The trivalent uranium compound, (MeC{sub 5}H{sub 4}){sub 3}U(thf), serves as a one- or two-electron reducing agent towards azides, RN{sub 3}. These reactions produce either the uranium(IV) azide, (MeC{sub 5}H{sub 4}){sub 3}UN{sub 3}, or uranium(V) imides, (MeC{sub 5}H{sub 4}){sub 3}UNR. The role of steric and electronic effects upon this reaction has been investigated using several series of azides. For Me{sub 3}XN{sub 3}, the imides are produced when X = C or Si, both products are formed when X = Ge, and the azide is produced when X = Sn. For Ph{sub 3}XN{sub 3}, the azide is produced when X = C or Sn. For Ph{sub 3-x}CH{sub 3}N{sub 3}, the imide is produced when x = 2 and both compounds are produced when x = 1. For substituted phenylazides, RC{sub 6}H{sub 4}N{sub 3}, only the imides are produced. The magnetic properties of uranium diimides, ((MeC{sub 5}H{sub 4}){sub 3}U){sub 2}({mu}-NRN), were investigated. Several uranium(III) amines, (MeC{sub 5}H{sub 4}){sub 3}U(NH{sub 2}R), were produced from (MeC{sub 5}H{sub 4}){sub 3}U(thf) and RNH{sub 2}, and NH{sub 3} was found to be a better ligand towards (MeC{sub 5}H{sub 4}){sub 3}U than is PMe{sub 3}.

  18. Current status of uranium enrichment by way of chemical exchange reactions

    International Nuclear Information System (INIS)

    El Basyouny, A.; Bechthold, H.C.; Knoechel, A.; Vollmer, H.J.

    1985-04-01

    For this report, conference proceedings, patents and other types of literature have been collected to present an account of the current status of uranium enrichment by way of chemical exchange reactions. The report further presents a new concept along with the relevant process strategy developed by the authors. The principal process of the new concept is a chemical exchange process with crown ethers, complexed or free, playing an important part in the reactions. The authors also describe their experiments carried out for establishing suitable chemical systems. (orig./PW) [de

  19. Uranium

    International Nuclear Information System (INIS)

    Whillans, R.T.

    1981-01-01

    Events in the Canadian uranium industry during 1980 are reviewed. Mine and mill expansions and exploration activity are described, as well as changes in governmental policy. Although demand for uranium is weak at the moment, the industry feels optimistic about the future. (LL)

  20. The shielded chemistry suite at BNL and its use in the study of the irradiated uranium-water reaction

    International Nuclear Information System (INIS)

    Bannister, G.H.; Tyfield, S.P.

    1977-11-01

    A versatile shielded facility for chemical studies is now in use at Berkeley Nuclear Laboratories. The suite was fully commissioned in 1976 and first utilised to study the aqueous corrosion of irradiated reactor grade uranium. The suite consists of three adjacent interconnected cells; a balance cell, a preparation cell and an experimental cell. The development, design and layout of the facilities are described, as are the details of the equipment installed to undertake a uranium corrosion study. The preparation cell is used for procedures that could results in high levels of contamination, such as cutting of uranium specimens. The uranium samples are corroded in sealed steel capsules installed in the experimental cell. The capsules are heated either isothermally or through a transient and the reaction monitored with a pressure transducer which records the rate of hydrogen evolution from the uranium-water reaction. The experimental results will be reported elsewhere. (author)

  1. Kinetic and reaction pathways of methanol oxidation on platinum

    International Nuclear Information System (INIS)

    McCabe, R.W.; McCready, D.F.

    1986-01-01

    Methanol oxidation kinetics were measured on Pt wires in a flow reactor at pressures between 30 and 130 Pa. The kinetics were measured as a function of oxygen-to-methanol equivalence ratio phi and wire temperature. In methanol-lean feeds (phi 2 CO, CO 2 , and H 2 O were the only products; in methanol-rich feeds (phi > 1), CO, H 2 , H 2 CO, CO 2 , and H 2 O were observed. Experiments with 18 O 2 showed that the principal methanol oxidation pathway does not involve C-O bond dissociation. However, the 18 O 2 experiments, together with other features of the methanol oxidation data, also provided evidence for a minor oxidation pathway (accounting for less than 1% of the product CO 2 ) which proceeds through a carbon intermediate. A mathematical model is presented which describes the principal CH 3 OH oxidation pathway as a series reaction involving adsorbed H 2 CO and CO intermediates. Consistent with experimental results, the model predicts that inhibition by adsorbed CO should be weaker for CH 3 OH and H 2 CO oxidation than for CO oxidation. 34 references, 10 figures, 2 tables

  2. Vibrational spectra of monouranates and uranium hydroxides as reaction products of alkali with uranyl nitrate

    International Nuclear Information System (INIS)

    Komyak, A.I.; Umrejko, D.S.; Posledovich, M.R.

    2013-01-01

    Vibrational (IR absorption and Raman scattering) spectra for the reaction products of uranyl nitrate hexahydrate with NaOH and KOH have been studied. As a result of exchange reactions, the uranyl-ion coordinated nitrate groups are completely replaced by hydroxyl ions and various uranium and uranyl oxides or hydrates are formed. An analysis of the vibrations has been performed in terms of the frequencies of a free or coordinated nitrate group; comparison with the vibrations of the well-known uranium oxides and of the uranyl group UO 2 2+ has been carried out. Vibrational spectra of a free nitrate group are characterized by four vibrational frequencies 1050, 724, 850, and 1380 cm -1 , among which the frequencies at 724 and 1380 cm -1 are doubly degenerate and attributed to E’ symmetry of the point group D 3h . When this group is uranium coordinated, its symmetry level is lowered to C 2v , all vibrations of this group being active both in Raman and IR spectra. The doubly degenerate vibrations are exhibited as two bands and a frequency of the out-of-plane vibration is lowered to 815 cm -1 . (authors)

  3. Thermodynamic analysis and experimental study on the chlorination of uranium oxide by gas-solid reaction

    International Nuclear Information System (INIS)

    Shin, Y.J.; Kim, I.S.; Shin, H.S.; Ro, S.G.; Park, H.S.

    1998-01-01

    In order to determine the operating condition of an uranium chlorination process with U 3 O 8 -C-Cl 2 system, the experimental conditions have been evaluated preliminarily by the thermochemical analysis and experimentally confirmed in this study. The dry-type chlorination of U 3 O 8 occurs as irreversible and exothermic reaction and produces many kinds of chloride compounds such as UCl 3 , UCl 4 , UCl 5 , and UCl 6 in the air and humidity controlled argon environment. Taking account of Gibbs free energy and vapor pressure for various chloride compounds, the proper temperature range of chlorination appears to be 863 to 953 K in aspects of increasing reaction rate and the yield of nonvolatile product. In the course of the experimental confirmation the powder of U 3 O 8 is perfectly converted into uranium chlorides within 4 hours above 863 K, and then the maximum fraction of uranium chloride remaining in the reactor is about 30% of total conversion mass. (author)

  4. Uranium analysis in urine by inductively coupled plasma dynamic reaction cell mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Ejnik, John W. [Northern Michigan University, Chemistry Department, Marquette, MI (United States); Todorov, Todor I.; Mullick, Florabel G.; Centeno, Jose A. [Armed Forces Institute of Pathology (AFIP), Division of Biophysical Toxicology, Washington, DC (United States); Squibb, Katherine; McDiarmid, Melissa A. [University of Maryland, School of Medicine, Baltimore, MD (United States)

    2005-05-01

    Urine uranium concentrations are the best biological indicator for identifying exposure to depleted uranium (DU). Internal exposure to DU causes an increased amount of urine uranium and a decreased ratio of {sup 235}U/{sup 238}U in urine samples, resulting in measurements that vary between 0.00725 and 0.002 (i.e., natural and depleted uranium's {sup 235}U/{sup 238}U ratios, respectively). A method based on inductively coupled plasma dynamic reaction cell mass spectrometry (ICP-DRC-MS) was utilized to identify DU in urine by measuring the quantity of total U and the {sup 235}U/{sup 238}U ratio. The quantitative analysis was achieved using {sup 233}U as an internal standard. The analysis was performed both with and without the reaction gas oxygen. The reaction gas converted ionized {sup 235}U{sup +} and {sup 238}U{sup +} into {sup 235}UO{sub 2}{sup +} (m/z=267) and {sup 238}UO{sub 2}{sup +} (m/z=270). This conversion was determined to be over 90% efficient. A polyatomic interference at m/z 234.8 was successfully removed from the {sup 235}U signal under either DRC operating conditions (with or without oxygen as a reaction gas). The method was validated with 15 urine samples of known uranium compositions. The method detection limit for quantification was determined to be 0.1 pg U mL{sup -1} urine and an average coefficient of variation (CV) of 1-2% within the sample measurements. The method detection limit for determining {sup 235}U/{sup 238}U ratio was 3.0 pg U mL{sup -1} urine. An additional 21 patient samples were analyzed with no information about medical history. The measured {sup 235}U/{sup 238}U ratio within the urine samples correctly identified the presence or absence of internal DU exposure in all 21 patients. (orig.)

  5. Influence of uranyl speciation and iron oxides on uranium biogeochemical redox reactions

    Energy Technology Data Exchange (ETDEWEB)

    Stewart, B.D.; Amos, R.T.; Nico, P.S.; Fendorf, S.

    2010-03-15

    Uranium is a pollutant of concern to both human and ecosystem health. Uranium's redox state often dictates its partitioning between the aqueous- and solid-phases, and thus controls its dissolved concentration and, coupled with groundwater flow, its migration within the environment. In anaerobic environments, the more oxidized and mobile form of uranium (UO{sub 2}{sup 2+} and associated species) may be reduced, directly or indirectly, by microorganisms to U(IV) with subsequent precipitation of UO{sub 2}. However, various factors within soils and sediments may limit biological reduction of U(VI), inclusive of alterations in U(VI) speciation and competitive electron acceptors. Here we elucidate the impact of U(VI) speciation on the extent and rate of reduction with specific emphasis on speciation changes induced by dissolved Ca, and we examine the impact of Fe(III) (hydr)oxides (ferrihydrite, goethite and hematite) varying in free energies of formation on U reduction. The amount of uranium removed from solution during 100 h of incubation with S. putrefaciens was 77% with no Ca or ferrihydrite present but only 24% (with ferrihydrite) and 14% (no ferrihydrite) were removed for systems with 0.8 mM Ca. Imparting an important criterion on uranium reduction, goethite and hematite decrease the dissolved concentration of calcium through adsorption and thus tend to diminish the effect of calcium on uranium reduction. Dissimilatory reduction of Fe(III) and U(VI) can proceed through different enzyme pathways, even within a single organism, thus providing a potential second means by which Fe(III) bearing minerals may impact U(VI) reduction. We quantify rate coefficients for simultaneous dissimilatory reduction of Fe(III) and U(VI) in systems varying in Ca concentration (0 to 0.8 mM), and using a mathematical construct implemented with the reactive transport code MIN3P, we reveal the predominant influence of uranyl speciation, specifically the formation of uranyl

  6. Reaction of Antimony-Uranium Composite Oxide in the Chlorination Treatment of Waste Catalyst - 13521

    Energy Technology Data Exchange (ETDEWEB)

    Sawada, Kayo [EcoTopia Science Institute (Japan); Hirabayashi, Daisuke; Enokida, Youichi [Department of Materials, Physics and Energy Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8603 (Japan)

    2013-07-01

    The effect of oxygen gas concentration on the chlorination treatment of antimony-uranium composite oxide catalyst waste was investigated by adding different concentrations of oxygen at 0-6 vol% to its chlorination agent of 0.6 or 6 vol% hydrogen chloride gas at 1173 K. The addition of oxygen tended to prevent the chlorination of antimony in the oxide. When 6 vol% hydrogen chloride gas was used, the addition of oxygen up to 0.1 vol% could convert the uranium contained in the catalyst to U{sub 3}O{sub 8} without any significant decrease in the reaction rate compared to that of the treatment without oxygen. (authors)

  7. Uranium

    Energy Technology Data Exchange (ETDEWEB)

    Williams, R M

    1976-01-01

    Evidence of expanding markets, improved prices and the short supply of uranium became abundantly clear in 1975, providing the much needed impetus for widespread activity in all phases of uranium operations. Exploration activity that had been at low levels in recent years in Canada was evident in most provinces as well as the Northwest Territories. All producers were in the process of expanding their uranium-producing facilities. Canada's Atomic Energy Control Board (AECB) by year-end had authorized the export of over 73,000 tons of U/sub 3/0/sub 8/ all since September 1974, when the federal government announced its new uranium export guidelines. World production, which had been in the order of 25,000 tons of U/sub 3/0/sub 8/ annually, was expected to reach about 28,000 tons in 1975, principally from increased output in the United States.

  8. Exposure pathways and biological receptors: baseline data for the canyon uranium mine, Coconino County, Arizona

    Science.gov (United States)

    Hinck, Jo E.; Linder, Greg L.; Darrah, Abigail J.; Drost, Charles A.; Duniway, Michael C.; Johnson, Matthew J.; Méndez-Harclerode, Francisca M.; Nowak, Erika M.; Valdez, Ernest W.; van Riper, Charles; Wolff, S.W.

    2014-01-01

    Recent restrictions on uranium mining within the Grand Canyon watershed have drawn attention to scientific data gaps in evaluating the possible effects of ore extraction to human populations as well as wildlife communities in the area. Tissue contaminant concentrations, one of the most basic data requirements to determine exposure, are not available for biota from any historical or active uranium mines in the region. The Canyon Uranium Mine is under development, providing a unique opportunity to characterize concentrations of uranium and other trace elements, as well as radiation levels in biota, found in the vicinity of the mine before ore extraction begins. Our study objectives were to identify contaminants of potential concern and critical contaminant exposure pathways for ecological receptors; conduct biological surveys to understand the local food web and refine the list of target species (ecological receptors) for contaminant analysis; and collect target species for contaminant analysis prior to the initiation of active mining. Contaminants of potential concern were identified as arsenic, cadmium, chromium, copper, lead, mercury, nickel, selenium, thallium, uranium, and zinc for chemical toxicity and uranium and associated radionuclides for radiation. The conceptual exposure model identified ingestion, inhalation, absorption, and dietary transfer (bioaccumulation or bioconcentration) as critical contaminant exposure pathways. The biological survey of plants, invertebrates, amphibians, reptiles, birds, and small mammals is the first to document and provide ecological information on .200 species in and around the mine site; this study also provides critical baseline information about the local food web. Most of the species documented at the mine are common to ponderosa pine Pinus ponderosa and pinyon–juniper Pinus–Juniperus spp. forests in northern Arizona and are not considered to have special conservation status by state or federal agencies; exceptions

  9. Reaction of uranium and plutonium carbides with austenitic steels; Reaction des carbures d'uranium et de plutonium avec des aciers austenitiques

    Energy Technology Data Exchange (ETDEWEB)

    Mouchnino, M [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1967-07-01

    The reaction of uranium and plutonium carbides with austenitic steels has been studied between 650 and 1050 deg. C using UC, steel and (UPu)C, steel diffusion couples. The steels are of the type CN 18.10 with or without addition of molybdenum. The carbides used are hyper-stoichiometric. Tests were also carried out with UCTi, UCMo, UPuCTi and UPuCMo. Up to 800 deg. C no marked diffusion of carbon into stainless steel is observed. Between 800 and 900 deg. C the carbon produced by the decomposition of the higher carbides diffuses into the steel. Above 900 deg. C, decomposition of the monocarbide occurs according to a reaction which can be written schematically as: (U,PuC) + (Fe,Ni,Cr) {yields} (U,Pu) Fe{sub 2} + Cr{sub 23}C{sub 6}. Above 950 deg. C the behaviour of UPuCMo and that of the titanium (CN 18.12) and nickel (NC 38. 18) steels is observed to be very satisfactory. (author) [French] La reaction des carbures d'uranium et de plutonium avec des aciers austenitiques a ete etudiee entre 650 deg. C et 1050 deg. C a partir de couples de diffusion UC, acier et (UPu)C, acier. Les aciers sont du type CN 18.10 avec ou sans addition de molybdene. Les carbures utilises sont hyper-stoechiometriques. En outre on a fait des essais avec UCTi, UCMo, UPuCTi, UPuCMo. Jusqu'a 800 deg. C on ne detecte pas de diffusion sensible du carbone dans l'acier inoxydable. Entre 800 et 900 deg. C il y a diffusion dans l'acier du carbone provenant de la decomposition des carbures superieurs. A partir de 900 deg. C il y a decomposition du monocarbure selon une reaction que l'on ecrit schematiquement: (U,PuC) + (Fe, Ni, Cr) {yields} (U,Pu)Fe{sub 2} + Cr{sub 23}C{sub 6}. Nous notons a 950 deg. C le bon comportement de UPuCMo ainsi que celui des aciers au titane (CN 18. 12) et au nickel (NC 38.18). (auteur)

  10. Study of reactions for the obtention of uranium tetrafluoride and hexafluoride

    International Nuclear Information System (INIS)

    Guzella, M.F.R.

    1984-01-01

    Based on an exhaustive bibliographical review, the main production processes of uranium hexafluoride in pilot plants and industrial facilities are described. The known reactions, confirmed in laboratory experiments, that lead to UF 6 or other intermediate fluorides, are presented and discussed. In order to determine a new thermodinamically feasible reaction involving the sulfur hexafluoride as fluorinating agent, a mock-up facility was designed and constructed as part of the R and D work planned at CDTN (NUCLEBRAS Center for Nuclear Technology Development, MG - Brazil). For the UF 4 synthesis employing U 3 O 8 and SF 6 , several experimental parameters were studied. The reaction time, gas flow, temperature and stoichiometric relations among reagents are described in detail. Suggestions for further investigations regarding this new reagent are made. (Author) [pt

  11. Dynamic Characteristics and Model for Centralization Reaction of Acidic Tailings From Heap Leaching of Uranium Ore

    International Nuclear Information System (INIS)

    Ding Dexin; Liu Yulong; Li Guangyue; Wang Youtuan

    2010-01-01

    Centralization tests were carried out on acidic tailings from heap leaching of uranium ore by using CaO, NaOH and NH 4 OH. The variations of pH with time were measured for the three centralization systems and the dynamic models for the systems were set up by regressing the measured data. The centralization process consists of the fast reaction phase representing the reaction between the centralization agent and the acid on the surface of the tailing's particles and the slow diffusion-reaction phase representing the diffusion-reaction between the centralization agent and the acid within the tailing's particles. The non-linear coupling and feedback function model for the diffusion-reaction of the centralization agent can reflect the process and mode of the centralization reaction. There is a non-linear oscillation in the variation of pH within the centralization systems. The dynamic model for the tailing's centralization reaction can fit the pH variation within the centralization systems. (authors)

  12. Mitigation of Hydrogen Gas Generation from the Reaction of Water with Uranium Metal in K Basins Sludge

    International Nuclear Information System (INIS)

    Sinkov, Sergey I.; Delegard, Calvin H.; Schmidt, Andrew J.

    2010-01-01

    Means to decrease the rate of hydrogen gas generation from the chemical reaction of uranium metal with water were identified by surveying the technical literature. The underlying chemistry and potential side reactions were explored by conducting 61 principal experiments. Several methods achieved significant hydrogen gas generation rate mitigation. Gas-generating side reactions from interactions of organics or sludge constituents with mitigating agents were observed. Further testing is recommended to develop deeper knowledge of the underlying chemistry and to advance the technology aturation level. Uranium metal reacts with water in K Basin sludge to form uranium hydride (UH3), uranium dioxide or uraninite (UO2), and diatomic hydrogen (H2). Mechanistic studies show that hydrogen radicals (H·) and UH3 serve as intermediates in the reaction of uranium metal with water to produce H2 and UO2. Because H2 is flammable, its release into the gas phase above K Basin sludge during sludge storage, processing, immobilization, shipment, and disposal is a concern to the safety of those operations. Findings from the technical literature and from experimental investigations with simple chemical systems (including uranium metal in water), in the presence of individual sludge simulant components, with complete sludge simulants, and with actual K Basin sludge are presented in this report. Based on the literature review and intermediate lab test results, sodium nitrate, sodium nitrite, Nochar Acid Bond N960, disodium hydrogen phosphate, and hexavalent uranium [U(VI)] were tested for their effects in decreasing the rate of hydrogen generation from the reaction of uranium metal with water. Nitrate and nitrite each were effective, decreasing hydrogen generation rates in actual sludge by factors of about 100 to 1000 when used at 0.5 molar (M) concentrations. Higher attenuation factors were achieved in tests with aqueous solutions alone. Nochar N960, a water sorbent, decreased hydrogen

  13. Mitigation of Hydrogen Gas Generation from the Reaction of Water with Uranium Metal in K Basins Sludge

    Energy Technology Data Exchange (ETDEWEB)

    Sinkov, Sergey I.; Delegard, Calvin H.; Schmidt, Andrew J.

    2010-01-29

    Means to decrease the rate of hydrogen gas generation from the chemical reaction of uranium metal with water were identified by surveying the technical literature. The underlying chemistry and potential side reactions were explored by conducting 61 principal experiments. Several methods achieved significant hydrogen gas generation rate mitigation. Gas-generating side reactions from interactions of organics or sludge constituents with mitigating agents were observed. Further testing is recommended to develop deeper knowledge of the underlying chemistry and to advance the technology aturation level. Uranium metal reacts with water in K Basin sludge to form uranium hydride (UH3), uranium dioxide or uraninite (UO2), and diatomic hydrogen (H2). Mechanistic studies show that hydrogen radicals (H·) and UH3 serve as intermediates in the reaction of uranium metal with water to produce H2 and UO2. Because H2 is flammable, its release into the gas phase above K Basin sludge during sludge storage, processing, immobilization, shipment, and disposal is a concern to the safety of those operations. Findings from the technical literature and from experimental investigations with simple chemical systems (including uranium metal in water), in the presence of individual sludge simulant components, with complete sludge simulants, and with actual K Basin sludge are presented in this report. Based on the literature review and intermediate lab test results, sodium nitrate, sodium nitrite, Nochar Acid Bond N960, disodium hydrogen phosphate, and hexavalent uranium [U(VI)] were tested for their effects in decreasing the rate of hydrogen generation from the reaction of uranium metal with water. Nitrate and nitrite each were effective, decreasing hydrogen generation rates in actual sludge by factors of about 100 to 1000 when used at 0.5 molar (M) concentrations. Higher attenuation factors were achieved in tests with aqueous solutions alone. Nochar N960, a water sorbent, decreased hydrogen

  14. Spectrographic determination of boron and silicon in uranium tetrafluoride: Study of the chemical reactions in the electrode cavity when ZnO is used as a uranium excitation suppressor

    International Nuclear Information System (INIS)

    Alduan, F. A.; Capdevila, C.; Roca, M.

    1973-01-01

    A method has been developed for determining traces of boron and silicon in uranium tetrafluoride. Use is made of zinc oxide to decrease the volatilization of uranium and achieve high sensitivities. The thermochemical reactions which occur in the anode cavity during the arcing process have been investigated. UO 2 and a uranium, zinc and fluorine compound, both less volatile than uranium tetrafluoride, are formed. (Author)

  15. Influence of a photochemical reaction on the controlled potential coulometric determination of plutonium in a mixture with uranium

    International Nuclear Information System (INIS)

    Le Duigou, Y.; Leidert, W.

    1976-01-01

    Data are provided in support of a photochemical reaction which takes place simultaneously with the electrochemical reduction of quadrivalent plutonium during the controlled potential coulometric determination of plutonium in a mixture with uranium. The interfering effect of this reaction is overcome by placing the cell in a dark environment. (orig.) [de

  16. Study of the reaction of uranium and plutonium with bone char

    International Nuclear Information System (INIS)

    Silver, G.L.; Koenst, J.W.

    1977-01-01

    A study of the reaction of plutonium with a commercial bone char indicates that this bone char has a high capacity for removing plutonium from aqueous wastes. The adsorption of plutonium by bone char is pH dependent, and for plutonium(IV) polymer appears to be maximized near pH 7.3 for plutonium concentrations typical of some waste streams. Adsorption is affected by dissolved salts, especially calcium and phosphate salts. Freundlich isotherms representing the adsorption of uranium and plutonium have been prepared. The low potential imposed upon aqueous solutions by commercial bone char is adequate for reduction of hexavalent plutonium to a lower plutonium oxidation state

  17. Sintering uranium oxide in the reaction product of hydrogen-carbon dioxide mixtures

    International Nuclear Information System (INIS)

    De Hollander, W.R.; Nivas, Y.

    1975-01-01

    Compacted pellets of uranium oxide alone or containing one or more additives such as plutonium dioxide, gadolinium oxide, titanium dioxide, silica, and alumina are heated to 900 to 1599 0 C in the presence of a mixture of hydrogen and carbon dioxide, either alone or with an inert carrier gas and held at the desired temperature in this atmosphere to sinter the pellets. The sintered pellets are then cooled in an atmosphere having an oxygen partial pressure of 10 -4 to 10 -18 atm of oxygen such as dry hydrogen, wet hydrogen, dry carbon monoxide, wet carbon monoxide, inert gases such as nitrogen, argon, helium, and neon and mixtures of ayny of the foregoing including a mixture of hydrogen and carbon dioxide. The ratio of hydrogen to carbon dioxide in the gas mixture fed to the furnace is controlled to give a ratio of oxygen to uranium atoms in the sintered particles within the range of 1.98:1 to about 2.10:1. The water vapor present in the reaction products in the furnace atmosphere acts as a hydrolysis agent to aid removal of fluoride should such impurity be present in the uranium oxide. (U.S.)

  18. Uranium

    International Nuclear Information System (INIS)

    Perkin, D.J.

    1982-01-01

    Developments in the Australian uranium industry during 1980 are reviewed. Mine production increased markedly to 1841 t U 3 O 8 because of output from the new concentrator at Nabarlek and 1131 t of U 3 O 8 were exported at a nominal value of $37.19/lb. Several new contracts were signed for the sale of yellowcake from Ranger and Nabarlek Mines. Other developments include the decision by the joint venturers in the Olympic Dam Project to sink an exploration shaft and the release of an environmental impact statement for the Honeymoon deposit. Uranium exploration expenditure increased in 1980 and additions were made to Australia's demonstrated economic uranium resources. A world review is included

  19. Uranium

    International Nuclear Information System (INIS)

    Gabelman, J.W.; Chenoweth, W.L.; Ingerson, E.

    1981-01-01

    The uranium production industry is well into its third recession during the nuclear era (since 1945). Exploration is drastically curtailed, and many staffs are being reduced. Historical market price production trends are discussed. A total of 3.07 million acres of land was acquired for exploration; drastic decrease. Surface drilling footage was reduced sharply; an estimated 250 drill rigs were used by the uranium industry during 1980. Land acquisition costs increased 8%. The domestic reserve changes are detailed by cause: exploration, re-evaluation, or production. Two significant discoveries of deposits were made in Mohave County, Arizona. Uranium production during 1980 was 21,850 short tons U 3 O 8 ; an increase of 17% from 1979. Domestic and foreign exploration highlights were given. Major producing areas for the US are San Juan basin, Wyoming basins, Texas coastal plain, Paradox basin, northeastern Washington, Henry Mountains, Utah, central Colorado, and the McDermitt caldera in Nevada and Oregon. 3 figures, 8 tables

  20. Reaction of H2 with O2 in Excited Electronic States: Reaction Pathways and Rate Constants.

    Science.gov (United States)

    Pelevkin, Alexey V; Loukhovitski, Boris I; Sharipov, Alexander S

    2017-12-21

    Comprehensive quantum chemical analysis with the use of the multireference state-averaged complete active space self-consistent field approach was carried out to study the reactions of H 2 with O 2 in a 1 Δ g , b 1 Σ g + , c 1 Σ u - , and A' 3 Δ u electronically excited states. The energetically favorable reaction pathways and possible intersystem crossings have been revealed. The energy barriers were refined employing the extended multiconfiguration quasi-degenerate second-order perturbation theory. It has been shown that the interaction of O 2 (a 1 Δ g ) and O 2 (A' 3 Δ u ) with H 2 occurs through the H-abstraction process with relatively low activation barriers that resulted in the formation of the HO 2 molecule in A″ and A' electronic states, respectively. Meanwhile, molecular oxygen in singlet sigma states (b 1 Σ g + and c 1 Σ u - ) was proved to be nonreactive with respect to the molecular hydrogen. Appropriate rate constants for revealed reaction and quenching channels have been estimated using variational transition-state theory including corrections for the tunneling effect, possible nonadiabatic transitions, and anharmonicity of vibrations for transition states and reactants. It was demonstrated that the calculated reaction rate constant for the H 2 + O 2 (a 1 Δ g ) process is in reasonable agreement with known experimental data. The Arrhenius approximations for these processes have been proposed for the temperature range T = 300-3000 K.

  1. Position-specific isotope modeling of organic micropollutants transformation through different reaction pathways

    DEFF Research Database (Denmark)

    Jin, Biao; Rolle, Massimo

    2016-01-01

    The degradation of organic micropollutants occurs via different reaction pathways. Compound specific isotope analysis is a valuable tool to identify such degradation pathways in different environmental systems. We propose a mechanism-based modeling approach that provides a quantitative framework ...

  2. Reactions of uranium (III) and (IV) compounds with ketones, nitriles and acid chlorides. Towards a use of uranium complexes in organic synthesis

    International Nuclear Information System (INIS)

    Adam, Raymond

    1993-01-01

    In this research thesis, the author shows that various organic molecules can be interestingly transformed into uranium complexes with degrees of oxidation of +3 or +4. In a first part, the author describes reactions of carbonyl compounds with the UCl 4 -Na(Hg) reducing system. Then, he addresses reductions of ketones, nitriles and acid chlorides by a uranium (III) complex: Cp 3 U(THF). The third part reports a detailed study of the reduction of ketones by U(BH 4 ) 4 [fr

  3. Reaction of active uranium and thorium with aromatic carbonyls and pinacols in hydrocarbon solvents

    International Nuclear Information System (INIS)

    Kahn, B.E.; Rieke, R.D.

    1988-01-01

    Highly reactive uranium and thorium metal powders have been prepared by reduction of the anhydrous metal(IV) chlorides in hydrocarbon solvents. The reduction employs the crystalline hydrocarbon-soluble reducing agent [(TMEDA)Li] 2 [Nap] (TMEDA = N,N,N',N'-tetramethylethylenediamine, Nap = naphthalene). The resulting active metal powders have been shown to be extremely reactive with oxygen-containing compounds and have been used in the reductive coupling of aromatic ketones giving tetra-arylethylenes. Reactions with pinacols have given some mechanistic insight into the ketone coupling reaction. These finely divided metal powders activate very weakly acidic C-H bonds forming metal hydrides, which can be transferred to organic substrates

  4. Uranium

    International Nuclear Information System (INIS)

    Anon.

    1981-01-01

    The French Government has decided to freeze a substantial part of its nuclear power programme. Work has been halted on 18 reactors. This power programme is discussed, as well as the effect it has on the supply of uranium by South Africa

  5. Monte carlo simulations of Yttrium reaction rates in Quinta uranium target

    Directory of Open Access Journals (Sweden)

    Suchopár M.

    2017-01-01

    Full Text Available The international collaboration Energy and Transmutation of Radioactive Waste (E&T RAW performed intensive studies of several simple accelerator-driven system (ADS setups consisting of lead, uranium and graphite which were irradiated by relativistic proton and deuteron beams in the past years at the Joint Institute for Nuclear Research (JINR in Dubna, Russia. The most recent setup called Quinta, consisting of natural uranium target-blanket and lead shielding, was irradiated by deuteron beams in the energy range between 1 and 8 GeV in three accelerator runs at JINR Nuclotron in 2011 and 2012 with yttrium samples among others inserted inside the setup to measure the neutron flux in various places. Suitable activation detectors serve as one of possible tools for monitoring of proton and deuteron beams and for measurements of neutron field distribution in ADS studies. Yttrium is one of such suitable materials for monitoring of high energy neutrons. Various threshold reactions can be observed in yttrium samples. The yields of isotopes produced in the samples were determined using the activation method. Monte Carlo simulations of the reaction rates leading to production of different isotopes were performed in the MCNPX transport code and compared with the experimental results obtained from the yttrium samples.

  6. Monte carlo simulations of Yttrium reaction rates in Quinta uranium target

    Science.gov (United States)

    Suchopár, M.; Wagner, V.; Svoboda, O.; Vrzalová, J.; Chudoba, P.; Tichý, P.; Kugler, A.; Adam, J.; Závorka, L.; Baldin, A.; Furman, W.; Kadykov, M.; Khushvaktov, J.; Solnyshkin, A.; Tsoupko-Sitnikov, V.; Tyutyunnikov, S.; Bielewicz, M.; Kilim, S.; Strugalska-Gola, E.; Szuta, M.

    2017-03-01

    The international collaboration Energy and Transmutation of Radioactive Waste (E&T RAW) performed intensive studies of several simple accelerator-driven system (ADS) setups consisting of lead, uranium and graphite which were irradiated by relativistic proton and deuteron beams in the past years at the Joint Institute for Nuclear Research (JINR) in Dubna, Russia. The most recent setup called Quinta, consisting of natural uranium target-blanket and lead shielding, was irradiated by deuteron beams in the energy range between 1 and 8 GeV in three accelerator runs at JINR Nuclotron in 2011 and 2012 with yttrium samples among others inserted inside the setup to measure the neutron flux in various places. Suitable activation detectors serve as one of possible tools for monitoring of proton and deuteron beams and for measurements of neutron field distribution in ADS studies. Yttrium is one of such suitable materials for monitoring of high energy neutrons. Various threshold reactions can be observed in yttrium samples. The yields of isotopes produced in the samples were determined using the activation method. Monte Carlo simulations of the reaction rates leading to production of different isotopes were performed in the MCNPX transport code and compared with the experimental results obtained from the yttrium samples.

  7. Experimental Observation of Nuclear Reactions in Palladium and Uranium - Possible Explanation by Hydrex Mode

    International Nuclear Information System (INIS)

    Dufour, J.; Murat, D.; Dufour, X.; Foos, J.

    2001-01-01

    Experiments with uranium are presented that show a highly exothermal reaction, which can only be of nuclear origin. One striking point of these results is that they clearly show that what is being observed is not some kind of fusion reaction of the deuterium present (only exceedingly small amounts of it are present). This is a strong indication that hydrogen can trigger nuclear reactions that seem to involve the nuclei of the lattice (which would yield a fission-like pattern of products). Confronted with a situation where some experiments in the field yield a fusion-like pattern of products (CF experiments) and others a fissionlike one (LENR experiments), one can reasonably wonder whether one is not observing two aspects of the same phenomenon. Thus, it is proposed to describe CF and LENR reactions as essentially the same phenomenon based on the possible existence of a still hypothetical proton/electron resonance, which would catalyze fissionlike reactions with a neutron sink. Finally, a series of experiments is proposed to assess this hypothesis

  8. Aquatic pathway variables affecting the estimation of dose commitment from uranium mill tailings

    International Nuclear Information System (INIS)

    Lush, D.L.; Snodgrass, W.J.; McKee, P.

    1982-01-01

    As one of a series of studies being carried out for the Atomic Energy Control Board of Canada, the environmental variables affecting population dose commitment and critical group dose rates from aquatic pathways were investigated. A model was developed to follow uranium and natural thorium decay series radionuclides through aquatic pathways leading both to long-term sediment sinks and to man. Pathways leading to man result in both a population dose commitment and a critical group dose rate. The key variables affecting population dose commitment are suspended particulate concentrations in the receiving aquatic systems, the settling velocities of these particulates and the solid-aqueous phase distribution coefficient associated with each radionuclide. Of secondary importance to population dose commitment are the rate at which radionuclides enter the receiving waters and the value of the water to food transfer coefficients that are used in the model. For the critical group dose rate, the rate at which the radionuclides leave the tailings, the water to food transfer coefficients, the rate of water and fish consumption and the dose conversion factors for 210 Pb and 210 Po are of secondary importance (author)

  9. Terminal uranium(V/VI) nitride activation of carbon dioxide and carbon disulfide. Factors governing diverse and well-defined cleavage and redox reactions

    Energy Technology Data Exchange (ETDEWEB)

    Cleaves, Peter A.; Gardner, Benedict M.; Liddle, Stephen T. [School of Chemistry, The University of Manchester (United Kingdom); Kefalidis, Christos E.; Maron, Laurent [LPCNO, CNRS and INSA, Universite Paul Sabatier, Toulouse (France); Tuna, Floriana; McInnes, Eric J.L. [School of Chemistry and Photon Science Institute, The University of Manchester (United Kingdom); Lewis, William [School of Chemistry, The University of Nottingham (United Kingdom)

    2017-02-24

    The reactivity of terminal uranium(V/VI) nitrides with CE{sub 2} (E=O, S) is presented. Well-defined C=E cleavage followed by zero-, one-, and two-electron redox events is observed. The uranium(V) nitride [U(Tren{sup TIPS})(N)][K(B15C5){sub 2}] (1, Tren{sup TIPS}=N(CH{sub 2}CH{sub 2}NSiiPr{sub 3}){sub 3}; B15C5=benzo-15-crown-5) reacts with CO{sub 2} to give [U(Tren{sup TIPS})(O)(NCO)][K(B15C5){sub 2}] (3), whereas the uranium(VI) nitride [U(Tren{sup TIPS})(N)] (2) reacts with CO{sub 2} to give isolable [U(Tren{sup TIPS})(O)(NCO)] (4); complex 4 rapidly decomposes to known [U(Tren{sup TIPS})(O)] (5) with concomitant formation of N{sub 2} and CO proposed, with the latter trapped as a vanadocene adduct. In contrast, 1 reacts with CS{sub 2} to give [U(Tren{sup TIPS})(κ{sup 2}-CS{sub 3})][K(B15C5){sub 2}] (6), 2, and [K(B15C5){sub 2}][NCS] (7), whereas 2 reacts with CS{sub 2} to give [U(Tren{sup TIPS})(NCS)] (8) and ''S'', with the latter trapped as Ph{sub 3}PS. Calculated reaction profiles reveal outer-sphere reactivity for uranium(V) but inner-sphere mechanisms for uranium(VI); despite the wide divergence of products the initial activation of CE{sub 2} follows mechanistically related pathways, providing insight into the factors of uranium oxidation state, chalcogen, and NCE groups that govern the subsequent divergent redox reactions that include common one-electron reactions and a less-common two-electron redox event. Caution, we suggest, is warranted when utilising CS{sub 2} as a reactivity surrogate for CO{sub 2}. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  10. Study of the Reactions Controlling the Mobility of Uranium in Ground and Surface Water Systems in Contact with Apatite

    International Nuclear Information System (INIS)

    Taffet, M

    2004-01-01

    The objective of this project was to define the mechanisms, equilibria, kinetics, and extent of sorption of aqueous uranium onto hydroxyapatite (Ca 5 (PO 4 ) 3 (OH)) for a range of pH, ionic strength, aqueous uranium concentration, dissolved carbon/air CO 2 , and mineral surface area. We conducted chemical modeling, batch and flow-through experiments, chemical analysis, x-ray absorption and diffraction measurement, and electron microscopy. Our motivation was the need to immobilize U in water and soil to prevent it's entry into water supplies and ultimately, biological systems. Applying hydroxyapatite to in-situ treatment of uranium-bearing ground water could be an effective, low cost technology. We found that hydroxyapatite quickly, effectively, and reversibly sorbed uranium at a high capacity by inner-sphere complexation over a wide range of conditions. Our results indicate that at aqueous uranium concentrations below 10-20 ppb: (1) equilibrium sorption of uranium to hydroxyapatite occurs in hours, regardless of pH; (2) in ambient and CO 2 -free atmospheres, over 98% of initial uranium is sorbed to hydroxyapatite, (3) in waters in equilibrium with higher air CO 2 concentrations, sorption removed over 97% of aqueous uranium, except above pH 9, where aqueous uranium concentrations were reduced by less than 40%, and (4) at near-neutral pH, bicarbonate alkalinities in excess of 500 slightly retarded sorption of uranium to hydroxyapatite, relative to lower alkalinities. Uranium sorption and precipitation are reversible and are not appreciably affected by ionic strength. The reversibility of these reactions requires that in situ treatment be carefully monitored to avoid breakthrough and de-sorption of uranium unto ground water. At typical surface conditions, sorption is the only mode of uranium sequestration below 20-50 ppb U - above this range, precipitation of uranium phosphate minerals begins to dominate sequestration processes. We verified that one m 2 of

  11. Analysis of nuclear reaction products and materials; Preliminary treatment of uranium analysis

    International Nuclear Information System (INIS)

    Soedyartomo.

    1976-01-01

    Pre-treatment of samples is necessary to be done in order to achieve the efficient steps and accurate results of uranium analysis. The pre-treatment is particularly affected by the type of sample, the uranium concentration predicated in the sample, and the uranium analytical method which will be applied. A brief discussion about the pre-treatment of uranium analysis in the uranium ore processing and the reprocessing of spent fuel is given. (author)

  12. Interest of uranium complexes for the mechanism study of the McMurry reaction; Interet des complexes de l`uranium pour l`etude du mecanisme de la reaction de McMurry

    Energy Technology Data Exchange (ETDEWEB)

    Maury, O

    1997-07-04

    The reducing coupling reactions of ketones in diols and olefins are generally carried out with titanium or samarium compounds. In this work uranium complexes have been used. They have allowed to study the chemical reaction mechanism. This thesis is divided into three parts: 1) the reduction mechanism of uranium tetrachloride by cyclic voltametry has been studied at first. It has been shown that this reduction is followed by a transfer reaction of chlorides between the reduced specie of the higher electronic density and UCl . 2) In the second part is described: the synthesis, the crystal structure, the reactivity of the chemical agents, the stereochemistry of diols and alkenes formation and the pinacolisation reaction catalysis. 3) In the last part, the limits of the McMurry reaction are given by the study of the aromatic ketones pinacolisation reaction by-products. The obtained results show that the complexes of the metals which present a high reducing and oxo-philic (Ti, Sm, U..) character react in a similar way with the carbonyl compounds. If the uranium compounds are less used than those of the titanium in the field of the organic synthesis applications, they are precious auxiliaries and excellent models for reactions mechanisms study and for the synthesis methods optimization. (O.M.). 284 refs.

  13. Analysis of reaction cross-section production in neutron induced fission reactions on uranium isotope using computer code COMPLET.

    Science.gov (United States)

    Asres, Yihunie Hibstie; Mathuthu, Manny; Birhane, Marelgn Derso

    2018-04-22

    This study provides current evidence about cross-section production processes in the theoretical and experimental results of neutron induced reaction of uranium isotope on projectile energy range of 1-100 MeV in order to improve the reliability of nuclear stimulation. In such fission reactions of 235 U within nuclear reactors, much amount of energy would be released as a product that able to satisfy the needs of energy to the world wide without polluting processes as compared to other sources. The main objective of this work is to transform a related knowledge in the neutron-induced fission reactions on 235 U through describing, analyzing and interpreting the theoretical results of the cross sections obtained from computer code COMPLET by comparing with the experimental data obtained from EXFOR. The cross section value of 235 U(n,2n) 234 U, 235 U(n,3n) 233 U, 235 U(n,γ) 236 U, 235 U(n,f) are obtained using computer code COMPLET and the corresponding experimental values were browsed by EXFOR, IAEA. The theoretical results are compared with the experimental data taken from EXFOR Data Bank. Computer code COMPLET has been used for the analysis with the same set of input parameters and the graphs were plotted by the help of spreadsheet & Origin-8 software. The quantification of uncertainties stemming from both experimental data and computer code calculation plays a significant role in the final evaluated results. The calculated results for total cross sections were compared with the experimental data taken from EXFOR in the literature, and good agreement was found between the experimental and theoretical data. This comparison of the calculated data was analyzed and interpreted with tabulation and graphical descriptions, and the results were briefly discussed within the text of this research work. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.

  14. Reaction of uranium (IV) with xenon difluoride by chemiluminescence, spectrophotometric, and spectrofluorimetric methods

    Energy Technology Data Exchange (ETDEWEB)

    Mamykin, A.V.; Kazakov, V.P.

    1988-07-01

    A study is made of the kinetics of the chemiluminescent reaction of oxidation of uranium (IV) by xenon difluoride in 1M HClO/sub 4/ U/sup 4 +/ + XeF/sub 2/ ..-->.. UO/sub 2//sup 2 +/ = h/eta/. The optical density D and the intensity of the photoluminescence of the solution I/sub PL/ were measured in parallel with recording of the luminescence intensity I/sub CL/. I/sub CL/ attains a maximum value some time after the beginning of the reaction, after which it decays exponentially. On the kinetic curves of the time dependence of D and I/sub PL/ an induction period is observed, the extent of which depends on concentrations of reagents and temperature of the solution. The maximum of I/sub CL/ coincides with the end of the induction period if the measurements are carried out under identical conditions. The rate of the reaction after the induction period is described by a first order equation in U/sup (IV)/. The rate constants of the reaction, obtained by chemiluminescence, spectrophotometric, and spectrofluorimetric methods, have close values 2.0 +- 0.4, 1.8 +- 0.3, and 2.1 +- 0.3 sec/sup /minus/1/ x 10/sup 2/, respectively. On the basis of the results obtained, we conclude that the stages of formation of UO/sub 2//sup 2 +/ and of chemiluminescence coincide, i.e., formation of the excited state (UD/sub 2//sup 2 +/) and of chemiluminescence coincide, i.e., formation of the excited state (UD/sub 2//sup 2 +/)* takes place during the reaction. It is proposed and experimentally verified that the reaction passes through an intermediate stage of formation of uranyl ion UO/sub 2//sup +/.

  15. A kinetic study of the reaction of water vapor and carbon dioxide on uranium; Cinetique de la reaction de la vapeur d'eau et du dioxyde de carbone sur l'uranium

    Energy Technology Data Exchange (ETDEWEB)

    Santon, J P [Commissariat a l' Energie Atomique, Grenoble (France). Centre d' Etudes Nucleaires

    1964-09-15

    The kinetic study of the reaction of water vapour and carbon dioxide with uranium has been performed by thermogravimetric methods at temperatures between 160 and 410 deg G in the first case, 350 and 1050 deg C in the second: Three sorts of uranium specimens were used: uranium powder, thin evaporated films, and small spheres obtained from a plasma furnace. The experimental results led in the case of water vapour, to a linear rate of reaction controlled by diffusion at the lower temperatures, and by a surface reaction at the upper ones. In the case of carbon dioxide, a parabolic law has been found, controlled by diffusional processes. (author) [French] L'etude cinetique de la reaction de la vapeur d'eau et du dioxyde de carbone sur l'uranium a ete entreprise au moyen de methodes thermogravimetriques, dans te premier cas entre 160 et 410 deg C et dans le second entre 350 et 1050 deg C. Le materiau utilise se presentait sous trois formes: poudres, couches minces evaporees et billes obtenues par fusion en chalumeau a plasma. Les resultats experimentaux ont permis de mettre en evidence, dans le cas de la vapeur d'eau, une cinetique lineaire controlee par la diffusion a basse temperature et d'interface a haute temperature. Dans le cas du dioxyde de carbone par contre, on trouve une cinetique parabolique controlee par la diffusion. (auteur)

  16. Some parameters of uranium hexafluoride plasma produced by products of nuclear reaction

    International Nuclear Information System (INIS)

    Batyrbekov, G.A.; Belyakova, Eh.A.

    1996-01-01

    The probe experimental results of investigation of uranium hexafluoride plasma produced in the centre of nuclear reactor core were demonstrated. Study of uranium hexafluoride plasma is continued by the following reasons: a possibility of U F 6 utilization as nuclear fuel, the utilization of U F 6 as volume source o ionization, search of active laser media compatible with U F 6 that is complicated by lack of constant rates data for most of plasma-chemical reactions with U F 6 and his dissociation products. Cylindrical probe volt-ampere characteristics (VAC) measured in U F 6 plasma at pressure 20 Torr and different thermal neutron fluxes and have following features: -firstly, it is possible to choose a linear part in the field of small positive potentials of probe (0-1) V; - secondary, ion branches of VAC have typical break which current of satiation corresponds to; -thirdly, probe VAC measured at small values of thermal neutron flux density are symmetrical. Diagnostics approaches were used for interpretation VAC of probe. The values of satiation current and linear part of electron branch were calculated, and such plasma parameters as conductivity, diffusion coefficient values of positive and negative ions were determined. The resonance recharge cross section was estimated on diffusion coefficient value

  17. The kinetics of the cerium(IV)-uranium(IV) reaction at low sulfate concentrations

    International Nuclear Information System (INIS)

    Michaille, P.; Kikindai, T.

    1977-01-01

    The rate of oxidation of uranium(IV) by cerium(IV) was measured with a stopped-flow spectrophotometer at sulfuric acid concentrations of 2 x 10 -6 to 0.5 M. At a constant hydrogen ion concentration of 0.5 M, the maximum rate constant was observed for 2 x 10 -3 M sulfuric acid; at that concentration, two sulfate ions were involved in the activated complex. The dependence of the rate constant on the hydrogen ion concentration showed that the reaction paths involving one or two sulfate ions also involved one hydroxyl ion, whereas one hydrogen ion was involved in the five sulfate dependent path. Spectrophotometric measurements supported the existence of a hydrolyzed monosulfatocomplex of cerium(IV). (author)

  18. The influence of alkali metal impurities on the uranium dioxide hydrofluorination reaction

    International Nuclear Information System (INIS)

    Ponelis, A.A.

    1989-01-01

    The effect alkali metal impurities (sodium and potassium) in the uranium dioxide (UO 2 ) feed material have on the conversion to uraniumtetrafluoride (UF 4 ) was examined. A direct correlation exists between impurity level and sintering with concomitant reduced conversion. The sintering mechanism is attributable to decreased specific surface area. The typical 'die-off' of reaction or conversion can be explained in terms of increased particle growth rather than an arbitray zero porosity function. Hydrofluorination temperatures varied from 250 to 650 degrees C using pellets varying in size from 0.42 mm to 10 mm. Scanning electron microscope photographs show clearly the particle or grain growth in the pellet as well as the increased size with impurity level. A new dimensionless constant, N KP , is defined to facilitate explanation of the reaction as a function of pellet radius. N KP is defined as the ratio of pellet diffusion resistance to particle diffusion resistance of the reacting HF gas. At high values of this number (N KP >40) the conversion is limited to the outer periphery of the pellet while at low values (N KP KP at higher reaction temperatures which means that the particle diffusion resistance increases with increasing impurity level and results in easier sintering of these materials. 53 refs., 206 figs., 94 tabs

  19. Deep groundwater redox reactions in the Palmottu uranium deposit: The role of uranium and iron in these processes

    International Nuclear Information System (INIS)

    Bruno, J.; Cera, E.; Duro, L.; Ahonen, L.

    1996-12-01

    The reduction oxidation properties of the deep bedrock and groundwater are important geochemical factors with respect to the chemical stability of the multibarrier system, which isolates the disposed nuclear fuel from biosphere. In the report are described the results of the redox experiments carried out in the field using the natural groundwaters of Palmottu, in Nummi-Pusula, Finland. The experiments include (1) measurements of natural water redox potential values during four to eight hours continuous pumping; (2) monitoring of the redox-potential response to an artificial change of pH of the groundwater. Separate tests were made in iron and uranium-rich groundwaters, respectively. The data of the field experiments were used in the redox-modelling of the iron and uranium systems. In accordance with earlier knowledge, it was showed that dissolved iron is an important redox electrolyte in natural waters, at least at concentration levels of milligrams per liter. However, a striking observation was that in the absence of dissolved iron dissolved uranium (in concentrations of about 200 nM or more) seems to be able to give nernstian response on platinum electrode in acid/base titrations. The effective redox properties of the bedrock-groundwater system depend on the availability and reactivity of solid phases able to exchange electrons with dissolved redox electrolytes. The present results indicate that, in the bedrock/groundwater system of the Palmottu uranium mineralization, uranium minerals are important redox buffers. (orig.) (refs.)

  20. Thermodynamic Simulation of Equilibrium Composition of Reaction Products at Dehydration of a Technological Channel in a Uranium-Graphite Reactor

    Science.gov (United States)

    Pavliuk, A. O.; Zagumennov, V. S.; Kotlyarevskiy, S. G.; Bespala, E. V.

    2018-01-01

    The problems of accumulation of nuclear fuel spills in the graphite stack in the course of operation of uranium-graphite nuclear reactors are considered. The results of thermodynamic analysis of the processes in the graphite stack at dehydration of a technological channel, fuel element shell unsealing and migration of fission products, and activation of stable nuclides in structural elements of the reactor and actinides inside the graphite moderator are given. The main chemical reactions and compounds that are produced in these modes in the reactor channel during its operation and that may be hazardous after its shutdown and decommissioning are presented. Thermodynamic simulation of the equilibrium composition is performed using the specialized code TERRA. The results of thermodynamic simulation of the equilibrium composition in different cases of technological channel dehydration in the course of the reactor operation show that, if the temperature inside the active core of the nuclear reactor increases to the melting temperature of the fuel element, oxides and carbides of nuclear fuel are produced. The mathematical model of the nonstationary heat transfer in a graphite stack of a uranium-graphite reactor in the case of the technological channel dehydration is presented. The results of calculated temperature evolution at the center of the fuel element, the replaceable graphite element, the air gap, and in the surface layer of the block graphite are given. The numerical results show that, in the case of dehydration of the technological channel in the uranium-graphite reactor with metallic uranium, the main reaction product is uranium dioxide UO2 in the condensed phase. Low probability of production of pyrophoric uranium compounds (UH3) in the graphite stack is proven, which allows one to disassemble the graphite stack without the risk of spontaneous graphite ignition in the course of decommissioning of the uranium-graphite nuclear reactor.

  1. Uranium

    International Nuclear Information System (INIS)

    Battey, G.C.; McKay, A.D.

    1988-01-01

    Production for 1986 was 4899 t U 3 O 8 (4154 t U), 30% greater than in 1985, mainly because of a 39% increase in production at Ranger. Exports for 1986 were 4166 t U 3 O 8 at an average f.o.b. unit value of $40.57/lb U 3 O 8 . Private exploration expenditure for uranium in Australia during the 1985-86 fiscal year was $50.2 million. Plans were announced to increase the nominal capacity of the processing plant at Ranger from 3000 t/year U 3 O 8 to 4500 t and later to 6000 t/year. Construction and initial mine development at Olympic Dam began in March. Production is planned for mid 1988 at an annual rate of 2000 t U 3 O 8 , 30 000 t Cu, and 90 000 oz (2800 kg) Au. The first long-term sales agreement was concluded in September 1986. At the Manyingee deposit, testing of the alkaline solution mining method was completed, and the treatment plant was dismantled. Spot market prices (in US$/lb U 3 O 8 ) quoted by Nuexco were generally stable. From January-October the exchange value fluctuated from US$17.00-US$17.25; for November and December it was US$16.75. Australia's Reasonably Assured Resources of uranium recoverable at less than US$80/kg U at December 1986 were estimated as 462 000 t U, 3000 t U less than in 1985. This represents 30% of the total low-cost RAR in the WOCA (World Outside the Centrally Planned Economy Areas) countries. Australia also has 257 000 t U in the low-cost Estimated Additional Resources Category I, 29% of the WOCA countries' total resources in this category

  2. Unexpected Reaction Pathway for butyrylcholinesterase-catalyzed inactivation of “hunger hormone” ghrelin

    Science.gov (United States)

    Yao, Jianzhuang; Yuan, Yaxia; Zheng, Fang; Zhan, Chang-Guo

    2016-02-01

    Extensive computational modeling and simulations have been carried out, in the present study, to uncover the fundamental reaction pathway for butyrylcholinesterase (BChE)-catalyzed hydrolysis of ghrelin, demonstrating that the acylation process of BChE-catalyzed hydrolysis of ghrelin follows an unprecedented single-step reaction pathway and the single-step acylation process is rate-determining. The free energy barrier (18.8 kcal/mol) calculated for the rate-determining step is reasonably close to the experimentally-derived free energy barrier (~19.4 kcal/mol), suggesting that the obtained mechanistic insights are reasonable. The single-step reaction pathway for the acylation is remarkably different from the well-known two-step acylation reaction pathway for numerous ester hydrolysis reactions catalyzed by a serine esterase. This is the first time demonstrating that a single-step reaction pathway is possible for an ester hydrolysis reaction catalyzed by a serine esterase and, therefore, one no longer can simply assume that the acylation process must follow the well-known two-step reaction pathway.

  3. Electron exchange reaction in anion exchangers as observed in uranium isotope separation

    International Nuclear Information System (INIS)

    Obanawa, Heiichiro; Takeda, Kunihiko; Seko, Maomi

    1991-01-01

    The mechanism of electron exchange in an ion exchanger, as occurring between U 4+ and UO 2 2+ in uranium isotope separation, was investigated. The height of the separation unit (H q ) in the presence of metal ion catalysts, as obtained from the separation experiments, was found to be almost coincident with the theoretical value of H q as calculated on the basis of the intrasolution acceleration mechanism of the metal ion, suggesting that the electron exchange mechanism in the ion-exchanger is essentially the same as that in the solution when metal ion catalysts are present. Separation experiments with no metal ion catalyst, on the other hand, showed the electron exchange reaction in the ion exchanger to be substantially higher than that in the solution, suggesting an acceleration of the electron exchange reaction by the ion-exchanger which is due to the close existence of higher order Cl - complexes of UO 2 2+ and U 4+ in the vicinity of the ion-exchange group. (author)

  4. Intermediate- and high-energy reactions of uranium with neon and carbon

    International Nuclear Information System (INIS)

    McGaughey, P.L.

    1982-11-01

    Target fragment production from the interactions of 1.0, 3.0, 4.8, and 12 GeV 12 C and 5.0, 8.0, 20, and 42 GeV 20 Ne with uranium has been measured using off-line gamma-ray spectroscopic techniques. The experimental charge and mass yield distributions are generally consistent with the concepts of limiting fragmentation and factorization at energies of 3.0 GeV and above. The total projectile kinetic energy was found to be the relevant scaling parameter for the comparison of reactions induced by projectiles of different sizes. Light fragments with mass number less than 60 were found to violate limiting fragmentation, and had excitation functions that were strongly increasing with projectile energy until 8.0 to 12.0 GeV. With the 1.0 GeV 12 C beam the pattern of mass yields was quite different from that of all the other reactions, with the normal peak in the fission mass region (80 < A < 145), but with much lower yields below mass number 60 and between mass numbers 145 and 210, indicating that these fragments are formed primarily in very energetic reactions in which large excitation energies are transferred to and significant amounts of mass are removed from the target nucleus. Theoretical predictions of the intra-nuclear cascade, nuclear fireball, and nuclear firestreak models are compared with the experimental results. The intra-nuclear cascade and nuclear firestreak models are both able to predict the general shapes of the experimental distributions, with the exception of the yields for the lightest fragments

  5. The Oklo natural nuclear reactors: neutron parameters, age and duration of the reactions, uranium and fission products migrations

    International Nuclear Information System (INIS)

    Ruffenach, J.-C.

    1979-09-01

    Mass spectrometry and isotopic dilution technique are used in order to carry out, on various samples from the fossil nuclear reactors at Oklo, Gabon, isotopic and chemical analyses of some particular elements involved in the nuclear reactions: uranium, lead, bismuth, thorium, rare gases (krypton, xenon), rare earths (neodymium, samarium, europium, gadolinium, dysprosium), ruthenium and palladium. Interpretations of these analyses lead to the determination of many neutron parameters such as the neutron fluence received by the samples, the spectrum index, the conversion coefficient, and also the percentages of fissions due to uranium-238 and plutonium-239 and the total number of fissions relative to uranium. All these results make it possible to determine the age of the nuclear reactions by measuring the amounts of fission rare earths formed, i.e. 1.97 billion years. This study brings some informations to the general problem of radioactive wastes storage in deep geological formations, the storage of uranium, plutonium and many fission products having been carried out naturally, and for about two billion years [fr

  6. Enzyme sequence similarity improves the reaction alignment method for cross-species pathway comparison

    Energy Technology Data Exchange (ETDEWEB)

    Ovacik, Meric A. [Chemical and Biochemical Engineering Department, Rutgers University, Piscataway, NJ 08854 (United States); Androulakis, Ioannis P., E-mail: yannis@rci.rutgers.edu [Chemical and Biochemical Engineering Department, Rutgers University, Piscataway, NJ 08854 (United States); Biomedical Engineering Department, Rutgers University, Piscataway, NJ 08854 (United States)

    2013-09-15

    Pathway-based information has become an important source of information for both establishing evolutionary relationships and understanding the mode of action of a chemical or pharmaceutical among species. Cross-species comparison of pathways can address two broad questions: comparison in order to inform evolutionary relationships and to extrapolate species differences used in a number of different applications including drug and toxicity testing. Cross-species comparison of metabolic pathways is complex as there are multiple features of a pathway that can be modeled and compared. Among the various methods that have been proposed, reaction alignment has emerged as the most successful at predicting phylogenetic relationships based on NCBI taxonomy. We propose an improvement of the reaction alignment method by accounting for sequence similarity in addition to reaction alignment method. Using nine species, including human and some model organisms and test species, we evaluate the standard and improved comparison methods by analyzing glycolysis and citrate cycle pathways conservation. In addition, we demonstrate how organism comparison can be conducted by accounting for the cumulative information retrieved from nine pathways in central metabolism as well as a more complete study involving 36 pathways common in all nine species. Our results indicate that reaction alignment with enzyme sequence similarity results in a more accurate representation of pathway specific cross-species similarities and differences based on NCBI taxonomy.

  7. Enzyme sequence similarity improves the reaction alignment method for cross-species pathway comparison

    International Nuclear Information System (INIS)

    Ovacik, Meric A.; Androulakis, Ioannis P.

    2013-01-01

    Pathway-based information has become an important source of information for both establishing evolutionary relationships and understanding the mode of action of a chemical or pharmaceutical among species. Cross-species comparison of pathways can address two broad questions: comparison in order to inform evolutionary relationships and to extrapolate species differences used in a number of different applications including drug and toxicity testing. Cross-species comparison of metabolic pathways is complex as there are multiple features of a pathway that can be modeled and compared. Among the various methods that have been proposed, reaction alignment has emerged as the most successful at predicting phylogenetic relationships based on NCBI taxonomy. We propose an improvement of the reaction alignment method by accounting for sequence similarity in addition to reaction alignment method. Using nine species, including human and some model organisms and test species, we evaluate the standard and improved comparison methods by analyzing glycolysis and citrate cycle pathways conservation. In addition, we demonstrate how organism comparison can be conducted by accounting for the cumulative information retrieved from nine pathways in central metabolism as well as a more complete study involving 36 pathways common in all nine species. Our results indicate that reaction alignment with enzyme sequence similarity results in a more accurate representation of pathway specific cross-species similarities and differences based on NCBI taxonomy

  8. Parallel proton transfer pathways in aqueous acid-base reactions

    NARCIS (Netherlands)

    Cox, M.J.; Bakker, H.J.

    2008-01-01

    We study the mechanism of proton transfer (PT) between the photoacid 8-hydroxy-1,3, 6-pyrenetrisulfonic acid (HPTS) and the base chloroacetate in aqueous solution. We investigate both proton and deuteron transfer reactions in solutions with base concentrations ranging from 0.25M to 4M. Using

  9. Exposure pathways and health effects associated with chemical and radiological toxicity of natural uranium: a review.

    Science.gov (United States)

    Brugge, Doug; de Lemos, Jamie L; Oldmixon, Beth

    2005-01-01

    Natural uranium exposure derives from the mining, milling, and processing of uranium ore, as well as from ingestion of groundwater that is naturally contaminated with uranium. Ingestion and inhalation are the primary routes of entry into the body. Absorption of uranium from the lungs or digestive track is typically low but can vary depending on compound specific solubility. From the blood, two-thirds of the uranium is excreted in urine over the first 24 hours and up to 80% to 90% of uranium deposited in the bone leaves the body within 1.5 years. The primary health outcomes of concern documented with respect to uranium are renal, developmental, reproductive, diminished bone growth, and DNA damage. The reported health effects derive from experimental animal studies and human epidemiology. The Lowest Observed Adverse Effect Level (LOAEL) derived from animal studies is 50 microg/m3 for inhalation and 60 ug/kg body weight/day for ingestion. The current respiratory standard of the Occupational Safety and Health Administration (OSHA), 50 microg/m3, affords no margin of safety. Considering the safety factors for species and individual variation, the ingestion LOAEL corresponds to the daily consumption set by the World Health Organization Drinking Water Standard at 2 microg/L. Based on economic considerations, the United States Environmental Protection Agency maximum contaminant level is 30 microg/L. Further research is needed, with particular attention on the impact of uranium on indigenous populations, on routes of exposure in communities near uranium sites, on the combined exposures present at many uranium sites, on human developmental defects, and on health effects at or below established exposure standards.

  10. Fixation and reduction of uranium by natural organic matter: reaction mechanisms and kinetics

    International Nuclear Information System (INIS)

    Nakashima, S.; Perruchot, A.; Trichet, J.; Disnar, J.R.

    1987-01-01

    The reactivity of lignite towards soluble uranyl species in an aqueous medium is experimentally investigated as a function of temperature (between 20 0 C and 400 0 C). The fixation process starts near 45 0 C, with reduction beginning around 120 0 C. The fixation process leads to the formation of chemically and thermally stable organo-uranyl species. The reduction of free uranyl species is accompanied by a stoichiometric (2:1) liberation of protons into the medium. These protons originate from the organic matter which thus undergoes dehydrogenation. The general evolution of the carbonaceous residue in the course of this reaction shows that alcoholic and aliphatic hydrocarbon groups are responsible for the reduction. This chemical dehydrogenation could explain the low hydrogen content of natural organic materials associated with uraniferous deposits. The kinetics of the reduction step have been studied at 180 0 C, 190 0 C and 200 0 C. The kinetic parameters determined over this temperature range, and the extrapolation made to 20 0 C, show that reduction can be a crucial process in the geochemical behaviour of uranium especially in the thermal conditions in which sedimentary basins evolve [fr

  11. Analytical definition of fission chain reaction parameters for cylindrical uranium bar and energy release evaluations for HIF hybrid targets

    International Nuclear Information System (INIS)

    Imshennik, V.S.

    2006-01-01

    Within the conditions of Heavy-Ion Fusion (HIF) arises a possibility to obtain the fission chain reaction for a cylindrical HIF target. The paper contains the solution interpolated with the diffusion approximation in order to receive the general approximation expressions for the bar critical radius as well as for over-critical state. The obtained critical parameters generalized for uranium envelope are used for rough evaluation of the energy release in HIF hybrid targets [ru

  12. Purification of hydrogen under a free or combined form in a gaseous mixture, by chemical reactions with uranium

    International Nuclear Information System (INIS)

    Caron Charles, M.

    1988-03-01

    Within the framework of the european fusion program, we are dealing with the purification of hydrogen (tritium) under a free or combined form, from a H 2 , N 2 , NH 3 , CH 4 , O 2 , gaseous mixture. The process consists in cracking the hydrogenated molecules and absorbing the impurities by chemical reactions with uranium, without holding back hydrogen. In the temperature range: 950 K [fr

  13. Subcritical hydrothermal conversion of organic wastes and biomass. Reaction pathways

    Directory of Open Access Journals (Sweden)

    Alejandro Amadeus Castro Vega

    2007-01-01

    Full Text Available Hydrothermal conversion is a procedure which emulates organic matter’s natural conversion into bio-crude having physical and chemical properties analogous to petroleum. The artificial transformation of biomass requi- res previous knowledge of the main reaction routes and product availability. The main component of biomass (depolymerisation by hydrolysis is presented in hydrothermal cellulose conversion, producing oligosaccharides which exhibit dehydration and retro-aldol condensation reactions for transforming into furfurals and carboxylic acids. Other biomass components (such as lignin, proteins, and fat esters present both hydrolysis and pyrolysis reaction routes. As long as biomass mainly contains carbohydrates, subcritical hydrothermal conversion products and their wastes will be fundamentally analogous to those displaying cellulose. These substances have added- value by far surpassing raw material’s acquisition cost. When the main hydrothermal conversion products’ O/C, H/C molar ratios as reported in literature are plotted, an evolutionary tralectory for conversion products appears to be closely or even overlapped with fossil fuels’ geological evolution.

  14. Permanganate oxidation of α-amino acids: kinetic correlations for the nonautocatalytic and autocatalytic reaction pathways.

    Science.gov (United States)

    Perez-Benito, Joaquin F

    2011-09-08

    The reactions of permanganate ion with seven α-amino acids in aqueous KH(2)PO(4)/K(2)HPO(4) buffers have been followed spectrophotometrically at two different wavelengths: 526 nm (decay of MnO(4)(-)) and 418 nm (formation of colloidal MnO(2)). All of the reactions studied were autocatalyzed by colloidal MnO(2), with the contribution of the autocatalytic reaction pathway decreasing in the order glycine > l-threonine > l-alanine > l-glutamic acid > l-leucine > l-isoleucine > l-valine. The rate constants corresponding to the nonautocatalytic and autocatalytic pathways were obtained by means of either a differential rate law or an integrated one, the latter requiring the use of an iterative method for its implementation. The activation parameters for the two pathways were determined and analyzed to obtain statistically significant correlations for the series of reactions studied. The activation enthalpy of the nonautocatalytic pathway showed a strong, positive dependence on the standard Gibbs energy for the dissociation of the protonated amino group of the α-amino acid. Linear enthalpy-entropy correlations were found for both pathways, leading to isokinetic temperatures of 370 ± 21 K (nonautocatalytic) and 364 ± 28 K (autocatalytic). Mechanisms in agreement with the experimental data are proposed for the two reaction pathways.

  15. On the deduction of chemical reaction pathways from measurements of time series of concentrations.

    Science.gov (United States)

    Samoilov, Michael; Arkin, Adam; Ross, John

    2001-03-01

    We discuss the deduction of reaction pathways in complex chemical systems from measurements of time series of chemical concentrations of reacting species. First we review a technique called correlation metric construction (CMC) and show the construction of a reaction pathway from measurements on a part of glycolysis. Then we present two new improved methods for the analysis of time series of concentrations, entropy metric construction (EMC), and entropy reduction method (ERM), and illustrate (EMC) with calculations on a model reaction system. (c) 2001 American Institute of Physics.

  16. Effects of reaction-kinetic parameters on modeling reaction pathways in GaN MOVPE growth

    Science.gov (United States)

    Zhang, Hong; Zuo, Ran; Zhang, Guoyi

    2017-11-01

    In the modeling of the reaction-transport process in GaN MOVPE growth, the selections of kinetic parameters (activation energy Ea and pre-exponential factor A) for gas reactions are quite uncertain, which cause uncertainties in both gas reaction path and growth rate. In this study, numerical modeling of the reaction-transport process for GaN MOVPE growth in a vertical rotating disk reactor is conducted with varying kinetic parameters for main reaction paths. By comparisons of the molar concentrations of major Ga-containing species and the growth rates, the effects of kinetic parameters on gas reaction paths are determined. The results show that, depending on the values of the kinetic parameters, the gas reaction path may be dominated either by adduct/amide formation path, or by TMG pyrolysis path, or by both. Although the reaction path varies with different kinetic parameters, the predicted growth rates change only slightly because the total transport rate of Ga-containing species to the substrate changes slightly with reaction paths. This explains why previous authors using different chemical models predicted growth rates close to the experiment values. By varying the pre-exponential factor for the amide trimerization, it is found that the more trimers are formed, the lower the growth rates are than the experimental value, which indicates that trimers are poor growth precursors, because of thermal diffusion effect caused by high temperature gradient. The effective order for the contribution of major species to growth rate is found as: pyrolysis species > amides > trimers. The study also shows that radical reactions have little effect on gas reaction path because of the generation and depletion of H radicals in the chain reactions when NH2 is considered as the end species.

  17. A method for integrating and ranking the evidence for biochemical pathways by mining reactions from text

    Science.gov (United States)

    Miwa, Makoto; Ohta, Tomoko; Rak, Rafal; Rowley, Andrew; Kell, Douglas B.; Pyysalo, Sampo; Ananiadou, Sophia

    2013-01-01

    Motivation: To create, verify and maintain pathway models, curators must discover and assess knowledge distributed over the vast body of biological literature. Methods supporting these tasks must understand both the pathway model representations and the natural language in the literature. These methods should identify and order documents by relevance to any given pathway reaction. No existing system has addressed all aspects of this challenge. Method: We present novel methods for associating pathway model reactions with relevant publications. Our approach extracts the reactions directly from the models and then turns them into queries for three text mining-based MEDLINE literature search systems. These queries are executed, and the resulting documents are combined and ranked according to their relevance to the reactions of interest. We manually annotate document-reaction pairs with the relevance of the document to the reaction and use this annotation to study several ranking methods, using various heuristic and machine-learning approaches. Results: Our evaluation shows that the annotated document-reaction pairs can be used to create a rule-based document ranking system, and that machine learning can be used to rank documents by their relevance to pathway reactions. We find that a Support Vector Machine-based system outperforms several baselines and matches the performance of the rule-based system. The success of the query extraction and ranking methods are used to update our existing pathway search system, PathText. Availability: An online demonstration of PathText 2 and the annotated corpus are available for research purposes at http://www.nactem.ac.uk/pathtext2/. Contact: makoto.miwa@manchester.ac.uk Supplementary information: Supplementary data are available at Bioinformatics online. PMID:23813008

  18. The Photoconversion of Phytochrome Includes an Unproductive Shunt Reaction Pathway.

    Science.gov (United States)

    Buhrke, David; Kuhlmann, Uwe; Michael, Norbert; Hildebrandt, Peter

    2018-03-05

    Phytochromes are modular bimodal photoswitches that control gene expression for morphogenetic processes in plants. These functions are triggered by photoinduced conversions between the inactive and active states of the photosensory module, denoted as Pr and Pfr, respectively. In the present time-resolved resonance Raman spectroscopic study of bacterial representatives of this photoreceptor family, we demonstrate that these phototransformations do not represent linear processes but include a branching reaction back to the initial state, prior to (de)activation of the output module. Thus, only a fraction of the photoreceptors undergoing the phototransformations can initiate the downstream signaling process, consistent with phytochrome's function as a sensor for more durable changes of light conditions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. X-ray photoelectron spectroscopy study of CO2 reaction with polycrystalline uranium surface

    International Nuclear Information System (INIS)

    Liu Kezhao; Yu Yong; Zhou Juesheng; Wu Sheng; Wang Xiaolin; Fu Yibei

    1999-10-01

    The adsorption of CO 2 on 'clean' depleted polycrystalline uranium metal surface has been studied by X-ray photoelectron spectroscopy (XPS) at 300 K. The 'clean' surface were prepared by Ar + ion sputtering under ultra-high vacuum (UHV) condition with a base pressure 6.7 x 10 -8 Pa. The result s shows that adsorption of CO 2 on 'clean' uranium metal took place in total dissociation, and leads to the formation of uranium dioxide, uranium carbides and free carbon. The total dissociation of CO 2 produced carbon, oxygen species, CO 2 2- and CO 3 2- species. The diffusion tendency of carbon was much stronger than that of oxygen, and led to form a carbide in oxide-metal interface while the oxygen remained on their surface as an oxide

  20. The reaction of uranium in the U-O2-H2O and U-H2O systems

    International Nuclear Information System (INIS)

    Pearce, R.J.; Kay, P.

    1987-09-01

    The reaction of uranium in dry air, moist air and oxygen free moisture has been studied thermogravimetrically over the temperature range 105-325 0 C and at water vapour pressures up to 100 kPa. It has been shown that in dry air the kinetics are complex and appear to result from parallel reactions involving both parabolic and linear rate laws. In oxygen free moisture, linear kinetics were obeyed and a near stoichiometric UO 2 reaction product was formed. Oxygen markedly inhibited the moisture reaction at the lower temperatures in the range examined but the degree of inhibition, as shown by weight gain measurements, decreased with increasing temperature such that, at the higher temperatures, there was little difference in reaction rates. At all temperatures, the production of hydrogen was markedly inhibited by the presence of air suggesting that the principal reaction was with free oxygen. However in moist conditions the reaction rate exhibited a dependency on the water vapour pressure according to k α psup(n) where n ∼ 0.3 in air and ∼ 0.5 in oxygen free conditions. The mechanism of the oxidation reaction is discussed. (author)

  1. Biological pathways of exposure and ecotoxicity values for uranium and associated radionuclides: Chapter D in Hydrological, geological, and biological site characterization of breccia pipe uranium deposits in Northern Arizona

    Science.gov (United States)

    Hinck, Jo E.; Linder, Greg L.; Finger, Susan E.; Little, Edward E.; Tillitt, Donald E.; Kuhne, Wendy

    2010-01-01

    This chapter compiles available chemical and radiation toxicity information for plants and animals from the scientific literature on naturally occurring uranium and associated radionuclides. Specifically, chemical and radiation hazards associated with radionuclides in the uranium decay series including uranium, thallium, thorium, bismuth, radium, radon, protactinium, polonium, actinium, and francium were the focus of the literature compilation. In addition, exposure pathways and a food web specific to the segregation areas were developed. Major biological exposure pathways considered were ingestion, inhalation, absorption, and bioaccumulation, and biota categories included microbes, invertebrates, plants, fishes, amphibians, reptiles, birds, and mammals. These data were developed for incorporation into a risk assessment to be conducted as part of an environmental impact statement for the Bureau of Land Management, which would identify representative plants and animals and their relative sensitivities to exposure of uranium and associated radionuclides. This chapter provides pertinent information to aid in the development of such an ecological risk assessment but does not estimate or derive guidance thresholds for radionuclides associated with uranium. Previous studies have not attempted to quantify the risks to biota caused directly by the chemical or radiation releases at uranium mining sites, although some information is available for uranium mill tailings and uranium mine closure activities. Research into the biological impacts of uranium exposure is strongly biased towards human health and exposure related to enriched or depleted uranium associated with the nuclear energy industry rather than naturally occurring uranium associated with uranium mining. Nevertheless, studies have reported that uranium and other radionuclides can affect the survival, growth, and reproduction of plants and animals. Exposure to chemical and radiation hazards is influenced by a

  2. Metabolic control analysis of biochemical pathways based on a thermokinetic description of reaction rates

    DEFF Research Database (Denmark)

    Nielsen, Jens Bredal

    1997-01-01

    Metabolic control analysis is a powerful technique for the evaluation of flux control within biochemical pathways. Its foundation is the elasticity coefficients and the flux control coefficients (FCCs). On the basis of a thermokinetic description of reaction rates it is here shown...... that the elasticity coefficients can be calculated directly from the pool levels of metabolites at steady state. The only requirement is that one thermodynamic parameter be known, namely the reaction affinity at the intercept of the tangent in the inflection point of the curve of reaction rate against reaction...... of the thermokinetic description of reaction rates to include the influence of effecters. Here the reaction rate is written as a linear function of the logarithm of the metabolite concentrations. With this type of rate function it is shown that the approach of Delgado and Liao [Biochem. J. (1992) 282, 919-927] can...

  3. Study of the optimal reaction conditions for assay of the mouse alternative complement pathway

    NARCIS (Netherlands)

    Dijk, H. van; Rademaker, P.M.; Klerx, J.P.A.M.; Willers, J.M.M.

    1985-01-01

    The optimal reaction conditions for hemolytic assay of alternative complement pathway activity in mouse serum were investigated. A microtiter system was used, in which a number of 7.5×106 rabbit erythrocytes per test well appeared to be optimal. Rabbit erythrocytes were superior as target cells over

  4. Catalytic Hydrotreatment of Fast Pyrolysis Oil : Model Studies on Reaction Pathways for the Carbohydrate Fraction

    NARCIS (Netherlands)

    Wildschut, J.; Arentz, J.; Rasrendra, C. B.; Venderbosch, R. H.; Heeres, H. J.

    2009-01-01

    Fast pyrolysis oil can be upgraded by a catalytic hydrotreatment (250-400 degrees C, 100-200 bar) using heterogeneous catalysts such as Ru/C to hydrocarbon-like products that can serve as liquid transportation fuels. Insight into the complex reaction pathways of the various component fractions

  5. Computed Potential Energy Surfaces and Minimum Energy Pathways for Chemical Reactions

    Science.gov (United States)

    Walch, Stephen P.; Langhoff, S. R. (Technical Monitor)

    1994-01-01

    Computed potential energy surfaces are often required for computation of such parameters as rate constants as a function of temperature, product branching ratios, and other detailed properties. For some dynamics methods, global potential energy surfaces are required. In this case, it is necessary to obtain the energy at a complete sampling of all the possible arrangements of the nuclei, which are energetically accessible, and then a fitting function must be obtained to interpolate between the computed points. In other cases, characterization of the stationary points and the reaction pathway connecting them is sufficient. These properties may be readily obtained using analytical derivative methods. We have found that computation of the stationary points/reaction pathways using CASSCF/derivative methods, followed by use of the internally contracted CI method to obtain accurate energetics, gives usefull results for a number of chemically important systems. The talk will focus on a number of applications including global potential energy surfaces, H + O2, H + N2, O(3p) + H2, and reaction pathways for complex reactions, including reactions leading to NO and soot formation in hydrocarbon combustion.

  6. RhoA/ROCK Signaling Pathway Mediates Shuanghuanglian Injection-Induced Pseudo-allergic Reactions.

    Science.gov (United States)

    Han, Jiayin; Zhao, Yong; Zhang, Yushi; Li, Chunying; Yi, Yan; Pan, Chen; Tian, Jingzhuo; Yang, Yifei; Cui, Hongyu; Wang, Lianmei; Liu, Suyan; Liu, Jing; Deng, Nuo; Liang, Aihua

    2018-01-01

    Background: Shuanghuanglian injection (SHLI) is a famous Chinese medicine used as an intravenous preparation for the treatment of acute respiratory tract infections. In the recent years, the immediate hypersensitivity reactions induced by SHLI have attracted broad attention. However, the mechanism involved in these reactions has not yet been elucidated. The present study aims to explore the characteristics of the immediate hypersensitivity reactions induced by SHLI and deciphers the role of the RhoA/ROCK signaling pathway in these reactions. Methods: SHLI-immunized mice or naive mice were intravenously injected (i.v.) with SHLI (600 mg/kg) once, and vascular leakage in the ears was evaluated. Passive cutaneous anaphylaxis test was conducted using sera collected from SHLI-immunized mice. Naive mice were administered (i.v.) with a single dose of 150, 300, or 600 mg/kg of SHLI, and vascular leakage, histamine release, and histopathological alterations in the ears, lungs, and intestines were tested. In vitro , human umbilical vein endothelial cell (HUVEC) monolayer was incubated with SHLI (0.05, 0.1, or 0.15 mg/mL), and the changes in endothelial permeability and cytoskeleton were observed. Western blot analysis was performed and ROCK inhibitor was employed to investigate the contribution of the RhoA/ROCK signaling pathway in SHLI-induced hypersensitivity reactions, both in HUVECs and in mice. Results: Our results indicate that SHLI was able to cause immediate dose-dependent vascular leakage, edema, and exudates in the ears, lungs, and intestines, and histamine release in mice. These were pseudo-allergic reactions, as SHLI-specific IgE was not elicited during sensitization. In addition, SHLI induced reorganization of actin cytoskeleton and disrupted the endothelial barrier. The administration of SHLI directly activated the RhoA/ROCK signaling pathway both in HUVECs and in the ears, lungs, and intestines of mice. Fasudil hydrochloride, a ROCK inhibitor, ameliorated the

  7. Density Functional Theory Study of Competitive Reaction Pathways of Ti+ with Fluorinated Acetone in the Gas Phase

    International Nuclear Information System (INIS)

    Hong, Kiryong; Kim, Tae Kyu

    2012-01-01

    We investigate the doublet and quartet potential energy surfaces associated with the gas-phase reaction between Ti + and CF 3 COCH 3 for two plausible reaction pathways, TiF 2 + and TiO + formation pathways by using the density functional theory (DFT) method. The molecular structures of intermediates and transition states involved in these reaction pathways are optimized at the DFT level by using the PBE0 functional. All transition states are identified by using the intrinsic reaction coordinate (IRC) method, and the resulting reaction coordinates describe how Ti + activates CF 3 COCH 3 and produces TiF 2 + and TiO + as products. On the basis of presented results, we propose the most favorable reaction pathway in the reaction between Ti + and CF 3 COCH 3

  8. Thermodynamic isotope effects of D2 and T2 reaction with uranium

    International Nuclear Information System (INIS)

    Huang Gang; Long Xinggui; Liang Jianhua; Yang Benfu; Liu Wenke

    2010-01-01

    The p-c-T curves of deuterium and tritium absorption by uranium and p-t curves of desorption were measured. The balance pressure of absorption and desorption on different temperatures were got and then the thermodynamic parameters were determined according to the Van't Hoff equation. It shows that the balance pressure of deuterium absorption is lower than that of tritium absorption on the same temperature and atom ratio. It has the same phenomena for desorption but there are obvious hysteresis effect for reversible process of absorption and desorption. There are a little thermodynamic isotope effects when deuterium and tritium absorption and desorption by uranium estimating from enthalpy and entropy values. (authors)

  9. Reaction pathways for catalytic gas-phase oxidation of glycerol over mixed metal oxides

    Energy Technology Data Exchange (ETDEWEB)

    Suprun, W.; Glaeser, R.; Papp, H. [Leipzig Univ. (Germany). Inst. of Chemical Technology

    2011-07-01

    Glycerol as a main by-product from bio-diesel manufacture is a cheap raw material with large potential for chemical or biochemical transformations to value-added C3-chemicals. One possible way of glycerol utilization involves its catalytic oxidation to acrylic acid as an alternative to petrochemical routes. However, this catalytic conversion exhibits various problems such as harsh reaction conditions, severe catalyst coking and large amounts of undesired by-products. In this study, the reaction pathways for gas-phase conversion of glycerol over transition metal oxides (Mo, V und W) supported on TiO{sub 2} and SiO{sub 2} were investigated by two methods: (i) steady state experiments of glycerol oxidation and possible reactions intermediates, i.e., acrolein, 3-hydroxy propionaldehyde and acetaldehyde, and (ii) temperature-programmed surface reaction (TPSR) studies of glycerol conversion in the presence and in the absence of gas-phase oxygen. It is shown that the supported W-, V and Mo-oxides possess an ability to catalyze the oxidation of glycerol to acrylic acid. These investigations allowed us to gain a deeper insight into the reaction mechanism. Thus, based on the obtained results, three possible reactions pathways for the selective oxidation of glycerol to acrylic acid on the transition metal-containing catalysts are proposed. The major pathways in presence of molecular oxygen are a fast successive destructive oxidation of glycerol to CO{sub x} and the dehydration of glycerol to acrolein which is a rate-limiting step. (orig.)

  10. Exploring the Reaction Pathways of Bioglycerol Hydrodeoxygenation to Propene over Molybdena-Based Catalysts.

    Science.gov (United States)

    Zacharopoulou, Vasiliki; Vasiliadou, Efterpi S; Lemonidou, Angeliki A

    2018-01-10

    The one-step reaction of glycerol with hydrogen to form propene selectively is a particularly challenging catalytic pathway that has not yet been explored thoroughly. Molybdena-based catalysts are active and selective to C-O bond scission; propene is the only product in the gas phase under the standard reaction conditions, and further hydrogenation to propane is impeded. Within this context, this work focuses on the exploration of the reaction pathways and the investigation of various parameters that affect the catalytic performance, such as the role of hydrogen on the product distribution and the effect of the catalyst pretreatment step. Under a hydrogen atmosphere, propene is produced primarily via 2-propenol, whereas under an inert atmosphere propanal and glycerol dissociation products are formed mainly. The reaction most likely proceeds through a reverse Mars-van Krevelen mechanism as partially reduced Mo species drive the reaction to the formation of the desired product. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Computed Potential Energy Surfaces and Minimum Energy Pathway for Chemical Reactions

    Science.gov (United States)

    Walch, Stephen P.; Langhoff, S. R. (Technical Monitor)

    1994-01-01

    Computed potential energy surfaces are often required for computation of such observables as rate constants as a function of temperature, product branching ratios, and other detailed properties. We have found that computation of the stationary points/reaction pathways using CASSCF/derivative methods, followed by use of the internally contracted CI method with the Dunning correlation consistent basis sets to obtain accurate energetics, gives useful results for a number of chemically important systems. Applications to complex reactions leading to NO and soot formation in hydrocarbon combustion are discussed.

  12. The role of grain boundaries and transient porosity increase as fluid pathways for reaction front propagation

    Science.gov (United States)

    Jonas, Laura; John, Timm; Geisler, Thorsten; Putnis, Andrew

    2013-04-01

    The pseudomorphic replacement of Carrara marble by calcium phosphates was studied as a model system to examine the influence of different fluid pathways for reaction front propagation induced by fluid-rock interaction. In this model system, the grain boundaries present in the rock and the transient porosity structures developing throughout the replacement reaction enable the reaction front to progress further into the rock as well as to the center of each single grain until complete transformation. Hydrothermal treatment of the marble using phosphate bearing solutions at temperature levels of 150° C and 200° C for different durations lead to the formation of two product phases which were identified as hydroxyapatite [Ca5(PO4)3OH] as well as β-tricalcium phosphate [β-Ca3(PO4)2] (β-TCP). The formation of β-TCP was probably favored by the presence of ~0.6wt.% of Mg in the parent phase. Completely transformed single grains show a distinctive zoning, both in composition and texture. Whereas areas next to the grain boundary consist of nearly pure hydroxyapatite and show a coarse porosity, areas close to the center of the single grains show a high amount of β-TCP and a very fine porous microstructure. If F was added as an additional solution component, the formation of β-TCP was avoided and up to 3wt.% of F were incorporated into the product apatite. The use of the isotope 18O as a chronometer for the replacement reaction makes it possible to reconstruct the chronological development of the calcium phosphate reaction front. Raman analysis revealed that the incorporation of 18O in the PO4 tetrahedron of hydroxyapatite results in the development of distinct profiles in the calcium phosphate reaction front perpendicular to the grain boundaries of the marble. Through the use of the 18O chronometer, it is possible to estimate and compare the time effectiveness of the different fluid pathways in this model system. The results show that the grain boundaries serve as a

  13. Spectrographic determination of boron and silicon in uranium tetrafluoride: Study of the chemical reactions in the electrode cavity when ZnO is used as a uranium excitation suppressor; Determinacion espectrografica de Boro y Silicio en Tetrafluoruro de Unraio: Estudio de las reacciones quimicas que tienen lugar en el crater del electrodo al autilizar ZnO como supresor de la excitacion del Uranio

    Energy Technology Data Exchange (ETDEWEB)

    Alduan, F. A.; Capdevila, C.; Rosa, M.

    1973-07-01

    A method has been developed for determining traces of boron and silicon in uranium tetrafluoride. Use is made of zinc oxide to decrease the volatilization of uranium and achieve high sensitivities. The thermochemical reactions which occur in the anode cavity during the arcing process have been investigated. UO{sub 2} and a uranium, zinc and fluorine compound, both less volatile than uranium tetrafluoride, are formed. (Author)

  14. Reaction-transport simulations of non-oxidative methane conversion with continuous hydrogen removal: Homogeneous-heterogeneous methane reaction pathways

    International Nuclear Information System (INIS)

    Li, Lin; Borry, Richard W.; Iglesia, Enrique

    2000-01-01

    Detailed kinetic-transport models were used to explore thermodynamic and kinetic barriers in the non-oxidative conversion of CH4 via homogeneous and homogeneous-heterogeneous pathways and the effects of continuous hydrogen removal and of catalytic sites on attainable yields of useful C2-C10 products. The homogeneous kinetic model combines separately developed models for low-conversion pyrolysis and for chain growth to form large aromatics and carbon. The H2 formed in the reaction decreases CH4 pyrolysis rates and equilibrium conversions and it favors the formation of lighter products. The removal of H2 along tubular reactors with permeable walls increases reaction rates and equilibrium CH4 conversions. C2-C10 yields reach values greater than 90 percent at intermediate values of dimensionless transport rates (delta=1-10), defined as the ratio hydrogen transport and methane conversion rates. Homogeneous reactions require impractical residence times, even with H2 removal, because of slow initiation and chain transfer rates. The introduction of heterogeneous chain initiation pathways using surface sites that form methyl radicals eliminates the induction period without influencing the homogeneous product distribution. Methane conversion, however, occurs predominately in the chain transfer regime, within which individual transfer steps and the formation of C2 intermediates become limited by thermodynamic constraints. Catalytic sites alone cannot overcome these constraints. Catalytic membrane reactors with continuous H2 removal remove these thermodynamic obstacles and decrease the required residence time. Reaction rates become limited by homogeneous reactions of C2 products to form C6+ aromatics. Higher delta values lead to subsequent conversion of the desired C2-C10 products to larger polynuclear aromatics. We conclude that catalytic methane pyrolysis at the low temperatures required for restricted chain growth and the elimination of thermodynamics constraints via

  15. Reaction pathways of model compounds of biomass-derived oxygenates on Fe/Ni bimetallic surfaces

    Science.gov (United States)

    Yu, Weiting; Chen, Jingguang G.

    2015-10-01

    Controlling the activity and selectivity of converting biomass-derivatives to fuels and valuable chemicals is critical for the utilization of biomass feedstocks. There are primarily three classes of non-food competing biomass, cellulose, hemicellulose and lignin. In the current work, glycolaldehyde, furfural and acetaldehyde are studied as model compounds of the three classes of biomass-derivatives. Monometallic Ni(111) and monolayer (ML) Fe/Ni(111) bimetallic surfaces are studied for the reaction pathways of the three biomass surrogates. The ML Fe/Ni(111) surface is identified as an efficient surface for the conversion of biomass-derivatives from the combined results of density functional theory (DFT) calculations and temperature programmed desorption (TPD) experiments. A correlation is also established between the optimized adsorption geometry and experimental reaction pathways. These results should provide helpful insights in catalyst design for the upgrading and conversion of biomass.

  16. Catalytic Hydrotreatment of Fast Pyrolysis Oil: Model Studies on Reaction Pathways for the Carbohydrate Fraction

    OpenAIRE

    Wildschut, J.; Arentz, J.; Rasrendra, C. B.; Venderbosch, R. H.; Heeres, H. J.

    2009-01-01

    Fast pyrolysis oil can be upgraded by a catalytic hydrotreatment (250-400 degrees C, 100-200 bar) using heterogeneous catalysts such as Ru/C to hydrocarbon-like products that can serve as liquid transportation fuels. Insight into the complex reaction pathways of the various component fractions during hydrotreatment is desirable to reduce the formation of by-products such as char and gaseous components. This paper deals with the catalytic hydrotreatment of representative model components for t...

  17. Cross Sections for the Production of Residual Nuclides by Proton-Induced Reactions with Uranium at Medium Energies

    International Nuclear Information System (INIS)

    Issa, S.A.M.; Michel, R.; Uosif, M.A.M.; Issa, S.A.M.; Flamentc, J.L.; David, J.C.; Leray, S.

    2009-01-01

    The production of residual nuclides by proton-induced reactions on uranium is investigated using activated targets from irradiation experiments at Saturne II synchrocyclotron at the Laboratory National Saturne/Saclay. These investigations contribute to the European research project NUDATRA within the IP EUROTRANS in which the feasibility of accelerator-driven transmutation of nuclear waste is evaluated. Experimental cross sections are derived from gamma-spectrometric measurements. A total of 1894 cross-section was deter-mined covering 44 residual nuclides in the energy range from 211 MeV to 2530 MeV. The experimental data together with those of earlier work of our group are discussed in the context of theoretical excitation functions calculated by the newly developed INCL4 + ABLA and the TALYS codes

  18. Some potential strategies for the treatment of waste uranium metal and uranium alloys

    International Nuclear Information System (INIS)

    Burns, C.J.; Frankcom, T.M.; Gordon, P.L.; Sauer, N.N.

    1993-01-01

    Large quantities of uranium metal chips and turnings stored throughout the DOE Complex represent a potential hazard, due to the reactivity of this material toward air and water. Methods are being sought to mitigate this by conversion of the metal, via room temperature solutions routes, to a more inert oxide form. In addition, the recycling of uranium and concomitant recovery of alloying metals is a desirable goal. The emphasis of the authors' research is to explore a variety of oxidation and reduction pathways for uranium and its compounds, and to investigate how these reactions might be applied to the treatment of bulk wastes

  19. Position-specific isotope modeling of organic micropollutants transformation through different reaction pathways

    International Nuclear Information System (INIS)

    Jin, Biao; Rolle, Massimo

    2016-01-01

    The degradation of organic micropollutants occurs via different reaction pathways. Compound specific isotope analysis is a valuable tool to identify such degradation pathways in different environmental systems. We propose a mechanism-based modeling approach that provides a quantitative framework to simultaneously evaluate concentration as well as bulk and position-specific multi-element isotope evolution during the transformation of organic micropollutants. The model explicitly simulates position-specific isotopologues for those atoms that experience isotope effects and, thereby, provides a mechanistic description of isotope fractionation occurring at different molecular positions. To demonstrate specific features of the modeling approach, we simulated the degradation of three selected organic micropollutants: dichlorobenzamide (BAM), isoproturon (IPU) and diclofenac (DCF). The model accurately reproduces the multi-element isotope data observed in previous experimental studies. Furthermore, it precisely captures the dual element isotope trends characteristic of different reaction pathways as well as their range of variation consistent with observed bulk isotope fractionation. It was also possible to directly validate the model capability to predict the evolution of position-specific isotope ratios with available experimental data. Therefore, the approach is useful both for a mechanism-based evaluation of experimental results and as a tool to explore transformation pathways in scenarios for which position-specific isotope data are not yet available. - Highlights: • Mechanism-based, position-specific isotope modeling of micropollutants degradation. • Simultaneous description of concentration and primary and secondary isotope effects. • Key features of the model are demonstrated with three illustrative examples. • Model as a tool to explore reaction mechanisms and to design experiments. - We propose a modeling approach incorporating mechanistic information and

  20. Kinetics of the oxidation-reduction reactions of uranium, neptunium, plutonium, and americium in aqueous solutions

    International Nuclear Information System (INIS)

    Newton, T.W.

    1975-01-01

    This is a review with about 250 references. Data for 240 reactions are cataloged and quantitative activation parameters are tabulated for 79 of these. Some empirical correlations are given. Twelve typical reactions are discussed in detail, along with the effects of self-irradiation and ionic strength. (U.S.)

  1. Reaction of UO/sub 2//sup 2 +/ with Chromazurol S and the spectrophotometric determination of uranium in the presence of Septonex

    Energy Technology Data Exchange (ETDEWEB)

    Kanicky, V [Geological Survey Ostrava, Establishment Brno (Czechoslovakia); Havel, J; Sommer, L [Universita J.E. Purkyne, Brno (Czechoslovakia). Prirodovedecka Fakulta

    1980-05-01

    A detailed study is described of the reaction of UO/sub 2//sup 2 +/ with chromazurol S in the presence of cationic surfactant Septonex which was found to be very promising of the group of cationic surfactants. A number of conclusions were drawn regarding the effect of the cationic surfactant on the reaction of triphenylmethane dyes with salicylic acid groups with metal cations. The optimum conditions for the spectrophotometric determination of uranium with chromazurol S in the presence of Septonex were found.

  2. Combustion modeling and kinetic rate calculations for a stoichiometric cyclohexane flame. 1. Major reaction pathways.

    Science.gov (United States)

    Zhang, Hongzhi R; Huynh, Lam K; Kungwan, Nawee; Yang, Zhiwei; Zhang, Shaowen

    2007-05-17

    The Utah Surrogate Mechanism was extended in order to model a stoichiometric premixed cyclohexane flame (P = 30 Torr). Generic rates were assigned to reaction classes of hydrogen abstraction, beta scission, and isomerization, and the resulting mechanism was found to be adequate in describing the combustion chemistry of cyclohexane. Satisfactory results were obtained in comparison with the experimental data of oxygen, major products and important intermediates, which include major soot precursors of C2-C5 unsaturated species. Measured concentrations of immediate products of fuel decomposition were also successfully reproduced. For example, the maximum concentrations of benzene and 1,3-butadiene, two major fuel decomposition products via competing pathways, were predicted within 10% of the measured values. Ring-opening reactions compete with those of cascading dehydrogenation for the decomposition of the conjugate cyclohexyl radical. The major ring-opening pathways produce 1-buten-4-yl radical, molecular ethylene, and 1,3-butadiene. The butadiene species is formed via beta scission after a 1-4 internal hydrogen migration of 1-hexen-6-yl radical. Cascading dehydrogenation also makes an important contribution to the fuel decomposition and provides the exclusive formation pathway of benzene. Benzene formation routes via combination of C2-C4 hydrocarbon fragments were found to be insignificant under current flame conditions, inferred by the later concentration peak of fulvene, in comparison with benzene, because the analogous species series for benzene formation via dehydrogenation was found to be precursors with regard to parent species of fulvene.

  3. Effects of Water Molecule on CO Oxidation by OH: Reaction Pathways, Kinetic Barriers, and Rate Constants.

    Science.gov (United States)

    Zhang, Linyao; Yang, Li; Zhao, Yijun; Zhang, Jiaxu; Feng, Dongdong; Sun, Shaozeng

    2017-07-06

    The water dilute oxy-fuel combustion is a clean combustion technology for near-zero emission power; and the presence of water molecule could have both kinetic and dynamic effects on combustion reactions. The reaction OH + CO → CO 2 + H, one of the most important elementary reactions, has been investigated by extensive electronic structure calculations. And the effects of a single water molecule on CO oxidation have been studied by considering the preformed OH(H 2 O) complex reacts with CO. The results show little change in the reaction pathways, but the additional water molecule actually increases the vibrationally adiabatic energy barriers (V a G ). Further thermal rate constant calculations in the temperature range of 200 to 2000 K demonstrate that the total low-pressure limit rate constant for the water assisted OH(H 2 O) + CO → CO 2 + H 2 O + H reaction is 1-2 orders lower than that of the water unassisted one, which is consistent with the change of V a G . Therefore, the hydrated radical OH(H 2 O) would actually slow down the oxidation of CO. Meanwhile, comparisons show that the M06-2X/aug-cc-pVDZ method gives a much better estimation in energy and thus is recommended to be employed for direct dynamics simulations.

  4. Laboratory-scale catalysis studies of uranium and plutonium fluorination reactions by solid metal-fluorides

    International Nuclear Information System (INIS)

    Hochel, R.C.

    1984-03-01

    Various catalysts were evaluated for their effect on the rate of fluorination of the tetrafluorides of uranium and plutonium to produce the hexafluorides. Results of this work show that CoF 3 and AgF 2 are more effective than NiF 2 for UF 4 fluorination, producing rate increases in the range of 150 to 300 compared to UF 4 and fluorine alone. The use of these three catalysts was also found effective in the fluorinations of PuO 2 /PuF 4 and pure PuF 4 . However, enhancements were less. NiF 2 produced the best increases which were 8.1 for PuO 2 /PuF 4 and 3.6 for PuF 4 . Experiments were conducted in a simple flow-loop. Even larger enhancements might be obtained with fluidized beds. Details of the apparatus, experiments, methods, and a discussion of results are presented

  5. Degradation of ibuprofen by hydrodynamic cavitation: Reaction pathways and effect of operational parameters.

    Science.gov (United States)

    Musmarra, Dino; Prisciandaro, Marina; Capocelli, Mauro; Karatza, Despina; Iovino, Pasquale; Canzano, Silvana; Lancia, Amedeo

    2016-03-01

    Ibuprofen (IBP) is an anti-inflammatory drug whose residues can be found worldwide in natural water bodies resulting in harmful effects to aquatic species even at low concentrations. This paper deals with the degradation of IBP in water by hydrodynamic cavitation in a convergent-divergent nozzle. Over 60% of ibuprofen was degraded in 60 min with an electrical energy per order (EEO) of 10.77 kWh m(-3) at an initial concentration of 200 μg L(-1) and a relative inlet pressure pin=0.35 MPa. Five intermediates generated from different hydroxylation reactions were identified; the potential mechanisms of degradation were sketched and discussed. The reaction pathways recognized are in line with the relevant literature, both experimental and theoretical. By varying the pressure upstream the constriction, different degradation rates were observed. This effect was discussed according to a numerical simulation of the hydroxyl radical production identifying a clear correspondence between the maximum kinetic constant kOH and the maximum calculated OH production. Furthermore, in the investigated experimental conditions, the pH parameter was found not to affect the extent of degradation; this peculiar feature agrees with a recently published kinetic insight and has been explained in the light of the intermediates of the different reaction pathways. Copyright © 2015 Elsevier B.V. All rights reserved.

  6. Applications of fluorescence techniques to the study of uranium in homogeneous and heterogeneous environments: hydrolysis and photo-reduction reactions on titanium dioxide

    International Nuclear Information System (INIS)

    Eliet, Veronique

    1996-01-01

    This thesis describes the use of Time-Resolved Fluorescence to characterise the spectroscopy of hydroxo-complexes of hexavalent Uranium, and to study photochemical reactions involving these species at mineral/water interfaces. The instrumentation used comprised of either an excimer laser coupled to an optical multichannel analyser OMA or a Nd-YAG laser coupled to a stroboscopic photomultiplier. The hydrolysis of Uranium at a constant temperature of 25 deg. C, has been studied in the pH ranges 0-5 and 9-12. Deconvolution of spectra and fluorescence decay curves for Uranium yielded individual fluorescence spectra and decay times for uranyl UO 2 2+ and its hydroxo-complexes UO 2 OH + , (UO 2 )2(OH) 2 2+ , (UO 2 ) 3 (OH) 5 + et UO 2 (OH) 3 - . The comparison of fluorescence efficiencies for the various species showed that the complex (UO 2 )2(OH) 2 2+ is up to 85 times more fluorescent than uranyl, depending on the emission wavelength. Further, investigations of fluorescence decays as a function of temperature in the pH range 0-6, yielded activation energies for the various Uranium hydroxo species. The knowledge gained in homogeneous media served in the study of the photochemical behaviour of Uranium in suspensions of the semi-conductor mineral, TiO 2 . After UV-light absorption, charge carriers formed at the mineral surface were found to reduce hexavalent Uranium to the tetravalent oxidation state. Time-Resolved Fluorescence Spectroscopy has been used to monitor the kinetics of the oxidation state change. A reaction mechanism is proposed on the basis of results obtained by studying the kinetics of the process at different values of pH The role of humic substances on the heterogeneous redox reaction has also been examined. (author) [fr

  7. Process for electrolytically preparing uranium metal

    Science.gov (United States)

    Haas, Paul A.

    1989-01-01

    A process for making uranium metal from uranium oxide by first fluorinating uranium oxide to form uranium tetrafluoride and next electrolytically reducing the uranium tetrafluoride with a carbon anode to form uranium metal and CF.sub.4. The CF.sub.4 is reused in the fluorination reaction rather than being disposed of as a hazardous waste.

  8. An Alternative Reaction Pathway for Iridium Catalyzed Water Oxidation Driven by CAN

    KAUST Repository

    Bucci, Alberto

    2016-06-10

    The generation of solar fuels by means of a photosynthetic apparatus strongly relies on the development of an efficient water oxidation catalyst (WOC). Cerium ammonium nitrate (CAN) is the most commonly used sacrificial oxidant to explore the potentiality of WOCs. It is usually assumed that CAN has the unique role to oxidatively energize WOCs, making them capable to offer a low energy reaction pathway to transform H2O to O2. Herein we show that CAN might have a much more relevant and direct role in WO, mainly related to the capture and liberation of O–O containing molecular moieties.

  9. An Alternative Reaction Pathway for Iridium Catalyzed Water Oxidation Driven by CAN

    KAUST Repository

    Bucci, Alberto; Menendez Rodriguez, Gabriel; Bellachioma, Gianfranco; Zuccaccia, Cristiano; Poater, Albert; Cavallo, Luigi; Macchioni, Alceo

    2016-01-01

    The generation of solar fuels by means of a photosynthetic apparatus strongly relies on the development of an efficient water oxidation catalyst (WOC). Cerium ammonium nitrate (CAN) is the most commonly used sacrificial oxidant to explore the potentiality of WOCs. It is usually assumed that CAN has the unique role to oxidatively energize WOCs, making them capable to offer a low energy reaction pathway to transform H2O to O2. Herein we show that CAN might have a much more relevant and direct role in WO, mainly related to the capture and liberation of O–O containing molecular moieties.

  10. Heterogeneous reaction of particulate chlorpyrifos with NO3 radicals: Products, pathways, and kinetics

    Science.gov (United States)

    Li, Nana; Zhang, Peng; Yang, Bo; Shu, Jinian; Wang, Youfeng; Sun, Wanqi

    2014-08-01

    Chlorpyrifos is a typical chlorinated organophosphorus pesticide. The heterogeneous reaction of chlorpyrifos particles with NO3 radicals was investigated using a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS) and a real-time atmospheric gas analysis mass spectrometer. Chlorpyrifos oxon, 3,5,6-trichloro-2-pyridinol, O,O-diethyl O-hydrogen phosphorothioate, O,O-diethyl ester thiophosphoric acid, diethyl hydrogen phosphate and a phosphinyl disulfide compound were identified as the main degradation products. The heterogeneous reaction pathways were proposed and their kinetic processes were investigated via a mixed-phase relative rate method. The observed effective rate constant is 3.4 ± 0.2 × 10-12 cm3 molecule-1 s-1.

  11. Elementary steps and reaction pathways in the aqueous phase alkylation of phenol with ethanol

    Energy Technology Data Exchange (ETDEWEB)

    Eckstein, Sebastian; Hintermeier, Peter H.; Olarte, Mariefel V.; Liu, Yue; Baráth, Eszter; Lercher, Johannes A.

    2017-08-01

    The hydronium ion normalized reaction rate in aqueous phase alkylation of phenol with ethanol on H-MFI zeolites increases with decreasing concentration of acid sites. Higher rates are caused by higher concentrations of phenol in the zeolite pores, as the concentration of hydronium ions generated by zeolite Brønsted acid sites decreases. Considering the different concentrations of reacting species it is shown that the intrinsic rate constant for alkylation is independent of the concentration of hydronium ions in the zeolite pores. Alkylation at the aromatic ring of phenol and of toluene as well as O-alkylation of phenol have the same activation energy, 104 ± 5 kJ/mol. This is energetic barrier to form the ethyl carbenium ion from ethanol associated to the hydronium ion. Thus, in both the reaction pathways the catalyst involves a carbenium ion, which forms a bond to a nucleophilic oxygen (ether formation) or carbon (alkylation).

  12. Reaction Pathways in Catechol/Primary Amine Mixtures: A Window on Crosslinking Chemistry.

    Directory of Open Access Journals (Sweden)

    Juan Yang

    Full Text Available Catechol chemistry is used as a crosslinking tool abundantly in both natural organisms (e.g. mussels, sandcastle worms and synthetic systems to achieve the desired mechanical properties. Despite this abundance and success, the crosslinking chemistry is still poorly understood. In this study, to simplify the system, yet to capture the essential chemistry, model compounds 4-methyl catechol and propylamine are used. The reaction of 4-methyl catechol (2 mM with propylamine (6 mM is carried out in the presence of NaIO4 (2 mM in 10 mM Na2CO3 aqueous solution. A variety of spectroscopic/spectrometric and chromatographic methods such as 1H NMR, LC-MS, and UV-VIS are used to track the reaction and identify the products/intermediates. It is found that the crosslinking chemistry of a catechol and an amine is both fast and complicated. Within five minutes, more than 60 products are formed. These products encompass 19 different masses ranging from molecular weight of 179 to 704. By combining time-dependent data, it is inferred that the dominant reaction pathways: the majority is formed via aryloxyl-phenol coupling and Michael-type addition, whereas a small fraction of products is formed via Schiff base reactions.

  13. Reaction pathways for reduction of nitrate ions on platinum, rhodium, and platinum-rhodium alloy electrodes

    International Nuclear Information System (INIS)

    Cunha, M.C.P.M. da; De Souza, J.P.I.; Nart, F.C.

    2000-01-01

    The reduction of nitrate ions on platinum, rhodium, and platinum-rhodium alloy electrodes has been investigated using differential electrochemical mass spectrometry and in situ FTIR measurements. For 3 M HNO 3 concentration it has been found that nitrate starts the reduction with partial N-O bond dissociation and N-N bond formation generating NO and N 2 O. At potentials lower than 0.2 V the reaction proceeds forming dissolved NH 4 + . For potentials lower than 0 V the reduction continues via a multiple pathway reaction leading to the nonselective production of N 2 , NH 2 OH, and N 2 H 2 . On the alloyed electrodes, the production of NO and N 2 O has been observed in both cathodic and anodic scans, while on pure platinum and rhodium electrodes the reaction has been observed only during the cathodic scan. Contrasting with the pure platinum and rhodium alloys, where the N-O bond break starts forming NO and N 2 O, on the alloys HNO 2 has been observed as the first reaction step. For alloys with higher rhodium composition, like Pt 75 Rh 25 , no N 2 has been detected for potentials lower than 0 V

  14. Electrophilic properties of patulin. Adduct structures and reaction pathways with 4-bromothiophenol and other model nucleophiles.

    Science.gov (United States)

    Fliege, R; Metzler, M

    2000-05-01

    The mycotoxin patulin (PAT) is believed to exert its cytotoxic and chromosome-damaging effects by forming covalent adducts with essential cellular thiols. Since the chemical structures of such adducts are unknown to date, we have studied the reaction of PAT and its O-acetylated derivative with the monofunctional thiol model compound 4-bromothiophenol (BTP), which was chosen due to analytical advantages. By means of analytical and preparative high-performance liquid chromatography, 16 adducts of PAT and 3 adducts of acetyl-PAT were isolated and their chemical structures elucidated by (1)H and (13)C NMR, IR, and UV spectroscopy. Time course studies and analysis of daughter product formation from isolated intermediate adducts led to a detailed scheme for the reaction of PAT with BTP. The structures of adducts of PAT formed with other model nucleophiles, e. g., the aliphatic thiol 2-mercaptoethanol and the aromatic amine 4-bromoaniline, were also elucidated and found to corroborate the reaction scheme. In addition, one further reaction pathway was observed with 2-mercaptoethanol, which appears to be independent from those found for BTP. Our study with model nucleophiles provides insights into the electrophilic reactivity of PAT and proved to be useful for the structure elucidation of PAT adducts with biological nucleophiles of toxicological relevance, as will be reported by Fliege and Metzler [(2000) Chem. Res. Toxicol. 13, 373-381].

  15. Matrix isolation infrared spectra of O2 and N2 insertion reactions with atomic uranium

    International Nuclear Information System (INIS)

    Hunt, R.D.; Toth, L.M.; Yustein, J.T.; Andrews, L.

    1993-01-01

    Laser ablation of refractory metals can be an effective source of vapor for matrix isolation IR studies. This combination of techniques was used for the first time to study the mechanisms of U vapor reactions with atmospheric components. U atoms and O 2 were codeposited with excess Ar at 12 K. The dominant codeposition products were UO 2 and UO 3 . In contrast, the UO yield was always small because UO 2 is formed by an insertion mechanism. This mechanism was verified in the 16 O 2 / 18 O 2 experiments which failed to produce 16 OU 18 O. The effects of UV photolysis and matrix annealings were also examined. The U atoms and O 2 reaction requires little or no activation energy since UO 2 was formed from cold reagents. New charge-transfer species, (UO 2+ 2 )(O 2- 2 ) and (UO + 2 )(O - 2 ), and a weak complex, UO 3 --O 2 , were primarily produced under conditions which favored further O 2 reactions. Similar U atom and N 2 experiments produced only linear NUN which is also produced by an insertion mechanism. This U reaction represents the first time that atom was observed breaking and inserting into the triple bond of N 2 . Photolysis dramatically increased the NUN yield by 3-fold. Matrix annealings produced weak UN 2 --N 2 and UN 2 --2N 2 complexes

  16. Matrix isolation infrared spectra of O2 and N2 insertion reactions with atomic uranium

    Science.gov (United States)

    Hunt, Rodney D.; Toth, L. Mac; Yustein, Jason T.; Andrews, Lester

    1993-10-01

    Laser ablation of refractory metals can be an effective source of vapor for matrix isolation IR studies. This combination of techniques was used for the first time to study the mechanisms of U vapor reactions with atmospheric components. U atoms and O2 were codeposited with excess Ar at 12 K. The dominant codeposition products were UO2 and UO3. In contrast, the UO yield was always small because UO2 is formed by an insertion mechanism. This mechanism was verified in the 16O2/18O2 experiments which failed to produce 16OU18O. The effects of UV photolysis and matrix annealings were also examined. The U atoms and O2 reaction requires little or no activation energy since UO2 was formed from cold reagents. New charge-transfer species, (UO2+2)(O2-2) and (UO+2)(O-2), and a weak complex, UO3-O2, were primarily produced under conditions which favored further O2 reactions. Similar U atom and N2 experiments produced only linear NUN which is also produced by an insertion mechanism. This U reaction represents the first time that atom was observed breaking and inserting into the triple bond of N2. Photolysis dramatically increased the NUN yield by 3-fold. Matrix annealings produced weak UN2-N2 and UN2-2N2 complexes.

  17. Reduction of uranium hexafluoride to uranium tetrafluoride

    International Nuclear Information System (INIS)

    Chang, I.S.; Do, J.B.; Choi, Y.D.; Park, M.H.; Yun, H.H.; Kim, E.H.; Kim, Y.W.

    1982-01-01

    The single step continuous reduction of uranium hexafluoride (UF 6 ) to uranium tetrafluoride (UF 4 ) has been investigated. Heat required to initiate and maintain the reaction in the reactor is supplied by the highly exothermic reaction of hydrogen with a small amount of elemental fluorine which is added to the uranium hexafluoride stream. When gases uranium hexafluoride and hydrogen react in a vertical monel pipe reactor, the green product, UF 4 has 2.5g/cc in bulk density and is partly contaminated by incomplete reduction products (UF 5 ,U 2 F 9 ) and the corrosion product, presumably, of monel pipe of the reactor itself, but its assay (93% of UF 4 ) is acceptable for the preparation of uranium metal with magnesium metal. Remaining problems are the handling of uranium hexafluoride, which is easily clogging the flowmeter and gas feeding lines because of extreme sensitivity toward moisture, and a development of gas nozzel for free flow of uranium hexafluoride gas. (Author)

  18. Reaction pathway and oxidation mechanisms of dibutyl phthalate by persulfate activated with zero-valent iron

    Energy Technology Data Exchange (ETDEWEB)

    Li, Huanxuan [School of Environment and Energy, South China University of Technology, Guangzhou 510006 (China); The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, China, Guangzhou 510640 (China); Wan, Jinquan, E-mail: ppjqwan@scut.edu.cn [School of Environment and Energy, South China University of Technology, Guangzhou 510006 (China); The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, China, Guangzhou 510640 (China); State Key Lab Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640 (China); Ma, Yongwen [School of Environment and Energy, South China University of Technology, Guangzhou 510006 (China); The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, China, Guangzhou 510640 (China); State Key Lab Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640 (China); Wang, Yan [School of Environment and Energy, South China University of Technology, Guangzhou 510006 (China); The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, China, Guangzhou 510640 (China)

    2016-08-15

    This study investigated reaction pathway and oxidation mechanisms of dibutyl phthalate (DBP) by persulfate (PS) activated with zero-valent iron (ZVI). The DBP degradation was studied at three pH values (acidic, neutral and basic) in the presence of different organic scavengers. Using a chemical probe method, both sulfate radical (SO{sub 4}·{sup −}) and hydroxyl radical (·OH) were found to be primary oxidants at pH 3.0 and pH 7.0, respectively while ·OH was the major specie to oxidize DBP at pH 11.0. A similar result was found in an experiment of Electron Spin Resonance spin-trapping where in addition to ·OH, superoxide radical (O{sub 2}·{sup −}) was detected at pH 11.0. The transformation of degradation products including dimethyl phthalate (DMP), diethyl phthalate (DEP), phthalic anhydride, and acetophenone exhibited diverse variation during the reaction processes. The phthalic anhydride concentration appeared to be maximum at all pHs. Another eleven intermediate products were also found at pH 3.0 by GC–MS and HPLC analysis, and their degradation mechanisms and pathways were proposed. It was suggested that dealkylation, hydroxylation, decarboxylation and hydrogen extraction were the dominant degradation mechanisms of DBP at pH 3.0. - Highlights: • Both SO{sub 4}{sup −}· and ·OH were found to be the major active species at pH 3.0 and pH 7.0. • ·OH and ·O2– were the primary oxidants pH 11.0. • The intermediate products were investigated as well as the degradation pathway. • Dealkylation, hydroxylation, decarboxylation, H-extraction were the major mechanisms.

  19. Conferring specificity in redox pathways by enzymatic thiol/disulfide exchange reactions.

    Science.gov (United States)

    Netto, Luis Eduardo S; de Oliveira, Marcos Antonio; Tairum, Carlos A; da Silva Neto, José Freire

    2016-01-01

    Thiol-disulfide exchange reactions are highly reversible, displaying nucleophilic substitutions mechanism (S(N)2 type). For aliphatic, low molecular thiols, these reactions are slow, but can attain million times faster rates in enzymatic processes. Thioredoxin (Trx) proteins were the first enzymes described to accelerate thiol-disulfide exchange reactions and their high reactivity is related to the high nucleophilicity of the attacking thiol. Substrate specificity in Trx is achieved by several factors, including polar, hydrophobic, and topological interactions through a groove in the active site. Glutaredoxin (Grx) enzymes also contain the Trx fold, but they do not share amino acid sequence similarity with Trx. A conserved glutathione binding site is a typical feature of Grx that can reduce substrates by two mechanisms (mono and dithiol). The high reactivity of Grx enzymes is related to the very acid pK(a) values of reactive Cys that plays roles as good leaving groups. Therefore, although distinct oxidoreductases catalyze similar thiol–disulfide exchange reactions, their enzymatic mechanisms vary. PDI and DsbA are two other oxidoreductases, but they are involved in disulfide bond formation, instead of disulfide reduction, which is related to the oxidative environment where they are found. PDI enzymes and DsbC are endowed with disulfide isomerase activity, which is related with their tetra-domain architecture. As illustrative description of specificity in thiol-disulfide exchange, redox aspects of transcription activation in bacteria, yeast, and mammals are presented in an evolutionary perspective. Therefore, thiol-disulfide exchange reactions play important roles in conferring specificity to pathways, a required feature for signaling.

  20. Oklo natural reactor. Study of uranium and rare earths migration on a core drilled through a reaction zone. Application to determination of the date of the nuclear reaction by measurement of fission products

    International Nuclear Information System (INIS)

    Ruffenach, J.C.

    1977-01-01

    Isotopic and chemical analysis of uranium and five rare earths: neodymium, samarium, europium, gadolinium and dysprosium were effected on fourteen samples taken in the same core drilled through a reaction zone of the Oklo uranium deposit. This study points out the general stability of uranium and fission rare earths; spatial distributions of these elements are quite analogous. Migrations have affected about 5% only of fission neodymium in the core of the reaction zone; corresponding values for samarium and gadolinium are slightly higher. These migration phenomena have carried rare earths to no more than 80 cm out of the core. By study of the europium it is shown that nuclear reactions have stayed in the ground since the time of reactions. On the other hand it is shown by analysis of the dysprosium that rare earths have not undergone an important movement. This study allow also the datation of nuclear reactions from the measurement of the quantity of fission neodymium produced. A value of 1.98x10 9 years is obtained slightly higher than the value obtained by geochronology [fr

  1. Standard Test Method for Measuring Reaction Rates by Radioactivation of Uranium-238

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2008-01-01

    1.1 This test method covers procedures for measuring reaction rates by assaying a fission product (F.P.) from the fission reaction 238U(n,f)F.P. 1.2 The reaction is useful for measuring neutrons with energies from approximately 1.5 to 7 MeV and for irradiation times up to 30 to 40 years. 1.3 Equivalent fission neutron fluence rates as defined in Practice E 261 can be determined. 1.4 Detailed procedures for other fast-neutron detectors are referenced in Practice E 261. 1.5 The values stated in SI units are to be regarded as standard. No other unites of measurement are included in this standard. 1.6 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

  2. NMR studies of stock process water and reaction pathways in hydrothermal carbonization of furfural residue

    Directory of Open Access Journals (Sweden)

    Fen Yue

    2018-04-01

    Full Text Available Hydrothermal carbonization (HTC is a valuable approach to convert furfural residue (FR into carbon material. The prepared biochars are usually characterized comprehensively, while the stock process water still remains to be studied in detail. Herein, a NMR study of the main components in stock process water generated at different HTC reaction conditions was reported. Various qualitative and quantitative NMR techniques (1H and 13C NMR, 1H–1H COSY and 1H13C HSQC etc. especially 1D selective gradient total correlation spectroscopy (TOCSY NMR were strategically applied in the analysis of HTC stock process water. Without separation and purification, it was demonstrated that the main detectable compounds are 5-hydroxymethylfurfural, formic acid, methanol, acetic acid, levulinic acid, glycerol, hydroxyacetone and acetaldehyde in this complicate mixture. Furthermore, the relationship between the concentration of major products and the reaction conditions (180–240 °C at 8 h, and 1–24 h at 240 °C was established. Finally, reasonable reaction pathways for hydrothermal conversion of FR were proposed based on this result and our previously obtained characteristics of biochars. The routine and challenging NMR methods utilized here would be an alternative other than HPLC or GC for biomass conversion research and can be extended to more studies. Keywords: NMR, Hydrothermal carbonization, Furfural residue, Stock process water

  3. Reaction pathways of producing and losing particles in atmospheric pressure methane nanosecond pulsed needle-plane discharge plasma

    Science.gov (United States)

    Zhao, Yuefeng; Wang, Chao; Li, Li; Wang, Lijuan; Pan, Jie

    2018-03-01

    In this work, a two-dimensional fluid model is built up to numerically investigate the reaction pathways of producing and losing particles in atmospheric pressure methane nanosecond pulsed needle-plane discharge plasma. The calculation results indicate that the electron collisions with CH4 are the key pathways to produce the neutral particles CH2 and CH as well as the charged particles e and CH3+. CH3, H2, H, C2H2, and C2H4 primarily result from the reactions between the neutral particles and CH4. The charge transfer reactions are the significant pathways to produce CH4+, C2H2+, and C2H4+. As to the neutral species CH and H and the charged species CH3+, the reactions between themselves and CH4 contribute to substantial losses of these particles. The ways responsible for losing CH3, H2, C2H2, and C2H4 are CH3 + H → CH4, H2 + CH → CH2 + H, CH4+ + C2H2 → C2H2+ + CH4, and CH4+ + C2H4 → C2H4+ + CH4, respectively. Both electrons and C2H4+ are consumed by the dissociative electron-ion recombination reactions. The essential reaction pathways of losing CH4+ and C2H2+ are the charge transfer reactions.

  4. Position-specific isotope modeling of organic micropollutants transformations through different reaction pathways

    Science.gov (United States)

    Jin, Biao; Rolle, Massimo

    2016-04-01

    Organic compounds are produced in vast quantities for industrial and agricultural use, as well as for human and animal healthcare [1]. These chemicals and their metabolites are frequently detected at trace levels in fresh water environments where they undergo degradation via different reaction pathways. Compound specific stable isotope analysis (CSIA) is a valuable tool to identify such degradation pathways in different environmental systems. Recent advances in analytical techniques have promoted the fast development and implementation of multi-element CSIA. However, quantitative frameworks to evaluate multi-element stable isotope data and incorporating mechanistic information on the degradation processes [2,3] are still lacking. In this study we propose a mechanism-based modeling approach to simultaneously evaluate concentration as well as bulk and position-specific multi-element isotope evolution during the transformation of organic micropollutants. The model explicitly simulates position-specific isotopologues for those atoms that experience isotope effects and, thereby, provides a mechanistic description of isotope fractionation occurring at different molecular positions. We validate the proposed approach with the concentration and multi-element isotope data of three selected organic micropollutants: dichlorobenzamide (BAM), isoproturon (IPU) and diclofenac (DCF). The model precisely captures the dual element isotope trends characteristic of different reaction pathways and their range of variation consistent with observed multi-element (C, N) bulk isotope fractionation. The proposed approach can also be used as a tool to explore transformation pathways in scenarios for which position-specific isotope data are not yet available. [1] Schwarzenbach, R.P., Egli, T., Hofstetter, T.B., von Gunten, U., Wehrli, B., 2010. Global Water Pollution and Human Health. Annu. Rev. Environ. Resour. doi:10.1146/annurev-environ-100809-125342. [2] Jin, B., Haderlein, S.B., Rolle, M

  5. Rapid Removal of Tetrabromobisphenol A by Ozonation in Water: Oxidation Products, Reaction Pathways and Toxicity Assessment.

    Directory of Open Access Journals (Sweden)

    Ruijuan Qu

    Full Text Available Tetrabromobisphenol A (TBBPA is one of the most widely used brominated flame retardants and has attracted more and more attention. In this work, the parent TBBPA with an initial concentration of 100 mg/L was completely removed after 6 min of ozonation at pH 8.0, and alkaline conditions favored a more rapid removal than acidic and neutral conditions. The presence of typical anions and humic acid did not significantly affect the degradation of TBBPA. The quenching test using isopropanol indicated that direct ozone oxidation played a dominant role during this process. Seventeen reaction intermediates and products were identified using an electrospray time-of-flight mass spectrometer. Notably, the generation of 2,4,6-tribromophenol was first observed in the degradation process of TBBPA. The evolution of reaction products showed that ozonation is an efficient treatment for removal of both TBBPA and intermediates. Sequential transformation of organic bromine to bromide and bromate was confirmed by ion chromatography analysis. Two primary reaction pathways that involve cleavage of central carbon atom and benzene ring cleavage concomitant with debromination were thus proposed and further justified by calculations of frontier electron densities. Furthermore, the total organic carbon data suggested a low mineralization rate, even after the complete removal of TBBPA. Meanwhile, the acute aqueous toxicity of reaction solutions to Photobacterium Phosphoreum and Daphnia magna was rapidly decreased during ozonation. In addition, no obvious difference in the attenuation of TBBPA was found by ozone oxidation using different water matrices, and the effectiveness in natural waters further demonstrates that ozonation can be adopted as a promising technique to treat TBBPA-contaminated waters.

  6. Rapid Removal of Tetrabromobisphenol A by Ozonation in Water: Oxidation Products, Reaction Pathways and Toxicity Assessment

    Science.gov (United States)

    Wang, Xinghao; Huang, Qingguo; Lu, Junhe; Wang, Liansheng; Wang, Zunyao

    2015-01-01

    Tetrabromobisphenol A (TBBPA) is one of the most widely used brominated flame retardants and has attracted more and more attention. In this work, the parent TBBPA with an initial concentration of 100 mg/L was completely removed after 6 min of ozonation at pH 8.0, and alkaline conditions favored a more rapid removal than acidic and neutral conditions. The presence of typical anions and humic acid did not significantly affect the degradation of TBBPA. The quenching test using isopropanol indicated that direct ozone oxidation played a dominant role during this process. Seventeen reaction intermediates and products were identified using an electrospray time-of-flight mass spectrometer. Notably, the generation of 2,4,6-tribromophenol was first observed in the degradation process of TBBPA. The evolution of reaction products showed that ozonation is an efficient treatment for removal of both TBBPA and intermediates. Sequential transformation of organic bromine to bromide and bromate was confirmed by ion chromatography analysis. Two primary reaction pathways that involve cleavage of central carbon atom and benzene ring cleavage concomitant with debromination were thus proposed and further justified by calculations of frontier electron densities. Furthermore, the total organic carbon data suggested a low mineralization rate, even after the complete removal of TBBPA. Meanwhile, the acute aqueous toxicity of reaction solutions to Photobacterium Phosphoreum and Daphnia magna was rapidly decreased during ozonation. In addition, no obvious difference in the attenuation of TBBPA was found by ozone oxidation using different water matrices, and the effectiveness in natural waters further demonstrates that ozonation can be adopted as a promising technique to treat TBBPA-contaminated waters. PMID:26430733

  7. Hydrogen oxidation mechanisms on Ni/yttria stabilized zirconia anodes: Separation of reaction pathways by geometry variation of pattern electrodes

    Science.gov (United States)

    Doppler, M. C.; Fleig, J.; Bram, M.; Opitz, A. K.

    2018-03-01

    Nickel/yttria stabilized zirconia (YSZ) electrodes are affecting the overall performance of solid oxide fuel cells (SOFCs) in general and strongly contribute to the cell resistance in case of novel metal supported SOFCs in particular. The electrochemical fuel conversion mechanisms in these electrodes are, however, still only partly understood. In this study, micro-structured Ni thin film electrodes on YSZ with 15 different geometries are utilized to investigate reaction pathways for the hydrogen electro-oxidation at Ni/YSZ anodes. From electrodes with constant area but varying triple phase boundary (TPB) length a contribution to the electro-catalytic activity is found that does not depend on the TPB length. This additional activity could clearly be attributed to a yet unknown reaction pathway scaling with the electrode area. It is shown that this area related pathway has significantly different electrochemical behavior compared to the TPB pathway regarding its thermal activation, sulfur poisoning behavior, and H2/H2O partial pressure dependence. Moreover, possible reaction mechanisms of this reaction pathway are discussed, identifying either a pathway based on hydrogen diffusion through Ni with water release at the TPB or a path with oxygen diffusion through Ni to be a very likely explanation for the experimental results.

  8. Modeling reaction histories to study chemical pathways in condensed phase detonation

    International Nuclear Information System (INIS)

    Scott Stewart, D.; Hernández, Alberto; Lee, Kibaek

    2016-01-01

    The estimation of pressure and temperature histories, which are required to understand chemical pathways in condensed phase explosives during detonation, is discussed. We argue that estimates made from continuum models, calibrated by macroscopic experiments, are essential to inform modern, atomistic-based reactive chemistry simulations at detonation pressures and temperatures. We present easy to implement methods for general equation of state and arbitrarily complex chemical reaction schemes that can be used to compute reactive flow histories for the constant volume, the energy process, and the expansion process on the Rayleigh line of a steady Chapman-Jouguet detonation. A brief review of state-of-the-art of two-component reactive flow models is given that highlights the Ignition and Growth model of Lee and Tarver [Phys. Fluids 23, 2362 (1980)] and the Wide-Ranging Equation of State model of Wescott, Stewart, and Davis [J. Appl. Phys. 98, 053514 (2005)]. We discuss evidence from experiments and reactive molecular dynamic simulations that motivate models that have several components, instead of the two that have traditionally been used to describe the results of macroscopic detonation experiments. We present simplified examples of a formulation for a hypothetical explosive that uses simple (ideal) equation of state forms and detailed comparisons. Then, we estimate pathways computed from two-component models of real explosive materials that have been calibrated with macroscopic experiments.

  9. Uranium recovery from slags of metallic uranium

    International Nuclear Information System (INIS)

    Fornarolo, F.; Frajndlich, E.U.C.; Durazzo, M.

    2006-01-01

    The Center of the Nuclear Fuel of the Institute of Nuclear Energy Research - IPEN finished the program of attainment of fuel development for research reactors the base of Uranium Scilicet (U 3 Si 2 ) from Hexafluoride of Uranium (UF 6 ) with enrichment 20% in weight of 235 U. In the process of attainment of the league of U 3 Si 2 we have as Uranium intermediate product the metallic one whose attainment generates a slag contend Uranium. The present work shows the results gotten in the process of recovery of Uranium in slags of calcined slags of Uranium metallic. Uranium the metallic one is unstable, pyrophoricity and extremely reactive, whereas the U 3 O 8 is a steady oxide of low chemical reactivity, what it justifies the process of calcination of slags of Uranium metallic. The calcination of the Uranium slag of the metallic one in oxygen presence reduces Uranium metallic the U 3 O 8 . Experiments had been developed varying it of acid for Uranium control and excess, nitric molar concentration gram with regard to the stoichiometric leaching reaction of temperature of the leaching process. The 96,0% income proves the viability of the recovery process of slags of Uranium metallic, adopting it previous calcination of these slags in nitric way with low acid concentration and low temperature of leaching. (author)

  10. Synthetic Control of Kinetic Reaction Pathway and Cationic Ordering in High-Ni Layered Oxide Cathodes

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Dawei [Sustainable Energy Technologies Department, Brookhaven National Laboratory, Upton NY 11973 USA; Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory Physical Chemistry Solid Surfaces, Department of Chemistry, Xiamen University, Xiamen Fujian 361005 China; Kou, Ronghui [X-Ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne IL 60439 USA; Ren, Yang [X-Ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne IL 60439 USA; Sun, Cheng-Jun [X-Ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne IL 60439 USA; Zhao, Hu [Sustainable Energy Technologies Department, Brookhaven National Laboratory, Upton NY 11973 USA; Zhang, Ming-Jian [Sustainable Energy Technologies Department, Brookhaven National Laboratory, Upton NY 11973 USA; School of Advanced Materials, Peking University Shenzhen Graduate School, Shenzhen Guangdong 518055 P. R. China; Li, Yan [Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne IL 60439 USA; Huq, Ashifia [Chemical and Engineering Materials Division, Oak Ridge National Laboratory, Oak Ridge TN 37831 USA; Ko, J. Y. Peter [The Cornell High Energy Synchrotron Source, Cornell University, Ithaca NY 14853 USA; Pan, Feng [School of Advanced Materials, Peking University Shenzhen Graduate School, Shenzhen Guangdong 518055 P. R. China; Sun, Yang-Kook [Department of Energy Engineering, Hanyang University, Seoul 133-791 South Korea; Yang, Yong [Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory Physical Chemistry Solid Surfaces, Department of Chemistry, Xiamen University, Xiamen Fujian 361005 China; Amine, Khalil [Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne IL 60439 USA; Bai, Jianming [National Synchrotron Light Source II, Brookhaven National Laboratory, Upton NY 11973 USA; Chen, Zonghai [Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne IL 60439 USA; Wang, Feng [Sustainable Energy Technologies Department, Brookhaven National Laboratory, Upton NY 11973 USA

    2017-08-25

    Nickel-rich layered transition metal oxides, LiNi1-x(MnCo)(x)O-2 (1-x >= 0.5), are appealing candidates for cathodes in next-generation lithium-ion batteries (LIBs) for electric vehicles and other large-scale applications, due to their high capacity and low cost. However, synthetic control of the structural ordering in such a complex quaternary system has been a great challenge, especially in the presence of high Ni content. Herein, synthesis reactions for preparing layered LiNi0.7Mn0.15Co0.15O2 (NMC71515) by solid-state methods are investigated through a combination of time-resolved in situ high-energy X-ray diffraction and absorption spectroscopy measurements. The real-time observation reveals a strong temperature dependence of the kinetics of cationic ordering in NMC71515 as a result of thermal-driven oxidation of transition metals and lithium/oxygen loss that concomitantly occur during heat treatment. Through synthetic control of the kinetic reaction pathway, a layered NMC71515 with low cationic disordering and a high reversible capacity is prepared in air. The findings may help to pave the way for designing high-Ni layered oxide cathodes for LIBs.

  11. Confirmation of the reaction pathway for obtaining 1-(stearamidoethyl-2-hepta-decyl-2-i midazoline

    Directory of Open Access Journals (Sweden)

    Ružić Nenad Lj.

    2002-01-01

    Full Text Available 2-lmidazolines are components of many products, used in industry and households. 1-(Stearamidoethyl-2-heptadecyl-2-imidazoline is a surface active compound, which after quaternization with dimethyl sulfate, is used in lubricants, detergents, shampoos, softeners and cosmetics products. Due to its importance, it was essential to establish the exact reaction pathway for obtaining this compound. Diethylene triamine and stearic acid were used as the starting components. Using titrimetric analysis, and IR and 1H NMR spectros-copic analysis, as well as UV-Vis spectrophotometry it was established that the main intermediate was the 1,3-diamide bis(stearamidoethylamine. Earlier investigations conducted by some authors, using exclusively titrimetric analysis, showed that the main intermediate was the 1,2-diamide. In this paper it was proved that the assumption of these authors that salicylaldehiyde would react only with the primary and not the secondary amine groups was wrong. 1,2-Diamide is the main product of the hydrolysis of 1-(stearamido-ethyl-2-heptadecyl-2-imidazoline. It was shown, in this paper that the reaction of diethylene triamine with stearic acid in xylene at the reflux temperature, yields the salt of 1-(stearamidoethyl-2-heptadecyl-2-imidazoline and stearic acid.

  12. Electrode Reaction Pathway in Oxide Anode for Solid Oxide Fuel Cells

    Science.gov (United States)

    Li, Wenyuan

    the electrolyte to change 3PB kinetics. Compared to Ni, Co doping activates the bulk oxygen more significantly, promoting the reaction at 2PB. The active surface reaction zone is found to be enlarged by the electrolyte with high oxygen activity (SSZ vs. YSZ) when charge transfer is one of the RDS. Due to the larger exchange current for charge transfer in 3PB with SSZ electrolyte, the adsorption gradient zone is broadened, leading to enhanced surface reaction kinetics. The potential application of such finding is demonstrated on SSZ/YSZ/SSZ sandwich, showing largely improved electrode performance, opening a wide door for the utilization of electrolytes that are too expensive, fragile or instable to be used before. The bulk path way in 2PB reaction can be affected by overpotential in terms of local vacancy concentration, built-in electrical field and stability. It is proven that an uneven distribution of lattice oxygen is established under operation conditions with overpotential by both qualitative analysis and analytic solution. An electrostatic field force is present besides the concentration gradient in the anode lattice to control the motion of oxygen ions. Compared to the usual estimation based on chemical diffusion mechanism, the real deviation of ionic defects concentration under polarization from the equilibrium state near electrode/electrolyte interface is smaller with the built-in electrical field. The overpotential is demonstrated to be able to open up or shut down the bulk pathway depending on the ionic defects of electrodes. The analysis on the bulk pathway in terms of local charged species and various potentials provides new insight in anion diffusion and electrode stability.

  13. Automated pathway and reaction prediction facilitates in silico identification of unknown metabolites in human cohort studies.

    Science.gov (United States)

    Quell, Jan D; Römisch-Margl, Werner; Colombo, Marco; Krumsiek, Jan; Evans, Anne M; Mohney, Robert; Salomaa, Veikko; de Faire, Ulf; Groop, Leif C; Agakov, Felix; Looker, Helen C; McKeigue, Paul; Colhoun, Helen M; Kastenmüller, Gabi

    2017-12-15

    Identification of metabolites in non-targeted metabolomics continues to be a bottleneck in metabolomics studies in large human cohorts. Unidentified metabolites frequently emerge in the results of association studies linking metabolite levels to, for example, clinical phenotypes. For further analyses these unknown metabolites must be identified. Current approaches utilize chemical information, such as spectral details and fragmentation characteristics to determine components of unknown metabolites. Here, we propose a systems biology model exploiting the internal correlation structure of metabolite levels in combination with existing biochemical and genetic information to characterize properties of unknown molecules. Levels of 758 metabolites (439 known, 319 unknown) in human blood samples of 2279 subjects were measured using a non-targeted metabolomics platform (LC-MS and GC-MS). We reconstructed the structure of biochemical pathways that are imprinted in these metabolomics data by building an empirical network model based on 1040 significant partial correlations between metabolites. We further added associations of these metabolites to 134 genes from genome-wide association studies as well as reactions and functional relations to genes from the public database Recon 2 to the network model. From the local neighborhood in the network, we were able to predict the pathway annotation of 180 unknown metabolites. Furthermore, we classified 100 pairs of known and unknown and 45 pairs of unknown metabolites to 21 types of reactions based on their mass differences. As a proof of concept, we then looked further into the special case of predicted dehydrogenation reactions leading us to the selection of 39 candidate molecules for 5 unknown metabolites. Finally, we could verify 2 of those candidates by applying LC-MS analyses of commercially available candidate substances. The formerly unknown metabolites X-13891 and X-13069 were shown to be 2-dodecendioic acid and 9

  14. Reaction pathways of biomass-derived oxygenates on noble metal surfaces

    Science.gov (United States)

    McManus, Jesse R.

    As the global demand for energy continues to rise, the environmental concerns associated with increased fossil fuel consumption have motivated the use of biomass as an alternative, carbon-renewable energy feedstock. Controlling reactive chemistry of the sugars that comprise biomass through the use of catalysis becomes essential in effectively producing green fuels and value-added chemicals. Recent work on biomass conversion catalysts have demonstrated the efficacy of noble metal catalyst systems for the reforming of biomass to hydrogen fuel, and the hydrodeoxygenation of biomass-derived compounds to value-added chemicals. In particular, Pt and Pd surfaces have shown considerable promise as reforming catalysts in preliminary aqueous phase reforming studies. It becomes important to understand the mechanisms by which these molecules react on the catalyst surfaces in order to determine structure-activity relationships and bond scission energetics as to provide a framework for engineering more active and selective catalysts. Fundamental surface science techniques provide the tools to do this; however, work in this field has been so far limited to simple model molecules like ethanol and ethylene glycol. Herein, temperature programmed desorption and high resolution electron energy loss spectroscopy are utilized in an ultra-high vacuum surface science study of the biomass-derived sugar glucose on Pt and Pd single crystal catalysts. Overall, it was determined that the aldehyde function of a ring-open glucose molecule plays an integral part in the initial bonding and reforming reaction pathway, pointing to the use of aldoses glycolaldehyde and glyceraldehyde as the most appropriate model compounds for future studies. Furthermore, the addition of adatom Zn to a Pt(111) surface was found to significantly decrease the C-H and C-C bond scission activity in aldehyde containing compounds, resulting in a preferred deoxygenation pathway in opposition to the decarbonylation pathway

  15. Pump-shaped dump optimal control reveals the nuclear reaction pathway of isomerization of a photoexcited cyanine dye.

    Science.gov (United States)

    Dietzek, Benjamin; Brüggemann, Ben; Pascher, Torbjörn; Yartsev, Arkady

    2007-10-31

    Using optimal control as a spectroscopic tool we decipher the details of the molecular dynamics of the essential multidimensional excited-state photoisomerization - a fundamental chemical reaction of key importance in biology. Two distinct nuclear motions are identified in addition to the overall bond-twisting motion: Initially, the reaction is dominated by motion perpendicular to the torsion coordinate. At later times, a second optically active vibration drives the system along the reaction path to the bottom of the excited-state potential. The time scales of the wavepacket motion on a different part of the excited-state potential are detailed by pump-shaped dump optimal control. This technique offers new means to control a chemical reaction far from the Franck-Condon point of absorption and to map details of excited-state reaction pathways revealing unique insights into the underlying reaction mechanism.

  16. Kinetics of the glucose/glycine Maillard reaction pathways: influences of pH and reactant initial concentrations

    NARCIS (Netherlands)

    Martins, S.I.F.S.; Boekel, van M.A.J.S.

    2005-01-01

    A previously proposed kinetic model for the glucose/glycine Maillard reaction pathways has been validated by changing the initial pH (4.8, 5.5, 6.0, 6.8 and 7.5) of the reaction and reactant initial concentrations (1:2 and 2:1 molar ratios were compared to the 1:1 ratio). The model consists of 10

  17. Mitigation of Hydrogen Gas Generation from the Reaction of Uranium Metal with Water in K Basin Sludge and Sludge Waste Forms

    Energy Technology Data Exchange (ETDEWEB)

    Sinkov, Sergey I.; Delegard, Calvin H.; Schmidt, Andrew J.

    2011-06-08

    Prior laboratory testing identified sodium nitrate and nitrite to be the most promising agents to minimize hydrogen generation from uranium metal aqueous corrosion in Hanford Site K Basin sludge. Of the two, nitrate was determined to be better because of higher chemical capacity, lower toxicity, more reliable efficacy, and fewer side reactions than nitrite. The present lab tests were run to determine if nitrate’s beneficial effects to lower H2 generation in simulated and genuine sludge continued for simulated sludge mixed with agents to immobilize water to help meet the Waste Isolation Pilot Plant (WIPP) waste acceptance drainable liquid criterion. Tests were run at ~60°C, 80°C, and 95°C using near spherical high-purity uranium metal beads and simulated sludge to emulate uranium-rich KW containerized sludge currently residing in engineered containers KW-210 and KW-220. Immobilization agents tested were Portland cement (PC), a commercial blend of PC with sepiolite clay (Aquaset II H), granulated sepiolite clay (Aquaset II G), and sepiolite clay powder (Aquaset II). In all cases except tests with Aquaset II G, the simulated sludge was mixed intimately with the immobilization agent before testing commenced. For the granulated Aquaset II G clay was added to the top of the settled sludge/solution mixture according to manufacturer application directions. The gas volumes and compositions, uranium metal corrosion mass losses, and nitrite, ammonia, and hydroxide concentrations in the interstitial solutions were measured. Uranium metal corrosion rates were compared with rates forecast from the known uranium metal anoxic water corrosion rate law. The ratios of the forecast to the observed rates were calculated to find the corrosion rate attenuation factors. Hydrogen quantities also were measured and compared with quantities expected based on non-attenuated H2 generation at the full forecast anoxic corrosion rate to arrive at H2 attenuation factors. The uranium metal

  18. Mitigation of Hydrogen Gas Generation from the Reaction of Uranium Metal with Water in K Basin Sludge and Sludge Waste Forms

    International Nuclear Information System (INIS)

    Sinkov, Sergey I.; Delegard, Calvin H.; Schmidt, Andrew J.

    2011-01-01

    Prior laboratory testing identified sodium nitrate and nitrite to be the most promising agents to minimize hydrogen generation from uranium metal aqueous corrosion in Hanford Site K Basin sludge. Of the two, nitrate was determined to be better because of higher chemical capacity, lower toxicity, more reliable efficacy, and fewer side reactions than nitrite. The present lab tests were run to determine if nitrate's beneficial effects to lower H2 generation in simulated and genuine sludge continued for simulated sludge mixed with agents to immobilize water to help meet the Waste Isolation Pilot Plant (WIPP) waste acceptance drainable liquid criterion. Tests were run at ∼60 C, 80 C, and 95 C using near spherical high-purity uranium metal beads and simulated sludge to emulate uranium-rich KW containerized sludge currently residing in engineered containers KW-210 and KW-220. Immobilization agents tested were Portland cement (PC), a commercial blend of PC with sepiolite clay (Aquaset II H), granulated sepiolite clay (Aquaset II G), and sepiolite clay powder (Aquaset II). In all cases except tests with Aquaset II G, the simulated sludge was mixed intimately with the immobilization agent before testing commenced. For the granulated Aquaset II G clay was added to the top of the settled sludge/solution mixture according to manufacturer application directions. The gas volumes and compositions, uranium metal corrosion mass losses, and nitrite, ammonia, and hydroxide concentrations in the interstitial solutions were measured. Uranium metal corrosion rates were compared with rates forecast from the known uranium metal anoxic water corrosion rate law. The ratios of the forecast to the observed rates were calculated to find the corrosion rate attenuation factors. Hydrogen quantities also were measured and compared with quantities expected based on non-attenuated H2 generation at the full forecast anoxic corrosion rate to arrive at H2 attenuation factors. The uranium metal

  19. Dealkylation of alkylbenzenes: a significant pathway in the toluene, o-, m-, p-xylene + OH reaction.

    Science.gov (United States)

    Noda, Jun; Volkamer, Rainer; Molina, Mario J

    2009-09-03

    The OH-radical initiated oxidation of a series of monocyclic aromatic hydrocarbons (benzene, toluene, o-, m-, and p-xylene) in the presence of oxygen and NO(x) was investigated in a flowtube coupled with a chemical ionization mass spectrometer (CIMS). OH-radical addition to the aromatic ring--the major reaction pathway--has previously been shown to have a particular sensitivity to experimental conditions. This is the first flowtube study that demonstrates the atmospheric relevance of product yields from the OH-addition channel on the millisecond time scale (35-75 ms); the phenol yield from benzene and cresol yields from toluene are found to be 51.0 +/- 4.3% and 17.7 +/- 2.1%, in excellent agreement with previous studies under close to atmospheric conditions. We further report unambiguous experimental evidence that dealkylation is a novel and significant pathway for toluene and o-, m-, and p-xylene oxidation. At 150 Torr of O2 partial pressure, toluene is found to dealkylate with a yield of 5.4 +/- 1.2% phenol; similarly, m-, o-, and p-xylene dealkylate with yields of 11.2 +/- 3.8%, 4.5 +/- 3.2%, and 4.3 +/- 3.1% cresol, respectively. A dealkylation mechanism via OH-addition in the ipso position is feasible (DeltaH = -9 kcal/mol for phenol formation from toluene) but does not lend itself easily to explain the significant isomer effect observed among xylenes; instead an alternative mechanism is presented that can explain this isomer effect and forms phenol and likely epoxide type products with identical m/z (indistinguishable in our CIMS analysis) via a carbene-type intermediate. Dealkylation adds to the atmospheric production of phenol- and likely epoxide-type products, with aldehydes as expected co-products, and helps improve the carbon balance in the initial stages of aromatic oxidation.

  20. Thermal reactions of uranium metal, UO 2, U 3O 8, UF 4, and UO 2F 2 with NF 3 to produce UF 6

    Science.gov (United States)

    McNamara, Bruce; Scheele, Randall; Kozelisky, Anne; Edwards, Matthew

    2009-11-01

    This paper demonstrates that NF 3 fluorinates uranium metal, UO 2, UF 4, UO 3, U 3O 8, and UO 2F 2·2H 2O to produce the volatile UF 6 at temperatures between 100 and 550 °C. Thermogravimetric and differential thermal analysis reaction profiles are described that reflect changes in the uranium fluorination/oxidation state, physiochemical effects, and instances of discrete chemical speciation. Large differences in the onset temperatures for each system investigated implicate changes in mode of the NF 3 gas-solid surface interaction. These studies also demonstrate that NF 3 is a potential replacement fluorinating agent in the existing nuclear fuel cycle and in actinide volatility reprocessing.

  1. Reactivity of Single-Walled Carbon Nanotubes in the Diels-Alder Cycloaddition Reaction: Distortion-Interaction Analysis along the Reaction Pathway.

    Science.gov (United States)

    Li, Yingzi; Osuna, Sílvia; Garcia-Borràs, Marc; Qi, Xiaotian; Liu, Song; Houk, Kendall N; Lan, Yu

    2016-08-26

    Diels-Alder cycloaddition is one of the most powerful tools for the functionalization of single-walled carbon nanotubes (SWCNTs). Density functional theory at the B3-LYP level of theory has been used to investigate the reactivity of different-diameter SWCNTs (4-9,5) in Diels-Alder reactions with 1,3-butadiene; the reactivity was found to decrease with increasing SWCNT diameter. Distortion/interaction analysis along the whole reaction pathway was found to be a better way to explore the reactivity of this type of reaction. The difference in interaction energy along the reaction pathway is larger than that of the corresponding distortion energy. However, the distortion energy plots for these reactions show the same trend. Therefore, the formation of the transition state can be determined from the interaction energy. A lower interaction energy leads to an earlier transition state, which indicates a lower activation energy. The computational results also indicate that the original distortion of the SWCNTs leads to an increase in the reactivity of the SWCNTs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. An integral experiment on thorium oxide/depleted uranium cylinders with D-T neutrons for 232Th(n, 2n) reaction

    International Nuclear Information System (INIS)

    Feng, S.; Yang, Y.W.; Lu, X.X.; Liu, R.; Jiang, L.; Zhu, T.H.; Wang, M.; Qin, J.G.

    2015-01-01

    Highlights: • An integral experiment for 232 Th(n, 2n) reaction was carried out on the newly-established ThO 2 /depleted uranium cylinders. • 232 Th(n, 2n) reaction rate distribution was obtained in the assemblies with an uncertainty of about 7%. • Experiments were analyzed by MCNP code with ENDF/B-VI.8, ENDF/B-VII.0, JENDL-4.0 and CENDL-3.1 libraries. • Experimental results could be used to re-evaluate the cross sections of 232 Th(n, 2n) reaction. - Abstract: In order to verify the evaluated cross sections of 232 Th(n, 2n) reaction for the conceptual design of the thorium based subcritical blanket in the fusion–fission hybrid reactor, an integral experiment on thorium oxide/depleted uranium cylinders was carried out with D-T neutrons using the activation technique. 232 Th(n, 2n) reaction rate distribution was obtained at the central axis direction in the assemblies with an uncertainty of about 7%. Experiments were analyzed by using MCNP code with ENDF/B-VI.8, ENDF/B-VII.0, JENDL-4.0 and CENDL-3.1 libraries to validate the nuclear data libraries of 232 Th(n, 2n) reaction, the calculated results with JENDL-4.0 agree with the measurements the best with discrepancies within the experimental uncertainty. The average values of C/E for the three benchmark assemblies are 1.058, 1.044 and 0.980. Calculations with different evaluated libraries in the benchmark assemblies show a large discrepancy. The experimental results can be used to re-evaluate the cross sections of the 232 Th(n, 2n) reaction

  3. A coupled transport and solid mechanics formulation with improved reaction kinetics parameters for modeling oxidation and decomposition in a uranium hydride bed.

    Energy Technology Data Exchange (ETDEWEB)

    Salloum, Maher N.; Shugard, Andrew D.; Kanouff, Michael P.; Gharagozloo, Patricia E.

    2013-03-01

    Modeling of reacting flows in porous media has become particularly important with the increased interest in hydrogen solid-storage beds. An advanced type of storage bed has been proposed that utilizes oxidation of uranium hydride to heat and decompose the hydride, releasing the hydrogen. To reduce the cost and time required to develop these systems experimentally, a valid computational model is required that simulates the reaction of uranium hydride and oxygen gas in a hydrogen storage bed using multiphysics finite element modeling. This SAND report discusses the advancements made in FY12 (since our last SAND report SAND2011-6939) to the model developed as a part of an ASC-P&EM project to address the shortcomings of the previous model. The model considers chemical reactions, heat transport, and mass transport within a hydride bed. Previously, the time-varying permeability and porosity were considered uniform. This led to discrepancies between the simulated results and experimental measurements. In this work, the effects of non-uniform changes in permeability and porosity due to phase and thermal expansion are accounted for. These expansions result in mechanical stresses that lead to bed deformation. To describe this, a simplified solid mechanics model for the local variation of permeability and porosity as a function of the local bed deformation is developed. By using this solid mechanics model, the agreement between our reacting bed model and the experimental data is improved. Additionally, more accurate uranium hydride oxidation kinetics parameters are obtained by fitting the experimental results from a pure uranium hydride oxidation measurement to the ones obtained from the coupled transport-solid mechanics model. Finally, the coupled transport-solid mechanics model governing equations and boundary conditions are summarized and recommendations are made for further development of ARIA and other Sandia codes in order for them to sufficiently implement the model.

  4. Combined quantum mechanical and molecular mechanical reaction pathway calculation for aromatic hydroxylation by p-hydroxybenzoate-3-hydroxylase

    NARCIS (Netherlands)

    Ridder, L.; Mulholland, A.; Rietjens, I.M.C.M.; Vervoort, J.

    1999-01-01

    The reaction pathway for the aromatic 3-hydroxylation of p-hydroxybenzoate by the reactive C4a-hydroperoxyflavin cofactor intermediate in p-hydroxybenzoate hydroxylase (PHBH) has been investigated by a combined quantum mechanical and molecular mechanical (QM/MM) method. A structural model for the

  5. Laccase-catalyzed removal of the antimicrobials chlorophene and dichlorophen from water: Reaction kinetics, pathway and toxicity evaluation.

    Science.gov (United States)

    Shi, Huanhuan; Peng, Jianbiao; Li, Jianhua; Mao, Liang; Wang, Zunyao; Gao, Shixiang

    2016-11-05

    As active agents in cleaning and disinfecting products, antimicrobials have been widely spread in the environment and have drawn extensive attention as potential threats to the ecological system and human health. In this study, the laccase-catalyzed removal of two emerging antimicrobials, chlorophene (CP) and dichlorophen (DCP), was investigated under simulated environmental conditions. Intrinsic reaction kinetics showed that the removal of CP and DCP followed second-order reaction kinetics, first-order with respect to both the enzyme and the substrate concentration. It was also found that fulvic acid could suppress the transformation of CP and DCP by reversing the oxidation reactions through its action as a scavenger of the free radical intermediates produced from reactions between laccase and the substrates. Several reaction products were identified by a quadrupole time-of-flight mass spectrometer, and detailed reaction pathways were proposed. For both CP and DCP, direct polymerization was the principal pathway, and the coupling patterns were further corroborated based on molecular modeling. The nucleophilic substitution of chlorine by the hydroxyl group was observed, and further oxidation products capable of coupling with each other were also found. Additionally, toxicity evaluation tests using Scenedesmus obliquus confirmed that the toxicity of CP and DCP was effectively eliminated during the reaction processes. Copyright © 2016 Elsevier B.V. All rights reserved.

  6. Developmentally programmed DNA deletion in Tetrahymena thermophila by a transposition-like reaction pathway.

    Science.gov (United States)

    Saveliev, S V; Cox, M M

    1996-01-01

    We provide a molecular description of key intermediates in the deletion of two internal eliminated sequences (IES elements), the M and R regions, during macronuclear development in Tetrahymena thermophila. Using a variety of PCR-based methods in vivo, double-strand breaks are detected that are generated by hydrolytic cleavage and correspond closely to the observed chromosomal junctions left behind in the macronuclei. The breaks exhibit a temporal and structural relationship to the deletion reaction that provides strong evidence that they are intermediates in the deletion pathway. Breaks in the individual strands are staggered by 4 bp, producing a four nucleotide 5' extension. Evidence is presented that breaks do not occur simultaneously at both ends. The results are most consistent with a deletion mechanism featuring initiation by double-strand cleavage at one end of the deleted element, followed by transesterification to generate the macronuclear junction on one DNA strand. An adenosine residue is found at all the nucleophilic 3' ends used in the postulated transesterification step. Evidence for the transesterification step is provided by detection of a 3' hydroxyl that would be liberated by such a step at a deletion boundary where no other DNA strand ends are detected. Images PMID:8654384

  7. Development and implementation of a critical pathway for prevention of adverse reactions to contrast media for computed tomography

    Energy Technology Data Exchange (ETDEWEB)

    Jang, Keun Jo [Presbyterian Medical Center, Seoul (Korea, Republic of); Kweon, Dae Cheol; Kim, Myeong Goo [Seoul National University Hospital, Seoul (Korea, Republic of); Yoo, Beong Gyu [Wonkwang Health Science College, Iksan (Korea, Republic of)

    2007-03-15

    The purpose of this study is to develop a critical pathway (CP) for the prevention of adverse reactions to contrast media for computed tomography. The CP was developed and implemented by a multidisciplinary group is Seoul National University Hospital. The CP was applied to CT patients. Patients who underwent CT scanning were included in the CP group from March in 2004. The satisfaction of the patients with CP was compared with non-CP groups. We also investigated the degree of satisfaction among the radiological technologists and nurses. The degree of patient satisfaction with the care process increased patient information (24%), prevention of adverse reactions to contrast media (19%), pre-cognitive effect of adverse reactions to contrast media (39%) and information degree of adverse reactions to contrast media (19%). This CP program can be used as one of the patient care tools for reducing the adverse reactions to contrast media and increasing the efficiency of care process in CT examination settings.

  8. Development and implementation of a critical pathway for prevention of adverse reactions to contrast media for computed tomography

    International Nuclear Information System (INIS)

    Jang, Keun Jo; Kweon, Dae Cheol; Kim, Myeong Goo; Yoo, Beong Gyu

    2007-01-01

    The purpose of this study is to develop a critical pathway (CP) for the prevention of adverse reactions to contrast media for computed tomography. The CP was developed and implemented by a multidisciplinary group is Seoul National University Hospital. The CP was applied to CT patients. Patients who underwent CT scanning were included in the CP group from March in 2004. The satisfaction of the patients with CP was compared with non-CP groups. We also investigated the degree of satisfaction among the radiological technologists and nurses. The degree of patient satisfaction with the care process increased patient information (24%), prevention of adverse reactions to contrast media (19%), pre-cognitive effect of adverse reactions to contrast media (39%) and information degree of adverse reactions to contrast media (19%). This CP program can be used as one of the patient care tools for reducing the adverse reactions to contrast media and increasing the efficiency of care process in CT examination settings

  9. Characterization of the Environmentally Induced Chemical Transformations of Uranium Tetrafluoride

    Energy Technology Data Exchange (ETDEWEB)

    Wellons, M. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2017-09-29

    A key challenge with nuclear safeguards environmental sampling is identification of the materials post release due to subsequent chemical reactions with ambient water and oxygen. Uranium Tetrafluoride (UF4) is of interest as an intermediate in both the upstream and downstream portions of uranium feedstock and metal production processes used in nuclear fuel production; however minimal published research exists relating to UF4 hydrolysis. FY16 efforts were dedicated to in-situ Raman spectroscopy and X-ray diffraction characterization of UF4 during exposure to various relative humidity conditions. This effort mapped several hydrolysis reaction pathways and identified both intermediate, and terminal progeny species.

  10. Natural uranium-series radionuclide inventories in coastal and oceanic waters of the south-western Pacific - insights into trace metal flux and removal pathway analysis

    International Nuclear Information System (INIS)

    Szymczak, R.; Jeffree, R.A.; Peck, G.A.

    2003-01-01

    Participate scavenging of trace metals plays a major role in determining their ecosystem flux and incident dissolved concentrations. Differences in the half-lives and biogeochemical behaviour of natural uranium series radioisotope pairs (eg. 238 U/ 234 Th, 210 Pb/ 210 Po) allow their application as oceanic process tracers. Coincidental measurements of dissolved and particulate trace element concentrations and inventories of radionuclides in the Noumea coral lagoon and adjacent offshore waters were used to quantify water column flux rates and provide insights on removal pathway analysis. Understanding prevailing pathways and respective flux rates of pollutants in specific coastal and oceanic systems will assist to establish the fate and consequence of pollutants and allow sustainable management strategies to be developed. Both natural and pollutant chemical species introduced to the marine environment may either remain benign in solution or undergo physiological uptake by biota, but most often associate with colloids and fine particles, which subsequent undergo aggregation, sedimentation and removal to the sea floor

  11. Fluid flow pathways through the oceanic crust: reaction permeability and isotopic tracing

    Science.gov (United States)

    McCaig, Andrew; Castelain, Teddy; Klein, Frieder

    2013-04-01

    It is generally assumed that the dominant means of creating permeability in ocean floor hydrothermal systems is fracturing, induced either by cooling or by tectonic stress. Here we show textural evidence that metamorphic reactions can create a hierarchy of permeable pathways through gabbroic rocks similar to a fracture hierarchy. Isotopic microsampling shows that just as with fractures, most flow occurs through the larger channelways, and that even at the microscale, flow can be extremely heterogeneous with alteration affecting only certain minerals in the framework, leaving others untouched. Reaction permeability is created in three ways; dissolution creating open porosity, microcracking due to volume increase reactions involving olivine, and expansion of water due to rapid heating in dyke margins, particularly when intruded into brecciated rocks. Our data comes from IODP Hole U1309D, which was drilled to 1400 mbsf in the footwall of the Atlantis Massif detachment fault at the Mid-Atlantic Ridge 30°N. The core is composed of gabbroic rocks interlayered with olivine rich troctolites, with several basalt/diabase sills in the top 130 m. The dominant alteration occurred in the greenschist facies, at depths at least 1 km below seafloor, and decreases in intensity downhole. Whole rock oxygen isotope values range from +5.5 permil to +1.5 permil, indicating variable degrees of interaction with seawater at temperatures generally > 250 °C. Gabbroic rocks and diabases exhibit a range of Sr isotope ratios from MORB values (0.70261) to intermediate ratios (0.70429). Microsampling shows that amphiboles are often more radiogenic than coexisting plagioclase and can sometimes be isotopically altered in the same rock as completely unaltered primary minerals. Large (10 cm) amphibole-filled vugs show values ranging up to 0.708, close to seawater. In some cases however the secondary minerals are virtually unaltered indicating low fluid fluxes in pervasive alteration. SEM textures in

  12. Reactions of plutonium dioxide with water and oxygen-hydrogen mixtures: Mechanisms for corrosion of uranium and plutonium

    Energy Technology Data Exchange (ETDEWEB)

    Haschke, John M.; Allen, Thomas H.; Morales, Luis A.

    1999-06-18

    Investigation of the interactions of plutonium dioxide with water vapor and with an oxygen-hydrogen mixture show that the oxide is both chemically reactive and catalytically active. Correspondence of the chemical behavior with that for oxidation of uranium in moist air suggests that similar catalytic processes participate in the mechanism of moisture-enhanced corrosion of uranium and plutonium. Evaluation of chemical and kinetic data for corrosion of the metals leads to a comprehensive mechanism for corrosion in dry air, water vapor, and moist air. Results are applied in confirming that the corrosion rate of Pu in water vapor decreases sharply between 100 and 200 degrees C.

  13. Natural Transmutation of Actinides via the Fission Reaction in the Closed Thorium-Uranium-Plutonium Fuel Cycle

    Science.gov (United States)

    Marshalkin, V. Ye.; Povyshev, V. M.

    2017-12-01

    It is shown for a closed thorium-uranium-plutonium fuel cycle that, upon processing of one metric ton of irradiated fuel after each four-year campaign, the radioactive wastes contain 54 kg of fission products, 0.8 kg of thorium, 0.10 kg of uranium isotopes, 0.005 kg of plutonium isotopes, 0.002 kg of neptunium, and "trace" amounts of americium and curium isotopes. This qualitatively simplifies the handling of high-level wastes in nuclear power engineering.

  14. Near field chemical speciation: the reaction of uranium and thorium with Hanford basalt and elevated pH

    International Nuclear Information System (INIS)

    Perry, D.L.

    1984-01-01

    The hydrolysis of radionuclides such as thorium and uranium and their subsequent chemisorption on Hanford basalt have been studied using a variety of techniques, including x-ray photoelectron and infrared spectroscopy. Data obtained to date indicate mixed complexes of uranium and thorium to be on the basalt surface, the complexes being radionuclide oxides, hydrated oxides (hydroxides), and carbonates. These findings are discussed with respect to their importance for input for models describing speciation and dissolution processes involving nuclear waste repository materials such as Hanford basalt. 5 figures, 2 tables

  15. The importance of a single methyl group in determining the reaction chemistry of pentamethylcyclopentadienyl cyclooctatetraenyl uranium metallocenes

    Energy Technology Data Exchange (ETDEWEB)

    Takase, Michael K.; Ziller, Joseph W.; Evans, William J. [Department of Chemistry, University of California, Irvine, CA (United States)

    2011-04-18

    The steric factors that allow trivalent [(C{sub 5}Me{sub 5}){sub 3}U] (1) to function as a three-electron reductant with C{sub 8}H{sub 8} to form tetravalent [{(C_5Me_5)(C_8H_8)U}{sub 2}(μ-C{sub 8}H{sub 8})] (2) have been explored by examining the synthesis and reactivity of the intermediate, ''[(C{sub 5}Me{sub 5}){sub 2}(C{sub 8}H{sub 8})U]'' (3), and the slightly less crowded analogues, [(C{sub 5}Me{sub 5})(C{sub 5}Me{sub 4}H)(C{sub 8}H{sub 8})U] and [(C{sub 5}Me{sub 4}H){sub 2}(C{sub 8}H{sub 8})U], that have, successively one less methyl group. The reaction of [{(C_5Me_5)(C_8H_8)U(μ-OTf)}{sub 2}] (4; OTf=OSO{sub 2}CF{sub 3}) with two equivalents of KC{sub 5}Me{sub 5} in THF gave ring-opening to ''[(C{sub 5}Me{sub 5})(C{sub 8}H{sub 8})U{O(CH_2)_4(C_5Me_5)}]'' consistent with in situ formation of 3. Reaction of 4 with two and four equivalents of KC{sub 5}Me{sub 4}H generates two equivalents of [(C{sub 5}Me{sub 5})(C{sub 5}Me{sub 4}H)(C{sub 8}H{sub 8})U] (5) and [(C{sub 5}Me{sub 4}H){sub 2}(C{sub 8}H{sub 8})U] (6), respectively, which in contrast to 3 were isolable. Tetravalent 5 reduces phenazine and PhEEPh (E=S, Se, and Te) to form the tetravalent uranium reduction products, [{(C_5Me_5)(C_8H_8)U}{sub 2}(μ-C{sub 12}H{sub 8}N{sub 2})] (7), [{(C_5Me_5)(C_8H_8)U}{sub 2}(μ-SPh){sub 2}] (8), [{(C_5Me_5)(C_8H_8)U}{sub 2}(μ-SePh){sub 2}] (9), and [{(C_5Me_5)(C_8H_8)U}{sub 2}(μ-TePh){sub 2}] (10), consistent with sterically induced reduction. In contrast, the less sterically crowded 6 does not react with these substrates. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  16. MRE: a web tool to suggest foreign enzymes for the biosynthesis pathway design with competing endogenous reactions in mind

    KAUST Repository

    Kuwahara, Hiroyuki; Alazmi, Meshari; Cui, Xuefeng; Gao, Xin

    2016-01-01

    To rationally design a productive heterologous biosynthesis system, it is essential to consider the suitability of foreign reactions for the specific endogenous metabolic infrastructure of a host. We developed a novel web server, called MRE, which, for a given pair of starting and desired compounds in a given chassis organism, ranks biosynthesis routes from the perspective of the integration of new reactions into the endogenous metabolic system. For each promising heterologous biosynthesis pathway, MRE suggests actual enzymes for foreign metabolic reactions and generates information on competing endogenous reactions for the consumption of metabolites. These unique, chassis-centered features distinguish MRE from existing pathway design tools and allow synthetic biologists to evaluate the design of their biosynthesis systems from a different angle. By using biosynthesis of a range of high-value natural products as a case study, we show that MRE is an effective tool to guide the design and optimization of heterologous biosynthesis pathways. The URL of MRE is http://www.cbrc.kaust.edu.sa/mre/.

  17. MRE: a web tool to suggest foreign enzymes for the biosynthesis pathway design with competing endogenous reactions in mind

    KAUST Repository

    Kuwahara, Hiroyuki

    2016-04-29

    To rationally design a productive heterologous biosynthesis system, it is essential to consider the suitability of foreign reactions for the specific endogenous metabolic infrastructure of a host. We developed a novel web server, called MRE, which, for a given pair of starting and desired compounds in a given chassis organism, ranks biosynthesis routes from the perspective of the integration of new reactions into the endogenous metabolic system. For each promising heterologous biosynthesis pathway, MRE suggests actual enzymes for foreign metabolic reactions and generates information on competing endogenous reactions for the consumption of metabolites. These unique, chassis-centered features distinguish MRE from existing pathway design tools and allow synthetic biologists to evaluate the design of their biosynthesis systems from a different angle. By using biosynthesis of a range of high-value natural products as a case study, we show that MRE is an effective tool to guide the design and optimization of heterologous biosynthesis pathways. The URL of MRE is http://www.cbrc.kaust.edu.sa/mre/.

  18. Investigation of (n, 2n) reaction and fission rates in iron-shielded uranium samples bombarded by 14.9 MeV neutrons

    International Nuclear Information System (INIS)

    Shani, G.

    1976-01-01

    The effect of the thickness of iron shielding on the (n, 2n) reaction rate in a fusion reactor (hybrid) blanket is investigated. The results are compared with the fission rate-dependence. Samples of natural uranium are irradiated with 14 MeV neutrons, with iron slabs of various thickness between the neutron generator target and the samples. Both reactions are threshold reactions but the fact that the 238 U (n, 2n) reaction threshold is at 6 MeV and that of fission is at 2 MeV makes the ratio between the two very much geometry-dependent. Two geometrical effects take place, the 1/r 2 and the build-up. While the build-up affects the (n, 2n) reaction rate, the fission rate is affected more by the 1/r 2 effect. The reason is that both elastic and inelastic scattering end up with neutrons with energy above fission threshold, while only elastic scattering brings high energy neutrons to the sample and causes (n, 2n) reaction. A comparison is made with calculated results where the geometrical effects do not exist. (author)

  19. Methane coupling reaction in an oxy-steam stream through an OH radical pathway by using supported alkali metal catalysts

    KAUST Repository

    Liang, Yin

    2014-03-24

    A universal reaction mechanism involved in the oxidative coupling of methane (OCM) is demonstrated under oxy-steam conditions using alkali-metal-based catalysts. Rigorous kinetic measurements indicated a reaction mechanism that is consistent with OH radical formation from a H 2O-O2 reaction followed by C-H activation in CH 4 with an OH radical. Thus, the presence of water enhances both the CH4 conversion rate and the C2 selectivity. This OH radical pathway that is selective for the OCM was observed for the catalyst without Mn, which suggests clearly that Mn is not the essential component in a selective OCM catalyst. The experiments with different catalyst compositions revealed that the OH.-mediated pathway proceeded in the presence of catalysts with different alkali metals (Na, K) and different oxo anions (W, Mo). This difference in catalytic activity for OH radical generation accounts for the different OCM selectivities. As a result, a high C2 yield is achievable by using Na2WO4/SiO2, which catalyzes the OH.-mediated pathway selectively. Make it methane: A universal reaction mechanism involved in the oxidative coupling of methane is demonstrated under oxy-stream conditions by using alkali-metal-based catalysts. Rigorous kinetic measurements indicated a reaction mechanism that is consistent with OH radical formation from an H2O-O2 reaction, followed by C-H activation in CH4 with an OH radical. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. A mechanistic study on the reaction pathways leading to benzene and naphthalene in cellulose vapor phase cracking

    International Nuclear Information System (INIS)

    Norinaga, Koyo; Yang, Huamei; Tanaka, Ryota; Appari, Srinivas; Iwanaga, Keita; Takashima, Yuka; Kudo, Shinji; Shoji, Tetsuya; Hayashi, Jun-ichiro

    2014-01-01

    The reaction pathways leading to aromatic hydrocarbons such as benzene and naphthalene in gas-phase reactions of multi-component mixtures derived from cellulose fast pyrolysis were studied both experimentally and numerically. A two-stage tubular reactor was used for evaluating the reaction kinetics of secondary vapor phase cracking of the nascent pyrolysates at temperature ranging from 400 to 900 °C, residence time from 0.2 to 4.3 s, and at 241 kPa. The products of alkyne and diene were identified from the primary pyrolysis of cellulose even at low temperature range 500–600 °C. These products include acetylene, propyne, propadiene, vinylacetylene, and cyclopentadiene. Experiments were also numerically validated by a detailed chemical kinetic model consisting of more than 8000 elementary step-like reactions with over 500 chemical species. Acceptable capabilities of the kinetic model in predicting concentration profiles of the products enabled us to assess reaction pathways leading to benzene and naphthalene via the alkyne and diene from primary pyrolysates of cellulose. C 3 alkyne and diene are primary precursors of benzene at 650 °C, while combination of ethylene and vinylacetylene produces benzene dominantly at 850 °C. Cyclopentadiene is a prominent precursor of naphthalene. Combination of acetylene with propyne or allyl radical leads to the formation of cyclopentadiene. Furan and acrolein are likely important alkyne precursors in cellulose pyrolysis at low temperature, whereas dehydrogenations of olefins are major route to alkyne at high temperatures. - Highlights: • Analytical pyrolysis experiments provided data for kinetic modeling. • Detailed chemical kinetic model was used and evaluated. • Alkyne and diene were important intermediates for aromatic hydrocarbon formation. • Reaction pathways leading to aromatic hydrocarbons were proposed

  1. Gas-Phase Reaction Pathways and Rate Coefficients for the Dichlorosilane-Hydrogen and Trichlorosilane-Hydrogen Systems

    Science.gov (United States)

    Dateo, Christopher E.; Walch, Stephen P.

    2002-01-01

    As part of NASA Ames Research Center's Integrated Process Team on Device/Process Modeling and Nanotechnology our goal is to create/contribute to a gas-phase chemical database for use in modeling microelectronics devices. In particular, we use ab initio methods to determine chemical reaction pathways and to evaluate reaction rate coefficients. Our initial studies concern reactions involved in the dichlorosilane-hydrogen (SiCl2H2--H2) and trichlorosilane-hydrogen (SiCl2H-H2) systems. Reactant, saddle point (transition state), and product geometries and their vibrational harmonic frequencies are determined using the complete-active-space self-consistent-field (CASSCF) electronic structure method with the correlation consistent polarized valence double-zeta basis set (cc-pVDZ). Reaction pathways are constructed by following the imaginary frequency mode of the saddle point to both the reactant and product. Accurate energetics are determined using the singles and doubles coupled-cluster method that includes a perturbational estimate of the effects of connected triple excitations (CCSD(T)) extrapolated to the complete basis set limit. Using the data from the electronic structure calculations, reaction rate coefficients are obtained using conventional and variational transition state and RRKM theories.

  2. Roles of different initial Maillard intermediates and pathways in meat flavor formation for cysteine-xylose-glycine model reaction systems.

    Science.gov (United States)

    Hou, Li; Xie, Jianchun; Zhao, Jian; Zhao, Mengyao; Fan, Mengdie; Xiao, Qunfei; Liang, Jingjing; Chen, Feng

    2017-10-01

    To explore initial Maillard reaction pathways and mechanisms for maximal formation of meaty flavors in heated cysteine-xylose-glycine systems, model reactions with synthesized initial Maillard intermediates, Gly-Amadori, TTCA (2-threityl-thiazolidine-4-carboxylic acids) and Cys-Amadori, were investigated. Relative relativities were characterized by spectrophotometrically monitoring the development of colorless degradation intermediates and browning reaction products. Aroma compounds formed were determined by solid-phase microextraction combined with GC-MS and GC-olfactometry. Gly-Amadori showed the fastest reaction followed by Cys-Amadori then TTCA. Free glycine accelerated reaction of TTCA, whereas cysteine inhibited that of Gly-Amadori due to association forming relatively stable thiazolidines. Cys-Amadori/Gly had the highest reactivity in development of both meaty flavors and brown products. TTCA/Gly favored yielding meaty flavors, whereas Gly-Amadori/Cys favored generation of brown products. Conclusively, initial formation of TTCA and pathway involving TTCA with glycine were more applicable to efficiently produce processed-meat flavorings in a cysteine-xylose-glycine system. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. Investigation of the kinetics of the reactions of oxidation, nitration, and hydrogenation of uranium; Etude cinetique de l'oxydation, de la nitruration et de l'hydruration de l'uranium

    Energy Technology Data Exchange (ETDEWEB)

    Adda, Y [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1955-06-15

    Various physico-chemical methods have been used to investigate the kinetics of the oxidation hydridation and nitridation of uranium. The experimental results show that the kinetics of these reactions are influenced by many factors also the Pilling and Bedworth rule is valid only under very limited conditions. The disagreement between this rule and the experimental results could be explained by the existence of numerous mechanical faults in the compounds obtained by the dry corrosion of the metal. (author) [French] Les cinetiques d'oxydation, d'hydruration et de nitruration de l'uranium ont ete etudiees au moyen de differentes methodes physico-chimiques. Les resultats experimentaux obtenus indiquent qu'un grand nombre de facteurs influencent les cinetiques d'attaque et que la regle de Pilling et Bedworth n'est verifiee que dans des cas tres limites. Les desaccords entre cette regle et les resultats experimentaux s'expliqueraient par l'existence de nombreux defauts mecaniques dans les composes obtenus par corrosion seche du metal. (auteur)

  4. Dexmedetomidine Inhibits Inflammatory Reaction in Lung Tissues of Septic Rats by Suppressing TLR4/NF-κB Pathway

    Directory of Open Access Journals (Sweden)

    Yuqing Wu

    2013-01-01

    and 20 μg/kg significantly decreased mortality and pulmonary inflammation of septic rats, as well as suppressed CLP-induced elevation of TNF-α and IL-6 and inhibited TLR4/MyD88 expression and NF-κB activation. These results suggest that dexmedetomidine may decrease mortality and inhibit inflammatory reaction in lung tissues of septic rats by suppressing TLR4/MyD88/NF-κB pathway.

  5. Transformation of aminopyrine in the presence of free available chlorine: Kinetics, products, and reaction pathways.

    Science.gov (United States)

    Cai, Mei-Quan; Feng, Li; Zhang, Li-Qiu

    2017-03-01

    Aminopyrine (AMP) has been frequently detected in the aquatic environment. In this study, the transformation mechanism of AMP by free available chlorine (FAC) oxidation was investigated. The results showed that FAC reacted with AMP rapidly, and a 74% elimination was achieved for 1.30 μM AMP after 2 min at 14.08 μM FAC dose. AMP chlorination was strongly pH-dependent, and its reaction included second- and third-order kinetic processes. Three active FAC species, including chlorine monoxide (Cl 2 O), molecular chlorine (Cl 2 ), and hypochlorous acid (HOCl), were observed to contribute to AMP degradation. The intrinsic rate constants of each FAC species with neutral (AMP 0 ) and cation (AMP + ) species were obtained by kinetic fitting. Cl 2 O exhibited the highest reactivity with AMP 0 (k AMP0, Cl2O  = (4.33 ± 1.4) × 10 9  M -1 s -1 ). In addition, Cl 2 showed high reactivity (10 6 -10 7  M -1 s -1 ) in the presence of chloride, compared with HOCl (k AMP+, HOCl  = (5.73 ± 0.23) × 10 2  M -1 s -1 , k AMP0, HOCl  = (9.68 ± 0.96) × 10 2  M -1 s -1 ). At pH 6.15 and 14.08 μM FAC dose without chloride addition, the contribution of Cl 2 O reached to the maximum (33.3%), but in the whole pH range, HOCl was the main contributor (>66.6%) for AMP degradation. The significance of Cl 2 was noticeable in water containing chloride. Moreover, 11 transformation products were identified, and the main transformation pathways included pyrazole ring breakage, hydroxylation, dehydrogenation, and halogenation. Copyright © 2016 Elsevier Ltd. All rights reserved.

  6. High-Resolution Mineralogical Characterization and Biogeochemical Modeling of Uranium Reduction Pathways at the NABIR Field-Research Center

    International Nuclear Information System (INIS)

    David R. Veblen; Chen Zhu; Lee Krumholz; Claudine Stirling; Emma-Kate Potter; Alex N. Halliday

    2004-01-01

    The effectiveness and feasibility of bioremediation at the field scale cannot be fully assessed until the mechanisms of immobilization and U speciation in the solid matrix are resolved. However, characterization of the immobilized U and its valence states is extremely difficult, because microbially mediated mineral precipitates are generally nanometer (nm)-sized, poorly crystalline, or amorphous. We are developing combined field emission gun--scanning electron microscopy (FEG-SEM, at Indiana University) and FEG transmission electron microscopy (TEM, at Hopkins) to detect and isolate uranium containing phases; (1) method developments for TEM sample preparations and parallel electron energy loss spectroscopy (EELS) determination of uranium valence; and (2) to determine the speciation, fate, reactivity, valence states of immobilized uranium, using the state-of-the-art 300-kV, FEG-TEM. We have obtained preliminary results on contaminated sediments from Area 3 at the Oak Ridge Field Research Center (FRC). TEM results show that the sediments contain numerous minerals, including quartz, mica/clay (muscovite and/or illite), rutile, ilmenite, zircon, and an Al-Sr-Ce-Ca phosphate mineral, none of which contain uranium above the EDS detection limit. Substantial U (up to ∼2 wt.%) is, however, clearly associated with two materials: (1) the Fe oxyhydroxide and (2) clots of a chemically complex material that is likely a mixture of several nm-scale phases. The Fe oxyhydroxide was identified as goethite from its polycrystalline SAED pattern and EDS analysis showing it to be very Fe-rich; the aggregate also displays one of several morphologies that are common for goethite. U is strongly sorbed to goethite in the FRC sediment, and the ubiquitous association with phosphorous suggests that complexes containing both U and P may play an important role in that sorption. Results from bulk analysis and SEM had previously demonstrated the association of U with Fe and thus suggested that U

  7. Recovery of uranium by chlorination

    International Nuclear Information System (INIS)

    Komoto, Shigetoshi; Taki, Tomihiro

    1988-01-01

    The recovery of uranium from uraniferous phosphate by conventional process is generally uneconomic, except that uranium is recovered as a by-product. If an economical process by which uranium is recovered efficiently as a chief product is discovered, uraniferous phosphate will be used effectively as uranium ore. By using chiorination which will be expected to be favorable in comparison with conventional process, the recovery of uranium from uraniferous phosphate has been carried out. The paper describes the reaction machanism and general characteristics of the uranium chiorination, and the research done so for. (author)

  8. Influence of uranium hydride oxidation on uranium metal behaviour

    International Nuclear Information System (INIS)

    Patel, N.; Hambley, D.; Clarke, S.A.; Simpson, K.

    2013-01-01

    This work addresses concerns that the rapid, exothermic oxidation of active uranium hydride in air could stimulate an exothermic reaction (burning) involving any adjacent uranium metal, so as to increase the potential hazard arising from a hydride reaction. The effect of the thermal reaction of active uranium hydride, especially in contact with uranium metal, does not increase in proportion with hydride mass, particularly when considering large quantities of hydride. Whether uranium metal continues to burn in the long term is a function of the uranium metal and its surroundings. The source of the initial heat input to the uranium, if sufficient to cause ignition, is not important. Sustained burning of uranium requires the rate of heat generation to be sufficient to offset the total rate of heat loss so as to maintain an elevated temperature. For dense uranium, this is very difficult to achieve in naturally occurring circumstances. Areas of the uranium surface can lose heat but not generate heat. Heat can be lost by conduction, through contact with other materials, and by convection and radiation, e.g. from areas where the uranium surface is covered with a layer of oxidised material, such as burned-out hydride or from fuel cladding. These rates of heat loss are highly significant in relation to the rate of heat generation by sustained oxidation of uranium in air. Finite volume modelling has been used to examine the behaviour of a magnesium-clad uranium metal fuel element within a bottle surrounded by other un-bottled fuel elements. In the event that the bottle is breached, suddenly, in air, it can be concluded that the bulk uranium metal oxidation reaction will not reach a self-sustaining level and the mass of uranium oxidised will likely to be small in relation to mass of uranium hydride oxidised. (authors)

  9. Influence of uranium hydride oxidation on uranium metal behaviour

    Energy Technology Data Exchange (ETDEWEB)

    Patel, N.; Hambley, D. [National Nuclear Laboratory (United Kingdom); Clarke, S.A. [Sellafield Ltd (United Kingdom); Simpson, K.

    2013-07-01

    This work addresses concerns that the rapid, exothermic oxidation of active uranium hydride in air could stimulate an exothermic reaction (burning) involving any adjacent uranium metal, so as to increase the potential hazard arising from a hydride reaction. The effect of the thermal reaction of active uranium hydride, especially in contact with uranium metal, does not increase in proportion with hydride mass, particularly when considering large quantities of hydride. Whether uranium metal continues to burn in the long term is a function of the uranium metal and its surroundings. The source of the initial heat input to the uranium, if sufficient to cause ignition, is not important. Sustained burning of uranium requires the rate of heat generation to be sufficient to offset the total rate of heat loss so as to maintain an elevated temperature. For dense uranium, this is very difficult to achieve in naturally occurring circumstances. Areas of the uranium surface can lose heat but not generate heat. Heat can be lost by conduction, through contact with other materials, and by convection and radiation, e.g. from areas where the uranium surface is covered with a layer of oxidised material, such as burned-out hydride or from fuel cladding. These rates of heat loss are highly significant in relation to the rate of heat generation by sustained oxidation of uranium in air. Finite volume modelling has been used to examine the behaviour of a magnesium-clad uranium metal fuel element within a bottle surrounded by other un-bottled fuel elements. In the event that the bottle is breached, suddenly, in air, it can be concluded that the bulk uranium metal oxidation reaction will not reach a self-sustaining level and the mass of uranium oxidised will likely to be small in relation to mass of uranium hydride oxidised. (authors)

  10. THE INTERPLAY BETWEEN GEOCHEMICAL REACTIONS AND ADVECTION-DISPERSION IN CONTAMINANT TRANSPORT AT A URANIUM MILL TAILINGS SITE

    Science.gov (United States)

    It is well known that the fate and transport of contaminants in the subsurface are controlled by complex processes including advection, dispersion-diffusion, and chemical reactions. However, the interplay between the physical transport processes and chemical reactions, and their...

  11. Production of uranium dioxide

    International Nuclear Information System (INIS)

    Hart, J.E.; Shuck, D.L.; Lyon, W.L.

    1977-01-01

    A continuous, four stage fluidized bed process for converting uranium hexafluoride (UF 6 ) to ceramic-grade uranium dioxide (UO 2 ) powder suitable for use in the manufacture of fuel pellets for nuclear reactors is disclosed. The process comprises the steps of first reacting UF 6 with steam in a first fluidized bed, preferably at about 550 0 C, to form solid intermediate reaction products UO 2 F 2 , U 3 O 8 and an off-gas including hydrogen fluoride (HF). The solid intermediate reaction products are conveyed to a second fluidized bed reactor at which the mol fraction of HF is controlled at low levels in order to prevent the formation of uranium tetrafluoride (UF 4 ). The first intermediate reaction products are reacted in the second fluidized bed with steam and hydrogen at a temperature of about 630 0 C. The second intermediate reaction product including uranium dioxide (UO 2 ) is conveyed to a third fluidized bed reactor and reacted with additional steam and hydrogen at a temperature of about 650 0 C producing a reaction product consisting essentially of uranium dioxide having an oxygen-uranium ratio of about 2 and a low residual fluoride content. This product is then conveyed to a fourth fluidized bed wherein a mixture of air and preheated nitrogen is introduced in order to further reduce the fluoride content of the UO 2 and increase the oxygen-uranium ratio to about 2.25

  12. Phospholyl-uranium complexes

    International Nuclear Information System (INIS)

    Gradoz, Philippe

    1993-01-01

    After having reported a bibliographical study on penta-methylcyclopentadienyl uranium complexes, and a description of the synthesis and radioactivity of uranium (III) and (IV) boron hydrides compounds, this research thesis reports the study of mono and bis-tetramethyl-phospholyl uranium complexes comprising chloride, boron hydride, alkyl and alkoxide ligands. The third part reports the comparison of structures, stabilities and reactions of homologue complexes in penta-methylcyclopentadienyl and tetramethyl-phospholyl series. The last part addresses the synthesis of tris-phospholyl uranium (III) and (IV) complexes. [fr

  13. Modeling position-specific isotope fractionation of organic micropollutants degradation via different reaction pathways

    DEFF Research Database (Denmark)

    Jin, Biao; Rolle, Massimo

    : dichlorobenzamide (BAM), isoproturon (IPU) and diclofenac (DCF). The model successfully reproduces the multi-element isotope data, and precisely captures the dual element isotope trends, characterizing the different degradation pathways. Besides illustrating the model capability of mechanistic evaluation...

  14. Charting an Alternate Pathway to Reaction Orders and Rate Laws in Introductory Chemistry Courses

    Science.gov (United States)

    Rushton, Gregory T.; Criswell, Brett A.; McAllister, Nicole D.; Polizzi, Samuel J.; Moore, Lamesha A.; Pierre, Michelle S.

    2014-01-01

    Reaction kinetics is an axiomatic topic in chemistry that is often addressed as early as the high school course and serves as the foundation for more sophisticated conversations in college-level organic, physical, and biological chemistry courses. Despite the fundamental nature of reaction kinetics, students can struggle with transforming their…

  15. Spectral pathways for exploration of secondary uranium: An investigation in the desertic tracts of Rajasthan and Gujarat, India

    Science.gov (United States)

    Bharti, Rishikesh; Kalimuthu, R.; Ramakrishnan, D.

    2015-10-01

    This study aims at identifying potential zones of secondary uranium enrichment using hyperspectral remote sensing, γ-ray spectrometry, fluorimetry and geochemical techniques in the western Rajasthan and northern Gujarat, India. The investigated area has suitable source rocks, conducive past-, and present-climate that can facilitate such enrichment. This enrichment process involves extensive weathering of uranium bearing source rocks, leaching of uranyl compounds in groundwater, and their precipitation in chemical deltas along with duricrusts like calcretes and gypcretes. Spatial distribution of groundwater calcretes (that are rich in Mg-calcite) and gypcretes (that are rich in gypsum) along palaeochannels and chemical deltas were mapped using hyperspectral remote sensing data based on spectral absorptions in 1.70 μm, 2.16 μm, 2.21 μm, 2.33 μm, 2.44 μm wavelength regions. Subsequently based on field radiometric survey, zones of U anomalies were identified and samples of duricrusts and groundwater were collected for geochemical analyses. Anomalous concentration of U (2345.7 Bq/kg) and Th (142.3 Bq/kg) are observed in both duricrusts and groundwater (U-1791 μg/l, Th-34 μg/l) within the palaeo-delta and river confluence. The estimated carnotite Solubility Index also indicates the secondary enrichment of U and the likelihood of occurrence of an unconventional deposit.

  16. DFT study of benzyl alcohol/TiO2 interfacial surface complex: reaction pathway and mechanism of visible light absorption.

    Science.gov (United States)

    Zhao, Lei; Gu, Feng Long; Kim, Minjae; Miao, Maosheng; Zhang, Rui-Qin

    2017-09-24

    We propose a new pathway for the adsorption of benzyl alcohol on the surface of TiO 2 and the formation of interfacial surface complex (ISC). The reaction free energies and reaction kinetics were thoroughly investigated by density functional calculations. The TiO 2 surfaces were modeled by clusters consisting of 4 Ti atoms and 18 O atoms passivated by H, OH group and H 2 O molecules. Compared with solid-state calculations utilizing the periodicity of the materials, such cluster modeling allows inclusion of the high-order correlation effects that seem to be essential for the adsorption of organic molecules onto solid surfaces. The effects of both acidity and solvation are included in our calculations, which demonstrate that the new pathway is competitive with a previous pathway. The electronic structure calculations based on the relaxed ISC structures reveal that the chemisorption of benzyl alcohol on the TiO 2 surface greatly alters the nature of the frontier molecular orbitals. The resulted reduced energy gap in ISC matches the energy of visible light, showing how the adsorption of benzyl alcohol sensitizes the TiO 2 surface. Graphical Abstract The chemisorption of benzyl alcohol on TiO 2 surface greatly alters the nature of the frontier molecular orbitals and the formed interfacial surface complex can be sensitized by visible light.

  17. Analysis of twenty five impurities in uranium matrix by ICP-MS with iron measurement optimized by using reaction collision cell, cold plasma or medium resolution

    International Nuclear Information System (INIS)

    Quemet, Alexandre; Brennetot, Rene; Chevalier, Emilie; Prian, Edwina; Laridon, Anne-Laure; Fichet, Pascal; Goutelard, Florence; Mariet, Clarisse; Laszak, Ivan

    2012-01-01

    An analytical procedure was developed to determine the concentration of 25 impurities (Li, Be, Ti, V. Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ag, Cd, In, Sm, Eu, Gd, Dy, W, Pb, Bi and Th) in a uranium matrix using the quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS). The dissolution of U 3 O 8 powder was made with a mixture of hydrochloric acid and nitric acid. Then, a selective separation of uranium using the UTEVA column was used before measurement by Q-ICP-MS. The procedure developed was verified using the Certified Reference Material 'Morille'. The analytical results agree well except for 5 elements where values are underestimated (Li, Be, In, Pb and Bi). Among the list of impurities, iron was particularly investigated because it is well known that this element possesses a polyatomic interference that increases the detection limit. A comparison between iron detection limits obtained with different methods was performed. Iron polyatomic interference was at least reduced, or at best entirely resolved in some cases, by using the cold plasma or the collision/reaction cell with several gases (He, NH 3 and CH 4 ). High-resolution ICP-MS was used to compare the results obtained. A detection limit as low as 8 ng L -1 was achieved. (authors)

  18. Analysis of twenty five impurities in uranium matrix by ICP-MS with iron measurement optimized by using reaction collision cell, cold plasma or medium resolution.

    Science.gov (United States)

    Quemet, Alexandre; Brennetot, Rene; Chevalier, Emilie; Prian, Edwina; Laridon, Anne-Laure; Mariet, Clarisse; Fichet, Pascal; Laszak, Ivan; Goutelard, Florence

    2012-09-15

    An analytical procedure was developed to determine the concentration of 25 impurities (Li, Be, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ag, Cd, In, Sm, Eu, Gd, Dy, W, Pb, Bi and Th) in a uranium matrix using the quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS). The dissolution of U(3)O(8) powder was made with a mixture of hydrochloric acid and nitric acid. Then, a selective separation of uranium using the UTEVA column was used before measurement by Q-ICP-MS. The procedure developed was verified using the Certified Reference Material "Morille". The analytical results agree well except for 5 elements where values are underestimated (Li, Be, In, Pb and Bi). Among the list of impurities, iron was particularly investigated because it is well known that this element possesses a polyatomic interference that increases the detection limit. A comparison between iron detection limits obtained with different methods was performed. Iron polyatomic interference was at least reduced, or at best entirely resolved in some cases, by using the cold plasma or the collision/reaction cell with several gases (He, NH(3) and CH(4)). High-resolution ICP-MS was used to compare the results obtained. A detection limit as low as 8 ng L(-1) was achieved. Copyright © 2012 Elsevier B.V. All rights reserved.

  19. Recoil properties of antimony isotopes produced by the reaction of 570 MeV and 18.2 GeV protons with uranium

    CERN Document Server

    Hagebø, E

    1969-01-01

    Using the method of thick target and thick catchers, the ranges and other recoil properties of 13 (12) antimony isotopes between A = 115 and A = 131 (130) have been measured for the reaction of 570 MeV (18·2 GeV) protons with uranium. The kinetic energies T are almost independent of product mass number at 570 MeV but show a strong dependence at 18·2 GeV, the lightest isotopes having only about half the kinetic energy of the heavy ones. \\\\ \\\\The cascade deposition energies for production of antimony isotopes are almost equal at 570 MeV and 18·2 GeV and fit well to straight lines of the form E$^{∗}$ (A, Z) = E$^{∗}$ (A$_{0}$, Z) + b(A − A$_{0}$). Exceptions are the cascade deposition energies for $^{115}$Sb and $^{116}$Sb which seem to be somewhat too high at 18·2 GeV. By comparison with other work it seems that the slope $b$ of these lines is independent of product element, target and of proton irradiation energy above 450 MeV. \\\\ \\\\If we assume at 570 MeV, that the fissioning nucleus is a uranium ...

  20. An approach to the calculation of dose commitment arising from different methods for the long-term management of uranium mill tailings through aquatic pathways

    International Nuclear Information System (INIS)

    1983-01-01

    This report describes the development and use of the aquatic pathway portion of a diagnostic model. The model was developed as part of a study intended to improve methods for estimating the environmental dispersion of radionuclides from uranium mill tailings disposal sites. This, the aquatic portion of the study, investigates radionuclide dispersion through aquatic pathways from a hypothetical mill tailings disposal site and presents dose commitment calculations for human exposure to the simulated patterns of radionuclide concentrations over time. Dose commitment estimates are made, based on the simulated geochemical behaviour of the hypothetical site and tailings, aquatic dispersion from the generic site located in northern Ontario and human exposure to and utilization of aquatic products (fish, water). The dose commitment estimates are presented based upon a range of input variable assumptions. This, the 'Aquatic Technical Appendix', describes all important aspects of: the aquatic portion of the diagnostic model, the modelling of the hypothetical tailings site and tailings mass, and findings resulting from use of the models. This report does not predict real radiation doses, or real radionuclide dispersion patterns for any site whether existing or projected

  1. Chemical Conversion Pathways and Kinetic Modeling for the OH-Initiated Reaction of Triclosan in Gas-Phase

    Directory of Open Access Journals (Sweden)

    Xue Zhang

    2015-04-01

    Full Text Available As a widely used antimicrobial additive in daily consumption, attention has been paid to the degradation and conversion of triclosan for a long time. The quantum chemistry calculation and the canonical variational transition state theory are employed to investigate the mechanism and kinetic property. Besides addition and abstraction, oxidation pathways and further conversion pathways are also considered. The OH radicals could degrade triclosan to phenols, aldehydes, and other easily degradable substances. The conversion mechanisms of triclosan to the polychlorinated dibenzopdioxin and furan (PCDD/Fs and polychlorinated biphenyls (PCBs are clearly illustrated and the toxicity would be strengthened in such pathways. Single radical and diradical pathways are compared to study the conversion mechanism of dichlorodibenzo dioxin (DCDD. Furthermore, thermochemistry is discussed in detail. Kinetic property is calculated and the consequent ratio of kadd/ktotal and kabs/ktotal at 298.15 K are 0.955 and 0.045, respectively. Thus, the OH radical addition reactions are predominant, the substitute position of OH radical on triclosan is very important to generate PCDD and furan, and biradical is also a vital intermediate to produce dioxin.

  2. Chemical conversion pathways and kinetic modeling for the OH-initiated reaction of triclosan in gas-phase.

    Science.gov (United States)

    Zhang, Xue; Zhang, Chenxi; Sun, Xiaomin; Kang, Lingyan; Zhao, Yan

    2015-04-10

    As a widely used antimicrobial additive in daily consumption, attention has been paid to the degradation and conversion of triclosan for a long time. The quantum chemistry calculation and the canonical variational transition state theory are employed to investigate the mechanism and kinetic property. Besides addition and abstraction, oxidation pathways and further conversion pathways are also considered. The OH radicals could degrade triclosan to phenols, aldehydes, and other easily degradable substances. The conversion mechanisms of triclosan to the polychlorinated dibenzopdioxin and furan (PCDD/Fs) and polychlorinated biphenyls (PCBs) are clearly illustrated and the toxicity would be strengthened in such pathways. Single radical and diradical pathways are compared to study the conversion mechanism of dichlorodibenzo dioxin (DCDD). Furthermore, thermochemistry is discussed in detail. Kinetic property is calculated and the consequent ratio of k add/k total and k abs/k total at 298.15 K are 0.955 and 0.045, respectively. Thus, the OH radical addition reactions are predominant, the substitute position of OH radical on triclosan is very important to generate PCDD and furan, and biradical is also a vital intermediate to produce dioxin.

  3. Use of a permeable biological reaction barrier for groundwater remediation at a uranium mill tailings remedial action (UMTRA) site

    International Nuclear Information System (INIS)

    Thombre, M.S.; Thomson, B.M.; Barton, L.L.

    1997-01-01

    Previous work at the University of New Mexico and elsewhere has shown that sulfate reducing bacteria are capable of reducing uranium from the soluble +6 oxidation state to the insoluble +4 oxidation state. This chemistry forms the basis of a proposed groundwater remediation strategy in which microbial reduction would be used to immobilize soluble uranium. One such system would consist of a subsurface permeable barrier which would stimulate microbial growth resulting in the reduction of sulfate and nitrate and immobilization of metals while permitting the unhindered flow of ground water through it. This research investigated some of the engineering considerations associated with a microbial reducing barrier such as identifying an appropriate biological substrate, estimating the rate of substrate utilization, and identifying the final fate of the contaminants concentrated in the barrier matrix. The performance of batch reactors and column systems that treated simulated plume water was evaluated using cellulose, wheat straw, alfalfa hay, sawdust, and soluble starch as substrates. The concentrations of sulfate, nitrate, and U(VI) were monitored over time. Precipitates from each system were collected and the precipitated U(IV) was determined to be crystalline UO 2 (s) by X-ray Diffraction. The results of this study support the proposed use of cellulosic substrates as candidate barrier materials

  4. Radical Rearrangement Chemistry in Ultraviolet Photodissociation of Iodotyrosine Systems: Insights from Metastable Dissociation, Infrared Ion Spectroscopy, and Reaction Pathway Calculations.

    Science.gov (United States)

    Ranka, Karnamohit; Zhao, Ning; Yu, Long; Stanton, John F; Polfer, Nicolas C

    2018-05-29

    We report on the ultraviolet photodissociation (UVPD) chemistry of protonated tyrosine, iodotyrosine, and diiodotyrosine. Distonic loss of the iodine creates a high-energy radical at the aromatic ring that engages in hydrogen/proton rearrangement chemistry. Based on UVPD kinetics measurements, the appearance of this radical is coincident with the UV irradiation pulse (8 ns). Conversely, sequential UVPD product ions exhibit metastable decay on ca. 100 ns timescales. Infrared ion spectroscopy is capable of confirming putative structures of the rearrangement products as proton transfers from the imine and β-carbon hydrogens. Potential energy surfaces for the various reaction pathways indicate that the rearrangement chemistry is highly complex, compatible with a cascade of rearrangements, and that there is no preferred rearrangement pathway even in small molecular systems like these. Graphical Abstract.

  5. Reaction progress pathways for glass and spent fuel under unsaturated conditions

    International Nuclear Information System (INIS)

    Bates, J.; Finn, P.; Bourcier, W.; Stout, R.

    1994-10-01

    The source term for the release of radionuclides from a nuclear waste repository is the waste form. In order to assess the performance of the repository and the engineered barrier system (EBS) compared to regulations established by the Nuclear Regulatory Commission and the Environmental Protection Agency it is necessary (1) to use available data to place bounding limits on release rates from the EBS, and (2) to develop a mechanistic predictive model of the radionuclide release and validate the model against tests done under a variety of different potential reaction conditions. The problem with (1) is that there is little experience to use when evaluating waste form reaction under unsaturated conditions such that errors in applying expert judgment to the problem may be significant. The second approach, to test and model the waste form reaction, is a more defensible means of providing input to the prediction of radionuclide release. In this approach, information related to the source term has a technical basis and provides a starting point to make reasonable assumptions for long-term behavior. Key aspects of this approach are an understanding of the reaction progress mechanism and the ability to model the tests using a geochemical code such as EQ3/6. Current knowledge of glass, UO 2 , and spent fuel reactions under different conditions are described below

  6. Directing Reaction Pathways through Controlled Reactant Binding at Pd-TiO2 Interfaces.

    Science.gov (United States)

    Zhang, Jing; Wang, Bingwen; Nikolla, Eranda; Medlin, J Will

    2017-06-01

    Recent efforts to design selective catalysts for multi-step reactions, such as hydrodeoxygenation (HDO), have emphasized the preparation of active sites at the interface between two materials having different properties. However, achieving precise control over interfacial properties, and thus reaction selectivity, has remained a challenge. Here, we encapsulated Pd nanoparticles (NPs) with TiO 2 films of regulated porosity to gain a new level of control over catalyst performance, resulting in essentially 100 % HDO selectivity for two biomass-derived alcohols. This catalyst also showed exceptional reaction specificity in HDO of furfural and m-cresol. In addition to improving HDO activity by maximizing the interfacial contact between the metal and metal oxide sites, encapsulation by the nanoporous oxide film provided a significant selectivity boost by restricting the accessible conformations of aromatics on the surface. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Directing reaction pathways by catalyst active-site selection using self-assembled monolayers.

    Science.gov (United States)

    Pang, Simon H; Schoenbaum, Carolyn A; Schwartz, Daniel K; Medlin, J Will

    2013-01-01

    One key route for controlling reaction selectivity in heterogeneous catalysis is to prepare catalysts that exhibit only specific types of sites required for desired product formation. Here we show that alkanethiolate self-assembled monolayers with varying surface densities can be used to tune selectivity to desired hydrogenation and hydrodeoxygenation products during the reaction of furfural on supported palladium catalysts. Vibrational spectroscopic studies demonstrate that the selectivity improvement is achieved by controlling the availability of specific sites for the hydrogenation of furfural on supported palladium catalysts through the selection of an appropriate alkanethiolate. Increasing self-assembled monolayer density by controlling the steric bulk of the organic tail ligand restricts adsorption on terrace sites and dramatically increases selectivity to desired products furfuryl alcohol and methylfuran. This technique of active-site selection simultaneously serves both to enhance selectivity and provide insight into the reaction mechanism.

  8. Production of uranium peroxide

    International Nuclear Information System (INIS)

    Caropreso, F.E.; Kreuz, D.F.

    1977-01-01

    A process is claimed of recovering uranium values as uranium peroxide from an aqueous uranyl solution containing dissolved vanadium and sodium impurities by treating the uranyl solution with hydrogen peroxide in an amount sufficient to have an excess of at least 0.5 parts H 2 O 2 per part of vanadium (V 2 O 5 ) above the stoichiometric amount required to form the uranium peroxide, the hydrogen peroxide treatment is carried out in three sequential phases consisting of I, a precipitation phase in which the hydrogen peroxide is added to the uranyl solution to precipitate the uranium peroxide and the pH of the reaction medium maintained in the range of 2.5 to 5.5 for a period of from about 1 to 60 minutes after the hydrogen peroxide addition; II, a digestion phase in which the pH of the reaction medium is maintained in the range of 3.0 to 7.0 for a period of about 5 to 180 minutes and III, a final phase in which the pH of the reaction medium is maintained in the range of 4.0 to 7.0 for a period of about 1 to 60 minutes during which time the uranium peroxide is separated from the reaction solution containing the dissolved vanadium and sodium impurities. The excess hydrogen peroxide is maintained during the entire treatment up until the uranium peroxide is separated from the reaction medium

  9. Aspartate aminotransferase: the kinetic barriers facing the covalent intermediates on the reaction pathway

    International Nuclear Information System (INIS)

    Kirsch, J.F.; Julin, D.A.; McLeish, M.; Wiesinger, H.

    1986-01-01

    The intermediates, aldimine (A), quinonoid (Q) and ketimine (K), along the transaminase reaction coordinate were probed by isotope transfer and solvent exchange kinetics. Less than 0.003% of 3 H is transferred from C/sub α/[ 3 H]-aspartate to pyridoxamine phosphate in the cytoplasmic aspartate aminotransferase (cAATase) reaction implying either that Q does not exist as a kinetically competent intermediate or that there is a rapid exchange of isotope with solvent. The ratio of the rate constants for C/sub α/ hydrogen exchange vs keto acid product formation (k/sub exge//k/sub prod/) are 2.5 and 0.5 for the reactions of cAATase with C/sub α/ [ 2 H]-aspartate and mitochondrial (m) AATase with C/sub α/[ 2 H]-glutamate respectively. The latter reaction was also probed from the α-keto-glutarate side with carbonyl 0-18 enriched keto acid. This experiment gave k/sub exge//k/sub prod/ = 1.0 for oxygen-18 exchange in α-ketoglutarate versus amino acid formation. The two exchange experiments with mAATase are interpreted in terms of a model in which the rate constant for diffusion of water from the active site is comparable with those for product forming steps

  10. Activation pathways taking place at molecular copper precatalysts for the oxygen evolution reaction

    NARCIS (Netherlands)

    van der Ham, C.J.M.; Işık, F.; Verhoeven, T.W.G.M.; Niemantsverdriet, J.W.; Hetterscheid, D.G.H.

    2017-01-01

    The activation processes of [CuII(bdmpza)2] in the water oxidation reaction were investigated using cyclic voltammetry and chronoamperometry. Two different paths wherein CuO is formed were distinguished. [CuII(bdmpza)2] can be oxidized at high potentials to form CuO, which was observed by a slight

  11. A kinetic model for the glucose/glycine Maillard reaction pathways

    NARCIS (Netherlands)

    Martins, S.I.F.S.; Boekel, van M.A.J.S.

    2005-01-01

    A comprehensive kinetic model for the glucose/glycine Maillard reaction is proposed based on an approach called multiresponse kinetic modelling. Special attention was paid to reactants, intermediates and end products: -fructose, N-(1-deoxy--fructos-1-yl)-glycine (DFG), 1-deoxy-2,3-hexodiulose and

  12. About the elaboration of pure uranium dicarbide

    International Nuclear Information System (INIS)

    Besson, J.; Blum, P.; Guinet, Ph.; Spitz, J.

    1963-01-01

    In order to develop methods for the elaboration of as pure as possible uranium dicarbide, the authors report the study of different elaboration processes based on the reaction between uranium and carbon, or between uranium and hydrocarbon, or between uranium oxide and carbon. They finally choose a method which comprises an arc-induced fusion of a mixture of uranium dioxide and carbon. The fusion process is described. The influence of thermal treatments is discussed as well as the graphite electrode carburization

  13. Modeling Ignition of a Heptane Isomer: Improved Thermodynamics, Reaction Pathways, Kinetic, and Rate Rule Optimizations for 2-Methylhexane

    KAUST Repository

    Mohamed, Samah; Cai, Liming; Khaled, Fathi; Banyon, Colin; Wang, Zhandong; Rachidi, Mariam El; Pitsch, Heinz; Curran, Henry J.; Farooq, Aamir; Sarathy, Mani

    2016-01-01

    Accurate chemical kinetic combustion models of lightly branched alkanes (e.g., 2-methylalkanes) are important to investigate the combustion behavior of real fuels. Improving the fidelity of existing kinetic models is a necessity, as new experiments and advanced theories show inaccuracies in certain portions of the models. This study focuses on updating thermodynamic data and the kinetic reaction mechanism for a gasoline surrogate component, 2-methylhexane, based on recently published thermodynamic group values and rate rules derived from quantum calculations and experiments. Alternative pathways for the isomerization of peroxy-alkylhydroperoxide (OOQOOH) radicals are also investigated. The effects of these updates are compared against new high-pressure shock tube and rapid compression machine ignition delay measurements. It is shown that rate constant modifications are required to improve agreement between kinetic modeling simulations and experimental data. We further demonstrate the ability to optimize the kinetic model using both manual and automated techniques for rate parameter tunings to improve agreement with the measured ignition delay time data. Finally, additional low temperature chain branching reaction pathways are shown to improve the model’s performance. The present approach to model development provides better performance across extended operating conditions while also strengthening the fundamental basis of the model.

  14. Modeling Ignition of a Heptane Isomer: Improved Thermodynamics, Reaction Pathways, Kinetic, and Rate Rule Optimizations for 2-Methylhexane

    KAUST Repository

    Mohamed, Samah

    2016-03-21

    Accurate chemical kinetic combustion models of lightly branched alkanes (e.g., 2-methylalkanes) are important to investigate the combustion behavior of real fuels. Improving the fidelity of existing kinetic models is a necessity, as new experiments and advanced theories show inaccuracies in certain portions of the models. This study focuses on updating thermodynamic data and the kinetic reaction mechanism for a gasoline surrogate component, 2-methylhexane, based on recently published thermodynamic group values and rate rules derived from quantum calculations and experiments. Alternative pathways for the isomerization of peroxy-alkylhydroperoxide (OOQOOH) radicals are also investigated. The effects of these updates are compared against new high-pressure shock tube and rapid compression machine ignition delay measurements. It is shown that rate constant modifications are required to improve agreement between kinetic modeling simulations and experimental data. We further demonstrate the ability to optimize the kinetic model using both manual and automated techniques for rate parameter tunings to improve agreement with the measured ignition delay time data. Finally, additional low temperature chain branching reaction pathways are shown to improve the model’s performance. The present approach to model development provides better performance across extended operating conditions while also strengthening the fundamental basis of the model.

  15. Reaction between peroxynitrite and boronates: EPR spin-trapping, HPLC analyses, and quantum mechanical study of the free radical pathway

    Science.gov (United States)

    Sikora, Adam; Zielonka, Jacek; Lopez, Marcos; Dybala-Defratyka, Agnieszka; Joseph, Joy; Marcinek, Andrzej; Kalyanaraman, Balaraman

    2013-01-01

    Recently we showed that peroxynitrite (ONOO−) reacts directly and rapidly with aromatic and aliphatic boronic acids (k ≈ 106 M−1s−1). Product analyses and substrate consumption data indicated that ONOO− reacts stoichiometrically with boronates, yielding the corresponding phenols as the major product (~85–90%), and the remaining products (10–15%) were proposed to originate from free radical intermediates (phenyl and phenoxyl radicals). Here we investigated in detail the minor, free radical pathway of boronate reaction with ONOO−. The electron paramagnetic resonance (EPR) spin-trapping technique was used to characterize the free radical intermediates formed from the reaction between boronates and ONOO−. Using 2-methyl-2-nitrosopropane (MNP) and 5-diethoxyphosphoryl-5-methyl-1-pyrroline-N-oxide (DEPMPO) spin traps, phenyl radicals were trapped and detected. Although phenoxyl radicals were not detected, the positive effects of molecular oxygen, and inhibitory effects of hydrogen atom donors (acetonitrile, and 2-propanol) and general radical scavengers (GSH, NADH, ascorbic acid and tyrosine) on the formation of phenoxyl radical-derived nitrated product, suggest that phenoxyl radical was formed as the secondary species. We propose that the initial step of the reaction involves the addition of ONOO− to the boron atom in boronates. The anionic intermediate undergoes both heterolytic (major pathway) and homolytic (minor pathway) cleavage of the peroxy (O-O) bond to form phenol and nitrite as a major product (via a non-radical mechanism), or a radical pair PhB(OH)2O•−…•NO2 as a minor product. It is conceivable that phenyl radicals are formed by the fragmentation of PhB(OH)2O•− radical anion. According to the DFT quantum mechanical calculations, the energy barrier for the dissociation of PhB(OH)2O•− radical anion to form phenyl radicals is only a few kcal/mol, suggesting rapid and spontaneous fragmentation of PhB(OH)2O•− radical anion

  16. Depleted uranium

    International Nuclear Information System (INIS)

    Huffer, E.; Nifenecker, H.

    2001-02-01

    This document deals with the physical, chemical and radiological properties of the depleted uranium. What is the depleted uranium? Why do the military use depleted uranium and what are the risk for the health? (A.L.B.)

  17. Oxidation of β-lactam antibiotics by peracetic acid: Reaction kinetics, product and pathway evaluation.

    Science.gov (United States)

    Zhang, Kejia; Zhou, Xinyan; Du, Penghui; Zhang, Tuqiao; Cai, Meiquan; Sun, Peizhe; Huang, Ching-Hua

    2017-10-15

    Peracetic acid (PAA) is a disinfection oxidant used in many industries including wastewater treatment. β-Lactams, a group of widely prescribed antibiotics, are frequently detected in wastewater effluents and surface waters. The reaction kinetics and transformation of seven β-lactams (cefalexin (CFX), cefadroxil (CFR), cefapirin (CFP), cephalothin (CFT), ampicillin (AMP), amoxicillin (AMX) and penicillin G (PG)) toward PAA were investigated to elucidate the behavior of β-lactams during PAA oxidation processes. The reaction follows second-order kinetics and is much faster at pH 5 and 7 than at pH 9 due to speciation of PAA. Reactivity to PAA follows the order of CFR ∼ CFX > AMP ∼ AMX > CFT ∼ CFP ∼ PG and is related to β-lactam's nucleophilicity. The thioether sulfur of β-lactams is attacked by PAA to generate sulfoxide products. Presence of the phenylglycinyl amino group on β-lactams can significantly influence electron distribution and the highest occupied molecular orbital (HOMO) location and energy in ways that enhance the reactivity to PAA. Reaction rate constants obtained in clean water matrix can be used to accurately model the decay of β-lactams by PAA in surface water matrix and only slightly overestimate the decay in wastewater matrix. Results of this study indicate that the oxidative transformation of β-lactams by PAA can be expected under appropriate wastewater treatment conditions. Copyright © 2017. Published by Elsevier Ltd.

  18. Maruhn-Greiner Maximum of Uranium Fission for Confirmation of Low Energy Nuclear Reactions LENR via a Compound Nucleus with Double Magic Numbers

    Science.gov (United States)

    Hora, H.; Miley, G. H.

    2007-12-01

    One of the most convincing facts about LENR due to deuterons of very high concentration in host metals as palladium is the measurement of the large scale minimum of the reaction probability depending on the nucleon number A of generated elements at A = 153 where a local maximum was measured. This is similar to the fission of uranium at A = 119 where the local maximum follows from the Maruhn-Greiner theory if the splitting nuclei are excited to about MeV energy. The LENR generated elements can be documented any time after the reaction by SIMS or K-shell X-ray excitation to show the very unique distribution with the local maximum. An explanation is based on the strong Debye screening of the Maxwellian deuterons within the degenerate rigid electron background especially within the swimming electron layer at the metal surface or at interfaces. The deuterons behave like neutrals at distances of about 2 picometers. They may form clusters due to soft attraction in the range above thermal energy. Clusters of 10 pm diameter may react over long time probabilities (megaseconds) with Pd nuclei leading to a double magic number compound nucleus which splits like in fission to the A = 153 element distribution.

  19. Cobalt catalyzed peroxymonosulfate oxidation of tetrabromobisphenol A: Kinetics, reaction pathways, and formation of brominated by-products

    Energy Technology Data Exchange (ETDEWEB)

    Ji, Yuefei [Department of Environmental Science and Engineering, Nanjing Agricultural University, Nanjing 210095 (China); Kong, Deyang [Nanjing Institute of Environmental Science, Ministry of Environmental Protection of PRC, Nanjing 210042 (China); Lu, Junhe, E-mail: jhlu@njau.edu.cn [Department of Environmental Science and Engineering, Nanjing Agricultural University, Nanjing 210095 (China); Jin, Hao; Kang, Fuxing; Yin, Xiaoming; Zhou, Quansuo [Department of Environmental Science and Engineering, Nanjing Agricultural University, Nanjing 210095 (China)

    2016-08-05

    Highlights: • Cobalt catalyzed peroxymonosulfate oxidation of tetrabromobisphenol A. • Phenolic moiety was the reactive site for sulfate radical attack. • Pathways include β-scission, oxidation, debromination and coupling reactions. • Brominated disinfection by-products were found during TBBPA degradation. • Humic acid inhibited TBBPA degradation but promoted DBPs formation. - Abstract: Degradation of tetrabromobisphenol A (TBBPA), a flame retardant widely spread in the environment, in Co(II) catalyzed peroxymonosulfate (PMS) oxidation process was systematically explored. The second-order-rate constant for reaction of sulfate radical (SO{sub 4}{sup ·−}) with TBBPA was determined to be 5.27 × 10{sup 10} M{sup −1} s{sup −1}. Apparently, degradation of TBBPA showed first-order kinetics to the concentrations of both Co(II) and PMS. The presence of humic acid (HA) and bicarbonate inhibited TBBPA degradation, most likely due to their competition for SO{sub 4}{sup ·−}. Degradation of TBBPA was initiated by an electron abstraction from one of the phenolic rings. Detailed transformation pathways were proposed, including β-scission of isopropyl bridge, phenolic ring oxidation, debromination and coupling reactions. Further oxidative degradation of intermediates in Co(II)/PMS process yielded brominated disinfection by-products (Br-DBPs) such as bromoform and brominated acetic acids. Evolution profile of Br-DBPs showed an initially increasing and then decreasing pattern with maximum concentrations occurring around 6–10 h. The presence of HA enhanced the formation of Br-DBPs significantly. These findings reveal potentially important, but previously unrecognized, formation of Br-DBPs during sulfate radical-based oxidation of bromide-containing organic compounds that may pose toxicological risks to human health.

  20. Uranium dioxide electrolysis

    Science.gov (United States)

    Willit, James L [Batavia, IL; Ackerman, John P [Prescott, AZ; Williamson, Mark A [Naperville, IL

    2009-12-29

    This is a single stage process for treating spent nuclear fuel from light water reactors. The spent nuclear fuel, uranium oxide, UO.sub.2, is added to a solution of UCl.sub.4 dissolved in molten LiCl. A carbon anode and a metallic cathode is positioned in the molten salt bath. A power source is connected to the electrodes and a voltage greater than or equal to 1.3 volts is applied to the bath. At the anode, the carbon is oxidized to form carbon dioxide and uranium chloride. At the cathode, uranium is electroplated. The uranium chloride at the cathode reacts with more uranium oxide to continue the reaction. The process may also be used with other transuranic oxides and rare earth metal oxides.

  1. Reaction

    African Journals Online (AJOL)

    abp

    19 oct. 2017 ... Reaction to Mohamed Said Nakhli et al. concerning the article: "When the axillary block remains the only alternative in a 5 year old child". .... Bertini L1, Savoia G, De Nicola A, Ivani G, Gravino E, Albani A et al ... 2010;7(2):101-.

  2. Synergistic reaction between SO2 and NO2 on mineral oxides: a potential formation pathway of sulfate aerosol.

    Science.gov (United States)

    Liu, Chang; Ma, Qingxin; Liu, Yongchun; Ma, Jinzhu; He, Hong

    2012-02-07

    Sulfate is one of the most important aerosols in the atmosphere. A new sulfate formation pathway via synergistic reactions between SO(2) and NO(2) on mineral oxides was proposed. The heterogeneous reactions of SO(2) and NO(2) on CaO, α-Fe(2)O(3), ZnO, MgO, α-Al(2)O(3), TiO(2), and SiO(2) were investigated by in situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (in situ DRIFTS) at ambient temperature. Formation of sulfate from adsorbed SO(2) was promoted by the coexisting NO(2), while surface N(2)O(4) was observed as the crucial oxidant for the oxidation of surface sulfite. This process was significantly promoted by the presence of O(2). The synergistic effect between SO(2) and NO(2) was not observed on other mineral particles (such as CaCO(3) and CaSO(4)) probably due to the lack of the surface reactive oxygen sites. The synergistic reaction between SO(2) and NO(2) on mineral oxides resulted in the formation of internal mixtures of sulfate, nitrate, and mineral oxides. The change of mixture state will affect the physicochemical properties of atmospheric particles and therefore further influence their environmental and climate effects.

  3. Progranulin protects vascular endothelium against atherosclerotic inflammatory reaction via Akt/eNOS and nuclear factor-κB pathways.

    Science.gov (United States)

    Hwang, Hwan-Jin; Jung, Tae Woo; Hong, Ho Cheol; Choi, Hae Yoon; Seo, Ji-A; Kim, Sin Gon; Kim, Nan Hee; Choi, Kyung Mook; Choi, Dong Seop; Baik, Sei Hyun; Yoo, Hye Jin

    2013-01-01

    Atherosclerosis is considered a chronic inflammatory disease, initiated by activation and dysfunction of the endothelium. Recently, progranulin has been regarded as an important modulator of inflammatory processes; however, the role for prgranulin in regulating inflammation in vascular endothelial cells has not been described. Signaling pathways mediated by progranulin were analyzed in human umbilical vein endothelial cells (HUVECs) treated with progranulin. Progranulin significantly induced Akt and endothelial nitric oxide synthase (eNOS) phosphorylation in HUVECs, an effect that was blocked with Akt inhibitor. Furthermore, nitric oxide (NO) level, the end product of Akt/eNOS pathway, was significantly upregulated after progranulin treatment. Next, we showed that progranulin efficiently inhibited lipopolysaccharide (LPS)-mediated pro-inflammatory signaling. LPS-induced phosphorylation of IκB and nuclear factor-κB (NF-κB) levels decreased after progranulin treatment. Also, progranulin blocked translocation of NF-κB from the cytosol to the nucleus. In addition, progranulin significantly reduced the expression of vascular cell adhesion molecule-1 (VCAM-1) and intercellular adhesion molecule-1 (ICAM-1) by inhibiting binding of NF- κB to their promoter regions and blocked attachment of monocytes to HUVECs. Progranulin also significantly reduced the expression of tumor necrosis factor receptor-α (TNF-α) and monocyte chemo-attractant protein-1 (MCP-1), the crucial inflammatory molecules known to aggravate atherosclerosis. Progranulin efficiently inhibited LPS-mediated pro-inflammatory signaling in endothelial cells through activation of the Akt/eNOS pathway and attenuation of the NF-κB pathway, suggesting its protective roles in vascular endothelium against inflammatory reaction underlying atherosclerosis.

  4. Progranulin protects vascular endothelium against atherosclerotic inflammatory reaction via Akt/eNOS and nuclear factor-κB pathways.

    Directory of Open Access Journals (Sweden)

    Hwan-Jin Hwang

    Full Text Available OBJECTIVE: Atherosclerosis is considered a chronic inflammatory disease, initiated by activation and dysfunction of the endothelium. Recently, progranulin has been regarded as an important modulator of inflammatory processes; however, the role for prgranulin in regulating inflammation in vascular endothelial cells has not been described. METHOD AND RESULTS: Signaling pathways mediated by progranulin were analyzed in human umbilical vein endothelial cells (HUVECs treated with progranulin. Progranulin significantly induced Akt and endothelial nitric oxide synthase (eNOS phosphorylation in HUVECs, an effect that was blocked with Akt inhibitor. Furthermore, nitric oxide (NO level, the end product of Akt/eNOS pathway, was significantly upregulated after progranulin treatment. Next, we showed that progranulin efficiently inhibited lipopolysaccharide (LPS-mediated pro-inflammatory signaling. LPS-induced phosphorylation of IκB and nuclear factor-κB (NF-κB levels decreased after progranulin treatment. Also, progranulin blocked translocation of NF-κB from the cytosol to the nucleus. In addition, progranulin significantly reduced the expression of vascular cell adhesion molecule-1 (VCAM-1 and intercellular adhesion molecule-1 (ICAM-1 by inhibiting binding of NF- κB to their promoter regions and blocked attachment of monocytes to HUVECs. Progranulin also significantly reduced the expression of tumor necrosis factor receptor-α (TNF-α and monocyte chemo-attractant protein-1 (MCP-1, the crucial inflammatory molecules known to aggravate atherosclerosis. CONCLUSION: Progranulin efficiently inhibited LPS-mediated pro-inflammatory signaling in endothelial cells through activation of the Akt/eNOS pathway and attenuation of the NF-κB pathway, suggesting its protective roles in vascular endothelium against inflammatory reaction underlying atherosclerosis.

  5. Impact of organic-mineral matter interactions on thermal reaction pathways for coal model compounds

    Energy Technology Data Exchange (ETDEWEB)

    Buchanan, A.C. III; Britt, P.F.; Struss, J.A. [Oak Ridge National Lab., TN (United States). Chemical and Analytical Sciences Div.

    1995-07-01

    Coal is a complex, heterogeneous solid that includes interdispersed mineral matter. However, knowledge of organic-mineral matter interactions is embryonic, and the impact of these interactions on coal pyrolysis and liquefaction is incomplete. Clay minerals, for example, are known to be effective catalysts for organic reactions. Furthermore, clays such as montmorillonite have been proposed to be key catalysts in the thermal alteration of lignin into vitrinite during the coalification process. Recent studies by Hatcher and coworkers on the evolution of coalified woods using microscopy and NMR have led them to propose selective, acid-catalyzed, solid state reaction chemistry to account for retained structural integrity in the wood. However, the chemical feasibility of such reactions in relevant solids is difficult to demonstrate. The authors have begun a model compound study to gain a better molecular level understanding of the effects in the solid state of organic-mineral matter interactions relevant to both coal formation and processing. To satisfy the need for model compounds that remain nonvolatile solids at temperatures ranging to 450 C, model compounds are employed that are chemically bound to the surface of a fumed silica (Si-O-C{sub aryl}linkage). The organic structures currently under investigation are phenethyl phenyl ether (C{sub 6}H{sub 5}CH{sub 2}CH{sub 2}OC{sub 6}H{sub 5}) derivatives, which serve as models for {beta}-alkyl aryl ether units that are present in lignin and lignitic coals. The solid-state chemistry of these materials at 200--450 C in the presence of interdispersed acid catalysts such as small particle size silica-aluminas and montmorillonite clay will be reported. Initial focus will be on defining the potential impact of these interactions on coal pyrolysis and liquefaction.

  6. Heat treatment effects on the surface chemisorption behavior of strained uranium: The H2O/U reaction

    International Nuclear Information System (INIS)

    Tiferet, E.; Mintz, M.H.; Zalkind, S.; Jacob, I.; Shamir, N.

    2007-01-01

    The initial interaction of H 2 O vapor with polycrystalline uranium surfaces was studied with samples initially strained, then strain relieved by heat treatments, performed in the temperature range up to ∼650 K. The chemisorption characteristics of these surfaces were studied by a combination of direct recoils spectrometry and X-ray photoelectron spectroscopy. X-ray diffraction measurements were used to determine the level of strain relief induced by each of the heat treatments. For all the samples, full water dissociation on the metal surface is observed. The reactivity of the samples towards water is clearly strain dependent, with the sticking coefficient decreasing as strain is relieved. It also seems that for strained samples the initial growth of the oxide is mostly inwards, while for the more relaxed samples lateral growth is dominant. Two interesting phenomena were observed for specific samples. For the 420 K relieved sample, partial dissociation process is observed on top of the forming oxide, in contrast to the full dissociation observed for the other samples. For the ∼650 K relieved sample, clustering of the adsorbed hydrogen atoms (resulted by water dissociation) on the metal surface is observed, in contrast to the homogeneous dispersion of H, occurring on the surface of all other samples. These two phenomena will further be studied in conjunction with microscopic metallurgical observations

  7. The role of reaction pathways and support interactions in the development of high activity hydrotreating catalysts

    DEFF Research Database (Denmark)

    Topsøe, Henrik; Hinnemann, Berit; Nørskov, Jens Kehlet

    2005-01-01

    structures may be present as single sulfide sheets. Thus, stacking is not an essential feature of Type II catalysts. The article illustrates how the new scientific insight has aided the introduction of the new high activity BRIM (TM) type catalysts for FCC pre-treatment and production of ultra low sulfur...... exhibiting a metallic character are observed to be involved in adsorption, hydrogenation and C-S bond cleavage. The insight is seen to provide a new framework for understanding the DDS and HYD pathways and the role of steric hindrance and poisons. Density functional theory (DFT) calculations have illustrated...... how support interactions may influence the activity of sulfided catalysts. The brim sites and the tendency to form vacancies are seen to differ in types I and II Co-Mo-S. High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) studies show that the high activity Type II...

  8. Neutron-induced transmutation reactions in Np-237, Pu-238, and Pu-239 at the massive natural uranium spallation target

    Czech Academy of Sciences Publication Activity Database

    Závorka, L.; Adam, Jindřich; Baldin, A. A.; Čaloun, Pavel; Chilap, V. V.; Furman, W.; Kadykov, M. G.; Khushvaktov, J.; Pronskikh, V. S.; Solnyshkin, A. A.; Sotnikov, V.; Stegailov, V. I.; Suchopár, Martin; Tsoupko-Sitnikov, V. M.; Tyutyunnikov, S. I.; Voronko, V.; Vrzalová, Jitka

    2015-01-01

    Roč. 349, APR (2015), s. 31-38 ISSN 0168-583X R&D Projects: GA MŠk LG14004 Institutional support: RVO:61389005 Keywords : ADS * spent nuclear fuel * transmutation reaction * spallation neutrons Subject RIV: BG - Nuclear , Atomic and Molecular Physics, Colliders Impact factor: 1.389, year: 2015

  9. Quantifying Fenton reaction pathways driven by self-generated H2O2 on pyrite surfaces

    Science.gov (United States)

    Gil-Lozano, C.; Davila, A. F.; Losa-Adams, E.; Fairén, A. G.; Gago-Duport, L.

    2017-03-01

    Oxidation of pyrite (FeS2) plays a significant role in the redox cycling of iron and sulfur on Earth and is the primary cause of acid mine drainage (AMD). It has been established that this process involves multi-step electron-transfer reactions between surface defects and adsorbed O2 and H2O, releasing sulfoxy species (e.g., S2O32-, SO42-) and ferrous iron (Fe2+) to the solution and also producing intermediate by-products, such as hydrogen peroxide (H2O2) and other reactive oxygen species (ROS), however, our understanding of the kinetics of these transient species is still limited. We investigated the kinetics of H2O2 formation in aqueous suspensions of FeS2 microparticles by monitoring, in real time, the H2O2 and dissolved O2 concentration under oxic and anoxic conditions using amperometric microsensors. Additional spectroscopic and structural analyses were done to track the dependencies between the process of FeS2 dissolution and the degradation of H2O2 through the Fenton reaction. Based on our experimental results, we built a kinetic model which explains the observed trend of H2O2, showing that FeS2 dissolution can act as a natural Fenton reagent, influencing the oxidation of third-party species during the long term evolution of geochemical systems, even in oxygen-limited environments.

  10. Reaction pathway towards formation of cobalt single chain magnets and nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Balaji, G.; Desilva, Rohini M.; Palshin, V. [Center for Advanced Microstructures and Devices, Louisiana State University, 6980 Jefferson Highway, Baton Rouge, LA 70806 (United States); Desilva, N. [Department of Chemistry, Louisiana State University, Baton Rouge, LA 70803 (United States); Palmer, G. [Department of Biochemistry and Cell Biology, Rice University, MS 140, 6100 Main street, Houston, TX 77251 (United States); Kumar, Challa S.S.R., E-mail: ckumar1@lsu.ed [Center for Advanced Microstructures and Devices, Louisiana State University, 6980 Jefferson Highway, Baton Rouge, LA 70806 (United States)

    2010-03-15

    With the advent of molecular magnets the quest for suitable high density magnetic storage materials has fuelled further research in this area. Here in this report, we present a detailed mechanistic investigation of thermal decomposition of cyclopentadienyl cobalt [CoCp(CO){sub 2}] precursor where Cp is the cyclopentadienyl moiety. The reaction revealed the formation of cobalt nanoparticles (Co-NPs) through an isolable reaction intermediate characterized as a Single Chain Magnet (SCM), [Co(Cp){sub 2}]{sub 2}CoCl{sub 4} (1). The SQUID magnetic measurements showed the presence of very strong antiferromagnetic interactions between Co{sup 2+} ions. The zero-field cooled (ZFC) and field cooled (FC) magnetization curves branch out below 5 K and there is evidence for frequency dependent complex susceptibility along with a maximum observed around 2.5 K. The optical studies indicated that the Co{sup 2+} d-d transition is influenced by the polarity of the solvents. The cobalt nanoparticles (Co-NPs) were obtained, either directly from 1 or from its precursor. They are spherical in shape with a mean size 15 nm, have fcc crystal structure and were found to be ferromagnetic at room temperature.

  11. Possible reaction pathways of the lincomycin molecule according to the DFT calculation method

    Directory of Open Access Journals (Sweden)

    Eren Bahar

    2017-01-01

    Full Text Available Human-used antibiotics are eliminated from the body with little or no transformation at all. Traces of eliminated antibiotics enter the receiving environment directly since they cannot be treated in prevalent wastewater treatment facilities. Thus, wastewaters containing traces of antibiotics have to be treated accordingly. Lincomycin is subsequently isolated from Streptomyces lincolnensis. Lincomycin and its derivatives are antibiotics exhibiting biological activity against Gram-positive bacteria, and are natural antibiotics in the environment as pollutants. This study aims to predict the degradation mechanism of lincomycin molecule in the gaseous phase and aqueous media. Probable reaction path of lincomycin molecule with OH radicals was analyzed. Optimized geometry was calculated via Gauss View 5. Subsequently, the lowest energy status was determined through geometric optimization via Gaussian 09 program. Aiming to determine the intermediates in photocatalytic degradation mechanism of lincomycin, geometric optimization of the molecule was realized through DFT method. Activation energy for the probable reaction path was calculated, and their most stable state from the thermodynamic perspective determined for the gaseous phase and aqueous media. Impact of water solvent was investigated using the conductor-like screening solvation model (COSMO. The predicted mechanism was confirmed by comparison with experimental results on simple structures reported in literature.

  12. Bridge mediated two-electron transfer reactions: Analysis of stepwise and concerted pathways

    International Nuclear Information System (INIS)

    Petrov, E.G.; May, V.

    2004-01-01

    A theory of nonadiabatic donor (D)-acceptor (A) two-electron transfer (TET) mediated by a single regular bridge (B) is developed. The presence of different intermediate two-electron states connecting the reactant state D -- BA with the product state DBA -- results in complex multiexponential kinetics. The conditions are discussed at which a reduction to two-exponential as well as single-exponential kinetics becomes possible. For the latter case the rate K TET is calculated, which describes the bridge-mediated reaction as an effective two-electron D-A transfer. In the limit of small populations of the intermediate TET states D - B - A, DB -- A, D - BA - , and DB - A - , K TET is obtained as a sum of the rates K TET (step) and K TET (sup) . The first rate describes stepwise TET originated by transitions of a single electron. It starts at D -- BA and reaches DBA -- via the intermediate state D - BA - . These transitions cover contributions from sequential as well as superexchange reactions all including reduced bridge states. In contrast, a specific two-electron superexchange mechanism from D -- BA to DBA -- defines K TET (sup) . An analytic dependence of K TET (step) and K TET (sup) on the number of bridging units is presented and different regimes of D-A TET are studied

  13. Uranium chemistry: significant advances

    International Nuclear Information System (INIS)

    Mazzanti, M.

    2011-01-01

    The author reviews recent progress in uranium chemistry achieved in CEA laboratories. Like its neighbors in the Mendeleev chart uranium undergoes hydrolysis, oxidation and disproportionation reactions which make the chemistry of these species in water highly complex. The study of the chemistry of uranium in an anhydrous medium has led to correlate the structural and electronic differences observed in the interaction of uranium(III) and the lanthanides(III) with nitrogen or sulfur molecules and the effectiveness of these molecules in An(III)/Ln(III) separation via liquid-liquid extraction. Recent work on the redox reactivity of trivalent uranium U(III) in an organic medium with molecules such as water or an azide ion (N 3 - ) in stoichiometric quantities, led to extremely interesting uranium aggregates particular those involved in actinide migration in the environment or in aggregation problems in the fuel processing cycle. Another significant advance was the discovery of a compound containing the uranyl ion with a degree of oxidation (V) UO 2 + , obtained by oxidation of uranium(III). Recently chemists have succeeded in blocking the disproportionation reaction of uranyl(V) and in stabilizing polymetallic complexes of uranyl(V), opening the way to to a systematic study of the reactivity and the electronic and magnetic properties of uranyl(V) compounds. (A.C.)

  14. A Pathway to Psychological Difficulty: Perceived Chronic Social Adversity and Its Symptomatic Reactions.

    Science.gov (United States)

    Ding, Cody; Zhang, Jingqiu; Yang, Dong

    2018-01-01

    In this paper, we attempt to predict and explain psychological maladjustment or difficulty. Specifically, we discuss the concept of perceived chronic social adversity, and we expect that such perceived chronic social adversity may potentially lead to chronic stress responses. Accordingly, we propose the symptomatic reactions of perceived chronic social adversity. We put forward a set of hypotheses regarding the relationships between perceived chronic social adversity and those chronic stress responses, and we further hypothesize a mediating role of individualized negative essentialism brought by perceived chronical social adversity. Resilience and individual differences in the ability to cope with perceived adversity are discussed. Future research and prevention need to pay more attention to effects of subjective personal experiences on psychological difficulty, focusing on the importance of exploring daily social experiences in improving cognitive construction processes and developing appropriate preventions.

  15. Kinetic and Reaction Pathway Analysis in the Application of Botulinum Toxin A for Wound Healing

    Directory of Open Access Journals (Sweden)

    Frank J. Lebeda

    2012-01-01

    Full Text Available A relatively new approach in the treatment of specific wounds in animal models and in patients with type A botulinum toxin is the focus of this paper. The indications or conditions include traumatic wounds (experimental and clinical, surgical (incision wounds, and wounds such as fissures and ulcers that are signs/symptoms of disease or other processes. An objective was to conduct systematic literature searches and take note of the reactions involved in the healing process and identify corresponding pharmacokinetic data. From several case reports, we developed a qualitative model of how botulinum toxin disrupts the vicious cycle of muscle spasm, pain, inflammation, decreased blood flow, and ischemia. We transformed this model into a minimal kinetic scheme for healing chronic wounds. The model helped us to estimate the rate of decline of this toxin's therapeutic effect by calculating the rate of recurrence of clinical symptoms after a wound-healing treatment with this neurotoxin.

  16. A Pathway to Psychological Difficulty: Perceived Chronic Social Adversity and Its Symptomatic Reactions

    Directory of Open Access Journals (Sweden)

    Cody Ding

    2018-04-01

    Full Text Available In this paper, we attempt to predict and explain psychological maladjustment or difficulty. Specifically, we discuss the concept of perceived chronic social adversity, and we expect that such perceived chronic social adversity may potentially lead to chronic stress responses. Accordingly, we propose the symptomatic reactions of perceived chronic social adversity. We put forward a set of hypotheses regarding the relationships between perceived chronic social adversity and those chronic stress responses, and we further hypothesize a mediating role of individualized negative essentialism brought by perceived chronical social adversity. Resilience and individual differences in the ability to cope with perceived adversity are discussed. Future research and prevention need to pay more attention to effects of subjective personal experiences on psychological difficulty, focusing on the importance of exploring daily social experiences in improving cognitive construction processes and developing appropriate preventions.

  17. Effect of temperature on the reaction pathway of calcium carbonate formation via precursor phases

    Science.gov (United States)

    Purgstaller, Bettina; Mavromatis, Vasileios; Konrad, Florian; Dietzel, Martin

    2016-04-01

    It has been earlier postulated that some biogenic and sedimentary calcium carbonate (CaCO3) minerals (e.g. calcite and aragonite) are secondary in origin and have originally formed via a metastable calcium carbonate precursor phase (e.g. amorphous CaCO3, [1-2]). Such formation pathways are likely affected by various physicochemical parameters including aqueous Mg and temperature. In an effort to improve our understanding on the formation mechanism of CaCO3 minerals, precipitation experiments were carried out by the addition of a 0.6 M (Ca,Mg)Cl2 solution at distinct Mg/Ca ratios (1/4 and 1/8) into a 1 M NaHCO3 solution under constant pH conditions(8.3 ±0.1). The formation of CaCO3 was systematically examined as a function of temperature (6, 12, 18 and 25 ±0.3° C). During the experimental runs mineral precipitation was monitored by in situ Raman spectroscopy as well as by continuous sampling and analyzing of precipitates and reactive solutions. The results revealed two pathways of CaCO3 formation depending on the initial Mg/Ca ratio and temperature: (i) In experiments with a Mg/Ca ratio of 1/4 at ≤ 12° C as well as in experiments with a Mg/Ca ratio of 1/8 at ≤ 18° C, ikaite (CaCO3 6H2O) acts as a precursor phase for aragonite formation. (ii) In contrast higher temperatures induced the formation of Mg-rich amorphous CaCO3 (Mg-ACC) which was subsequently transformed to Mg-rich calcite. In situ Raman spectra showed that the transformation of Mg-ACC to Mg-calcite occurs at a higher rate (˜ 8 min) compared to that of ikaite to aragonite (> 2 h). Thus, the formation of aragonite rather than of Mg-calcite occurs due to the slower release of Ca2+and CO32- ions into the Mg-rich reactive solution during retarded ikaite dissolution. This behavior is generally consistent with the observation that calcite precipitation is inhibited at elevated aqueous Mg/Ca ratios. [1] Addadi L., Raz S. and Weiner S. (2003) Advanced Materials 15, 959-970. [2] Rodriguez-Blanco J. D

  18. Coupled reaction-diffusion equations to model the fission gas release in the irradiation of the uranium dioxide

    International Nuclear Information System (INIS)

    Moyano, Edgardo A.; Scarpettini, Alberto F.

    2003-01-01

    A semi linear model of weakly coupled parabolic p.d.e. with reaction-diffusion is investigated. The system describes fission gas transfer from grain interior of UO 2 to grain boundaries. The problem is studied in a bounded domain. Using the upper-lower solutions method, two monotone sequences for the finite differences equations are constructed. Reasons are mentioned that allow to affirm that in the proposed functional sector the algorithm converges to the unique solution of the differential system. (author)

  19. A critical assessment of theoretical methods for finding reaction pathways and transition states of surface processes

    International Nuclear Information System (INIS)

    Klimes, JirI; Michaelides, Angelos; Bowler, David R

    2010-01-01

    The performance of a variety of techniques for locating transition states on potential energy surfaces is evaluated within the density functional theory framework. Diffusion of a water molecule across NaCl(001) and HCl bond breaking on the same surface are treated as general test cases; the former is an example of a low barrier diffusion process and the latter an example of a relatively high barrier covalent bond rupture event. The methods considered include the nudged elastic band (NEB), Dewar, Healy and Stewart (DHS), dimer, constrained optimization (CO), activation-relaxation technique (ART) and one-side growing string (OGS) as well as novel combinations of the DHS with growing string (DHS + GS) and DHS plus climbing image (CI-DHS). A key conclusion to come from this study is that the NEB method is relatively fast, especially when just a single (climbing) image is used. Indeed, using more images represents an unnecessary computational burden for our set of processes. The dimer method exhibits variable performance; being poor for the water diffusion processes, which have small activation energies, but much more efficient for the HCl bond breaking process which has a higher barrier. When only a poor initial guess of the transition state geometry is available, the CI-DHS scheme is one of the most efficient techniques considered. And as a means to quickly establish an approximate minimum energy pathway the DHS + GS scheme offers some potential.

  20. Nitric oxide and nitrous oxide turnover in natural and engineered microbial communities: biological pathways, chemical reactions, and novel technologies

    Science.gov (United States)

    Schreiber, Frank; Wunderlin, Pascal; Udert, Kai M.; Wells, George F.

    2012-01-01

    Nitrous oxide (N2O) is an environmentally important atmospheric trace gas because it is an effective greenhouse gas and it leads to ozone depletion through photo-chemical nitric oxide (NO) production in the stratosphere. Mitigating its steady increase in atmospheric concentration requires an understanding of the mechanisms that lead to its formation in natural and engineered microbial communities. N2O is formed biologically from the oxidation of hydroxylamine (NH2OH) or the reduction of nitrite (NO−2) to NO and further to N2O. Our review of the biological pathways for N2O production shows that apparently all organisms and pathways known to be involved in the catabolic branch of microbial N-cycle have the potential to catalyze the reduction of NO−2 to NO and the further reduction of NO to N2O, while N2O formation from NH2OH is only performed by ammonia oxidizing bacteria (AOB). In addition to biological pathways, we review important chemical reactions that can lead to NO and N2O formation due to the reactivity of NO−2, NH2OH, and nitroxyl (HNO). Moreover, biological N2O formation is highly dynamic in response to N-imbalance imposed on a system. Thus, understanding NO formation and capturing the dynamics of NO and N2O build-up are key to understand mechanisms of N2O release. Here, we discuss novel technologies that allow experiments on NO and N2O formation at high temporal resolution, namely NO and N2O microelectrodes and the dynamic analysis of the isotopic signature of N2O with quantum cascade laser absorption spectroscopy (QCLAS). In addition, we introduce other techniques that use the isotopic composition of N2O to distinguish production pathways and findings that were made with emerging molecular techniques in complex environments. Finally, we discuss how a combination of the presented tools might help to address important open questions on pathways and controls of nitrogen flow through complex microbial communities that eventually lead to N2O build

  1. Nitric oxide and nitrous oxide turnover in natural and engineered microbial communities: biological pathways, chemical reactions and novel technologies

    Directory of Open Access Journals (Sweden)

    Frank eSchreiber

    2012-10-01

    Full Text Available Nitrous oxide (N2O is an environmentally important atmospheric trace gas because it is an effective greenhouse gas and it leads to ozone depletion through photo-chemical nitric oxide (NO production in the stratosphere. Mitigating its steady increase in atmospheric concentration requires an understanding of the mechanisms that lead to its formation in natural and engineered microbial communities. N2O is formed biologically from the oxidation of hydroxylamine (NH2OH or the reduction of nitrite (NO2- to NO and further to N2O. Our review of the biological pathways for N2O production shows that apparently all organisms and pathways known to be involved in the catabolic branch of microbial N-cycle have the potential to catalyze the reduction of NO2- to NO and the further reduction of NO to N2O, while N2O formation from NH2OH is only performed by ammonia oxidizing bacteria. In addition to biological pathways, we review important chemical reactions that can lead to NO and N2O formation due to the reactivity of NO2-, NH2OH and nitroxyl (HNO. Moreover, biological N2O formation is highly dynamic in response to N-imbalance imposed on a system. Thus, understanding NO formation and capturing the dynamics of NO and N2O build-up are key to understand mechanisms of N2O release. Here, we discuss novel technologies that allow experiments on NO and N2O formation at high temporal resolution, namely NO and N2O microelectrodes and the dynamic analysis of the isotopic signature of N2O with quantum cascade laser based absorption spectroscopy. In addition, we introduce other techniques that use the isotopic composition of N2O to distinguish production pathways and findings that were made with emerging molecular techniques in complex environments. Finally, we discuss how a combination of the presented tools might help to address important open questions on pathways and controls of nitrogen flow through complex microbial communities that eventually lead to N2O build-up.

  2. Uranium conversion

    International Nuclear Information System (INIS)

    Oliver, Lena; Peterson, Jenny; Wilhelmsen, Katarina

    2006-03-01

    FOI, has performed a study on uranium conversion processes that are of importance in the production of different uranium compounds in the nuclear industry. The same conversion processes are of interest both when production of nuclear fuel and production of fissile material for nuclear weapons are considered. Countries that have nuclear weapons ambitions, with the intention to produce highly enriched uranium for weapons purposes, need some degree of uranium conversion capability depending on the uranium feed material available. This report describes the processes that are needed from uranium mining and milling to the different conversion processes for converting uranium ore concentrate to uranium hexafluoride. Uranium hexafluoride is the uranium compound used in most enrichment facilities. The processes needed to produce uranium dioxide for use in nuclear fuel and the processes needed to convert different uranium compounds to uranium metal - the form of uranium that is used in a nuclear weapon - are also presented. The production of uranium ore concentrate from uranium ore is included since uranium ore concentrate is the feed material required for a uranium conversion facility. Both the chemistry and principles or the different uranium conversion processes and the equipment needed in the processes are described. Since most of the equipment that is used in a uranium conversion facility is similar to that used in conventional chemical industry, it is difficult to determine if certain equipment is considered for uranium conversion or not. However, the chemical conversion processes where UF 6 and UF 4 are present require equipment that is made of corrosion resistant material

  3. Reaction pathway of the degradation of the p-hydroxybenzoic acid by sulfate radical generated by ionizing radiations

    International Nuclear Information System (INIS)

    Criquet, Justine; Leitner, Nathalie Karpel Vel

    2015-01-01

    The degradation of p-hydroxybenzoic acid (HBA) in aqueous solutions by ionizing radiation was studied. The phenolic pollutant was easily removed by the electron beam irradiation, as more than 80% of the initial 100 µM introduced was degraded for a dose of 600 Gy. It was shown that the addition of persulfate, producing the sulfate radical as additional reactive species, induced a change in the reaction pathway. LC–MS analyses were performed in order to identify the different by-products formed. In the absence of persulfate, the main by-product formed was 3,4-dihydroxybenzoic acid, while in presence of persulfate, 1,4-benzoquinone was detected and the hydroxylated by-products were not present. A reaction pathway of HBA degradation by hydroxyl and sulfate radicals was proposed from the identification of the chemical structure of the different by-products detected. The influences of pH and dissolved oxygen were also studied. A high decline of HBA degradation was observed at pH 11 compared to pH 4.5, this decrease was minimized in the presence of persulfate. The dissolved oxygen concentration was found to be a limiting parameter of HBA degradation, however an excess of dissolved oxygen in solution did not improve the degradation to a large extent. - Highlights: • p-Hydroxybenzoic acid (HBA) is easily removed by e-beam irradiation. • The sulfate radicals formed from persulfate induce loss of the benzoic acid skeleton. • The dissolved oxygen concentration is a limiting parameter of the HBA degradation. • The effect of pH is minimized in presence of persulfate

  4. Uranium recovery from AVLIS slag

    International Nuclear Information System (INIS)

    D'Agostino, A.E.; Mycroft, J.R.; Oliver, A.J.; Schneider, P.G.; Richardson, K.L.

    2000-01-01

    Uranium metal for the Atomic Vapor Laser Isotope Separation (AVLIS) project was to have been produced by the magnesiothermic reduction of uranium tetrafluoride. The other product from this reaction is a magnesium fluoride slag, which contains fine and entrained natural uranium as metal and oxide. Recovery of the uranium through conventional mill leaching would not give a magnesium residue free of uranium but to achieve more complete uranium recovery requires the destruction of the magnesium fluoride matrix and liberation of the entrapped uranium. Alternate methods of carrying out such treatments and the potential for recovery of other valuable byproducts were examined. Based on the process flowsheets, a number of economic assessments were performed, conclusions were drawn and the preferred processing alternatives were identified. (author)

  5. Uranium exploration

    International Nuclear Information System (INIS)

    De Voto, R.H.

    1984-01-01

    This paper is a review of the methodology and technology that are currently being used in varying degrees in uranium exploration activities worldwide. Since uranium is ubiquitous and occurs in trace amounts (0.2 to 5 ppm) in virtually all rocks of the crust of the earth, exploration for uranium is essentially the search of geologic environments in which geologic processes have produced unusual concentrations of uranium. Since the level of concentration of uranium of economic interest is dependent on the present and future price of uranium, it is appropriate here to review briefly the economic realities of uranium-fueled power generation. (author)

  6. Formation of nitrogen-containing compounds during microwave pyrolysis of microalgae: Product distribution and reaction pathways.

    Science.gov (United States)

    Huang, Feng; Tahmasebi, Arash; Maliutina, Kristina; Yu, Jianglong

    2017-12-01

    The formation of nitrogen-containing compounds in bio-oil during microwave pyrolysis of Chlorella and Spirulina microalgae has been investigated in this study. Activated carbon (AC) and magnetite (Fe 3 O 4 ) were used as microwave receptors during microwave pyrolysis experiments. It has been found that the use of Fe 3 O 4 increased the total yield of bio-oil. The use of different microwave receptors did not seem to have affected the total yield of nitrogen-containing compounds in the bio-oil. However, Fe 3 O 4 promoted the formation of nitrogen-containing aliphatics, thereby reducing the formation of nitrogen-containing aromatics. The use of AC promoted the dehydration reactions during amino acid decomposition, thereby enhancing the formation of nitrogen-containing aromatics during pyrolysis. From the gas chromatography-mass spectrometry (GC-MS) analysis results, the major high-value nitrogen-containing compounds in the pyrolysis bio-oil of Chlorella and Spirulina were identified as indole and dodecamide. The formation mechanisms of nitrogen-containing compounds were proposed and discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. Reaction pathways of photoexcited retinal in proteorhodopsin studied by pump-dump-probe spectroscopy.

    Science.gov (United States)

    Rupenyan, Alisa; van Stokkum, Ivo H M; Arents, Jos C; van Grondelle, Rienk; Hellingwerf, Klaas J; Groot, Marie Louise

    2009-12-17

    Proteorhodopsin (pR) is a membrane-embedded proton pump from the microbial rhodopsin family. Light absorption by its retinal chromophore initiates a photocycle, driven by trans/cis isomerization on the femtosecond to picosecond time scales. Here, we report a study on the photoisomerization dynamics of the retinal chromophore of pR, using dispersed ultrafast pump-dump-probe spectroscopy. The application of a pump pulse initiates the photocycle, and with an appropriately tuned dump pulse applied at a time delay after the dump, the molecules in the initial stages of the photochemical process can be de-excited and driven back to the ground state. In this way, we were able to resolve an intermediate on the electronic ground state that represents chromophores that are unsuccessful in isomerization. In particular, the fractions of molecules that undergo slow isomerization (20 ps) have a high probability to enter this state rather than the isomerized K-state. On the ground state reaction surface, return to the stable ground state conformation via a structural or vibrational relaxation occurs in 2-3 ps. Inclusion of this intermediate in the kinetic scheme led to more consistent spectra of the retinal-excited state, and to a more accurate estimation of the quantum yield of isomerization (Phi = 0.4 at pH 6).

  8. Transformation products and reaction pathways of carbamazepine during photocatalytic and sonophotocatalytic treatment

    International Nuclear Information System (INIS)

    Jelic, A.; Michael, I.; Achilleos, A.; Hapeshi, E.; Lambropoulou, D.; Perez, S.; Petrovic, M.; Fatta-Kassinos, D.; Barcelo, D.

    2013-01-01

    Highlights: • Degradation of CBZ during US, TiO 2 /UV and TiO 2 /UV/US processes has been evaluated. • The combined TiO 2 /UV/US oxidation resulted in significant enhancement of the CBZ degradation rate. • Transformation products were identified and the transformation pathways were proposed. • An acute toxicity test showed an increase in toxicity over the time-course of the studied processes. -- Abstract: This study examines the degradation of the antiepileptic carbamazepine (CBZ) by sonolysis, TiO 2 -based heterogeneous photocatalysis under UV-A and simulated solar irradiation, and by the combined use of UV-A and ultrasound irradiation (i.e. sonophotocatalysis) in demineralized water, ground water and effluent wastewater. The processes were compared with respect to substrate conversion rate and the extent of DOC reduction as a measure of mineralization. CBZ was degraded following a pseudo-first order kinetics. Sonophotocatalysis provided the highest rate of CBZ transformation over the time-course of the experiment while the degree of DOC removal in pure water was similar for all the studied treatments (around 40%), and always lower than CBZ conversion. This indicated that a considerable organic load remained in the treated solutions that could also be attributed to the presence of persistent oxidation products. UPLC–(+ESI)-QToF-MS was employed to determine major CBZ-related transformation products. Several recalcitrant hydroxy- and keto-derivatives of CBZ were tentatively identified. A Daphnia magna bioassay was used to evaluate the potential toxicity of the samples collected at different time points showing that the mixtures were highly toxic to D. magna

  9. Transformation products and reaction pathways of carbamazepine during photocatalytic and sonophotocatalytic treatment

    Energy Technology Data Exchange (ETDEWEB)

    Jelic, A. [Department of Environmental Chemistry, Institute of Environmental Assessment and Water Research (IDAEA), Spanish Council for Scientific Research (CSIC), Jordi Girona 18-26, 08034 Barcelona (Spain); Michael, I.; Achilleos, A.; Hapeshi, E. [Department of Civil and Environmental Engineering, University of Cyprus, 1 Panepistimiou Avenue, P.O. Box 20537, 1678 Nicosia (Cyprus); Nireas, International Water Research Centre, University of Cyprus, 1 Panepistimiou Avenue, P.O. Box 20537, 1678 Nicosia (Cyprus); Lambropoulou, D. [Department of Chemistry, Aristotle University of Thessaloniki, Thessaloniki 54124 (Greece); Perez, S., E-mail: spsqam@idaea.csic.es [Department of Environmental Chemistry, Institute of Environmental Assessment and Water Research (IDAEA), Spanish Council for Scientific Research (CSIC), Jordi Girona 18-26, 08034 Barcelona (Spain); Petrovic, M. [Catalan Institute for Water Research (ICRA), H2O Building, Scientific and Technological Park of the University of Girona, 101-E-17003 Girona (Spain); Catalan Institution for Research and Advanced Studies (ICREA), Passeig Lluis Companys 23, 08010 Barcelona (Spain); Fatta-Kassinos, D. [Department of Civil and Environmental Engineering, University of Cyprus, 1 Panepistimiou Avenue, P.O. Box 20537, 1678 Nicosia (Cyprus); Nireas, International Water Research Centre, University of Cyprus, 1 Panepistimiou Avenue, P.O. Box 20537, 1678 Nicosia (Cyprus); Barcelo, D. [Catalan Institute for Water Research (ICRA), H2O Building, Scientific and Technological Park of the University of Girona, 101-E-17003 Girona (Spain); Catalan Institution for Research and Advanced Studies (ICREA), Passeig Lluis Companys 23, 08010 Barcelona (Spain)

    2013-12-15

    Highlights: • Degradation of CBZ during US, TiO{sub 2}/UV and TiO{sub 2}/UV/US processes has been evaluated. • The combined TiO{sub 2}/UV/US oxidation resulted in significant enhancement of the CBZ degradation rate. • Transformation products were identified and the transformation pathways were proposed. • An acute toxicity test showed an increase in toxicity over the time-course of the studied processes. -- Abstract: This study examines the degradation of the antiepileptic carbamazepine (CBZ) by sonolysis, TiO{sub 2}-based heterogeneous photocatalysis under UV-A and simulated solar irradiation, and by the combined use of UV-A and ultrasound irradiation (i.e. sonophotocatalysis) in demineralized water, ground water and effluent wastewater. The processes were compared with respect to substrate conversion rate and the extent of DOC reduction as a measure of mineralization. CBZ was degraded following a pseudo-first order kinetics. Sonophotocatalysis provided the highest rate of CBZ transformation over the time-course of the experiment while the degree of DOC removal in pure water was similar for all the studied treatments (around 40%), and always lower than CBZ conversion. This indicated that a considerable organic load remained in the treated solutions that could also be attributed to the presence of persistent oxidation products. UPLC–(+ESI)-QToF-MS was employed to determine major CBZ-related transformation products. Several recalcitrant hydroxy- and keto-derivatives of CBZ were tentatively identified. A Daphnia magna bioassay was used to evaluate the potential toxicity of the samples collected at different time points showing that the mixtures were highly toxic to D. magna.

  10. Simulation of coupled geochemical reactions and hydrodynamical processes in porous media - application to CO2 storage and uranium exploitation

    International Nuclear Information System (INIS)

    Lagneau, Vincent

    2013-01-01

    to mitigate greenhouse gas emissions. Before the technology spreads out, a demonstration of its efficiency is required. The methods detailed in the document focus of the integrity of barriers: wells and cap-rock. Uranium exploitation by ISR is a technique used for high reserve but low grade deposits. The economic element is retrieved by circulation of a fluid (e.g. acid) in the ore body. Reactive transport simulation is particularly adapted to describe the system. The work described here aim at simulating the ore formation and its exploitation. (author)

  11. PROCESS FOR PREPARING URANIUM METAL

    Science.gov (United States)

    Prescott, C.H. Jr.; Reynolds, F.L.

    1959-01-13

    A process is presented for producing oxygen-free uranium metal comprising contacting iodine vapor with crude uranium in a reaction zone maintained at 400 to 800 C to produce a vaporous mixture of UI/sub 4/ and iodine. Also disposed within the maction zone is a tungsten filament which is heated to about 1600 C. The UI/sub 4/, upon contacting the hot filament, is decomposed to molten uranium substantially free of oxygen.

  12. An unexpected reaction pathway in the synthesis of the ABCE framework of strychnine-type alkaloids - A multidisciplinary study

    Science.gov (United States)

    Šoral, Michal; Markus, Jozef; Doháňošová, Jana; Šoralová, Stanislava; Dvoranová, Dana; Chyba, Andrej; Moncol, Ján; Berkeš, Dušan; Liptaj, Tibor

    2017-01-01

    Acid-catalyzed cyclization of spirocyclic 1‧-benzyl-2‧-(prop-2-en-1-yl)spiro[indole-3,3‧-pyrrolidine]-5‧-one (1) was performed. The pentacyclic product of Povarov-like imino-Diels-Alder reaction was isolated in high yield instead of expected tetracyclic aza-Prins intermediate. The unusual exotic alkaloid-type structure of the resulting molecule 2 was unambiguously confirmed by a detailed NMR analysis using a set of 2D NMR spectra including an INADEQUATE experiment. The relative configuration of 2 was predicted from the synthesis mechanism and DFT geometry calculations and independently confirmed using NOESY and residual dipolar coupling (RDC) assisted NMR analysis in stretched crosslinked polystyrene gels. The reversibility of the cycloaddition in aprotic solvents was observed. A new reaction pathway yielding a rare 6-5-5-5 tetracyclic spiroindoline 3 was suggested. The relative configuration within the tetracyclic framework was ultimately proved using Single-crystal X-ray diffraction analysis of compound 4.

  13. Reaction pathways of furfural, furfuryl alcohol and 2-methylfuran on Cu(111) and NiCu bimetallic surfaces

    Science.gov (United States)

    Xiong, Ke; Wan, Weiming; Chen, Jingguang G.

    2016-10-01

    Hydrodeoxygenation (HDO) is an important reaction for converting biomass-derived furfural to value-added 2-methylfuran, which is a promising fuel additive. In this work, the HDO of furfural to produce 2-methylfuran occurred on the NiCu bimetallic surfaces prepared on either Ni(111) or Cu(111). The reaction pathways of furfural were investigated on Cu(111) and Ni/Cu(111) surfaces using density functional theory (DFT) calculations, temperature-programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS) experiments. These studies provided mechanistic insights into the effects of bimetallic formation on enhancing the HDO activity. Specifically, furfural weakly adsorbed on Cu(111), while it strongly adsorbed on Ni/Cu(111) through an η2(C,O) configuration, which led to the HDO of furfural on Ni/Cu(111). The ability to dissociate H2 on Ni/Cu(111) is also an important factor for enhancing the HDO activity over Cu(111).

  14. Study of the reaction between Uranium(III) and Lanthanide oxide by using the UV-VIS spectrophotometer

    International Nuclear Information System (INIS)

    Kim, Tack-Jin; Cho, Young-Hwan; Choi, In-Kyu; Choi, Kwang-Soon; Jee, Kwang-Yong

    2006-01-01

    Recently, ionic melts have become attractive reaction media in many fields. Molten salt based electrochemical processes have been proposed as a promising method for future nuclear programs and more specifically for spent fuel processing. Molten alkaline chloride based melts are considered as a promising reaction media. For this, it is interesting to understand the chemical nature of the actinides and lanthanides in high-temperature melt. Some spectroscopy provides essential information on the exact nature of f-block elements LiCl-KCl melt system. The knowledge on the basic chemical properties of these lanthanide oxides and U(III) in molten salt media is essential for developing suitable processes. However, few studies have been reported until now on the interaction between U metal and lanthanide oxides in LiCl-KCl melt. So, we studied the interaction between U(III) and Ln(III) by using the UV-VIS spectra. UV-vis spectrometry is a strong analytical technique for characterizing chemical species and their behavior in molten salt

  15. Initiation of nuclear reactions under laser irradiation of Au nanoparticles in the aqueous solution of Uranium salt

    Energy Technology Data Exchange (ETDEWEB)

    Simakin, A.V.; Shafeev, G.A. [Wave Research Center of A.M. Prokhorov General Physics Institute of the Russian Academy of Sciences, Moscow (Russian Federation)

    2010-10-15

    Laser exposure of a suspension of either gold or palladium nanoparticles in aqueous solutions of UO{sub 2}Cl{sub 2} of natural isotope abundance was experimentally studied. Picosecond Nd:YAG lasers at peak power of 10{sup 11}-10{sup 13} W/cm{sup 2} at the wavelength of 1.06-0.355 {mu}m were used as well as a visible-range Cu vapor laser at a peak power of 10{sup 10} W/cm{sup 2}. The composition of colloidal solutions before and after laser exposure was analyzed using atomic absorption and gamma spectroscopy in the 0.06-1 MeV range of photon energy. Real-time gamma spectroscopy was used to characterize the kinetics of nuclear reactions during laser exposure. It was found that laser exposure initiated nuclear reactions involving both {sup 238}U and {sup 235}U nuclei via different channels in H{sub 2}O and D{sub 2}O. The influence of saturation of both the liquid and nanoparticles by gaseous H{sub 2} and D{sub 2} on the kinetics of nuclear transformations was found. Possible mechanisms of observed processes are discussed. (orig.)

  16. Using H2O2 as oxidant in leaching of uranium ores. The new research on the reaction of H2O2 with Fe2+

    International Nuclear Information System (INIS)

    Gao Xizhen

    1997-05-01

    The new research on the reaction of H 2 O 2 with Fe 2+ has been studied. Through determining the electric potential, pH and O 2 release during the mutual titration between H 2 O 2 solution and FeSO 4 solution, deduced the chemical equations of H 2 O 2 (without free hydroxyl) oxidizing FeSO 4 and Fe 2 (SO 4 ) 3 oxidizing H 2 O 2 . The research results show that acid is a catalytic agent for decomposing H 2 O 2 to be O 2 and H 2 O besides iron ions. The maximum oxidizing potential is up to about 640 mV. While using H 2 O 2 as an oxidant in uranium heap leaching and in-situ leaching, controlling electric potential can be regarded as a method for adjusting the feeding speed of H 2 O 2 to keep the electric potential below 500 mV, thus the H 2 O 2 decomposition can be reduced. (13 refs., 3 tabs., 1 fig.)

  17. Reaction-Based Reactive Transport Modeling of Iron Reduction and Uranium Immobilization at Area 2 of the NABIR Field Research Center

    Energy Technology Data Exchange (ETDEWEB)

    Burgos, W.D.

    2009-09-02

    This report summarizes research conducted in conjunction with a project entitled “Reaction-Based Reactive Transport Modeling of Iron Reduction and Uranium Immobilization at Area 2 of the NABIR Field Research Center”, which was funded through the Integrative Studies Element of the former NABIR Program (now the Environmental Remediation Sciences Program) within the Office of Biological and Environmental Research. Dr. William Burgos (The Pennsylvania State University) was the overall PI/PD for the project, which included Brian Dempsey (Penn State), Gour-Tsyh (George) Yeh (Central Florida University), and Eric Roden (formerly at The University of Alabama, now at the University of Wisconsin) as separately-funded co-PIs. The project focused on development of a mechanistic understanding and quantitative models of coupled Fe(III)/U(VI) reduction in FRC Area 2 sediments. The work builds on our previous studies of microbial Fe(III) and U(VI) reduction, and was directly aligned with the Scheibe et al. ORNL FRC Field Project at Area 2.

  18. Structural snapshots along the reaction pathway of Yersinia pestis RipA, a putative butyryl-CoA transferase

    Energy Technology Data Exchange (ETDEWEB)

    Torres, Rodrigo; Lan, Benson; Latif, Yama; Chim, Nicholas [UC Irvine, 2212 Natural Sciences I, Irvine, CA 92697 (United States); Goulding, Celia W., E-mail: celia.goulding@uci.edu [UC Irvine, 2212 Natural Sciences I, Irvine, CA 92697 (United States); UC Irvine, 2302 Natural Sciences I, Irvine, CA 92697 (United States)

    2014-04-01

    The crystal structures of Y. pestis RipA mutants were determined to provide insights into the CoA transferase reaction pathway. Yersinia pestis, the causative agent of bubonic plague, is able to survive in both extracellular and intracellular environments within the human host, although its intracellular survival within macrophages is poorly understood. A novel Y. pestis three-gene rip (required for intracellular proliferation) operon, and in particular ripA, has been shown to be essential for survival and replication in interferon γ-induced macrophages. RipA was previously characterized as a putative butyryl-CoA transferase proposed to yield butyrate, a known anti-inflammatory shown to lower macrophage-produced NO levels. RipA belongs to the family I CoA transferases, which share structural homology, a conserved catalytic glutamate which forms a covalent CoA-thioester intermediate and a flexible loop adjacent to the active site known as the G(V/I)G loop. Here, functional and structural analyses of several RipA mutants are presented in an effort to dissect the CoA transferase mechanism of RipA. In particular, E61V, M31G and F60M RipA mutants show increased butyryl-CoA transferase activities when compared with wild-type RipA. Furthermore, the X-ray crystal structures of E61V, M31G and F60M RipA mutants, when compared with the wild-type RipA structure, reveal important conformational changes orchestrated by a conserved acyl-group binding-pocket phenylalanine, Phe85, and the G(V/I)G loop. Binary structures of M31G RipA and F60M RipA with two distinct CoA substrate conformations are also presented. Taken together, these data provide CoA transferase reaction snapshots of an open apo RipA, a closed glutamyl-anhydride intermediate and an open CoA-thioester intermediate. Furthermore, biochemical analyses support essential roles for both the catalytic glutamate and the flexible G(V/I)G loop along the reaction pathway, although further research is required to fully

  19. Structural snapshots along the reaction pathway of Yersinia pestis RipA, a putative butyryl-CoA transferase

    International Nuclear Information System (INIS)

    Torres, Rodrigo; Lan, Benson; Latif, Yama; Chim, Nicholas; Goulding, Celia W.

    2014-01-01

    The crystal structures of Y. pestis RipA mutants were determined to provide insights into the CoA transferase reaction pathway. Yersinia pestis, the causative agent of bubonic plague, is able to survive in both extracellular and intracellular environments within the human host, although its intracellular survival within macrophages is poorly understood. A novel Y. pestis three-gene rip (required for intracellular proliferation) operon, and in particular ripA, has been shown to be essential for survival and replication in interferon γ-induced macrophages. RipA was previously characterized as a putative butyryl-CoA transferase proposed to yield butyrate, a known anti-inflammatory shown to lower macrophage-produced NO levels. RipA belongs to the family I CoA transferases, which share structural homology, a conserved catalytic glutamate which forms a covalent CoA-thioester intermediate and a flexible loop adjacent to the active site known as the G(V/I)G loop. Here, functional and structural analyses of several RipA mutants are presented in an effort to dissect the CoA transferase mechanism of RipA. In particular, E61V, M31G and F60M RipA mutants show increased butyryl-CoA transferase activities when compared with wild-type RipA. Furthermore, the X-ray crystal structures of E61V, M31G and F60M RipA mutants, when compared with the wild-type RipA structure, reveal important conformational changes orchestrated by a conserved acyl-group binding-pocket phenylalanine, Phe85, and the G(V/I)G loop. Binary structures of M31G RipA and F60M RipA with two distinct CoA substrate conformations are also presented. Taken together, these data provide CoA transferase reaction snapshots of an open apo RipA, a closed glutamyl-anhydride intermediate and an open CoA-thioester intermediate. Furthermore, biochemical analyses support essential roles for both the catalytic glutamate and the flexible G(V/I)G loop along the reaction pathway, although further research is required to fully

  20. Process for producing uranium oxide rich compositions from uranium hexafluoride

    International Nuclear Information System (INIS)

    DeHollander, W.R.; Fenimore, C.P.

    1978-01-01

    Conversion of gaseous uranium hexafluoride to a uranium dioxide rich composition in the presence of an active flame in a reactor defining a reaction zone is achieved by separately introducing a first gaseous reactant comprising a mixture of uranium hexafluoride and a reducing carrier gas, and a second gaseous reactant comprising an oxygen-containing gas. The reactants are separated by a shielding gas as they are introduced to the reaction zone. The shielding gas temporarily separates the gaseous reactants and temporarily prevents substantial mixing and reacting of the gaseous reactants. The flame occurring in the reaction zone is maintained away from contact with the inlet introducing the mixture to the reaction zone. After suitable treatment, the uranium dioxide rich composition is capable of being fabricated into bodies of desired configuration for loading into nuclear fuel rods. Alternatively, an oxygen-containing gas as a third gaseous reactant is introduced when the uranium hexafluoride conversion to the uranium dioxide rich composition is substantially complete. This results in oxidizing the uranium dioxide rich composition to a higher oxide of uranium with conversion of any residual reducing gas to its oxidized form

  1. A review of uranium corrosion by hydrogen and the formation of uranium hydride

    OpenAIRE

    Banos, A.; Harker, N. J.; Scott, T. B.

    2018-01-01

    Uranium hydride (UH3) is the direct product of the reaction between uranium metal and gaseous hydrogen. In the context of uranium storage, this corrosion reaction is considered deleterious, not just because the structure of the metal may become significantly degraded but also because the resulting hydride is pyrophoric and therefore potentially flammable in air if present in significant quantity. The current review draws from the literature surrounding the uranium-hydrogen system accrued over...

  2. One-step simultaneous differential scanning calorimetry-FTIR microspectroscopy to quickly detect continuous pathways in the solid-state glucose/asparagine Maillard reaction.

    Science.gov (United States)

    Hwang, Deng-Fwu; Hsieh, Tzu-Feng; Lin, Shan-Yang

    2013-01-01

    The stepwise reaction pathway of the solid-state Maillard reaction between glucose (Glc) and asparagine (Asn) was investigated using simultaneous differential scanning calorimetry (DSC)-FTIR microspectroscopy. The color change and FTIR spectra of Glc-Asn physical mixtures (molar ratio = 1:1) preheated to different temperatures followed by cooling were also examined. The successive reaction products such as Schiff base intermediate, Amadori product, and decarboxylated Amadori product in the solid-state Glc-Asn Maillard reaction were first simultaneously evidenced by this unique DSC-FTIR microspectroscopy. The color changed from white to yellow-brown to dark brown, and appearance of new IR peaks confirmed the formation of Maillard reaction products. The present study clearly indicates that this unique DSC-FTIR technique not only accelerates but also detects precursors and products of the Maillard reaction in real time.

  3. Method for preparation of uranium hydride

    International Nuclear Information System (INIS)

    Gorski, M.S.; Goncalves, Miriam; Mirage, A.; Lima, W. de.

    1985-01-01

    A method for preparation of Uranium Hydride starting from Hidrogen and Uranium is described. In the temperature range of 250 0 up to 350 0 C, and pressures above 10torr, Hydrogen reacts smoothly with Uranium turnings forming a fine black or dark gray powder (UH 3 ). Samples containing a significant amount of oxides show a delay before the reaction begging. (Author) [pt

  4. Uranium contaminated drinking water linked to leukaemia-Revisiting a case study from South Africa taking alternative exposure pathways into account.

    Science.gov (United States)

    Winde, Frank; Erasmus, Ewald; Geipel, Gerhard

    2017-01-01

    The paper presents results of a follow-up to an earlier study which established a geospatial link between naturally elevated uranium (U) levels in borehole water and haematological abnormalities in local residents serving as a proxy for leukaemia prevalent in the area. While the original study focussed on drinking water only, this paper also explores alternative exposure pathways including the inhalation of dust and the food chain. U-levels in grass and tissue of sheep generally reflect U-levels in nearby borehole water and exceed background concentrations by 20 to nearly 500 times. U-levels in sheep tissue increase with age of the animal. Wool showed the highest U-concentration followed by other non-consumable tissue such as hooves, teeth and bones. Lower levels occur in edible parts such as meat and inner organs. The U-deposition rate in wool is several orders of magnitudes higher than in bone as a known target organ. Wool is an easy-to-sample non-invasive bioindicator for U-levels in meat. Depending on the original water content, dried samples show up to 5 times higher U-levels than identical fresh material. Contaminated drinking water is the main exposure pathway for farm residents resulting in U-uptake rates exceeding the WHO's tolerable daily intake (TDI) limit by up to 900%. This is somewhat mitigated by the fact that U-speciation is dominated by a neutral calcium-uranyl-carbonate complex of relatively low toxicity. Commercially available household filters are able to significantly reduce U-levels in well water and are thus recommended as a short-term intervention. Based on average consumption rates sheep meat, as local staple food, accounts for 34% of the TDI for U. Indoor levels of radon should be monitored, too, since it is linked to both, U and leukaemia. With elevated U-levels being present in other geological formations across South Africa boreholes in these areas should be surveyed. Copyright © 2016 Elsevier B.V. All rights reserved.

  5. Optimization of uranium leach mining

    International Nuclear Information System (INIS)

    Schecter, R.S.; Bommer, P.M.

    1982-01-01

    The effects of well pattern and well spacing on uranium recovery and oxidant utilization are considered. As expected, formation permeability heterogeneities and anisotropies are found to be important issues requiring careful consideration; however, it also is shown that the oxidant efficiency and the produced uranium solution concentrations are sensitive to the presence of other minerals competing with uranium for oxidant. If the Damkohler number for competing minerals, which measures the speed of the reaction, exceeds that for uranium, the competing mineral will have to be oxidized completely to recover a large proportion of the uranium. If the Damkohler number is smaller, it may be possible to achieve considerable selectivity for uranium by adjusting the well spacing. 9 refs

  6. The existence state of uranium(VI) in portland cement matrix material immobilization body

    International Nuclear Information System (INIS)

    Tan Hongbin; Li Yuxiang

    2005-01-01

    The basis of Portland cement material reaction with uranium, the corrosion of uranium minerals in nature and the state of study on immobilization of uranium by Portland cement matrix material are introduced, and some considerations are presented. (authors)

  7. Transformation of methylparaben during water chlorination: Effects of bromide and dissolved organic matter on reaction kinetics and transformation pathways.

    Science.gov (United States)

    Yoom, Hoonsik; Shin, Jaedon; Ra, Jiwoon; Son, Heejong; Ryu, Dongchoon; Kim, Changwon; Lee, Yunho

    2018-09-01

    The reaction kinetics, products, and pathways of methylparaben (MeP) during water chlorination with and without bromide (Br - ) were investigated to better understand the fate of parabens in chlorinated waters. During the chlorination of MeP-spiked waters without Br - , MeP was transformed into mono-Cl-MeP and di-Cl-MeP with apparent second-order rate constants (k app ) of 64M -1 s -1 and 243M -1 s -1 at pH7, respectively, while further chlorination of di-Cl-MeP was relatively slower (k app =1.3M -1 s -1 at pH7). With increasing Br - concentration, brominated MePs, such as mono-Br-MeP, Br-Cl-MeP, and di-Br-MeP, became major transformation products. The di-halogenated MePs (di-Cl-MeP, Br,Cl-MeP, and di-Br-MeP) showed relatively low reactivity to chlorine at pH7 (k app =1.3-4.6M -1 s -1 ) and bromine (k app =32-71M -1 s -1 ), which explains the observed high stability of di-halogenated MePs in chlorinated waters. With increasing pH from 7 to 8.5, the transformation of di-halogenated MePs was further slowed due to the decreasing reactivity of di-MePs to chlorine. The formation of the di-halogenated MePs and their further transformation become considerably faster at Br - concentrations higher than 0.5μM (40μg/L). Nonetheless, the accelerating effect of Br - diminishes in the presence of dissolved organic matter (DOM) extract (Suwannee River humic acid (SRHA)) due to a more rapid consumption of bromine by DOM than chlorine. The effect of Br - on the fate of MeP was less in the tested real water matrices, possibly due to a more rapid bromine consumption by the real water DOM compared to SRHA. A kinetic model was developed based on the determined species-specific second-order rate constants for chlorination/bromination of MeP and its chlorinated and brominated MePs and the transformation pathway information, which could reasonably simulate the transformation of MePs during the chlorination of water in the presence of Br - and selected DOM. Copyright © 2017 Elsevier B

  8. Investigation of the O+allyl addition/elimination reaction pathways from the OCH2CHCH2 radical intermediate

    International Nuclear Information System (INIS)

    FitzPatrick, Benjamin L.; Lau, K.-C.; Butler, Laurie J.; Lee, S.-H.; Lin, Jim Jr-Min

    2008-01-01

    These experiments study the preparation of and product channels resulting from OCH 2 CHCH 2 , a key radical intermediate in the O+allyl bimolecular reaction. The data include velocity map imaging and molecular beam scattering results to probe the photolytic generation of the radical intermediate and the subsequent pathways by which the radicals access the energetically allowed product channels of the bimolecular reaction. The photodissociation of epichlorohydrin at 193.3 nm produces chlorine atoms and c-OCH 2 CHCH 2 radicals; these undergo a facile ring opening to the OCH 2 CHCH 2 radical intermediate. State-selective resonance-enhanced multiphoton ionization (REMPI) detection resolves the velocity distributions of ground and spin-orbit excited state chlorine independently, allowing for a more accurate determination of the internal energy distribution of the nascent radicals. We obtain good agreement detecting the velocity distributions of the Cl atoms with REMPI, vacuum ultraviolet (VUV) photoionization at 13.8 eV, and electron bombardment ionization; all show a bimodal distribution of recoil kinetic energies. The dominant high recoil kinetic energy feature peaks near 33 kcal/mol. To elucidate the product channels resulting from the OCH 2 CHCH 2 radical intermediate, the crossed laser-molecular beam experiment uses VUV photoionization and detects the velocity distribution of the possible products. The data identify the three dominant product channels as C 3 H 4 O (acrolein)+H, C 2 H 4 +HCO (formyl radical), and H 2 CO (formaldehyde)+C 2 H 3 . A small signal from C 2 H 2 O (ketene) product is also detected. The measured velocity distributions and relative signal intensities at m/e=27, 28, and 29 at two photoionization energies show that the most exothermic product channel, C 2 H 5 +CO, does not contribute significantly to the product branching. The higher internal energy onset of the acrolein+H product channel is consistent with the relative barriers en route to

  9. Investigation of the O+allyl addition/elimination reaction pathways from the OCH2CHCH2 radical intermediate

    Science.gov (United States)

    Fitzpatrick, Benjamin L.; Lau, Kai-Chung; Butler, Laurie J.; Lee, Shih-Huang; Lin, Jim-Min, Jr.

    2008-08-01

    These experiments study the preparation of and product channels resulting from OCH2CHCH2, a key radical intermediate in the O+allyl bimolecular reaction. The data include velocity map imaging and molecular beam scattering results to probe the photolytic generation of the radical intermediate and the subsequent pathways by which the radicals access the energetically allowed product channels of the bimolecular reaction. The photodissociation of epichlorohydrin at 193.3 nm produces chlorine atoms and c-OCH2CHCH2 radicals; these undergo a facile ring opening to the OCH2CHCH2 radical intermediate. State-selective resonance-enhanced multiphoton ionization (REMPI) detection resolves the velocity distributions of ground and spin-orbit excited state chlorine independently, allowing for a more accurate determination of the internal energy distribution of the nascent radicals. We obtain good agreement detecting the velocity distributions of the Cl atoms with REMPI, vacuum ultraviolet (VUV) photoionization at 13.8 eV, and electron bombardment ionization; all show a bimodal distribution of recoil kinetic energies. The dominant high recoil kinetic energy feature peaks near 33 kcal/mol. To elucidate the product channels resulting from the OCH2CHCH2 radical intermediate, the crossed laser-molecular beam experiment uses VUV photoionization and detects the velocity distribution of the possible products. The data identify the three dominant product channels as C3H4O (acrolein)+H, C2H4+HCO (formyl radical), and H2CO (formaldehyde)+C2H3. A small signal from C2H2O (ketene) product is also detected. The measured velocity distributions and relative signal intensities at m/e=27, 28, and 29 at two photoionization energies show that the most exothermic product channel, C2H5+CO, does not contribute significantly to the product branching. The higher internal energy onset of the acrolein+H product channel is consistent with the relative barriers en route to each of these product channels

  10. Degradation of sulfadimethoxine catalyzed by laccase with soybean meal extract as natural mediator: Mechanism and reaction pathway.

    Science.gov (United States)

    Liang, Shangtao; Luo, Qi; Huang, Qingguo

    2017-08-01

    Natural laccase-mediator systems have been well recognized as an eco-friendly and energy-saving approach in environmental remediation, whose further application is however limited by the high cost of natural mediators and relatively long treatment time span. This study evaluated the water extract of soybean meal, a low-cost compound system, in mediating the laccase catalyzed degradation of a model contaminant of emerging concern, sulfadimethoxine (SDM), and demonstrated it as a promising alternative mediator for soil and water remediation. Removal of 73.3% and 65.6% was achieved in 9 h using soybean meal extract (SBE) as the mediating system for laccase-catalyzed degradation of sulfadimethoxine at the concentration of 1 ppm and 10 ppm, respectively. Further degradation of sulfadimethoxine was observed with multiple SBE additions. Using SBE as mediator increased the 9-h removal of SDM at 1 ppm initial concentration by 52.9%, 49.4%, and 36.3% in comparison to the system mediated by 1-Hydroxybenzotriazole (HBT), p-Coumaric acid (COU) and 2,2'-azinobis(3-ethylbenzthiazoline-6-sulfonate) (ABTS), respectively. With the detection of stable coupling products formed with radical scavenger (5,5-Dimethyl-1-pyrroline N-oxide, DMPO), three phenolic compounds (vanillin, apocynin, and daidzein) in SBE were confirmed to serve as mediators for Trametes versicolor laccase. Reaction pathways were proposed based on the results of High Resolution Mass Spectrometry. SO 2 excursion happened during SDM transformation, leading to elimination of antimicrobial activity. Therefore, as a natural, phenol rich, and affordable compound system, the future application of SBE in wastewater and soil remediation is worth exploring. Copyright © 2017 Elsevier Ltd. All rights reserved.

  11. Czechoslovak uranium

    International Nuclear Information System (INIS)

    Pluskal, O.

    1992-01-01

    Data and knowledge related to the prospecting, mining, processing and export of uranium ores in Czechoslovakia are presented. In the years between 1945 and January 1, 1991, 98,461.1 t of uranium were extracted. In the period 1965-1990 the uranium industry was subsidized from the state budget to a total of 38.5 billion CSK. The subsidies were put into extraction, investments and geologic prospecting; the latter was at first, ie. till 1960 financed by the former USSR, later on the two parties shared costs on a 1:1 basis. Since 1981 the prospecting has been entirely financed from the Czechoslovak state budget. On Czechoslovak territory uranium has been extracted from deposits which may be classified as vein-type deposits, deposits in uranium-bearing sandstones and deposits connected with weathering processes. The future of mining, however, is almost exclusively being connected with deposits in uranium-bearing sandstones. A brief description and characteristic is given of all uranium deposits on Czechoslovak territory, and the organization of uranium mining in Czechoslovakia is described as is the approach used in the world to evaluate uranium deposits; uranium prices and actual resources are also given. (Z.S.) 3 figs

  12. Methane coupling reaction in an oxy-steam stream through an OH radical pathway by using supported alkali metal catalysts

    KAUST Repository

    Liang, Yin; Li, Zhikao; Nourdine, Mohamed; Shahid, Salman; Takanabe, Kazuhiro

    2014-01-01

    A universal reaction mechanism involved in the oxidative coupling of methane (OCM) is demonstrated under oxy-steam conditions using alkali-metal-based catalysts. Rigorous kinetic measurements indicated a reaction mechanism that is consistent with OH

  13. The concern of emergence of multi-station reaction pathways that might make stepwise the mechanism of the 1,3-dipolar cycloadditions of azides and alkynes

    Science.gov (United States)

    Mohtat, Bita; Siadati, Seyyed Amir; Khalilzadeh, Mohammad Ali; Zareyee, Daryoush

    2018-03-01

    After hot debates on the concerted or stepwise nature of the mechanism of the catalyst-free 1,3-dipolar cycloadditions (DC)s, nowadays, it is being believed that for the reaction of each dipole and dipolarophile, there is a possibility that the reaction mechanism becomes stepwise, intermediates emerge, and the reaction becomes non-stereospecific. Yield of even minimal amounts of unwanted side products or stereoisomers as impurities could bring many troubles like difficult purification steps. In this project, we have made attempts to study all probable reaction channels of the azide cycloadditions with two functionalized alkynes, in order to answer this question: "is there any possibility that intermediates evolve in the catalyst-free click 1,3-DC reaction of azide-alkynes?". During the calculations, several multi-station reaction pathways supporting the stepwise and concerted mechanisms were detected. Also, the born-oppenheimer molecular dynamic (BOMD) simulation was used to find trustable geometries which could be emerged during the reaction coordinate.

  14. Isotopic composition of uranium in U3O8 by neutron induced reactions utilizing thermal neutrons from critical facility and high resolution gamma-ray spectrometry

    International Nuclear Information System (INIS)

    Acharya, R.; Pujari, P.K.; Goel, Lokesh

    2015-01-01

    Uranium in oxide and metal forms is used as fuel material in nuclear power reactors. For chemical quality control, it is necessary to know the isotopic composition (IC) of uranium i.e., 235 U to 238 U atom ratio as well as 235 U atom % in addition to its total concentration. Uranium samples can be directly assayed by passive gamma ray spectrometry for obtaining IC by utilizing 185 keV (γ-ray abundance 57.2%) of 235 U and 1001 keV (γ-ray abundance 0.837%) of 234m Pa (decay product of 238 U). However, due to low abundance of 1001 keV, often it is not practiced to obtain IC by this method as it gives higher uncertainty even if higher mass of sample and counting time are used. IC of uranium can be determined using activity ratio of neutron induced fission product of 235 U to activation product of 238 U ( 239 Np). In the present work, authors have demonstrated methodologies for determination of IC of U as well as 235 U atom% in natural ( 235 U 0.715%) and low enriched uranium (LEU, 3-20 atom % of 235 U) samples of uranium oxide (U 3 O 8 ) by utilizing ratio of counts at 185 keV γ-ray or γ-rays of fission products with respect to 277 keV of 239 Np. Natural and enriched samples (about 25 mg) were neutron irradiated for 4 hours in graphite reflector position of AHWR Critical Facility (CF) using highly thermalized (>99.9% thermal component) neutron flux (∼10 7 cm -2 s -1 )

  15. Research of the Mass Spectra of the Fission Products and Yields of (n, gamma) and (n, 2n) Reactions in a Model Subcritical Uranium Blanket of the Electronuclear System "Energy Plus Transmutation" on Proton Beam of the Dubna Synchrophasotron at 1.5 Ge

    CERN Document Server

    Chultem, D; Krivopustov, M I; Gerbish, S; Tumendemberel, B; Pavlyuk, A B; Zaveryukha, O S

    2002-01-01

    This paper is devoted to the research of the spatial distributions of the yields of (n, f), (n, gamma) and (n, 2n) reactions in a two-section model of the uranium blanket electronuclear installation constructed at the Laboratory of High Energies, JINR (Dubna) for experiments according to the program "Research of physical aspects of the electronuclear method of energy production and of radioactive waste transmutation in atomic power-engineering on beams of the synchrophasotron and nuclotron" - project "Energy plus Transmutation". The mass spectrum of the fission products and yields of above reactions in uranium activation detectors placed on the radii of the so-called detector plates is determined. The experimental results testify that the fission of nuclei in the uranium blanket is made by fast neutrons. This conclusion coincides with the result obtained with track integrators of uranium fission.

  16. A study on the formation of uranium carbide in an induction furnace

    International Nuclear Information System (INIS)

    Song, In Young; Lee, Yoon Sang; Kim, Eung Soo; Lee, Don Bae; Kim, Chang Kyu

    2005-01-01

    Uranium is a typical carbide-forming element. Three carbides, UC, U 2 C 3 and UC 2 , are formed in the uranium-carbon system. The most important of these as fuel is uranium monocarbide UC. It is well known that Uranium carbides can be obtained by three basic methods: 1) by reaction of uranium metal with carbon; 2) by reaction of uranium metal powder with gaseous hydrocarbons; 3) by reaction of uranium oxides with carbon. The use of uranium monocarbide, or materials based on it, has great prospects as fuel for nuclear reactors. It is quite possible that uranium dicarbide UC 2 may also acquire great importance as a fuel, particularly in dispersion fuel elements with graphite matrix. In the present study, uranium carbides are obtained by direct reaction of uranium metal with graphite in a high frequency induction furnace

  17. Buckling and reaction rate experiments in plutonium/uranium metal fuelled, graphite moderated lattices at temperatures up to 400 deg. C. Part I: Experimental techniques and results

    Energy Technology Data Exchange (ETDEWEB)

    Carter, D H; Clarke, W G; Gibson, M; Hobday, R; Hunt, C; Marshall, J; Puckett, B J; Symons, C R; Wass, T [General Reactor Physics Division, Atomic Energy Establishment, Winfrith, Dorchester, Dorset (United Kingdom)

    1964-07-15

    This report presents experimental measurements of bucklings, flux fine structure and fission rate distributions in graphite moderated lattices fuelled with plutonium/uranium metal at temperatures up to 400 deg. C in the sub-critical assemblies SCORPIO I and SCORPIO II. The experimental techniques employed are described in some detail. The accuracy of the experimental measurements appears to be adequate for testing methods of calculation being developed for the calculation of reactivity and temperature coefficient of reactivity for power reactors containing plutonium and uranium. (author) 26 refs, 17 tabs, 17 figs

  18. Uranium ores

    International Nuclear Information System (INIS)

    Poty, B.; Roux, J.

    1998-01-01

    The processing of uranium ores for uranium extraction and concentration is not much different than the processing of other metallic ores. However, thanks to its radioactive property, the prospecting of uranium ores can be performed using geophysical methods. Surface and sub-surface detection methods are a combination of radioactive measurement methods (radium, radon etc..) and classical mining and petroleum prospecting methods. Worldwide uranium prospecting has been more or less active during the last 50 years, but the rise of raw material and energy prices between 1970 and 1980 has incited several countries to develop their nuclear industry in order to diversify their resources and improve their energy independence. The result is a considerable increase of nuclear fuels demand between 1980 and 1990. This paper describes successively: the uranium prospecting methods (direct, indirect and methodology), the uranium deposits (economical definition, uranium ores, and deposits), the exploitation of uranium ores (use of radioactivity, radioprotection, effluents), the worldwide uranium resources (definition of the different categories and present day state of worldwide resources). (J.S.)

  19. Uranium market

    International Nuclear Information System (INIS)

    Rubini, L.A.; Asem, M.A.D.

    1990-01-01

    The historical development of the uranium market is present in two periods: The initial period 1947-1970 and from 1970 onwards, with the establishment of a commercial market. The world uranium requirements are derived from the corresponding forecast of nuclear generating capacity, with, particular emphasis to the brazilian requirements. The forecast of uranium production until the year 2000 is presented considering existing inventories and the already committed demand. The balance between production and requirements is analysed. Finally the types of contracts currently being used and the development of uranium prices in the world market are considered. (author)

  20. Uranium enrichment

    International Nuclear Information System (INIS)

    1990-01-01

    This report looks at the following issues: How much Soviet uranium ore and enriched uranium are imported into the United States and what is the extent to which utilities flag swap to disguise these purchases? What are the U.S.S.R.'s enriched uranium trading practices? To what extent are utilities required to return used fuel to the Soviet Union as part of the enriched uranium sales agreement? Why have U.S. utilities ended their contracts to buy enrichment services from DOE?

  1. Diversion of the melanin synthetic pathway by dopamine product scavengers: A quantum chemical modeling of the reaction mechanisms

    Directory of Open Access Journals (Sweden)

    T. B. Demissie

    2017-01-01

    Full Text Available We report the stability and reactivity of the oxidation products as well as L-cysteine and N-acetylcysteine adducts of dopamine studied using quantum chemical calculations. The overall reactions studied were subdivided into four reaction channels. The first reaction channel is the oxidation of dopamine to form dopaminoquinone. The second reaction channel leads to melanin formation through subsequent reactions. The third and fourth reaction channels are reactions leading to the formation of dopaminoquinone adducts which are aimed to divert the synthesis of melanin. The results indicate that L-cysteine and N-acetylcysteine undergo chemical reactions mainly at C5 position of dopaminoquinone. The analyses of the thermodynamic energies indicate that L-cysteine and N-acetylcysteine covalently bind to dopaminoquinone by competing with the internal cyclization reaction of dopaminoquinone which leads to the synthesis of melanin. The analysis of the results, based on the reaction free energies, is also supported by the investigation of the natural bond orbitals of the reactants and products.

  2. Medical effects of internal contamination with uranium.

    Science.gov (United States)

    Duraković, A

    1999-03-01

    The purpose of this work is to present an outline of the metabolic pathways of uranium isotopes and compounds, medical consequences of uranium poisoning, and an evaluation of the therapeutic alternatives in uranium internal contamination. The chemical toxicity of uranium has been recognized for more than two centuries. Animal experiments and human studies are conclusive about metabolic adverse affects and nephro- toxicity of uranium compounds. Radiation toxicity of uranium isotopes has been recognized since the beginning of the nuclear era, with well documented evidence of reproductive and developmental toxicity, as well as mutagenic and carcinogenic consequences of uranium internal contamination. Natural uranium (238U), an alpha emitter with a half-life of 4.5x10(9) years, is one of the primordial substances of the universe. It is found in the earth's crust, combined with 235U and 234U, alpha, beta, and gamma emitters with respective half-lives of 7.1x10(8) and 2.5x10(5) years. A special emphasis of this paper concerns depleted uranium. The legacy of radioactive waste, environmental and health hazards in the nuclear industry, and, more recently, the military use of depleted uranium in the tactical battlefield necessitates further insight into the toxicology of depleted uranium. The present controversy over the radiological and chemical toxicity of depleted uranium used in the Gulf War warrants further experimental and clinical investigations of its effects on the biosphere and human organisms.

  3. Proposal of method for quantifying uranium weight in the interior of gas centrifuge, and performance evaluation of IF7 treatment reaction product separation and refinement

    International Nuclear Information System (INIS)

    Ema, Akira; Kado, Kazumi; Suzuki, Kazuhiko

    2011-01-01

    In uranium enrichment plant decommissioning, it is important to treat and dispose the gas centrifuge reasonably. At the Ningyo-Toge Environmental Engineering Center of JAEA, it has been planned to carry out IF 7 treatment for the gas centrifuge in the uranium enrichment plant for decontamination before dismantling. In order to carry out this IF 7 treatment, a nondestructive measurement technology to estimate the uranium weight in the interior of the gas centrifuge was needed. However, it was difficult to estimate exactly uranium weight using former methods. Therefore, in this study, we investigated a new nondestructive measurement. As a result, we succeeded in constructing theoretically the methodology using γ-ray intensity measured outside the gas centrifuge and MCNP code. Furthermore, the UF 6 and IF 5 mixture was recovered by IF 7 treatment. A technology to separate and refine IF 5 from this mixture was needed in order to use as a material of IF 7 gas. Therefore, in this study, we carried out IF 5 separation and refinement examination. This paper shows the investigation result of reasonable separation condition and the full-scale examination result. As a result, it could be proved that 86% of IF 5 was separated and refined from UF 6 and IF 5 mixture. (author)

  4. Dynamic pathways to mediate reactions buried in thermal fluctuations. I. Time-dependent normal form theory for multidimensional Langevin equation.

    Science.gov (United States)

    Kawai, Shinnosuke; Komatsuzaki, Tamiki

    2009-12-14

    We present a novel theory which enables us to explore the mechanism of reaction selectivity and robust functions in complex systems persisting under thermal fluctuation. The theory constructs a nonlinear coordinate transformation so that the equation of motion for the new reaction coordinate is independent of the other nonreactive coordinates in the presence of thermal fluctuation. In this article we suppose that reacting systems subject to thermal noise are described by a multidimensional Langevin equation without a priori assumption for the form of potential. The reaction coordinate is composed not only of all the coordinates and velocities associated with the system (solute) but also of the random force exerted by the environment (solvent) with friction constants. The sign of the reaction coordinate at any instantaneous moment in the region of a saddle determines the fate of the reaction, i.e., whether the reaction will proceed through to the products or go back to the reactants. By assuming the statistical properties of the random force, one can know a priori a well-defined boundary of the reaction which separates the full position-velocity space in the saddle region into mainly reactive and mainly nonreactive regions even under thermal fluctuation. The analytical expression of the reaction coordinate provides the firm foundation on the mechanism of how and why reaction proceeds in thermal fluctuating environments.

  5. Study of the production of residual evaporation nuclei issued from the spallation reaction of uranium-238 by 1 GeV protons; Etude de la production de noyaux residuels d'evaporation issus de la reaction de spallation de l'uranium-238 par des protons a 1 GeV

    Energy Technology Data Exchange (ETDEWEB)

    Taieb, J

    2000-10-01

    The spallation reaction by high energy protons is one of the envisaged nuclear reactions for production of exotic nuclei. We have measured the production of more than 300 different evaporation residues issued by the spallation reaction of Uranium-238 by 1 GeV protons. We used the reverse kinematics technique in order to produce the relativistic nuclei and therefore to be able to detect those nuclides within a very short time, shorter in most cases than the radioactive disintegration period. The achieved nuclear charge and mass resolution are excellent. They allow a good accuracy on the values of the measured cross-sections (10 to 15%). We have observed for the first time the nuclide Actinium-235 obtained consequently to the loss of 3 protons by the projectile. The measured isotopic distribution are strongly influenced by the mechanism of fission which leads to a strong reduction of the production of the heavy neutron deficient isotopes. We have compared our results to some other measurements achieved with radio-chemical methods at a similar energy. We observed a systematic disagreement of about 40%. Some comparison with the available systematics show that those are presently not able to reproduce the data with a reasonable precision. We could also measure the recoil momentum distribution for each studied isotopes. We show that Goldhaber's model agrees very well with the experiment in case. of 'cold' channels where the evaporation of particles never occurs. On the other hand, when the produced pre-fragment is excited the data show that Goldhaber's model does not reproduce.the data showing the limitation of such an approach. We finally tried to reproduce the measurement of evaporation residue cross-section thanks to the coupling of intra-nuclear cascade and statistical evaporation codes. The influence of the fission process is rather important is the system p+U; we therefore had to account for the dynamical aspect of the fission. We also showed

  6. Mechanisms for the inversion of chirality: Global reaction route mapping of stereochemical pathways in a probable chiral extraterrestrial molecule, 2-aminopropionitrile

    International Nuclear Information System (INIS)

    Kaur, Ramanpreet; Vikas

    2015-01-01

    2-Aminopropionitrile (APN), a probable candidate as a chiral astrophysical molecule, is a precursor to amino-acid alanine. Stereochemical pathways in 2-APN are explored using Global Reaction Route Mapping (GRRM) method employing high-level quantum-mechanical computations. Besides predicting the conventional mechanism for chiral inversion that proceeds through an achiral intermediate, a counterintuitive flipping mechanism is revealed for 2-APN through chiral intermediates explored using the GRRM. The feasibility of the proposed stereochemical pathways, in terms of the Gibbs free-energy change, is analyzed at the temperature conditions akin to the interstellar medium. Notably, the stereoinversion in 2-APN is observed to be more feasible than the dissociation of 2-APN and intermediates involved along the stereochemical pathways, and the flipping barrier is observed to be as low as 3.68 kJ/mol along one of the pathways. The pathways proposed for the inversion of chirality in 2-APN may provide significant insight into the extraterrestrial origin of life

  7. Uranium mining

    International Nuclear Information System (INIS)

    Lange, G.

    1975-01-01

    The winning of uranium ore is the first stage of the fuel cycle. The whole complex of questions to be considered when evaluating the profitability of an ore mine is shortly outlined, and the possible mining techniques are described. Some data on uranium mining in the western world are also given. (RB) [de

  8. Uranium enrichment

    International Nuclear Information System (INIS)

    1989-01-01

    GAO was asked to address several questions concerning a number of proposed uranium enrichment bills introduced during the 100th Congress. The bill would have restructured the Department of Energy's uranium enrichment program as a government corporation to allow it to compete more effectively in the domestic and international markets. Some of GAO's findings discussed are: uranium market experts believe and existing market models show that the proposed DOE purchase of a $750 million of uranium from domestic producers may not significantly increase production because of large producer-held inventories; excess uranium enrichment production capacity exists throughout the world; therefore, foreign producers are expected to compete heavily in the United States throughout the 1990s as utilities' contracts with DOE expire; and according to a 1988 agreement between DOE's Offices of Nuclear Energy and Defense Programs, enrichment decommissioning costs, estimated to total $3.6 billion for planning purposes, will be shared by the commercial enrichment program and the government

  9. Uranium resources

    International Nuclear Information System (INIS)

    1976-01-01

    This is a press release issued by the OECD on 9th March 1976. It is stated that the steep increases in demand for uranium foreseen in and beyond the 1980's, with doubling times of the order of six to seven years, will inevitably create formidable problems for the industry. Further substantial efforts will be needed in prospecting for new uranium reserves. Information is given in tabular or graphical form on the following: reasonably assured resources, country by country; uranium production capacities, country by country; world nuclear power growth; world annual uranium requirements; world annual separative requirements; world annual light water reactor fuel reprocessing requirements; distribution of reactor types (LWR, SGHWR, AGR, HWR, HJR, GG, FBR); and world fuel cycle capital requirements. The information is based on the latest report on Uranium Resources Production and Demand, jointly issued by the OECD's Nuclear Energy Agency (NEA) and the International Atomic Energy Agency. (U.K.)

  10. Review of uranium market price

    International Nuclear Information System (INIS)

    Maragatham Kumar; Nik Arlina Nik Ali; Koh You Beng

    2007-01-01

    Uranium is used as an abundant source of concentrated energy and is the principal fuel for the generation of electricity by nuclear reactors. In nuclear reactors, the uranium fuel is assembled in such a way that a controlled fission chain reaction can be achieved. Since uranium is the main source of nuclear energy, demand prospects for uranium has increased dramatically with the renewed global interest in nuclear power generation in recent years. Although the global uranium market is relatively small worldwide, compared to other mineral and energy sources, it is a very important market as nuclear power generation accounts for about 18% of global electricity supply. After reaching historic lows in 1990s, uranium prices have risen substantially in recent years. The outlook for nuclear power has changed since 2000, with concerns over global warming, proven excellent safety record, competitive costs, progress on nuclear waste disposal issues and also continuing new nuclear plant construction around the world. These and various other influencing factors have resulted in the uranium market evolving from one that was driven by excess secondary supplies to that by primary production. This paper reviews the global market prices for the years 1987 until 2006 and the factors, which influence the changes in global uranium market prices. (Author)

  11. Molecular weight growth in Titan's atmosphere: branching pathways for the reaction of 1-propynyl radical (H3CC≡C˙) with small alkenes and alkynes.

    Science.gov (United States)

    Kirk, Benjamin B; Savee, John D; Trevitt, Adam J; Osborn, David L; Wilson, Kevin R

    2015-08-28

    The reaction of small hydrocarbon radicals (i.e.˙CN, ˙C2H) with trace alkenes and alkynes is believed to play an important role in molecular weight growth and ultimately the formation of Titan's characteristic haze. Current photochemical models of Titan's atmosphere largely assume hydrogen atom abstraction or unimolecular hydrogen elimination reactions dominate the mechanism, in contrast to recent experiments that reveal significant alkyl radical loss pathways during reaction of ethynyl radical (˙C2H) with alkenes and alkynes. In this study, the trend is explored for the case of a larger ethynyl radical analogue, the 1-propynyl radical (H3CC[triple bond, length as m-dash]C˙), a likely product from the high-energy photolysis of propyne in Titan's atmosphere. Using synchrotron vacuum ultraviolet photoionization mass spectrometry, product branching ratios are measured for the reactions of 1-propynyl radical with a suite of small alkenes (ethylene and propene) and alkynes (acetylene and d4-propyne) at 4 Torr and 300 K. Reactions of 1-propynyl radical with acetylene and ethylene form single products, identified as penta-1,3-diyne and pent-1-en-3-yne, respectively. These products form by hydrogen atom loss from the radical-adduct intermediates. The reactions of 1-propynyl radical with d4-propyne and propene form products from both hydrogen atom and methyl loss, (-H = 27%, -CH3 = 73%) and (-H = 14%, -CH3 = 86%), respectively. Together, these results indicate that reactions of ethynyl radical analogues with alkenes and alkynes form significant quantities of products by alkyl loss channels, suggesting that current photochemical models of Titan over predict both hydrogen atom production as well as the efficiency of molecular weight growth in these reactions.

  12. Uranium supply and demand

    Energy Technology Data Exchange (ETDEWEB)

    Spriggs, M J

    1976-01-01

    Papers were presented on the pattern of uranium production in South Africa; Australian uranium--will it ever become available; North American uranium resources, policies, prospects, and pricing; economic and political environment of the uranium mining industry; alternative sources of uranium supply; whither North American demand for uranium; and uranium demand and security of supply--a consumer's point of view. (LK)

  13. Reactions of carbonyl compounds with α,β-unsaturated nitriles as a convenient pathway to carbo- and heterocycles

    International Nuclear Information System (INIS)

    Sharanin, Yu A; Goncharenko, M P; Litvinov, Victor P

    1998-01-01

    Published data on the methods for synthesis of carbo- and heterocyclic compounds based on reactions of α,β-unsaturated nitriles with carbonyl compounds and activated phenols are surveyed. It is demonstrated that all these reactions occur via nucleophilic addition of the carbanion generated from a carbonyl compound to the double bond of an unsaturated nitrile (the Michael reaction). The main routes of transformation of the adducts into carbo- and heterocyclic compounds are considered. The methods for regioselective preparation of fused 4H-pyrans or 1,4-dihydropyridines by varying conditions of cyclisation of Michael adducts are discussed. The bibliography includes 249 references.

  14. Hydrolysis of uranium monocarbide

    International Nuclear Information System (INIS)

    Hajek, B.; Karen, P.; Brozek, V.

    1984-01-01

    The substoichiometric uranium monocarbide UCsub(0.95) was hydrolyzed in acid medium at 80 degC. The composition of the products of hydrolysis corresponds to published data but it correlates better with the stoichiometric composition of the hydrolyzable carbide. The mechanisms of the hydrolytic reaction are discussed and a modified radical mechanism is suggested based on the concept of initiation of the radical process by Hsup(.) radicals formed owing to the nonstoichiometry of the substance. A relation is proposed for calculating the content of free hydrogen in the hydrolysis products of carbides of metallic nature for which a radical mechanism of their reaction with water can be assumed. Some effects occurring during the hydrolysis of uranium carbide, as described in literature, are explained in terms of the concept suggested. The results obtained by the authors for carbides of manganese (Mn 7 C 3 ) and for rare earth elements are discussed. (author)

  15. Leading coordinate analysis of reaction pathways in proton chain transfer: Application to a two-proton transfer model for the green fluorescent protein

    International Nuclear Information System (INIS)

    Wang Sufan; Smith, Sean C.

    2006-01-01

    The 'leading coordinate' approach to computing an approximate reaction pathway, with subsequent determination of the true minimum energy profile, is applied to a two-proton chain transfer model based on the chromophore and its surrounding moieties within the green fluorescent protein (GFP). Using an ab initio quantum chemical method, a number of different relaxed energy profiles are found for several plausible guesses at leading coordinates. The results obtained for different trial leading coordinates are rationalized through the calculation of a two-dimensional relaxed potential energy surface (PES) for the system. Analysis of the 2-D relaxed PES reveals that two of the trial pathways are entirely spurious, while two others contain useful information and can be used to furnish starting points for successful saddle-point searches. Implications for selection of trial leading coordinates in this class of proton chain transfer reactions are discussed, and a simple diagnostic function is proposed for revealing whether or not a relaxed pathway based on a trial leading coordinate is likely to furnish useful information

  16. Vapor-Phase Hydrodeoxygenation of Guaiacol to Aromatics over Pt/HBeta: Identification of the Role of Acid Sites and Metal Sites on the Reaction Pathway

    Energy Technology Data Exchange (ETDEWEB)

    Nie, Lei [Collaborative Innovation Center of Chemical Science and Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 P.R. China; Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Peng, Bo [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Zhu, Xinli [Collaborative Innovation Center of Chemical Science and Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 P.R. China

    2018-02-05

    Hydrodeoxygenation of guaiacol, a phenolic compound derived from lignin fraction of biomass, over a Pt/HBeta catalyst at 350 °C and atmospheric pressure produces benzene, toluene, xylenes, and C9+ aromatics with yield of 42%, 29%, 12%, and 5%, respectively. Reaction pathways for conversion of two functional groups (hydroxyl and methoxyl) over the bifunctional catalyst were studied. Both guaiacol and intermediate products (catechol and cyclopentanone) were fed onto zeolite HBeta and Pt/SiO2 to identify the individual role of acid site and metal site. Acid sites (mainly Brønsted acid site, BAS) catalyze transalkylation and dehydroxylation reactions in sequence, producing phenol, cresols and xylenols as the major products at high conversion. Pt sites catalyze demethylation reaction resulting in catechol as the primary product, which can either be deoxygenated to phenol followed by phenol to benzene, or decarbonylated to cyclopentanone and further to butane. The close proximity of Pt and BAS in bifunctional Pt/HBeta enables both transalkylation and deoxygenation reactions with inhibited demethylation and decarbonylation reactions, producing aromatics as major final products with a total yield > 85%. Both activity and stability of bifunctional Pt/HBeta during hydrodeoxygenation of guaiacol is improved compared to HBeta and Pt/SiO2. The addition of water to the feed further improves the activity and stability via hydrolysis of O-CH3 bond of guaiacol on BAS and removing coke around Pt.

  17. High-pressure vapor-phase hydrodeoxygenation of lignin-derived oxygenates to hydrocarbons by a PtMo bimetallic catalyst: Product selectivity, reaction pathway, and structural characterization

    Energy Technology Data Exchange (ETDEWEB)

    Yohe, Sara L.; Choudhari, Harshavardhan J.; Mehta, Dhairya D.; Dietrich, Paul J.; Detwiler, Michael D.; Akatay, Cem M.; Stach, Eric A.; Miller, Jeffrey T.; Delgass, W. Nicholas; Agrawal, Rakesh; Ribeiro, Fabio H.

    2016-12-01

    High-pressure, vapor-phase, hydrodeoxygenation (HDO) reactions of dihydroeugenol (2-methoxy-4-propylphenol), as well as other phenolic, lignin-derived compounds, were investigated over a bimetallic platinum and molybdenum catalyst supported on multi-walled carbon nanotubes (5%Pt2.5%Mo/MWCNT). Hydrocarbons were obtained in 100% yield from dihydroeugenol, including 98% yield of the hydrocarbon propylcyclohexane. The final hydrocarbon distribution was shown to be a strong function of hydrogen partial pressure. Kinetic analysis showed three main dihydroeugenol reaction pathways: HDO, hydrogenation, and alkylation. The major pathway occurred via Pt catalyzed hydrogenation of the aromatic ring and methoxy group cleavage to form 4-propylcyclohexanol, then Mo catalyzed removal of the hydroxyl group by dehydration to form propylcyclohexene, followed by hydrogenation of propylcyclohexene on either the Pt or Mo to form the propylcyclohexane. Transalkylation by the methoxy group occurred as a minor side reaction. Catalyst characterization techniques including chemisorption, scanning transmission electron microscopy, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy were employed to characterize the catalyst structure. Catalyst components identified were Pt particles, bimetallic PtMo particles, a Mo carbide-like phase, and Mo oxide phases.

  18. Synthesis of UN coatings on uranium

    International Nuclear Information System (INIS)

    Mar, R.W.; Hastings, J.C.

    1975-04-01

    A single-displacement reaction approach was used to form uranium mononitride as a protective coating for uranium; the source of the nitrogen was a solid nitride, and magnesium nitride was chosen as the most attractive candidate for the experiment. While the goal of synthesizing a single-phase uranium mononitride coating at temperatures lower than 1405 K was met, a number of problems inherent in the process were identified. 6 figures, 2 tables

  19. Molybdenum from uranium solutions

    International Nuclear Information System (INIS)

    Gardner, H.E.

    1981-01-01

    A method of removing molybdenum from a uranium bearing solution is claimed. It comprises adding sufficient reactive lead compound to supply at least 90 percent of the stoichiometric quantity of lead ion required to fully react with the molybdenum present to form insoluble lead molybdate and continuing the reaction with agitation until the desired percentage of the molybdenum present has reacted with the lead ion

  20. Uranium, depleted uranium, biological effects; Uranium, uranium appauvri, effets biologiques

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2001-07-01

    Physicists, chemists and biologists at the CEA are developing scientific programs on the properties and uses of ionizing radiation. Since the CEA was created in 1945, a great deal of research has been carried out on the properties of natural, enriched and depleted uranium in cooperation with university laboratories and CNRS. There is a great deal of available data about uranium; thousands of analyses have been published in international reviews over more than 40 years. This presentation on uranium is a very brief summary of all these studies. (author)

  1. Uranium toxicology

    International Nuclear Information System (INIS)

    Ferreyra, Mariana D.; Suarez Mendez, Sebastian

    1997-01-01

    In this paper are presented the methods and procedures optimized by the Nuclear Regulatory Authority (ARN) for the determination of: natural uranium mass, activity of enriched uranium in samples of: urine, mucus, filters, filter heads, rinsing waters and Pu in urine, adopted and in some cases adapted, by the Environmental Monitoring and Internal Dosimetry Laboratory. The analyzed material corresponded to biological and environmental samples belonging to the staff professionally exposed that work in plants of the nuclear fuel cycle. For a better comprehension of the activities of this laboratory, it is included a brief description of the uranium radiochemical toxicity and the limits internationally fixed to preserve the workers health

  2. Kinetics of the chain uranium decay

    International Nuclear Information System (INIS)

    Zel'dovich, Ya.B.; Khariton, Yu.B.

    1984-01-01

    The development of chain reaction in uranium mass, when passing through the mass critical value, is studied. It is shown that thermal expanson is a powerful regulating factor, making the limit passing quite safe. The case of convergence of two uranium masses of precritical dimensions is considered in particular. The critical mass value is assessed and it is shown that its gradual increase above the critical value results in the reaction vibrational regime with the period inversely proportional to the square root of uranium supply rate. The role of delaying neutrons in the fission chain reaction development is pointed out

  3. Adsorption of uranium on halloysite

    International Nuclear Information System (INIS)

    Kilislioglu, A.; Bilgin, B.

    2002-01-01

    Adsorption of uranium (U(VI)) from aqueous solutions on halloysite type clay was studied as a function of amount of adsorbent, initial concentration and pH. The values of adsorption data were fitted to Freundlich, Langmuir and Dubinin-Radushkevich (D-R) adsorption isotherms. The mean energy of adsorption was calculated as 5.91 kJ/mol from D-R adsorption isotherm. Lagergren and Bangham equation has been used for dynamic modelling of process and the rate constants of adsorption of uranium on halloysite type clay were calculated at 293, 313 and 333 K. In order to explain the mechanism of adsorption reaction, the rate constants were calculated at high and low uranium concentrations. Adsorption reaction was studied at 293, 303, 313, 323 and 333 K for halloysite type clay and also thermodynamic constants have been calculated. The results show that the adsorption reaction was endothermic and more spontaneous at high temperature. (orig.)

  4. Adsorption of uranium on halloysite

    Energy Technology Data Exchange (ETDEWEB)

    Kilislioglu, A.; Bilgin, B. [Istanbul Univ. (Turkey). Faculty of Engineering

    2002-07-01

    Adsorption of uranium (U(VI)) from aqueous solutions on halloysite type clay was studied as a function of amount of adsorbent, initial concentration and pH. The values of adsorption data were fitted to Freundlich, Langmuir and Dubinin-Radushkevich (D-R) adsorption isotherms. The mean energy of adsorption was calculated as 5.91 kJ/mol from D-R adsorption isotherm. Lagergren and Bangham equation has been used for dynamic modelling of process and the rate constants of adsorption of uranium on halloysite type clay were calculated at 293, 313 and 333 K. In order to explain the mechanism of adsorption reaction, the rate constants were calculated at high and low uranium concentrations. Adsorption reaction was studied at 293, 303, 313, 323 and 333 K for halloysite type clay and also thermodynamic constants have been calculated. The results show that the adsorption reaction was endothermic and more spontaneous at high temperature. (orig.)

  5. The neurotoxicology of uranium

    International Nuclear Information System (INIS)

    Dinocourt, Céline; Legrand, Marie; Dublineau, Isabelle; Lestaevel, Philippe

    2015-01-01

    The brain is a target of environmental toxic pollutants that impair cerebral functions. Uranium is present in the environment as a result of natural deposits and release by human applications. The first part of this review describes the passage of uranium into the brain, and its effects on neurological functions and cognitive abilities. Very few human studies have looked at its cognitive effects. Experimental studies show that after exposure, uranium can reach the brain and lead to neurobehavioral impairments, including increased locomotor activity, perturbation of the sleep-wake cycle, decreased memory, and increased anxiety. The mechanisms underlying these neurobehavioral disturbances are not clearly understood. It is evident that there must be more than one toxic mechanism and that it might include different targets in the brain. In the second part, we therefore review the principal mechanisms that have been investigated in experimental models: imbalance of the anti/pro-oxidant system and neurochemical and neurophysiological pathways. Uranium effects are clearly specific according to brain area, dose, and time. Nonetheless, this review demonstrates the paucity of data about its effects on developmental processes and the need for more attention to the consequences of exposure during development.

  6. Theoretical investigation of the oxidation pathways of the Cl-initiated reaction of 2-methyl-3-buten-2-ol

    Science.gov (United States)

    Zhang, Weichao; Zhang, Dongju

    2012-12-01

    The mechanism and products of the reaction of 2-methyl-3-buten-2-ol (MBO232) with Cl atoms in the presence of O2 have been elucidated by performing high-level quantum chemistry calculations. The geometries of the reactants, intermediates, transition states, and products are optimized at the MP2(full)/6-311G(d, p) level, and their single-point energies are refined at the CCSD(T)/6-311 + G(d, p) level. The potential energy surface profiles have been constructed at the CCSD(T)/6-311 + G(d, p)//MP2(full)/6-311G(d, p) + 0.95 × ZPE level of theory, and the possible channels involved in the reaction are also discussed. The calculations indicate that the reaction predominantly proceeds via the addition of Cl atoms to the double bond rather than the direct abstraction of the H atoms in MBO232. The nascent adducts (CH3)2C(OH)CHCH2Cl (IM1) and (CH3)2C(OH)CHClCH2 (IM2) do not undergo subsequent isomerization and dissociation reactions, but rather react with O2. The theoretical results show that the major products are CH2ClCHO and CH3C(O)CH3 for the reaction of MBO232 + Cl in the presence of O2, which is in good agreement with the experimental finding.

  7. Synthesis of Uranium nitride powders using metal uranium powders

    International Nuclear Information System (INIS)

    Yang, Jae Ho; Kim, Dong Joo; Oh, Jang Soo; Rhee, Young Woo; Kim, Jong Hun; Kim, Keon Sik

    2012-01-01

    Uranium nitride (UN) is a potential fuel material for advanced nuclear reactors because of their high fuel density, high thermal conductivity, high melting temperature, and considerable breeding capability in LWRs. Uranium nitride powders can be fabricated by a carbothermic reduction of the oxide powders, or the nitriding of metal uranium. The carbothermic reduction has an advantage in the production of fine powders. However it has many drawbacks such as an inevitable engagement of impurities, process burden, and difficulties in reusing of expensive N 15 gas. Manufacturing concerns issued in the carbothermic reduction process can be solved by changing the starting materials from oxide powder to metals. However, in nitriding process of metal, it is difficult to obtain fine nitride powders because metal uranium is usually fabricated in the form of bulk ingots. In this study, a simple reaction method was tested to fabricate uranium nitride powders directly from uranium metal powders. We fabricated uranium metal spherical powder and flake using a centrifugal atomization method. The nitride powders were obtained by thermal treating those metal particles under nitrogen containing gas. We investigated the phase and morphology evolutions of powders during the nitriding process. A phase analysis of nitride powders was also a part of the present work

  8. Rossing uranium

    International Nuclear Information System (INIS)

    Anon.

    1979-01-01

    In this article the geology of the deposits of the Rossing uranium mine in Namibia is discussed. The planning of the open-pit mining, the blasting, drilling, handling and the equipment used for these processes are described

  9. Oxidation of uranium and uranium alloys

    International Nuclear Information System (INIS)

    Orman, S.

    1976-01-01

    The corrosion behaviour of uranium in oxygen, water and water + oxygen mixtures is compared and contrasted. A considerable amount of work, much of it conflicting, has been published on the U + H 2 O and U + H 2 O + O 2 systems. An attempt has been made to summarise this data and to explain the reasons for the lack of agreement between the experimental results. The evidence for the mechanism involving OH - ion diffusion as the reacting entity in both the U + H 2 O and U + O 2 + H 2 O reactions is advanced. The more limited corrosion data on some lean uranium alloys and on some higher addition alloys referred to as stainless materials is summarised together with some previously unreported results obtained with these materials at AWRE. The data indicates that in the absence of oxygen the lean alloys behave in a similar manner to uranium and evolve hydrogen in approximately theoretical quantities. But the stainless alloys absorb most of the product hydrogen and assessments of reactivity based on hydrogen evolution would be very inaccurate. The direction that future corrosion work on these materials should take is recommended

  10. Computer-assisted study on the reaction between pyruvate and ylide in the pathway leading to lactyl-ThDP.

    Science.gov (United States)

    Alvarado, Omar; Jaña, Gonzalo; Delgado, Eduardo J

    2012-08-01

    In this study the formation of the lactyl-thiamin diphosphate intermediate (L-ThDP) is addressed using density functional theory calculations at X3LYP/6-31++G(d,p) level of theory. The study includes potential energy surface scans, transition state search, and intrinsic reaction coordinate calculations. Reactivity is analyzed in terms of Fukui functions. The results allow to conclude that the reaction leading to the formation of L-ThDP occurs via a concerted mechanism, and during the nucleophilic attack on the pyruvate molecule, the ylide is in its AP form. The calculated activation barrier for the reaction is 19.2 kcal/mol, in agreement with the experimental reported value.

  11. Uranium, depleted uranium, biological effects

    International Nuclear Information System (INIS)

    2001-01-01

    Physicists, chemists and biologists at the CEA are developing scientific programs on the properties and uses of ionizing radiation. Since the CEA was created in 1945, a great deal of research has been carried out on the properties of natural, enriched and depleted uranium in cooperation with university laboratories and CNRS. There is a great deal of available data about uranium; thousands of analyses have been published in international reviews over more than 40 years. This presentation on uranium is a very brief summary of all these studies. (author)

  12. Pathways for the OH + Br2 → HOBr + Br and HOBr + Br → HBr + BrO Reactions.

    Science.gov (United States)

    Wang, Hongyan; Qiu, Yudong; Schaefer, Henry F

    2016-02-11

    The OH radical reaction with Br2 and the subsequent reaction HOBr + Br are of exceptional importance to atmospheric chemistry and environmental chemistry. The entrance complex, transition state, and exit complex for both reactions have been determined using the coupled-cluster method with single, double, and perturbative triple excitations CCSD(T) with correlation consistent basis sets up to size cc-pV5Z and cc-pV5Z-PP. Coupled cluster effects with full triples (CCSDT) and full quadruples (CCSDTQ) are explicitly investigated. Scalar relativistic effects, spin-orbit coupling, and zero-point vibrational energy corrections are evaluated. The results from the all-electron basis sets are compared with those from the effective core potential (ECP) pseudopotential (PP) basis sets. The results are consistent. The OH + Br2 reaction is predicted to be exothermic 4.1 ± 0.5 kcal/mol, compared to experiment, 3.9 ± 0.2 kcal/mol. The entrance complex HO···BrBr is bound by 2.2 ± 0.2 kcal/mol. The transition state lies similarly well below the reactants OH + Br2. The exit complex HOBr···Br is bound by 2.7 ± 0.6 kcal/mol relative to separated HOBr + Br. The endothermicity of the reaction HOBr + Br → HBr + BrO is 9.6 ± 0.7 kcal/mol, compared with experiment 8.7 ± 0.3 kcal/mol. For the more important reverse (exothermic) HBr + BrO reaction, the entrance complex BrO···HBr is bound by 1.8 ± 0.6 kcal/mol. The barrier for the HBr + BrO reaction is 6.8 ± 0.9 kcal/mol. The exit complex (Br···HOBr) for the HBr + BrO reaction is bound by 1.9 ± 0.2 kcal/mol with respect to the products HOBr + Br.

  13. An Intramolecular Heck reaction that Prefers a 5-endo- to a 6-exo-trig Cyclization Pathway

    DEFF Research Database (Denmark)

    Vital, Paulo; Norrby, Per-Ola; Tanner, David Ackland

    2006-01-01

    A regioselective aromatic Claisen rearrangement was used to prepare 17a, the precursor of triflate 17e. The intramolecular Heck reaction of 17e is promoted only by bidentate phosphine ligands, giving exclusively and in excellent yield 20, the product of a 5-endo-trig cyclization, despite the poss......A regioselective aromatic Claisen rearrangement was used to prepare 17a, the precursor of triflate 17e. The intramolecular Heck reaction of 17e is promoted only by bidentate phosphine ligands, giving exclusively and in excellent yield 20, the product of a 5-endo-trig cyclization, despite...

  14. Reactions of ferrate(VI) with iodide and hypoiodous acid: kinetics, pathways, and implications for the fate of iodine during water treatment.

    Science.gov (United States)

    Shin, Jaedon; von Gunten, Urs; Reckhow, David A; Allard, Sebastien; Lee, Yunho

    2018-06-01

    Oxidative treatment of iodide-containing waters can form iodinated disinfection by-products (I-DBPs) that are more toxic than the regulated DBPs. To better understand the fate of iodine during water treatment with ferrate(VI), kinetics, products, and stoichiometries for the reactions of ferrate(VI) with iodide (I - ) and hypoiodous acid (HOI) were determined. Ferrate(VI) showed considerable reactivities to both I - and HOI with higher reactivities at lower pH. Interestingly, the reaction of ferrate(VI) with HOI ( k = 6.0×10 3 M -1 s -1 at pH 9) was much faster than with I - ( k = 5.6×10 M -1 s -1 at pH 9). The main reaction pathway during treatment of I - -containing waters was the oxidation of I - to HOI and its further oxidation to IO 3 - by ferrate(VI). However, for pH > 9, the HOI disproportionation catalyzed by ferrate(VI) became an additional transformation pathway forming I - and IO 3 - . The reduction of HOI by hydrogen peroxide ( k = 2.0×10 8 M -1 s -1 for the reaction, HOI + HO 2 - → I - + O 2 + 2H + ), the latter being produced from ferrate(VI) decomposition, also contributes to the I - regeneration in the pH range 9 - 11. A kinetic model was developed that could well simulate the fate of iodine in the ferrate(VI)-I - system. Overall, due to a rapid oxidation of I - to IO 3 - with short-lifetimes of HOI, ferrate(VI) oxidation appears to be a promising option for I-DBP mitigation during treatment of I - -containing waters.

  15. Protective Effects of Maillard Reaction Products of Whey Protein Concentrate against Oxidative Stress through an Nrf2-Dependent Pathway in HepG2 Cells.

    Science.gov (United States)

    Pyo, Min Cheol; Yang, Sung-Yong; Chun, Su-Hyun; Oh, Nam Su; Lee, Kwang-Won

    2016-09-01

    Whey protein concentrate (WPC), which contains α-lactalbumin and β-lactoglobulin, is utilized widely in the food industry. The Maillard reaction is a complex reaction that produces Maillard reaction products (MRPs), which are associated with the formation of antioxidant compounds. In this study, the hepatoprotection activity of MRPs of WPC against oxidative stress through the nuclear factor-E2-related factor 2 (Nrf2)-dependent antioxidant pathway in HepG2 cells was examined. Glucose-whey protein concentrate conjugate (Glc-WPC) was obtained from Maillard reaction between WPC and glucose. The fluorescence intensity of Glc-WPC increased after 7 d compared to native WPC, and resulted in loss of 48% of the free amino groups of WPC. The sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) patterns of Glc-WPC showed the presence of a high-molecular-weight portion. Treatment of HepG2 cells with Glc-WPC increased cell viability in the presence of oxidative stress, inhibited the generation of intracellular reactive oxygen species by tert-butyl hydroperoxide (t-BHP), and increased the glutathione level. Nrf2 translocation and Nrf2, reduced nicotinamide adenine dinucleotide phosphate (NAD(P)H)-quinone oxidoreductase 1 (NOQ1), heme oxygenase-1 (HO-1), glutamate-L-cysteine ligase (GCL)M and GCLC mRNA levels were increased by Glc-WPC. Also, Glc-WPC increased the phosphorylation of extracellular signal-regulated kinase (ERK) 1/2 and c-Jun N-terminal kinase (JNK). The results of this study demonstrate that Glc-WPC activates the Nrf2-dependent pathway through the phosphorylation of ERK1/2 and JNK in HepG2 cells, and induces production of antioxidant enzymes and phase II enzymes.

  16. Uranium loans

    International Nuclear Information System (INIS)

    Anon.

    1990-01-01

    When NUEXCO was organized in 1968, its founders conceived of a business based on uranium loans. The concept was relatively straightforward; those who found themselves with excess supplies of uranium would deposit those excesses in NUEXCO's open-quotes bank,close quotes and those who found themselves temporarily short of uranium could borrow from the bank. The borrower would pay interest based on the quantity of uranium borrowed and the duration of the loan, and the bank would collect the interest, deduct its service fee for arranging the loan, and pay the balance to those whose deposits were borrowed. In fact, the original plan was to call the firm Nuclear Bank Corporation, until it was discovered that using the word open-quotes Bankclose quotes in the name would subject the firm to various US banking regulations. Thus, Nuclear Bank Corporation became Nuclear Exchange Corporation, which was later shortened to NUEXCO. Neither the nuclear fuel market nor NUEXCO's business developed quite as its founders had anticipated. From almost the very beginning, the brokerage of uranium purchases and sales became a more significant activity for NUEXCO than arranging uranium loans. Nevertheless, loan transactions have played an important role in the international nuclear fuel market, requiring the development of special knowledge and commercial techniques

  17. Use of ESI-MS to determine reaction pathway for hydrogen sulphide scavenging with 1,3,5-tri-(2-hydroxyethyl)-hexahydro-s-triazine.

    Science.gov (United States)

    Madsen, Henrik T; Søgaard, Erik G

    2012-01-01

    To study the reaction between hydrogen sulphide and 1,3,5-tri-(2-hydroxyethyl)-hexahydro-s-triazine, which is an often used hydrogen sulphide scavenger, electro spray ionisation mass spectrometry (ESI-MS) was used. The investigation was carried out in positive mode, and tandem mass spectrometry was used to investigate the nature of unknown peaks in the mass spectra. The reaction was found to proceed as expected from theory with the triazine reacting with hydrogen sulphide to form the corresponding thiadiazine. This species subsequently reacted with a second hydrogen sulphide molecule to form the dithiazine species, hereby confirming previously obtained results and showing the ability of the ESI-MS method for studying the scavenging reaction. The final theoretical product s-trithiane was not detected. Furthermore, fragmentation products of thiadiazine and dithiazine were detected in the solution, and possible pathways and structures were suggested to describe the observed fragments. In these, thiadiazine fragmented to 2-(methylidene amino)-ethanol and 2-(1,3-thiazetidin-3-yl)-ethanol and N-(2-hydroxyethyl)-N-(sulfanylmethyl)-ethaniminium, which underwent a further fragmentation to N-methyl-N-(2-oxoethyl)-methaniminium. Dithiazine fragmented to N-methyl-N-(2-oxoethyl)-methaniminium as well. The by-product from this reaction is methanedithiol, which was not detected due to its low polarity.

  18. Using proteomic data to assess a genome-scale "in silico" model of metal reducing bacteria in the simulation of field-scale uranium bioremediation

    Science.gov (United States)

    Yabusaki, S.; Fang, Y.; Wilkins, M. J.; Long, P.; Rifle IFRC Science Team

    2011-12-01

    A series of field experiments in a shallow alluvial aquifer at a former uranium mill tailings site have demonstrated that indigenous bacteria can be stimulated with acetate to catalyze the conversion of hexavalent uranium in a groundwater plume to immobile solid-associated uranium in the +4 oxidation state. While this bioreduction of uranium has been shown to lower groundwater concentrations below actionable standards, a viable remediation methodology will need a mechanistic, predictive and quantitative understanding of the microbially-mediated reactions that catalyze the reduction of uranium in the context of site-specific processes, properties, and conditions. At the Rifle IFRC site, we are investigating the impacts on uranium behavior of pulsed acetate amendment, acetate-oxidizing iron and sulfate reducing bacteria, seasonal water table variation, spatially-variable physical (hydraulic conductivity, porosity) and geochemical (reactive surface area) material properties. The simulation of three-dimensional, variably saturated flow and biogeochemical reactive transport during a uranium bioremediation field experiment includes a genome-scale in silico model of Geobacter sp. to represent the Fe(III) terminal electron accepting process (TEAP). The Geobacter in silico model of cell-scale physiological metabolic pathways is comprised of hundreds of intra-cellular and environmental exchange reactions. One advantage of this approach is that the TEAP reaction stoichiometry and rate are now functions of the metabolic status of the microorganism. The linkage of in silico model reactions to specific Geobacter proteins has enabled the use of groundwater proteomic analyses to assess the accuracy of the model under evolving hydrologic and biogeochemical conditions. In this case, the largest predicted fluxes through in silico model reactions generally correspond to high abundances of proteins linked to those reactions (e.g. the condensation reaction catalyzed by the protein

  19. A review of the environmental behavior of uranium derived from depleted uranium alloy penetrators

    Energy Technology Data Exchange (ETDEWEB)

    Erikson, R.L.; Hostetler, C.J.; Divine, J.R.; Price, K.R.

    1990-01-01

    The use of depleted uranium (DU) penetrators as armor-piercing projectiles in the field results in the release of uranium into the environment. Elevated levels of uranium in the environment are of concern because of radioactivity and chemical toxicity. In addition to the direct contamination of the soil with uranium, the penetrators will also chemically react with rainwater and surface water. Uranium may be oxidized and leached into surface water or groundwater and may subsequently be transported. In this report, we review some of the factors affecting the oxidation of the DU metal and the factors influencing the leaching and mobility of uranium through surface water and groundwater pathways, and the uptake of uranium by plants growing in contaminated soils. 29 refs., 10 figs., 3 tabs.

  20. A new pathway for transmembrane electron transfer in photosynthetic reaction centers of Rhodobacter sphaeroides not involving the excited special pair.

    NARCIS (Netherlands)

    van Brederode, M.E.; Jones, M.R.; van Mourik, F.; van Stokkum, I.H.M.; van Grondelle, R.

    1997-01-01

    It is generally accepted that electron transfer in bacterial photosynthesis is driven by the first singlet excited state of a special pair of bacteriochlorophylls (P*). We have examined the first steps of electron transfer in a mutant of the Rhodobacter sphaeroides reaction center in which charge

  1. A new pathway for transmembrane electron transfer in photosyntetic reaction centers of Rhodobacter sphaeroides not involving the excited special pair.

    NARCIS (Netherlands)

    van Brederode, M.E.; Jones, M.R.; van Mourik, F.; van Stokkum, I.H.M.; van Grondelle, R.

    1997-01-01

    It is generally accepted that electron transfer in bacterial photosynthesis is driven by the first singlet excited state of a special pair of bacteriochlorophylls (P*). We have examined the first steps of electron transfer in a mutant of the Rhodobacter sphaeroides reaction center in which charge

  2. Influence of Ligand Architecture in Tuning Reaction Bifurcation Pathways for Chlorite Oxidation by Non-Heme Iron Complexes

    NARCIS (Netherlands)

    Barman, Prasenjit; Faponle, Abayomi S; Vardhaman, Anil Kumar; Angelone, Davide; Löhr, Anna-Maria; Browne, Wesley R; Comba, Peter; Sastri, Chivukula V; de Visser, Sam P

    2016-01-01

    Reaction bifurcation processes are often encountered in the oxidation of substrates by enzymes and generally lead to a mixture of products. One particular bifurcation process that is common in biology relates to electron transfer versus oxygen atom transfer by high-valent iron(IV)-oxo complexes,

  3. A study on chlorination of uranium metal using ammonium chloride

    International Nuclear Information System (INIS)

    Eun, H.C.; Kim, T.J.; Jang, J.H.; Kim, G.Y.; Lee, S.J.; Hur, J.M.

    2017-01-01

    In this study, the chlorination of uranium metal using ammonium chloride (NH 4 Cl) was conducted to derive an easy and simple uranium chloride production method without impurities. In thermodynamic equilibrium calculations, it was predicted that only uranium chlorides can be produced by the reactions between uranium metal and NH 4 Cl. Experimental conditions for the chlorination of uranium metal were determined using a chlorination test of cerium metal using NH 4 Cl. It was confirmed that UCl 3 and UCl 4 in the form of particles as uranium chlorination products can be obtained from the chlorination method using NH 4 Cl. (author)

  4. Synthesis and reactivity of triscyclopentadienyl uranium (III) and (IV) complexes

    International Nuclear Information System (INIS)

    Berthet, J.C.

    1992-01-01

    The reactions of (RC 5 H 4 ) 3 U with R=trimethylsilylcyclopentadienyl or tertiobutylcyclopentadienyl are studied for the synthesis of new uranium organometallic compounds. Reactions with sodium hydride are first described uranium (III) anionic hydrides obtained are oxidized for synthesis of stable uranium (IV) organometallic hydrides. Stability of these compounds is discussed. Reactivity of these uranium (III) and (IV) hydrides are studied. Formation of new binuclear compounds with strong U-O and U-N bonds is examined and crystal structure are presented. Monocyclooctatetraenylic uranium complexes are also investigated

  5. Uranium isotopic effect studies on cation and anion exchange resins

    International Nuclear Information System (INIS)

    Sarpal, S.K.; Gupta, A.R.

    1975-01-01

    Uranium isotope effects in exchange reactions involving hexavalent and tetravalent uranium, on ion exchange resins, have been re-examined. The earlier work on uranium isotope effects in electron exchange reactions involving hexavalent and tetravalent uranium, has been critically reviewed. New experimental data on these systems in hydrochloric acid medium, has been obtained, using break-through technique on anion-exchange columns. The isotope effects in these break-through experiments have been reinterpreted in a way which is consistent with the anion exchange behaviour of the various uranium species in these systems. (author)

  6. Uranium extraction from gold-uranium ores

    Energy Technology Data Exchange (ETDEWEB)

    Laskorin, B.N.; Golynko, Z.Sh.

    1981-01-01

    The process of uranium extraction from gold-uranium ores in the South Africa is considered. Flowsheets of reprocessing gold-uranium conglomerates, pile processing and uranium extraction from the ores are presented. Continuous counter flow ion-exchange process of uranium extraction using strong-active or weak-active resins is noted to be the most perspective and economical one. The ion-exchange uranium separation with the succeeding extraction is also the perspective one.

  7. Evaluation of a setting reaction pathway in the novel composite TiHA-CSD bone cement by FT-Raman and FT-IR spectroscopy

    Science.gov (United States)

    Paluszkiewicz, Czesława; Czechowska, Joanna; Ślósarczyk, Anna; Paszkiewicz, Zofia

    2013-02-01

    The aim of this study was to determine a setting reaction pathway in a novel, surgically handy implant material, based on calcium sulfate hemihydrate (CSH) and titanium doped hydroxyapatite (TiHA). The previous studies confirmed superior biological properties of TiHA in comparison to the undoped hydroxyapatite (HA) what makes it highly attractive for future medical applications. In this study the three types of titanium modified HA powders: untreated, calcined at 800 °C, sintered at 1250 °C and CSH were used to produce bone cements. The Fourier Transform-InfraRed (FT-IR) spectroscopy and Raman spectroscopy were applied to evaluate processes taking place during the setting of the studied materials. Our results undoubtedly confirmed that the reaction pathways and the phase compositions differed significantly for set cements and were dependent on the initial heat treatment of TiHA powder. Final materials were multiphase composites consisting of calcium sulfate dihydrate, bassanite, tricalcium phosphate, hydroxyapatite and calcium titanate (perovskite). The FT-IR and Scanning Electron Microscopy (SEM) measurements performed after the incubation of the cement samples in the simulated body fluid (SBF), indicate on high bioactive potential of the obtained bone cements.

  8. Theoretical study of the oxidation mechanisms of naphthalene initiated by hydroxyl radicals: the O2 addition reaction pathways.

    Science.gov (United States)

    Shiroudi, A; Deleuze, M S; Canneaux, S

    2015-05-28

    Atmospheric oxidation of the naphthalene-OH adduct [C10H8OH]˙ (R1) by molecular oxygen in its triplet electronic ground state has been studied using density functional theory along with the B3LYP, ωB97XD, UM05-2x and UM06-2x exchange-correlation functionals. From a thermodynamic viewpoint, the most favourable process is O2 addition at the C2 position in syn mode, followed by O2 addition at the C2 position in anti mode, O2 addition at the C4 position in syn mode, and O2 addition at the C4 position in anti mode, as the second, third and fourth most favourable processes. The syn modes of addition at these positions are thermodynamically favoured over the anti ones by the formation of an intramolecular hydrogen bond between the hydroxyl and peroxy substituents. Analysis of the computed structures, bond orders and free energy profiles demonstrate that the reaction steps involved in the oxidation of the naphthalene-OH adduct by O2 satisfy Hammond's principle. Kinetic rate constants and branching ratios under atmospheric pressure and in the fall-off regime have been supplied, using transition state and RRKM theories. By comparison with experiment, these data confirm the relevance of a two-step reaction mechanism. Whatever the addition mode, O2 addition in C4 position is kinetically favoured over O2 addition in C2 position, in contrast with the expectations drawn from thermodynamics and reaction energies. Under a kinetic control of the reaction, and in line with the computed reaction energy barriers, the most efficient process is O2 addition at the C4 position in syn mode, followed by O2 addition at the C2 position in syn mode, O2 addition at the C4 position in anti mode, and O2 addition at the C2 position in anti mode as the second, third and fourth most rapid processes. The computed branching ratios also indicate that the regioselectivity of the reaction decreases with increasing temperatures and decreasing pressures.

  9. Uranium mining

    International Nuclear Information System (INIS)

    2008-01-01

    Full text: The economic and environmental sustainability of uranium mining has been analysed by Monash University researcher Dr Gavin Mudd in a paper that challenges the perception that uranium mining is an 'infinite quality source' that provides solutions to the world's demand for energy. Dr Mudd says information on the uranium industry touted by politicians and mining companies is not necessarily inaccurate, but it does not tell the whole story, being often just an average snapshot of the costs of uranium mining today without reflecting the escalating costs associated with the process in years to come. 'From a sustainability perspective, it is critical to evaluate accurately the true lifecycle costs of all forms of electricity production, especially with respect to greenhouse emissions, ' he says. 'For nuclear power, a significant proportion of greenhouse emissions are derived from the fuel supply, including uranium mining, milling, enrichment and fuel manufacture.' Dr Mudd found that financial and environmental costs escalate dramatically as the uranium ore is used. The deeper the mining process required to extract the ore, the higher the cost for mining companies, the greater the impact on the environment and the more resources needed to obtain the product. I t is clear that there is a strong sensitivity of energy and water consumption and greenhouse emissions to ore grade, and that ore grades are likely to continue to decline gradually in the medium to long term. These issues are critical to the current debate over nuclear power and greenhouse emissions, especially with respect to ascribing sustainability to such activities as uranium mining and milling. For example, mining at Roxby Downs is responsible for the emission of over one million tonnes of greenhouse gases per year and this could increase to four million tonnes if the mine is expanded.'

  10. Pathways for the reaction of the butadiene radical cation, [C{sub 4}H{sub 6}]{sup {sm{underscore}bullet}+}, with ethylene

    Energy Technology Data Exchange (ETDEWEB)

    Hofmann, M.; Schaefer, H.F. III

    1999-11-04

    The Diels-Alder (DA) reaction, a [4+2] cycloaddition used to build six membered rings, is one of the most valuable cycloadditions in organic chemistry. In cases where the ene does not add to the diene (even with the help of Lewis acids which may reduce the electron density of one reactant by complexation) one electron oxidation (by an oxidizing agent or by photoinduced electron transfer (PET)) may accelerate the reaction. Reaction pathways for the addition of ethylene, 1, to butadiene radical cation, 2, involving H-shifts have been investigated at the coupled cluster UCCSD(T)/DZP//UMP2(fc)/DZP + ZPE level of theory. Activation energies are relatively low for [1,2]- (10.0 kcal mol{sup {minus}1}, TS-4/20) and [1,5]-hydrogen shifts (7.7 kcal mol{sup {minus}1}, TS-4/26) but are relatively high for [1,4]-(33.8 kcal mol{sup {minus}1}, TS-4/14) and [1,3]-H shifts (e.g., 42.2 kcal mol{sup {minus}1}, TS-12/13; 57.2 kcal mol{sup {minus}1}, TS-16/21). Several rearrangement reactions have been found to occur below the energy limit of separated 1 + 2. The cyclopentenyl cation, [C{sub 5}{sub 7}]{sup +}, 18, experimentally observed as reaction product of the butadiene radical cation, 2, and ethylene, 1, in the gas phase may origin from various reaction pathways. The following reaction sequence has been identified as the lowest in energy path from 1 + 2 to 18 with all relative energies ({Delta}E{degree}) of transition structures below that of 1 + 2: (a) ethylene adds to the butadiene radical cation to form an open-chain distonic intermediate, that undergoes a [1,5]-H shift to the 1,4-hexadiene radical cation; (b) intramolecular [2+1] cycloaddition to methyl-cyclopenta-1,3-diyl intermediates, which can interconvert through a bicyclo[2.1.0]pentane radical cation; (c) [1,2]-H shift to the 3-methyl cyclopentene radical cation; (d) methyl radical loss to give cyclopenten-3-yl cation. Along this reaction pathway, {Delta}H{sup 298} is below that of 1 + 2; max. ({Delta}G{sup 298} by

  11. Kinetic modelling of Amadori N-(1-deoxy-D-fructos-1-yl)-glycine degradation pathways. Part I - Reaction mechanism

    NARCIS (Netherlands)

    Martins, S.I.F.S.; Marcelis, A.T.M.; Boekel, van M.A.J.S.

    2003-01-01

    The fate of the Amadori compound N-(1-deoxy--fructos-1-yl)-glycine (DFG) was studied in aqueous model systems as a function of pH and temperature. The samples were heated at 100 and 120 °C with initial reaction pH of 5.5 and 6.8. Special attention was paid to the formation of the free amino acid,

  12. [Effects and mechanisms of the inflammatory reaction related to NASH and induced by activation of the cholinergic anti-inflammatory pathway].

    Science.gov (United States)

    Zhou, Zhou; Chen, Xiaomei; Li, Fuqiang; Tang, Cuilan

    2015-01-01

    To investigate the effects and mechanisms of the inflammatory reaction related to nonalcoholic steatohepatitis (NASH) and induced by activation of the cholinergic anti-inflammatory pathway. A mouse model of NASH was established by feeding a high-fat and high-sugar diet.Activation of the cholinergic anti-inflammatory pathway was achieved by nicotine administration to the NASH modeled mice and normal controls. Liver biopsies were taken and the concentrations of cytokines were measured. Isolated liver primary Kupffer cells and RAw264.7 cells were cultured, pre-treated or not with lipopolysaccharide (LPS) and exposed to nicotine, after which the supernatant concentrations of IL-6 and TNFa were determined by ELISA. The protein expression levels of phosphorylated (p)-NF-kB and I k B were detected in primary cultured Kupffer cells by western blotting. The mouse model of NASH was successfully established, as evidenced by findings from liver biopsy and serum liver function tests. The degree of liver inflammation in the NASH mice decreased after nicotine administration, and the level of serum TNFa also significantly decreased. The levels of serum TNFa were 21.95+/-0.8 pg/mL in nicotine-treated mice and 38.07+/-1.7 pg/mL in the non-nicotine-treated NASH mice (P less than 0.05). The nicotine treatment also significantly reduced the concentration of TNFa in the culture supernatants of Kupffer cells after LPS stimulation; moreover, the supernatant level of TNFa decreased significantly after the nicotine treatment (Pless than 0.05). LPS stimulation of the RAw264.7 cells led to an increased level ofp-NF-kB and a reduced level ofI-kB, suggesting that the NF-kB pathway had been activated; different doses of nicotine pre-treatment led to down-regulation of the p-NF-kB level and up-regulation of the I-kB level, both in dose-dependent manners. Activating the cholinergic anti-inflammatory pathway inhibits the NASH-related inflammatory reaction, and the mechanism for this inhibition

  13. Dissociation pathways of a single dimethyl disulfide on Cu(111): Reaction induced by simultaneous excitation of two vibrational modes

    Energy Technology Data Exchange (ETDEWEB)

    Motobayashi, Kenta, E-mail: kmotobayashi@cat.hokudai.ac.jp [Catalysis Research Center, Hokkaido University, Sapporo 001-0021 (Japan); Department of Advanced Materials Science, The University of Tokyo, Kashiwa 277-8561 (Japan); Surface and Interface Science Laboratory, RIKEN, Wako 351-0198 (Japan); Kim, Yousoo [Surface and Interface Science Laboratory, RIKEN, Wako 351-0198 (Japan); Arafune, Ryuichi [International Center for Materials Nanoarchitectonics, National Institute for Materials Science, Tsukuba 305-0044 (Japan); Ohara, Michiaki; Ueba, Hiromu; Kawai, Maki, E-mail: maki@k.u-tokyo.ac.jp [Department of Advanced Materials Science, The University of Tokyo, Kashiwa 277-8561 (Japan)

    2014-05-21

    We present a novel reaction mechanism for a single adsorbed molecule that proceeds via simultaneous excitation of two different vibrational modes excited by inelastic tunneling electrons from a scanning tunneling microscope. Specifically, we analyze the dissociation of a single dimethyl disulfide (DMDS, (CH{sub 3}S){sub 2}) molecule on Cu(111) by using a versatile theoretical method, which permits us to simulate reaction rates as a function of sample bias voltage. The reaction is induced by the excitation of C-H stretch and S-S stretch modes by a two-electron process at low positive bias voltages. However, at increased voltages, the dissociation becomes a single-electron process that excites a combination mode of these stretches, where excitation of the C-H stretch is the energy source and excitation of the S-S stretch mode enhances the anharmonic coupling rate. A much smaller dissociation yield (few orders of magnitude) at negative bias voltages is understood in terms of the projected density of states of a single DMDS on Cu(111), which reflects resonant excitation through the molecular orbitals.

  14. Method to manufacture a nuclear fuel from uranium-plutonium monocarbide or uranium-plutonium mononitride

    International Nuclear Information System (INIS)

    Krauth, A.; Mueller, N.

    1977-01-01

    Pure uranium carbide or nitride is converted with plutonium oxide and carbon (all in powder form) to uranium-plutonium monocarbide or mononitride by cold pressing and sintering at about 1600 0 C. Pure uranium carbide or uranium nitride powder is firstly prepared without extensive safety measures. The pure uranium carbide or nitride powder can also be inactivated by using chemical substances (e.g. stearic acid) and be handled in air. The sinterable uranium carbide or nitride powder (or also granulate) is then introduced into the plutonium line and mixed with a nonstoichiometrically adjusted, prereacted mixture of plutonium oxide and carbon, pressed to pellets and reaction sintered. The surface of the uranium-plutonium carbide (higher metal content) can be nitrated towards the end of the sinter process in a stream of nitrogen. The protective layer stabilizes the carbide against the water and oxygen content in air. (IHOE) [de

  15. Uranium enrichment

    International Nuclear Information System (INIS)

    Rae, H.K.; Melvin, J.G.

    1988-06-01

    Canada is the world's largest producer and exporter of uranium, most of which is enriched elsewhere for use as fuel in LWRs. The feasibility of a Canadian uranium-enrichment enterprise is therefore a perennial question. Recent developments in uranium-enrichment technology, and their likely impacts on separative work supply and demand, suggest an opportunity window for Canadian entry into this international market. The Canadian opportunity results from three particular impacts of the new technologies: 1) the bulk of the world's uranium-enrichment capacity is in gaseous diffusion plants which, because of their large requirements for electricity (more than 2000 kW·h per SWU), are vulnerable to competition from the new processes; 2) the decline in enrichment costs increases the economic incentive for the use of slightly-enriched uranium (SEU) fuel in CANDU reactors, thus creating a potential Canadian market; and 3) the new processes allow economic operation on a much smaller scale, which drastically reduces the investment required for market entry and is comparable with the potential Canadian SEU requirement. The opportunity is not open-ended. By the end of the century the enrichment supply industry will have adapted to the new processes and long-term customer/supplier relationships will have been established. In order to seize the opportunity, Canada must become a credible supplier during this century

  16. 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.

  17. Electrochemical preparation of new uranium oxide phases

    International Nuclear Information System (INIS)

    Smolenskij, V.V.; Lyalyushkin, N.V.; Bove, A.L.; Komarov, V.K.; Kapshukov, I.I.

    1992-01-01

    Behaviour of uranium ions in oxidation states 3+ and 4+ in molten chlorides of alkali metals in the temperature range of 700-900 degC in the atmosphere of an inert gas was studied by the method of cyclic voltametry. It is shown that as a result of introduction of crystal uranium dioxide into the salt melt formation of uranium oxide ions of the composition UO + and UO 2+ occurs, the ions participating in electrode reactions and bringing about formation of the following uranium oxides on the cathode: UO and, presumably, U 3 O 4 . Oxides UO and U 3 O 4 are thermodynamically unstable at low temperatures and decompose into uranium oxide of the composition UO 2-x , where x varies from 0 to 0.05, and metal uranium

  18. [Polyketone Reaction in Biosynthetic Pathways of 2, 3, 5, 4'-Tetrahydroxy Stilhene-2-O-β-D-glucoside in Polygonum multiflorum by Biocatalysis].

    Science.gov (United States)

    Lei, Lei; Xia, Wan-xia; Shao, Li; Zhao, Shu-jin

    2015-10-01

    2, 3, 5, 4'-Tetrahydroxy stilbene-2-O-β-D-glucoside (THSG), the active ingredient of Polygonum multiflorum, its polyketone reaction in the biosynthesis pathways was studied by biocatalysis method. The substrates 4-coumaroyl-CoA and malonyl-CoA were catalyzed in vitro by the crude enzyme extracted from Polygonum multiflorum callus, then the products were verified by HPLC and LC-MS methods. And the crude enzyme was analyzed by ammonium sulfate precipitation method and SDS-PAGE. HPLC chromatogram showed the same retention time of both the product and resveratrol standards; LC-MS spectra showed that the m/z of product was 227, which was consistent with resveratrol standards under the mode of negative ion; Ammonium sulfate (AS) precipitation method showed AS of 40% - 70% had catalytic activity,and 50% - 60% was the optimum; SDS-PAGE showed protein bands were obviously different among different AS concentration between 20% - 80%, the protein band of 42 kDa was found in AS of 50% - 60%, which had the same molecular weight with stilbene synthase. The product of polyketone reaction in the biosynthesis of THSG is resveratrol rather than THSG, so it is speculated that THSG is the conversion product of resveratrol instead of the direct product of the polyketone reaction.

  19. Oxidation of fluoroquinolone antibiotics and structurally related amines by chlorine dioxide: Reaction kinetics, product and pathway evaluation.

    Science.gov (United States)

    Wang, Pei; He, Yi-Liang; Huang, Ching-Hua

    2010-12-01

    Fluoroquinolones (FQs) are a group of widely prescribed antibiotics and have been frequently detected in the aquatic environment. The reaction kinetics and transformation of seven FQs (ciprofloxacin (CIP), enrofloxacin (ENR), norfloxacin (NOR), ofloxacin (OFL), lomefloxacin (LOM), pipemidic acid (PIP) and flumequine (FLU)) and three structurally related amines (1-phenylpiperazine (PP), N-phenylmorpholine (PM) and 4-phenylpiperidine (PD)) toward chlorine dioxide (ClO(2)) were investigated to elucidate the behavior of FQs during ClO(2) disinfection processes. The reaction kinetics are highly pH-dependent, can be well described by a second-order kinetic model incorporating speciation of FQs, and follow the trend of OFL > ENR > CIP ∼ NOR ∼ LOM > > PIP in reactivity. Comparison among FQs and related amines and product characterization indicate that FQs' piperazine ring is the primary reactive center toward ClO(2). ClO(2) likely attacks FQ's piperazinyl N4 atom followed by concerted fragmentation involving piperazinyl N1 atom, leading to dealkylation, hydroxylation and intramolecular ring closure at the piperazine moiety. While FQs with tertiary N4 react faster with ClO(2) than FQs with secondary N4, the overall reactivity of the piperazine moiety also depends strongly on the quinolone ring through electronic effects. The reaction rate constants obtained in clean water matrix can be used to model the decay of CIP by ClO(2) in surface water samples, but overestimate the decay in wastewater samples. Overall, transformation of FQs, particularly for those with tertiary N4 amines, could be expected under typical ClO(2) disinfection conditions. However, the transformation may not eliminate antibacterial activity because of little destruction at the quinolone ring. Copyright © 2010 Elsevier Ltd. All rights reserved.

  20. MicroRNA-124-3p expression and its prospective functional pathways in hepatocellular carcinoma: A quantitative polymerase chain reaction, gene expression omnibus and bioinformatics study.

    Science.gov (United States)

    He, Rong-Quan; Yang, Xia; Liang, Liang; Chen, Gang; Ma, Jie

    2018-04-01

    The present study aimed to explore the potential clinical significance of microRNA (miR)-124-3p expression in the hepatocarcinogenesis and development of hepatocellular carcinoma (HCC), as well as the potential target genes of functional HCC pathways. Reverse transcription-quantitative polymerase chain reaction was performed to evaluate the expression of miR-124-3p in 101 HCC and adjacent non-cancerous tissue samples. Additionally, the association between miR-124-3p expression and clinical parameters was also analyzed. Differentially expressed genes identified following miR-124-3p transfection, the prospective target genes predicted in silico and the key genes of HCC obtained from Natural Language Processing (NLP) were integrated to obtain potential target genes of miR-124-3p in HCC. Relevant signaling pathways were assessed with protein-protein interaction (PPI) networks, Gene Ontology (GO) enrichment analysis, Kyoto Encyclopedia of Genes and Genomes (KEGG) and Protein Annotation Through Evolutionary Relationships (PANTHER) pathway enrichment analysis. miR-124-3p expression was significantly reduced in HCC tissues compared with expression in adjacent non-cancerous liver tissues. In HCC, miR-124-3p was demonstrated to be associated with clinical stage. The mean survival time of the low miR-124-3p expression group was reduced compared with that of the high expression group. A total of 132 genes overlapped from differentially expressed genes, miR-124-3p predicted target genes and NLP identified genes. PPI network construction revealed a total of 109 nodes and 386 edges, and 20 key genes were identified. The major enriched terms of three GO categories included regulation of cell proliferation, positive regulation of cellular biosynthetic processes, cell leading edge, cytosol and cell projection, protein kinase activity, transcription activator activity and enzyme binding. KEGG analysis revealed pancreatic cancer, prostate cancer and non-small cell lung cancer as the

  1. Buckling and reaction rate measurements in graphite moderated lattices fuelled with plutonium-uranium oxide clusters at temperatures up to 400 deg. C

    International Nuclear Information System (INIS)

    Carter, D.H.; Gibson, M.; King, D.C.; Marshall, J.; Puckett, B.J.; Richards, A.E.; Wass, T.; Wilson, D.J.

    1965-07-01

    The Report describes a series of experiments carried out in SCORPIO I and II on sub-critical graphite moderated lattices fuelled with 21-rod clusters of PuO 2 /UO 2 fuel. Three fuel batches with nominal plutonium: uranium ratios of 0.25%, 0.8% and 1.2% were investigated at temperatures between 20 deg. C and 400 deg. C. Because of the limited amounts of the three fuels, exponential measurements were made in 2-zone stacks, the outer regions of which were loaded with suitably matched 'reference fuel'. Fine structure distributions in the lattice cell were obtained with manganese and indium foils. Pu239/U235 fission ratios were determined both by fission chambers and by fission-product counting techniques. (author)

  2. Buckling and reaction rate measurements in graphite moderated lattices fuelled with plutonium-uranium oxide clusters at temperatures up to 400 deg. C

    Energy Technology Data Exchange (ETDEWEB)

    Carter, D H; Gibson, M; King, D C; Marshall, J; Puckett, B J; Richards, A E; Wass, T; Wilson, D J [General Reactor Physics Division, Atomic Energy Establishment, Winfrith, Dorchester, Dorset (United Kingdom)

    1965-07-15

    The Report describes a series of experiments carried out in SCORPIO I and II on sub-critical graphite moderated lattices fuelled with 21-rod clusters of PuO{sub 2}/UO{sub 2} fuel. Three fuel batches with nominal plutonium: uranium ratios of 0.25%, 0.8% and 1.2% were investigated at temperatures between 20 deg. C and 400 deg. C. Because of the limited amounts of the three fuels, exponential measurements were made in 2-zone stacks, the outer regions of which were loaded with suitably matched 'reference fuel'. Fine structure distributions in the lattice cell were obtained with manganese and indium foils. Pu239/U235 fission ratios were determined both by fission chambers and by fission-product counting techniques. (author) 14 refs, 30 figs, 18 tabs

  3. Method to determine the thermal conductivity of uranium dioxide and the surface conductance at the cladding-core interface from internal reactions

    Energy Technology Data Exchange (ETDEWEB)

    Tsykanov, V A; Samsonov, B F; Spiridonov, Yu G; Fomin, N A

    1975-01-01

    A method is given for determining the temperature-dependent thermal conductivity of uranium dioxide and the contact conductance of the gas gap between the core and cladding of a fuel element. These quantities should be determined on various samples with different diameters. A method is described for determining the heat-production rate of a fuel element to within 1.5 to 2.5 percent. The method is based on using a calibrated electric heater and a sensor to measure the specific energy evolution from reactor gamma-radiation. The total errors in determining the thermal conductivity and the contact conductance do not exceed 4.5 and 8 percent, respectively.

  4. Structures and reaction pathways of the molybdenum centres of sulfite-oxidizing enzymes by pulsed EPR spectroscopy.

    Science.gov (United States)

    Enemark, John H; Astashkin, Andrei V; Raitsimring, Arnold M

    2008-12-01

    SOEs (sulfite-oxidizing enzymes) are physiologically vital and occur in all forms of life. During the catalytic cycle, the five-co-ordinate square pyramidal oxo-molybdenum active site passes through the Mo(V) state, and intimate details of the structure can be obtained from variable frequency pulsed EPR spectroscopy through the hyperfine and nuclear quadrupole interactions of nearby magnetic nuclei. By employing variable spectrometer operational frequencies, it is possible to optimize the measurement conditions for difficult quadrupolar nuclei of interest (e.g. (17)O, (33)S, (35)Cl and (37)Cl) and to simplify the interpretation of the spectra. Isotopically labelled model Mo(V) compounds provide further insight into the electronic and geometric structures and chemical reactions of the enzymes. Recently, blocked forms of SOEs having co-ordinated sulfate, the reaction product, were detected using (33)S (I=3/2) labelling. This blocking of product release is a possible contributor to fatal human sulfite oxidase deficiency in young children.

  5. Uranium update

    International Nuclear Information System (INIS)

    Steane, R.

    1997-01-01

    This paper is about the current uranium mining situation, especially that in Saskatchewan. Canada has a unique advantage with the Saskatchewan uranium deposits. Making the most of this opportunity is important to Canada. The following is reviewed: project development and the time and capital it takes to bring a new project into production; the supply and demand situation to show where the future production fits into the world market; and our foreign competition and how we have to be careful not to lose our opportunity. (author)

  6. Airborne uranium, its concentration and toxicity in uranium enrichment facilities

    International Nuclear Information System (INIS)

    Thomas, J.; Mauro, J.; Ryniker, J.; Fellman, R.

    1979-02-01

    The release of uranium hexafluoride and its hydrolysis products into the work environment of a plant for enriching uranium by means of gas centrifuges is discussed. The maximum permissible mass and curie concentration of airborne uranium (U) is identified as a function of the enrichment level (i.e., U-235/total U), and chemical and physical form. A discussion of the chemical and radiological toxicity of uranium as a function of enrichment and chemical form is included. The toxicity of products of UF 6 hydrolysis in the atmosphere, namely, UO 2 F 2 and HF, the particle size of toxic particulate material produced from this hydrolysis, and the toxic effects of HF and other potential fluoride compounds are also discussed. Results of an investigation of known effects of humidity and temperature on particle size of UO 2 F 2 produced by the reaction of UF 6 with water vapor in the air are reported. The relationship of the solubility of uranium compounds to their toxic effects was studied. Identification and discussion of the standards potentially applicable to airborne uranium compounds in the working environment are presented. The effectiveness of High Efficiency Particulate (HEPA) filters subjected to the corrosive environment imposed by the presence of hydrogen fluoride is discussed

  7. Reaction of tricyclopentadienyl uranium chloride (C5H5)3UCl with triethylaluminium Al(C2H5)3

    International Nuclear Information System (INIS)

    Vasil'ev, V.K.; Sokolov, V.N.; Kondratenkov, G.P.

    1977-01-01

    The mechanism of reaction of tricyclopentadienyluranchloride with triethylaluminium was studied by the NMR 1 method. The kinetic and thermodynamic parameters of this reaction (k=(6+-1)x10 5 sec -1 , E=27+-4 kJ/molxK) were estimated from the temperature dependence of the chemical shifts with due regard for the paramagnetic shift and the half-width of the averaged-signal line

  8. Degradation of γ-HCH spiked soil using stabilized Pd/Fe0 bimetallic nanoparticles: Pathways, kinetics and effect of reaction conditions

    International Nuclear Information System (INIS)

    Singh, Ritu; Misra, Virendra; Mudiam, Mohana Krishna Reddy; Chauhan, Lalit Kumar Singh; Singh, Rana Pratap

    2012-01-01

    Highlights: ► This study explores the potential of CMC-Pd/nFe 0 to degrade γ-HCH in spiked soil. ► Sorption–desorption characteristics and partitioning of γ-HCH is investigated. ► Three degradation pathways has been proposed and discussed. ► γ-HCH degradation mechanism and kinetics is elucidated. ► Activation energy reveals that γ-HCH degradation is a surface mediated reaction. - Abstract: This study investigates the degradation pathway of gamma-hexachlorocyclohexane (γ-HCH) in spiked soil using carboxymethyl cellulose stabilized Pd/Fe 0 bimetallic nanoparticles (CMC-Pd/nFe 0 ). GC–MS analysis of γ-HCH degradation products showed the formation of pentachlorocyclohexene, tri- and di-chlorobenzene as intermediate products while benzene was formed as the most stable end product. On the basis of identified intermediates and final products, degradation pathway of γ-HCH has been proposed. Batch studies showed complete γ-HCH degradation at a loading of 0.20 g/L CMC-Pd/nFe 0 within 6 h of incubation. The surface area normalized rate constant (k SA ) was found to be 7.6 × 10 −2 L min −1 m −2 . CMC-Pd/nFe 0 displayed ∼7-fold greater efficiency for γ-HCH degradation in comparison to Fe 0 nanoparticles (nFe 0 ), synthesized without CMC and Pd. Further studies showed that increase in CMC-Pd/nFe 0 loading and reaction temperature facilitates γ-HCH degradation, whereas a declining trend in degradation was noticed with the increase in pH, initial γ-HCH concentration and in the presence of cations. The data on activation energy (33.7 kJ/mol) suggests that γ-HCH degradation is a surface mediated reaction. The significance of the study with respect to remediation of γ-HCH contaminated soil using CMC-Pd/nFe 0 has been discussed.

  9. Method of precipitating uranium from an aqueous solution and/or sediment

    Science.gov (United States)

    Tokunaga, Tetsu K; Kim, Yongman; Wan, Jiamin

    2013-08-20

    A method for precipitating uranium from an aqueous solution and/or sediment comprising uranium and/or vanadium is presented. The method includes precipitating uranium as a uranyl vanadate through mixing an aqueous solution and/or sediment comprising uranium and/or vanadium and a solution comprising a monovalent or divalent cation to form the corresponding cation uranyl vanadate precipitate. The method also provides a pathway for extraction of uranium and vanadium from an aqueous solution and/or sediment.

  10. Machining of uranium and uranium alloys

    International Nuclear Information System (INIS)

    Morris, T.O.

    1981-01-01

    Uranium and uranium alloys can be readily machined by conventional methods in the standard machine shop when proper safety and operating techniques are used. Material properties that affect machining processes and recommended machining parameters are discussed. Safety procedures and precautions necessary in machining uranium and uranium alloys are also covered. 30 figures

  11. Coprecipitation of {sup 14}C and Sr with carbonate precipitates: The importance of reaction kinetics and recrystallization pathways

    Energy Technology Data Exchange (ETDEWEB)

    Hodkin, David J. [School of Earth and Environment, University of Leeds, Leeds LS2 9JT (United Kingdom); Stewart, Douglas I. [School of Civil Engineering, University of Leeds (United Kingdom); Graham, James T. [National Nuclear Laboratory, Sellafield, Cumbria (United Kingdom); Burke, Ian T., E-mail: I.T.Burke@leeds.ac.uk [School of Earth and Environment, University of Leeds, Leeds LS2 9JT (United Kingdom)

    2016-08-15

    This study investigated the simultaneous removal of Sr{sup 2+} and {sup 14}CO{sub 3}{sup 2−} from pH > 12 Ca(OH){sub 2} solution by the precipitation of calcium carbonate. Initial Ca{sup 2+}:CO{sub 3}{sup 2−} ratios ranged from 10:1 to 10:100 (mM:mM). Maximum removal of {sup 14}C and Sr{sup 2+} both occurred in the system containing 10 mM Ca{sup 2+} and 1 mM CO{sub 3}{sup 2−} (99.7% and 98.6% removal respectively). A kinetic model is provided that describes {sup 14}C and Sr removal in terms of mineral dissolution and precipitation reactions. The removal of {sup 14}C was achieved during the depletion of the initial TIC in solution, and was subsequently significantly affected by recrystallization of the calcite precipitate from an elongate to isotropic morphology. This liberated > 46% of the {sup 14}C back to solution. Sr{sup 2+} removal occurred as Ca{sup 2+} became depleted in solution and was not significantly affected by the recrystallization process. The proposed reaction could form the basis for low cost remediation scheme for {sup 90}Sr and {sup 14}C in radioactively contaminated waters (<$0.25 reagent cost per m{sup 3} treated). - Highlights: • 99.7% of {sup 14}C and 98.6% of Sr removed from aqueous solution by CaCO{sub 3} precipitation. • Remobilization of {sup 14}C observed during calcium carbonate recrystallization. • Sr displayed variable distribution coefficient (possibly affected by Ca:Sr ratio). • Reagent cost of $0.22/m{sup 3} of treated groundwater.

  12. Study of electrolytic reduction of uranium VI to uranium IV in nitrate systems

    Energy Technology Data Exchange (ETDEWEB)

    Araujo, B.F. de; Almeida, S.G. de; Forbicini, S; Matsuda, H T; Araujo, J.A. de [Instituto de Pesquisas Energeticas e Nucleares, Sao Paulo (Brazil). Centro de Engenharia Quimica

    1980-01-01

    Experimental parameters are optimized in order to obtain uranium (IV) nitrate solutions at maximum yield, using hydrazine as stabilizer. Uranium (VI) electrolytic reduction was chosen because: there is no increase in the volume of radioactive effluents; there are no secondary reactions; there is no need for further separations; all reagents used are not inflammable. The method is, therefore, efficient and of low cost.

  13. Uranium in the Black Sea

    International Nuclear Information System (INIS)

    Babinets, A.E.; Zhorov, V.A.; Bezborodov, A.A.; Kobylyanskaya, A.G.; Solov'eva, L.V.; Urdenko, V.A.

    1975-01-01

    Water samples for uranium analysis have been collected over the entire Black Sea, from the surface to the sea floor. As distinct from the previously known facts, it has been established that the uranium content in different parts of the sea appears to vary both in extent and with depth. A behaviour of uranium is governed by redox conditions of the environment. A decrease in pH value of water to 7.5 and a change of Eh value from +0.4 to -0.2 v lead to reduction of U 6+ → U 4+ and ensure higher sorption properties of the solid phases. The reducing reaction is proved possible through the calculated data. It is shown that the rate of uranium isolation is increasing with depth and its content is going down. Using optical properties of water, a hydrogeochemical behaviour of organic matter and uranium in water thickness is explained. Role of organic matter and mineral components in the uranium deposition is described. Sorption of U 6+ ions on twelve components, which constitute a base of suspensions and floor sediments, has been also studied [ru

  14. A study of fundamental reaction pathways for transition metal alkyl complexes. I. The reaction of a nickel methyl complex with alkynes. Ii. The mechanism of aldehyde formation in the reaction of a molybdenum hydride with molybdenum alkyls

    Energy Technology Data Exchange (ETDEWEB)

    Huggins, John Mitchell [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)

    1980-06-12

    I. This study reports the rapid reaction under mild conditions of internal or terminal alkynes with methyl (acetyl-acetonato) (triphenylphosphine) nickel (1) in either aromatic or ether solvents. In all cases vinylnickel products 2 are formed by insertion of the alkyne into the nickel=methyl bond. These complexes may be converted into a variety of organic products (e.g. alkenes, esters, vinyl halides) by treatment with appropriate reagents. Unsymmetrical alkynes give selectively the one regioisomer with the sterically largest substituent next to the nickel atom. In order to investigate the stereochemistry of the initial insertion, a x-ray diffraction study of the reaction of 1 with diphenylacetylene was carried out. This showed that the vinylnickel complex formed by overall trans insertion was the product of the reaction. Furthermore, subsequent slow isomerization of this complex, to a mixture of it and the corresponding cis isomer, demonstrated that this trans addition product is the kinetic product of the reaction. In studies with other alkynes, the product of trans addition was not always exclusively (or even predominantly) formed, but the ratio of the stereoisomers formed kinetically was substantially different from the thermodynamic ratio. Isotope labeling, added phosphine, and other experiments have allowed us to conclude that the mechanism of this reaction does involve initial cis addition. However, a coordinatively unsaturated vinylnickel complex is initially formed which can undergo rapid, phosphine-catalyzed cis-trans isomerization in competition with its conversion to the isolable phosphine-substituted kinetic reaction products. II. The reaction of CpMo(CO)3H (1a) with CpMo(CO)3R (2, R= CH3, C2H5) at 50°C in THF gives the aldehyde RCHO and the dimers [CpMo(CO)3]2 (3a) and [CpMo(CO)2]2 (4a). Labeling one of the reactants with a methylcyclopentadienyl ligand

  15. TLR4-HMGB1 signaling pathway affects the inflammatory reaction of autoimmune myositis by regulating MHC-I.

    Science.gov (United States)

    Wan, Zemin; Zhang, Xiujuan; Peng, Anping; He, Min; Lei, Zhenhua; Wang, Yunxiu

    2016-12-01

    To analyze the effects of TLR4 on the expression of the HMGB1, MHC-I and downstream cytokines IL-6 and TNF-α, and to investigate the biological role of the TLR4-HMGB1 signaling pathway in the development of the autoimmune myositis. We built mice models with experimental autoimmune myositis (EAM) and used the inverted screen experiment to measure their muscle endurance; we also examined inflammatory infiltration of muscle tissues after HE staining; and we assessed the expression of MHC-I using immunohistochemistry. In addition, peripheral blood mononuclear cells (PBMC) were extracted and flow cytometry was utilized to detect the effect of IFN-γ on the expression of MHC-I. Furthermore, PBMCs were treated with IFN-γ, anti-TLR4, anti-HMGB1 and anti-MHC-I. Real-time PCR and western blotting were employed to examine the expressions of TLR4, HMGB1 and MHC-I in different groups. The ELISA method was also utilized to detect the expression of the downstream cytokines TNF-α and IL-6. The expressions of TLR4, HMGB1 and MHC-I in muscle tissues from mice with EAM were significantly higher than those in the control group (all Pmyositis inflammation by regulating the expression of MHC-I and other pro-inflammatory cytokines. Copyright © 2016 Elsevier B.V. All rights reserved.

  16. Uranium mining

    International Nuclear Information System (INIS)

    Cheeseman, E.W.

    1980-01-01

    The international uranium market appears to be currently over-supplied with a resultant softening in prices. Buyers on the international market are unhappy about some of the restrictions placed on sales by the government, and Canadian sales may suffer as a result. About 64 percent of Canada's shipments come from five operating Ontario mines, with the balance from Saskatchewan. Several other properties will be producing within the next few years. In spite of the adverse effects of the Three Mile Island incident and the default by the T.V.A. of their contract, some 3 600 tonnes of new uranium sales were completed during the year. The price for uranium had stabilized at US $42 - $44 by mid 1979, but by early 1980 had softened somewhat. The year 1979 saw the completion of major environmental hearings in Ontario and Newfoundland and the start of the B.C. inquiry. Two more hearings are scheduled for Saskatchewan in 1980. The Elliot Lake uranium mining expansion hearings are reviewed, as are other recent hearings. In the production of uranium for nuclear fuel cycle, environmental matters are of major concern to the industry, the public and to governments. Research is being conducted to determine the most effective method for removing radium from tailings area effluents. Very stringent criteria are being drawn up by the regulatory agencies that must be met by the industry in order to obtain an operating licence from the AECB. These criteria cover seepages from the tailings basin and through the tailings retention dam, seismic stability, and both short and long term management of the tailings waste management area. (auth)

  17. Uranium industry annual 1996

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-04-01

    The Uranium Industry Annual 1996 (UIA 1996) provides current statistical data on the US uranium industry`s activities relating to uranium raw materials and uranium marketing. The UIA 1996 is prepared for use by the Congress, Federal and State agencies, the uranium and nuclear electric utility industries, and the public. Data on uranium raw materials activities for 1987 through 1996 including exploration activities and expenditures, EIA-estimated reserves, mine production of uranium, production of uranium concentrate, and industry employment are presented in Chapter 1. Data on uranium marketing activities for 1994 through 2006, including purchases of uranium and enrichment services, enrichment feed deliveries, uranium fuel assemblies, filled and unfilled market requirements, uranium imports and exports, and uranium inventories are shown in Chapter 2. A feature article, The Role of Thorium in Nuclear Energy, is included. 24 figs., 56 tabs.

  18. Uranium industry annual 1996

    International Nuclear Information System (INIS)

    1997-04-01

    The Uranium Industry Annual 1996 (UIA 1996) provides current statistical data on the US uranium industry's activities relating to uranium raw materials and uranium marketing. The UIA 1996 is prepared for use by the Congress, Federal and State agencies, the uranium and nuclear electric utility industries, and the public. Data on uranium raw materials activities for 1987 through 1996 including exploration activities and expenditures, EIA-estimated reserves, mine production of uranium, production of uranium concentrate, and industry employment are presented in Chapter 1. Data on uranium marketing activities for 1994 through 2006, including purchases of uranium and enrichment services, enrichment feed deliveries, uranium fuel assemblies, filled and unfilled market requirements, uranium imports and exports, and uranium inventories are shown in Chapter 2. A feature article, The Role of Thorium in Nuclear Energy, is included. 24 figs., 56 tabs

  19. Uranium industry annual, 1991

    International Nuclear Information System (INIS)

    1992-10-01

    In the Uranium Industry Annual 1991, data on uranium raw materials activities including exploration activities and expenditures, resources and reserves, mine production of uranium, production of uranium concentrate, and industry employment are presented in Chapter 1. Data on uranium marketing activities including domestic uranium purchases, commitments by utilities, procurement arrangements, uranium imports under purchase contracts and exports, deliveries to enrichment suppliers, inventories, secondary market activities, utility market requirements, and uranium for sale by domestic suppliers are presented in Chapter 2. A feature article entitled ''The Uranium Industry of the Commonwealth of Independent States'' is included in this report

  20. Novel pathway of SO2 oxidation in the atmosphere: reactions with monoterpene ozonolysis intermediates and secondary organic aerosol

    Science.gov (United States)

    Ye, Jianhuai; Abbatt, Jonathan P. D.; Chan, Arthur W. H.

    2018-04-01

    Ozonolysis of monoterpenes is an important source of atmospheric biogenic secondary organic aerosol (BSOA). While enhanced BSOA formation has been associated with sulfate-rich conditions, the underlying mechanisms remain poorly understood. In this work, the interactions between SO2 and reactive intermediates from monoterpene ozonolysis were investigated under different humidity conditions (10 % vs. 50 %). Chamber experiments were conducted with ozonolysis of α-pinene or limonene in the presence of SO2. Limonene SOA formation was enhanced in the presence of SO2, while no significant changes in SOA yields were observed during α-pinene ozonolysis. Under dry conditions, SO2 primarily reacted with stabilized Criegee intermediates (sCIs) produced from ozonolysis, but at 50 % RH heterogeneous uptake of SO2 onto organic aerosol was found to be the dominant sink of SO2, likely owing to reactions between SO2 and organic peroxides. This SO2 loss mechanism to organic peroxides in SOA has not previously been identified in experimental chamber studies. Organosulfates were detected and identified using an electrospray ionization-ion mobility spectrometry-high-resolution time-of-flight mass spectrometer (ESI-IMS-TOF) when SO2 was present in the experiments. Our results demonstrate the synergistic effects between BSOA formation and SO2 oxidation through sCI chemistry and SO2 uptake onto organic aerosol and illustrate the importance of considering the chemistry of organic and sulfur-containing compounds holistically to properly account for their reactive sinks.

  1. Degradation of a cationic dye (Rhodamine 6G) using hydrodynamic cavitation coupled with other oxidative agents: Reaction mechanism and pathway.

    Science.gov (United States)

    Rajoriya, Sunil; Bargole, Swapnil; Saharan, Virendra Kumar

    2017-01-01

    In the present study, decolorization and mineralization of a cationic dye, Rhodamine 6G (Rh6G), has been carried out using hydrodynamic cavitation (HC). Two cavitating devices such as slit and circular venturi were used to generate cavitation in HC reactor. The process parameters such as initial dye concentration, solution pH, operating inlet pressure, and cavitation number were investigated in detail to evaluate their effects on the decolorization efficiency of Rh6G. Decolorization of Rh6G was marginally higher in the case of slit venturi as compared to circular venturi. The kinetic study showed that decolorization and mineralization of the dye fitted first-order kinetics. The loadings of H 2 O 2 and ozone have been optimized to intensify the decolorization and mineralization efficiency of Rh6G using HC. Nearly 54% decolorization of Rh6G was obtained using a combination of HC and H 2 O 2 at a dye to H 2 O 2 molar ratio of 1:30. The combination of HC with ozone resulted in 100% decolorization in almost 5-10min of processing time depending upon the initial dye concentration. To quantify the extent of mineralization, total organic carbon (TOC) analysis was also performed using various processes and almost 84% TOC removal was obtained using HC coupled with 3g/h of ozone. The degradation by-products formed during the complete degradation process were qualitatively identified by liquid chromatography-mass spectrometry (LC-MS) and a detailed degradation pathway has been proposed. Copyright © 2016 Elsevier B.V. All rights reserved.

  2. Reactivity of Uranium and Ferrous Iron with Natural Iron Oxyhydroxides.

    Science.gov (United States)

    Stewart, Brandy D; Cismasu, A Cristina; Williams, Kenneth H; Peyton, Brent M; Nico, Peter S

    2015-09-01

    Determining key reaction pathways involving uranium and iron oxyhydroxides under oxic and anoxic conditions is essential for understanding uranium mobility as well as other iron oxyhydroxide mediated processes, particularly near redox boundaries where redox conditions change rapidly in time and space. Here we examine the reactivity of a ferrihydrite-rich sediment from a surface seep adjacent to a redox boundary at the Rifle, Colorado field site. Iron(II)-sediment incubation experiments indicate that the natural ferrihydrite fraction of the sediment is not susceptible to reductive transformation under conditions that trigger significant mineralogical transformations of synthetic ferrihydrite. No measurable Fe(II)-promoted transformation was observed when the Rifle sediment was exposed to 30 mM Fe(II) for up to 2 weeks. Incubation of the Rifle sediment with 3 mM Fe(II) and 0.2 mM U(VI) for 15 days shows no measurable incorporation of U(VI) into the mineral structure or reduction of U(VI) to U(IV). Results indicate a significantly decreased reactivity of naturally occurring Fe oxyhydroxides as compared to synthetic minerals, likely due to the association of impurities (e.g., Si, organic matter), with implications for the mobility and bioavailability of uranium and other associated species in field environments.

  3. Bioelectrocatalytic dechlorination of trichloroacetic acid at gel-immobilized hemoglobin on multiwalled carbon nanotubes modified graphite electrode: Kinetic modeling and reaction pathways

    International Nuclear Information System (INIS)

    Liu, Qi; Yu, Jianming; Xu, Yinghua; Wang, Jiade; Ying, Le; Song, Xinxin; Zhou, Gendi; Chen, Jianmeng

    2013-01-01

    Highlights: ► The electrons transfer from enzyme in the electrode to COCs was the key step. ► The average current efficiency was influenced by pH and temperature of the systems. ► The most favourable degradation conditions for TCA were found to be pH 3 and 310 K. ► The activation energy of 26.2 kJ mol −1 was also calculated by the Arrhenius equation. ► Bioelectrocatalytic mechanism of TCA was verified by kinetic expressions. -- Abstract: In bioelectrochemically reductive dechlorination of chlorinated organic compounds (COCs), the electrons transfer from enzyme in the electrode to COCs was the key step, which determined the average current efficiency (CE) and was influenced by the pH and temperature of the systems. In this work, the effect of temperature (288–318 K) and pH (2–11) of the electrolyte on decholrination of trichloroacetic acid (TCA) was investigated in the sodium alginate/hemoglobin-multiwalled carbon nanotubes-graphite composite electrode (Hb/SA–MWCNT–GE). The results showed that the most favourable degradation conditions for TCA by Hb/SA–MWCNT–GE were found to be pH 3 and 310 K. By varying the pH of the systems, it was found that a proton accompanied with an electron transfer between the electrode and heme Fe(III)/Fe(II) of Hb during the reaction. Additionally, the activation energy of 26.2 kJ mol −1 was also calculated by the Arrhenius equation for the reaction. The total mass balance of the reactant and the products was in the range of 97–105% during the bioelectrochemically reductive reaction. The CE only decreased from 87% to 83% when the Hb/SA–MWCNT–GE was used 5 times. Based on the intermediates detected, a pathway was proposed for TCA degradation in which it underwent dechlorination process. The main degradation mechanism described by a parallel reaction rather than by a sequential reaction for dechlorination of TCA in Hb/SA–MWCNT–GE system was proposed. These data provided relevant information about the

  4. Formation of iodo-trihalomethanes, iodo-acetic acids, and iodo-acetamides during chloramination of iodide-containing waters: Factors influencing formation and reaction pathways

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Shaogang [Key Laboratory of Drinking Water Science and Technology, Research Center for Eco-Environmental Sciences, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 18 Shuang-qing Road, Beijing, 100085 (China); Guangxi Colleges and Universities Key Laboratory of Food Safety and Pharmaceutical Analytical Chemistry, Guangxi Key Laboratory of Chemistry and Engineering of Forest Products, School of Chemistry and Chemical Engineering, Guangxi University for Nationalities, Nanning, 530006, Guangxi (China); Li, Zhenlin [Guangxi Colleges and Universities Key Laboratory of Food Safety and Pharmaceutical Analytical Chemistry, Guangxi Key Laboratory of Chemistry and Engineering of Forest Products, School of Chemistry and Chemical Engineering, Guangxi University for Nationalities, Nanning, 530006, Guangxi (China); Dong, Huiyu [Key Laboratory of Drinking Water Science and Technology, Research Center for Eco-Environmental Sciences, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 18 Shuang-qing Road, Beijing, 100085 (China); Goodman, Bernard A. [College of Physical Science and Engineering, State Key Laboratory for Conservation and Utilization of Subtropical Agro-Bioresources, Guangxi University, Nanning, 520004, Guangxi (China); Qiang, Zhimin, E-mail: qiangz@rcees.ac.cn [Key Laboratory of Drinking Water Science and Technology, Research Center for Eco-Environmental Sciences, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 18 Shuang-qing Road, Beijing, 100085 (China)

    2017-01-05

    This study investigated systematically the factors influencing the formation of iodinated disinfection by-products (I-DBPs) during chloramination of I{sup −}-containing waters, including reaction time, NH{sub 2}Cl dose, I{sup −} concentration, pH, natural organic matter (NOM) concentration, Br{sup −}/I{sup −} molar ratio, and water matrix. Among the I-DBPs detected, iodoform (CHI{sub 3}), iodoacetic acid (IAA), diiodoacetic acid (DIAA), triiodoacetic acid (TIAA), and diiodoacetamide (DIAcAm) were the major species produced from reactions between reactive iodine species (HOI/I{sub 2}) and NOM. A kinetic model involving the reactions of NH{sub 2}Cl auto-decomposition, iodine species transformation and NOM consumption was developed, which could well describe NH{sub 2}Cl decay and HOI/I{sub 2} evolution. Higher concentrations of CHI{sub 3}, IAA, DIAA, TIAA, and DIAcAm were observed in chloramination than in chlorination, whereas IO{sub 3}{sup −} was only formed significantly in chlorination. Maximum formation of I-DBPs occurred at pH 8.0, but acidic conditions favored the formation of iodinated haloacetic acids and DIAcAm. Increasing Br{sup −}/I{sup −} molar ratio from 1 to 10 did not increase the total amount of I-DBPs, but produced more bromine-substituting species. In addition, chloramination of 18 model compounds indicated that low-SUVA{sub 254} (specific ultraviolet absorbance at 254 nm) NOM generally favored the formation of I-DBPs compared to high-SUVA{sub 254} NOM. Finally, potential pathways for I-DBPs formation from chloramination of NOM were proposed.

  5. Removal of uranium from uranium plant wastewater using zero-valent iron in an ultrasonic field

    Energy Technology Data Exchange (ETDEWEB)

    Li, Jing; Zhang, Libo; Peng, Jinhui; Ma, Aiyuan; Xia, Hong Ying; Guo, Wen Qian; Yu, Xia [Yunnan Provincial Key Laboratory of Intensification Metallurgy, Kunming (China); Hu, Jinming; Yang, Lifeng [Nuclear Group Two Seven Two Uranium Industry Limited Liability Company, Hengyang (China)

    2016-06-15

    Uranium removal from uranium plant wastewater using zero-valent iron in an ultrasonic field was investigated. Batch experiments designed by the response surface methodology (RSM) were conducted to study the effects of pH, ultrasonic reaction time, and dosage of zero-valent iron on uranium removal efficiency. From the experimental data obtained in this work, it was found that the ultrasonic method employing zero-valent iron powder effectively removes uranium from uranium plant wastewater with a uranium concentration of 2,772.23 μg/L. The pH ranges widely from 3 to 7 in the ultrasonic field, and the prediction model obtained by the RSM has good agreement with the experimental results.

  6. Uranium - what role

    International Nuclear Information System (INIS)

    Grey, T.; Gaul, J.; Crooks, P.; Robotham, R.

    1980-01-01

    Opposing viewpoints on the future role of uranium are presented. Topics covered include the Australian Government's uranium policy, the status of nuclear power around the world, Australia's role as a uranium exporter and problems facing the nuclear industry

  7. Brazilian uranium exploration program

    International Nuclear Information System (INIS)

    Marques, J.P.M.

    1981-01-01

    General information on Brazilian Uranium Exploration Program, are presented. The mineralization processes of uranium depoits are described and the economic power of Brazil uranium reserves is evaluated. (M.C.K.) [pt

  8. Uranium enrichment

    International Nuclear Information System (INIS)

    1991-11-01

    This paper analyzes under four different scenarios the adequacy of a $500 million annual deposit into a fund to pay for the cost of cleaning up the Department of Energy's (DOE) three aging uranium enrichment plants. These plants are located in Oak Ridge, Tennessee; Paducah, Kentucky; and Portsmouth, Ohio. In summary the following was found: A fixed annual $500 million deposit made into a cleanup fund would not be adequate to cover total expected cleanup costs, nor would it be adequate to cover expected decontamination and decommissioning (D and D) costs. A $500 million annual deposit indexed to an inflation rate would likely be adequate to pay for all expected cleanup costs, including D and D costs, remedial action, and depleted uranium costs

  9. Uranium production

    International Nuclear Information System (INIS)

    Spriggs, M.

    1980-01-01

    The balance between uranium supply and demand is examined. Should new resources become necessary, some unconventional sources which could be considered include low-grade extensions to conventional deposits, certain types of intrusive rock, tuffs, and lake and sea-bed sediments. In addition there are large but very low grade deposits in carbonaceous shales, granites, and seawater. The possibility of recovery is discussed. Programmes of research into the feasibility of extraction of uranium from seawater, as a by-product from phosphoric acid production, and from copper leach solutions, are briefly discussed. Other possible sources are coal, old mine dumps and tailings, the latter being successfully exploited commercially in South Africa. The greatest constraints on increased development of U from lower grade sources are economics and environmental impact. It is concluded that apart from U as a by-product from phosphate, other sources are unlikely to contribute much to world requirements in the foreseeable future. (U.K.)

  10. Research on using depleted uranium as nuclear fuel for HWR

    International Nuclear Information System (INIS)

    Zhang Jiahua; Chen Zhicheng; Bao Borong

    1999-01-01

    The purpose of our work is to find a way for application of depleted uranium in CANDU reactor by using MOX nuclear fuel of depleted U and Pu instead of natural uranium. From preliminary evaluation and calculation, it was shown that MOX nuclear fuel consisting of depleted uranium enrichment tailings (0.25% 235 U) and plutonium (their ratio 99.5%:0.5%) could replace natural uranium in CANDU reactor to sustain chain reaction. The prospects of application of depleted uranium in nuclear energy field are also discussed

  11. Study of the dry processing of uranium ores

    International Nuclear Information System (INIS)

    Guillet, H.

    1959-02-01

    A description is given of direct fluorination of pre-concentrated uranium ores in order to obtain the hexafluoride. After normal sulfuric acid treatment of the ore to eliminate silica, the uranium is precipitated by a load of lime to obtain: either impure calcium uranate of medium grade, or containing around 10% of uranium. This concentrate is dried in an inert atmosphere and then treated with a current of elementary fluorine. The uranium hexafluoride formed is condensed at the outlet of the reaction vessel and may be used either for reduction to tetrafluoride and the subsequent manufacture of uranium metal or as the initial product in a diffusion plant. (author) [fr

  12. The behaviour of uranium metal in hydrogen atmospheres

    International Nuclear Information System (INIS)

    Allen, G.C.; Stevens, J.C.H.

    1988-01-01

    The reaction between commercial H 2 and uranium metal leads to the formation of UO 2 due to traces of water vapour or oxygen. When extremely pure H 2 is used uranium hydride may be formed but, even with 99.9999% H 2 , uranium dioxide forms preferentially. The present work identifies the presence of UH 3 in the X-ray photoelectron spectrum of a uranium sample which has been exposed to ca. 10 10 L† H 2 at ca. 200 0 C. This spectrum indicates that the hydride possesses a high degree of covalency, since the oxidation state of uranium in UH 3 appears to be ca. 1.4. (author)

  13. Depleted uranium: Metabolic disruptor?; Uranium appauvri: perturbateur metabolique?

    Energy Technology Data Exchange (ETDEWEB)

    Souidi, Maamar; Dublineau, Isabelle; Lestaevel, Philippe [Institut de Radioprotection et de Surete Nucleaire - IRSN, Direction de la radioprotection de l' homme, Laboratoire de radiotoxicologie experimentale, Service de radiobiologie et d' epidemiologie, BP 17, 92262 Fontenay-aux-Roses cedex (France)

    2011-11-15

    The presence of uranium in the environment can lead to long-term contamination of the food chain and of water intended for human consumption and thus raises many questions about the scientific and societal consequences of this exposure on population health. Although the biological effects of chronic low-level exposure are poorly understood, results of various recent studies show that contamination by depleted uranium (DU) induces subtle but significant biological effects at the molecular level in organs including the brain, liver, kidneys and testicles. For the first time, it has been demonstrated that DU induces effects on several metabolic pathways, including those metabolizing vitamin D, cholesterol, steroid hormones, acetylcholine and xenobiotics. This evidence strongly suggests that DU might well interfere with many metabolic pathways. It might thus contribute, together with other man-made substances in the environment, to increased health risks in some regions. (authors)

  14. Uranium enrichment

    International Nuclear Information System (INIS)

    1991-08-01

    This paper reports that in 1990 the Department of Energy began a two-year project to illustrate the technical and economic feasibility of a new uranium enrichment technology-the atomic vapor laser isotope separation (AVLIS) process. GAO believes that completing the AVLIS demonstration project will provide valuable information about the technical viability and cost of building an AVLIS plant and will keep future plant construction options open. However, Congress should be aware that DOE still needs to adequately demonstrate AVLIS with full-scale equipment and develop convincing cost projects. Program activities, such as the plant-licensing process, that must be completed before a plant is built, could take many years. Further, an updated and expanded uranium enrichment analysis will be needed before any decision is made about building an AVLIS plant. GAO, which has long supported legislation that would restructure DOE's uranium enrichment program as a government corporation, encourages DOE's goal of transferring AVLIS to the corporation. This could reduce the government's financial risk and help ensure that the decision to build an AVLIS plant is based on commercial concerns. DOE, however, has no alternative plans should the government corporation not be formed. Further, by curtailing a planned public access program, which would have given private firms an opportunity to learn about the technology during the demonstration project, DOE may limit its ability to transfer AVLIS to the private sector

  15. Derived enriched uranium market

    International Nuclear Information System (INIS)

    Rutkowski, E.

    1996-01-01

    The potential impact on the uranium market of highly enriched uranium from nuclear weapons dismantling in the Russian Federation and the USA is analyzed. Uranium supply, conversion, and enrichment factors are outlined for each country; inventories are also listed. The enrichment component and conversion components are expected to cause little disruption to uranium markets. The uranium component of Russian derived enriched uranium hexafluoride is unresolved; US legislation places constraints on its introduction into the US market

  16. Dissolution of metallic uranium and its alloys. Part 1. Review of analytical and process-scale metallic uranium dissolution

    International Nuclear Information System (INIS)

    Laue, C.A.; Gates-Anderson, D.; Fitch, T.E.

    2004-01-01

    This review focuses on dissolution/reaction systems capable of treating uranium metal waste to remove its pyrophoric properties. The primary emphasis is the review of literature describing analytical and production-scale dissolution methods applied to either uranium metal or uranium alloys. A brief summary of uranium's corrosion behavior is included since the corrosion resistance of metals and alloys affects their dissolution behavior. Based on this review, dissolution systems were recommended for subsequent screening studies designed to identify the best system to treat depleted uranium metal wastes at Lawrence Livermore National Laboratory (LLNL). (author)

  17. Uranium industry annual, 1986

    International Nuclear Information System (INIS)

    1987-01-01

    Uranium industry data collected in the EIA-858 survey provide a comprehensive statistical characterization of annual activities of the industry and include some information about industry plans over the next several years. This report consists of two major sections. The first addresses uranium raw materials activities and covers the following topics: exploration activities and expenditures, resources and reserves, mine production of uranium, production of uranium concentrate, and industry employment. The second major section is concerned with the following uranium marketing activities: uranium purchase commitments, uranium prices, procurement arrangements, uranium imports and exports, enrichment services, inventories, secondary market activities utility market requirements and related topics

  18. Uranium Industry. Annual 1984

    International Nuclear Information System (INIS)

    Lawrence, M.S.S.

    1985-01-01

    This report provides a statistical description of activities of the US uranium industry during 1984 and includes a statistical profile of the status of the industry at the end of 1984. It is based on the results of an Energy Information Administration (EIA) survey entitled ''Uranium Industry Annual Survey'' (Form EIA-858). The principal findings of the survey are summarized under two headings - Uranium Raw Materials Activities and Uranium Marketing Activities. The first heading covers exploration and development, uranium resources, mine and mill production, and employment. The second heading covers uranium deliveries and delivery commitments, uranium prices, foreign trade in uranium, inventories, and other marketing activities. 32 figs., 48 tabs

  19. Study of ammonia synthesis over uranium catalysts

    International Nuclear Information System (INIS)

    Spitsyn, V.I.; Erofeev, B.V.; Mikhajlenko, I.E.; Gorelkin, I.I.; Ivanov, L.S.

    1980-01-01

    The effect of induced radiactivity and chemical composition of uranium catalysts on their catalytic activity in the ammonia synthesis reaction has been studied. The catalyst samples comprise pieces of metal uranium and chip irradiated in nuclear reactor by the 4.3x10 16 n/cm 2 integral flux of slow neutrons. Studies of catalytic activity was carried out at 1 atm and 340-510 deg C when stoichiometric nitrogen-hydrogen mixture passed through the following installation. At different temperatures uranium nitrides of different composition are shown to be formed. Uranium nitrides with the composition close to UN 2 are the samples with the highest catalYtic activity. The reduction of catalytic activity of uranium catalysts with the increased temperature of their formation above 400 deg C is explained by low catalytic activity of forming UNsub(1.7) in comparison with UN 2 . Catalytic properties of irradiated and nonirradiated samples do not differ from one another

  20. Pathways to diagnosis: a qualitative study of the experiences and emotional reactions of parents of children diagnosed with type 1 diabetes.

    Science.gov (United States)

    Rankin, David; Harden, Jeni; Waugh, Norman; Noyes, Kathryn; Barnard, Katharine D; Stephen, John; Robertson, Kenneth J; Bath, Louise; Robertson, Linda; Lawton, Julia

    2014-12-01

    The aim of this study was to explore from parents' perspectives the circumstances and events which led to their child being diagnosed with type 1 diabetes (T1D). The objective was to understand reasons for delays in seeking treatment and parents' emotional reactions to diagnosis so others can be better informed and supported in future. In-depth interviews with 54 parents of children (aged ≤12 yr) with T1D were conducted. Data analysis used an inductive, thematic approach. Parents described a 'prompt' and a 'delayed' pathway to their child being diagnosed. Parents who considered the diagnosis to be 'prompt' reported how they, or other people, had recognized their child had developed symptoms of T1D which resulted in a rapid presentation to health care professionals. In contrast, parents who perceived their child's diagnosis to be 'delayed' did not recognize signs of T1D and attributed their child's deteriorating health to other conditions, being out of routines and/or their stage of development. These parents often only sought medical help when symptoms became extreme. All parents were distressed by their child's diagnosis; however, parents in the 'delayed' pathway expressed unresolved feelings of guilt, particularly when their child was diagnosed with diabetic ketoacidosis. Parents' and other people's knowledge about T1D can affect the duration between onset of their child's symptoms and diagnosis. Campaigns to raise awareness should ensure that parents are made aware of symptoms and that T1D can develop during childhood. Health care professionals could discuss with parents the events preceding their child's diagnosis to better determine their emotional support needs. © 2014 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  1. Uranium ... long-term confidence

    International Nuclear Information System (INIS)

    Anon.

    1983-01-01

    Half way through 1983 the outlook for the world's uranium producers was far from bright if one takes a short term view. The readily accessible facts present a gloomy picture. The spot prices of uranium over the past few years decreased from a high of $42-$43/lb to a low of $17 in 1982. It now hovers between $23 and $24. the contract prices negotiated between producers and consumers are not so accessible but they do not reflect the spot price. The reasons why contractual uranium prices do not follow the usual dictates of supply and demand are related to the position in which uranium and associated power industries find themselves. There is public reaction with strong emotional overtones as well as much reduced expectations about the electric power needs of the world. Furthermore the supply of uranium is not guaranteed despite present over production. However the people in the industry, taking the medium- and long-term view, are not despondent

  2. Reducing emissions from uranium dissolving

    International Nuclear Information System (INIS)

    Griffith, W.L.; Compere, A.L.; Huxtable, W.P.; Googin, J.M.

    1992-10-01

    This study was designed to assess the feasibility of decreasing NO x emissions from the current uranium alloy scrap tray dissolving facility. In the current process, uranium scrap is dissolved in boiling nitric acid in shallow stainless-steel trays. As scrap dissolves, more metal and more nitric acid are added to the tray by operating personnel. Safe geometry is assured by keeping liquid level at or below 5 cm, the depth of a safe infinite slab. The accountability batch control system provides additional protection against criticality. Both uranium and uranium alloys are dissolved. Nitric acid is recovered from the vapors for reuse. Metal nitrates are sent to uranium recovery. Brown NO x fumes evolved during dissolving have occasionally resulted in a visible plume from the trays. The fuming is most noticeable during startup and after addition of fresh acid to a tray. Present environmental regulations are expected to require control of brown NO x emissions. A detailed review of the literature, indicated the feasibility of slightly altering process chemistry to favor the production of NO 2 which can be scrubbed and recycled as nitric acid. Methods for controlling the process to manage offgas product distribution and to minimize chemical reaction hazards were also considered

  3. Reaction-Based Reactive Transport Modeling of Iron Reduction and Uranium Immobilization at Area 2 of the NABIR Field Research Center, Subproject to Co-PI Eric E. Roden. Final Report

    International Nuclear Information System (INIS)

    Roden, Eric E.

    2011-01-01

    This report summarizes research conducted in conjunction with a project entitled 'Reaction-Based Reactive Transport Modeling of Iron Reduction and Uranium Immobilization at Area 2 of the NABIR Field Research Center', which was funded through the Integrative Studies Element of the former NABIR Program (now the Environmental Remediation Sciences Program) within the Office of Biological and Environmental Research. Dr. William Burgos (The Pennsylvania State University) was the overall PI/PD for the project, which included Brian Dempsey (Penn State), Gour-Tsyh (George) Yeh (Central Florida University), and Eric Roden (formerly at The University of Alabama, now at the University of Wisconsin) as separately-funded co-PIs. The project focused on development of a mechanistic understanding and quantitative models of coupled Fe(III)/U(VI) reduction in FRC Area 2 sediments. The work builds on our previous studies of microbial Fe(III) and U(VI) reduction, and was directly aligned with the Scheibe et al. ORNL FRC Field Project at Area 2.

  4. Uranium price reporting systems

    International Nuclear Information System (INIS)

    1987-09-01

    This report describes the systems for uranium price reporting currently available to the uranium industry. The report restricts itself to prices for U 3 O 8 natural uranium concentrates. Most purchases of natural uranium by utilities, and sales by producers, are conducted in this form. The bulk of uranium in electricity generation is enriched before use, and is converted to uranium hexafluoride, UF 6 , prior to enrichment. Some uranium is traded as UF 6 or as enriched uranium, particularly in the 'secondary' market. Prices for UF 6 and enriched uranium are not considered directly in this report. However, where transactions in UF 6 influence the reported price of U 3 O 8 this influence is taken into account. Unless otherwise indicated, the terms uranium and natural uranium used here refer exclusively to U 3 O 8 . (author)

  5. Uranium Industry Annual, 1992

    International Nuclear Information System (INIS)

    1993-01-01

    The Uranium Industry Annual provides current statistical data on the US uranium industry for the Congress, Federal and State agencies, the uranium and electric utility industries, and the public. The feature article, ''Decommissioning of US Conventional Uranium Production Centers,'' is included. Data on uranium raw materials activities including exploration activities and expenditures, resources and reserves, mine production of uranium, production of uranium concentrate, and industry employment are presented in Chapter 1. Data on uranium marketing activities including domestic uranium purchases, commitments by utilities, procurement arrangements, uranium imports under purchase contracts and exports, deliveries to enrichment suppliers, inventories, secondary market activities, utility market requirements, and uranium for sale by domestic suppliers are presented in Chapter 2

  6. Uranium Industry Annual, 1992

    Energy Technology Data Exchange (ETDEWEB)

    1993-10-28

    The Uranium Industry Annual provides current statistical data on the US uranium industry for the Congress, Federal and State agencies, the uranium and electric utility industries, and the public. The feature article, ``Decommissioning of US Conventional Uranium Production Centers,`` is included. Data on uranium raw materials activities including exploration activities and expenditures, resources and reserves, mine production of uranium, production of uranium concentrate, and industry employment are presented in Chapter 1. Data on uranium marketing activities including domestic uranium purchases, commitments by utilities, procurement arrangements, uranium imports under purchase contracts and exports, deliveries to enrichment suppliers, inventories, secondary market activities, utility market requirements, and uranium for sale by domestic suppliers are presented in Chapter 2.

  7. Oxidation of Tris (2-chloroethyl) phosphate in aqueous solution by UV-activated peroxymonosulfate: Kinetics, water matrix effects, degradation products and reaction pathways.

    Science.gov (United States)

    Xu, Xinxin; Chen, Jing; Qu, Ruijuan; Wang, Zunyao

    2017-10-01

    The feasibility of UV-activated peroxymonosulfate (PMS) technology for the degradation of Tris (2-chloroethyl) phosphate (TCEP) in an aqueous solution was investigated in this study. The conditions of [PMS] 0 : [TCEP] 0  = 20:1, T = 25 ± 2 °C and pH = 5.5 ± 0.5 cause a 94.6% removal of TCEP (1 mg L -1 ) after 30 min of Hg lamp irradiation. The effects of operating parameters (the oxidant doses, pH and presence of typical cations (Fe 3+ , Cu 2+ , Ni 2+ , NH 4 + ), anions (Cl - , HCO 3 - , NO 3 - , HPO 4 2- ) and humic acid (HA)) were evaluated. It was found that an increase of the PMS dose and the presence of Fe 3+ could accelerate the reaction, while the anions and HA inhibited the reaction. Meanwhile, TCEP removal in various water matrices was compared, and the order for TCEP removal was as follows: ultrapure water > tap water > synthetic water > secondary clarifier effluent > Jiuxiang river water. Twenty-two oxidation products were identified using an electrospray time-of-flight mass spectrometer, and the degradation pathways mainly involved radicals' addition and CO bond cleavage. Furthermore, ECOSAR analysis revealed that the intermediate products during the TCEP oxidation process were generally not harmful to three typical aquatic species. Hence, UV/PMS can be used as an efficient technology to treat TCEP-containing water and wastewaters. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. Photothermal deflection spectroscopy investigations of uranium electrochemistry

    International Nuclear Information System (INIS)

    Russo, R.E.; Rudnicki, J.D.

    1993-01-01

    Photothermal Deflection Spectroscopy (PDS) has been successfully applied to the study of uranium oxide electrochemistry. A brief description of PDS and preliminary results that demonstrate the technique are presented. Concentration gradients formed at the electrode surface are measured by this technique. The gradients give insight into the reaction mechanisms. There is some evidence of the initiation of non-electrochemical dissolution of the uranium oxide. Optical absorption by the uranium oxide is measured by PDS and the first results indicate that the absorption of the surface does not change during electrochemical experiments. This result is contrary to literature measurements of bulk samples that indicate that the optical absorption should be strongly changing

  9. Provision by the uranium and uranium products

    International Nuclear Information System (INIS)

    Elagin, Yu.P.

    2005-01-01

    International uranium market is converted from the buyer market into the seller market. The prices of uranium are high and the market attempts to adapt to changing circumstances. The industry of uranium enrichment satisfies the increasing demands but should to increase ots capacities. On the whole the situation is not stable and every year may change the existing position [ru

  10. Final Scientific/Technical Report - DE-FG02-06ER64172 - Reaction-Based Reactive Transport Modeling of Iron Reduction and Uranium Immobilization at Area 2 of the NABIR Field Research Center - Subproject to Co-PI Eric E. Roden

    International Nuclear Information System (INIS)

    Roden, Eric E.

    2009-01-01

    This report summarizes research conducted in conjunction with a project entitled 'Reaction-Based Reactive Transport Modeling of Iron Reduction and Uranium Immobilization at Area 2 of the NABIR Field Research Center', which was funded through the Integrative Studies Element of the former NABIR Program (now the Environmental Remediation Sciences Program) within the Office of Biological and Environmental Research. Dr. William Burgos (The Pennsylvania State University) was the overall PI/PD for the project, which included Brian Dempsey (Penn State), Gour-Tsyh (George) Yeh (Central Florida University), and Eric Roden (formerly at The University of Alabama, now at the University of Wisconsin) as separately-funded co-PIs. The project focused on development of a mechanistic understanding and quantitative models of coupled Fe(III)/U(VI) reduction in FRC Area 2 sediments. The work builds on our previous studies of microbial Fe(III) and U(VI) reduction, and was directly aligned with the Scheibe et al. ORNL FRC Field Project at Area 2. Area 2 is a shallow pathway for migration of contaminated groundwater to seeps in the upper reach of Bear Creek at ORNL, mainly through a ca. 1 m thick layer of gravel located 4-5 m below the ground surface. The gravel layer is sandwiched between an overlying layer of disturbed fill material, and 2-3 m of undisturbed shale saprolite derived from the underlying Nolichucky Shale bedrock. The fill was put in place when contaminated soils were excavated and replaced by native saprolite from an uncontaminated area within Bear Creek Valley; the gravel layer was presumably installed prior to addition of the fill in order to provide a stable surface for the operation of heavy machinery. The undisturbed saprolite is highly weathered bedrock that has unconsolidated character but retains much of the bedding and fracture structure of the parent rock (shale with interbedded limestone). Hydrological tracer studies conducted during the Scheibe et al. field

  11. Neutron-Induced Fission Cross Section of Uranium, Americium and Curium Isotopes. Progress report - Research Contract 14485, Coordinated Research Project on Minor Actinide Neutron Reaction Data (MANREAD)

    International Nuclear Information System (INIS)

    Alekseev, A.A.; Bergman, A.A.; Berlev, A.I.; Koptelov, E.A.; Samylin, B.F.; Trufanov, A.M.; Fursov, B.I.; Shorin, V.S.

    2009-12-01

    This report contains brief description of the Lead Slowing Down Spectrometer and results of measurements of neutron-induced fission cross sections for 236 U, 242m Am, 243 Cm, 244 Cm, 245 Cm and 246 Cm done at this spectrometer. The work was partially supported through the IAEA research contract RC-14485-RD in the framework of the IAEA Coordinated Research Project 'Minor Actinide Neutron Reaction Data (MANREAD)'. The detailed description of the experimental set up, measurements procedure and data treatment can be found in the JIA-1182 (2007) and JIA-1212 (2009) reports from the Institute of Nuclear Research of the Russian Academy of Science published in Russian. Part 1 contains the first year report of the research contract and part 2 the second year report. (author)

  12. Uranium enrichment

    International Nuclear Information System (INIS)

    Mohrhauer, H.

    1982-01-01

    The separation of uranium isotopes in order to enrich the fuel for light water reactors with the light isotope U-235 is an important part of the nuclear fuel cycle. After the basic principals of isotope separation the gaseous diffusion and the centrifuge process are explained. Both these techniques are employed on an industrial scale. In addition a short review is given on other enrichment techniques which have been demonstrated at least on a laboratory scale. After some remarks on the present situation on the enrichment market the progress in the development and the industrial exploitation of the gas centrifuge process by the trinational Urenco-Centec organisation is presented. (orig.)

  13. Bioaccumulation of uranium and thorium from the solution containing both elements using various microorganisms

    International Nuclear Information System (INIS)

    Tsuruta, T.

    2006-01-01

    The effects of proton, thorium and uranium on the bioaccumulation of thorium and uranium from the solution (pH 3.5) containing uranium and thorium using Streptomyces levoris cells were examined. The amount of thorium accumulated using the cells decreased by the pre-contact between the cells and the solution (pH 3.5) containing no metals, whereas that of uranium was almost unaffected by the treatment. The amount of thorium was almost unaffected by the existence of uranium. On the other hand, the amount of uranium accumulated was strongly affected by the thorium, especially thorium addition after uranium accumulation. The decrease of uranium accumulated by the addition of thorium after the accumulation of uranium was higher than that from the solution containing both elements. Therefore, the contribution of uranium-thorium exchange reaction was higher than that of competition reaction. Accordingly, proton-uranium-thorium exchange reaction was occurred in the accumulation of thorium from the solution containing thorium and uranium. The gram-positive bacteria, such as Micrococcus luteus, Arthrobacter nicotianae, Bacillus subtilis and B. megaterium, has a much higher separation factor as thorium/uranium than that of actinomycetes. These gram-positive bacterial strains can be used for the accumulation of thorium from the solution containing uranium and thorium

  14. Uranium conversion; Urankonvertering

    Energy Technology Data Exchange (ETDEWEB)

    Oliver, Lena; Peterson, Jenny; Wilhelmsen, Katarina [Swedish Defence Research Agency (FOI), Stockholm (Sweden)

    2006-03-15

    FOI, has performed a study on uranium conversion processes that are of importance in the production of different uranium compounds in the nuclear industry. The same conversion processes are of interest both when production of nuclear fuel and production of fissile material for nuclear weapons are considered. Countries that have nuclear weapons ambitions, with the intention to produce highly enriched uranium for weapons purposes, need some degree of uranium conversion capability depending on the uranium feed material available. This report describes the processes that are needed from uranium mining and milling to the different conversion processes for converting uranium ore concentrate to uranium hexafluoride. Uranium hexafluoride is the uranium compound used in most enrichment facilities. The processes needed to produce uranium dioxide for use in nuclear fuel and the processes needed to convert different uranium compounds to uranium metal - the form of uranium that is used in a nuclear weapon - are also presented. The production of uranium ore concentrate from uranium ore is included since uranium ore concentrate is the feed material required for a uranium conversion facility. Both the chemistry and principles or the different uranium conversion processes and the equipment needed in the processes are described. Since most of the equipment that is used in a uranium conversion facility is similar to that used in conventional chemical industry, it is difficult to determine if certain equipment is considered for uranium conversion or not. However, the chemical conversion processes where UF{sub 6} and UF{sub 4} are present require equipment that is made of corrosion resistant material.

  15. Issues in uranium availability

    International Nuclear Information System (INIS)

    Schanz, J.J. Jr.; Adams, S.S.; Gordon, R.L.

    1982-01-01

    The purpose of this publication is to show the process by which information about uranium reserves and resources is developed, evaluated and used. The following three papers in this volume have been abstracted and indexed for the Energy Data Base: (1) uranium reserve and resource assessment; (2) exploration for uranium in the United States; (3) nuclear power, the uranium industry, and resource development

  16. Australian uranium industry

    Energy Technology Data Exchange (ETDEWEB)

    Warner, R K

    1976-04-01

    Various aspects of the Australian uranium industry are discussed including the prospecting, exploration and mining of uranium ores, world supply and demand, the price of uranium and the nuclear fuel cycle. The market for uranium and the future development of the industry are described.

  17. Irradiated uranium reprocessing

    International Nuclear Information System (INIS)

    Gal, I.

    1961-12-01

    Task concerned with reprocessing of irradiated uranium covered the following activities: implementing the method and constructing the cell for uranium dissolving; implementing the procedure for extraction of uranium, plutonium and fission products from radioactive uranium solutions; studying the possibilities for using inorganic ion exchangers and adsorbers for separation of U, Pu and fission products

  18. Uranium processing and properties

    CERN Document Server

    2013-01-01

    Covers a broad spectrum of topics and applications that deal with uranium processing and the properties of uranium Offers extensive coverage of both new and established practices for dealing with uranium supplies in nuclear engineering Promotes the documentation of the state-of-the-art processing techniques utilized for uranium and other specialty metals

  19. Recovering uranium from phosphates

    Energy Technology Data Exchange (ETDEWEB)

    Bergeret, M [Compagnie de Produits Chimiques et Electrometallurgiques Pechiney-Ugine Kuhlmann, 75 - Paris (France)

    1981-06-01

    Processes for the recovery of the uranium contained in phosphates have today become competitive with traditional methods of working uranium sources. These new possibilities will make it possible to meet more rapidly any increases in the demand for uranium: it takes ten years to start working a new uranium deposit, but only two years to build a recovery plant.

  20. Uranium enrichment plans

    International Nuclear Information System (INIS)

    Gagne, R.W.; Thomas, D.C.

    1977-01-01

    The status of existing uranium enrichment contracts in the US is reviewed and expected natural uranium requirements for existing domestic uranium enrichment contracts are evaluated. Uncertainty in natural uranium requirements associated with requirements-type and fixed-commitment type contracts is discussed along with implementation of variable tails assay

  1. Uranium enrichment plans

    International Nuclear Information System (INIS)

    Thomas, D.C.; Gagne, R.W.

    1978-01-01

    The following topics are covered: the status of the Government's existing uranium enrichment services contracts, natural uranium requirements based on the latest contract information, uncertainty in predicting natural uranium requirements based on uranium enrichment contracts, and domestic and foreign demand assumed in enrichment planning

  2. Metabolomics identifies a biological response to chronic low-dose natural uranium contamination in urine samples.

    Science.gov (United States)

    Grison, Stéphane; Favé, Gaëlle; Maillot, Matthieu; Manens, Line; Delissen, Olivia; Blanchardon, Eric; Banzet, Nathalie; Defoort, Catherine; Bott, Romain; Dublineau, Isabelle; Aigueperse, Jocelyne; Gourmelon, Patrick; Martin, Jean-Charles; Souidi, Maâmar

    2013-01-01

    Because uranium is a natural element present in the earth's crust, the population may be chronically exposed to low doses of it through drinking water. Additionally, the military and civil uses of uranium can also lead to environmental dispersion that can result in high or low doses of acute or chronic exposure. Recent experimental data suggest this might lead to relatively innocuous biological reactions. The aim of this study was to assess the biological changes in rats caused by ingestion of natural uranium in drinking water with a mean daily intake of 2.7 mg/kg for 9 months and to identify potential biomarkers related to such a contamination. Subsequently, we observed no pathology and standard clinical tests were unable to distinguish between treated and untreated animals. Conversely, LC-MS metabolomics identified urine as an appropriate biofluid for discriminating the experimental groups. Of the 1,376 features detected in urine, the most discriminant were metabolites involved in tryptophan, nicotinate, and nicotinamide metabolic pathways. In particular, N -methylnicotinamide, which was found at a level seven times higher in untreated than in contaminated rats, had the greatest discriminating power. These novel results establish a proof of principle for using metabolomics to address chronic low-dose uranium contamination. They open interesting perspectives for understanding the underlying biological mechanisms and designing a diagnostic test of exposure.

  3. Pyrophoricity of uranium in long-term storage environments

    International Nuclear Information System (INIS)

    Solbrig, C.W.; Krsul, J.R.; Olsen, D.N.

    1994-01-01

    A corrosion cycle for uranium is postulated which can be used to assess whether a given storage situation might produce fire hazards and/or continual uranium corrosion. A significant reaction rate of uranium and moisture occurs at room temperature which produces uranium oxide and hydrogen. If the hydrogen cannot escape, it will react slowly with uranium to form uranium hydride. The hydride is pyrophoric at room temperature when exposed to air. Either the hydrogen or the hydride can produce a dangerous situation as demonstrated by two different incidents described here. Long-term corrosion will occur even if the normal precautions are taken as is demonstrated by the long-term storage of stainless steel clad uranium fuel plates. The major initiator of these problems is attributed to any moisture condensed on the metal or any brought in by the cover gas. The postulated corrosion cycle is used to suggest ways to circumvent these problems

  4. Ghrelin protects against depleted uranium-induced apoptosis of MC3T3-E1 cells through oxidative stress-mediated p38-mitogen-activated protein kinase pathway

    Energy Technology Data Exchange (ETDEWEB)

    Hao, Yuhui; Liu, Cong; Huang, Jiawei; Gu, Ying; Li, Hong; Yang, Zhangyou; Liu, Jing [State Key Laboratory of Trauma, Burns and Combined Injury, Institute of Combined Injury, Chongqing Engineering Research Center for Nanomedicine, College of Preventive Medicine, Third Military Medical University, No. 30 Gaotanyan Street, Shapingba District, Chongqing 400038 (China); Wang, Weidong, E-mail: wwdwyl@sina.com [Department of Radiation Oncology, Shanghai Jiao Tong University Affiliated Sixth People Hospital, Shanghai 200233 (China); Li, Rong, E-mail: yuhui_hao@126.com [State Key Laboratory of Trauma, Burns and Combined Injury, Institute of Combined Injury, Chongqing Engineering Research Center for Nanomedicine, College of Preventive Medicine, Third Military Medical University, No. 30 Gaotanyan Street, Shapingba District, Chongqing 400038 (China)

    2016-01-01

    Depleted uranium (DU) mainly accumulates in the bone over the long term. Osteoblast cells are responsible for the formation of bone, and they are sensitive to DU damage. However, studies investigating methods of reducing DU damage in osteoblasts are rarely reported. Ghrelin is a stomach hormone that stimulates growth hormones released from the hypothalamic–pituitary axis, and it is believed to play an important physiological role in bone metabolism. This study evaluates the impact of ghrelin on DU-induced apoptosis of the osteoblast MC3T3-E1 and investigates its underlying mechanisms. The results show that ghrelin relieved the intracellular oxidative stress induced by DU, eliminated reactive oxygen species (ROS) and reduced lipid peroxidation by increasing intracellular GSH levels; in addition, ghrelin effectively suppressed apoptosis, enhanced mitochondrial membrane potential, and inhibited cytochrome c release and caspase-3 activation after DU exposure. Moreover, ghrelin significantly reduced the expression of DU-induced phosphorylated p38-mitogen-activated protein kinase (MAPK). A specific inhibitor (SB203580) or specific siRNA of p38-MAPK could significantly suppress DU-induced apoptosis and related signals, whereas ROS production was not affected. In addition, ghrelin receptor inhibition could reduce the anti-apoptosis effect of ghrelin on DU and reverse the effect of ghrelin on intracellular ROS and p38-MAPK after DU exposure. These results suggest that ghrelin can suppress DU-induced apoptosis of MC3T3-E1 cells, reduce DU-induced oxidative stress by interacting with its receptor, and inhibit downstream p38-MAPK activation, thereby suppressing the mitochondrial-dependent apoptosis pathway. - Highlights: • Ghrelin suppressed DU-induced apoptosis of MC3T3-E1 cells. • Ghrelin inhibited DU-induced oxidative stress and further p38-MAPK activation. • Ghrelin further suppressed mitochondrial-dependent apoptosis pathway. • The anti-oxidation effect of

  5. Uranium industry annual 1985

    International Nuclear Information System (INIS)

    1986-11-01

    This report consists of two major sections. The first addresses uranium raw materials activities and covers the following topics: exploration activities and expenditures, resources and reserves, mine production of uranium, production of uranium concentrate, and industry employment. The second major section is concerned with the following uranium marketing activities: uranium purchase commitments, uranium prices, procurement arrangements, uranium imports and exports, enrichment services, inventories, secondary market activities, utility market requirements, and related topics. A glossary and appendices are included to assist the reader in interpreting the substantial array of statistical data in this report and to provide background information about the survey

  6. Uranium industry framework

    International Nuclear Information System (INIS)

    Riley, K.

    2008-01-01

    The global uranium market is undergoing a major expansion due to an increase in global demand for uranium, the highest uranium prices in the last 20 years and recognition of the potential greenhouse benefits of nuclear power. Australia holds approximately 27% of the world's uranium resources (recoverable at under US$80/kg U), so is well placed to benefit from the expansion in the global uranium market. Increasing exploration activity due to these factors is resulting in the discovery and delineation of further high grade uranium deposits and extending Australia's strategic position as a reliable and safe supplier of low cost uranium.

  7. Formation mechanism of uranium minerals at sandstone-type uranium deposits

    International Nuclear Information System (INIS)

    Li Shengfu; Zhang Yun

    2004-01-01

    By analyzing the behavior and existence form of uranium in different geochemical environments, existence form of uranium and uranium minerals species, this paper expounds the formation mechanism of main commercial uranium mineral--pitchblende: (1) uranium is a valence-changeable element. It is reactivated and migrates in oxidized environment, and is reduced and precipitated in reducing environment; (2) [UO 2 (CO 3 ) 3 ] 4- , [UO 2 (CO 3 ) 2 ] 2- coming from oxidized environment react with reductants such as organic matter, sulfide and low-valence iron at the redox front to form simple uranium oxide--pitchblende; (3)the adsorption of uranium by organic matter and clay minerals accelerates the reduction and the concentration of uranium. Therefore, it is considered, that the reduction of SO 4 2- by organic matter to form H 2 S, and the reduction of UO 2 2+ by H 2 S are the main reasons for the formation of pitchblende. This reaction is extensively and universally available in neutral and weakly alkaline carbonate solution. The existense of reductants such as H 2 S is the basic factor leading to the decrease of Eh in environments and the oversaturation of UO 2 2+ at the redox front in groundwater, thus accelerating the adsorption and the precipitation of uranium

  8. Energy consumption of chemical uranium enrichment

    International Nuclear Information System (INIS)

    Miyake, T.; Takeda, K.; Obanawa, H.

    1987-01-01

    A quantitative study of chemical separation energy for enriching uranium-235 by the redox chromatography was conducted. Isotope exchange reactions between U 4+ -UO 2 2+ ions in the enrichment column are maintained by the redox reactions. The chemical separation energy is ultimately supplied by hydrogen and oxygen gas for regenerating redox agents. The redox energy for the isotope separation is theoretically predicted as a function of the dynamic enrichment factor observed in the chromatographic development of uranium adsorption band. Thermodynamic treatments of the equilibrium reactions implies and inverse redox reaction which can be enhanced by the chemical potential of the ion-exchange reaction of oxidant. Experimental results showed 30 to 90% recovery of the redox energy by the inverse reaction. These results will devise a simplified redox chromatography process where a number of columns in one module is reduced

  9. Preparation and Purification of natural uranium metal by Iodine method

    International Nuclear Information System (INIS)

    Taies, J.A.

    2008-01-01

    In this work ,glass-metal apparatus was designed and manufactured which used for preparing a high purity uranium.The reaction is simply take place between iodine vapour and uranium metal at 500C in closed system to form uranium tetra iodide which is decomposed on hot wire at high temperature around 1100C.Also another apparatus was made from Glass and used for preparing a high purity of UI 4 more than 99.9%purity

  10. Uranium - the world picture

    International Nuclear Information System (INIS)

    Silver, J.M.; Wright, W.J.

    1976-01-01

    The world resources of uranium and the future demand for uranium are discussed. The amount of uranium available depends on the price which users are prepared to pay for its recovery. As the price is increased, there is an incentive to recover uranium from lower grade or more difficult deposits. In view of this, attention is drawn to the development of the uranium industry in Australias

  11. Retention and reduction of uranium on pyrite surface

    International Nuclear Information System (INIS)

    Eglizaud, N.

    2006-12-01

    In the hypothesis of a storage of the spent fuel in a deep geological formation, understanding the uranium dispersion in the environment is important. Pyrite is a reducing mineral present in the Callovo-Oxfordian argilites, the geological formation actually studied for such a storage. However, pyrite impact on uranium migration has already been poorly studied. The aim of the study was to understand the mechanisms of uranium(VI) retention and reduction on the pyrite surface (FeS 2 ). Solution chemistry was therefore coupled with solid spectroscopic studies (XPS and Raman spectroscopy). All uranium-pyrite interactions experiments were performed under an anoxic atmosphere, in a glove box. Pyrite dissolution under anoxic conditions releases sulfoxy-anions and iron(II), which can then be adsorbed on the pyrite surface. This adsorption was confirmed by interaction experiments using iron(II) isotopic dilution. Uranium(VI) is retained by an exchange reaction with iron(II) adsorbed on sulphur sites, with a maximal amount of sorbed uranium at pH ≥ 5.5. Cobalt(II) and europium(III) are also adsorbed on the pyrite surface above pH 5.5 confirming then that reduction is not required for species to adsorb on pyrite. When the concentration of uranium retained is lower than 4 x 10 -9 mol g -1 , an oxidation-reduction reaction leads to the formation of a uranium (VI) (IV) mixed oxide and to solid sulphur (d.o. ≥ -I). During this reaction, iron remains mostly at the +II oxidation degree. The reaction products seem to passivate the pyrite surface: at higher amounts of retained uranium, the oxidation-reduction reaction is no longer observed. The surface is saturated by the retention of (3.4 ± 0.8) x 10 -7 mol L -1 of uranium(VI). Modelling of uranium sorption at high surface coverage (≥ 4 x 10 -9 mol g -1 ) by the Langmuir model yields an adsorption constant of 8 x 10 7 L mol -1 . Finally, a great excess of uranium(VI) above the saturation concentration allows the observation of

  12. Effects of urban air pollution on the inflammatory reaction: involvement of the chemokine pathways; Impact de la pollution atmospherique urbaine sur la reponse inflammatoire: implication des chimiokines

    Energy Technology Data Exchange (ETDEWEB)

    Fahy, O.

    2000-12-01

    Urban air pollution is both gaseous and particulate, and diesel exhausts are now the main source of particles. Diesel particles consist of a carbon core with multiple adsorbed organic compounds, among witch poly-aromatic hydrocarbons. These diesel particles and associated poly-aromatic hydrocarbons are likely to play a role in the recent increase in allergic diseases. In this study, we evaluated the effects of diesel organic extracts on the initiation and the orientation of the allergen-dependent inflammatory reaction by analyzing the dis-regulation of a family of mediators involved in cellular recruitment: the chemokines. We demonstrated that mononuclear cells and alveolar macrophages from normal subjects displayed a dis-regulation in pro-inflammatory chemokine expression and production (IL-8, MCP-1, RANTES) when exposed to diesel organic extracts. In addition we observed a synergy between the effects of diesel and allergen when cells from allergic patients were exposed to both simultaneously, leading to a strong over-production of chemokines, and to the increased capacity of recruiting effector cells such as neutrophils and eosinophils. The MAP kinase pathways seemed largely involved in the transduction of diesel and allergen stimulus, since a specific inhibition almost abolished the dis-regulation of chemokine production. Diesel and allergen also appeared to favour the establishment of a type 2 immune response (pro-allergenic), by preferentially recruiting Th2 lymphocytes via the dis-regulation of chemokine expression (MDC and IP-10). Finally, the humanized SCID mouse model grafted with autologous human skin allowed the in vivo evaluation of a local over-production of chemokine, by analyzing the cellular recruitment in the skin after intra-dermal injection of recombinant chemokines. This model appears useful for the study of the mechanisms of cellular recruitment by chemokines and the potential therapeutic approaches. In conclusion, our study underlines the

  13. Natural uranium

    International Nuclear Information System (INIS)

    Ammerich, Marc; Frot, Patricia; Gambini, Denis-Jean; Gauron, Christine; Moureaux, Patrick; Herbelet, Gilbert; Lahaye, Thierry; Pihet, Pascal; Rannou, Alain

    2014-08-01

    This sheet belongs to a collection which relates to the use of radionuclides essentially in unsealed sources. Its goal is to gather on a single document the most relevant information as well as the best prevention practices to be implemented. These sheets are made for the persons in charge of radiation protection: users, radioprotection-skill persons, labor physicians. Each sheet treats of: 1 - the radio-physical and biological properties; 2 - the main uses; 3 - the dosimetric parameters; 4 - the measurement; 5 - the protection means; 6 - the areas delimitation and monitoring; 7 - the personnel classification, training and monitoring; 8 - the effluents and wastes; 9 - the authorization and declaration administrative procedures; 10 - the transport; and 11 - the right conduct to adopt in case of incident or accident. This sheet deals specifically with natural uranium

  14. Synthesis of uranium metal using laser-initiated reduction of uranium tetrafluoride by calcium metal

    International Nuclear Information System (INIS)

    West, M.H.; Martinez, M.M.; Nielsen, J.B.; Court, D.C.; Appert, Q.D.

    1995-09-01

    Uranium metal has numerous uses in conventional weapons (armor penetrators) and nuclear weapons. It also has application to nuclear reactor designs utilizing metallic fuels--for example, the former Integral Fast Reactor program at Argonne National Laboratory. Uranium metal also has promise as a material of construction for spent-nuclear-fuel storage casks. A new avenue for the production of uranium metal is presented that offers several advantages over existing technology. A carbon dioxide (CO 2 ) laser is used to initiate the reaction between uranium tetrafluoride (UF 4 ) and calcium metal. The new method does not require induction heating of a closed system (a pressure vessel) nor does it utilize iodine (I 2 ) as a chemical booster. The results of five reductions of UF 4 , spanning 100 to 200 g of uranium, are evaluated, and suggestions are made for future work in this area

  15. Uranium management activities

    International Nuclear Information System (INIS)

    Jackson, D.; Marshall, E.; Sideris, T.; Vasa-Sideris, S.

    2001-01-01

    One of the missions of the Department of Energy's (DOE) Oak Ridge Office (ORO) has been the management of the Department's uranium materials. This mission has been accomplished through successful integration of ORO's uranium activities with the rest of the DOE complex. Beginning in the 1980's, several of the facilities in that complex have been shut down and are in the decommissioning process. With the end of the Cold War, the shutdown of many other facilities is planned. As a result, inventories of uranium need to be removed from the Department facilities. These inventories include highly enriched uranium (HEU), low enriched uranium (LEU), normal uranium (NU), and depleted uranium (DU). The uranium materials exist in different chemical forms, including metals, oxides, solutions, and gases. Much of the uranium in these inventories is not needed to support national priorities and programs. (author)

  16. Preliminary study of the preparation of uranium 232 by irradiation of protactinium 231

    International Nuclear Information System (INIS)

    Guillot, Ph.

    1965-01-01

    A bibliography about preparation of uranium 232 is done. This even-even isotope of uranium is suitable for radioactive tracer, neutron source through α,n reaction and heat source applications. The irradiation of protactinium 231, the chemical separation and the purification of uranium are studied. (author) [fr

  17. Uranium industry annual 1998

    International Nuclear Information System (INIS)

    1999-01-01

    The Uranium Industry Annual 1998 (UIA 1998) provides current statistical data on the US uranium industry's activities relating to uranium raw materials and uranium marketing. It contains data for the period 1989 through 2008 as collected on the Form EIA-858, ''Uranium Industry Annual Survey.'' Data provides a comprehensive statistical characterization of the industry's activities for the survey year and also include some information about industry's plans and commitments for the near-term future. Data on uranium raw materials activities for 1989 through 1998, including exploration activities and expenditures, EIA-estimated reserves, mine production of uranium, production of uranium concentrate, and industry employment, are presented in Chapter 1. Data on uranium marketing activities for 1994 through 2008, including purchases of uranium and enrichment services, enrichment feed deliveries, uranium fuel assemblies, filled and unfilled market requirements, and uranium inventories, are shown in Chapter 2. The methodology used in the 1998 survey, including data edit and analysis, is described in Appendix A. The methodologies for estimation of resources and reserves are described in Appendix B. A list of respondents to the ''Uranium Industry Annual Survey'' is provided in Appendix C. The Form EIA-858 ''Uranium Industry Annual Survey'' is shown in Appendix D. For the readers convenience, metric versions of selected tables from Chapters 1 and 2 are presented in Appendix E along with the standard conversion factors used. A glossary of technical terms is at the end of the report. 24 figs., 56 tabs

  18. Uranium industry annual 1994

    International Nuclear Information System (INIS)

    1995-01-01

    The Uranium Industry Annual 1994 (UIA 1994) provides current statistical data on the US uranium industry's activities relating to uranium raw materials and uranium marketing during that survey year. The UIA 1994 is prepared for use by the Congress, Federal and State agencies, the uranium and nuclear electric utility industries, and the public. It contains data for the 10-year period 1985 through 1994 as collected on the Form EIA-858, ''Uranium Industry Annual Survey.'' Data collected on the ''Uranium Industry Annual Survey'' (UIAS) provide a comprehensive statistical characterization of the industry's activities for the survey year and also include some information about industry's plans and commitments for the near-term future. Where aggregate data are presented in the UIA 1994, care has been taken to protect the confidentiality of company-specific information while still conveying accurate and complete statistical data. A feature article, ''Comparison of Uranium Mill Tailings Reclamation in the United States and Canada,'' is included in the UIA 1994. Data on uranium raw materials activities including exploration activities and expenditures, EIA-estimated resources and reserves, mine production of uranium, production of uranium concentrate, and industry employment are presented in Chapter 1. Data on uranium marketing activities, including purchases of uranium and enrichment services, and uranium inventories, enrichment feed deliveries (actual and projected), and unfilled market requirements are shown in Chapter 2

  19. The discovery of uranium fission

    International Nuclear Information System (INIS)

    Brix, P.

    1990-01-01

    Uranium was discovered 200 years ago. Its radioactive character was first demonstrated in 1896 and two years later radium was extracted from uranium minerals. In 1911 studies with alpha rays from radioactive decay led to the unexpected discovery of the atomic nucleus. Exposure of beryllium to alpha rays yielded neutrons, first detected in 1932. Starting in 1934, neutron irradiation of uranium produced radioactive substances erroneously attributed to transuranium elements but with confusing properties. Painstaking experiments by chemists left no doubt on 17 December 1938 that barium was produced by these irradiations: the neutrons had split some uranium nuclei. The physics of the fission process was understood two weeks later; after a few months, neutron multiplication was found to be probable. This review deals with the eminent scientists involved, their successes, errors and disappointments, and the unexpected insights which occurred on the paths and detours of scientific research. It is, therefore, instructive also to discuss how fission was not discovered. The momentous discovery must be considered inevitable; the great tragedy was that Germany started World War II just at the time when the possibility of nuclear chain reactions and bombs became known. The consequences and anxieties that remain after 50 years of nuclear fission demand that mankind act with reason and conscience to maintain peace. (author)

  20. Uranium: a basic evaluation

    International Nuclear Information System (INIS)

    Crull, A.W.

    1978-01-01

    All energy sources and technologies, including uranium and the nuclear industry, are needed to provide power. Public misunderstanding of the nature of uranium and how it works as a fuel may jeopardize nuclear energy as a major option. Basic chemical facts about uranium ore and uranium fuel technology are presented. Some of the major policy decisions that must be made include the enrichment, stockpiling, and pricing of uranium. Investigations and lawsuits pertaining to uranium markets are reviewed, and the point is made that oil companies will probably have to divest their non-oil energy activities. Recommendations for nuclear policies that have been made by the General Accounting Office are discussed briefly

  1. Uranium health physics

    International Nuclear Information System (INIS)

    1980-01-01

    This report contains the papers delivered at the Summer School on Uranium Health Physics held in Pretoria on the 14 and 15 April 1980. The following topics were discussed: uranium producton in South Africa; radiation physics; internal dosimetry and radiotoxicity of long-lived uranium isotopes; uranium monitoring; operational experience on uranium monitoring; dosimetry and radiotoxicity of inhaled radon daughters; occupational limits for inhalation of radon-222, radon-220 and their short-lived daughters; radon monitoring techniques; radon daughter dosimeters; operational experience on radon monitoring; and uranium mill tailings management

  2. Uranium: one utility's outlook

    International Nuclear Information System (INIS)

    Gass, C.B.

    1983-01-01

    The perspective of the Arizona Public Service Company (APS) on the uncertainty of uranium as a fuel supply is discussed. After summarizing the history of nuclear power and the uranium industries, a projection is made for the future uranium market. An uncrtain uranium market is attributed to various determining factors that include international politics, production costs, non-commercial government regulation, production-company stability, and questionable levels of uranium sales. APS offers its solutions regarding type of contract, choice of uranium producers, pricing mechanisms, and aids to the industry as a whole. 5 references, 10 figures, 1 table

  3. Dry uranium tetrafluoride process preparation using the uranium hexafluoride reconversion process effluents

    International Nuclear Information System (INIS)

    Silva Neto, Joao Batista da

    2008-01-01

    It is a well known fact that the use of uranium tetrafluoride allows flexibility in the production of uranium suicide and uranium oxide fuel. To its obtention there are two conventional routes, the one which reduces uranium from the UF 6 hydrolysis solution with stannous chloride, and the hydro fluorination of a solid uranium dioxide. In this work we are introducing a third and a dry way route, mainly utilized to the recovery of uranium from the liquid effluents generated in the uranium hexafluoride reconversion process, at IPEN/CNEN-SP. Working in the liquid phase, this route comprises the recuperation of ammonium fluoride by NH 4 HF 2 precipitation. Working with the solid residues, the crystallized bifluoride is added to the solid UO 2 , which comes from the U mini plates recovery, also to its conversion in a solid state reaction, to obtain UF 4 . That returns to the process of metallic uranium production unity to the U 3 Si 2 obtention. This fuel is considered in IPEN CNEN/SP as the high density fuel phase for IEA-R1m reactor, which will replace the former low density U 3 Si 2 -Al fuel. (author)

  4. Recovery of uranium from crude uranium tetrafluoride

    International Nuclear Information System (INIS)

    Ghosh, S.K.; Bellary, M.P.; Keni, V.S.

    1994-01-01

    An innovative process has been developed for recovery of uranium from crude uranium tetrafluoride cake. The process is based on direct dissolution of uranium tetrafluoride in nitric acid in presence of aluminium hydroxide and use of solvent extraction for removal of fluorides and other bulk impurities to make uranium amenable for refining. It is a simple process requiring minimum process step and has advantage of lesser plant corrosion. This process can be applied for processing of uranium tetrafluoride generated from various sources like uranium by-product during thorium recovery from thorium concentrate, first stage product of uranium recovery from phosphoric acid by OPPA process and off grade uranium tetrafluoride material. The paper describes the details of the process developed and demonstrated on bench and pilot scale and its subsequent modification arising out of bulky solid waste generation. The modified process uses a lower quantity of aluminium hydroxide by allowing a lower dissolution of uranium per cycle and recycles the undissolved material to the next cycle, maintaining the overall recovery at high level. This innovation has reduced the solid waste generated by a factor of four at the cost of a slightly larger dissolution vessel and its increased corrosion rate. (author)

  5. Recovery of uranium from crude uranium tetrafluoride

    Energy Technology Data Exchange (ETDEWEB)

    Ghosh, S K; Bellary, M P; Keni, V S [Chemical Engineering Division, Bhabha Atomic Research Centre, Mumbai (India)

    1994-06-01

    An innovative process has been developed for recovery of uranium from crude uranium tetrafluoride cake. The process is based on direct dissolution of uranium tetrafluoride in nitric acid in presence of aluminium hydroxide and use of solvent extraction for removal of fluorides and other bulk impurities to make uranium amenable for refining. It is a simple process requiring minimum process step and has advantage of lesser plant corrosion. This process can be applied for processing of uranium tetrafluoride generated from various sources like uranium by-product during thorium recovery from thorium concentrate, first stage product of uranium recovery from phosphoric acid by OPPA process and off grade uranium tetrafluoride material. The paper describes the details of the process developed and demonstrated on bench and pilot scale and its subsequent modification arising out of bulky solid waste generation. The modified process uses a lower quantity of aluminium hydroxide by allowing a lower dissolution of uranium per cycle and recycles the undissolved material to the next cycle, maintaining the overall recovery at high level. This innovation has reduced the solid waste generated by a factor of four at the cost of a slightly larger dissolution vessel and its increased corrosion rate. (author). 4 refs., 1 fig., 3 tabs.

  6. Production and analysis of ultradispersed uranium oxide powders

    Science.gov (United States)

    Zajogin, A. P.; Komyak, A. I.; Umreiko, D. S.; Umreiko, S. D.

    2010-05-01

    Spectroscopic studies are made of the laser plasma formed near the surface of a porous body containing nanoquantities of uranium compounds which is irradiated by two successive laser pulses. The feasibility of using laser chemical methods for obtaining nanoclusters of uranium oxide particles in the volume of a porous body and the simultaneous possibility of determining the uranium content with good sensitivity are demonstrated. The thermochemical and spectral characteristics of the analogs of their compounds with chlorine are determined and studied. The possibility of producing uranium dioxides under ordinary conditions and their analysis in the reaction products is demonstrated.

  7. Uranium production

    International Nuclear Information System (INIS)

    Jones, J.Q.

    1981-01-01

    The domestic uranium industry is in a state of stagflation. Costs continue to rise while the market for the product remains stagnant. During the last 12 months, curtailments and closures of mines and mills have eliminated over 5000 jobs in the industry, plus many more in those industries that furnish supplies and services. By January 1982, operations at four mills and the mines that furnish them ore will have been terminated. Other closures may follow, depending on cost trends, duration of current contracts, the degree to which mills have been amortized, the feasibility of placing mines on standby, the grade of the ore, and many other factors. Open-pit mines can be placed on standby without much difficulty, other than the possible cost of restoration before all the ore has been removed. There are a few small, dry, underground mines that could be mothballed; however, the major underground producers are wet sandstone mines that in most cases could not be reopened after a prolonged shutdown; mills can be mothballed for several years. Figure 8 shows the location of all the production centers in operation, as well as those that have operated or are on standby. Table 1 lists the same production centers plus those that have been deferred, showing nominal capacity of conventional mills in tons of ore per calendar day, and the industry production rate for those mills as of October 1, 1981

  8. Uranium Sequestration by Aluminum Phosphate Minerals in Unsaturated Soils

    International Nuclear Information System (INIS)

    Jerden, James L. Jr.

    2007-01-01

    A mineralogical and geochemical study of soils developed from the unmined Coles Hill uranium deposit (Virginia) was undertaken to determine how phosphorous influences the speciation of uranium in an oxidizing soil/saprolite system typical of the eastern United States. This paper presents mineralogical and geochemical results that identify and quantify the processes by which uranium has been sequestered in these soils. It was found that uranium is not leached from the saturated soil zone (saprolites) overlying the deposit due to the formation of a sparingly soluble uranyl phosphate mineral of the meta-autunite group. The concentration of uranium in the saprolites is approximately 1000 mg uranium per kg of saprolite. It was also found that a significant amount of uranium was retained in the unsaturated soil zone overlying uranium-rich saprolites. The uranium concentration in the unsaturated soils is approximately 200 mg uranium per kg of soil (20 times higher than uranium concentrations in similar soils adjacent to the deposit). Mineralogical evidence indicates that uranium in this zone is sequestered by a barium-strontium-calcium aluminum phosphate mineral of the crandallite group (gorceixite). This mineral is intimately inter-grown with iron and manganese oxides that also contain uranium. The amount of uranium associated with both the aluminum phosphates (as much as 1.4 weight percent) has been measured by electron microprobe micro-analyses and the geochemical conditions under which these minerals formed has been studied using thermodynamic reaction path modeling. The geochemical data and modeling results suggest the meta-autunite group minerals present in the saprolites overlying the deposit are unstable in the unsaturated zone soils overlying the deposit due to a decrease in soil pH (down to a pH of 4.5) at depths less than 5 meters below the surface. Mineralogical observations suggest that, once exposed to the unsaturated environment, the meta-autunite group

  9. Uranium mining in Australia

    International Nuclear Information System (INIS)

    Anon.

    1980-01-01

    Known uranium deposits and the companies involved in uranium mining and exploration in Australia are listed. The status of the development of the deposits is outlined and reasons for delays to mining are given

  10. Uranium Processing Facility

    Data.gov (United States)

    Federal Laboratory Consortium — An integral part of Y‑12's transformation efforts and a key component of the National Nuclear Security Administration's Uranium Center of Excellence, the Uranium...

  11. Uranium in Niger

    International Nuclear Information System (INIS)

    Gabelmann, E.

    1978-03-01

    This document presents government policy in the enhancement of uranium resources, existing mining companies and their productions, exploitation projects and economical outcome related to the uranium mining and auxiliary activities [fr

  12. Price of military uranium

    International Nuclear Information System (INIS)

    Klimenko, A.V.

    1998-01-01

    The theoretical results about optimum strategy of use of military uranium confirmed by systems approach accounts are received. The numerical value of the system approach price of the highly enriched military uranium also is given

  13. Uranium market and resources

    International Nuclear Information System (INIS)

    Capus, G.; Arnold, Th.

    2004-01-01

    The controversy about the extend of the uranium resources worldwide is still important, this article sheds some light on this topic. Every 2 years IAEA and NEA (nuclear energy agency) edit an inventory of uranium resources as reported by contributing countries. It appears that about 4.6 millions tons of uranium are available at a recovery cost less than 130 dollars per kg of uranium and a total of 14 millions tons of uranium can be assessed when including all existing or supposed resources. In fact there is enough uranium to sustain a moderate growth of the park of nuclear reactors during next decades and it is highly likely that the volume of uranium resources can allow a more aggressive development of nuclear energy. It is recalled that a broad use of the validated breeder technology can stretch the durability of uranium resources by a factor 50. (A.C.)

  14. Uranium from phosphate ores

    International Nuclear Information System (INIS)

    Hurst, F.J.

    1983-01-01

    The following topics are described briefly: the way phosphate fertilizers are made; how uranium is recovered in the phosphate industry; and how to detect covert uranium recovery operations in a phsophate plant

  15. Industrial realities: Uranium

    International Nuclear Information System (INIS)

    Thiron, H.

    1990-01-01

    In this special issue are examined ores and metals in France and in the world for 1988. The chapter on uranium gives statistical data on the uranium market: Demand, production, prices and reserves [fr

  16. Brazilian uranium deposits

    International Nuclear Information System (INIS)

    Santos, L.C.S. dos.

    1985-01-01

    Estimatives of uranium reserves carried out in Figueira, Itataia, Lagoa Real and Espinharas, in Brazil are presented. The samples testing allowed to know geological structures, and the characteristics of uranium mineralization. (M.C.F.) [pt

  17. Uranium mining in Australia

    International Nuclear Information System (INIS)

    Anon.

    1984-01-01

    The mining of uranium in Australia is criticised in relation to it's environmental impact, economics and effects on mine workers and Aborigines. A brief report is given on each of the operating and proposed uranium mines in Australia

  18. Uranium mining in Australia

    International Nuclear Information System (INIS)

    Mackay, G.A.

    1978-01-01

    Western world requirements for uranium based on increasing energy consumption and a changing energy mix, will warrant the development of Australia's resources. By 1985 Australian mines could be producing 9500 tonnes of uranium oxide yearly and by 1995 the export value from uranium could reach that from wool. In terms of benefit to the community the economic rewards are considerable but, in terms of providing energy to the world, Australias uranium is vital

  19. Radiation damage of uranium

    International Nuclear Information System (INIS)

    Lazarevic, Dj.

    1966-11-01

    Study of radiation damage covered the following: Kinetics of electric resistance of uranium and uranium alloy with 1% of molybdenum dependent on the second phase and burnup rate; Study of gas precipitation and diffusion of bubbles by transmission electron microscopy; Numerical analysis of the influence of defects distribution and concentration on the rare gas precipitation in uranium; study of thermal sedimentation of uranium alloy with molybdenum; diffusion of rare gas in metal by gas chromatography method

  20. Bicarbonate leaching of uranium

    International Nuclear Information System (INIS)

    Mason, C.

    1998-01-01

    The alkaline leach process for extracting uranium from uranium ores is reviewed. This process is dependent on the chemistry of uranium and so is independent on the type of mining system (conventional, heap or in-situ) used. Particular reference is made to the geochemical conditions at Crownpoint. Some supporting data from studies using alkaline leach for remediation of uranium-contaminated sites is presented