A new approach to study cadmium complexes with oxalic acid in soil solution.

Science.gov (United States)

Dytrtová, Jana Jaklová; Jakl, Michal; Sestáková, Ivana; Zins, Emilie-Laure; Schröder, Detlef; Navrátil, Tomáš

2011-05-05

This study presents a new analytical approach for the determination of heavy metals complexed to low-molecular-weight-organic acids in soil solutions, which combines the sensitivity of differential pulse anodic stripping voltammetry (DPASV) with the molecular insight gained by electrospray ionization mass spectrometry (ESI-MS). The combination of these analytical methods allows the investigation of such complexes in complex matrixes. On the voltammograms of the soil solutions, in addition to the expected complexes of oxalic acid with cadmium and lead, respectively, also peaks belonging to mixed complexes of cadmium, lead, and oxalic acid (OAH(2)) were observed. In order to verify the possible formation of complexes with OAH(2), aqueous solutions of OAH(2) with traces of Cd(II) were investigated as model systems. Signals corresponding to several distinct molecular complexes between cadmium and oxalic acid were detected in the model solutions using negative-ion ESI-MS, which follow the general formula [Cd(n)(X,Y)((2n+1))](-), where n is the number of cadmium atoms, X=Cl(-), and Y=OAH(-). Some of these complexes were also identified in the ESI mass spectra taken from the soil solutions. Copyright © 2011 Elsevier B.V. All rights reserved.

A new approach to study cadmium complexes with oxalic acid in soil solution

International Nuclear Information System (INIS)

Jaklova Dytrtova, Jana; Jakl, Michal; Sestakova, Ivana; Zins, Emilie-Laure; Schroeder, Detlef; Navratil, Tomas

2011-01-01

This study presents a new analytical approach for the determination of heavy metals complexed to low-molecular-weight-organic acids in soil solutions, which combines the sensitivity of differential pulse anodic stripping voltammetry (DPASV) with the molecular insight gained by electrospray ionization mass spectrometry (ESI-MS). The combination of these analytical methods allows the investigation of such complexes in complex matrixes. On the voltammograms of the soil solutions, in addition to the expected complexes of oxalic acid with cadmium and lead, respectively, also peaks belonging to mixed complexes of cadmium, lead, and oxalic acid (OAH 2 ) were observed. In order to verify the possible formation of complexes with OAH 2 , aqueous solutions of OAH 2 with traces of Cd(II) were investigated as model systems. Signals corresponding to several distinct molecular complexes between cadmium and oxalic acid were detected in the model solutions using negative-ion ESI-MS, which follow the general formula [Cd n (X,Y) (2n+1) ] - , where n is the number of cadmium atoms, X = Cl - , and Y = OAH - . Some of these complexes were also identified in the ESI mass spectra taken from the soil solutions.

A new approach to study cadmium complexes with oxalic acid in soil solution

Energy Technology Data Exchange (ETDEWEB)

Jaklova Dytrtova, Jana, E-mail: dytrtova@uochb.cas.cz [Institute of Organic Chemistry and Biochemistry of the AS CR, v.v.i., Flemingovo namesti 2, 16610 Prague 6 (Czech Republic); Jakl, Michal [Department of Agro-Environmental Chemistry and Plant Nutrition, Faculty of Agrobiology, Food and Natural Resources, Czech University of Life Sciences, Kamycka 129, 16521 Prague - Suchdol (Czech Republic); Sestakova, Ivana [J. Heyrovsky Institute of Physical Chemistry of the AS CR, v.v.i., Dolejskova 3, 182 23 Prague 8 (Czech Republic); Zins, Emilie-Laure; Schroeder, Detlef [Institute of Organic Chemistry and Biochemistry of the AS CR, v.v.i., Flemingovo namesti 2, 16610 Prague 6 (Czech Republic); Navratil, Tomas [J. Heyrovsky Institute of Physical Chemistry of the AS CR, v.v.i., Dolejskova 3, 182 23 Prague 8 (Czech Republic)

2011-05-05

This study presents a new analytical approach for the determination of heavy metals complexed to low-molecular-weight-organic acids in soil solutions, which combines the sensitivity of differential pulse anodic stripping voltammetry (DPASV) with the molecular insight gained by electrospray ionization mass spectrometry (ESI-MS). The combination of these analytical methods allows the investigation of such complexes in complex matrixes. On the voltammograms of the soil solutions, in addition to the expected complexes of oxalic acid with cadmium and lead, respectively, also peaks belonging to mixed complexes of cadmium, lead, and oxalic acid (OAH{sub 2}) were observed. In order to verify the possible formation of complexes with OAH{sub 2}, aqueous solutions of OAH{sub 2} with traces of Cd(II) were investigated as model systems. Signals corresponding to several distinct molecular complexes between cadmium and oxalic acid were detected in the model solutions using negative-ion ESI-MS, which follow the general formula [Cd{sub n}(X,Y){sub (2n+1)}]{sup -}, where n is the number of cadmium atoms, X = Cl{sup -}, and Y = OAH{sup -}. Some of these complexes were also identified in the ESI mass spectra taken from the soil solutions.

Vibrational spectroscopy and structural analysis of uranium complexes

Energy Technology Data Exchange (ETDEWEB)

Umrejko, D.S.; Nikanovich, M.V.

1984-12-01

On the basis of experimental and theoretical studies of vibbrational spectra for halides, sulfates, phosphates, uranyl oxalates (and uranium) as well as for more complicated complex systems, reliable spectroscopic criteria have been established for estimation of their structural features by more simple and accessible (than direct) methods. Due to coordination to a central ion of U/sup 6/(U/sup 4/) ligands a geometry variation specific for each method of addition occurs and concomitant redistribution of the force interaction in the mentioned system as well, which directly affects the variation of their frequency characteristics and vibration modes. On this ground stable indications of particular types of coordination for mono- and polyatomic groups (including bridge-type, characteristic of polymetric structures) are pointed out in the IR absorption and Raman spectra. In the investigated structures the predominant effect of coordination on the spectral properties of complexes, as compared with other factors (for example, outer-sphere binding) is established. The presence of water molecules in an interlayer space does not tell essentially on the state of polyatomic ligands with all donor atoms bound with the uranium central atom (particularly, in binary uranyl phosphates). In the presence of free oxygen atoms the H/sub 2/O effect can lead only to some shift of the maxima of separate bands and their additional weak splitting (in uranyl sulfates).

Plasma oxalic acid and calcium levels in oxalate poisoning

Science.gov (United States)

Zarembski, P. M.; Hodgkinson, A.

1967-01-01

Observations are reported on five cases of suicide or attempted suicide by poisoning with oxalic acid or ethylene glycol. Elevated oxalic acid levels were observed in the plasma, stomach contents, and a number of tissues. Raised oxalic acid levels in plasma were associated with reduced total and ultrafilterable calcium levels. It is suggested that the reduction in plasma total calcium level is due mainly to the deposition of calcium oxalate in the soft tissues, but inhibition of the parathyroid glands may be a contributory factor. Microscopic examination of various tissues indicated that oxalic acid is deposited in the tissues in two forms: (1) crystalline calcium oxalate dihydrate in the kidney and (2) a non-crystalline complex of calcium oxalate and lipid in liver and other tissues. PMID:5602563

Turbulent precipitation of uranium oxalate in a vortex reactor - experimental study and modelling; Precipitation turbulente d'oxalate d'uranium en reacteur vortex - etude experimentale et modelisation

Energy Technology Data Exchange (ETDEWEB)

Sommer de Gelicourt, Y

2004-03-15

Industrial oxalic precipitation processed in an un-baffled magnetically stirred tank, the Vortex Reactor, has been studied with uranium simulating plutonium. Modelling precipitation requires a mixing model for the continuous liquid phase and the solution of population balance for the dispersed solid phase. Being chemical reaction influenced by the degree of mixing at molecular scale, that commercial CFD code does not resolve, a sub-grid scale model has been introduced: the finite mode probability density functions, and coupled with a model for the liquid energy spectrum. Evolution of the dispersed phase has been resolved by the quadrature method of moments, first used here with experimental nucleation and growth kinetics, and an aggregation kernel based on local shear rate. The promising abilities of this local approach, without any fitting constant, are strengthened by the similarity between experimental results and simulations. (author)

Synthesis and X-ray diffraction study of new uranyl malonate and oxalate complexes with carbamide

Energy Technology Data Exchange (ETDEWEB)

Medvedkov, Ya. A.; Serezhkina, L. B., E-mail: Lserezh@samsu.ru [Samara State University (Russian Federation); Grigor’ev, M. S. [Russian Academy of Sciences, Frumkin Institute of Physical Chemistry and Electrochemistry (Russian Federation); Serezhkin, V. N. [Samara State University (Russian Federation)

2016-05-15

Two new malonate-containing uranyl complexes with carbamide of the formulas [UO{sub 2}(C{sub 3}H{sub 2}O{sub 4})(Urea){sub 2}] (I) and [UO{sub 2}(C{sub 3}H{sub 2}O{sub 4})(Urea){sub 3}] (II), where Urea is carbamide, and one uranyl oxalate complex of the formula [UO{sub 2}(C{sub 2}O{sub 4})(Urea){sub 3}] (III) were synthesized, and their crystals were studied by X-ray diffraction. The main structural units in crystals I are the electroneutral chains [UO{sub 2}(C{sub 3}H{sub 2}O{sub 4})(Urea){sub 2}]{sub ∞} belonging to the crystal-chemical group AT{sup 11}M{sub 2}{sup 1} (A = UO{sub 2}{sup 2+}, T{sup 11} = C{sub 3}H{sub 2}O{sub 4}{sup 2-}, M{sup 1} = Urea) of uranyl complexes. Crystals II and III are composed of the molecular complexes [UO{sub 2}(L)(Urea){sub 3}], where L = C{sub 3}H{sub 2}O{sub 4}{sup 2-} or C{sub 2}O{sub 4}{sup 2-}, belonging to the crystal-chemical group AB{sup 01}M{sub 3}{sup 1} (A = UO{sub 2}{sup 2+}, B{sup 01} = C{sub 3}H{sub 2}O{sub 4}{sup 2-} or C{sub 2}O{sub 4}{sup 2-}, M{sup 1} = Urea). The characteristic features of the packing of the uranium-containing complexes are discussed in terms of molecular Voronoi–Dirichlet polyhedra. The effect of the Urea: U ratio on the structure of uranium-containing structural units is considered.

Behaviour study of trace radioelements in the cycles of uranium conversion

International Nuclear Information System (INIS)

Bertaux, M.

1998-01-01

The aim of this work was to study the presence of ultra-trace radioelements in the cycles of uranium conversion. Radiochemical methods for determining ultra-trace amounts of various elements in uranium have been perfected. These methods are based on the chromatographic separation of anionic complexes and on the measurement of various activities by alpha spectrometry. Thus, the source of these traces has been determined and a work of tracing has been carried out in the Malvesi site (uranium purification unit). This work has revealed an accumulation of these traces in the uranium purification column, consequently to their extraction by the TBP. A decontamination process of weakly contaminated uranium batches has been proposed using the Parex computer model and tested at the industrial scale. This process is based on the U(VI) extraction by the TBP/ISOPAR mixture and on the use of oxalic acid as the complexing agent of the tetravalent actinides in aqueous phase. It has been tested with success during a purification study of a batch of about 4 tons of uranium contaminated by traces of various radioelements. The preliminary study had taken into account the influence of metallic impurities (iron, nickel, copper) on the radioelements complexation by the oxalate ions. (O.M.)

Neptunium (IV) oxalate solubility

International Nuclear Information System (INIS)

Luerkens, D.W.

1983-07-01

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

Solubility Determination of Uranium (IV) Oxalates U(C2O4)2.6H2O and M2U2(C2O4)5.nH2O (M = mono-charged cation)

International Nuclear Information System (INIS)

Costenoble, Sylvain; Grandjean, Stephane; Arab-Chapelet, Benedicte; Abraham, Francis

2008-01-01

The solubility of uranium (IV) oxalate compounds was studied in order to have a precise insight of the behaviour of An(IV)-An(III) (An(IV) = U, Np or Pu and An(III) = Pu or Am) mixed oxalate in the context of oxalic co-conversion for actinide co-management. Concepts of thermodynamics of aqueous-solid solution are reviewed by introducing LIPPMANN theory and THORSTENSON and PLUMMER 'stoichiometric saturation' model in a way to understand and model the system of interest. Different analytical techniques have been developed in order to titrate uranium and/or other actinides at trace levels in solution. This thorough investigation is the basis of further experiments on the solubility of mixed U(IV)- An(III) oxalate solid solutions as a function of the nature of the trivalent actinide and the An(III)/U(IV) ratio. (authors)

Turbulent precipitation of uranium oxalate in a vortex reactor - experimental study and modelling; Precipitation turbulente d'oxalate d'uranium en reacteur vortex - etude experimentale et modelisation

Energy Technology Data Exchange (ETDEWEB)

Sommer de Gelicourt, Y

2004-03-15

Industrial oxalic precipitation processed in an un-baffled magnetically stirred tank, the Vortex Reactor, has been studied with uranium simulating plutonium. Modelling precipitation requires a mixing model for the continuous liquid phase and the solution of population balance for the dispersed solid phase. Being chemical reaction influenced by the degree of mixing at molecular scale, that commercial CFD code does not resolve, a sub-grid scale model has been introduced: the finite mode probability density functions, and coupled with a model for the liquid energy spectrum. Evolution of the dispersed phase has been resolved by the quadrature method of moments, first used here with experimental nucleation and growth kinetics, and an aggregation kernel based on local shear rate. The promising abilities of this local approach, without any fitting constant, are strengthened by the similarity between experimental results and simulations. (author)

Contribution of analytical techniques coupled to the knowledge of the uranium speciation in natural conditions

International Nuclear Information System (INIS)

Petit, J.

2009-06-01

To understand the transport mechanisms and the radionuclides behaviour in the bio-geosphere is necessary to evaluate healthy and environmental risks of nuclear industry. These mechanisms are monitored by radioelements speciation, namely the distribution between their different physico-chemical forms in the environment. From this perspective, this PhD thesis deals with uranium speciation in a natural background. A detailed summary of uranium biogeochemistry has been written, which enables to restrict the PhD issue to uranium complexation with oxalic acid, a hydrophilic organic acid with good binding properties, ubiquitous in soil waters. Analytical conditions have been established by means of speciation diagrams. The speciation diagrams building by means of literature stability constants has allowed to define the analytical conditions of complex formation. The chosen analytical technique is the hyphenation of a separative technique (liquid chromatography LC or capillary electrophoresis CE) with mass spectrometry (ICPMS). The studied complexes presence in the synthetic samples has been confirmed with UV/visible spectrophotometry. LC-ICPMS analyses have proved the lability of the uranyl-organic acid complexes, namely their tendency to dissociate during analysis, which prevents from studying uranium speciation. CE-ICPMS study of labile complexes from a metal-ligand system has been made possible by employing affinity capillary electrophoresis, which enables to determine stability constants and electrophoretic mobilities. This PhD thesis has allowed to compare the different mathematical treatments of binding isotherm and to take into account ionic strength and real ligand concentration. Affinity CE has been applied successfully to lanthanum-oxalate (model system) and uranium-oxalate systems. The obtained results have been applied to a real system (situated in Le Bouchet). This shows the contribution of the developed method to the modelling of uranium speciation. (author)

Literature review for oxalate oxidation processes and plutonium oxalate solubility

Energy Technology Data Exchange (ETDEWEB)

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

2015-10-01

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

Coordination of manganous ion at the active site of pyruvate, phosphate dikinase: the complex of oxalate with the phosphorylated enzyme

International Nuclear Information System (INIS)

Kofron, J.L.; Ash, D.E.; Reed, G.H.

1988-01-01

Electron paramagnetic resonance spectroscopy has been used to investigate the structure of the complex of manganous ion with the phosphorylated form of pyruvate, phosphate dikinase (E/sub p/) and the inhibitor oxalate. Oxalate, an analogue of the enolate of pyruvate, is competitive with respect to pyruvate in binding to the phosphorylated form of the enzyme. Superhyperfine coupling between the unpaired electrons of Mn(I) and ligands specifically labeled with 17 O has been used to identify oxygen ligands to Mn(II) in the complex with oxalate and the phosphorylated form of the enzyme. Oxalate binds at the active site as a bidentate chelate with Mn(II). An oxygen from the 3'-N-phosphohistidyl residue of the protein is in the coordination sphere of Mn(II), and at least two water molecules are also bound to Mn(II) in the complex. Oxalate also binds directly to Mn(II) in a complex with nonphosphorylated enzyme. The structure for the E/sub p/-Mn(II)-oxalate complex implies that simultaneous coordination of a phospho group and of the attacking nucleophile to the divalent cation is likely an important factor in catalysis of this phospho-transfer reaction

Potentiometric determination of uranium in simulated Purex Process solutions by acidiometry

International Nuclear Information System (INIS)

Cohen, V.H.; Matsuda, H.T.; Araujo, B.F. de; Araujo, J.A. de

1983-01-01

A potentiometric methods for sequential free acidity and uranium determination in simulated Purex Process solutions is described. An oxalate solution or a mixture of fluoride-oxalate pellets were used as complexing agent for free titration. Following this first equivalent point, uranium is determined-by indirect titration of H + liberated in the peruanate reaction. Some elements present in the standard fuel elements with a burn-up of 33.000 Mwd/t, neutron flux of 3,2 x 10 13 n.cm -2 .s -1 and cooling time of two years were considered as interfering elements in uranium analyses. As a substitute of Pu-IV, Th(NO 3 ) 4 solution was used. The method can be applied to aqueous and organic (TBP/diluent) solutions with 2% precision and 2% accuracy. (Autor) [pt

Potentiometric determination of uranium in simulated Purex Process solutions by acidiometry

Energy Technology Data Exchange (ETDEWEB)

Cohen, V H; Matsuda, H T; Araujo, B.F. de; Araujo, J.A. de

1984-01-01

A potentiometric methods for sequential free acidity and uranium determination in simulated Purex Process solutions is described. An oxalate solution or a mixture of fluoride-oxalate pellets were used as complexing agent for free titration. Following this first equivalent point, uranium is determined-by indirect titration of H/sup +/ liberated in the peruanate reaction. Some elements present in the standard fuel elements with a burn-up of 33.000 Mwd/t, neutron flux of 3,2 x 10/sup 13/n.cm/sup -2/.s/sup -1/ and cooling time of two years were considered as interfering elements in uranium analyses. As a substitute of Pu-IV, Th(NO/sub 3/)/sub 4/ solution was used. The method can be applied to aqueous and organic (TBP/diluent) solutions with 2% precision and 2% accuracy. (Autor).

Protection of metal artefacts with the formation of metal-oxalates complexes by Beauveria bassiana.

Directory of Open Access Journals (Sweden)

Edith eJoseph

2012-01-01

Full Text Available Several fungi present high tolerance to toxic metals and some are able to transform metals into metal-oxalate complexes. In this study, the ability of Beauveria bassiana to produce copper oxalates was evaluated in vitro. Growth performance was tested on various copper-containing media. B. bassiana proved highly resistant to copper, tolerating concentrations of up to 20 g.L-1, and precipitating copper oxalates on all media tested. Chromatographic analyses showed that this species produced oxalic acid as sole metal chelator. The production of metal-oxalates can be used in the restoration and conservation of archaeological and modern metal artefacts. The production of copper-oxalates was confirmed directly using metallic pieces (both archaeological and modern. The conversion of corrosion products into copper oxalates was demonstrated as well. In order to assess whether the capability of B. bassiana to produce metal-oxalates could be applied to other metals, iron and silver were tested as well. Iron appears to be directly sequestered in the wall of the fungal hyphae forming oxalates and probably goethite. However, the formation of a homogeneous layer on the object is not yet optimal. Silver nitrate was extracellularly reduced into nanoparticles of elemental silver by an unknown mechanism. The production of copper oxalates is immediately applicable for the conservation of copper-based artefacts. For iron and silver this is not yet the case. However, the vast ability of B. bassiana to transform toxic metals using different immobilization mechanisms seems to offer considerable possibilities for industrial applications, such as the bioremediation of contaminated soils or the green synthesis of chemicals.

LITERATURE REVIEW FOR OXALATE OXIDATION PROCESSES AND PLUTONIUM OXALATE SOLUBILITY

Energy Technology Data Exchange (ETDEWEB)

Nash, C.

2012-02-03

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

Analytical Study of Oxalates Coprecipitation

Directory of Open Access Journals (Sweden)

Liana MARTA

2003-03-01

Full Text Available The paper deals with the establishing of the oxalates coprecipitation conditions in view of the synthesis of superconducting systems. A systematic analytical study of the oxalates precipitation conditions has been performed, for obtaining superconducting materials, in the Bi Sr-Ca-Cu-O system. For this purpose, the formulae of the precipitates solubility as a function of pH and oxalate excess were established. The possible formation of hydroxo-complexes and soluble oxalato-complexes was taken into account. A BASIC program was used for tracing the precipitation curves. The curves of the solubility versus pH for different oxalate excess have plotted for the four oxalates, using a logaritmic scale. The optimal conditions for the quantitative oxalate coprecipitation have been deduced from the diagrams. The theoretical curves were confirmed by experimental results. From the precursors obtained by this method, the BSCCO superconducting phases were obtained by an appropriate thermal treatment. The formation of the superconducting phases was identified by X-ray diffraction analysis.

Turbulent precipitation of uranium oxalate in a vortex reactor - experimental study and modelling

International Nuclear Information System (INIS)

Sommer de Gelicourt, Y.

2004-03-01

Industrial oxalic precipitation processed in an un-baffled magnetically stirred tank, the Vortex Reactor, has been studied with uranium simulating plutonium. Modelling precipitation requires a mixing model for the continuous liquid phase and the solution of population balance for the dispersed solid phase. Being chemical reaction influenced by the degree of mixing at molecular scale, that commercial CFD code does not resolve, a sub-grid scale model has been introduced: the finite mode probability density functions, and coupled with a model for the liquid energy spectrum. Evolution of the dispersed phase has been resolved by the quadrature method of moments, first used here with experimental nucleation and growth kinetics, and an aggregation kernel based on local shear rate. The promising abilities of this local approach, without any fitting constant, are strengthened by the similarity between experimental results and simulations. (author)

Uranyl Oxalate Solubility

Energy Technology Data Exchange (ETDEWEB)

Leturcq, G.; Costenoble, S.; Grandjean, S. [CEA Marcoule DEN/DRCP/SCPS/LCA - BP17171 - 30207 Bagnols sur Ceze cedex (France)

2008-07-01

The solubility of uranyl oxalate was determined at ambient temperature by precipitation in oxalic-nitric solutions, using an initial uranyl concentration of 0.1 mol/L. Oxalic concentration varied from 0.075 to 0.3 mol/L while nitric concentration ranged between 0.75 and 3 mol/L. Dissolution tests, using complementary oxalic-nitric media, were carried out for 550 hours in order to study the kinetic to reach thermodynamic equilibrium. Similar solubility values were reached by dissolution and precipitation. Using the results, it was possible to draw the solubility surface versus oxalic and nitric concentrations and to determine both the apparent solubility constant of UO{sub 2}C{sub 2}O{sub 4}, 3H{sub 2}O (Ks) and the apparent formation constant of the first uranyl-oxalate complex UO{sub 2}C{sub 2}O{sub 4} (log {beta}1), for ionic strengths varying between 1 and 3 mol/L. Ks and log {beta}1 values were found to vary from 1.9 10{sup -8} to 9.2 10{sup -9} and from 5.95 to 6.06, respectively, when ionic strength varied from 1 to 3 mol/L. A second model may fit our data obtained at an ionic strength of 3 mol/L suggesting as reported by Moskvin et al. (1959) that no complexes are formed for [H{sup +}] at 3 M. The Ks value would then be 1.3 10{sup -8}. (authors)

On the americium oxalate solubility

International Nuclear Information System (INIS)

Zakolupin, S.A.; Korablin, Eh.V.

1977-01-01

The americium oxalate solubility at different nitric (0.0-1 M) and oxalic (0.0-0.4 M) acid concentrations was investigated in the temperature range from 14 to 60 deg C. The dependence of americium oxalate solubility on the oxalic acid concentration was determined. Increasing oxalic acid concentration was found to reduce the americium oxalate solubility. The dependence of americium oxalate solubility on the oxalic acid concentration was noted to be a minimum at low acidity (0.1-0.3 M nitric acid). This is most likely due to Am(C 2 O 4 ) + , Am(C 2 O 4 ) 2 - and Am(C 2 O 4 ) 3 3- complex ion formation which have different unstability constants. On the basis of the data obtained, a preliminary estimate was carried out for the product of americium oxalate solubility in nitric acid medium (10 -29 -10 -31 ) and of the one in water (6.4x10 -20 )

Synthesis and structural characterization of actinide oxalate compounds

International Nuclear Information System (INIS)

Tamain, C.

2011-01-01

Oxalic acid is a well-known reagent to recover actinides thanks to the very low solubility of An(IV) and An(III) oxalate compounds in acidic solution. Therefore, considering mixed-oxide fuel or considering minor actinides incorporation in ceramic fuel materials for transmutation, oxalic co-conversion is convenient to synthesize mixed oxalate compounds, precursors of oxide solid solutions. As the existing oxalate single crystal syntheses are not adaptable to the actinide-oxalate chemistry or to their manipulation constrains in gloves box, several original crystal growth methods were developed. They were first validate and optimized on lanthanides and uranium before the application to transuranium elements. The advanced investigations allow to better understand the syntheses and to define optimized chemical conditions to promote crystal growth. These new crystal growth methods were then applied to a large number of mixed An1(IV)-An2(III) or An1(IV)-An2(IV) systems and lead to the formation of the first original mixed An1(IV)-An2(III) and An1(IV)-An2(IV) oxalate single crystals. Finally thanks to the first thorough structural characterizations of these compounds, single crystal X-ray diffraction, EXAFS or micro-RAMAN, the particularly weak oxalate-actinide compounds structural database is enriched, which is essential for future studied nuclear fuel cycles. (author) [fr

Cordilleran metamorphic core complexes and their uranium favorability

International Nuclear Information System (INIS)

Coney, P.J.; Reynolds, S.J.

1980-11-01

The objective of this report is to provide a descriptive body of knowledge on Cordilleran metamorphic core complexes including their lithologic and structural characteristics, their distribution within the Cordillera, and their evolutionary history and tectonic setting. The occurrence of uranium in the context of possibility for uranium concentration is also examined. This volume contains appendices of the following: annotated bibliography of Cordilleran metamorphic core complexes; annotated bibliography of the uranium favorability of Cordilleran metamorphic core complexes; uranium occurrences in the Cordilleran metamorphic core complex belt; and geology, uranium favorability, uranium occurrences and tectonic maps of individual Cordilleran metamorphic core complexes; and locations, lithologic descriptions, petrographic information and analytical data for geochemical samples

Uranium extraction by complexation with siderophores

Science.gov (United States)

Bahamonde Castro, Cristina

One of the major concerns of energy production is the environmental impact associated with the extraction of natural resources. Nuclear energy fuel is obtained from uranium, an abundant and naturally occurring element in the environment, but the currently used techniques for uranium extraction leave either a significant fingerprint (open pit mines) or a chemical residue that alters the pH of the environment (acid or alkali leaching). It is therefore clear that a new and greener approach to uranium extraction is needed. Bioleaching is one potential alternative. In bioleaching, complexants naturally produced from fungi or bacteria may be used to extract the uranium. In the following research, the siderophore enterobactin, which is naturally produced by bacteria to extract and solubilize iron from the environment, is evaluated to determine its potential for complexing with uranium. To determine whether enterobactin could be used for uranium extraction, its acid dissociation and its binding strength with the metal of interest must be determined. Due to the complexity of working with radioactive materials, lanthanides were used as analogs for uranium. In addition, polyprotic acids were used as structural and chemical analogs for the siderophore during method development. To evaluate the acid dissociation of enterobactin and the subsequent binding constants with lanthanides, three different analytical techniques were studied including: potentiometric titration, UltraViolet Visible (UV-Vis) spectrophotometry and Isothermal Titration Calorimetry (ITC). After evaluation of three techniques, a combination of ITC and potentiometric titrations was deemed to be the most viable way for studying the siderophore of interest. The results obtained from these studies corroborate the ideal pH range for enterobactin complexation to the lanthanide of interest and pave the way for determining the strength of complexation relative to other naturally occurring metals. Ultimately, this

Extraction of {sup 95}(Zr, Nb) from oxalic acid solutions by means of tri-iso-octyl amine, Annex 8

Energy Technology Data Exchange (ETDEWEB)

Susic, M V; Maksimovic, Z B [Institute of Nuclear Sciences Boris Kidric, Laboratorija za visoku aktivnost, Vinca, Beograd (Serbia and Montenegro)

1963-12-15

The extractability of {sup 95}(Zr, Nb) with tri-iso-octyl amine in xylene from an oxalic acid solution has been investigated. The behaviour of uranium and other fission products has also been observed. The extraction of {sup 95}(Zr, Nb) has been studied as u function of oxalic acid and amine concentrations. Effects of the aqueous phase pH, uranium and the presence of other electrolytes have also been observed and the possibility of separating {sup 95}(Zr, Nb) from uranium and from other fission products considered (author)

Solubility Determination of Uranium (IV) Oxalates U(C{sub 2}O{sub 4}){sub 2}.6H{sub 2}O and M{sub 2}U{sub 2}(C{sub 2}O{sub 4}){sub 5}.nH{sub 2}O (M = mono-charged cation)

Energy Technology Data Exchange (ETDEWEB)

Costenoble, Sylvain; Grandjean, Stephane; Arab-Chapelet, Benedicte [CEA, Nuclear Energy Division, Radiochemistry and Process Department, Actinide Chemistry Laboratory, CEA Marcoule, bat 399, BP17171, 30207 Bagnols sur Ceze cedex (France); Abraham, Francis [UCCS - Solid Chemistry Unit, UMR CNRS 8181, ENSCL-USTL, B.P. 108, 59652 Villeneuve d' Ascq cedex (France)

2008-07-01

The solubility of uranium (IV) oxalate compounds was studied in order to have a precise insight of the behaviour of An(IV)-An(III) (An(IV) = U, Np or Pu and An(III) = Pu or Am) mixed oxalate in the context of oxalic co-conversion for actinide co-management. Concepts of thermodynamics of aqueous-solid solution are reviewed by introducing LIPPMANN theory and THORSTENSON and PLUMMER 'stoichiometric saturation' model in a way to understand and model the system of interest. Different analytical techniques have been developed in order to titrate uranium and/or other actinides at trace levels in solution. This thorough investigation is the basis of further experiments on the solubility of mixed U(IV)- An(III) oxalate solid solutions as a function of the nature of the trivalent actinide and the An(III)/U(IV) ratio. (authors)

Variation in oxalate and oxalate decarboxylase production by six species of brown and white rot fungi

DEFF Research Database (Denmark)

Hastrup, Anne Christine Steenkjær; Oliver, Jason; Howell, Caitlin

  Oxalic acid (C2O4H2), the strongest of the organic acids is produced by both brown and white rot decay fungi and has been connected to various aspects of brown- and white rot decay including the Fenton reaction (Green and Highley, 1997; Munir et al.,2001). Oxalic acid is secreted into the wood...... cell lumen where it quickly dissociates into hydrogen ions and oxalate, resulting in a pH decrease of the environment, and oxalate-cation complexes. Generally, brown rot fungi accumulate larger quantities of oxalic acid in the wood than white rot fungi. The amount of oxalic acid has been shown to vary...... of formic acid and CO2 (Makela et al., 2002). So far only a few species of brown rot fungi have been shown to accumulate this enzyme (Micales, 1995, Howell and Jellison, 2006).   The purpose of this study was to investigate the variation in the levels of soluble oxalate and total oxalate, in correlation...

Mechanism and kinetics of thermal decomposition of ammoniacal complex of copper oxalate

International Nuclear Information System (INIS)

Prasad, R.

2003-01-01

A complex precursor has been synthesized by dissolving copper oxalate in liquor ammonia followed by drying. The thermal decomposition of the precursor has been studied in different atmospheres, air/nitrogen. The mechanism of decomposition of the precursor in air is not as simple one as in nitrogen. In nitrogen, it involves endothermic deammoniation followed by decomposition to finely divided elemental particles of copper. Whereas in air, decomposition and simultaneous oxidation of the residual products (oxidative decomposition), make the process complex and relatively bigger particle of cupric oxide are obtained as final product. The products of decomposition in different atmospheres have been characterized by X-ray diffraction and particle size analysis. The stoichiometric formula, Cu(NH 3 ) 2 C 2 O 4 of the precursor is established from elemental analysis and TG measurements, and it is designated as copper amino oxalate (CAO). In nitrogen atmosphere, the deammoniation and decomposition have been found to be zero and first order, respectively. The values of activation energy have been found to be 102.52 and 95.38 kJ/mol for deammoniation and decomposition, respectively

Process for recovery of plutonium from fabrication residues of mixed fuels consisting of uranium oxide and plutonium oxide

International Nuclear Information System (INIS)

Heremanns, R.H.; Vandersteene, J.J.

1983-01-01

The invention concerns a process for recovery of plutonium from fabrication residues of mixed fuels consisting of uranium oxide and plutonium oxide in the form of PuO 2 . Mixed fuels consisting of uranium oxide and plutonium oxide are being used more and more. The plants which prepare these mixed fuels have around 5% of the total mass of fuels as fabrication residue, either as waste or scrap. In view of the high cost of plutonium, it has been attempted to recover this plutonium from the fabrication residues by a process having a purchase price lower than the price of plutonium. The problem is essentially to separate the plutonium, the uranium and the impurities. The residues are fluorinated, the UF 6 and PuF 6 obtained are separated by selective absorption of the PuF 6 on NaF at a temperature of at least 400 0 C, the complex obtained by this absorption is dissolved in nitric acid solution, the plutonium is precipitated in the form of plutonium oxalate by adding oxalic acid, and the precipitated plutonium oxalate is calcined

Extractants for uranium recovery from wet phosphoric acid

International Nuclear Information System (INIS)

Musikas, C.; Benjelloun, N.; Lours, S.

1981-08-01

It must be pointed out that despite their lower affinity for uranyl, the dialkyldithiophosphates show higher extraction coefficients than dialkylphosphates. In addition, it is possible to back extract uranium with oxalate solutions at pH levels where the solvents remain in their acidic form. This last possibility seems to be correlated with the presence of a H 2 PO 4 - ion in the U(VI) organic complexes

Oxalic acid complexes: Promising draw solutes for forward osmosis (FO) in protein enrichment

KAUST Repository

Ge, Qingchun; Chung, Neal Tai-Shung

2015-01-01

Highly soluble oxalic acid complexes (OACs) were synthesized through a one-pot reaction. The OACs exhibit excellent performance as draw solutes in FO processes with high water fluxes and negligible reverse solute fluxes. Efficient protein enrichment was achieved. The diluted OACs can be recycled via nanofiltration and are promising as draw solutes.

Separation and purification of uranium product from thorium in thorex process by precipitation technique

International Nuclear Information System (INIS)

Ramanujam, A.; Dhami, P.S.; Gopalakrishnan, V.; Mukherjee, A.; Dhumwad, R.K.

1989-01-01

A sequential precipitation technique is reported for the separation of uranium and thorium present in the uranium product stream of a single cycle 5 per cent TBP Thorex Process. It involves the precipitation of thorium as oxalate in 1M HNO 3 medium at 60-70degC and after filtration, precipitation of uranium as ammonium diuranate at 80-90degC from the oxalate supernatant. This technique has several advantages over the ion-exchange process normally used for treating these products. In order to meet the varying feed conditions, this method has been tested for feeds containing 10 g/1 uranium and 1-50 g/1 thorium in 1-6M HNO 3 . Various parameters like feed acidities, uranium and thorium concentrations, excess oxalic acid concentrations in the oxalate supernatant, precipitation temperatures, precipitate wash volumes etc. have been optimised to obtain more than 99 per cent recovery of thorium and uranium as their oxides with less than 50 ppm uranium losses to ammonium diuranate filtrate. The distribution patterns of different fission products and stainless steel corrosion products during various steps of this procedure have also been studied. For simulating the actual Thorex plant scale operation, experiments have been conducted with 25g and 100g lots of uranium per batch. (author). 6 tabs., 8 figs., 22 refs

Photodegradation of orange I in the heterogeneous iron oxide-oxalate complex system under UVA irradiation

International Nuclear Information System (INIS)

Lei, Jing; Liu Chengshuai; Li Fangbai; Li Xiaomin; Zhou Shungui; Liu Tongxu; Gu Minghua; Wu Qitang

2006-01-01

To understand the photodegradation of azo dyes in natural aquatic environment, a novel photo-Fenton-like system, the heterogeneous iron oxide-oxalate complex system was set up with the existence of iron oxides and oxalate. Five iron oxides, including γ-FeOOH, IO-250, IO-320, IO-420 and IO-520, were prepared and their adsorption capacity was investigated in the dark. The results showed that the saturated adsorption amount (Γ max ) was ranked the order of IO-250>IO-320>γ-FeOOH>IO-420>IO-520 and the adsorption equilibrium constant (K a ) followed the order of IO-250>IO-520>γ-FeOOH>IO-420>IO-320. The effect of initial pH value, the initial concentrations of oxalate and orange I on the photodegradation of orange I were also investigated in different iron oxide-oxalate systems. The results showed that the photodegradation of orange I under UVA irradiation could be enhanced greatly in the presence of oxalate. And the optimal oxalate concentrations (C ox 0 ) for γ-FeOOH, IO-250, IO-320, IO-420 and IO-520 were 1.8, 1.6, 3.5, 3.0 and 0.8mM, respectively. The photodegradation of orange I in the presence of optimal C ox 0 was ranked as the order of γ-FeOOH>IO-250>IO-320>IO-420>IO-520. The optimal range of initial pH was at about 3-4. The first-order kinetic constant for the degradation of orange I decreased with the increase in the initial concentration of orange I. Furthermore, the variation of pH, the concentrations of Fe 3+ and Fe 2+ during the photoreaction were also strongly dependent on the C ox 0 and iron oxides

Evaluation of oxalate decarboxylase and oxalate oxidase for industrial applications.

Science.gov (United States)

Cassland, Pierre; Sjöde, Anders; Winestrand, Sandra; Jönsson, Leif J; Nilvebrant, Nils-Olof

2010-05-01

Increased recirculation of process water has given rise to problems with formation of calcium oxalate incrusts (scaling) in the pulp and paper industry and in forest biorefineries. The potential in using oxalate decarboxylase from Aspergillus niger for oxalic acid removal in industrial bleaching plant filtrates containing oxalic acid was examined and compared with barley oxalate oxidase. Ten different filtrates from chemical pulping were selected for the evaluation. Oxalate decarboxylase degraded oxalic acid faster than oxalate oxidase in eight of the filtrates, while oxalate oxidase performed better in one filtrate. One of the filtrates inhibited both enzymes. The potential inhibitory effect of selected compounds on the enzymatic activity was tested. Oxalate decarboxylase was more sensitive than oxalate oxidase to hydrogen peroxide. Oxalate decarboxylase was not as sensitive to chlorate and chlorite as oxalate oxidase. Up to 4 mM chlorate ions, the highest concentration tested, had no inhibitory effect on oxalate decarboxylase. Analysis of the filtrates suggests that high concentrations of chlorate present in some of the filtrates were responsible for the higher sensitivity of oxalate oxidase in these filtrates. Oxalate decarboxylase was thus a better choice than oxalate oxidase for treatment of filtrates from chlorine dioxide bleaching.

Recovery of uranium from uranium bearing black shale

International Nuclear Information System (INIS)

Das, Amrita; Yadav, Manoj; Singh, Ajay K.

2016-01-01

Black shale is the unconventional resource of uranium. Recovery of uranium from black shale has been carried out by the following steps: i) size reduction, ii) leaching of uranium in the aqueous medium, iii) fluoride ion removal, iv) solvent extraction of uranium from the aqueous leach solution, v) scrubbing of the loaded solvent after extraction to remove impurities as much as possible and vi) stripping of uranium from the loaded organic into the aqueous phase. Leaching of black shale has been carried out in hydrochloric acid. Free acidity of the leach solution has been determined by potentiometric titration method. Removal of fluoride ions has been done using sodium chloride. Solvent extraction has been carried out by both tributyl phosphate and alamine-336 as extractants. Scrubbing has been tried with oxalic acid and sulphuric acid. Stripping with sodium carbonate solution has been carried out. Overall recovery of uranium is 95%. (author)

Use of a pulsed column contactor as a continuous oxalate precipitation reactor

International Nuclear Information System (INIS)

Borda, Gilles; Brackx, Emmanuelle; Boisset, Laurence; Duhamet, Jean; Ode, Denis

2011-01-01

Research highlights: → A new type of continuous precipitating device was patented by CEA and tested with reaction between a surrogate nitrate cerium(III) or neodymium(III) and oxalate complexing agent. → Precipitate is confined in aqueous phase emulsion in tetrapropylene hydrogen and does not form deposit on the vessel walls. → Measure size of the precipitate ranges from 20 to 40 μm, it meets the process requirements to filter, and the precipitation reaction is complete. → The laboratory design can be extrapolated to an industrial uranium(IV) and minor actinide(III) coprecipitating column. - Abstract: The current objective of coprecipitating uranium, and minor actinides in order to fabricate a new nuclear fuel by direct (co)precipitation for further transmutation, requires to develop specific technology in order to meet the following requirements: nuclear maintenance, criticity, and potentially high flowrates due to global coprecipitation. A new type of device designed and patented by the CEA was then tested in 2007 under inactive conditions and with uranium. The patent is for organic confinement in a pulsed column (PC). Actually, pulsed columns have been working for a long time in a nuclear environment, as they allow high capacity, sub-critical design (annular geometry) and easy high activity maintenance. The precipitation reaction between the oxalate complexing agent and a surrogate nitrate - cerium(III) or neodymium(III) alone, or coprecipitated uranium(IV) and cerium(III) - occurs within an emulsion created in the device by these two phases flowing with a counter-current chemically inert organic phase (for example tetrapropylene hydrogen-TPH) produced by the stirring action of the column pulsator. The precipitate is confined and thus does not form deposits on the vessel walls (which are also water-repellent); it flows downward by gravity and exits the column continuously into a settling tank. The results obtained for precipitation of cerium or

Non-invasive identification of metal-oxalate complexes on polychrome artwork surfaces by reflection mid-infrared spectroscopy.

Science.gov (United States)

Monico, Letizia; Rosi, Francesca; Miliani, Costanza; Daveri, Alessia; Brunetti, Brunetto G

2013-12-01

In this work a reflection mid-infrared spectroscopy study of twelve metal-oxalate complexes, of interest in art conservation science as alteration compounds, was performed. Spectra of the reference materials highlighted the presence of derivative-like and/or inverted features for the fundamental vibrational modes as result of the main contribution from the surface component of the reflected light. In order to provide insights in the interpretation of theses spectral distortions, reflection spectra were compared with conventional transmission ones. The Kramers-Kronig (KK) algorithm, employed to correct for the surface reflection distortions, worked properly only for the derivative-like bands. Therefore, to pay attention to the use of this algorithm when interpreting the reflection spectra is recommended. The outcome of this investigation was exploited to discriminate among different oxalates on thirteen polychrome artworks analyzed in situ by reflection mid-infrared spectroscopy. The visualization of the νs(CO) modes (1400-1200 cm(-1)) and low wavenumber bands (below 900 cm(-1)) in the raw reflection profiles allowed Ca, Cu and Zn oxalates to be identified. Further information about the speciation of different hydration forms of calcium oxalates were obtained by using the KK transform. The work proves reflection mid-infrared spectroscopy to be a reliable and sensitive spectro-analytical method for identifying and mapping different metal-oxalate alteration compounds on the surface of artworks, thus providing conservation scientists with a non-invasive tool to obtain information on the state of conservation and causes of alteration of artworks. Copyright © 2013 Elsevier B.V. All rights reserved.

Estimation of the oxalate content of foods and daily oxalate intake

Science.gov (United States)

Holmes, R. P.; Kennedy, M.

2000-01-01

BACKGROUND: The amount of oxalate ingested may be an important risk factor in the development of idiopathic calcium oxalate nephrolithiasis. Reliable food tables listing the oxalate content of foods are currently not available. The aim of this research was to develop an accurate and reliable method to measure the food content of oxalate. METHODS: Capillary electrophoresis (CE) and ion chromatography (IC) were compared as direct techniques for the estimation of the oxalate content of foods. Foods were thoroughly homogenized in acid, heat extracted, and clarified by centrifugation and filtration before dilution in water for analysis. Five individuals consuming self-selected diets maintained food records for three days to determine their mean daily oxalate intakes. RESULTS: Both techniques were capable of adequately measuring the oxalate in foods with a significant oxalate content. With foods of very low oxalate content (choice over IC for estimating the oxalate content of foods with a medium (>10 mg/100 g) to high oxalate content due to a faster analysis time and lower running costs, whereas IC may be better suited for the analysis of foods with a low oxalate content. Accurate estimates of the oxalate content of foods should permit the role of dietary oxalate in urinary oxalate excretion and stone formation to be clarified. Other factors, apart from the amount of oxalate ingested, appear to exert a major influence over the amount of oxalate excreted in the urine.

Role of cellular oxalate in oxalate clearance of patients with calcium oxalate monohydrate stone formation and normal controls.

Science.gov (United States)

Oehlschläger, Sven; Fuessel, Susanne; Meye, Axel; Herrmann, Jana; Froehner, Michael; Albrecht, Steffen; Wirth, Manfred P

2009-03-01

To examine the cellular, plasma, and urinary oxalate and erythrocyte oxalate flux in patients with calcium oxalate monohydrate (COM) stone formation vs normal controls. Pathologic oxalate clearance in humans is mostly integrated in calcium oxalate stone formation. An underlying cause of deficient oxalate clearance could be defective transmembrane oxalate transport, which, in many tissues, is regulated by an anion exchanger (SLC26). We studied 2 groups: 40 normal controls and 41 patients with COM stone formation. Red blood cells were divided for cellular oxalate measurement and for resuspension in a buffered solution (pH 7.40); 0.1 mmol/L oxalate was added. The supernatant was measured for oxalate immediately and 1 hour after incubation. The plasma and urinary oxalate were analyzed in parallel. The mean cellular oxalate concentrations were significantly greater in the normal controls (5.25 +/- 0.47 micromol/L) than in those with COM stone formation (2.36 +/- 0.28 micromol/L; P stone formation (0.31 +/- 0.02 mmol/L) than in the controls (0.24 +/- 0.02 mmol/L; P r = 0.49-0.63; P r = -0.29-0.41; P r = -0.30; P r = 0.25; P stone formation. Our data implicate the presence of a cellular oxalate buffer to stabilize plasma and urinary oxalate concentrations in normal controls.

Two New Families of Lanthanide Mixed-Ligand Complexes, Oxalate-Carbonate and Oxalate-Formate: Synthesis and Structure of [Ce(H 2O)] 2(C 2O 4) 2(CO 3)·2.5 H 2O and Ce(C 2O 4)(HCO 2)

Science.gov (United States)

Romero, S.; Mosset, A.; Trombe, J. C.

1996-12-01

Two new families of lanthanide complexes associating the ligands oxalate and carbonate or oxalate and formate have been prepared under autogenous pressure at 200°C using a pseudo-hydrothermal method. The two families have been extended to some lanthanides ( Ln): oxalate-carbonate Ln= Ce, Pr, Nd, and Eu; oxalate-formate Ln= La, Ce, and Sm. The starting suspension contains either oxalate or a mixture of oxalate and oxalic acid. The structures have been solved for the element cerium. In both cases, the structure is built up from cerium atoms sharing all their oxygen atoms with oxalate and carbonate or oxalate and formate ligands, thus forming a three-dimensional network. The cerium polyhedra share either faces or edges or corners. The coordination scheme of the oxalate ligands is variable: bischelating, bischelating and monodentate, or bischelating and bismonodentate. The carbonate group acts as a bischelating and bismonodentate ligand while the formate group is chelating and monodentate. The characterization of these two original families by infrared spectra and thermal behavior is presented for some pure phases. A tentative explanation of the synthesis of these two phases will be emphasized.

Recovery of plutonium from oxalate supernatant using 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone

International Nuclear Information System (INIS)

Mohapatra, P.K.; Manchanda, V.K.; Gupta, K.K.; Singh, R.K.

1997-01-01

Extraction of Pu(IV) from oxalate supernatant was carried out employing varying concentrations of 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (PMBP). Near quantitative extraction of Pu(IV) from an aqueous solution of 0.2M oxalic acid and 3M HNO 3 was possible employing 0.05M PMBP solution in xylene. Extraction studies at different uranium loading conditions were carried out and conditions for quantitative stripping were arrived at. (author). 2 refs., 4 tabs

Determination of natural uranium in urine (233U)

International Nuclear Information System (INIS)

Jeanmaire, L.; Jammet, H.

1959-01-01

A procedure for the quantitative analysis of uranium in urine is described. The residue obtained by mineralization is dissolved in diluted hydrochloric acid. Uranium is separated by fixation on a permutit 50 column, elution with 0,2 M oxalic acid and electrodeposition on nickel. Uranium is then measured by α counting. It is thus possible to detect less than 1 pico-curie of uranium in the sample. (author) [fr

Radiolysis of titanium potassium oxalate in aqueous solution. [. gamma. rays

Energy Technology Data Exchange (ETDEWEB)

Bundo, Y; Ono, I [Industrial Research Inst. of Kanagawa Prefecture, Yokohama (Japan); Ogawa, T

1975-01-01

The dissolution state of titanium potassium oxalate in aqueous solution is different according to the pH. The yellowish brown titanium complex produced by the reaction of titanium potassium oxalate and hydrogen peroxide seems to be different in its structure according to the pH. Considering these points, gamma-ray irradiation was carried out on the sample by dissolving titanium potassium oxalate in purified water under the conditions of oxygen saturation and nitrogen saturation, and the relation between irradiation dose and the production of titanium complex was determined. On the basis of the experimental result, the mechanism of forming hydrogen peroxide was presumed. The radiation source used was 2,000 Ci of /sup 60/Co. For photometric analysis, a 139 type photoelectric spectrophotometer of Hitachi Ltd. was used. From the experimental results, in neutral water, titanium potassium oxalate exists in the state that two oxalic acid ions are coordinated to titanyl ion, while in case of the pH lowered by the addition of sulfuric acid, it can exist in the state that one oxalic acid ion is coordinated to titanyl ion. The yield of hydrogen peroxide produced by irradiating titanium potassium oxalate aqueous solution with gamma-ray is the sum of the molecular product from water and the radiolysis product from titanium potassium oxalate.

Structure and reactivity of oxalate surface complexes on lepidocrocite derived from infrared spectroscopy, DFT-calculations, adsorption, dissolution and photochemical experiments

Science.gov (United States)

Borowski, Susan C.; Biswakarma, Jagannath; Kang, Kyounglim; Schenkeveld, Walter D. C.; Hering, Janet G.; Kubicki, James D.; Kraemer, Stephan M.; Hug, Stephan J.

2018-04-01

Oxalate, together with other ligands, plays an important role in the dissolution of iron(hdyr)oxides and the bio-availability of iron. The formation and properties of oxalate surface complexes on lepidocrocite were studied with a combination of infrared spectroscopy (IR), density functional theory (DFT) calculations, dissolution, and photochemical experiments. IR spectra measured as a function of time, concentration, and pH (50-200 μM oxalate, pH 3-7) showed that several surface complexes are formed at different rates and in different proportions. Measured spectra could be separated into three contributions described by Gaussian line shapes, with frequencies that agreed well with the theoretical frequencies of three different surface complexes: an outer-sphere complex (OS), an inner-sphere monodentate mononuclear complex (MM), and a bidentate mononuclear complex (BM) involving one O atom from each carboxylate group. At pH 6, OS was formed at the highest rate. The contribution of BM increased with decreasing pH. In dissolution experiments, lepidocrocite was dissolved at rates proportional to the surface concentration of BM, rather than to the total adsorbed concentration. Under UV-light (365 nm), BM was photolyzed at a higher rate than MM and OS. Although the comparison of measured spectra with calculated frequencies cannot exclude additional possible structures, the combined results allowed the assignment of three main structures with different reactivities consistent with experiments. The results illustrate the importance of the surface speciation of adsorbed ligands in dissolution and photochemical reactions.

Raman spectral titration method: an informative technique for studying the complexation of uranyl with uranyl(vi)-DPA/oxalate systems as examples.

Science.gov (United States)

Liu, Qian; Zhang, Qianci; Yang, Suliang; Zhu, Haiqiao; Liu, Quanwei; Tian, Guoxin

2017-10-10

The Raman band at about 870 cm -1 originating from the symmetric stretch vibration (ν 1 ) of uranyl, UO 2 2+ , has proven to be very informative for investigating the complexation of uranyl using perchlorate or nitrate of known concentration as internal standards. The concentration of uranyl can be conveniently calculated by using the ratio of the directly read band intensities of uranyl and the added reference, ClO 4 - , with a factor of 1.72. While with NO 3 - of concentration lower than 1.8 M as the reference, a factor of 0.85 should be used. Furthermore, with added internal standards, the linear relationship between the Raman intensity and the concentration of the corresponding species is illustrated by the spectral titration of U(vi) with a very strong ligand, dipicolinic acid (DPA); and the application of a spectral titration method with Raman spectroscopy in studying the complexation of uranyl is demonstrated by the titration of U(vi) with oxalate. The stepwise changes in the Raman shift of 18, 17, and 6 cm -1 , corresponding to the three oxalate anions successively bonding to UO 2 2+ , imply that the coordination modes are different. In the 1 : 1 and 1 : 2 ratios of metal to ligand complexes, the oxalate anions bond to the uranyl ion in side-on bidentate mode, but in the 1 : 3 complex the third oxalate bonds in head-on mode, which is much weaker than the first two.

Optimisation of parameters for co-precipitation of uranium and plutonium - results of simulation studies

International Nuclear Information System (INIS)

Pandey, N.K.; Velvandan, P.V.; Murugesan, S.; Ahmed, M.K.; Koganti, S.B.

1999-01-01

Preparation of plutonium oxide from plutonium nitrate solution generally proceeds via oxalate precipitation route. In a nuclear fuel reprocessing scheme this step succeeds the partitioning step (separation of uranium and plutonium). Results of present studies confirm that it is possible to avoid partitioning step and recover plutonium and uranium as co-precipitated product. This also helps in minimising the risk of proliferation of fissile material. In this procedure, the solubility of uranium oxalate in nitric acid is effectively used. Co-precipitation parameters are optimised with simulated solutions of uranium nitrate and thorium nitrate (in place of plutonium). On the basis of obtained results a reconversion flow-sheet is designed and reported here. (author)

Cordilleran metamorphic core complexes and their uranium favorability. Final report

International Nuclear Information System (INIS)

Coney, P.J.; Reynolds, S.J.

1980-11-01

The objective of this report is to provide a descriptive body of knowledge on Cordilleran metamorphic core complexes including their lithologic and structural characteristics, their distribution within the Cordillera, and their evolutionary history and tectonic setting. The occurrence of uranium in the context of possibility for uranium concentration is also examined. Chapter 1 is an overview of Cordilleran metamorphic core complexes which describes their physical characteristics, tectonic setting and geologic history. This overview is accompanied by a tectonic map. Chapter 2 is a discussion of the mantled gneiss dome concept. The purpose of including this work is to provide a basic history of this concept and to describe the characteristics and distribution of gneiss domes throughout the world to enable one to compare and contrast them with the metamorphic core complexes as discussed in this report. Some gneiss domes are known producers of uranium (as are also some core complexes). Chapter 3 is an examination of the effects of the core complex process on adjacent sedimentary and volcanic cover terranes. Also included is a discussion of the kinematic significance of these cover terranes as they are related to process within the cores of the complexes. Some of the cover terranes have uranium prospects in them. Chapter 4 is a detailed discussion of uranium in Cordilleran metamorphic core complexes and includes the conceptual basis for the various types of occurrences and the processes that might favor concentration of uranium. The report is supported by a 5-part Appendix. The majority of the core complexes discussed in this report either do not appear or are not recognizable on existing published geologic maps

an oxalate-peroxide complex used in the preparation of doped barium titanate

NARCIS (Netherlands)

van der Gijp, S.; Winnubst, Aloysius J.A.; Verweij, H.

1998-01-01

A method is described for the preparation of homogeneously doped barium titanate, which can be applied in non-linear dielectric elements. Ba and Ti salts are dissolved, mixed with hydrogen peroxide and added to a solution of ammonium oxalate, resulting in the formation of an insoluble peroxo-oxalate

Origin of Urinary Oxalate

Science.gov (United States)

Holmes, Ross P.; Knight, John; Assimos, Dean G.

2007-04-01

Urinary oxalate is mostly derived from the absorption of ingested oxalate and endogenous synthesis. The breakdown of vitamin C may also contribute small amounts to the urinary oxalate pool. The amount of oxalate absorbed is influenced by the oxalate content of the diet, the concentrations of divalent cations in the gut, the presence of oxalate-degrading organisms, transport characteristics of the intestinal epithelium, and other factors associated with the intestinal environment. Knowledge of pathways associated with endogenous oxalate synthesis is limited. Urinary oxalate excretion can be modified using strategies that limit dietary oxalate absorption and the ingestion of oxalogenic substrates such as hydroxyproline.

Ligand influences on properties of uranium coordination complexes. Structure, reactivity, and spectroscopy

International Nuclear Information System (INIS)

Kosog, Boris

2012-01-01

In this thesis several different aspects of uranium chemistry are presented. It was shown that terminal uranium(V) oxo and imido complexes [(( R ArO) 3 tacn)U V (O)] and [(( R ArO) 3 tacn)U V (NSiMe 3 )] (R = t Bu, Ad) can be oxidized by silver(I) hexafluoro-antimonate to the uranium(VI) oxo and imido complexes [(( R ArO) 3 tacn)U VI (O)]SbF 6 and [(( R ArO) 3 tacn)U VI (NSiMe 3 )]SbF 6 . While for the t Bu-derivative of the oxo complex an equatorial coordination is observed due to stabilization by the inverse trans-influence, normal axial coordination is observed for the Ad-derivative and both imido complexes. The inverse trans-influence was thus proven to be a key factor for the coordination mode of a terminal ligand on high valent uranium complexes. L III XANES was shown to be a great tool for the determination of oxidation states of uranium complexes. Therefore, a series of uranium complexes in all stable oxidation states for uranium, +III to +VI was prepared, and their spectra analyzed. All compounds bear only O-donor ligands in addition to the chlating trisaryloxide-tacn-ligand. A separation of 1.5 to 3 eV in the white line energy is observed between the different oxidation states. This series can be used as reference for compounds, where oxidation state assignment is not obvious, such as a ketyl radical complex [(( t-Bu Ar)O 3 tacn)U(O-C( t-Bu Ph) 2 .- )]. For this complex, the oxidation state of +IV could be assigned. Moreover, a series of isostructural uranium(IV) complexes was prepared. The influence of different ligands according to the spectrochemical series on the electronic and magnetic properties could be shown using UV/vis/NIR spectroscopy and variable temperature SQUID measurements. Calculations of uranium L III XANES spectra show a variation in the shape of the spectra and thus high resolution PFY-XANES would be a great tool to determine the electronic influence of these different axial ligands. Using the single N-anchored ligand system, the first

Mixing state of oxalic acid containing particles in the rural area of Pearl River Delta, China: implications for the formation mechanism of oxalic acid

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C. Cheng

2017-08-01

Full Text Available The formation of oxalic acid and its mixing state in atmospheric particulate matter (PM were studied using a single-particle aerosol mass spectrometer (SPAMS in the summer and winter of 2014 in Heshan, a supersite in the rural area of the Pearl River Delta (PRD region in China. Oxalic-acid-containing particles accounted for 2.5 and 2.7 % in total detected ambient particles in summer and winter, respectively. Oxalic acid was measured in particles classified as elemental carbon (EC, organic carbon (OC, elemental and organic carbon (ECOC, biomass burning (BB, heavy metal (HM, secondary (Sec, sodium-potassium (NaK, and dust. Oxalic acid was found predominantly mixing with sulfate and nitrate during the whole sampling period, likely due to aqueous-phase reactions. In summer, oxalic-acid-containing particle number and ozone concentration followed a very similar trend, which may reflect the significant contribution of photochemical reactions to oxalic acid formation. The HM particles were the most abundant oxalic acid particles in summer and the diurnal variations in peak area of iron and oxalic acid show opposite trends, which suggests a possible loss of oxalic acid through the photolysis of iron oxalato-complexes during the strong photochemical activity period. In wintertime, carbonaceous particles contained a substantial amount of oxalic acid as well as abundant carbon clusters and BB markers. The general existence of nitric acid in oxalic-acid-containing particles indicates an acidic environment during the formation process of oxalic acid. The peak areas of nitrate, sulfate and oxalic had similar temporal change in the carbonaceous type oxalic acid particles, and the organosulfate-containing oxalic acid particles correlated well with total oxalic acid particles during the haze episode, which suggests that the formation of oxalic acid is closely associated with the oxidation of organic precursors in the aqueous phase.

Determination of Food Oxalates Using Silica–Titania Xerogel Modified with Eriochrome Cyanine R

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Maria A. Morosanova

2018-03-01

Full Text Available The interaction of silica–titania xerogel with triphenylmethane dyes (pyrocatechol violet, chrome azurol S, eriochrome cyanine R has been investigated to create a new sensor material for solid phase spectrophotometric determination of food oxalates. The complex forming reaction between xerogel incorporated titanium(IV and triphenylmethane dyes has been studied; half-reaction periods, complex composition, equilibrium constants, and xerogel sorption capacity have been calculated for each dye. Eriochrome cyanine R (ECR is characterized by the shortest half-reaction period, the smallest equilibrium constant, and the greatest capacity; it has been chosen for the sensor material construction because titanium(IV-ECR complex is formed faster and can be destroyed easier than other studied complexes. The interaction of this sensor material with oxalates has been described: the presence of oxalates causes sensor material discoloration and the absorbance is used as analytical signal. The analytical range is 35–900 mg/L (LOD 10.5 mg/L, n = 7. High concentrations of interfering inorganic anions, organic acids, and sucrose did not affect oxalate determination. Proposed solid phase spectrophotometric procedure has been successfully applied for the determination of oxalates in food samples (sorrel, spinach, parsley, ginger, and black pepper and the results are in good agreement with HPLC oxalate determination.

Hygroscopic properties of oxalic acid and atmospherically relevant oxalates

Science.gov (United States)

Ma, Qingxin; He, Hong; Liu, Chang

2013-04-01

Oxalic acid and oxalates represent an important fraction of atmospheric organic aerosols, however, little knowledge about the hygroscopic behavior of these particles is known. In this study, the hygroscopic behavior of oxalic acid and atmospherically relevant oxalates (H2C2O4, (NH4)2C2O4, CaC2O4, and FeC2O4) were studied by Raman spectrometry and vapor sorption analyzer. Under ambient relative humidity (RH) of 10-90%, oxalic acid and these oxalates hardly deliquesce and exhibit low hygroscopicity, however, transformation between anhydrous and hydrated particles was observed during the humidifying and dehumidifying processes. During the water adsorption process, conversion of anhydrous H2C2O4, (NH4)2C2O4, CaC2O4, and FeC2O4 to their hydrated particles (i.e., H2C2O4·2H2O, (NH4)2C2O4·H2O, CaC2O4·H2O, and FeC2O4·2H2O) occurred at about 20% RH, 55% RH, 10% RH, and 75% RH, respectively. Uptake of water on hydrated Ca-oxalate and Fe-oxalate particles can be described by a multilayer adsorption isotherm. During the dehumidifying process, dehydration of H2C2O4·2H2O and (NH4)2C2O4·H2O occurred at 5% RH while CaC2O4·H2O and FeC2O4·2H2O did not undergo dehydration. These results implied that hydrated particles represent the most stable state of oxalic acid and oxalates in the atmosphere. In addition, the assignments of Raman shift bands in the range of 1610-1650 cm-1 were discussed according to the hygroscopic behavior measurement results.

Ultraviolet-B radiation mobilizes uranium from uranium-dissolved organic carbon complexes in aquatic systems, demonstrated by asymmetrical flow field-flow fractionation.

Science.gov (United States)

Nehete, Sachin Vilas; Christensen, Terje; Salbu, Brit; Teien, Hans-Christian

2017-05-05

Humic substances have a tendency to form complexes with metal ions in aquatic medium, impacting the metal mobility, decreasing bioavailability and toxicity. Ultraviolet-B (UV-B) radiation exposure degrades the humic substance, changes their molecular weight distribution and their metal binding capacity in aquatic medium. In this study, we experimented the effect of UV-B radiation on the uranium complexed with fulvic acids and humic acids in a soft water system at different pH, uranium concentrations and radiant exposure. The concentration and distribution of uranium in a complexed form were investigated by asymmetrical flow field-flow fractionation coupled to multi detection technique (AsFlFFF-UV-ICP-MS). The major concentration of uranium present in complexes was primarily associated with average and higher molecular weight fulvic and humic acids components. The concentration of uranium in a complexed form increased with increasing fulvic and humic acid concentrations as well as pH of the solution. The higher molecular weight fraction of uranium was degraded due to the UV-B exposure, transforming about 50% of the uranium-dissolved organic carbon complexes into low molecular weight uranium species in complex form with organic ligands and/or free form. The result also suggests AsFlFFF-UV-ICP-MS to be an important separation and detection technique for understanding the interaction of radionuclides with dissolved organic matter, tracking size distribution changes during degradation of organic complexes for understanding mobility, bioavailability and ecosystem transfer of radionuclides as well as metals. Copyright © 2017 Elsevier B.V. All rights reserved.

Quantum mechanical calculation of aqueuous uranium complexes: carbonate, phosphate, organic and biomolecular species

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Jha Prashant

2009-08-01

Full Text Available Abstract Background Quantum mechanical calculations were performed on a variety of uranium species representing U(VI, U(V, U(IV, U-carbonates, U-phosphates, U-oxalates, U-catecholates, U-phosphodiesters, U-phosphorylated N-acetyl-glucosamine (NAG, and U-2-Keto-3-doxyoctanoate (KDO with explicit solvation by H2O molecules. These models represent major U species in natural waters and complexes on bacterial surfaces. The model results are compared to observed EXAFS, IR, Raman and NMR spectra. Results Agreement between experiment and theory is acceptable in most cases, and the reasons for discrepancies are discussed. Calculated Gibbs free energies are used to constrain which configurations are most likely to be stable under circumneutral pH conditions. Reduction of U(VI to U(IV is examined for the U-carbonate and U-catechol complexes. Conclusion Results on the potential energy differences between U(V- and U(IV-carbonate complexes suggest that the cause of slower disproportionation in this system is electrostatic repulsion between UO2 [CO3]35- ions that must approach one another to form U(VI and U(IV rather than a change in thermodynamic stability. Calculations on U-catechol species are consistent with the observation that UO22+ can oxidize catechol and form quinone-like species. In addition, outer-sphere complexation is predicted to be the most stable for U-catechol interactions based on calculated energies and comparison to 13C NMR spectra. Outer-sphere complexes (i.e., ion pairs bridged by water molecules are predicted to be comparable in Gibbs free energy to inner-sphere complexes for a model carboxylic acid. Complexation of uranyl to phosphorus-containing groups in extracellular polymeric substances is predicted to favor phosphonate groups, such as that found in phosphorylated NAG, rather than phosphodiesters, such as those in nucleic acids.

Behaviour of Pu-IV with various ion exchangers in solutions containing nitric acid and oxalates

International Nuclear Information System (INIS)

Walter, E.; Ali, S.A.

1982-02-01

The distribution of Pu-IV on the ion exchangers Dowex 50W-X8, Dowex 1-X8 und Dowex Chelating Resin Al-X8 in the presence of various concentrations of nitric acid and oxalate were investigated. The results indicate that nitric acid and oxalic acid influence each other during complexation of Pu-IV with oxalate ions solutions containing nitric acid it is not possible to neglect the formation of Pu-IV nitrate complexes. The complex Pu(IV) (C 2 O 4 ) 3 2 - only is formed in solutions containing low nitric acid and high oxalic acid concentrations. The separation of Pu-IV in Dowex Chelating Resin from nitric acid solution in the presence of higher oxalate concentrations is possible, provided that the nitric acid concentration is lower than 0.25 molar [fr

More light on the U clan. [Uranium behaviour in complex ores

Energy Technology Data Exchange (ETDEWEB)

De Waal, S.A. (Potchefstroom Univ. for C.H.E. (South Africa). Dept. of Geology)

1983-07-01

A thorough knowledge of the geochemistry of uranium is necessary for the exploration and beneficiation of this mineral. At present we lack knowledge of the behaviour of uranium minerals in complex ores. This article deals with the geochemistry of uranium, its group identity, uranium minerals and the extraction mineralogy.

Structure of the oxalate-ATP complex with pyruvate kinase: ATP as a bridging ligand for the two divalent cations

International Nuclear Information System (INIS)

Lodato, D.T.; Reed, G.H.

1987-01-01

The 2 equiv of divalent cation that are required cofactors for pyruvate kinase reside in sites of different affinities for different species of cation. The intrinsic selectivity of the protein-based site for Mn(II) and of the nucleotide-based site for Mg(II) has been exploited in electron paramagnetic resonance (EOR) investigations of ligands for Mn(II) at the protein-based site. Oxalate, a structural analogue of the enolate of pyruvate, has been used as a surrogate for the reactive form of pyruvate in complexes with enzyme, Mn(II), Mg(II), and ATP. Superhyperfine coupling between the unpaired electron spin of Mn(II) and the nuclear spin of 17 O, specifically incorporated into oxalate, shows that oxalate is bound at the active site as a bidentate chelate with Mn(II). Coordination of the γ-phosphate of ATP to this same Mn(II) center is revealed by observation of superhyperfine coupling from 17 O regiospecifically incorporated into the γ-phosphate group of ATP. By contrast, 17 O in the α-phosphate or in the β-phosphate groups of ATP does not influence the spectrum. Experiments in 17 O-enriched water show that there is also a single water ligand bound to the Mn(II). These data indicate that ATP bridges Mn(II) and Mg(II) at the active site. A close spacing of the two divalent cations is also evident from the occurrence of magnetic interactions for complexes in which 2 equiv of Mn(II) are present at the active site. The structure for the enzyme-Mn(II)-oxalate-Mg(II)-ATP complex suggests a scheme for the normal reverse reaction of pyruvate kinase in which the divalent cation at the protein-based site activates the keto acid substrate through chelation and promotes phospho transfer by simultaneous coordination to the enolate oxygen and to a pendant oxygen from the γ-phosphate of ATP

Further Studies on Oxalic Acid Biosynthesis in Oxalate-accumulating Plants 1

Science.gov (United States)

Nuss, Richard F.; Loewus, Frank A.

1978-01-01

l-Ascorbic acid functions as a precursor of oxalic acid in several oxalate-accumulating plants. The present study extends this observation to include Rumex crispus L. (curly dock), Amaranthus retroflexus L. (red root pigweed), Chenopodium album L. (lamb's-quarters), Beta vulgaris L. (sugar beet), Halogeton glomeratus M. Bieb. (halogeton), and Rheum rhabarbarum L. (rhubarb). Several species with low oxalate content are also examined. When l-[1-14C]ascorbic acid is supplied to young seedlings of R. crispus or H. glomeratus, a major portion of the 14C is released over a 24-hour period as 14CO2 and only a small portion is recovered as [14C]oxalate, unlike cuttings from 2- or 4-month-old plants which retain a large part of the 14C as [14C]oxalic acid and release very little 14CO2. Support for an intermediate role of oxalate in the release of 14CO2 from l-[1-14C]ascorbic acid is seen in the rapid release of 14CO2 by R. crispus and H. glomeratus seedlings labeled with [14C]oxalic acid. The common origin of oxalic acid carbon in the C1 and C2 fragment from l-ascorbic acid is demonstrated by comparison of 14C content of oxalic acid in several oxalate-accumulators after cuttings or seedlings are supplied equal amounts of l-[1-14C]- or l-[UL-14C]ascorbic acid. Theoretically, l-[1-14C]ascorbic acid will produce labeled oxalic acid containing three times as much 14C as l-[UL-14C]ascorbic acid when equal amounts of label are provided. Experimentally, a ratio of 2.7 ± 0.5 is obtained in duplicate experiments with six different species. PMID:16660342

Uranium complexes with macrosyclic polyethers. Synthesis and structural chemical analysis

International Nuclear Information System (INIS)

Elbasyouny, A.

1983-01-01

This dissertation reports about studies on the chemical coordination behaviour of uranium of oxidation stages IV and VI with regard to twelve different macrocyclic ligands. For the preparation of the complexes, for every system a different method has been developed. The elementary analysis of the various complexes including the uranium had been done by X-ray fluorescence analysis, and the structural characterization proceeded via vibrational, uv-vis and emission spectroscopy as well as 1 H-NMR and 13 C-spin-lattice relaxation time studies. Conformational analysis of the polyethers used allowed the structural changes in the complexes to be observed. The structural analysis of the hydrous uranium VI crown ether complexes yielded information of characteristic features of these types of complexes. The first coordination sphere of the uranyl ion with covalently bonded anion remains unchanged. As to the water content, there is a certain range. Depending upon the solvent used, the complexes have two or four H 2 O molecules per formula unit. (orig./EF) [de

Single-molecule magnetism in a single-ion triamidoamine uranium(V) terminal mono-oxo complex

International Nuclear Information System (INIS)

King, David M.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Liddle, Stephen T.; Tuna, Floriana; McInnes, Eric J.L.

2013-01-01

Straightforward oxidation of a triamidoamine uranium(III) complex with trimethyl-N-oxide affords a uranium(V) terminal mono-oxo complex which is the first clear-cut example of a uranium(V) single-molecule magnet (SMM). This monometallic complex unambiguously shows that a strongly axially ligated and thus anisotropic ligand field can be used to overcome the limited magnetic anisotropy of uranium(V). [de

Kinetic study of nucleation and crystal growth during oxalic precipitation in the nuclear industry

International Nuclear Information System (INIS)

Andrieu, Murielle

1999-01-01

In spite of an extensive use in chemical industry, most of precipitation processes are based on global and empirical knowledge. However, in the recent years, fundamental and phenomenological theories have been developed and they can be used to better understand the mechanisms of precipitation of plutonium IV oxalate, which is a significant stage of the irradiated fuel reprocessing. For this reason, appropriate methods were developed to study nucleation and crystal growth kinetics in a nuclear environment under a wide range of operating conditions. Each phenomena was studied individually in order to reduce the free parameters of the System. This study bears on the oxalates of plutonium and elements which simulate plutonium behaviour during the precipitation, neodymium III and uranium IV. A compact apparatus of a specific construction was used for nucleation measurements in accordance with the Nielsen's method. The state of the mixing was characterised at the reactor scale (macro-mixing) and at molecular scale (micro-mixing). The experimental results for the studied oxalates are in good agreement with the Volmer and Weber's theory. We propose primary nucleation kinetic laws over a wide range of operating conditions (temperature, non-stoichiometric conditions, acidity...). An original method, using a high seed charge, was developed for the determination of crystal growth kinetics, in a batch crystallizer. The crystal growth rate is first order with respect to the supersaturation and the kinetic constant follows an Arrhenius type relation with activation energies of 14, 29 and 36 kJ.mol -1 for respectively neodymium III, uranium IV and plutonium IV oxalates. The overall growth process is surface integration controlled, with a screw dislocation mechanism. [fr

Uranium nucleophilic carbene complexes

International Nuclear Information System (INIS)

Tourneux, Jean-Christophe

2012-01-01

The only stable f-metal carbene complexes (excluding NHC) metals f present R 2 C 2- groups having one or two phosphorus atoms in the central carbon in alpha position. The objective of this work was to develop the chemistry of carbenes for uranium (metal 5f) with the di-anion C{Ph 2 P(=S)} 2 2- (SCS 2- ) to extend the organometallic chemistry of this element in its various oxidation states (+3-+6), and to reveal the influence of the 5f orbitals on the nature and reactivity of the double bond C=U. We first isolated the reactants M(SCHS) (M = Li and K) and demonstrated the role of the cation M + on the evolution of the di-anion M 2 SCS (M = Li, K, Tl) which is transformed into LiSCHS in THF or into product of intramolecular cyclization K 2 [C(PhPS) 2 (C 6 H 4 )]. We have developed the necessary conditions mono-, bis- and tris-carbene directly from the di-anion SCS 2- and UCl 4 , as the precursor used in uranium chemistry. The protonolysis reactions of amides compounds (U-NEt 2 ) by the neutral ligand SCH 2 S were also studied. The compounds [Li(THF)] 2 [U(SCS)Cl 3 ] and [U(SCS)Cl 2 (THF) 2 ] were then used to prepare a variety of cyclopentadienyl and mono-cyclo-octa-tetra-enyliques uranium(IV) carbene compounds of the DFT analysis of compounds [M(SCS)Cl 2 (py) 2 ] and [M(Cp) 2 (SCS)] (M = U, Zr) reveals the strong polarization of the M=C double bond, provides information on the nature of the σ and π interactions in this binding, and shows the important role of f orbitals. The influence of ancillary ligands on the M=C bond is revealed by examining the effects of replacing Cl - ligands and pyridine by C 5 H 5 - groups. Mulliken and NBO analyzes show that U=C bond, unlike the Zr=C bond, is not affected by the change in environment of the metal center. While the oxidation tests of carbene complexes of U(IV) were disappointing, the first carbene complex of uranium (VI), [UO 2 (SCS)(THF) 2 ], was isolated with the uranyl ion UO 2 2+ . The reactions of compounds UO 2 X 2

Competitive and Cooperative Effects during Nickel Adsorption to Iron Oxides in the Presence of Oxalate

Energy Technology Data Exchange (ETDEWEB)

Flynn, Elaine D. [Department of Earth and Planetary; Catalano, Jeffrey G. [Department of Earth and Planetary

2017-08-09

Iron oxides are ubiquitous in soils and sediments and play a critical role in the geochemical distribution of trace elements and heavy metals via adsorption and coprecipitation. The presence of organic acids may potentially alter how metals associate with iron oxide minerals through a series of cooperative or competitive processes: solution complexation, ternary surface complexation, and surface site competition. The macroscopic and molecular-scale effects of these processes were investigated for Ni adsorption to hematite and goethite at pH 7 in the presence of oxalate. The addition of this organic acid suppresses Ni uptake on both minerals. Aqueous speciation suggests that this is dominantly the result of oxalate complexing and solubilizing Ni. Comparison of the Ni surface coverage to the concentration of free (uncomplexed) Ni²⁺ in solution suggests that the oxalate also alters Ni adsorption affinity. EXAFS and ATR-FTIR spectroscopies indicate that these changes in binding affinity are due to the formation of Ni–oxalate ternary surface complexes. These observations demonstrate that competition between dissolved oxalate and the mineral surface for Ni overwhelms the enhancement in adsorption associated with ternary complexation. Oxalate thus largely enhances Ni mobility, thereby increasing micronutrient bioavailability and inhibiting contaminant sequestration.

Electrolytic destruction of oxalate ions in plutonium oxalate supernatant

International Nuclear Information System (INIS)

Michael, K.M.; Talnikar, S.G.; Jambunathan, U.; Kapoor, S.C.; Ramanujam, A.; Venkataraman, N.

1996-01-01

A simple and efficient electrolytic method is described for the destruction of the oxalate ions present in plutonium oxalate supernatant. Using platinum electrode and very little KMnO 4 , in situ generation of Mn 3+ ions is achieved which in turn destroys the oxalate. The use of lower current density helps in achieving maximum current efficiency. The end point is easily detectable by the pink colour of permanganate. By reversing the current, this slight excess of permanganate can be destroyed, thus avoiding the use of hydrogen peroxide. By this simple electrolytic method, the corrosive oxalate ion is completely destroyed and the salt content of the waste solution is considerably reduced. (author). 4 refs., 1 fig., 6 tabs

Controlled thermolysis of uranium (alkoxy)siloxy complexes: a route to polymetallic complexes of Low-Valent uranium

Energy Technology Data Exchange (ETDEWEB)

Camp, Clement; Pecaut, Jacques; Mazzanti, Marinella [Laboratoire de Reconnaissance Ionique et Chimie de Coordination, SCIB, UMR-E3 CEA-UJF, INAC, CEA-Grenoble (France); Kefalidis, Christos E.; Maron, Laurent [LPCNO, CNRS et INSA, UPS, Universite de Toulouse (France)

2013-07-01

Decomposition into higher species: Intramolecular U{sup III}-mediated homolytic C-O bond cleavage in U{sup III} (alkoxy)siloxy complexes at low temperature and subsequent reduction with KC{sub 8} led to unprecedented polymetallic complexes containing siloxy, silanediolate, and silanetriolate ligands. Such compounds may be useful precursors to uranium ceramics relevant for catalysis and the storage of spent nuclear fuel. (Copyright copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

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

Oxo-group-14-element bond formation in binuclear uranium(V) pacman complexes

International Nuclear Information System (INIS)

Jones, Guy M.; Arnold, Polly L.; Love, Jason B.

2013-01-01

Simple and versatile routes to the functionalization of uranyl-derived U"V-oxo groups are presented. The oxo-lithiated, binuclear uranium(V)-oxo complexes [{(py)_3LiOUO}_2(L)] and [{(py)_3LiOUO}(OUOSiMe_3)(L)] were prepared by the direct combination of the uranyl(VI) silylamide ''ate'' complex [Li(py)_2][(OUO)(N'')_3](N''=N(SiMe_3)_2) with the polypyrrolic macrocycle H_4L or the mononuclear uranyl (VI) Pacman complex [UO_2(py)(H_2L)], respectively. These oxo-metalated complexes display distinct U-O single and multiple bonding patterns and an axial/equatorial arrangement of oxo ligands. Their ready availability allows the direct functionalization of the uranyl oxo group leading to the binuclear uranium(V) oxo-stannylated complexes [{(R_3Sn)OUO}_2(L)] (R=nBu, Ph), which represent rare examples of mixed uranium/tin complexes. Also, uranium-oxo-group exchange occurred in reactions with [TiCl(OiPr)_3] to form U-O-C bonds [{(py)_3LiOUO}(OUOiPr)(L)] and [(iPrOUO)_2(L)]. Overall, these represent the first family of uranium(V) complexes that are oxo-functionalised by Group 14 elements. (Copyright copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Method of purifying uranium tetrafluoride hydrate and preparing uranium (VI) peroxide hydrate using a fluoride complexing agent

International Nuclear Information System (INIS)

Barreiro, A.J.; Lowe, C.M.T.; Lefever, J.A.; Pyman, R.L.

1983-01-01

The annual production of phosphate rock, on the order of about 30-40 million tons yearly, represents several million pounds of uranium. The present invention provides a process of purifying uranium tetrafluoride hydrate to produce a uranium (VI) peroxide product meeting 'yellow cake' standards using a double precipitation procedure. A fluoride complexing agent is used in the precipitation

URANIUM DECONTAMINATION WITH RESPECT TO ZIRCONIUM

Science.gov (United States)

Vogler, S.; Beederman, M.

1961-05-01

A process is given for separating uranium values from a nitric acid aqueous solution containing uranyl values, zirconium values and tetravalent plutonium values. The process comprises contacting said solution with a substantially water-immiscible liquid organic solvent containing alkyl phosphate, separating an organic extract phase containing the uranium, zirconium, and tetravalent plutonium values from an aqueous raffinate, contacting said organic extract phase with an aqueous solution 2M to 7M in nitric acid and also containing an oxalate ion-containing substance, and separating a uranium- containing organic raffinate from aqueous zirconium- and plutonium-containing extract phase.

Electrodeposition of milligram amounts of uranium on electropolished stainless steel disks

International Nuclear Information System (INIS)

Aggarwal, S.K.; Shah, P.M.; Duggal, R.K.; Jain, H.C.

1991-01-01

Investigations have been carried out for the electrodeposition of milligram amounts of uranium on electropolished stainless steel disks with an objective of preparing good quality sources for α-spectrometric studies on uranium. The parameters studied include the vatiation of electrodeposition yield as a function of voltage, time, distance between the cathode and anode, and the volume of 0.2M ammonium oxalate solution. The conditions selected for preparing good quality sources with nearly 100% yield were: electrodeposition voltage 25 V, time of deposition 15 min, volume of 0.2M ammonium oxalate solution in the cell 4 ml and a distance of 2 cm between the cathode and anode. The sources prepared using this method have been used successfully for the α-spectrometric determination of 234 U/ 238 U ratios in uranium samples. (author) 6 refs.; 4 figs

Single-molecule magnetism in a single-ion triamidoamine uranium(V) terminal mono-oxo complex

Energy Technology Data Exchange (ETDEWEB)

King, David M.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Liddle, Stephen T. [School of Chemistry, University of Nottingham (United Kingdom); Tuna, Floriana; McInnes, Eric J.L. [School of Chemistry and Photon Science Institute, University of Manchester (United Kingdom)

2013-04-26

Straightforward oxidation of a triamidoamine uranium(III) complex with trimethyl-N-oxide affords a uranium(V) terminal mono-oxo complex which is the first clear-cut example of a uranium(V) single-molecule magnet (SMM). This monometallic complex unambiguously shows that a strongly axially ligated and thus anisotropic ligand field can be used to overcome the limited magnetic anisotropy of uranium(V). (Copyright copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Single-molecule magnetism in a single-ion triamidoamine uranium(V) terminal mono-oxo complex

International Nuclear Information System (INIS)

King, David M.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Liddle, Stephen T.; Tuna, Floriana; McInnes, Eric J.L.

2013-01-01

Straightforward oxidation of a triamidoamine uranium(III) complex with trimethyl-N-oxide affords a uranium(V) terminal mono-oxo complex which is the first clear-cut example of a uranium(V) single-molecule magnet (SMM). This monometallic complex unambiguously shows that a strongly axially ligated and thus anisotropic ligand field can be used to overcome the limited magnetic anisotropy of uranium(V). (Copyright copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Magnetic study of solid uranium-fluorine complexes; Contribution a l'etude magnetique de composes fluores solides de l'uranium

Energy Technology Data Exchange (ETDEWEB)

Dianoux, A J [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1969-06-01

A study of the magnetic susceptibility of uranium V fluorine complexes and of the magnetic resonance of fluorine atoms in uranium VI fluorine complexes has made it possible to put forward a structural model for these compounds for which it is impossible, because of the lack of suitable single crystals for X-ray diffraction work, to deduce the exact position of the fluorine atoms. It is shown that it is difficult to interpret the paramagnetism of uranium fluorides, because the uranium ions are in low-symmetry sites. A theoretical study of the magnetism of the U{sup V} ion in complex fluorides of the type M{sub 3}UF{sub 8} (M = NH{sub 4}, Na, Rb, Cs) leads to an interpretation based on a trigonal deformation of the eight fluorine atom structure surrounding the uranium atom. By applying a Hamiltonian spin formalism and making a systematic use of group theory, it is possible to present the susceptibility calculations very concisely. Study of the resonance and of the relaxation of the fluorine atoms in powdered uranium VI complex fluorides suggests a structural model in the case of NaUF{sub 7}. It is shown that the shape of the magnetic resonance absorption lines is strongly affected by the presence of large anisotropic chemical shifts. In the model proposed here, six fluorine atoms are linked to the uranium, atom by strongly covalent bonds in a deformed UF{sub 6} octahedral structure; the seventh fluorine atom remains ionic. The occurrence of a rotational movement of the octahedron is confirmed by a study of the longitudinal relaxation of the fluorine atoms, the activation energy being 0.46 eV. (author) [French] L'etude de la susceptibilite magnetique de complexes fluores d'uranium V et la resonance magnetique des fluors dans des complexes fluores d'uranium VI permettent de proposer un modele structural pour ces composes, ou la diffraction des rayons X, en l'absence de monocristaux convenables, est incapable de preciser la position des atomes de fluor. Nous montrons

Oxo-group-14-element bond formation in binuclear uranium(V) pacman complexes

Energy Technology Data Exchange (ETDEWEB)

Jones, Guy M.; Arnold, Polly L.; Love, Jason B. [EaStCHEM School of Chemistry, University of Edinburgh (United Kingdom)

2013-07-29

Simple and versatile routes to the functionalization of uranyl-derived U{sup V}-oxo groups are presented. The oxo-lithiated, binuclear uranium(V)-oxo complexes [{(py)_3LiOUO}{sub 2}(L)] and [{(py)_3LiOUO}(OUOSiMe{sub 3})(L)] were prepared by the direct combination of the uranyl(VI) silylamide ''ate'' complex [Li(py){sub 2}][(OUO)(N''){sub 3}](N''=N(SiMe{sub 3}){sub 2}) with the polypyrrolic macrocycle H{sub 4}L or the mononuclear uranyl (VI) Pacman complex [UO{sub 2}(py)(H{sub 2}L)], respectively. These oxo-metalated complexes display distinct U-O single and multiple bonding patterns and an axial/equatorial arrangement of oxo ligands. Their ready availability allows the direct functionalization of the uranyl oxo group leading to the binuclear uranium(V) oxo-stannylated complexes [{(R_3Sn)OUO}{sub 2}(L)] (R=nBu, Ph), which represent rare examples of mixed uranium/tin complexes. Also, uranium-oxo-group exchange occurred in reactions with [TiCl(OiPr){sub 3}] to form U-O-C bonds [{(py)_3LiOUO}(OUOiPr)(L)] and [(iPrOUO){sub 2}(L)]. Overall, these represent the first family of uranium(V) complexes that are oxo-functionalised by Group 14 elements. (Copyright copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

The uranium potential of the Bushveld igneous complex

International Nuclear Information System (INIS)

Andreoli, M.A.G.; Hart, R.J.; Brynard, H.J.; Camisani-Calzolari, F.A.G.M.

1987-06-01

A review of published literature supported by field observations on the uranium potential of the Bushveld Complex indicates that this geological region may host deposits with reserves in the range of a few thousand tons U 3 O 8 . The possibility that the Bushveld Complex or its cover rocks hosts, or has ever hosted in the past, giant uranium deposits such as those of Olympic Dam, Key Lake, Jabiluka or Rossing is considered to be unlikely. The potential for volcanogenic, caldera-type deposits in the Rooiberg Felsites remains at present untested. Recommendations for research currently sponsored by the AEC at the University of Pretoria are presented

Nitrogen reduction and functionalization by a multimetallic uranium nitride complex

Science.gov (United States)

Falcone, Marta; Chatelain, Lucile; Scopelliti, Rosario; Živković, Ivica; Mazzanti, Marinella

2017-07-01

Molecular nitrogen (N2) is cheap and widely available, but its unreactive nature is a challenge when attempting to functionalize it under mild conditions with other widely available substrates (such as carbon monoxide, CO) to produce value-added compounds. Biological N2 fixation can do this, but the industrial Haber-Bosch process for ammonia production operates under harsh conditions (450 degrees Celsius and 300 bar), even though both processes are thought to involve multimetallic catalytic sites. And although molecular complexes capable of binding and even reducing N2 under mild conditions are known, with co-operativity between metal centres considered crucial for the N2 reduction step, the multimetallic species involved are usually not well defined, and further transformation of N2-binding complexes to achieve N-H or N-C bond formation is rare. Haber noted, before an iron-based catalyst was adopted for the industrial Haber-Bosch process, that uranium and uranium nitride materials are very effective heterogeneous catalysts for ammonia production from N2. However, few examples of uranium complexes binding N2 are known, and soluble uranium complexes capable of transforming N2 into ammonia or organonitrogen compounds have not yet been identified. Here we report the four-electron reduction of N2 under ambient conditions by a fully characterized complex with two UIII ions and three K+ centres held together by a nitride group and a flexible metalloligand framework. The addition of H2 and/or protons, or CO to the resulting complex results in the complete cleavage of N2 with concomitant N2 functionalization through N-H or N-C bond-forming reactions. These observations establish that a molecular uranium complex can promote the stoichiometric transformation of N2 into NH3 or cyanate, and that a flexible, electron-rich, multimetallic, nitride-bridged core unit is a promising starting point for the design of molecular complexes capable of cleaving and functionalizing N2 under

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

International Nuclear Information System (INIS)

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

1981-01-01

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

Density functional theory studies on the structures and water-exchange reactions of aqueous Al(III)-oxalate complexes.

Science.gov (United States)

Jin, Xiaoyan; Yan, Yu; Shi, Wenjing; Bi, Shuping

2011-12-01

The structures and water-exchange reactions of aqueous aluminum-oxalate complexes are investigated using density functional theory. The present work includes (1) The structures of Al(C(2)O(4))(H(2)O)(4)(+) and Al(C(2)O(4))(2)(H(2)O)(2)(-) were optimized at the level of B3LYP/6-311+G(d,p). The geometries obtained suggest that the Al-OH(2) bond lengths trans to C(2)O(4)(2-) ligand in Al(C(2)O(4))(H(2)O)(4)(+) are much longer than the Al-OH(2) bond lengths cis to C(2)O(4)(2-). For Al(C(2)O(4))(2)(H(2)O)(2)(-), the close energies between cis and trans isomers imply the coexistence in aqueous solution. The (27)Al NMR and (13)C NMR chemical shifts computed with the consideration of sufficient solvent effect using HF GIAO method and 6-311+G(d,p) basis set are in agreement with the experimental values available, indicating the appropriateness of the applied models; (2) The water-exchange reactions of Al(III)-oxalate complexes were simulated at the same computational level. The results show that water exchange proceeds via dissociative pathway and the activation energy barriers are sensitive to the solvent effect. The energy barriers obtained indicate that the coordinated H(2)O cis to C(2)O(4)(2-) in Al(C(2)O(4))(H(2)O)(4)(+) is more labile than trans H(2)O. The water-exchange rate constants (k(ex)) of trans- and cis-Al(C(2)O(4))(2)(H(2)O)(2)(-) were estimated by four methods and their respective characteristics were explored; (3) The significance of the study on the aqueous aluminum-oxalate complexes to environmental chemistry is discussed. The influences of ubiquitous organic ligands in environment on aluminum chemistry behavior can be elucidated by extending this study to a series of Al(III)-organic system.

Determination of natural uranium in urine ({sup 233}U); Dosage de l'uranium dans l'urine ({sup 233}U)

Energy Technology Data Exchange (ETDEWEB)

Jeanmaire, L; Jammet, H [Commissariat a l' Energie Atomique, Saclay (France).Centre d' Etudes Nucleaires

1959-07-01

A procedure for the quantitative analysis of uranium in urine is described. The residue obtained by mineralization is dissolved in diluted hydrochloric acid. Uranium is separated by fixation on a permutit 50 column, elution with 0,2 M oxalic acid and electrodeposition on nickel. Uranium is then measured by {alpha} counting. It is thus possible to detect less than 1 pico-curie of uranium in the sample. (author) [French] Cet article decrit une technique de dosage de l'uranium dans l'urine. Apres mineralisation, le residu est dissous dans l'acide chlorhydrique dilue. L'uranium est separe par fixation, sur une colonne de permutite 50, elution au moyen d'acide oxalique 0,2 M et depot electrolytique sur nickel. La mesure faite par comptage {alpha} permet de detecter moins de 1 picocurie d'uranium dans l'echantillon. (auteur)

Spectroscopic confirmation of uranium(VI)-carbonato adsorption complexes on hematite

Science.gov (United States)

Bargar, John R.; Reitmeyer, Rebecca; Davis, James A.

1999-01-01

Evaluating societal risks posed by uranium contamination from waste management facilities, mining sites, and heavy industry requires knowledge about uranium transport in groundwater, often the most significant pathway of exposure to humans. It has been proposed that uranium mobility in aquifers may be controlled by adsorption of U(VI)−carbonato complexes on oxide minerals. The existence of such complexes has not been demonstrated, and little is known about their compositions and reaction stoichiometries. We have used attenuated total reflectance Fourier transform infrared (ATR-FTIR) and extended X-ray absorption fine structure (EXAFS) spectroscopies to probe the existence, structures, and compositions of ≡FeOsurface−U(VI)−carbonato complexes on hematite throughout the pH range of uranyl uptake under conditions relevant to aquifers. U(VI)−carbonato complexes were found to be the predominant adsorbed U(VI) species at all pH values examined, a much wider pH range than previously postulated based on analogy to aqueous U(VI)−carbonato complexes, which are trace constituents at pH carbonato complexes may be of major importance to the groundwater transport of similar actinide contaminants such as neptunium and plutonium.

EXAFS investigation of uranium(6) complexes formed at Acidithiobacillus ferro oxidans types

International Nuclear Information System (INIS)

Merroun, M.; Reich, T.; Hennig, Ch.; Selenska-Pobell, S.

2002-01-01

Mining activities have brought excessive amounts of uranium into the environment. In uranium deposits a number of acidophilic chemo-litho-autotrophic bacteria have been identified which are able to oxidize sulphide minerals, elemental sulphur, ferrous iron and also (in the presence of uranium mineral) U(IV). In particular, the interaction of one representative of the group Acidithiobacillus ferro oxidans (new designation of Thiobacillus ferro oxidans) with uranium has been investigated. Uranium(VI) complex formations at the surfaces of Acidithiobacillus ferro oxidans were studied using uranium L III -edge extended X-ray absorption fine structure (EXAFS) spectroscopy. In all samples uranium is co-ordinated by two axial oxygen atoms (O ax ) at a distance of 1.77-1.78 angstrom. The average distance between uranium and the equatorial oxygen atoms (O eq ) is 2.35 angstrom. The co-ordination number for O eq is 5-6. In comparison to the uranium crystal structure data, the U-O eq distance indicates a co-ordination number of the equatorial oxygen of 5. Within the experimental error, there are no differences in the U-O bond distances between samples from the three types of A. ferro oxidans investigated. The fit to the EXAFS data of samples measured as wet pastes gave the same results as for dried samples. No significant structural differences were observed for the uranium complexes formed by the eco-types of A. ferro oxidans. However, the EXAFS spectra do indicate a formation of uranium complexes which are different from those formed by Bacilli where the bond length of 2.28 angstrom indicates a co-ordination number of 4 for the equatorial oxygen atoms. (authors)

Ligand Influences on Properties of Uranium Coordination Complexes - Structure, Reactivity, and Spectroscopy

OpenAIRE

Kosog, Boris

2012-01-01

In this thesis several different aspects of uranium chemistry are presented. It was shown that terminal uranium(V) oxo and imido complexes [((RArO)3tacn)UV(O)] and [((RArO)3tacn)UV(NSiMe3)] (R = t Bu, Ad) can be oxidized by silver(I) hexafluoro-antimonate to the uranium(VI) oxo and imido complexes [((RArO)3tacn)UVI(O)]SbF6 and [((RArO)3tacn)UVI(NSiMe3)]SbF6. While for the t Bu-derivative of the oxo complex an equatorial coordination is observed due to stabilization by the inverse trans-influe...

Structure of some complex halides of uranium(III)

International Nuclear Information System (INIS)

Volkov, V.A.; Suglobova, I.G.; Chirkst, D.E.

1987-01-01

Polycrystals of some halide complexes of uranium(III) were obtained and investigated by x-ray diffraction. The M 2 UCl 5 compounds (M = K, Rb) are isostructural with K 2 PrCl 5 ; RbU 2 Cl 7 is of the same type as RbDy 2 Cl 7 or KDy 2 Cl 7 . The coordination number of the uranium is 7. The M 2 UBr 5 compounds (M = K-Cs) are isostructural with Cs 2 DyCl 5 , and the coordination number of the uranium is 6. Rb 2 NaUCl 6 is a 12L-hexagonal polytype, the structural analog of Cs 2 NaCrF 6 . The most characteristic coordination number of uranium in the UHal 3 -MHal systems is 8 for Hal = F, 7 for Hal = Cl, and 6 for Hal = Br

Study of the temperature influence during the uranium (Vi) sorption on surface of ZrP{sub 2}O{sub 7} in presence of oxalic and salicylic acid; Estudio de la influencia de la temperatura durante la sorcion de uranio (VI) en la superficie del ZrP{sub 2}O{sub 7} en presencia de acidos oxalico y salicilico

Energy Technology Data Exchange (ETDEWEB)

Garcia G, N.

2013-07-01

This work studies the effect of temperature on the uranium (Vi) sorption onto zirconium diphosphate in the presence of organic acids (oxalic and salicylic acids). Zirconium diphosphate was synthesized by a chemical condensation reaction and characterized using several analytical techniques, in order to check its purity. This point is very important because the presence of any impurities or secondary phases may interfere with the hydration and sorption process. Prior to the sorption experiments, three batches of zirconium diphosphate were pre-equilibrated with NaClO{sub 4}, oxalic acid or salicylic acid solutions. The hydrated solids were washed and dried and then again characterized in order to study the interactions between organic acids and zirconium diphosphate surface. Uranium sorption onto zirconium diphosphate (pre-equilibrated with NaClO{sub 4}, oxalic acid and salicylic acid solutions) was investigated as a function of ph, organic acid and temperature (20, 40 y 60 grades C). Thermodynamic parameters for the sorption reactions (enthalpy change, entropy change and Gibbs free energy change) were determined from temperature dependence of distribution coefficient by using the Vant Hoff equation. Solids characterization after hydration shows that exist an interaction between organic acids and ZrP{sub 2}O{sub 7}. This fact was confirmed with the microcalorimetry study, the reaction heat for hydration of zirconium diphosphate in NaClO{sub 4} solution was exothermic (-269.59 mJ) and for hydration of zirconium diphosphate in oxalic acid solution was endothermic (53.64 mJ). The experimental results showed important differences in the sorption mechanisms for the reaction of Uranium with ZrP{sub 2}O{sub 7} in the presence and absence of organic acids. For the zirconium diphosphate hydrated with oxalic acid, the sorption percentage was 50% from lowest ph values. For the zirconium diphosphate hydrated with salicylic acid, the initial concentration of uranium was 6 x 10

Reaction of hydrazine hydrate with oxalic acid: synthesis and crystal structure of dihydrazinium oxalate

OpenAIRE

Selvakumar, Rajendran; Premkumar, Thathan; Manivannan, Vadivelu; Saravanan, Kaliannan; Govindarajan, Subbiah

2014-01-01

The reaction of oxalic acid with hydrazine hydrate (in appropriate mole ratio) forms the dihydrazinium oxalate under specific experimental condition. The title compound is a molecular salt containing two discrete hydrazinium cations and an oxalate anion. The oxalate anion is perfectly planar and there is a crystallographic centre of symmetry in the middle of the C-C bond. The C-O bond distances are almost equal indicating the presence of resonance in the oxalate ion. The crystal packing is st...

Determination of microquantities of zirconium and thorium in uranium dioxide

International Nuclear Information System (INIS)

Weber de D'Alessio, Ana; Zucal, Raquel.

1975-07-01

A method for the determination of 10 to 50 ppm of zirconium and thorium in uranium IV oxide of nuclear purity is established. Zirconium and thorium are retained in a strong cation-exchange resin Dowex 50 WX8 in 1 M HCl. Zirconium is eluted with 0,5% oxalic acid solution and thorium with 4% ammonium oxalate. The colorimetric determination of zirconium with xilenol orange is done in perchloric acid after destructtion of oxalic acid and thorium is determined with arsenazo III in 5 M HCl. 10 μg of each element were determined with a standard deviation of 2,1% for thorium and 3,4% for zirconium. (author) [es

Multiscale structural characterizations of mixed U(iv)-An(iii) oxalates (An(iii) = Pu or Am) combining XAS and XRD measurements.

Science.gov (United States)

Arab-Chapelet, B; Martin, P M; Costenoble, S; Delahaye, T; Scheinost, A C; Grandjean, S; Abraham, F

2016-04-28

Mixed actinide(III,IV) oxalates of the general formula M2.2UAn(C2O4)5·nH2O (An = Pu or Am and M = H3O(+) and N2H5(+)) have been quantitatively precipitated by oxalic precipitation in nitric acid medium (yield >99%). Thorough multiscale structural characterization using XRD and XAS measurements confirmed the existence of mixed actinide oxalate solid solutions. The XANES analysis confirmed that the oxidation states of the metallic cations, tetravalent for uranium and trivalent for plutonium and americium, are maintained during the precipitation step. EXAFS measurements show that the local environments around U(+IV), Pu(+III) and Am(+III) are comparable, and the actinides are surrounded by ten oxygen atoms from five bidentate oxalate anions. The mean metal-oxygen distances obtained by XAS measurements are in agreement with those calculated from XRD lattice parameters.

Uranium (Vi) sorption onto zirconium diphosphate chemically modified

International Nuclear Information System (INIS)

Garcia G, N.; Ordonez R, E.

2010-10-01

This work deals with the uranium (Vi) speciation after sorption onto zirconium diphosphate (ZrP 2 O 7 ) surface, hydrated and in a surface modified with organic acids. Oxalic and citric acids were chosen to modify the ZrP 2 O 7 surface because they have poly carboxylic groups and they mimic the organic matter in nature. Thus the interest of this work is to evaluate the uranium (Vi) sorption edge at different s ph values in natural and modified surfaces. The luminescence technique (fluorescence and phosphorescence, respectively) was used for the quantification and speciation of uranyl sorbed at the zirconium diphosphate interface. The fluorescence experiment, showed that adsorption of uranyl on surface of zirconium diphosphate tends to 100%. The speciation shows that there are different complexes in surface which were formed between zirconium diphosphate and uranyl, since it is produced a displacement of wavelength in fluorescence spectra of each system. (Author)

Reactivity of uranium(IV) bridged chalcogenido complexes UIV–E–UIV (E = S, Se) with elemental sulfur and selenium: synthesis of polychalcogenido-bridged uranium complexes

OpenAIRE

Franke, Sebastian M.; Heinemann, Frank W.; Meyer, Karsten

2014-01-01

We report the syntheses, electronic properties, and molecular structures of a series of polychalcogenido-bridged dinuclear uranium species. These complexes are supported by the sterically encumbering but highly flexible, single N-anchored tris(aryloxide) chelator (AdArO)3N3−. Reaction of an appropriate uranium precursor, either the U(III) starting material, [((AdArO)3N)U(DME)], or the dinuclear mono-chalcogenido-bridged uranium(IV/IV) compounds [{((AdArO)3N)U(DME)}2(μ-E)] (E = S, Se), with el...

Formation and uranium explorating prospect of sub-volcanic granitic complex and rich uranium ore deposit in South China

International Nuclear Information System (INIS)

Wang Yusheng

1997-01-01

The rich uranium ore deposits are all closely related to tecto-magmatism of late-magmatic cycle whether volcanic types or granitic types in south China. Volcanic type rich uranium deposit has closely relationship with sub-volcanic activity, and granitic type rich uranium deposit is also closely related to mid-fine, unequal particle small massif in late main invasion stage. Based on characteristics of magmatism, we name the rock sub-volcanic granite complex, which is a unique style and closely related to the formation of rich uranium ore deposit

An extraction method of uranium 233 from the thorium irradiates in a reactor core; Une methode d'extraction de l'uranium-233 a partir du thorium irradie dans une pile

Energy Technology Data Exchange (ETDEWEB)

Chesne, A; Regnaut, P [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1955-07-01

Description of the conditions of separation of the thorium, of the uranium 233 and of the protactinium 233 in hydrochloric solution by absorption then selective elution on anion exchange resin. A precipitation of the thorium by the oxalic acid permits the recuperation of the hydrochloric acid which is recycled, the main, raw material consumed being the oxalic acid. (authors) [French] Description des conditions de separation du thorium, de l'uranium 233 et du protactinium 233 en solution chlorhydrique par absorption puis elution selective sur resine echangeuse d'anions. Une precipitation du thoriun par l'acide oxalique permet la recuperation de l'acide chlorhydrique qui est recycle, la principale matiere premiere consommee etant l'acide oxalique. (auteurs)

Thorium oxalate solubility and morphology

International Nuclear Information System (INIS)

Monson, P.R. Jr.; Hall, R.

1981-10-01

Thorium was used as a stand-in for studying the solubility and precipitation of neptunium and plutonium oxalates. Thorium oxalate solubility was determined over a range of 0.001 to 10.0 in the concentration parameter [H 2 C 2 O 4 ]/[HNO 3 ] 2 . Morphology of thorium oxide made from the oxalate precipitates was characterized by scanning electron microscopy. The different morphologies found for oxalate-lean and oxalate-rich precipitations were in agreement with predictions based on precipitation theory

Magnetic study of solid uranium-fluorine complexes; Contribution a l'etude magnetique de composes fluores solides de l'uranium

Energy Technology Data Exchange (ETDEWEB)

Dianoux, A.J. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1969-06-01

A study of the magnetic susceptibility of uranium V fluorine complexes and of the magnetic resonance of fluorine atoms in uranium VI fluorine complexes has made it possible to put forward a structural model for these compounds for which it is impossible, because of the lack of suitable single crystals for X-ray diffraction work, to deduce the exact position of the fluorine atoms. It is shown that it is difficult to interpret the paramagnetism of uranium fluorides, because the uranium ions are in low-symmetry sites. A theoretical study of the magnetism of the U{sup V} ion in complex fluorides of the type M{sub 3}UF{sub 8} (M = NH{sub 4}, Na, Rb, Cs) leads to an interpretation based on a trigonal deformation of the eight fluorine atom structure surrounding the uranium atom. By applying a Hamiltonian spin formalism and making a systematic use of group theory, it is possible to present the susceptibility calculations very concisely. Study of the resonance and of the relaxation of the fluorine atoms in powdered uranium VI complex fluorides suggests a structural model in the case of NaUF{sub 7}. It is shown that the shape of the magnetic resonance absorption lines is strongly affected by the presence of large anisotropic chemical shifts. In the model proposed here, six fluorine atoms are linked to the uranium, atom by strongly covalent bonds in a deformed UF{sub 6} octahedral structure; the seventh fluorine atom remains ionic. The occurrence of a rotational movement of the octahedron is confirmed by a study of the longitudinal relaxation of the fluorine atoms, the activation energy being 0.46 eV. (author) [French] L'etude de la susceptibilite magnetique de complexes fluores d'uranium V et la resonance magnetique des fluors dans des complexes fluores d'uranium VI permettent de proposer un modele structural pour ces composes, ou la diffraction des rayons X, en l'absence de monocristaux convenables, est incapable de preciser la position des atomes de

An extraction method of uranium 233 from the thorium irradiates in a reactor core

International Nuclear Information System (INIS)

Chesne, A.; Regnaut, P.

1955-01-01

Description of the conditions of separation of the thorium, of the uranium 233 and of the protactinium 233 in hydrochloric solution by absorption then selective elution on anion exchange resin. A precipitation of the thorium by the oxalic acid permits the recuperation of the hydrochloric acid which is recycled, the main, raw material consumed being the oxalic acid. (authors) [fr

The metabolic and ecological interactions of oxalate-degrading bacteria in the Mammalian gut.

Science.gov (United States)

Miller, Aaron W; Dearing, Denise

2013-12-06

Oxalate-degrading bacteria comprise a functional group of microorganisms, commonly found in the gastrointestinal tract of mammals. Oxalate is a plant secondary compound (PSC) widely produced by all major taxa of plants and as a terminal metabolite by the mammalian liver. As a toxin, oxalate can have a significant impact on the health of mammals, including humans. Mammals do not have the enzymes required to metabolize oxalate and rely on their gut microbiota for this function. Thus, significant metabolic interactions between the mammalian host and a complex gut microbiota maintain the balance of oxalate in the body. Over a dozen species of gut bacteria are now known to degrade oxalate. This review focuses on the host-microbe and microbe-microbe interactions that regulate the degradation of oxalate by the gut microbiota. We discuss the pathways of oxalate throughout the body and the mammalian gut as a series of differentiated ecosystems that facilitate oxalate degradation. We also explore the mechanisms and functions of microbial oxalate degradation along with the implications for the ecological and evolutionary interactions within the microbiota and for mammalian hosts. Throughout, we consider questions that remain, as well as recent technological advances that can be employed to answer them.

Reaction of uranyl nitrate with carboxylic di-acids under hydrothermal conditions. Crystal structure of complexes with L(+)-tartaric and oxalic acids

International Nuclear Information System (INIS)

Thuery, P.

2007-01-01

L(+)-tartaric acid reacts with uranyl nitrate in the presence of KOH, under mild hydrothermal conditions, to give the complex [UO 2 (C 4 H 4 O 6 )(H 2 O)] (1), the first uranyl tartrate to be crystallographically characterized. Each tartrate ligand bridges three uranyl ions, one of them in chelating fashion through proximal carboxylate and hydroxyl groups. The resulting assemblage is two-dimensional, with the uranyl pentagonal bipyramidal coordination polyhedra separated from one another. Prolonged heating of an uranyl tartrate solution resulted in oxidative cleavage of the acid and formation of the oxalate complex [(UO 2 ) 2 (C 2 O 4 ) 2 (OH)Na(H 2 O) 2 ] (2). The bis-bidentate oxalate and bridging hydroxide groups ensure the formation of sheets with corner-sharing uranyl pentagonal bipyramidal coordination polyhedra, in which six-membered metallacycles encompass the sodium ions. These sheets are assembled into a three-dimensional framework through further oxo-bonding of the sodium ions. (authors)

Ultrafine yttria-stabilized zirconia powders prepared by pyrolysis of a metal-oxalate-cellulose complex

Energy Technology Data Exchange (ETDEWEB)

Solov`eva, L.V.; Bashmakov, I.A.; Kaputskii, F.N. [Research Institute of Physicochemical Problems, Minsk (Belarus)] [and others

1995-12-01

Preparation of high-purity submicron powders with uniform particles is a key stage in the fabrication of high-quality ceramics. For this purpose, chemical methods are commonly used. Recently, pyrolysis of salt-cellulose compositions has gained acceptance for the preparation of mixed oxide powders. This method ensures control of the morphology and particle size of the resultant powders. In this work, the authors present an environmentally safe method for preparing ZrO{sub 2}-based powders from metal-oxalate-cellulose complexes (MOCC) used as precursors instead of soluble metal salts physisorbed on the cellulose surface. The powders obtained by this method feature higher dispersity than their commercially available analogs.

Synthesis, characterization and study of some physical properties of some lanthanide complexes of salicylaldehyde oxal-dihydrazone

International Nuclear Information System (INIS)

Shrestha, S.; Rao, T.R.; Narang, K.K.; Shrestha, S.P.

2006-05-01

Some Lanthanoid complexes of the type [Ln (L-2H).A.H 2 O] [Ln = Y, La, Nd, Gd, Tb, Dy, A=OAc; and L = Salicyaldehyde oxal di-hydrazone] was synthesized and characterized by various physico- chemical techniques. Dehydration study at two specific temperatures (110 deg. C and 150 deg. C) indicates the presence of water molecules only in co-ordination sphere of the metal ion. IR, electronic spectra, DTA-TG have been recorded to establish the bonding sites of the ligand. All the complexes decomposed above and not melting up to 350 deg. C. The complexes are insoluble in any common organic solvent even in DMF and DMSO. Solid state electrical conductivities at various frequencies show a semiconducting nature of the complexes. Optical band gap measurement of the complex [Dy(SODH-2H).OAc.H 2 O] shows that complex behaves as direct band gap material. No well-defined peaks, except broad humps were observed in X-ray diffractogram of these complexes, indicating an amorphous nature of the complexes. (author)

Solubility of Plutonium (IV) Oxalate During Americium/Curium Pretreatment

International Nuclear Information System (INIS)

Rudisill, T.S.

1999-01-01

Approximately 15,000 L of solution containing isotopes of americium and curium (Am/Cm) will undergo stabilization by vitrification at the Savannah River Site (SRS). Prior to vitrification, an in-tank pretreatment will be used to remove metal impurities from the solution using an oxalate precipitation process. Material balance calculations for this process, based on solubility data in pure nitric acid, predict approximately 80 percent of the plutonium in the solution will be lost to waste. Due to the uncertainty associated with the plutonium losses during processing, solubility experiments were performed to measure the recovery of plutonium during pretreatment and a subsequent precipitation process to prepare a slurry feed for a batch melter. A good estimate of the plutonium content of the glass is required for planning the shipment of the vitrified Am/Cm product to Oak Ridge National Laboratory (ORNL).The plutonium solubility in the oxalate precipitation supernate during pretreatment was 10 mg/mL at 35 degrees C. In two subsequent washes with a 0.25M oxalic acid/0.5M nitric acid solution, the solubility dropped to less than 5 mg/mL. During the precipitation and washing steps, lanthanide fission products in the solution were mostly insoluble. Uranium, and alkali, alkaline earth, and transition metal impurities were soluble as expected. An elemental material balance for plutonium showed that greater than 94 percent of the plutonium was recovered in the dissolved precipitate. The recovery of the lanthanide elements was generally 94 percent or higher except for the more soluble lanthanum. The recovery of soluble metal impurities from the precipitate slurry ranged from 15 to 22 percent. Theoretically, 16 percent of the soluble oxalates should have been present in the dissolved slurry based on the dilution effects and volumes of supernate and wash solutions removed. A trace level material balance showed greater than 97 percent recovery of americium-241 (from the beta dec

Dissolution of oxalate precipitate and destruction of oxalate ion by hydrogen peroxide in nitric acid solution

International Nuclear Information System (INIS)

Kim, Eung-Ho; Chung, Dong-Yong; Park, Jin-Ho; Yoo, Jae-Hyung

2000-01-01

This study aims at developing an oxalate precipitation process, which is applicable to a partitioning of long-lived radionuclides from the high-level radioactive liquid waste. In order to achieve this, a study for decomposition-reaction of oxalic acid by hydrogen peroxide was first carried out. The decomposition rates of H 2 O 2 and oxalic acid increased with an increase of nitric acid concentration, and especially those decomposition rates steeply increased at more than 2 M HNO 3 . Based on this result, the decomposition kinetics of H 2 O 2 and oxalic acid were suggested in this work. Then, the dissolution of oxalate precipitate and the destruction of oxalate ion in the solution were examined. Oxalate precipitates were prepared by adding oxalic acid into a simulated radioactive waste containing 8 metallic elements. The precipitates obtained thereby were dissolved in various nitric acid concentrations and reacted with H 2 O 2 at 90degC. When the oxalates were completely dissolved, most of the oxalates were decomposed by adding H 2 O 2 , but in a slurry state the decomposition yield of the oxalate decreased with an increase of the slurry density in the solution. Such phenomenon was considered to be due to a catalytic decomposition of H 2 O 2 on a solid surface of oxalate and the decomposition mechanism was explained by a charge transfer from a surface of oxalate solid to H 2 O 2 , producing OH radicals which can destruct H 2 O 2 explosively. Accordingly, the experimental condition for the decomposition of the oxalate precipitates was found to be most favorable at 3 M HNO 3 under the initial concentrations of 0.2 M oxalate and 1 M H 2 O 2 . At 3M HNO 3 , oxalate precipitates could be safely and completely dissolved, and almost decomposed. Additionally, it was observed that the presence of ferric ion in the solution largely affects the decomposition rate of H 2 O 2 . This could be explained by a chain reaction of hydrogen peroxide with ferric ion in the solution

Spectroscopic Confirmation of Uranium (VI)-Carbonato Adsorption Complexes on Hematite

International Nuclear Information System (INIS)

Bargar, John R

1999-01-01

Evaluating societal risks posed by uranium contamination from waste management facilities, mining sites, and heavy industry requires knowledge about uranium transport in groundwater, often the most significant pathway of exposure to humans. It has been proposed that uranium mobility in aquifers may be controlled by adsorption of U(VI)-carbonato complexes on oxide minerals. The existence of such complexes has not been demonstrated, and little is known about their compositions and reaction stoichiometries. We have used Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) and Extended X-ray Absorption Fine Structure (EXAFS) spectroscopies to probe the existence, structures, and compositions of FeO surface -U(VI)-carbonato complexes on hematite throughout the pH range of uranyl uptake under conditions relevant to aquifers. U(VI)-carbonato complexes were found to be the predominant adsorbed U(VI) species at all pH values examined, a much wider pH range than previously postulated based on analogy to aqueous U(VI)-carbonato complexes, which are trace constituents at pH < 6. This result indicates the inadequacy of the common modeling assumption that the compositions and predominance of adsorbed species can be inferred from aqueous species. By extension, adsorbed carbonato complexes may be of major importance to the groundwater transport of similar actinide contaminants such as neptunium and plutonium

Vibrational studies in aqueous solutions. Part II. The acid oxalate ion and oxalic acid

Science.gov (United States)

Shippey, T. A.

1980-08-01

Assignments for oxalic acid in solution are re-examined. A detailed assignment of the IR and Raman spectra of the acid oxalate ion is presented for the first time. Raman spectroscopy is used to study the first ionization of oxalic acid.

Single-molecule magnetism in a single-ion triamidoamine uranium(V) terminal mono-oxo complex

Energy Technology Data Exchange (ETDEWEB)

King, David M.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Liddle, Stephen T. [Nottingham Univ. (United Kingdom). School of Chemistry; Tuna, Floriana; McInnes, Eric J.L. [Manchester Univ. (United Kingdom). School of Chemistry

2013-04-26

Straightforward oxidation of a triamidoamine uranium(III) complex with trimethyl-N-oxide affords a uranium(V) terminal mono-oxo complex which is the first clear-cut example of a uranium(V) single-molecule magnet (SMM). This monometallic complex unambiguously shows that a strongly axially ligated and thus anisotropic ligand field can be used to overcome the limited magnetic anisotropy of uranium(V). [German] Die direkte Oxidation eines Triamidoamin-Uran(III)-Komplexes mit Trimethyl-N-oxid liefert einen terminalen Uran(V)-Mono(oxo)komplex, der das erste gesicherte Beispiel eines Uran(V)-Einzelmolekuelmagnets ist. Dieser monometallische Komplex zeigt eindeutig, dass ein starkes axiales und somit anisotropes Ligandenfeld die begrenzte magnetische Anisotropie von Uran(V) beseitigen kann.

Determination of U and Impurities Elements in The Uranium Tetra Fluoride by Potentiometric and Atomic Absorption Spectrophotometric Methods

International Nuclear Information System (INIS)

Putro Kasino, P

1998-01-01

The determination of u and impurities contents in the Uranium tetra fluoride (UF 4 )has been carried out by potentiometric titration using modified 'Davies-Gray' and atomic absorption spectrophotometric methods. Dissolution process of the powder sample using saturated Al 2 (SO 4 ) 3 solution introduced to determine UF 4 compound content in the UF 4 sample. The uranium Content in the obtained filtrate is analyzed by potentiometric. The impurities content is determined by ato-Mic absorption spectrophotometric using ammonium oxalate powder in introducing of the sample preparation. The experiment covered the observation on influence of stirring time of UF 4 sample dissolution in respect to separate UF 4 from its impurities in determination of uranium content. Also the effects of Ammonium Oxalate added and agitating time were observed deal with the sample preparation for the determination of Impurities content.The analysis result found that UF 4 content was 96.15 ± 0.04% the relative station 0.7%. However the best impurities determination was achieved by addition of ammonium oxalate powder and 15 Minutes of agitation time at temperature of 800 0 C

High variability of the heterogeneous ice nucleation potential of oxalic acid dihydrate and sodium oxalate

Directory of Open Access Journals (Sweden)

R. Wagner

2010-08-01

Full Text Available The heterogeneous ice nucleation potential of airborne oxalic acid dihydrate and sodium oxalate particles in the deposition and condensation mode has been investigated by controlled expansion cooling cycles in the AIDA aerosol and cloud chamber of the Karlsruhe Institute of Technology at temperatures between 244 and 228 K. Previous laboratory studies have highlighted the particular role of oxalic acid dihydrate as the only species amongst a variety of other investigated dicarboxylic acids to be capable of acting as a heterogeneous ice nucleus in both the deposition and immersion mode. We could confirm a high deposition mode ice activity for 0.03 to 0.8 μm sized oxalic acid dihydrate particles that were either formed by nucleation from a gaseous oxalic acid/air mixture or by rapid crystallisation of highly supersaturated aqueous oxalic acid solution droplets. The critical saturation ratio with respect to ice required for deposition nucleation was found to be less than 1.1 and the size-dependent ice-active fraction of the aerosol population was in the range from 0.1 to 22%. In contrast, oxalic acid dihydrate particles that had crystallised from less supersaturated solution droplets and had been allowed to slowly grow in a supersaturated environment from still unfrozen oxalic acid solution droplets over a time period of several hours were found to be much poorer heterogeneous ice nuclei. We speculate that under these conditions a crystal surface structure with less-active sites for the initiation of ice nucleation was generated. Such particles partially proved to be almost ice-inactive in both the deposition and condensation mode. At times, the heterogeneous ice nucleation ability of oxalic acid dihydrate significantly changed when the particles had been processed in preceding cloud droplet activation steps. Such behaviour was also observed for the second investigated species, namely sodium oxalate. Our experiments address the atmospheric scenario

High variability of the heterogeneous ice nucleation potential of oxalic acid dihydrate and sodium oxalate

Science.gov (United States)

Wagner, R.; Möhler, O.; Saathoff, H.; Schnaiter, M.; Leisner, T.

2010-08-01

The heterogeneous ice nucleation potential of airborne oxalic acid dihydrate and sodium oxalate particles in the deposition and condensation mode has been investigated by controlled expansion cooling cycles in the AIDA aerosol and cloud chamber of the Karlsruhe Institute of Technology at temperatures between 244 and 228 K. Previous laboratory studies have highlighted the particular role of oxalic acid dihydrate as the only species amongst a variety of other investigated dicarboxylic acids to be capable of acting as a heterogeneous ice nucleus in both the deposition and immersion mode. We could confirm a high deposition mode ice activity for 0.03 to 0.8 μm sized oxalic acid dihydrate particles that were either formed by nucleation from a gaseous oxalic acid/air mixture or by rapid crystallisation of highly supersaturated aqueous oxalic acid solution droplets. The critical saturation ratio with respect to ice required for deposition nucleation was found to be less than 1.1 and the size-dependent ice-active fraction of the aerosol population was in the range from 0.1 to 22%. In contrast, oxalic acid dihydrate particles that had crystallised from less supersaturated solution droplets and had been allowed to slowly grow in a supersaturated environment from still unfrozen oxalic acid solution droplets over a time period of several hours were found to be much poorer heterogeneous ice nuclei. We speculate that under these conditions a crystal surface structure with less-active sites for the initiation of ice nucleation was generated. Such particles partially proved to be almost ice-inactive in both the deposition and condensation mode. At times, the heterogeneous ice nucleation ability of oxalic acid dihydrate significantly changed when the particles had been processed in preceding cloud droplet activation steps. Such behaviour was also observed for the second investigated species, namely sodium oxalate. Our experiments address the atmospheric scenario that coating layers

X-ray studies on crystalline complexes involving amino acids and peptides. XXXII. Effect of chirality on ionisation state, stoichiometry and aggregation in the complexes of oxalic acid with DL- and L-lysine.

Science.gov (United States)

Venkatraman, J; Prabu, M M; Vijayan, M

1997-08-01

Crystals of the oxalic acid complex of DL-lysine (triclinic P1; a = 5.540(1), b = 10.764(2), c = 12.056(2) A, alpha = 77.8(1), beta = 80.6(1), gamma = 75.6(1).; R = 4.7% for 2023 observed reflections) contain lysine and semioxalate ions in the 1:1 ratio, whereas the ratio of lysine and semioxalate/oxalate ions is 2:3 in the crystals of the L-lysine complex (monoclinic P2(1); alpha = 4.906(1), b = 20.145(4), c = 12.455(1) A, beta = 92.5(1).; R = 4.4% for 1494 observed reflections). The amino acid molecule in the L-lysine complex has an unusual ionisation state with positively charged alpha- and side-chain amino groups and a neutral carboxyl group. The unlike molecules aggregate into separate alternating layers in the DL-lysine complex in a manner similar to that observed in several of the amino acid complexes. The L-lysine complex exhibits a new aggregation pattern which cannot be easily explained in terms of planar features, thus emphasizing the fundamental dependence of aggregation on molecular characteristics. Despite the differences in stoichiometry, ionisation state and long-range aggregation patterns, the basic element of aggregation in the two complexes exhibits considerable similarity.

Metabolic Conversion of l-Ascorbic Acid to Oxalic Acid in Oxalate-accumulating Plants 1

Science.gov (United States)

Yang, Joan C.; Loewus, Frank A.

1975-01-01

l-Ascorbic acid-1-14C and its oxidation product, dehydro-l-ascorbic acid, produced labeled oxalic acid in oxalate-accumulating plants such as spinach seedlings (Spinacia oleracea) and the detached leaves of woodsorrel (Oxalis stricta and O. oregana), shamrock (Oxalis adenopylla), and begonia (Begonia evansiana). In O. oregana, conversion occurred equally well in the presence or absence of light. This relationship between l-ascorbic acid metabolism and oxalic acid formation must be given careful consideration in attempts to explain oxalic accumulation in plants. PMID:16659288

Forward osmosis for oily wastewater reclamation: Multi-charged oxalic acid complexes as draw solutes

KAUST Repository

Ge, Qingchun

2017-06-11

Forward osmosis (FO) has demonstrated its merits in hybrid FO seawater desalination. However, FO may have a potential for other applications if suitable draw solutes are available. In this study, a series of novel draw solutes based on oxalic acid (OA)-transitional metal complexes are presented. Influential factors of FO performance have been systematically investigated by varying the transitional metals, cations of the complex draw solutes as well as the experimental conditions. Compared to NaCl and other recently synthesized draw solutes, the OA complexes show superior FO performance in terms of high water fluxes up to 27.5 and 89.1 LMH under the respective FO and PRO (pressure retarded osmosis) modes, both with negligible reverse solute fluxes. The features of octahedral geometry, abundant hydrophilic groups and ionic species are crucial for the OA complexes as appropriate draw solutes with satisfactory FO performance. Among the synthesized OA complexes, the ammonium salt of chromic complex (NH4-Cr-OA) outperforms others due to the presence of more ionic species in its complex system. NH4-Cr-OA also performs better than the typical NaCl draw solute in FO oily wastewater treatment with higher water recovery and negligible reverse fluxes. Dilute solutions of OA complexes have been reconcentrated through membrane distillation (MD) and reused to new round of FO processes. The OA complexes have demonstrated their suitability and superiority as a novel class of draw solutes for the FO process in this study.

Effects of solution pH and complexing reagents on uranium and thorium desorption under saturated equilibrium conditions

International Nuclear Information System (INIS)

Wang, Yug-Yea; Yu, C.

1992-01-01

Three contaminated bulk surface soils were used for investigating the effect of solution pH and complexing reagents on uranium and thorium desorption. At a low solution pH, the major chemical species of uranium and thorium, uranyl UO 2 +2 , thorium dihydroxide Th(OH) 2 +2 , and thorium hydroxide Th(OH) +3 , tend to form complexes with acetates in the solution phase, which increases the fractions of uranium and thorium desorbed into this phase. At a high solution pH, important uranium and thorium species such as uranyl tricarbonate complex UO 2 (CO) 33 -4 and thorium tetrahydroxide complex Th(OH) 4 tend to resist complexation with acetates. The presence of complexing reagents in solution can release radionuclides such as uranium and/or thorium from the soil to the solution by forming soluble complexes. Sodium bicarbonate (NaHCO 3 ) and diethylenetriaminepentaacetic acid (DTPA) are strong complex formers that released 38% to 62% of total uranium activity and 78% to 86% of total thorium activity, respectively, from the soil samples investigated. Solutions of 0.1 molar sodium nitrate (NaNO 3 ) and 0.1 molar sodium sulfate (Na 2 SO 4 ) were not effective complex formers with uranium and thorium under the experimental conditions. Fractions of uranium and thorium desorbed by 0.15g/200ml humic acid ranged from 4.62% to 6.17% and 1.59% to 7.09%, respectively. This work demonstrates the importance of a knowledge of solution chemistry in investigating the desorption of radionuclides

Determining the biochemical properties of the Oxalate Biosynthetic Component (Obc)1 from Burkholderia mallei

Science.gov (United States)

Oxalic acid is produced by a variety of organisms ranging from simple microbes to complex animals. This acid has been proposed to fulfill various physiological and pathological functions which vary between organisms. In bacteria from the Burkholderia genus, oxalate secretion has been shown to be quo...

DISSOLUTION OF METAL OXIDES AND SEPARATION OF URANIUM FROM LANTHANIDES AND ACTINIDES IN SUPERCRITICAL CARBON DIOXIDE

Energy Technology Data Exchange (ETDEWEB)

Donna L. Quach; Bruce J. Mincher; Chien M. Wai

2013-10-01

This paper investigates the feasibility of extracting and separating uranium from lanthanides and other actinides by using supercritical fluid carbon dioxide (sc-CO2) as a solvent modified with tri-n-butylphosphate (TBP) for the development of a counter current stripping technique, which would be a more efficient and environmentally benign technology for spent nuclear fuel reprocessing compared to traditional solvent extraction. Several actinides (U, Pu, and Np) and europium were extracted in sc-CO2 modified with TBP over a range of nitric acid concentrations and then the actinides were exposed to reducing and complexing agents to suppress their extractability. According to this study, uranium/europium and uranium/plutonium extraction and separation in sc-CO2 modified with TBP is successful at nitric acid concentrations of less than 6 M and at nitric acid concentrations of less than 3 M with acetohydroxamic acid or oxalic acid, respectively. A scheme for recycling uranium from spent nuclear fuel by using sc-CO2 and counter current stripping columns is presented.

Oxalate: Effect on calcium absorbability

International Nuclear Information System (INIS)

Heaney, R.P.; Weaver, C.M.

1989-01-01

Absorption of calcium from intrinsically labeled Ca oxalate was measured in 18 normal women and compared with absorption of Ca from milk in these same subjects, both when the test substances were ingested in separate meals and when ingested together. Fractional Ca absorption from oxalate averaged 0.100 +/- 0.043 when ingested alone and 0.140 +/- 0.063 when ingested together with milk. Absorption was, as expected, substantially lower than absorption from milk (0.358 +/- 0.113). Nevertheless Ca oxalate absorbability in these women was higher than we had previously found for spinach Ca. When milk and Ca oxalate were ingested together, there was no interference of oxalate in milk Ca absorption and no evidence of tracer exchange between the two labeled Ca species

The bioavailability of oxalate from Oca (Oxalis tuberosa).

Science.gov (United States)

Albihn, P B; Savage, G P

2001-08-01

It is believed that soluble oxalate has higher bioavailability than insoluble oxalate. Oca (Oxalis tuberosa) is moderately high in oxalate and contains oxalate in soluble form only. We estimated the bioavailability of oxalate in oca based on the urinary excretion of oxalate after oxalate loading with oca to estimate the bioavailability of oxalate in oca. We also clarified whether bioavailability differs in various oxalate loads from the same food source and studied the effect of an additional calcium source on the bioavailability of oxalate from oca. Four men and 4 women ingested 50, 100 and 150 gm. oca as well as 100 gm. oca with 100 gm. sour cream. Oxalate was measured in a 6-hour urine sample from each volunteer. The mean bioavailability of oxalate from oca plus or minus standard deviation was 1.44% +/- 1.31% during the 6-hour period after intake. There was no significant difference in oxalate bioavailability among oxalate intake levels in this study, although oca consumption with sour cream significantly decreased the uptake of oxalate (p oca appears to be similar to that in spinach. However, bioavailability varies among individuals and depends on other constituents of a combined meal.

Calcium oxalate stone and gout.

Science.gov (United States)

Marickar, Y M Fazil

2009-12-01

Gout is well known to be produced by increased uric acid level in blood. The objective of this paper is to assess the relationship between gout and calcium oxalate stone formation in the humans. 48 patients with combination of gout and calcium oxalate stone problem were included. The biochemical values of this group were compared with 38 randomly selected uric acid stone patients with gout, 43 stone patients with gout alone, 100 calcium oxalate stone patients without gout and 30 controls, making a total of 259 patients. Various biochemical parameters, namely serum calcium, phosphorus and uric acid and 24-h urine calcium, phosphorus, uric acid, oxalate, citrate and magnesium were analysed. ANOVA and Duncan's multiple-range tests were performed to assess statistical significance of the variations. The promoters of stone formation, namely serum calcium (P stone patients and gouty calcium oxalate stone patients compared to the non-gouty patients and controls. Urine oxalate (P stones patients. The inhibitor urine citrate (P stone gouty patients, followed by the gouty uric acid stone formers and gouty calcium oxalate stone patients. The high values of promoters, namely uric acid and calcium in the gouty stone patients indicate the tendency for urinary stone formation in the gouty stone patients. There is probably a correlation between gout and calcium oxalate urinary stone. We presume this mechanism is achieved through the uric acid metabolism. The findings point to the summation effect of metabolic changes in development of stone disease.

Bioreduction of Uranium(VI) Complexed with Citric Acid by Clostridia Affects its Structure and Mobility

International Nuclear Information System (INIS)

Francis, A.; Dodge, C.

2008-01-01

Uranium contamination of the environment from mining and milling operations, nuclear-waste disposal, and ammunition use is a widespread global problem. Natural attenuation processes such as bacterial reductive precipitation and immobilization of soluble uranium is gaining much attention. However, the presence of naturally occurring organic ligands can affect the precipitation of uranium. Here, we report that the anaerobic spore-forming bacteria Clostridia, ubiquitous in soils, sediments, and wastes, capable of reduction of Fe(III) to Fe(II), Mn(IV) to Mn(II), U(VI) to U(IV), Pu(IV) to Pu(III), and Tc(VI) to Tc(IV); reduced U(VI) associated with citric acid in a dinuclear 2:2 U(VI):citric acid complex to a biligand mononuclear 1:2 U(IV):citric acid complex, which remained in solution, in contrast to reduction and precipitation of uranium. Our findings show that U(VI) complexed with citric acid is readily accessible as an electron acceptor despite the inability of the bacterium to metabolize the complexed organic ligand. Furthermore, it suggests that the presence of organic ligands at uranium-contaminated sites can affect the mobility of the actinide under both oxic and anoxic conditions by forming such soluble complexes.

Computational and experimental studies on oxalic acid imprinted ...

Indian Academy of Sciences (India)

e-mail: rkkawadkar@chm.vnit.ac.in. MS received 13 ... vent or porogen to form a pre-polymerization complex, followed by .... tered off and the filtrate was analysed for oxalic acid by. UV/VIS ... The experimental binding data were fitted to the.

Environmental significance of copper, lead, manganese, uranium and zinc speciation in the event of contaminated waters release from the Ranger Uranium Mining Complex

International Nuclear Information System (INIS)

Noller, B.N.; Currey, N.A.

1983-01-01

The likely impact of the accidental release of tailings dam water during the dry season at the Ranger Uranium Mining Complex was examined. A speciation scheme utilising sizing by filtration and ion-exchange with Chelex 100 has given an insight into the likely partitioning of zinc, copper, lead, manganese and uranium following the addition of tailings dam water to samples from waterbodies in the vicinity of the uranium mining/milling complex. The speciation findings are discussed in terms of likely toxic effects on fish

Unique advantages of organometallic supporting ligands for uranium complexes

Energy Technology Data Exchange (ETDEWEB)

Diaconescu, Paula L. [Univ. of California, Los Angeles, CA (United States); Garcia, Evan [Univ. of California, Los Angeles, CA (United States)

2014-05-31

The objective of our research project was to study the reactivity of uranium complexes supported by ferrocene-based ligands. In addition, this research provides training of graduate students as the next generation of actinide scientists.

Unique advantages of organometallic supporting ligands for uranium complexes

International Nuclear Information System (INIS)

Diaconescu, Paula L.; Garcia, Evan

2014-01-01

The objective of our research project was to study the reactivity of uranium complexes supported by ferrocene-based ligands. In addition, this research provides training of graduate students as the next generation of actinide scientists.

Forward osmosis for oily wastewater reclamation: Multi-charged oxalic acid complexes as draw solutes.

Science.gov (United States)

Ge, Qingchun; Amy, Gary Lee; Chung, Tai-Shung

2017-10-01

Forward osmosis (FO) has demonstrated its merits in hybrid FO seawater desalination. However, FO may have a potential for other applications if suitable draw solutes are available. In this study, a series of novel draw solutes based on oxalic acid (OA)-transitional metal complexes are presented. Influential factors of FO performance have been systematically investigated by varying the transitional metals, cations of the complex draw solutes as well as the experimental conditions. Compared to NaCl and other recently synthesized draw solutes, the OA complexes show superior FO performance in terms of high water fluxes up to 27.5 and 89.1 LMH under the respective FO and PRO (pressure retarded osmosis) modes, both with negligible reverse solute fluxes. The features of octahedral geometry, abundant hydrophilic groups and ionic species are crucial for the OA complexes as appropriate draw solutes with satisfactory FO performance. Among the synthesized OA complexes, the ammonium salt of chromic complex (NH 4 -Cr-OA) outperforms others due to the presence of more ionic species in its complex system. NH 4 -Cr-OA also performs better than the typical NaCl draw solute in FO oily wastewater treatment with higher water recovery and negligible reverse fluxes. Dilute solutions of OA complexes have been reconcentrated through membrane distillation (MD) and reused to new round of FO processes. The OA complexes have demonstrated their suitability and superiority as a novel class of draw solutes for the FO process in this study. Copyright © 2017 Elsevier Ltd. All rights reserved.

Surface complexation modeling of uranium (Vi) retained onto zirconium diphosphate in presence of organic acids

International Nuclear Information System (INIS)

Almazan T, M. G.; Garcia G, N.; Ordonez R, E.

2010-10-01

In the field of nuclear waste disposal, predictions regarding radionuclide migration through the geosphere, have to take account the effects of natural organic matter. This work presents an investigation of interaction mechanisms between U (Vi) and zirconium diphosphate (ZrP 2 O 7 ) in presence of organic acids (citric acid and oxalic acid). The retention reactions were previously examined using a batch equilibrium method. Previous results showed that U (Vi) retention was more efficient when citric acid or oxalic acid was present in solid surface at lower ph values. In order to determine the retention equilibria for both systems studied, a phosphorescence spectroscopy study was carried out. The experimental data were then fitted using the Constant Capacitance Model included in the FITEQL4.0 code. Previous results concerning surface characterization of ZrP 2 O 7 (surface sites density and surface acidity constants) were used to constraint the modeling. The best fit for U (Vi)/citric acid/ZrP 2 O 7 and U (Vi)/oxalic acid/ZrP 2 O 7 systems considered the formation of a ternary surface complex. (Author)

Decomposition of oxalate precipitates by photochemical reaction

International Nuclear Information System (INIS)

Jae-Hyung Yoo; Eung-Ho Kim

1999-01-01

A photo-radiation method was applied to decompose oxalate precipitates so that it can be dissolved into dilute nitric acid. This work has been studied as a part of partitioning of minor actinides. Minor actinides can be recovered from high-level wastes as oxalate precipitates, but they tend to be coprecipitated together with lanthanide oxalates. This requires another partitioning step for mutual separation of actinide and lanthanide groups. In this study, therefore, some experimental work of photochemical decomposition of oxalate was carried out to prove its feasibility as a step of partitioning process. The decomposition of oxalic acid in the presence of nitric acid was performed in advance in order to understand the mechanistic behaviour of oxalate destruction, and then the decomposition of neodymium oxalate, which was chosen as a stand-in compound representing minor actinide and lanthanide oxalates, was examined. The decomposition rate of neodymium oxalate was found as 0.003 mole/hr at the conditions of 0.5 M HNO 3 and room temperature when a mercury lamp was used as a light source. (author)

Synthesis and structure determination of a stable organometallic uranium(V) imine complex and its isolobal anionic U(IV)-ate complex

Energy Technology Data Exchange (ETDEWEB)

Sharma, M.; Botoshanskii, M.; Eisen, M.S. [Schulich Faculty of Chemistry, and Institute of Catalysis Science and Technology, Technion Israel Institute of Technology, Haifa (Israel); Bannenberg, Th.; Tamm, M. [Institut fur Anorganische und Analytische Chemie, Technische Universitat Braunschweig (Germany)

2010-06-15

The reaction of one equivalent of Cp*{sub 2}UCl{sub 2} with 2-(trimethylsilyl-imino)-1,3-di-tert-butyl-imidazoline in boiling toluene afforded a one electron oxidation of the uranium metal and the opening of the N-heterocyclic ring, resulting in the formation of an organometallic uranium(V) imine complex. This complex crystallized with one molecule of toluene in the unit cell, and its solid-state structure was determined by X-ray diffraction analysis. When the same reaction was performed in perdeuterated toluene, a myriad of organometallic complexes were obtained, however, when equimolar amounts of water were used in toluene, the same complex was obtained, and its solid state characterization shows two independent molecules in the unit cell with an additional water molecule. For comparison of the geometric parameters, the corresponding isolobal anionic uranium(IV) complex [Cp*{sub 2}UCl{sub 3}]{sup -} was synthesized by the reaction of Cp*{sub 2}UCl{sub 2} with 1,3-di-tert-butyl-imidazolium chloride, and the resulting U(IV)-ate complex was characterized by X-ray diffraction analysis. (authors)

Uranium hetero-bimetallic complexes: synthesis, structure and magnetic properties; Complexes heterobimetalliques de l'uranium: synthese, structure et proprietes magnetiques

Energy Technology Data Exchange (ETDEWEB)

Le Borgne, Th

2000-10-04

The aim of this thesis is to synthesize molecular complexes with uranium and transition metal ions in close proximity, to determine the nature of the magnetic interaction between them. We decided to use Schiff bases as assembling ligands, which are unusual for uranium (IV). Although the simplest Schiff bases, such as H{sub 2}Salen, lead to ligand exchange reactions, the bi-compartmental Schiff base H{sub 4}L{sup 6} (bis(3-hydroxy-salicylidene) - 2,2-dimethyl-propylene) allows the crystal structure determination of the complex [L{sup 6}Cu(pyr)]U[L{sup 6}Cu].2pyr, obtained by reaction of the metallo-ligand H{sub 2}L{sup 6}Cu with U(acac){sub 4}. In this manner, the complexes [L{sup 6}Co(pyr)]{sub 2}U and [L{sup 6}Ni(pyr)]{sub 2}U.pyr were also isolated, as well as the compounds in which the paramagnetic ions have been exchanged by the diamagnetic ions Zn{sup II}, Zr{sup IV} and Th{sup IV}': [L{sup 6}Zn(pyr)]{sub 2}U, [L{sup 6}Cu]{sub 2}Zr and [L{sup 6}Cu(pyr)]Th[L{sup 6}Cu].2pyr. These complexes are the first which involve three metallic centres assembling by the means of a hexa-dentate Schiff base. The crystalline structures show, for all these complexes, the outstanding orthogonal arrangement of the two fragments L{sup 6}M around the central atom which is in a dodecahedral environment of eight oxygen atoms of two Schiff bases. The syntheses of the isostructural complexes Cu2{sup II} and Zn{sub 2}U in which the uranium (IV) ion is close, in the first one, to the paramagnetic ion Cu{sup II} and, in the second one, to the diamagnetic ion Zn{sup II}, has allowed the use of the empiric method to determine the nature of the magnetic interaction between an f element and a transition metal. The comparison of the magnetic behaviour of two complexes Cu{sub 2}U and Zn{sub 2}U, expressed by the variation of {chi}T vs T, reveals the ferromagnetic interaction in the heart of the triad Cu-U-Cu. The magnetic behaviour of the complexes Cu{sub 2}Th et Cu{sub 2}Zr which does not

In vivo oxalate degradation by liposome encapsulated oxalate oxidase in rat model of hyperoxaluria

Directory of Open Access Journals (Sweden)

Tulika Dahiya

2013-01-01

Interpretation & conclusions: EMA-oxalate oxidase encapsulated liposome caused oxalate degradation in experimental hyperoxaluria indicating that the enzyme could be used as a therapeutic agent in hyperoxaluria leading to urinary stones.

Characterization of ZrP{sub 2}O{sub 7} modified with oxalic acid and thermodynamic analysis associated to the uranyl (Vi) sorption; Caracterizacion de ZrP{sub 2}O{sub 7} modificado con acido oxalico y analisis termodinamico asociado a la sorcion de uranilo (VI)

Energy Technology Data Exchange (ETDEWEB)

Garcia G, N.; Ordonez R, E. [ININ, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico); Solis C, D. A. [Universidad Autonoma del Estado de Mexico, Facultad de Quimica, Paseo Colon y Paseo Tollocan, 50120 Toluca, Estado de Mexico (Mexico); Simoni, E.; Drot, R.; Jeanson, A., E-mail: eduardo.ordonez@inin.gob.mx [Universite Paris-Sud, Institut de Physique Nucleaire, Georges Clemenceau No. 15, Orsay (France)

2013-10-15

Several physical and chemical tests were carried out to evaluate the influence of the oxalic acid in the uranium (Vi) sorption on the surface of the zirconium diphosphate. The physical analyses consist of atomic force microscopy (AFM) and total organic coal, and the chemists are the calculation of the reaction heat for the hydrate and sorption processes, the reaction speed constant and the sorption yield in the sodium perchlorate systems and of oxalic acid; these tests allow to corroborate that the oxalic acid influences positively in the uranium (Vi) sorption forming a ternary system of ZrP{sub 2}O{sub 7}/(C{sub 2}O{sub 4})/U(Vi), with a single configuration along the ph interval studied. (Author)

Synthesis and reactivity of uranium (III) cyclopentadienyl complexes

International Nuclear Information System (INIS)

Foyentin, M.

1987-01-01

New uranium organometallic complexes are synthetized from the addition compound Cp U (THF). Reactions with lithium compounds, chlorides, alkynes and borohydrides. Oxidizing addition reactions are evidenced with alkyl halogenides. With a strong reducing agent, the complex Cp-UCH-Li allows the fixation and the reduction of nitrogen into ammonia. Lability of ligands bound to U (III) is evidenced, giving very reactive species and hence catalytic properties for these compounds. Catalytic hydrogenation of olefins is studied. Substitution reactions of alkyl groups of these complexes with olefins in presence or not of hydrogen or with alkyllithium are original [fr

Recovery Ce from Ce - TBP Used Oxalic Acid

International Nuclear Information System (INIS)

Purwani, MV; Subagiono, R.; Suyanti

2007-01-01

Recovery or stripping Ce from Ce - TBP product of monazite sand used oxalic acid. Ce - TBP as organic phase and oxalic acid as aqueous phase and as strong precipitant compound to precipitate metal element. The stripping product as Ce - oxalic precipitate. The influence parameter were percentage of oxalic acid, volume ratio of Ce-TBP with oxalic acid, time and rate of stripping. At stripping of 25 ml Ce - TBP used oxalic acid, the optimum condition were achieve at using 5% oxalic acid, volume ratio of Ce - TBP : 5% oxalic acid = 1 : 1, time of stripping 7.5 minute and rate of stripping 150 rpm. At the optimum condition was obtained the recovery efficiency was 100%. (author)

Investigations on the elution behaviour of TOPO complexes of uranium and thorium using supercritical fluid chromatography

International Nuclear Information System (INIS)

Kumar, R.; Sivaraman, N.; Srinivasan, T.G.; Vasudeva Rao, P.R.

2004-01-01

In summary uranium and thorium could be separated by supercritical fluid chromatography technique as their TOPO complexes. The elution profiles with pre-complexation of the metal nitrate indicate a better separation than the in-situ complexation. The technique can also be employed for the assay of uranium and thorium at low levels

On the origin of whewellite in a hydrothermal uranium deposit

International Nuclear Information System (INIS)

Galimov, Eh.M.; Tugarinov, A.I.; Nikitin, A.A.

1975-01-01

Whewellite (calcium oxalate - Ca(COO) 2 H 2 O) is one of the rare minerals that occur principally in rocks of sedimentary origin. The authors of the article explained the origin of whewellite selected on a hydrothermal uranium deposit. To do this, they investigated the isotope composition of the carbon contained in the mineral and also of the carbon in the accompanying calcite and carbonaceous material. It was established that hydrothermal whewellite is markedly different in isotope composition from diagenetic whewellite. The whewellite investigated is a product of oxidation-reduction reactions that have taken place in a hydrothermal solution and in which organic substances are involved. U 6+ was reduced and precipitated in the form of pitchblende and the oxidized forms of organic substances including oxalic acid, were formed, with subsequent precipitation of the oxalate in the form of whewellite. (V.Ya.)

Radium removal from Canadian uranium mining effluents by a radium-selective ion exchange complexer

International Nuclear Information System (INIS)

1984-07-01

A laboratory test program was initiated by the Department of Energy, Mines and Resources as part of the National Uranium Tailings Program to investigate the applicability of a radium-selective ion exchange complexer for removing radium from Canadian uranium mining effluents. The ion exchange complexer was shown to be efficient in removing radium from contaminated water of uranium mining operations, with the ultimate loading capacity of the resin on one type of water treated being determined as approximately 1,600 Bq/cm 3 of new resin. The results showed that the resin was effective in removing radium but not any other contaminants

Applications in environmental bioinorganic: Nutritional and ultrastructural evaluation and calculus of thermodynamic and structural properties of metal-oxalate complexes.

Science.gov (United States)

Tolentino, Terezinha Alves; Bertoli, Alexandre Carvalho; dos Santos Pires, Maíra; Carvalho, Ruy; Labory, Claudia Regina Gontijo; Nunes, Janaira Santana; Bastos, Ana Rosa Ribeiro; de Freitas, Matheus Puggina

2015-01-01

Lead (Pb) is known by its toxicity both for animals and plants. In order to evaluate its toxicity, plants of Brachiaria brizantha were cultivated on nutritive solution of Hoagland during 90 days and submitted to different concentrations of Pb. The content of macro and micronutrients was evaluated and there was a reduction on root content of Ca, besides the lowest dosages of Pb had induced an increase of N, S, Mn, Cu, Zn and Fe. The cell ultrastructure of leaves and roots were analyzed by transmission electronic microscopy (TEM). Among the main alterations occurred there were invaginations on cell walls, the presence of crystals on the root cells, accumulation of material on the interior of cells and vacuolar compartmentalization. On the leaves the degradation of chloroplasts was observed, as well as the increase of vacuoles. Structures for the formation of oxalate crystals were proposed through molecular modeling and thermodynamic stability. Calculi suggest the formation of highly stable metal-oxalate complexes. Copyright © 2015 Elsevier B.V. All rights reserved.

Study of new complexes of uranium and comba radical. I.- Complexes defective in sodium carbonate

International Nuclear Information System (INIS)

Vera Palomino, J.; Galiano Sedano, J. A.; Parellada Bellod, R.; Bellido Gonzalez, A.

1975-01-01

Some complexes formed in presence of defect of sodium carbonate with respect to the stoichiometric ratio (U): (C0 3 ) = 1:3 are studied. This ratio corresponds to the main complex which is responsible for the uranium extraction with CDMBAC organic solutions and from U(VI) aqueous solutions with an excess of sodium carbonate. (Author) 10 refs

Interactions of quercetin-uranium complexes with biomembranes and DNA

Energy Technology Data Exchange (ETDEWEB)

Attia, Enas Mohammed Hassan

2014-07-21

Uranium decontamination gains a great importance with the spread of nuclear waste in both soil and water systems across the planet. All known remediation methods of uranium can be exclusively based either on synthetic materials with high adsorbent power and known physical chemistry or life organisms by which the uranium eventually accumulated inside their tissues. In the present thesis, it was attempted to design a rational approach for uranyl removal primarily from waters using the reducing potential of quercetin, which is a plant-derived small organic molecules, along with its photochemical activities. Such approach, which is neither a fully synthetic nor an organism-based approach, was chosen here to avoid disadvantages with both traditional strategies. Here, complexation experiments were designed to assess the use of uranyl-quercetin complexes for the photoreduction of water-soluble U(VI) to insoluble U(IV) by comparing absorption properties of uranyl-quercetin complexes in acetone, water, and hydrophobic bilayer lipid vesicles. The UV-vis data show that uranyl quercetin complex can form in both hydrophobic and hydrophilic environments. In both cases the B-ring band in quercetin structure becomes reduced, red shifted and a pronounced absorption arises in the 400-500 nm range. Such data suggests that U(VI) binds at the 3-OH and 4-carbonyl of ring C of quercetin. Interestingly, the results of UV-Vis spectroscopy part hint at a crucial role of a stable or transiently ionized hydroxyl for the efficient uranyl-dependent photodegradation of quercetin. FTIR spectroscopy absorption changes further demonstrates that the UV-vis-spectroscopic changes are indeed accompanied by changes in the chemical structure of the complex as expected for a uranyl-dependent photodegradation. IR data thus suggest that U(VI) becomes reduced by the photoreaction, rather than merely changing its coordination shell. The frequency shifts in the C=C and C=O absorption range on the other hand

Interactions of quercetin-uranium complexes with biomembranes and DNA

International Nuclear Information System (INIS)

Attia, Enas Mohammed Hassan

2014-01-01

Uranium decontamination gains a great importance with the spread of nuclear waste in both soil and water systems across the planet. All known remediation methods of uranium can be exclusively based either on synthetic materials with high adsorbent power and known physical chemistry or life organisms by which the uranium eventually accumulated inside their tissues. In the present thesis, it was attempted to design a rational approach for uranyl removal primarily from waters using the reducing potential of quercetin, which is a plant-derived small organic molecules, along with its photochemical activities. Such approach, which is neither a fully synthetic nor an organism-based approach, was chosen here to avoid disadvantages with both traditional strategies. Here, complexation experiments were designed to assess the use of uranyl-quercetin complexes for the photoreduction of water-soluble U(VI) to insoluble U(IV) by comparing absorption properties of uranyl-quercetin complexes in acetone, water, and hydrophobic bilayer lipid vesicles. The UV-vis data show that uranyl quercetin complex can form in both hydrophobic and hydrophilic environments. In both cases the B-ring band in quercetin structure becomes reduced, red shifted and a pronounced absorption arises in the 400-500 nm range. Such data suggests that U(VI) binds at the 3-OH and 4-carbonyl of ring C of quercetin. Interestingly, the results of UV-Vis spectroscopy part hint at a crucial role of a stable or transiently ionized hydroxyl for the efficient uranyl-dependent photodegradation of quercetin. FTIR spectroscopy absorption changes further demonstrates that the UV-vis-spectroscopic changes are indeed accompanied by changes in the chemical structure of the complex as expected for a uranyl-dependent photodegradation. IR data thus suggest that U(VI) becomes reduced by the photoreaction, rather than merely changing its coordination shell. The frequency shifts in the C=C and C=O absorption range on the other hand

PRETREATING URANIUM FOR METAL PLATING

Science.gov (United States)

Wehrmann, R.F.

1961-05-01

A process is given for anodically treating the surface of uranium articles, prior to metal plating. The metal is electrolyzed in an aqueous solution of about 10% polycarboxylic acid, preferably oxalic acid, from 1 to 5% by weight of glycerine and from 1 to 5% by weight of hydrochloric acid at from 20 to 75 deg C for from 30 seconds to 15 minutes. A current density of from 60 to 100 amperes per square foot is used.

Magnetic-superexchange interactions of uranium(IV) chloride-addition complexes with amides, 2

International Nuclear Information System (INIS)

Miyake, Chie; Hinatsu, Yukio; Imoto, Shosuke

1983-01-01

The magnetic susceptibilities of five cyclic amide (lactam)-addition complexes of uranium(IV) chloride were measured between room temperature and 2 K. Magnetic-exchange interaction was found only for N-methyl-substituted amide complexes, and a dimer structure was assumed for them on the basis of their chemical properties. Treating interdimer interaction with a molecular-field approximation, the magnetic susceptibilities were calculated to be in good agreement with the experimental results in the temperature region of the maxima in chi sub(A). The transmission of antiparallel spin coupling via the π orbitals of the bridging amide ligands is proposed to explain the strong intradimer superexchange interaction for the uranium(IV) chloride-amide complexes with the magnetic-susceptibility maximum. (author)

High variability of the heterogeneous ice nucleation potential of oxalic acid dihydrate and sodium oxalate

OpenAIRE

R. Wagner; O. Möhler; H. Saathoff; M. Schnaiter; T. Leisner

2010-01-01

The heterogeneous ice nucleation potential of airborne oxalic acid dihydrate and sodium oxalate particles in the deposition and condensation mode has been investigated by controlled expansion cooling cycles in the AIDA aerosol and cloud chamber of the Karlsruhe Institute of Technology at temperatures between 244 and 228 K. Previous laboratory studies have highlighted the particular role of oxalic acid dihydrate as the only species amongst a variety of other investigated dicarboxylic acids to ...

The comparability of oxalate excretion and oxalate:creatinine ratio in the investigation of primary hyperoxaluria: review of data from a referral centre.

Science.gov (United States)

Clifford-Mobley, Oliver; Tims, Christopher; Rumsby, Gill

2015-01-01

Urine oxalate measurement is an important investigation in the evaluation of renal stone disease. Primary hyperoxaluria (PH) is a rare inherited metabolic disease characterised by persistently elevated urine oxalate, but the diagnosis may be missed in adults until renal failure has developed. Urine oxalate results were reviewed to compare oxalate:creatinine ratio and oxalate excretion, and to estimate the potential numbers of undiagnosed PH. Urine oxalate results from August 2011 to April 2013 were reviewed. Oxalate excretion and oxalate:creatinine ratio were evaluated for 24 h collections and ratio alone for spot urine samples. Oxalate:creatinine ratio and oxalate excretion were moderately correlated (R=0.63) in 24-h urine collections from patients aged 18 years and above. Sex-related differences were found requiring implementation of male and female reference ranges for oxalate:creatinine ratio. Of samples with both ratio and excretion above the reference range, 7% came from patients with confirmed PH. There were 24 patients with grossly elevated urine oxalate who had not been evaluated for PH. Oxalate:creatinine ratio and oxalate excretion were discordant in many patients, which is likely to be a result of intra-individual variation in creatinine output and imprecision in the collection itself. Some PH patients had urine oxalate within the reference range on occasion, and therefore it is not possible to exclude PH on the finding of a single normal result. A significant number of individuals had urine oxalate results well above the reference range who potentially have undiagnosed PH and are consequently at risk of renal failure. © The Author(s) 2014 Reprints and permissions: sagepub.co.uk/journalsPermissions.nav.

Enhancement of Extraction of Uranium from Seawater

International Nuclear Information System (INIS)

Al-Sheikhly, Mohamad; Dietz, Travis; Tsinas, Zois; Tomaszewski, Claire; Pazos, Ileana M.; Nigliazzo, Olga; Li, Weixing; Adel-Hadadi, Mohamad; Barkatt, Aaron

2016-01-01

Even at a concentration of 3 @@g/L, the world@@@s oceans contain a thousand times more uranium than currently know terrestrial sources. In order to take advantage of this stockpile, methods and materials must be developed to extract it efficiently, a difficult task considering the very low concentration of the element and the competition for extraction by other atoms in seawater such as sodium, calcium, and vanadium. The majority of current research on methods to extract uranium from seawater are vertical explorations of the grafting of amidoxime ligand, which was originally discovered and promoted by Japanese studies in the late 1980s. Our study expands on this research horizontally by exploring the effectiveness of novel uranium extraction ligands grafted to the surface of polymer substrates using radiation. Through this expansion, a greater understanding of uranium binding chemistry and radiation grafting effects on polymers has been obtained. While amidoxime-functionalized fabrics have been shown to have the greatest extraction efficiency so far, they suffer from an extensive chemical processing step which involves treatment with powerful basic solutions. Not only does this add to the chemical waste produced in the extraction process and add to the method@@@s complexity, but it also significantly impacts the regenerability of the amidoxime fabric. The approach of this project has been to utilize alternative, commercially available monomers capable of extracting uranium and containing a carbon-carbon double bond to allow it to be grafted using radiation, specifically phosphate, oxalate, and azo monomers. The use of commercially available monomers and radiation grafting with electron beam or gamma irradiation will allow for an easily scalable fabrication process once the technology has been optimized. The need to develop a cheap and reliable method for extracting uranium from seawater is extremely valuable to energy independence and will extend the quantity of

Equilibrium aluminium hydroxo-oxalate phases during initial clay formation; H +-Al 3+-oxalic acid-Na + system

Science.gov (United States)

Bilinski, Halka; Horvath, Laszlo; Ingri, Nils; Sjöberg, Staffan

1986-09-01

The conditions necessary for initial clay formation have been studied in different model systems comprising different organic acids besides Si and Al. In the present paper the solid phases and the precipitation boundary characterizing the subsystem H +-Al 3+-oxalic acid (H 2L) are discussed. pH and tyndallometric measurements were performed in an ionic medium of 0.6 M Na(Cl) at 25 °C. The two phases Al 3(OH) 7(C 2O 4) · 3H 2O (phase I) and NaAl(OH) 2(C 2O 4) · 3H 2O (phase II) determine the precipitation boundary. The following formation constants for the two phases were deduced: lgβ1 = lg([ Al3+] -3[ H2C2O4] -1[ H+] 9 = -21.87 ± 0.08 and lgβ11 = lg([ Al3+] -1[ H2C2O4] -1[ H+] 4 = -5.61 ± 0.06. Phase I exists in the range [ Al] tot≥ 10 -4.4moldm-3,[ H2C2O4] tot ≥ 10 -4.9moldm-3 and at pH oxalic-rich natural waters. The more soluble sodium phase is unlikely to exist in natural waters. The two phases are metastable relative to crystalline gibbsite and may be considered as the first precipitation step in the transition from aqueous Al oxalates down to stable Al hydroxide. Model calculations illustrating these competing hydrolysis-complexation reactions are discussed in terms of predominance and speciation diagrams. The solid phases have been characterized by X-ray analysis of powders, TGA and IR spectra, and tentative structures are proposed. Phase I seems to be an octahedral layer structure, in which 3/5 of the octahedral sites between two close packed oxygen sheets are occupied by Al 3+ and the oxalate ion acts as a bridge ligand between two aluminium atoms. Phase II forms a more open sheet structure and has ion exchange properties. Powder data for a phase crystallized from the studied solution after a year are also presented. This phase, Na 4Al 2(OH) 2(C 2O 4) 4 · 10H 2O, supports the results from the equilibrium analysis of recent solution data by SJöBERG and ÖHMAN (1985), who have found the dinuclear complex Al 2(OH) 2(C 2O 4) 44- to exist in a

Controlled thermolysis of uranium (alkoxy)siloxy complexes. A route to polymetallic complexes of low-valent uranium

Energy Technology Data Exchange (ETDEWEB)

Camp, Clement; Pecaut, Jacques; Mazzanti, Marinella [CEA-Grenoble (France). Lab. de Reconnaissance Ionique et Chimie de Coordination; Kefalidis, Christos E.; Maron, Laurent [Toulouse Univ. (France). LPCNO, CNRS et INSA, UPS

2013-11-25

Decomposition into higher species: Intramolecular U{sup III}-mediated homolytic C-O bond cleavage in U{sup III} (alkoxy)siloxy complexes at low temperature and subsequent reduction with KC{sub 8} led to unprecedented polymetallic complexes containing siloxy, silanediolate, and silanetriolate ligands (see example: U green, Si yellow, K blue, O red). Such compounds may be useful precursors to uranium ceramics relevant for catalysis and the storage of spent nuclear fuel. [German] Zerfall in hoehere Spezies: Die intramolekulare U{sup III}-vermittelte homolytische C-O-Spaltung in U{sup III}-(Alkoxy)siloxy-Komplexen bei tiefer Temperatur mit nachfolgender Reduktion mit KC{sub 8} fuehrte zu ungewoehnlichen Polymetallkomplexen mit Siloxy-, Silandiolat- und Silantriolatliganden (siehe Beispiel: U gruen, Si gelb, K blau, O rot). Solche Verbindungen sind nuetzliche Vorstufen von Urankeramiken, die fuer die Katalyse und fuer die Speicherung verbrauchter Kernbrennstoffe wichtig sind.

Process for iron separation from an organic solution containing uranium

International Nuclear Information System (INIS)

Textoris, A.; Lyaudet, G.; Bathelier, A.

1987-01-01

Iron is separated from an organic solution of U and Fe in a phosphine oxide and an acid organic phosphorus compound by reaction on oxalic acid or a mixture of sulfuric and phosphoric acid or phosphoric acid. Uranium stays in the initial organic solution and iron is transferred to the aqueous phase [fr

Hydroxyproline Metabolism and Oxalate Synthesis in Primary Hyperoxaluria.

Science.gov (United States)

Fargue, Sonia; Milliner, Dawn S; Knight, John; Olson, Julie B; Lowther, W Todd; Holmes, Ross P

2018-06-01

Background Endogenous oxalate synthesis contributes to calcium oxalate stone disease and is markedly increased in the inherited primary hyperoxaluria (PH) disorders. The incomplete knowledge regarding oxalate synthesis complicates discovery of new treatments. Hydroxyproline (Hyp) metabolism results in the formation of oxalate and glycolate. However, the relative contribution of Hyp metabolism to endogenous oxalate and glycolate synthesis is not known. Methods To define this contribution, we performed primed, continuous, intravenous infusions of the stable isotope [ 15 N, 13 C 5 ]-Hyp in nine healthy subjects and 19 individuals with PH and quantified the levels of urinary 13 C 2 -oxalate and 13 C 2 -glycolate formed using ion chromatography coupled to mass detection. Results The total urinary oxalate-to-creatinine ratio during the infusion was 73.1, 70.8, 47.0, and 10.6 mg oxalate/g creatinine in subjects with PH1, PH2, and PH3 and controls, respectively. Hyp metabolism accounted for 12.8, 32.9, and 14.8 mg oxalate/g creatinine in subjects with PH1, PH2, and PH3, respectively, compared with 1.6 mg oxalate/g creatinine in controls. The contribution of Hyp to urinary oxalate was 15% in controls and 18%, 47%, and 33% in subjects with PH1, PH2, and PH3, respectively. The contribution of Hyp to urinary glycolate was 57% in controls, 30% in subjects with PH1, and synthesis in individuals with PH2 and PH3. In patients with PH1, who have the highest urinary excretion of oxalate, the major sources of oxalate remain to be identified. Copyright © 2018 by the American Society of Nephrology.

Synthesis of uranium and thorium dioxides by Complex Sol-Gel Processes (CSGP). Synthesis of uranium oxides by Complex Sol-Gel Processes (CSGP)

International Nuclear Information System (INIS)

Deptula, A.; Brykala, M.; Lada, W.; Olczak, T.; Wawszczak, D.; Chmielewski, A.G.; Modolo, G.; Daniels, H.

2010-01-01

In the Institute of Nuclear Chemistry and Technology (INCT), a new method of synthesis of uranium and thorium dioxides by original variant of sol-gel method - Complex Sol-Gel Process (CSGP), has been elaborated. The main modification step is the formation of nitrate-ascorbate sols from components alkalized by aqueous ammonia. Those sols were gelled into: - irregularly agglomerates by evaporation of water; - medium sized microspheres (diameter <150) by IChTJ variant of sol-gel processes by water extraction from drops of emulsion sols in 2-ethylhexanol-1 by this solvent. Uranium dioxide was obtained by a reduction of gels with hydrogen at temperatures >700 deg. C, while thorium dioxide by a simple calcination in the air atmosphere. (authors)

Uranium hetero-bimetallic complexes: synthesis, structure and magnetic properties

International Nuclear Information System (INIS)

Le Borgne, Th.

2000-01-01

The aim of this thesis is to synthesize molecular complexes with uranium and transition metal ions in close proximity, to determine the nature of the magnetic interaction between them. We decided to use Schiff bases as assembling ligands, which are unusual for uranium (IV). Although the simplest Schiff bases, such as H 2 Salen, lead to ligand exchange reactions, the bi-compartmental Schiff base H 4 L 6 (bis(3-hydroxy-salicylidene) - 2,2-dimethyl-propylene) allows the crystal structure determination of the complex [L 6 Cu(pyr)]U[L 6 Cu].2pyr, obtained by reaction of the metallo-ligand H 2 L 6 Cu with U(acac) 4 . In this manner, the complexes [L 6 Co(pyr)] 2 U and [L 6 Ni(pyr)] 2 U.pyr were also isolated, as well as the compounds in which the paramagnetic ions have been exchanged by the diamagnetic ions Zn II , Zr IV and Th IV ': [L 6 Zn(pyr)] 2 U, [L 6 Cu] 2 Zr and [L 6 Cu(pyr)]Th[L 6 Cu].2pyr. These complexes are the first which involve three metallic centres assembling by the means of a hexa-dentate Schiff base. The crystalline structures show, for all these complexes, the outstanding orthogonal arrangement of the two fragments L 6 M around the central atom which is in a dodecahedral environment of eight oxygen atoms of two Schiff bases. The syntheses of the isostructural complexes Cu2 II and Zn 2 U in which the uranium (IV) ion is close, in the first one, to the paramagnetic ion Cu II and, in the second one, to the diamagnetic ion Zn II , has allowed the use of the empiric method to determine the nature of the magnetic interaction between an f element and a transition metal. The comparison of the magnetic behaviour of two complexes Cu 2 U and Zn 2 U, expressed by the variation of χT vs T, reveals the ferromagnetic interaction in the heart of the triad Cu-U-Cu. The magnetic behaviour of the complexes Cu 2 Th et Cu 2 Zr which does not show any coupling between the two copper (II) ions and the weak antiferromagnetic interaction in the Ni 2 U compound, favour the

Uranium in 50 years? - Deeper, lower grade and more metallurgically complex? - 5312

International Nuclear Information System (INIS)

Polak, C.

2015-01-01

The economic exploitation of uranium deposits in the next 50 years will benefit from advances in mining and processing technology. The 'easiness' to find uranium deposits are a relic of the past. Exploration will need to make use of new technologies to help find blind or deep deposits. These issues are already being addressed by the uranium industry. Another issue will be to obtain social and environmental acceptation of the industry. To summarize the uranium mining industry is faced with 3 main challenges that are not necessarily mutually exclusive: deeper deposits, lower grades and chemically complex ores. The deposits of the next half of 21. century are likely to face at least one but potentially a combination of two or three of these challenges

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

Decomposition of oxalate precipitates by photochemical reaction

International Nuclear Information System (INIS)

Yoo, J.H.; Kim, E.H.

1998-01-01

A photo-radiation method was applied to decompose oxalate precipitates so that it can be dissolved into dilute nitric acid. This work has been studied as a part of partitioning of minor actinides. Minor actinides can be recovered from high-level wastes as oxalate precipitates, but they tend to be coprecipitated together with lanthanide oxalates. This requires another partitioning step for mutual separation of actinide and lanthanide groups. In this study, therefore, the photochemical decomposition mechanism of oxalates in the presence of nitric acid was elucidated by experimental work. The decomposition of oxalates was proved to be dominated by the reaction with hydroxyl radical generated from the nitric acid, rather than with nitrite ion also formed from nitrate ion. The decomposition rate of neodymium oxalate, which was chosen as a stand-in compound representing minor actinide and lanthanide oxalates, was found to be 0.003 M/hr at the conditions of 0.5 M HNO 3 and room temperature when a mercury lamp was used as a light source. (author)

Co-precipitation of plutonium(IV) and americium(III) from nitric acid-oxalic acid solutions with bismuth oxalate

International Nuclear Information System (INIS)

Pius, I.C.; Noronha, D.M.; Chaudhury, Satyajeet

2017-01-01

Co-precipitation of plutonium and americium from nitric acid-oxalic acid solutions with bismuth oxalate has been investigated for the removal of these long lived α-active nuclides from waste solutions. Effect of concentration of bismuth and oxalic acid on the co-precipitation of Pu(IV) from 3 M HNO_3 has been investigated. Similar experiments were also carried out from 3.75 M HNO_3 on co-precipitation of Am(III) to optimize the conditions of precipitation. Strong co-precipitation of Pu(IV) and Am(III) with bismuth oxalate indicate feasibility of treatment of plutonium and americium bearing waste solutions. (author)

Oxalates in oca (New Zealand yam) (Oxalis tuberosa Mol.).

Science.gov (United States)

Ross, A B; Savage, G P; Martin, R J; Vanhanen, L

1999-12-01

Oca (Oxalis tuberosa Mol.) or New Zealand yam, in common with other members of this genus, contains oxalate, an antinutritive factor. Twelve South American and two New Zealand cultivars of oca were analyzed for total and soluble oxalate contents of the tubers. The range of total oxalate levels was 92-221 mg/100 g of fresh weight. Levels of soluble and total oxalate extracted from the tubers were not significantly different, suggesting that no calcium oxalate is formed in the tubers. The oxalate concentrations obtained in this study for oca suggest that previously reported values are too low and that oca is a moderately high oxalate-containing food. This is the first report of a tuber crop containing moderate to high levels of soluble oxalates in the tubers and no insoluble oxalates.

Coordination phenomena of cationic uranium(iv) complexes

International Nuclear Information System (INIS)

Rohwer, H.E.

1974-12-01

The coordination properties of the cationic uranium(IV) complexes UCl 3 + , UCl 2 2+ , UCl 3+ , and U 4+ were studied in a non-aqueous medium in the presence of perchlorate as counterion which, however, proved to coordinate to a much greater extent than expected. The strong neutral ligand, HMPA, could successively displace some of the perchlorates. An electrostatic model for the U(CIO 4 ) 4 -HMPA-acetone system compared favourably with the actual results. This emphasized the high ionic content in the bonding with actenoid cations, even with such a high charge as +4 . These conclusions are in agreement with studies 75 in which nitrate acts as counter ion. Correspondingly the uranium (IV) chemistry is characterized by the absence of typical 3d-organometallic chemistry, for example, strong bonding with CO, P(Phi) 3 etc, which strongly depends on covalent bonding. This stresses the fact that the d and f orbitals are not readily available for strong bond formation with the actenoids. 76

Isolation of oxalic acid tolerating fungi and decipherization of its potential to control Sclerotinia sclerotiorum through oxalate oxidase like protein.

Science.gov (United States)

Yadav, Shivani; Srivastava, Alok K; Singh, Dhanajay P; Arora, Dilip K

2012-11-01

Oxalic acid plays major role in the pathogenesis by Sclerotinia sclerotiorum; it lowers the pH of nearby environment and creates the favorable condition for the infection. In this study we examined the degradation of oxalic acid through oxalate oxidase and biocontrol of Sclerotinia sclerotiorum. A survey was conducted to collect the rhizospheric soil samples from Indo-Gangetic Plains of India to isolate the efficient fungal strains able to tolerate oxalic acid. A total of 120 fungal strains were isolated from root adhering soils of different vegetable crops. Out of 120 strains a total of 80 isolates were able to grow at 10 mM of oxalic acid whereas only 15 isolates were grow at 50 mM of oxalic acid concentration. Then we examined the antagonistic activity of the 15 isolates against Sclerotinia sclerotiorum. These strains potentially inhibit the growth of the test pathogen. A total of three potential strains and two standard cultures of fungi were tested for the oxalate oxidase activity. Strains S7 showed the maximum degradation of oxalic acid (23 %) after 60 min of incubation with fungal extract having oxalate oxidase activity. Microscopic observation and ITS (internally transcribed spacers) sequencing categorized the potential fungal strains into the Aspergillus, Fusarium and Trichoderma. Trichoderma sp. are well studied biocontrol agent and interestingly we also found the oxalate oxidase type activity in these strains which further strengthens the potentiality of these biocontrol agents.

A Highly Expressed High-Molecular-Weight S-Layer Complex of Pelosinus sp. Strain UFO1 Binds Uranium

Energy Technology Data Exchange (ETDEWEB)

Thorgersen, Michael P. [Univ. of Georgia, Athens, GA (United States). Dept. of Biochemistry and Molecular Biology; Lancaster, W. Andrew [Univ. of Georgia, Athens, GA (United States). Dept. of Biochemistry and Molecular Biology; Rajeev, Lara [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Biological Systems and Engineering Division; Ge, Xiaoxuan [Univ. of Georgia, Athens, GA (United States). Dept. of Biochemistry and Molecular Biology; Vaccaro, Brian J. [Univ. of Georgia, Athens, GA (United States). Dept. of Biochemistry and Molecular Biology; Poole, Farris L. [Univ. of Georgia, Athens, GA (United States). Dept. of Biochemistry and Molecular Biology; Arkin, Adam P. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Biological Systems and Engineering Division; Mukhopadhyay, Aindrila [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Biological Systems and Engineering Division; Adams, Michael W. W. [Univ. of Georgia, Athens, GA (United States). Dept. of Biochemistry and Molecular Biology

2016-12-02

Cell suspensions of Pelosinus sp. strain UFO1 were previously shown, using spectroscopic analysis, to sequester uranium as U(IV) complexed with carboxyl and phosphoryl group ligands on proteins. The goal of our present study was to characterize the proteins involved in uranium binding. Virtually all of the uranium in UFO1 cells was associated with a heterodimeric protein, which was termed the uranium-binding complex (UBC). The UBC was composed of two S-layer domain proteins encoded by UFO1_4202 and UFO1_4203. Samples of UBC purified from the membrane fraction contained 3.3 U atoms/heterodimer, but significant amounts of phosphate were not detected. The UBC had an estimated molecular mass by gel filtration chromatography of 15 MDa, and it was proposed to contain 150 heterodimers (UFO1_4203 and UFO1_4202) and about 500 uranium atoms. The UBC was also the dominant extracellular protein, but when purified from the growth medium, it contained only 0.3 U atoms/heterodimer. The two genes encoding the UBC were among the most highly expressed genes within the UFO1 genome, and their expressions were unchanged by the presence or absence of uranium. Therefore, the UBC appears to be constitutively expressed and is the first line of defense against uranium, including by secretion into the extracellular medium. Although S-layer proteins were previously shown to bind U(VI), here we showed that U(IV) binds to S-layer proteins, we identified the proteins involved, and we quantitated the amount of uranium bound. Widespread uranium contamination from industrial sources poses hazards to human health and to the environment. Here in this paper, we identified a highly abundant uranium-binding complex (UBC) from Pelosinus sp. strain UFO1. The complex makes up the primary protein component of the S-layer of strain UFO1 and binds 3.3 atoms of U(IV) per heterodimer. Finally, while other bacteria have been shown to bind U(VI) on their S-layer, we demonstrate here an example of U(IV) bound by

Public communication on times of environmental crisis. The opening of San Rafael 's uranium complex

International Nuclear Information System (INIS)

Calvino, Carlos; Cisneros, Martin

2008-01-01

Full text: Argentina has had a lot of cultural changes in the last few years. An environmental movement has gathered and is trying to stop the opening of the Sierra Pintada uranium complex, near the city of San Rafael, in the south of Mendoza province. Since 2005, several 'groundless information' have been published in the local media about the dangers of this re-opening. These news exaggerate the properties of radon gas, claiming that it will reach San Rafael city (20 miles from the complex), rising radiological risk among the population, etc. This scene shows a 'non-real' picture of the regulatory activities that the Nuclear Regulatory Authority (ARN), a government agency that regulates nuclear facilities in Argentina, is really and systematically accomplishing. In this situation, the board of Directors of ARN decided to entrust a full analysis of the environmental issue in the area. The Office of Press and Communication implemented a local communication plan, using a Strategic and Systemic tool kit. The period to be analyzed is from second semester 2005 to February 2007. A little bit of history: the San Rafael Complex started in September 20 of 1979. It belongs to the National Commission of Atomic Energy (CNEA), a government agency. Until its temporary suspension in 1995 for international market reasons (uranium price was U$S 10 / pound), almost 2 million tons of uranium were processed. Besides its temporary suspension, the ARN has been constantly monitoring this particular former complex. In the year 2001, CNEA notices that the uranium price starts to rise and entrust National Technology University, Avellaneda Branch, to accomplish an Environmental Impact Report, according to the argentine law 25.585. Due especially to the rising of uranium price, (actually, the uranium price is approximately U$S 200) the national government determined to restart the extraction of the mineral again. By the year 2004, with the results of the Environmental Impact report, CNEA

Phthalocyaninato complexes of thorium, protactinium and uranium

International Nuclear Information System (INIS)

Beck, O.F.

1985-01-01

For the preparation of Bis(phthalocyaninato)-actinoid(IV) complexes, AnPc 2 , a new optimizing synthesis procedure was developed, with which it was possible to prepare spectrally pure, that is, H 2 Pc-free, ThPc 2 , UPc 2 and the isostructurally similar 231 PaPc 2 .PaPc 2 . This was verified with the help of electron spectra, which were compared to preparations which were synthesized in another manner. The corresponding perfluorinated compounds were also produced for thorium and uranium by use of tetrafluorophthalic acid nitrile instead of phthalic acid nitrile as initial product. Electron and infrared spectra show the typical bands of the non-substituted complexes. By the attempt to produce a mono(phthalocyaninato)-thorium complex with the use of ThI 4 as initial material a pyridine-extracted pure ThPcI 2 (py) 2 was obtained with a typical mono(phthalocyaninato) complex electron spectrum, an extremely moisture sensitive compound which in water or acids decomposes and produces H 2 Pc. (orig./RB) [de

Agpaitic nepheline syenites from the Ilimaussaq Complex, south Greenland; an important new uranium ore type (v.2)

International Nuclear Information System (INIS)

Mair, J.L.; Bunn, S.

2010-01-01

The Ilimaussaq Intrusive Complex in south Greenland is a layered alkaline igneous body that is predominantly comprised of agpaitic nepheline syenites. The Complex is now recognized as containing vast resources of uranium in polymetallic ores that are also strongly enriched in rare earth elements (REEs) and zinc. Uranium and REEs are dominantly hosted in phosphate minerals with a minor proportion hosted in zirconium silicate minerals. Equivalent ores are yet to be mined for uranium anywhere in the world; however, studies are well advanced in confirming a process route to economically extract uranium. The Ilimaussaq Complex is considered the world's type-locality for agpaitic rocks. Formation of the complex is attributed to four successive pulses of magma. The first produced an augite syenite, which now forms a marginal shell. This was followed by intrusion of a sheet of peralkaline granite. The third and fourth stages make up the bulk of the intrusion and are peralkaline to hyper-agpaitic in composition. The third batch of magma differentiated to produce pulaskite, foyaite and naujaite. Stage four produced the kakortokites and lujavrites, which are the units of particular economic significance. Kakortokites are strongly enriched in zirconium, niobium and tantalum, whereas the lujavrites are strongly enriched in uranium, rare earth elements, fluorine and zinc. Lujavrites are vertically zoned with arfvedonsite (black) lujavrites grading downward into aegerine (green) lujavrites. The upper most portions of the black lujavrites contain uranium concentrations of greater than 450 ppm, which decreases downward over 200 - 300m toward green lujavrites where uranium concentrations rarely exceeds 200 ppm. Resources defined to date in accordance with the Australian JORC code include 192 million lb. of U_3O_8 at 350 ppm within an overall resource of 282 million lb. of uranium oxide at a grade of 280 ppm. With scope for several other similar sized resources within complex, the

Preparation and characterization of alumina supported nickel-oxalate catalyst for the hydrodeoxygenation of oleic acid into normal and iso-octadecane biofuel

International Nuclear Information System (INIS)

Ayodele, O.B.; Togunwa, Olayinka S.; Abbas, Hazzim F.; Daud, Wan Mohd Ashri Wan

2014-01-01

Highlights: • Preparation of nickel oxalate complex as catalyst precursor. • Incorporation of nickel oxalate complex into alumina support. • Characterization of the alumina supported nickel oxalate catalyst. • Hydrodeoxygenation of oleic acid with nickel oxalate catalyst. • Nickel oxalate catalyst reusability studies. - Abstract: In this study, nickel II oxalate complex (NiOx) was prepared by functionalization of nickel with oxalic acid (OxA) and incorporated into Al 2 O 3 to synthesize alumina supported nickel oxalate (NiOx/Al 2 O 3 ) catalyst for the hydrodeoxygenation (HDO) of oleic acid (OA) into biofuel. The synthesized NiOx/Al 2 O 3 was characterized and the X-ray fluorescence and elemental dispersive X-ray results showed that NiOx was successfully incorporated into the structure of Al 2 O 3 . The X-ray diffraction and Raman spectroscopy results confirmed that highly dispersed Ni species are present in the NiOx/Al 2 O 3 due to the functionalization with OxA. The catalytic activity of the NiOx/Al 2 O 3 on the HDO of OA produced a mixture of 21% iso-C18 and 72% n-C18 at a 360 °C, 20 bar, 30 mg NiOx/Al 2 O 3 loading pressure and gas flow rate of 100 mL/min. The presence of i-C 18 was ascribed to the OxA functionalization which increased the acidity of NiOx/Al 2 O 3 . The NiOx/Al 2 O 3 reusability study showed consistent HDO ability after 5 runs. These results are promising for further research into biofuel production for commercialization

Efficient electron-induced removal of oxalate ions and formation of copper nanoparticles from copper(II oxalate precursor layers

Directory of Open Access Journals (Sweden)

Kai Rückriem

2016-06-01

Full Text Available Copper(II oxalate grown on carboxy-terminated self-assembled monolayers (SAM using a step-by-step approach was used as precursor for the electron-induced synthesis of surface-supported copper nanoparticles. The precursor material was deposited by dipping the surfaces alternately in ethanolic solutions of copper(II acetate and oxalic acid with intermediate thorough rinsing steps. The deposition of copper(II oxalate and the efficient electron-induced removal of the oxalate ions was monitored by reflection absorption infrared spectroscopy (RAIRS. Helium ion microscopy (HIM reveals the formation of spherical nanoparticles with well-defined size and X-ray photoelectron spectroscopy (XPS confirms their metallic nature. Continued irradiation after depletion of oxalate does not lead to further particle growth giving evidence that nanoparticle formation is primarily controlled by the available amount of precursor.

(Dimethylphosphorylmethanaminium hydrogen oxalate–oxalic acid (2/1

Directory of Open Access Journals (Sweden)

Sebastian Bialek

2014-03-01

Full Text Available The reaction of (dimethylphosphorylmethanamine (dpma with oxalic acid in ethanol yielded the title solvated salt, C3H11NOP+·C2HO4−·0.5C2H2O4. Its asymmetric unit consists of one dpmaH+ cation, one hydrogen oxalate anion and a half-molecule of oxalic acid located around a twofold rotation axis. The H atom of the hydrogen oxalate anion is statistically disordered over two positions that are trans to each other. The hydrogen oxalate monoanion is not planar (bend angle ∼16° whereas the oxalic acid molecule shows a significantly smaller bend angle (∼7°. In the crystal, the components are connected by strong O—H...O and much weaker N—H...O hydrogen bonds, leading to the formation of layers extending parallel to (001. The structure was refined from a racemically twinned crystal with twin components in an approximate 1:1 ratio.

Dating oxalate minerals in rock surface deposits

International Nuclear Information System (INIS)

Watchman, A.

2001-01-01

Oxalate minerals are found associated with rocks, mineral coatings, micro-organisms, plants and animals. They are important in archaeology because they have been found intimately associated with organic binders in prehistoric paints. Oxalate minerals also accumulate in the coatings on rock shelter walls and fallen ceiling slabs where they form the natural backing supports for painting and opaque laminates covering engravings. Though the relationship between anthropogenic activity in a rock shelter and oxalate formation is often uncertain, the radiocarbon age of the oxalate may provide the only means for determining the antiquity of a rock painting or engraving. This paper examines the history of dating oxalate minerals at archaeological sites and provides insights into achieving reliable age estimates. (author). 37 refs., 1 fig., 2 tabs

Cerium oxalate precipitation

International Nuclear Information System (INIS)

Chang, T.P.

1987-02-01

Cerium, a nonradioactive, common stand-in for plutonium in development work, has been used to simulate several plutonium precipitation processes at the Savannah River Laboratory. There are similarities between the plutonium trifluoride and the cerium oxalate precipitations in particle size and extent of plating, but not particle morphology. The equilibrium solubility, precipitation kinetics, particle size, extent of plating, and dissolution characteristics of cerium oxalate have been investigated. Interpretations of particle size and plating based on precipitation kinetics (i.e., nucleation and crystal growth) are presented. 16 refs., 7 figs., 6 tabs

Pathology and Epidemiology of Oxalate Nephrosis in Cheetahs.

Science.gov (United States)

Mitchell, Emily P; Church, Molly E; Nemser, Sarah M; Yakes, Betsy Jean; Evans, Eric R; Reimschuessel, Renate; Lemberger, Karin; Thompson, Peter N; Terio, Karen A

2017-11-01

To investigate cases of acute oxalate nephrosis without evidence of ethylene glycol exposure, archived data and tissues from cheetahs ( Acinonyx jubatus) from North America ( n = 297), southern Africa ( n = 257), and France ( n = 40) were evaluated. Renal and gastrointestinal tract lesions were characterized in a subset of animals with ( n = 100) and without ( n = 165) oxalate crystals at death. Crystals were confirmed as calcium oxalate by Raman spectroscopy in 45 of 47 cheetahs tested. Crystals were present in cheetahs from 3.7 months to 15.9 years old. Cheetahs younger than 1.5 years were less likely to have oxalates than older cheetahs ( P = .034), but young cheetahs with oxalates had more oxalate crystals than older cheetahs ( P Cheetahs with oxalate crystals were more likely to have renal amyloidosis, interstitial nephritis, or colitis and less likely to have glomerular loop thickening or gastritis than those without oxalates. Crystal number was positively associated with renal tubular necrosis ( P ≤ .001), regeneration ( P = .015), and casts ( P ≤ .001) but inversely associated with glomerulosclerosis, renal amyloidosis, and interstitial nephritis. Crystal number was unrelated to the presence or absence of colitis and was lower in southern African than American and European animals ( P = .01). This study found no evidence that coexisting chronic renal disease (amyloidosis, interstitial nephritis, or glomerulosclerosis), veno-occlusive disease, gastritis, or enterocolitis contributed significantly to oxalate nephrosis. Oxalate-related renal disease should be considered as a potential cause of acute renal failure, especially in young captive cheetahs. The role of location, diet, stress, and genetic predisposition in the pathogenesis of oxalate nephrosis in cheetahs warrants further study.

Synthesis, characterization, and reactivity of a uranium(VI) carbene imido oxo complex

Energy Technology Data Exchange (ETDEWEB)

Lu, Erli; Cooper, Oliver J.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Liddle, Stephen T. [Nottingham Univ. (United Kingdom). School of Chemistry; Tuna, Floriana; McInnes, Eric J.L. [Manchester Univ. (United Kingdom). School of Chemistry and Photon Science Inst.

2014-06-23

We report the uranium(VI) carbene imido oxo complex [U(BIPM{sup TMS})(NMes)(O)(DMAP){sub 2}] (5, BIPM{sup TMS}=C(PPh{sub 2}NSiMe{sub 3}){sub 2}; Mes=2,4,6-Me{sub 3}C{sub 6}H{sub 2}; DMAP=4-(dimethylamino)pyridine) which exhibits the unprecedented arrangement of three formal multiply bonded ligands to one metal center where the coordinated heteroatoms derive from different element groups. This complex was prepared by incorporation of carbene, imido, and then oxo groups at the uranium center by salt elimination, protonolysis, and two-electron oxidation, respectively. The oxo and imido groups adopt axial positions in a T-shaped motif with respect to the carbene, which is consistent with an inverse trans-influence. Complex 5 reacts with tert-butylisocyanate at the imido rather than carbene group to afford the uranyl(VI) carbene complex [U(BIPM{sup TMS})(O){sub 2}(DMAP){sub 2}] (6).

Precipitation of plutonium oxalate from homogeneous solutions

International Nuclear Information System (INIS)

Rao, V.K.; Pius, I.C.; Subbarao, M.; Chinnusamy, A.; Natarajan, P.R.

1986-01-01

A method for the precipitation of plutonium(IV) oxalate from homogeneous solutions using diethyl oxalate is reported. The precipitate obtained is crystalline and easily filterable with yields in the range of 92-98% for precipitations involving a few mg to g quantities of plutonium. Decontamination factors for common impurities such as U(VI), Am(III) and Fe(III) were determined. TGA and chemical analysis of the compound indicate its composition as Pu(Csub(2)Osub(4))sub(2).6Hsub(2)O. Data are obtained on the solubility of the oxalate in nitric acid and in mixtures of nitric acid and oxalic acid of varying concentrations. Green PuOsub(2) obtained by calcination of the oxalate has specifications within the recommended values for trace foreign substances such as chlorine, fluorine, carbon and nitrogen. (author)

Update on probiotics for the treatment of calcium oxalate stones

Directory of Open Access Journals (Sweden)

Di ZHANG

2016-09-01

Full Text Available Urolithiasis is one of the common diseases in urinary system, among which calcium oxalate stone is the most common one with a high recurrence rate. An important pathological factor for the formation of calcium oxalate stone is the increased absorption of oxalate from intestine, which leads to a high urine oxalate concentration. Intestinal bacteria known to be able to degrade oxalate includes Oxalobacter formigenes, Enterococcus faecalis, Escherichia coli, Eubacterium lentum, Providencia rettgeri, Lactobacillus and Bifidobacterium species, etc. Among those, Oxalobacter formigenes is the first oxalate-degrading obligate anaerobe found in human, while the rest are just conditioned bacteria with the function to degrade intestinal oxalate. There are three kinds of enzymes in Oxalobacter formigenes involved in the metabolism of oxalate, namely oxalate-formate antiporter (OxlT, formyl-CoA transferase (Frc and oxalyl-CoA decarboxylase (Oxc. Animal experiments have verified that Oxalobacter formigenes could reduce intestinal oxalate absorption by promoting the secretion of oxalate and degradation as well, thus decrease the excretion of urine oxalate. The present review will focus on the research progress of probiotics treatment for the calcium oxalate stones so as to provide reference for further research and development. DOI: 10.11855/j.issn.0577-7402.2016.08.16

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.

Plasma spheroidization and high temperature stability of lanthanum phosphate and its compatibility with molten uranium

International Nuclear Information System (INIS)

Ananthapadmanabhan, P.V.; Sreekumar, K.P.; Thiyagarajan, T.K.; Satpute, R.U.; Krishnan, K.; Kulkarni, N.K.; Kutty, T.R.G.

2009-01-01

Lanthanum phosphate has excellent thermal stability and corrosion resistance against many molten metals and other chemically corrosive environments. Lanthanum phosphate (LaPO 4 ) was synthesized from lanthanum oxalate by thermal dissociation of the oxalate to the oxide, followed by conversion to hydrated lanthanum phosphate (LaPO 4 .0.5H 2 O). Thermal treatment of LaPO 4 .0.5H 2 O above 773 K resulted in the irreversible transformation of the hydrated phase to the stable monazite phase. Thermal and chemical stability of monazite was studied by plasma spheroidization experiments using a DC thermal plasma reactor set up. Compatibility of monazite with molten uranium was studied by thermal analysis. Results showed that monazite is thermally stable up to its melting point and also is resistant towards attack by molten uranium. Adherent coatings of LaPO 4 could be deposited onto various substrates by atmospheric plasma spray technique

Advanced Oxidation: Oxalate Decomposition Testing With Ozone

International Nuclear Information System (INIS)

Ketusky, E.; Subramanian, K.

2012-01-01

At the Savannah River Site (SRS), oxalic acid is currently considered the preferred agent for chemically cleaning the large underground Liquid Radioactive Waste Tanks. It is applied only in the final stages of emptying a tank when generally less than 5,000 kg of waste solids remain, and slurrying based removal methods are no-longer effective. The use of oxalic acid is preferred because of its combined dissolution and chelating properties, as well as the fact that corrosion to the carbon steel tank walls can be controlled. Although oxalic acid is the preferred agent, there are significant potential downstream impacts. Impacts include: (1) Degraded evaporator operation; (2) Resultant oxalate precipitates taking away critically needed operating volume; and (3) Eventual creation of significant volumes of additional feed to salt processing. As an alternative to dealing with the downstream impacts, oxalate decomposition using variations of ozone based Advanced Oxidation Process (AOP) were investigated. In general AOPs use ozone or peroxide and a catalyst to create hydroxyl radicals. Hydroxyl radicals have among the highest oxidation potentials, and are commonly used to decompose organics. Although oxalate is considered among the most difficult organic to decompose, the ability of hydroxyl radicals to decompose oxalate is considered to be well demonstrated. In addition, as AOPs are considered to be 'green' their use enables any net chemical additions to the waste to be minimized. In order to test the ability to decompose the oxalate and determine the decomposition rates, a test rig was designed, where 10 vol% ozone would be educted into a spent oxalic acid decomposition loop, with the loop maintained at 70 C and recirculated at 40L/min. Each of the spent oxalic acid streams would be created from three oxalic acid strikes of an F-area simulant (i.e., Purex = high Fe/Al concentration) and H-area simulant (i.e., H area modified Purex = high Al/Fe concentration) after nearing

ADVANCED OXIDATION: OXALATE DECOMPOSITION TESTING WITH OZONE

Energy Technology Data Exchange (ETDEWEB)

Ketusky, E.; Subramanian, K.

2012-02-29

At the Savannah River Site (SRS), oxalic acid is currently considered the preferred agent for chemically cleaning the large underground Liquid Radioactive Waste Tanks. It is applied only in the final stages of emptying a tank when generally less than 5,000 kg of waste solids remain, and slurrying based removal methods are no-longer effective. The use of oxalic acid is preferred because of its combined dissolution and chelating properties, as well as the fact that corrosion to the carbon steel tank walls can be controlled. Although oxalic acid is the preferred agent, there are significant potential downstream impacts. Impacts include: (1) Degraded evaporator operation; (2) Resultant oxalate precipitates taking away critically needed operating volume; and (3) Eventual creation of significant volumes of additional feed to salt processing. As an alternative to dealing with the downstream impacts, oxalate decomposition using variations of ozone based Advanced Oxidation Process (AOP) were investigated. In general AOPs use ozone or peroxide and a catalyst to create hydroxyl radicals. Hydroxyl radicals have among the highest oxidation potentials, and are commonly used to decompose organics. Although oxalate is considered among the most difficult organic to decompose, the ability of hydroxyl radicals to decompose oxalate is considered to be well demonstrated. In addition, as AOPs are considered to be 'green' their use enables any net chemical additions to the waste to be minimized. In order to test the ability to decompose the oxalate and determine the decomposition rates, a test rig was designed, where 10 vol% ozone would be educted into a spent oxalic acid decomposition loop, with the loop maintained at 70 C and recirculated at 40L/min. Each of the spent oxalic acid streams would be created from three oxalic acid strikes of an F-area simulant (i.e., Purex = high Fe/Al concentration) and H-area simulant (i.e., H area modified Purex = high Al/Fe concentration

Synthesis, Crystal structure and Characterization of a New Oxalate ...

Indian Academy of Sciences (India)

in a slightly distorted octahedral environment, by two O atoms from two water molecules and four O atoms of two oxalate anions acting as chelating ligands. ... component for building up supramolecular systems and for participating in hydrogen bonding ... heating rate of 10◦C min−1. 2.2 Synthesis of the complex. Aqueous ...

A kinetic and ESR investigation of iron(II) oxalate oxidation by hydrogen peroxide and dioxygen as a source of hydroxyl radicals

DEFF Research Database (Denmark)

Park, J S; Wood, P M; Davies, Michael Jonathan

1997-01-01

The reaction of Fe(II) oxalate with hydrogen peroxide and dioxygen was studied for oxalate concentrations up to 20 mM and pH 2-5, under which conditions mono- and bis-oxalate complexes (Fe[II](ox) and Fe[II](ox)2[2-]) and uncomplexed Fe2+ must be considered. The reaction of Fe(II) oxalate...... with hydrogen peroxide (Fe2+ + H2O2 --> Fe3+ + .OH + OH-) was monitored in continuous flow by ESR with t-butanol as a radical trap. The reaction is much faster than for uncomplexed Fe2+ and a rate constant, k = 1 x 10(4) M(-1) s(-1) is deduced for Fe(II)(ox). The reaction of Fe(II) oxalate with dioxygen...... by oxalate. Further ESR studies with DMPO as spin trap reveal that reaction of Fe(II) oxalate with hydrogen peroxide can also lead to formation of the carboxylate radical anion (CO2-), an assignment confirmed by photolysis of Fe(II) oxalate in the presence of DMPO....

3.2.1. Synthesis, crystal and molecular structure of catena-(bis(µ1-oxalic acid-µ3-hydrogen oxalate-di-aqua-sodium(I.

Directory of Open Access Journals (Sweden)

Olga Kovalchukova*, Sergey Aldoshin, Andrey Utenyshev, Konstantin Bogenko, Valeriy Tkachev

2015-07-01

Full Text Available The crystal and molecular structure of catena-(bis(µ- oxalic acid-µ-hydrogen oxalate-di-aqua-sodium(I was detected by X-Ray analysis. The compound crystallizes in the triclinic space group P-1, with a(Å 6.2378(12; b(Å 7,1115(14; c(Å 10.489(2; α(° 94.65(3; β(° 100.12(3; γ(° 97.78(3. The sodium cation in the title compound is eight coordinated and forms a square antiprism. It is surrounded by two molecules of oxalic acid, one hydrogen oxalate anion and one water molecule. Both oxalic acid and hydrogen oxalate anion act as polydentate bridging ligands. Centrosymmetric sodium cations are bounded by hydrogen oxalate anions through a system of H bonds involving the molecules of oxalic acid. In the lattice, the 3D structure stabilized by H bonds is formed.

Potentiometric titration of free acid in uranium solutions

International Nuclear Information System (INIS)

Suh, M. Y.; Kim, W. H.; Kim, J. S.; Sohn, S. C.; Eom, T. Y.; Lee, C. H.; Jeon, Y. S.; Han, S. H.

1998-02-01

Hydrolysis properties of metal cations and fundamental principles of the potentiometric titration of free acid in aqueous solutions containing metal cations were described. The published papers and reports for the alkalimetric and acidimetric titration of free acid were surveyed, and the applicability of these titration methods to the uranium and/or plutonium solutions were discussed. This technical report also includes the various results obtained from the authors' researches to establish the alkalimetric and acidimetric titration methods for the determination of free acid in nitric acid solutions containing uranium and/or oxalic acid, and aluminum. The procedure manuals used in chemical processes and the newly prepared manuals based on the authors' researches are appended. (author). 26 refs., 54 figs

Potentiometric titration of free acid in uranium solutions

Energy Technology Data Exchange (ETDEWEB)

Suh, M. Y.; Kim, W. H.; Kim, J. S.; Sohn, S. C.; Eom, T. Y.; Lee, C. H.; Jeon, Y. S.; Han, S. H.

1998-02-01

Hydrolysis properties of metal cations and fundamental principles of the potentiometric titration of free acid in aqueous solutions containing metal cations were described. The published papers and reports for the alkalimetric and acidimetric titration of free acid were surveyed, and the applicability of these titration methods to the uranium and/or plutonium solutions were discussed. This technical report also includes the various results obtained from the authors` researches to establish the alkalimetric and acidimetric titration methods for the determination of free acid in nitric acid solutions containing uranium and/or oxalic acid, and aluminum. The procedure manuals used in chemical processes and the newly prepared manuals based on the authors` researches are appended. (author). 26 refs., 54 figs.

Total and soluble oxalate content of some Indian spices.

Science.gov (United States)

Ghosh Das, Sumana; Savage, G P

2012-06-01

Spices, such as cinnamon, cloves, cardamom, garlic, ginger, cumin, coriander and turmeric are used all over the world as flavouring and colouring ingredients in Indian foods. Previous studies have shown that spices contain variable amounts of total oxalates but there are few reports of soluble oxalate contents. In this study, the total, soluble and insoluble oxalate contents of ten different spices commonly used in Indian cuisine were measured. Total oxalate content ranged from 194 (nutmeg) to 4,014 (green cardamom) mg/100 g DM, while the soluble oxalate contents ranged from 41 (nutmeg) to 3,977 (green cardamom) mg/100 g DM. Overall, the percentage of soluble oxalate content of the spices ranged from 4.7 to 99.1% of the total oxalate content which suggests that some spices present no risk to people liable to kidney stone formation, while other spices can supply significant amounts of soluble oxalates and therefore should be used in moderation.

Method of preparation of uranium nitride

Science.gov (United States)

Kiplinger, Jaqueline Loetsch; Thomson, Robert Kenneth James

2013-07-09

Method for producing terminal uranium nitride complexes comprising providing a suitable starting material comprising uranium; oxidizing the starting material with a suitable oxidant to produce one or more uranium(IV)-azide complexes; and, sufficiently irradiating the uranium(IV)-azide complexes to produce the terminal uranium nitride complexes.

Process development study on production of uranium metal from monazite sourced crude uranium tetra-fluoride

International Nuclear Information System (INIS)

Chowdhury, S; Satpati, S.K.; Hareendran, K.N.; Roy, S.B.

2014-01-01

Development of an economic process for recovery, process flow sheet development, purification and further conversion to nuclear grade uranium metal from the crude UF 4 has been a technological challenge and the present paper, discusses the same.The developed flow-sheet is a combination of hydrometallurgical and pyrometallurgical processes. Crude UF 4 is converted to uranium di-oxide (UO 2 ) by chemical conversion route and UO 2 produced is made fluoride-free by repeated repulping, followed by solid liquid separation. Uranium di-oxide is then purified by two stages of dissolution and suitable solvent extraction methods to get uranium nitrate pure solution (UNPS). UNPS is then precipitated with air diluted ammonia in a leak tight stirred vessel under controlled operational conditions to obtain ammonium di-uranate (ADU). The ADU is then calcined and reduced to produce metal grade UO 2 followed by hydro-fluorination using anhydrous hydrofluoric acid to obtain metal grade UF 4 with ammonium oxalate insoluble (AOI) content of 4 is essential for critical upstream conversion process. Nuclear grade uranium metal ingot is finally produced by metallothermic reduction process at 650℃ in a closed vessel, called bomb reactor. In the process, metal-slag separation plays an important role for attaining metal purity as well as process yield. Technological as well economic feasibility of indigenously developed process for large scale production of uranium metal from the crude UF 4 has been established in Bhabha Atomic Research Centre (BARC), India

Investigation on clean-up of Zr and HDBP in PUREX process with UDMH oxalate

International Nuclear Information System (INIS)

Zhang Youzhi; Wang Xuanjun; Li Zhengli; Liu Xiangxuan

2007-01-01

It is generally accepted that the interracial crud formation is related to the complex formation of Zr with degradation products of TBP, such as DBP and MBP, in PUREX process, especially in the first cycle. The crud seriously deteriorates the operation of extraction column and therefore must be properly cleared up. Various clear up methods were studied and those with salt-free washing agents were recently focused. In this paper a new scrubbing agent 1,1- dimethylhydrazine (UDMH) oxalate was proposed, the optimized experimental conditions were described, and the possible mechanism was discussed. The influence of different factors, including reaction temperature, UDMH oxalate concentration, organic-to-aqueous phase ratio, and free UDMH concentration, on the decontamination factors were examined with simulated Zr- and/or DBP-loaded solvents. The optical experimental parameters are found as follows: temperature 40-60 degree C, phase ratio V (o) /V (a) =1, concentration of UDMH oxalate solution 0.4-0.6 mol/L. Especialy some UDMH was added into the UDMH oxalate queues solution to make the concentration of free UDMH 0.2-0.3 mol/L. Under these conditions, the decontaminator factor of Zr from the corresponding simulated solvent with UDMH oxalate is up to 143, slightly higher than that with sodium carbonate. The decontamination factor of HDBP from the corresponding simulated solvent with UDMH oxalate is up to 100, similar to sodium carbonate. (authors)

Studies in the solubility of Pu(III) oxalate

Energy Technology Data Exchange (ETDEWEB)

Hasilkar, S P; Khedekar, N B; Chander, K; Jadhav, V; Jain, H C [Bhabha Atomic Research Centre, Bombay (India). Fuel Reprocessing Div.

1994-11-01

Studies have been carried out on the solubility of Pu(III) oxalate by precipitation of Pu(III) oxalate from varying concentrations of HNO[sub 3]/HCl (0.5-2.0M) solutions and also by equilibrating freshly prepared Pu(III) oxalate with solutions containing varying concentrations of HNO[sub 3]/HCl, oxalic acid and ascorbic acid. Pu(III) solutions in HNO[sub 3] and HCl media were prepared by reduction of Pu(IV) with ascorbic acid. 0.01-0.10M ascorbic acid concentration in the aqueous solution was maintained as holding reductant. The solubility of Pu(III) oxalate was found to be a minimum in 0.5M-1M HNO[sub 3]/HCl solutions containing 0.05M ascorbic acid and 0.2M excess oxalic acid in the supernatant. (author) 6 refs.; 6 tabs.

Atmospheric production of oxalic acid/oxalate and nitric acid/nitrate in the Tampa Bay airshed: Parallel pathways

Science.gov (United States)

Martinelango, P. Kalyani; Dasgupta, Purnendu K.; Al-Horr, Rida S.

Oxalic acid is the dominant dicarboxylic acid (DCA), and it constitutes up to 50% of total atmospheric DCAs, especially in non-urban and marine atmospheres. A significant amount of particulate H 2Ox/oxalate (Ox) occurred in the coarse particle fraction of a dichotomous sampler, the ratio of oxalate concentrations in the PM 10 to PM 2.5 fractions ranged from 1 to 2, with mean±sd being 1.4±0.2. These results suggest that oxalate does not solely originate in the gas phase and condense into particles. Gaseous H 2Ox concentrations are much lower than particulate Ox concentrations and are well correlated with HNO 3, HCHO, and O 3, supporting a photochemical origin. Of special relevance to the Bay Region Atmospheric Chemistry Experiment (BRACE) is the extent of nitrogen deposition in the Tampa Bay estuary. Hydroxyl radical is primarily responsible for the conversion of NO 2 to HNO 3, the latter being much more easily deposited. Hydroxyl radical is also responsible for the aqueous phase formation of oxalic acid from alkenes. Hence, we propose that an estimate of rad OH can be obtained from H 2Ox/Ox production rate and we accordingly show that the product of total oxalate concentration and NO 2 concentration approximately predicts the total nitrate concentration during the same period.

Uranium leaching using mixed organic acids produced by Aspergillus niger

International Nuclear Information System (INIS)

Yong-dong Wang; Guang-yue Li; De-xin Ding; Zhi-xiang Zhou; Qin-wen Deng; Nan Hu; Yan Tan

2013-01-01

Both of culture temperature and pH value had impacts on the degree of uranium extraction through changing types and concentrations of mixed organic acids produced by Aspergillus niger, and significant interactions existed between them though pH value played a leading role. And with the change of pH value of mixed organic acids, the types and contents of mixed organic acids changed and impacted on the degree of uranium extraction, especially oxalic acid, citric acid and malic acid. The mean degree of uranium extraction rose to peak when the culture temperature was 25 deg C (76.14 %) and pH value of mixed organic acids was 2.3 (82.40 %) respectively. And the highest one was 83.09 %. The optimal culture temperature (25 deg C) of A. niger for uranium leaching was different from the most appropriate growing temperature (37 deg C). (author)

Determination of the stability constants of uranium-tetracycline complexes

International Nuclear Information System (INIS)

Tarenzi, L.R.; Saiki, M.

1983-01-01

Stability constants of complexes formed with tetracycline (TC) and uranium have been determined by solvent extraction technique. The site on the tetracycline molecule at which uranyl ion may be bound has been studied by means of potentiometric titration and spectrophotometric techniques. The complex species with 1:1 and 1:2 for UO 2 : TC ratio have been identified by conductometric titration. Solvent extraction studies have also shown that the complexes are mononuclear of the type UO 2 (TC) sub (n) (n=1,2) and that no hidroxocomplexes or negatively charged complexes have been formed. Stability constant values have been calculated by numerical weighted least square method and by graphical methods of two parameters, of the average number of ligands and of the limiting value. (Author) [pt

Recycled Uranium Mass Balance Project Y-12 National Security Complex Site Report

Energy Technology Data Exchange (ETDEWEB)

NONE

2000-12-01

This report has been prepared to summarize the findings of the Y-12 National Security Complex (Y-12 Complex) Mass Balance Project and to support preparation of associated U. S. Department of Energy (DOE) site reports. The project was conducted in support of DOE efforts to assess the potential for health and environmental issues resulting from the presence of transuranic (TRU) elements and fission products in recycled uranium (RU) processed by DOE and its predecessor agencies. The United States government used uranium in fission reactors to produce plutonium and tritium for nuclear weapons production. Because uranium was considered scarce relative to demand when these operations began almost 50 years ago, the spent fuel from U.S. fission reactors was processed to recover uranium for recycling. The estimated mass balance for highly enriched RU, which is of most concern for worker exposure and is the primary focus of this project, is summarized in a table. A discrepancy in the mass balance between receipts and shipments (plus inventory and waste) reflects an inability to precisely distinguish between RU and non-RU shipments and receipts involving the Y-12 Complex and Savannah River. Shipments of fresh fuel (non-RU) and sweetener (also non-RU) were made from the Y-12 Complex to Savannah River along with RU shipments. The only way to distinguish between these RU and non-RU streams using available records is by enrichment level. Shipments of {le}90% enrichment were assumed to be RU. Shipments of >90% enrichment were assumed to be non-RU fresh fuel or sweetener. This methodology using enrichment level to distinguish between RU and non-RU results in good estimates of RU flows that are reasonably consistent with Savannah River estimates. Although this is the best available means of distinguishing RU streams, this method does leave a difference of approximately 17.3 MTU between receipts and shipments. Slightly depleted RU streams received by the Y-12 Complex from ORGDP and

Pseudomonas fluorescens ATCC 13525 Containing an Artificial Oxalate Operon and Vitreoscilla Hemoglobin Secretes Oxalic Acid and Solubilizes Rock Phosphate in Acidic Alfisols

Science.gov (United States)

Archana, G.; Naresh Kumar, G.

2014-01-01

Oxalate secretion was achieved in Pseudomonas fluorescens ATCC 13525 by incorporation of genes encoding Aspergillus niger oxaloacetate acetyl hydrolase (oah), Fomitopsis plaustris oxalate transporter (FpOAR) and Vitreoscilla hemoglobin (vgb) in various combinations. Pf (pKCN2) transformant containing oah alone accumulated 19 mM oxalic acid intracellularly but secreted 1.2 mM. However, in the presence of an artificial oxalate operon containing oah and FpOAR genes in plasmid pKCN4, Pf (pKCN4) secreted 13.6 mM oxalate in the medium while 3.6 mM remained inside. This transformant solubilized 509 μM of phosphorus from rock phosphate in alfisol which is 4.5 fold higher than the Pf (pKCN2) transformant. Genomic integrants of P. fluorescens (Pf int1 and Pf int2) containing artificial oxalate operon (plac-FpOAR-oah) and artificial oxalate gene cluster (plac-FpOAR-oah, vgb, egfp) secreted 4.8 mM and 5.4 mM oxalic acid, released 329 μM and 351 μM P, respectively, in alfisol. The integrants showed enhanced root colonization, improved growth and increased P content of Vigna radiata plants. This study demonstrates oxalic acid secretion in P. fluorescens by incorporation of an artificial operon constituted of genes for oxalate synthesis and transport, which imparts mineral phosphate solubilizing ability to the organism leading to enhanced growth and P content of V. radiata in alfisol soil. PMID:24705024

Pseudomonas fluorescens ATCC 13525 containing an artificial oxalate operon and Vitreoscilla hemoglobin secretes oxalic acid and solubilizes rock phosphate in acidic alfisols.

Directory of Open Access Journals (Sweden)

Kavita Yadav

Full Text Available Oxalate secretion was achieved in Pseudomonas fluorescens ATCC 13525 by incorporation of genes encoding Aspergillus niger oxaloacetate acetyl hydrolase (oah, Fomitopsis plaustris oxalate transporter (FpOAR and Vitreoscilla hemoglobin (vgb in various combinations. Pf (pKCN2 transformant containing oah alone accumulated 19 mM oxalic acid intracellularly but secreted 1.2 mM. However, in the presence of an artificial oxalate operon containing oah and FpOAR genes in plasmid pKCN4, Pf (pKCN4 secreted 13.6 mM oxalate in the medium while 3.6 mM remained inside. This transformant solubilized 509 μM of phosphorus from rock phosphate in alfisol which is 4.5 fold higher than the Pf (pKCN2 transformant. Genomic integrants of P. fluorescens (Pf int1 and Pf int2 containing artificial oxalate operon (plac-FpOAR-oah and artificial oxalate gene cluster (plac-FpOAR-oah, vgb, egfp secreted 4.8 mM and 5.4 mM oxalic acid, released 329 μM and 351 μM P, respectively, in alfisol. The integrants showed enhanced root colonization, improved growth and increased P content of Vigna radiata plants. This study demonstrates oxalic acid secretion in P. fluorescens by incorporation of an artificial operon constituted of genes for oxalate synthesis and transport, which imparts mineral phosphate solubilizing ability to the organism leading to enhanced growth and P content of V. radiata in alfisol soil.

Development of complex electrokinetic decontamination method for soil contaminated with uranium

International Nuclear Information System (INIS)

Kim, Gye-Nam; Kim, Seung-Soo; Park, Hye-Min; Kim, Wan-Suk; Moon, Jei-Kwon; Hyeon, Jay-Hyeok

2012-01-01

520L complex electrokinetic soil decontamination equipment was manufactured to clean up uranium contaminated soils from Korean nuclear facilities. To remove uranium at more than 95% from the radioactive soil through soil washing and electrokinetic technology, decontamination experiments were carried out. To reduce the generation of large quantities of metal oxides in cathode, a pH controller is used to control the pH of the electrolyte waste solution between 0.5 and 1 for the formation of UO 2+ . More than 80% metal oxides were removed through pre-washing, an electrolyte waste solution was circulated by a pump, and a metal oxide separator filtered the metal oxide particles. 80–85% of the uranium was removed from the soil by soil washing as part of the pre-treatment. When the initial uranium concentration of the soil was 21.7 Bq/g, the required electrokinetic decontamination time was 25 days. When the initial concentration of 238 U in the soil was higher, a longer decontamination time was needed, but the removal rate of 238 U from the soil was higher.

Enhancement of Extraction of Uranium from Seawater

Energy Technology Data Exchange (ETDEWEB)

Al-Sheikhly, Mohamad [Univ. of Maryland, College Park, MD (United States); Dietz, Travis [Univ. of Maryland, College Park, MD (United States); Tsinas, Zois [Univ. of Maryland, College Park, MD (United States); Tomaszewski, Claire [Univ. of Maryland, College Park, MD (United States); Pazos, Ileana M. [Univ. of Maryland, College Park, MD (United States); Nigliazzo, Olga [The Catholic Univ. of America, Washington, DC (United States); Li, Weixing [The Catholic Univ. of America, Washington, DC (United States); Adel-Hadadi, Mohamad [Univ. of Maryland, College Park, MD (United States); Barkatt, Aaron [Univ. of Palermo (Italy)

2016-04-01

Even at a concentration of 3 μg/L, the world’s oceans contain a thousand times more uranium than currently know terrestrial sources. In order to take advantage of this stockpile, methods and materials must be developed to extract it efficiently, a difficult task considering the very low concentration of the element and the competition for extraction by other atoms in seawater such as sodium, calcium, and vanadium. The majority of current research on methods to extract uranium from seawater are vertical explorations of the grafting of amidoxime ligand, which was originally discovered and promoted by Japanese studies in the late 1980s. Our study expands on this research horizontally by exploring the effectiveness of novel uranium extraction ligands grafted to the surface of polymer substrates using radiation. Through this expansion, a greater understanding of uranium binding chemistry and radiation grafting effects on polymers has been obtained. While amidoxime-functionalized fabrics have been shown to have the greatest extraction efficiency so far, they suffer from an extensive chemical processing step which involves treatment with powerful basic solutions. Not only does this add to the chemical waste produced in the extraction process and add to the method’s complexity, but it also significantly impacts the regenerability of the amidoxime fabric. The approach of this project has been to utilize alternative, commercially available monomers capable of extracting uranium and containing a carbon-carbon double bond to allow it to be grafted using radiation, specifically phosphate, oxalate, and azo monomers. The use of commercially available monomers and radiation grafting with electron beam or gamma irradiation will allow for an easily scalable fabrication process once the technology has been optimized. The need to develop a cheap and reliable method for extracting uranium from seawater is extremely valuable to energy independence and will extend the quantity of

Characterization of the sorption of uranium(VI) on different complexing resins

Energy Technology Data Exchange (ETDEWEB)

Pesavento, Maria; Biesuz, Raffaela; Alberti, Giancarla; Sturini, Michela [Dipartimento di Chimica Generale dell' Universita degli Studi di Pavia, Via Taramelli 12, 27100, Pavia (Italy)

2003-08-01

The sorption of uranium(VI) on two cationic resins containing different complexing groups, the iminodiacetic resin Chelex 100 and the weak carboxylic resin Amberlite CG-50, was investigated. The Gibbs-Donnan model was used to describe and to predict the sorption through the determination of the intrinsic complexation constants. These quantities, even though non-thermodynamic, characterize the sorption as being independent of experimental conditions. The sorption mechanism of the metal on the complexing resins was also studied by adding a competitive soluble ligand that shifts the sorption curves to higher pH values. The ligand competes with the resin for the complexation with the metal ion. Uranium is also strongly sorbed on Chelex 100 at very acid pH, through formation of two complexes in the resin phase: ML with log{beta}{sub 110i}=-1.16, in more acidic solution, and ML{sub 2}with log {beta}{sub 120i}=-5.72. Only the presence of the competitive ligand in solution makes the determination of the second complex possible. Also on Amberlite CG-50 the sorption is strong and involves the formation of the complex ML {sub 2}, in more acidic solution, with log {beta}{sub 120i}=-3.16. In the presence of the ligand EDTA, the complex ML {sub 2}(OH) {sub 2}was characterized with log {beta}{sub 12-2i}=-5.15. In all the experiments the hydrolysis reaction in the aqueous phase was quantitatively considered. (orig.)

Characterization of the sorption of uranium(VI) on different complexing resins

International Nuclear Information System (INIS)

Pesavento, Maria; Biesuz, Raffaela; Alberti, Giancarla; Sturini, Michela

2003-01-01

The sorption of uranium(VI) on two cationic resins containing different complexing groups, the iminodiacetic resin Chelex 100 and the weak carboxylic resin Amberlite CG-50, was investigated. The Gibbs-Donnan model was used to describe and to predict the sorption through the determination of the intrinsic complexation constants. These quantities, even though non-thermodynamic, characterize the sorption as being independent of experimental conditions. The sorption mechanism of the metal on the complexing resins was also studied by adding a competitive soluble ligand that shifts the sorption curves to higher pH values. The ligand competes with the resin for the complexation with the metal ion. Uranium is also strongly sorbed on Chelex 100 at very acid pH, through formation of two complexes in the resin phase: ML with logβ 110i =-1.16, in more acidic solution, and ML 2 with log β 120i =-5.72. Only the presence of the competitive ligand in solution makes the determination of the second complex possible. Also on Amberlite CG-50 the sorption is strong and involves the formation of the complex ML 2 , in more acidic solution, with log β 120i =-3.16. In the presence of the ligand EDTA, the complex ML 2 (OH) 2 was characterized with log β 12-2i =-5.15. In all the experiments the hydrolysis reaction in the aqueous phase was quantitatively considered. (orig.)

Oxalic acid decreases calcium absorption in rats

International Nuclear Information System (INIS)

Weaver, C.M.; Martin, B.R.; Ebner, J.S.; Krueger, C.A.

1987-01-01

Calcium absorption from salts and foods intrinsically labeled with 45 Ca was determined in the rat model. Calcium bioavailability was nearly 10 times greater for low oxalate kale, CaCO 3 and CaCl 2 than from CaC 2 O 4 (calcium oxalate) and spinach (high in oxalates). Extrinsic and intrinsic labeling techniques gave a similar assessment of calcium bioavailability from kale but not from spinach

Adsorption of uranium(VI) to manganese oxides: X-ray absorption spectroscopy and surface complexation modeling.

Science.gov (United States)

Wang, Zimeng; Lee, Sung-Woo; Catalano, Jeffrey G; Lezama-Pacheco, Juan S; Bargar, John R; Tebo, Bradley M; Giammar, Daniel E

2013-01-15

The mobility of hexavalent uranium in soil and groundwater is strongly governed by adsorption to mineral surfaces. As strong naturally occurring adsorbents, manganese oxides may significantly influence the fate and transport of uranium. Models for U(VI) adsorption over a broad range of chemical conditions can improve predictive capabilities for uranium transport in the subsurface. This study integrated batch experiments of U(VI) adsorption to synthetic and biogenic MnO(2), surface complexation modeling, ζ-potential analysis, and molecular-scale characterization of adsorbed U(VI) with extended X-ray absorption fine structure (EXAFS) spectroscopy. The surface complexation model included inner-sphere monodentate and bidentate surface complexes and a ternary uranyl-carbonato surface complex, which was consistent with the EXAFS analysis. The model could successfully simulate adsorption results over a broad range of pH and dissolved inorganic carbon concentrations. U(VI) adsorption to synthetic δ-MnO(2) appears to be stronger than to biogenic MnO(2), and the differences in adsorption affinity and capacity are not associated with any substantial difference in U(VI) coordination.

Oxalate Content of Taro Leaves Grown in Central Vietnam

Science.gov (United States)

Du Thanh, Hang; Phan Vu, Hai; Vu Van, Hai; Le Duc, Ngoan; Le Minh, Tuan; Savage, Geoffrey

2017-01-01

Leaves were harvested from four different cultivars of Colocasia esculenta and three cultivars of Alocasia odora that were growing on nine different farms in central Vietnam. The total, soluble and insoluble oxalate contents of the leaves were extracted and measured using HPLC chromatography. Total calcium determinations were also carried out on the same samples. The total oxalate content of the leaves ranged from 433.8 to 856.1 mg/100 g wet matter (WM) while the soluble oxalate ranged from 147.8 to 339.7 mg/100 g WM. The proportion of soluble oxalate ranged from 28% to 41% (overall mean 35%) of the total oxalate content of the leaves. The equivalent insoluble oxalate proportion ranged from 59% to 72% of the total (overall mean 65%). There was little difference between the Colocasia esculenta and Alocasia odora taro cultivars, although the total oxalate content was significantly higher in Alocasia odora cultivars. The overall mean total calcium content was 279.5 mg/100 WM and the percentage of insoluble calcium bound as calcium oxalate ranged from 31.7% to 57.3% of the total calcium content (overall mean 47.1%). The oxalate content in taro leaves is a major factor to consider when different cultivars of taro are recommended for human or animal consumption. PMID:28231080

Thermodynamic analysis of stability in iron removal from kaolin by using oxalic acid

Directory of Open Access Journals (Sweden)

C. Ocampo-López

2013-06-01

Full Text Available The graphical representation of global stability for a system, or Pourbaix diagram, was constructed to perform a thermodynamic study of iron removal from kaolin using oxalic acid as an oxidant. To do this the free energies of formation of the oxalate complex of the system were calculated, and it was found that the more stable specie is Fe(C2O43-3, with a calculated free energy of formation of -3753.88 kcal/mol. Thermodynamic stability functions were estimated for the system as a function of pH and Eh known as potential of oxide reduction. It was built a global stability diagram for the removal system; it showed that the specie trioxalate Fe(C2O43-3 is the only oxalate in equilibrium with other compounds associated with the removal of iron in kaolin.

Synthesis, characterization, and reactivity of a uranium(VI) carbene imido oxo complex

Energy Technology Data Exchange (ETDEWEB)

Lu, Erli; Cooper, Oliver J.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Liddle, Stephen T. [School of Chemistry, University of Nottingham (United Kingdom); Tuna, Floriana; McInnes, Eric J.L. [School of Chemistry and Photon Science Institute, University of Manchester (United Kingdom)

2014-06-23

We report the uranium(VI) carbene imido oxo complex [U(BIPM{sup TMS})(NMes)(O)(DMAP){sub 2}] (5, BIPM{sup TMS}=C(PPh{sub 2}NSiMe{sub 3}){sub 2}; Mes=2,4,6-Me{sub 3}C{sub 6}H{sub 2}; DMAP=4-(dimethylamino)pyridine) which exhibits the unprecedented arrangement of three formal multiply bonded ligands to one metal center where the coordinated heteroatoms derive from different element groups. This complex was prepared by incorporation of carbene, imido, and then oxo groups at the uranium center by salt elimination, protonolysis, and two-electron oxidation, respectively. The oxo and imido groups adopt axial positions in a T-shaped motif with respect to the carbene, which is consistent with an inverse trans-influence. Complex 5 reacts with tert-butylisocyanate at the imido rather than carbene group to afford the uranyl(VI) carbene complex [U(BIPM{sup TMS})(O){sub 2}(DMAP){sub 2}] (6). (copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Complex formation of uranium(VI) with fructose and glucose phosphates

International Nuclear Information System (INIS)

Koban, A.; Geipel, G.; Bernhard, G.; Fanghaenel, T.

2002-01-01

The uptake of heavy metals into plants is commonly quantified by the soil-plant transfer factor. Up to now little is known about the chemical speciation of actinides in plants. To compare the obtained spectroscopic data of uranium complexes in plants with model compounds, we investigate the complexation of uranium with relevant bioligands of various functionalities. A very important class of ligands consists of phosphate esters, which serve as phosphate group and energy transmitters as well as energy storage media in biological systems. Heavy metal ions bound to the phosphate esters can be transported into living cells and then deposited. Therefore, in our study we present the results of uranium complexation with glucose-6-phosphate (G6P), and fructose-6-phosphate (F6P) obtained by time-resolved laser-induced fluorescence spectroscopy (TRLFS). The experiments were performed at a fixed uranyl concentration (10 -5 M) as a function of the ligand concentrations (10 -5 to 10 -3 M) in a pH range from 2 to 4.5. For the glucose phosphate system we observed, using increasing ligand concentrations, a decrease in the fluorescence intensity and a small red shift of the emission bands. From this we conclude that the complexed uranyl glucose phosphate species show only minor or no fluorescence properties. The TRLFS spectra of the glucose phosphate samples indicated the presence of a single species with fluorescence properties. This species has a lifetime of approximately 1.5 μs and was identified as the free uranyl ion. An opposite phenomenon was observed for the fructose phosphate system: there was no decrease in fluorescence intensity. However, a strong red shift of the spectra was observed, illustrating the fluorescence properties of the uranyl fructose phosphate complex. The TRLFS spectra of the fructose phosphate system showed a second lifetime ( 2 2+ UO 2 (lig) x (2-y)+ + y H + (lig = sugar phosphate). Applying the mass action law and transformation to the logarithmic

Plasma spheroidization and high temperature stability of lanthanum phosphate and its compatibility with molten uranium

Energy Technology Data Exchange (ETDEWEB)

Ananthapadmanabhan, P.V. [Laser and Plasma Technology Division, Bhabha Atomic Research Centre, Mumbai 400085 (India)], E-mail: pvananth@barc.gov.in; Sreekumar, K.P.; Thiyagarajan, T.K.; Satpute, R.U. [Laser and Plasma Technology Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Krishnan, K.; Kulkarni, N.K. [Fuel Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Kutty, T.R.G. [Radiometallurgy Division, Bhabha Atomic Research Centre, Mumbai 400085 (India)

2009-01-15

Lanthanum phosphate has excellent thermal stability and corrosion resistance against many molten metals and other chemically corrosive environments. Lanthanum phosphate (LaPO{sub 4}) was synthesized from lanthanum oxalate by thermal dissociation of the oxalate to the oxide, followed by conversion to hydrated lanthanum phosphate (LaPO{sub 4}.0.5H{sub 2}O). Thermal treatment of LaPO{sub 4}.0.5H{sub 2}O above 773 K resulted in the irreversible transformation of the hydrated phase to the stable monazite phase. Thermal and chemical stability of monazite was studied by plasma spheroidization experiments using a DC thermal plasma reactor set up. Compatibility of monazite with molten uranium was studied by thermal analysis. Results showed that monazite is thermally stable up to its melting point and also is resistant towards attack by molten uranium. Adherent coatings of LaPO{sub 4} could be deposited onto various substrates by atmospheric plasma spray technique.

Radioactive effluents, Portsmouth Uranium Enrichment Complex, calendar year 1983

International Nuclear Information System (INIS)

Acox, T.A.; Klein, L.S.

1984-03-01

Radioactive discharges from the Portsmouth Uranium Enrichment Complex are discussed and tabulated. Tables indicate both the location of the discharge and the nuclides discharged. Routine discharges for 1983 are well below the Radioactive Concentration Guide limits specified in DOE Order 5480.1, Chapter XI. There was, however, an unplanned release in December from the X-326 Building Side Purge which exceeded the limits. 1 figure

Short communication: Urinary oxalate and calcium excretion by dogs and cats diagnosed with calcium oxalate urolithiasis

NARCIS (Netherlands)

Dijcker, J.C.; Kummeling, A.; Hagen-Plantinga, E.A.; Hendriks, W.H.

2012-01-01

Introduction Urine concentrations of oxalate and calcium play an important role in calcium oxalate (CaOx) urolith formation in dogs and cats, with high excretions of both substances increasing the chance of CaOx urolithiasis. In 17 CaOx-forming dogs, urine calcium:creatinine ratio (Ca:Cr) was found

Oxalate quantification in hemodialysate to assess dialysis adequacy for primary hyperoxaluria.

Science.gov (United States)

Tang, Xiaojing; Voskoboev, Nikolay V; Wannarka, Stacie L; Olson, Julie B; Milliner, Dawn S; Lieske, John C

2014-01-01

Patients with primary hyperoxaluria (PH) overproduce oxalate which is eliminated via the kidneys. If end-stage kidney disease develops they are at high risk for systemic oxalosis, unless adequate oxalate is removed during hemodialysis (HD) to equal or exceed ongoing oxalate production. The purpose of this study was to validate a method to measure oxalate removal in this unique group of dialysis patients. Fourteen stable patients with a confirmed diagnosis of PH on HD were included in the study. Oxalate was measured serially in hemodialysate and plasma samples in order to calculate rates of oxalate removal. HD regimens were adjusted according to a given patient's historical oxalate production, amount of oxalate removal at dialysis, residual renal clearance of oxalate, and plasma oxalate levels. After a typical session of HD, plasma oxalate was reduced by 78.4 ± 7.7%. Eight patients performed HD 6 times/week, 2 patients 5 times/week, and 3 patients 3 times/week. Combined oxalate removal by HD and the kidneys was sufficient to match or exceed endogenous oxalate production. After a median period of 9 months, pre-dialysis plasma oxalate was significantly lower than initially (75.1 ± 33.4 vs. 54.8 ± 46.6 mmol/l, p = 0.02). This methodology can be used to individualize the dialysis prescription of PH patients to prevent oxalosis during the time they are maintained on HD and to reduce risk of oxalate injury to a transplanted kidney.

Acute oxalate nephropathy caused by ethylene glycol poisoning

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Jung Woong Seo

2012-12-01

Full Text Available Ethylene glycol (EG is a sweet-tasting, odorless organic solvent found in many agents, such as anti-freeze. EG is composed of four organic acids: glycoaldehyde, glycolic acid, glyoxylic acid and oxalic acid in vivo. These metabolites are cellular toxins that can cause cardio-pulmonary failure, life-threatening metabolic acidosis, central nervous system depression, and kidney injury. Oxalic acid is the end product of EG, which can precipitate to crystals of calcium oxalate monohydrate in the tubular lumen and has been linked to acute kidney injury. We report a case of EG-induced oxalate nephropathy, with the diagnosis confirmed by kidney biopsy, which showed acute tubular injury of the kidneys with extensive intracellular and intraluminal calcium oxalate monohydrate crystal depositions.

Oxalate Content of the Herb Good-King-Henry, Blitum Bonus-Henricus

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Wanying Li

2015-05-01

Full Text Available The total, soluble and insoluble oxalate contents of the leaves, stems and buds of Good-King-Henry (Blitum Bonus-Henricus were extracted and measured using HPLC chromatography. The large, mature leaves contained 42% more total oxalate than in the small leaves and the soluble oxalate content of the large leaves was 33% higher than the smaller leaves. Cooking the mixed leaves, stems and buds in boiling water for two minutes significantly (p < 0.05 reduced the total oxalate when compared to the raw plant parts. Pesto sauce made from mixed leaves contained 257 mg total oxalate/100 g fresh weight; this was largely made up of insoluble oxalates (85% of the total oxalate content. Soup made from mixed leaves contained lower levels of total oxalates (44.26 ± 0.49 mg total oxalate/100 g fresh weight and insoluble oxalate made up 49% of the oxalate contents. The levels of oxalates in the Good-King-Henry leaves were high, suggesting that the leaves should be consumed occasionally as a delicacy because of their unique taste rather than as a significant part of the diet. However, the products made from Good-King-Henry leaves indicated that larger amounts could be consumed as the oxalate levels were reduced by dilution and processing.

Oxalate Content of Taro Leaves Grown in Central Vietnam

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Hang Du Thanh

2017-01-01

Full Text Available Leaves were harvested from four different cultivars of Colocasia esculenta and three cultivars of Alocasia odora that were growing on nine different farms in central Vietnam. The total, soluble and insoluble oxalate contents of the leaves were extracted and measured using HPLC chromatography. Total calcium determinations were also carried out on the same samples. The total oxalate content of the leaves ranged from 433.8 to 856.1 mg/100 g wet matter (WM while the soluble oxalate ranged from 147.8 to 339.7 mg/100 g WM. The proportion of soluble oxalate ranged from 28% to 41% (overall mean 35% of the total oxalate content of the leaves. The equivalent insoluble oxalate proportion ranged from 59% to 72% of the total (overall mean 65%. There was little difference between the Colocasia esculenta and Alocasia odora taro cultivars, although the total oxalate content was significantly higher in Alocasia odora cultivars. The overall mean total calcium content was 279.5 mg/100 WM and the percentage of insoluble calcium bound as calcium oxalate ranged from 31.7% to 57.3% of the total calcium content (overall mean 47.1%. The oxalate content in taro leaves is a major factor to consider when different cultivars of taro are recommended for human or animal consumption.

Urinary oxalate to creatinine ratios in healthy Turkish schoolchildren.

Science.gov (United States)

Dursun, Ismail; Çelik, İlknur; Poyrazoglu, Hakan M; Köse, Kader; Tanrıkulu, Esen; Sahin, Habibe; Yılmaz, Kenan; Öztürk, Ahmet; Yel, Sibel; Gündüz, Zübeyde; Düşünsel, Ruhan

2017-11-01

we aimed to establish reference values for urinary oxalate to creatinine ratios in healthy children aged 6-15 years and to investigate the relationship between their nutritional habits and oxalate excretion. Random urine specimens from 953 healthy children aged 6-15 years were obtained and analyzed for oxalate and creatinine. Additionally, a 24-h dietary recall form was prepared and given to them. The ingredient composition of the diet was calculated. The children were divided into three groups according to age: Group I (69 years, n = 353), Group II (10-12 years, n = 335), and Group III (13-15 years, n = 265). The 95th percentile of the oxalate to creatinine ratio for subjects aged 6-9, 10-12, and 13-15 years were 0.048, 0.042, and 0.042 mg/mg, respectively. The oxalate to creatinine ratio was significantly higher in Group 1 than in Group 2 and Group 3. Urinary oxalate excretion was positively correlated with increased protein intake and negatively correlated with age. A significant positive correlation was determined between urinary oxalate excretion and the proline, serine, protein, and glycine content of diet. Dietary proline intake showed a positive correlation with the urine oxalate to creatinine ratio and was found to be an independent predictor for urinary oxalate. These data lend support to the idea that every country should have its own normal reference values to determine the underlying metabolic risk factor for kidney stone disease since regional variation in the dietary intake of proteins and other nutrients can affect normal urinary excretion of oxalate.

Catalytic ozonation of oxalate with a cerium supported palladium oxide: An efficient degradation not relying on hydroxyl radical oxidation

KAUST Repository

Zhang, Tao; Li, Weiwei; Croue, Jean-Philippe

2011-01-01

The cerium supported palladium oxide (PdO/CeO 2) at a low palladium loading was found very effective in catalytic ozonation of oxalate, a probe compound that is difficult to be efficiently degraded in water with hydroxyl radical oxidation and one of the major byproducts in ozonation of organic matter. The oxalate was degraded into CO 2 during the catalytic ozonation. The molar ratio of oxalate degraded to ozone consumption increased with increasing catalyst dose and decreasing ozone dosage and pH under the conditions of this study. The maximum molar ratio reached around 1, meaning that the catalyst was highly active and selective for oxalate degradation in water. The catalytic ozonation, which showed relatively stable activity, does not promote hydroxyl radical generation from ozone. Analysis with ATR-FTIR and in situ Raman spectroscopy revealed that 1) oxalate was adsorbed on CeO 2 of the catalyst forming surface complexes, and 2) O 3 was adsorbed on PdO of the catalyst and further decomposed to surface atomic oxygen (*O), surface peroxide (*O 2), and O 2 gas in sequence. The results indicate that the high activity of the catalyst is related to the synergetic function of PdO and CeO 2 in that the surface atomic oxygen readily reacts with the surface cerium-oxalate complex. This kind of catalytic ozonation would be potentially effective for the degradation of polar refractory organic pollutants and hydrophilic natural organic matter. © 2011 American Chemical Society.

Catalytic ozonation of oxalate with a cerium supported palladium oxide: An efficient degradation not relying on hydroxyl radical oxidation

KAUST Repository

Zhang, Tao

2011-11-01

The cerium supported palladium oxide (PdO/CeO 2) at a low palladium loading was found very effective in catalytic ozonation of oxalate, a probe compound that is difficult to be efficiently degraded in water with hydroxyl radical oxidation and one of the major byproducts in ozonation of organic matter. The oxalate was degraded into CO 2 during the catalytic ozonation. The molar ratio of oxalate degraded to ozone consumption increased with increasing catalyst dose and decreasing ozone dosage and pH under the conditions of this study. The maximum molar ratio reached around 1, meaning that the catalyst was highly active and selective for oxalate degradation in water. The catalytic ozonation, which showed relatively stable activity, does not promote hydroxyl radical generation from ozone. Analysis with ATR-FTIR and in situ Raman spectroscopy revealed that 1) oxalate was adsorbed on CeO 2 of the catalyst forming surface complexes, and 2) O 3 was adsorbed on PdO of the catalyst and further decomposed to surface atomic oxygen (*O), surface peroxide (*O 2), and O 2 gas in sequence. The results indicate that the high activity of the catalyst is related to the synergetic function of PdO and CeO 2 in that the surface atomic oxygen readily reacts with the surface cerium-oxalate complex. This kind of catalytic ozonation would be potentially effective for the degradation of polar refractory organic pollutants and hydrophilic natural organic matter. © 2011 American Chemical Society.

The Y-12 National Security Complex Foreign Research Reactor Uranium Supply Production

Energy Technology Data Exchange (ETDEWEB)

Nelson, T. [Nuclear Technology and Nonproliferation Programs, B and W Y-12, L.L.C., Y-12 National Security Complex, Oak Ridge, Tennessee (United States); Keller, A.P. [Disposition and Supply Programs, B and W Y-12, L.L.C., Y-12 National Security Complex, Oak Ridge, Tennessee (United States)

2011-07-01

The Foreign Research Reactor (FRR) Uranium Supply Program at the Y-12 National Security Complex supports the nonproliferation objectives of the National Nuclear Security Administration (NNSA) HEU Disposition, the Reduced Enrichment Research and Test Reactors (RERTR), and the United States (U.S.) FRR Spent Nuclear Fuel (SNF) Acceptance Programs. The FRR Supply Program supports the important U.S. government nuclear nonproliferation commitment to serve as a reliable and cost-effective uranium supplier for those foreign research reactors that are converting or have converted to Low-Enriched Uranium (LEU) fuel under the RERTR Program. The NNSA Y-12 Site Office maintains the prime contracts with foreign government agencies for the supply of LEU for their research reactors. The LEU is produced by down blending Highly Enriched Uranium (HEU) that has been declared surplus to the U.S. national defense needs. The down blending and sale of the LEU supports the Surplus HEU Disposition Program Record of Decision to make the HEU non-weapons usable and to recover the economic value of the uranium to the extent feasible. In addition to uranium metal feedstock for fuel fabrication, Y-12 can produce LEU in different forms to support new fuel development or target fabrication for medical isotope production. With production improvements and efficient delivery preparations, Y-12 continues to successfully support the global research reactor community. (author)

Pseudomonas fluorescens ATCC 13525 Containing an Artificial Oxalate Operon and Vitreoscilla Hemoglobin Secretes Oxalic Acid and Solubilizes Rock Phosphate in Acidic Alfisols

OpenAIRE

Yadav, Kavita; Kumar, Chanchal; Archana, G.; Naresh Kumar, G.

2014-01-01

Oxalate secretion was achieved in Pseudomonas fluorescens ATCC 13525 by incorporation of genes encoding Aspergillus niger oxaloacetate acetyl hydrolase (oah), Fomitopsis plaustris oxalate transporter (FpOAR) and Vitreoscilla hemoglobin (vgb) in various combinations. Pf (pKCN2) transformant containing oah alone accumulated 19 mM oxalic acid intracellularly but secreted 1.2 mM. However, in the presence of an artificial oxalate operon containing oah and FpOAR genes in plasmid pKCN4, Pf (pKCN4) s...

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)

Recovery of plutonium from nitric acid containing oxalate and fluoride by a macroporous bifunctional phosphinic acid resin (MPBPA)

International Nuclear Information System (INIS)

Venugopal Chetty, K.; Godbole, A.G.; Swarup, R.; Vaidya, V.N.; Venugopal, V.; Vasudeva Rao, P.R.

2006-01-01

The sorption of Pu from nitric acid solutions containing oxalate/fluoride was studied using an indigenously available macroporous bifunctional phosphinic acid (MPBPA) resin. Batch experiments were carried out to obtain the distribution data of Pu(IV) with a view to optimize conditions for its recovery from nitric acid waste solutions containing oxalate or fluoride ions. The measurements showed high distribution ratio (D) values even in the presence of strong complexing ions, like oxalate and fluoride, indicating the possibility of recovery of Pu from these types of waste solution. Column studies were carried out using this resin to recover Pu from the oxalate supernatant waste solution, which showed that up to 99% of Pu could be adsorbed on the resin. Elution of Pu loaded on the resin was studied using different eluting agents. (author)

Vibrational spectroscopy and structural analysis of complex uranium compounds (review)

International Nuclear Information System (INIS)

Umreiko, D.S.; Nikanovich, M.V.

1985-01-01

The paper reports on the combined application of experimental and theoretical methods of vibrational spectroscopy together with low-temperature luminescence data to determine the characteristic features of the formation and structure of complex systems, not only containing ligands directly coordinated to the CA uranium, but also associated with the extraspherical polyatomic electrically charged particles: organic cations. These include uranyl complexes and heterocyclical amines. Studied here were compounds of tetra-halouranylates with pyridine and its derivates, as well as dipyridyl, quinoline and phenanthroline. Structural schemes are also proposed for other uranyl complexes with protonated heterocyclical amines with a more complicated composition, which correctly reflect their spectroscopic properties

Addition of calcium compounds to reduce soluble oxalate in a high oxalate food system.

Science.gov (United States)

Bong, Wen-Chun; Vanhanen, Leo P; Savage, Geoffrey P

2017-04-15

Spinach (Spinacia oleracea L.) is often used as a base vegetable to make green juices that are promoted as healthy dietary alternatives. Spinach is known to contain significant amounts of oxalates, which are toxic and, if consumed regularly, can lead to the development of kidney stones. This research investigates adding 50-500mg increments of calcium carbonate, calcium chloride, calcium citrate and calcium sulphate to 100g of raw homogenates of spinach to determine whether calcium would combine with the soluble oxalate present in the spinach. Calcium chloride was the most effective additive while calcium carbonate was the least effective. The formation of insoluble oxalate after incubation at 25°C for 30min is a simple practical step that can be incorporated into the juicing process. This would make the juice considerably safer to consume on a regular basis. Copyright © 2016 Elsevier Ltd. All rights reserved.

Surface activation of MnNb{sub 2}O{sub 6} nanosheets by oxalic acid for enhanced photocatalysis

Energy Technology Data Exchange (ETDEWEB)

Wu, Junshu; Wang, Jinshu, E-mail: wangjsh@bjut.edu.cn; Li, Hongyi; Li, Yongli; Du, Yucheng; Yang, Yilong; Jia, Xinjian

2017-05-01

Graphical abstract: Visible light driven photoreduction of Cr(VI) over MnNb{sub 2}O{sub 6} nanosheets is enhanced via oxalic acid surface complex to generate activation layer. - Highlights: • MnNb{sub 2}O{sub 6} nanosheets are crystallized by a surface capping route of sulfonate groups. • Oxalic acid on MnNb{sub 2}O{sub 6} nanosheets forms an excited surface complex hybrid layer. • Surface activation enhances visible-light induced reduction of Cr(VI) into Cr(III). - Abstract: MnNb{sub 2}O{sub 6} nanosheets (P-MNOs) is selectively crystallized by using surface capping ligand with functional sulfonate group (sodium dodecyl benzene sulphonate), which binds to the (131) surface of MnNb{sub 2}O{sub 6} inducing the morphology-controlled crystallization of MnNb{sub 2}O{sub 6} materials. Surface modification of photoactive P-MNOs with electron-rich oxalic acid ligands establishes an excited surface complex layer on phase-pure P-MNO as evidenced by spectroscopic analyses (FT-IR, UV–vis, Raman, PL, etc.), and thus more efficiently photocatalyzes the reduction of Cr(VI) into Cr(III) than solely P-MNOs or oxalic acid under visible light (λ > 420 nm) via a ligand-to-metal interfacial electron transfer pathway. However, the interaction between oxalic acid and MnNb{sub 2}O{sub 6} is highly dependent upon the morphology of solid MnNb{sub 2}O{sub 6} substrate due to the higher surface-area-to-volume ratio and higher surface activity of (131) planes in the sheet-like morphology. This study could assist the construction of stable niobate material systems to allow a versatile solid surface activation for establishing more energy efficient and robust catalysis process under visible light.

Colorimetric sensing of oxalate based on its inhibitory effect on the reaction of Fe (III) with curcumin nanoparticles

Science.gov (United States)

Pourreza, Nahid; Lotfizadeh, Neda; Golmohammadi, Hamed

2018-03-01

In this research, a new colorimetric method for the determination of oxalate using curcumin nanoparticles (CURNs) in the presence Fe (III) is introduced. The method is based on the inhibitory effect of oxalate ion on the reaction of (CURNs) with Fe (III) in acidic media. This reaction was monitored by measuring the increase in absorbance of CURNs-Fe3 + complex in the presence of oxalate ion at 427 nm. The effect of different parameters such as the pH of the sample solution, concentration of Fe (III), concentration of CURNs and the reaction time was examined and optimized. Under optimum experimental conditions, the absorption intensity was linear with the concentration of oxalate in the range of 0.15 to 1.70 μg mL- 1. The limit of detection (LOD) was 0.077 μg mL- 1 and the relative standard deviations (RSD) for 8 replicate measurements of 0.40 and 1.05 μg mL- 1 of oxalate were 4.20% and 2.74%, respectively. The developed method was successfully employed to the determination of oxalate in water, food and urine samples with satisfactory results.

4-Methoxybenzamidinium hydrogen oxalate monohydrate

Directory of Open Access Journals (Sweden)

Simona Irrera

2012-12-01

Full Text Available The title hydrated salt, C8H11N2O+·C2HO4−·H2O, was synthesized by a reaction of 4-methoxybenzamidine (4-amidinoanisole and oxalic acid in water solution. In the cation, the amidinium group forms a dihedral angle of 15.60 (6° with the mean plane of the benzene ring. In the crystal, each amidinium unit is bound to three acetate anions and one water molecule by six distinct N—H...O hydrogen bonds. The ion pairs of the asymmetric unit are joined by two N—H...O hydrogen bonds into ionic dimers in which the carbonyl O atom of the semi-oxalate anion acts as a bifurcated acceptor, thus generating an R12(6 motif. These subunits are then joined through the remaining N—H...O hydrogen bonds to adjacent semi-oxalate anions into linear tetrameric chains running approximately along the b axis. The structure is stabilized by N—H...O and O—H...O intermolecular hydrogen bonds. The water molecule plays an important role in the cohesion and the stability of the crystal structure being involved in three hydrogen bonds connecting two semi-oxalate anions as donor and a benzamidinium cation as acceptor.

1. Mono([8]annulene)Uranium(4) half-sandwich complexes, 2. Novel syntheses of symmetrically substituted cyclooctatetetraenes

International Nuclear Information System (INIS)

Boussie, T.R.

1991-10-01

A reproducible, high-yield synthesis of mono([8]annulene)uranium(4)dichloride (1) is reported, along with the X-ray crystal structural of the bis(pyridine) adduct. Metathesis reactions of the half-sandwich complex 1 with a variety of simple alkyl and alkoxy reagents failed to generate any isolable mono-ring complexes. Reactions of 1 with polydentate, delocalized anions did produce stable derivatives, including mono([8]annulene)uranium(4)bis(acetylacetonate) (4). An X-ray crystal structure of 4 is reported

1. Mono([8]annulene)Uranium(4) half-sandwich complexes, 2. Novel syntheses of symmetrically substituted cyclooctatetetraenes

Energy Technology Data Exchange (ETDEWEB)

Boussie, Thomas Richard [Univ. of California, Berkeley, CA (United States)

1991-10-01

A reproducible, high-yield synthesis of mono([8]annulene)uranium(4)dichloride (1) is reported, along with the X-ray crystal structural of the bis(pyridine) adduct. Metathesis reactions of the half-sandwich complex 1 with a variety of simple alkyl and alkoxy reagents failed to generate any isolable mono-ring complexes. Reactions of 1 with polydentate, delocalized anions did produce stable derivatives, including mono([8]annulene)uranium(4)bis(acetylacetonate) (4). An X-ray crystal structure of 4 is reported.

1. Mono((8)annulene)Uranium(4) half-sandwich complexes, 2. Novel syntheses of symmetrically substituted cyclooctatetetraenes

Energy Technology Data Exchange (ETDEWEB)

Boussie, T.R.

1991-10-01

A reproducible, high-yield synthesis of mono((8)annulene)uranium(4)dichloride (1) is reported, along with the X-ray crystal structural of the bis(pyridine) adduct. Metathesis reactions of the half-sandwich complex 1 with a variety of simple alkyl and alkoxy reagents failed to generate any isolable mono-ring complexes. Reactions of 1 with polydentate, delocalized anions did produce stable derivatives, including mono((8)annulene)uranium(4)bis(acetylacetonate) (4). An X-ray crystal structure of 4 is reported.

Acute oxalate nephropathy after ingestion of star fruit.

Science.gov (United States)

Chen, C L; Fang, H C; Chou, K J; Wang, J S; Chung, H M

2001-02-01

Acute oxalate nephropathy associated with ingestion of star fruit (carambola) has not been reported before. We report the first two cases. These patients developed nausea, vomiting, abdominal pain, and backache within hours of ingesting large quantities of sour carambola juice; then acute renal failure followed. Both patients needed hemodialysis for oliguric acute renal failure, and pathologic examinations showed typical changes of acute oxalate nephropathy. The renal function recovered 4 weeks later without specific treatment. Sour carambola juice is a popular beverage in Taiwan. The popularity of star fruit juice is not compatible with the rare discovery of star fruit-associated acute oxalate nephropathy. Commercial carambola juice usually is prepared by pickling and dilution processes that reduce oxalate content markedly, whereas pure fresh juice or mild diluted postpickled juice for traditional remedies, as used in our cases, contain high quantities of oxalate. An empty stomach and dehydrated state may pose an additional risk for development of renal injury. To avoid acute oxalate nephropathy, pure sour carambola juice or mild diluted postpickled juice should not be consumed in large amounts, especially on an empty stomach or in a dehydrated state.

Fabrication of uranium dioxide of different granulation from uranyl nitrate by ammonia diuranate; Dobijanje urandioksida razlicitih granulacija iz uranilnitrata preko amonijumdiuranata

Energy Technology Data Exchange (ETDEWEB)

Vojnovic, J; Stamenkovic, I [Institute of Nuclear Sciences Boris Kidric, Laboratorija za termotehniku reaktora, Vinca, Beograd (Serbia and Montenegro)

1961-12-15

Uranium dioxide is most frequently produced by reduction of higher oxides (UO{sub 3}, U{sub 3}O{sub 8}) or reduction of uranium salts (uranium diuranate, uranium peroxide, uranyl oxalate). Reduction is most frequently done in hydrogen or carbon monoxide atmosphere under temperatures from 500 - 1700 deg C. One of the most frequently methods for producing uranium oxide is certainly reduction of ammonia diuranate by hydrogen (ADU method). Properties of uranium dioxide obtained by ADU method depend on properties of the initial substance. Investigations shown in this report are concerned with determining the properties of UO{sub 2} powders for determining the connection between their properties and conditions of fabrication and reduction of ADU and U{sub 3}O{sub 8}.

Fungi, bacteria and soil pH: the oxalate-carbonate pathway as a model for metabolic interaction.

Science.gov (United States)

Martin, Gaëtan; Guggiari, Matteo; Bravo, Daniel; Zopfi, Jakob; Cailleau, Guillaume; Aragno, Michel; Job, Daniel; Verrecchia, Eric; Junier, Pilar

2012-11-01

The oxalate-carbonate pathway involves the oxidation of calcium oxalate to low-magnesium calcite and represents a potential long-term terrestrial sink for atmospheric CO(2). In this pathway, bacterial oxalate degradation is associated with a strong local alkalinization and subsequent carbonate precipitation. In order to test whether this process occurs in soil, the role of bacteria, fungi and calcium oxalate amendments was studied using microcosms. In a model system with sterile soil amended with laboratory cultures of oxalotrophic bacteria and fungi, the addition of calcium oxalate induced a distinct pH shift and led to the final precipitation of calcite. However, the simultaneous presence of bacteria and fungi was essential to drive this pH shift. Growth of both oxalotrophic bacteria and fungi was confirmed by qPCR on the frc (oxalotrophic bacteria) and 16S rRNA genes, and the quantification of ergosterol (active fungal biomass) respectively. The experiment was replicated in microcosms with non-sterilized soil. In this case, the bacterial and fungal contribution to oxalate degradation was evaluated by treatments with specific biocides (cycloheximide and bronopol). Results showed that the autochthonous microflora oxidized calcium oxalate and induced a significant soil alkalinization. Moreover, data confirmed the results from the model soil showing that bacteria are essentially responsible for the pH shift, but require the presence of fungi for their oxalotrophic activity. The combined results highlight that the interaction between bacteria and fungi is essential to drive metabolic processes in complex environments such as soil. © 2012 Society for Applied Microbiology and Blackwell Publishing Ltd.

Uranium and thorium recovery from a sub-product of monazite industrial processing

International Nuclear Information System (INIS)

Gomiero, L.A.; Ribeiro, J.S.; Scassiotti Filho, W.

1994-01-01

In the monazite alkaline leaching industrial process for the production of rare earth elements, a by-product is formed, which has a high concentration of thorium and a lower but significant one of uranium. A procedure for recovery of the thorium and uranium contents in this by-product is presented. The first step of this procedure is the leaching with sulfuric acid, followed by uranium extraction from the acid liquor with a tertiary amine, stripping with a Na Cl solutions and precipitation as ammonium diuranate with N H 4 O H. In order to obtain thorium concentrates with higher purity, it is performed by means of the extraction of thorium from the acid liquor, with a primary amine, stripping by a Na Cl solution and precipitation as thorium hydroxide or oxalate. (author)

Determination of {sup 90}Sr in uranium fission products

Energy Technology Data Exchange (ETDEWEB)

Bajo, S; Tobler, L [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

1996-02-01

A previously published radiochemical procedure for the determination of {sup 90}Sr in grass and soil has been successfully employed - with minor modifications - for the determination of this nuclide in a solution of uranium fission products. It is suitable for the determination of {sup 90}Sr in environmental materials following a nuclear accident. The procedure is based on tributylphosphate extraction of {sup 90}Y, precipitation of Y-oxalate, and counting in a proportional counter. (author) figs., tabs., 10 refs.

Enhancement of Extraction of Uranium from Seawater - Final Report

International Nuclear Information System (INIS)

Dietz, Travis Cameron; Tsinas, Zois; Tomaszewski, Claire; Pazos, Ileana; Nigliazzo, Olga; Li, Weixing; Adel-Hadadi, Mohammad; Barkatt, Aaron; Al-Sheikhly, Mohamad

2016-01-01

Even at a concentration of 3 μg/L, the world's oceans contain a thousand times more uranium than currently know terrestrial sources. In order to take advantage of this stockpile, methods and materials must be developed to extract it efficiently, a difficult task considering the very low concentration of the element and the competition for extraction by other atoms in seawater such as sodium, calcium, and vanadium. The majority of current research on methods to extract uranium from seawater are vertical explorations of the grafting of amidoxime ligand, which was originally discovered and promoted by Japanese studies in the late 1980s. Our study expands on this research horizontally by exploring the effectiveness of novel uranium extraction ligands grafted to the surface of polymer substrates using radiation. Through this expansion, a greater understanding of uranium binding chemistry and radiation grafting effects on polymers has been obtained. While amidoxime-functionalized fabrics have been shown to have the greatest extraction efficiency so far, they suffer from an extensive chemical processing step which involves treatment with powerful basic solutions. Not only does this add to the chemical waste produced in the extraction process and add to the method's complexity, but it also significantly impacts the regenerability of the amidoxime fabric. The approach of this project has been to utilize alternative, commercially available monomers capable of extracting uranium and containing a carbon-carbon double bond to allow it to be grafted using radiation, specifically phosphate, oxalate, and azo monomers. The use of commercially available monomers and radiation grafting with electron beam or gamma irradiation will allow for an easily scalable fabrication process once the technology has been optimized. The need to develop a cheap and reliable method for extracting uranium from seawater is extremely valuable to energy independence, and will extend the

New South African complex leaches gold, uranium, and sulphur from slimes

Energy Technology Data Exchange (ETDEWEB)

Payne, A.

1978-01-01

Slimes dams at various mines in the Orange Free State and the Transvaal are being re-treated to recover U, Au, and H/sub 2/SO/sub 4/. Components of the Free State Metallurgical Complex include flotation plants, a uranium plant, the President Brand plant for H/sub 2/SO/sub 4/ production from the pyrite concentrates, and a calcine leaching plant for producing gold from the calcines of the acid plant. Reasons for the complex and its operation are discussed. (DLC)

OXALATE MASS BALANCE DURING CHEMICAL CLEANING IN TANK 6F

Energy Technology Data Exchange (ETDEWEB)

Poirier, M.; Fink, S.

2011-07-22

The Savannah River Remediation (SRR) is preparing Tank 6F for closure. The first step in preparing the tank for closure is mechanical sludge removal. Following mechanical sludge removal, SRS performed chemical cleaning with oxalic acid to remove the sludge heel. Personnel are currently assessing the effectiveness of the chemical cleaning to determine whether the tank is ready for closure. SRR personnel collected liquid samples during chemical cleaning and submitted them to Savannah River National Laboratory (SRNL) for analysis. Following chemical cleaning, they collected a solid sample (also known as 'process sample') and submitted it to SRNL for analysis. The authors analyzed these samples to assess the effectiveness of the chemical cleaning process. Analysis of the anions showed the measured oxalate removed from Tank 6F to be approximately 50% of the amount added in the oxalic acid. To close the oxalate mass balance, the author collected solid samples, leached them with nitric acid, and measured the concentration of cations and anions in the leachate. Some conclusions from this work are: (1) Approximately 65% of the oxalate added as oxalic acid was removed with the decanted liquid. (2) Approximately 1% of the oxalate (added to the tank as oxalic acid) formed precipitates with compounds such as nickel, manganese, sodium, and iron (II), and was dissolved with nitric acid. (3) As much as 30% of the oxalate may have decomposed forming carbon dioxide. The balance does not fully account for all the oxalate added. The offset represents the combined uncertainty in the analyses and sampling.

Biotransformation of uranium and transition metal citrate complexes by clostridia

International Nuclear Information System (INIS)

Francis, A.J.; Joshi-Tope, G.A.; Dodge, C.J.; Gillow, J.B.

2002-01-01

Clostridium sphenoides, which uses citric acid as its sole carbon source, metabolized equimolar Fe(III)-citrate with the degradation of citric acid and the reduction of Fe(III) to Fe(II), but not the U(VI)-citrate complex. However, in the presence of excess citric acid or added glucose it was reduced to U(IV)-citrate. In contrast, Clostridium sp., which ferments glucose but not citrate, reduced Fe(III)-citrate to Fe(II)-citrate and U(VI)-citrate to U(IV)-citrate only when supplied with glucose. These results show that complexed uranium is readily accessible as an electron acceptor despite the bacterium's inability to metabolize the organic ligand complexed to the actinide. These results also show that the metabolism of the metal-citrate complex depends upon the type of complex formed between the metal and citric acid. Fe(III) forms a bidentate complex with citric acid and was metabolized, whereas U forms a binuclear complex with citric acid and was recalcitrant. (author)

Oxalic acid has an additional, detoxifying function in Sclerotinia sclerotiorum pathogenesis.

Directory of Open Access Journals (Sweden)

Annerose Heller

Full Text Available The mechanism of the diseases caused by the necrotroph plant pathogen Sclerotinia sclerotiorum is not well understood. To investigate the role of oxalic acid during infection high resolution, light-, scanning-, transmission electron microscopy and various histochemical staining methods were used. Our inoculation method allowed us to follow degradation of host plant tissue around single hyphae and to observe the reaction of host cells in direct contact with single invading hyphae. After penetration the outer epidermal cell wall matrix appeared degraded around subcuticular hyphae (12-24 hpi. Calcium oxalate crystals were detected in advanced (36-48 hpi and late (72 hpi infection stages, but not in early stages. In early infection stages, surprisingly, no toxic effect of oxalic acid eventually secreted by S. sclerotiorum was observed. As oxalic acid is a common metabolite in plants, we propose that attacked host cells are able to metabolize oxalic acid in the early infection stage and translocate it to their vacuoles where it is stored as calcium oxalate. The effects, observed on healthy tissue upon external application of oxalic acid to non-infected, living tissue and cell wall degradation of dead host cells starting at the inner side of the walls support this idea. The results indicate that oxalic acid concentrations in the early stage of infection stay below the toxic level. In plant and fungi oxalic acid/calcium oxalate plays an important role in calcium regulation. Oxalic acid likely could quench calcium ions released during cell wall breakdown to protect growing hyphae from toxic calcium concentrations in the infection area. As calcium antimonate-precipitates were found in vesicles of young hyphae, we propose that calcium is translocated to the older parts of hyphae and detoxified by building non-toxic, stable oxalate crystals. We propose an infection model where oxalic acid plays a detoxifying role in late infection stages.

Growth of strontium oxalate crystals in agar–agar gel

Indian Academy of Sciences (India)

Growth of strontium oxalate crystals in agar–agar gel. P V DALAL. ∗ and K B SARAF. Postgraduate Department of Physics, Pratap College, Amalner 425 401, India. MS received 16 March 2008; revised 5 April 2010. Abstract. Single crystals of strontium oxalate have been grown by using strontium chloride and oxalic acid in.

Thermochemistry of the complex oxides of uranium, vanadium, and alkali metals

International Nuclear Information System (INIS)

Karyakin, N.V.; Chernorukov, N.G.; Suleimanov, E.V.; Kharyushina, E.A.

1992-01-01

The standard enthalpies of the formation at T 298.15 K of complex oxides of uranium(VI), vanadium(V) and alkali metals with the general formula M 1 VUO 6 where M 1 = Na, K, Rb, and Cs, were calculated from the results of calorimetric experiments and from published data. 8 refs., 1 tab

Radiological risk assessment of U(nat) in the ground water around Jaduguda uranium mining complex

International Nuclear Information System (INIS)

Sethy, N.K.; Jha, V.N.; Shukla, A.K.; Tripathi, R.M.; Puranik, V.D.

2010-01-01

Uranium is present naturally in earth crust and hence at trace level in ground water, sea water, building materials etc. Naturally occurring radionuclide originating from industrial activities, metal mining and waste depository may contribute to the nearby ground water by radionuclide migration. Ground water ecosystem surrounding the uranium processing facility at Jaduguda has been studied for natural uranium distribution. In the present study, the drinking water sources at various distance zone (with in 1.6 km, 1.6-5 km and > 5km) covering all directions around the waste depository (tailings pond) have been investigated for uranium content. Evaluation of intake, ingestion dose and subsequent risk for population residing around the tailings pond has been carried out. Annual intake of uranium through drinking water for members of public residing around the uranium complex is found to be in the range of 41.8 - 44.4 Bq.y -1 . The intake and ingestion dose is appreciably low ( -1 ) which is far below the WHO recommended level of 100 Sv.y -1 . The life time radiological risk due to uranium natural in drinking water is insignificant and found to be of the order of 10 -6 . (author)

Calcium oxalate contribution to calcium cycling in forests of contrasting nutrient status

Science.gov (United States)

Dauer, Jenny M.; Perakis, Steven S.

2014-01-01

Calcium oxalate (Ca oxalate) is an insoluble biomineral that forms in plants and fungi, and occurs in soils across many types of ecosystems. Assessing how Ca oxalate may shape ecosystem Ca cycling requires information on the distribution of Ca oxalate among plant biomass, detritus, and mineral soil, and how it varies with ecosystem Ca status. We compared two Douglas-fir forests of contrasting ecosystem Ca availability, and found that Ca oxalate was partitioned similarly among plant biomass, detritus and mineral soil major ecosystem compartments at both sites, and total pools of Ca oxalate were greater in the high-Ca forest. However, the proportional importance of Ca oxalate was greater in the low-Ca than high-Ca forest (18% versus 4% of actively cycling ecosystem Ca, respectively). And calcium oxalate in mineral soil, which is of particular interest as a potential long-term Ca reservoir, was a larger portion of total available Ca (exchangeable Ca plus Ca oxalate Ca) in the low-Ca site than the high-Ca site (9% versus 1% of available soil Ca, respectively). Calcium oxalate was the dominant form of Ca returned from plants to soil as leaf litterfall at the high-Ca site, yet calcium oxalate disappeared rapidly from decomposing litter (0.28 yr−1 or faster) at both sites. We conclude that accumulation of Ca oxalate in forest ecosystems appears most closely related to overall Ca supply for live biomass pools, and that the accumulation of Ca oxalate in forest floor and mineral soil is limited by rapid microbial degradation of putatively unavailable Ca oxalate.

Surface analysis of transition metal oxalates: Damage aspects

Energy Technology Data Exchange (ETDEWEB)

Chenakin, S.P., E-mail: chenakin@imp.kiev.ua [Université Libre de Bruxelles (ULB), Chimie-Physique des Matériaux, B-1050 Bruxelles (Belgium); Institute of Metal Physics, Nat. Acad. Sci. of Ukraine, Akad. Vernadsky Blvd. 36, 03680 Kiev (Ukraine); Szukiewicz, R. [Université Libre de Bruxelles (ULB), Chimie-Physique des Matériaux, B-1050 Bruxelles (Belgium); Barbosa, R.; Kruse, N. [Université Libre de Bruxelles (ULB), Chimie-Physique des Matériaux, B-1050 Bruxelles (Belgium); Voiland School of Chemical Engineering and Bioengineering, Washington State University, 155 Wegner Hall, Pullman, WA 99164-6515 (United States)

2016-05-15

Highlights: • Gas evolution from the Mn, Co, Ni and Cu oxalate hydrates in vacuum, during exposure to X-rays and after termination of X-ray irradiation is studied. • A comparative study of the damage caused by X-rays in NiC{sub 2}O{sub 4} and CuC{sub 2}O{sub 4} is carried out. • Effect of Ar{sup +} bombardment on the structure and composition of CoC{sub 2}O{sub 4} is studied. - Abstract: The behavior of transition metal oxalates in vacuum, under X-ray irradiation and low-energy Ar{sup +} ion bombardment was studied. A comparative mass-spectrometric analysis was carried out of gas evolution from the surface of Mn, Co, Ni and Cu oxalate hydrates in vacuum, during exposure to X-rays and after termination of X-ray irradiation. The rates of H{sub 2}O and CO{sub 2} liberation from the oxalates were found to be in an inverse correlation with the temperatures of dehydration and decomposition, respectively. X-ray photoelectron spectroscopy (XPS) was employed to study the X-ray induced damage in NiC{sub 2}O{sub 4} and CuC{sub 2}O{sub 4} by measuring the various XP spectral characteristics and surface composition of the oxalates as a function of time of exposure to X-rays. It was shown that Cu oxalate underwent a significantly faster degradation than Ni oxalate and demonstrated a high degree of X-ray induced reduction from the Cu{sup 2+} to the Cu{sup 1+} chemical state. 500 eV Ar{sup +} sputter cleaning of CoC{sub 2}O{sub 4} for 10 min was found to cause a strong transformation of the oxalate structure which manifested itself in an appreciable alteration of the XP core-level and valence band spectra. The analysis of changes in stoichiometry and comparison of XP spectra of bombarded oxalate with respective spectra of a reference carbonate CoCO{sub 3} implied that the bombardment-induced decomposition of CoC{sub 2}O{sub 4} gave rise to the formation of CoO-like and disordered CoCO{sub 3}-like phases.

Effect of heat treatment on the structure of incorporated oxalate species and photoluminescent properties of porous alumina films formed in oxalic acid

Science.gov (United States)

Vrublevsky, I.; Jagminas, A.; Hemeltjen, S.; Goedel, W. A.

2008-09-01

The present work focuses on the use of IR spectroscopy and photoluminescence spectral measurements for studying the treatment temperature effect on the compositional and luminescent properties of oxalic acid alumina films. In line with the recent researches we have also found that heat treatment of porous alumina films formed in oxalic acid leads to considerable changes in their photoluminescence properties: upon annealing the intensity of photoluminescence (PL) increases reaching a maximum at the temperature of around 500 °C and then decreases. IR spectra of as-grown and heat-treated films have proved that PL emission in the anodic alumina films is related with the state of 'structural' oxalate species incorporated in the oxide lattice. These results allowed us to conclude that PL behavior of oxalic acid alumina films can be explained through the concept of variations in the bonding molecular orbitals of incorporated oxalate species including σ- and π-bonds.

New indium selenite-oxalate and indium oxalate with two- and three-dimensional structures

International Nuclear Information System (INIS)

Cao Junjun; Li Guodong; Chen Jiesheng

2009-01-01

Two new indium(III) compounds with extended structures, [In 2 (SeO 3 ) 2 (C 2 O 4 )(H 2 O) 2 ].2H 2 O (I) and [NH 3 (CH 2 ) 2 NH 3 ][In(C 2 O 4 ) 2 ] 2 .5H 2 O (II), have been prepared under mild hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction, thermogravimetric analysis and infrared spectroscopy. Compound I crystallizes in the triclinic system, space group P-1, with a=5.2596(11) A, b=6.8649(14) A, c=9.3289(19) A, α=101.78(3) o , β=102.03(3) o , γ=104.52(3) o , while compound II crystallizes in the orthorhombic system, space group Fdd2, with a=15.856(3) A, b=31.183(6) A, c=8.6688(17) A. In compound I, indium-selenite chains are bridged by oxalate units to form two-dimensional (2D) In 2 (SeO 3 ) 2 C 2 O 4 layers, separated by non-coordinating water molecules. In compound II, the indium atoms are connected through the oxalate units to generate a 3D open framework containing cross-linked 12- and 8-membered channels. - Graphical abstract: Two new indium(III) compounds have been hydrothermally synthesized and structurally characterized. In I, the indium-selenite chains are bridged by oxalate units to form 2D In 2 (SeO 3 ) 2 C 2 O 4 layers. In II, the indium atoms are connected through the oxalate units to generate a 3D open framework containing cross-linked 12- and 8-membered ring channels

Fully-differential spectrophotometry determination of trace thorium in uranium-containing waste water separated by CL-TBP levextrel resin

International Nuclear Information System (INIS)

You Jiannan

2000-01-01

A method for separation by CL-TBP levextrel resin and determination of trace thorium in uranium-containing waste water by fully-differential spectrophotometry is developed. In 4 mol/L HNO 3 medium, in presence of tartaric acid, CL-TBP levextrel resin is used for adsorption of thorium and separating from other elements. The thorium on the resin is stripped by 4 mol/L HCl, with oxalic acid and urea as screening agent, thorium forms red complex with arsenazo III. The maximum absorption of the complex is at 668 nm, and the molar absorptivity is 1.27 x 10 5 L/(mol·cm) . The complex can be steady for 2.5 h. By regulating micro-current of differential spectrophotometry, the method can realize determination with high precision. Sensitivity of this method increase 10 times than usual spectrophotometry. The relative standard deviation is better than +- 5% and recovery of thorium is 99%-107%

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.

Chromatographic retention of molybdenum, titanium and uranium complexes for removal of some interferences in inductively-coupled plasma mass spectrometry

International Nuclear Information System (INIS)

Jiang, S.-J.; Palmieri, M.D.; Fritz, J.S.; Houk, R.S.; Iowa State Univ., of Science and Technology, Ames

1987-01-01

Complexes of molybdenum(VI) or titanium(IV) with N-methylfurohydroxamic acid (N-MFHA) are retained on a column packed with polystyrene/divinylbenzene. At the pH values chosen, copper, zinc and cadmium are washed rapidly through the column and are detected by inductively-coupled plasma mass spectrometry without interference from metal oxide ions of titanium or molybdenum. Detection limits are 1 to 2 μg l -1 , and analyte recoveries are essentially 100%. The resin capacity for the titanium and molybdenum complexes is sufficient for several hundred injections, and the complexes can be readily washed from the column. Uranium(VI) also forms a stable complex with N-MFHA, and ionization interference caused by excess of uranium can be avoided by chromatographic removal of the uranium complex. Various other potentially interfering elements with aqueous oxidation states of +4 or higher (e.g. Sn, W, Hf or Zr) could also be separated by this technique. 33 refs.; 4 figs.; 3 tabs

Synthesis and structural characterisation of mixed An(IV)-An(III) actinide oxalates used as precursors for dedicated fuel or target

International Nuclear Information System (INIS)

Tamain, Christelle; Grandjean, Stephane; Arab Chapelet, Benedicte; Abraham, Francis

2010-01-01

Oxalic co-conversion process plays an important role by producing mixed-actinide compounds used as starting materials as they are particularly suitable precursors of actinide oxide solid solutions. In these oxalate compounds, a mixed crystallographic site which accommodates both elements in spite of their different oxidation states has been established. The charge compensation is ensured by monovalent cations present in the acidic solution. This communication reviews the various mixed-actinide oxalates obtained by crystallization from acidic solution. First, crystallographic structures determined by X-ray diffraction from single crystals are described. Then completing data obtained by powder X-ray diffraction are presented on various systems. The different supramolecular arrangements underline the complexity of An(IV)-An(III)/Ln(III) oxalate system and the need to pursue studies on single crystals. (authors)

Neurotoxic effects of carambola in rats: the role of oxalate.

Science.gov (United States)

Chen, Chien-Liang; Chou, Kang-Ju; Wang, Jyh-Seng; Yeh, Jeng-Hsien; Fang, Hua-Chang; Chung, Hsiao-Min

2002-05-01

Carambola (star fruit) has been reported to contain neurotoxins that cause convulsions, hiccups, or death in uremic patients, and prolong barbiturate-induced sleeping time in rats. The constituent responsible for these effects remains uncertain. Carambola contains a large quantity of oxalate, which can induce depression of cerebral function and seizures. This study was conducted to investigate the role of oxalate in carambola toxicity in rats. The effects on barbiturate-induced sleeping time and death caused by intraperitoneal administration of carambola juice were observed in Sprague-Dawley rats. To obtain a dose-dependent response curve and evaluate the lethal dose, rats were treated with serial amounts of pure carambola juice diluted with normal saline in a volume of 1:1. To test the role of oxalate in the neurotoxic effect of carambola, either 5.33 g/kg carambola after oxalate removal or 5.33 g/kg of pure carambola juice diluted with normal saline were administered intraperitoneally, while the control group was given normal saline before pentobarbital injection. The effects of carambola and oxalate-removed carambola on barbiturate-induced sleeping time were compared with those of saline. To assess the lethal effect of oxalate in carambola, we gave rats chemical oxalate at comparable concentrations to the oxalate content of carambola. Carambola juice administration prolonged barbiturate-induced sleeping time in a dose-dependent manner. The sleeping time of rats that received normal saline and 1.33 g/kg, 2.67 g/kg, 5.33 g/kg, and 10.67 g/kg of carambola juice were 66 +/- 16.6, 93.7 +/- 13.4, 113.3 +/- 11.4, 117.5 +/- 29.0, and 172.5 +/- 38.8 minutes, respectively. The three higher-dose groups had longer sleeping times than controls (p carambola juice. Four of eight rats in the 10.67-g/kg group and all rats in the 21.33 g/kg and chemical oxalate groups died after seizure. Lethal doses of carambola juice were rendered harmless by the oxalate removal procedure

3.2.1. Synthesis, crystal and molecular structure of catena-(bis(µ1-oxalic acid)-µ3-hydrogen oxalate-di-aqua-sodium(I)).

OpenAIRE

Olga Kovalchukova*, Sergey Aldoshin, Andrey Utenyshev, Konstantin Bogenko, Valeriy Tkachev

2015-01-01

The crystal and molecular structure of catena-(bis(µ- oxalic acid)-µ-hydrogen oxalate-di-aqua-sodium(I)) was detected by X-Ray analysis. The compound crystallizes in the triclinic space group P-1, with a(Å) 6.2378(12); b(Å) 7,1115(14); c(Å) 10.489(2); α(°) 94.65(3); β(°) 100.12(3); γ(°) 97.78(3). The sodium cation in the title compound is eight coordinated and forms a square antiprism. It is surrounded by two molecules of oxalic acid, one hydrogen oxalate anion and one water molecule. Both ox...

Extraction of uranium from sea water by means of fibrous complex adsorbents

International Nuclear Information System (INIS)

Miyamatsu, Tokuhisa; Oguchi, Noboru; Kanchiku, Yoshihiko; Aoyagi, Takanobu

1982-01-01

Fibrous complex adsorbents for uranium extraction from sea water were prepared by introducing titanic acid or basic zinc carbonate as effective constituents into fibrous ion exchangers. A fibrous chelate type adsorbent was also tested. Among the adsorbents examined, the following ones demonstrated excellent properties for the recovery of uranium from sea water. a) A fibrous, weakly acidic cation exchanger was treated with titanyl sulfate in aqueous sulfuric acid solution, which was followed by neutralization to afford a fibrous adsorbent containing titanic acid (QC-1f(Ti)). The adsorption capacity for uranium in sea water was estimated by extrapolation to be 50μg-U/g-Ad or 1170 μg-U/g-Ti. b) A fibrous, strongly acidic cation exchanger was treated in a similar way to afford another type of fibrous adsorbent with titanic acid incorporated (QCS-Ti). The adsorption capacity was estimated by extrapolation to be 20-30 μg-U/g-Ad. (author)

Recovery and purification of uranium-234 from aged plutonium-238

International Nuclear Information System (INIS)

Keister, P.L.; Figgins, P.W.; Watrous, R.M.

1978-01-01

The current production methods used to recover and purify uranium-234 from aged plutonium-238 at Mound Laboratory are presented. The three chemical separation steps are described in detail. In the initial separation step, the bulk of the plutonium is precipitated as the oxalate. Successively lower levels of plutonium are achieved by anion exchange in nitrate media and by anion exchange in chloride media. The procedures used to characterize and analyze the final U 3 O 8 are given

Spectroscopic investigations on sorption of uranium onto suspended bentonite. Effects of pH, ionic strength and complexing anions

Energy Technology Data Exchange (ETDEWEB)

Verma, Parveen Kumar; Pathak, Priyanath; Mohapatra, Manoj; Mohapatra, Prasanta Kumar [Bhabha Atomic Research Centre, Mumbai (India). Radiochemistry Div.; Yadav, Ashok Kumar; Jha, Sambhunath; Bhattacharyya, Dibyendu [Bhabha Atomic Research Centre, Mumbai (India). Atomic and Molecular Physics Div.

2015-06-01

Batch sorption experiments were carried out under aerobic conditions to understand the sorption behavior of U(VI) onto bentonite clay under varying pH (2-8) and ionic strength (I = 0.01 - 1 M (NaClO{sub 4})) conditions. The influences of different complexing anions (1 x 10{sup -4} M) such as oxalic acid (ox), carbonate (CO{sub 3}{sup 2-}), citric acid (cit), and humic acid (HA, 10 mg/L) on the sorption behavior were also investigated. The sorption of U(VI) increased with increasing pH up to pH 6 beyond which a decrease was attributed to the formation of anionic carbonate species. Marginal influence of the change in the ionic strength of the medium on the sorption profile of uranium suggested inner-sphere complexation onto the bentonite surface. The presence of humic acid showed interesting sorption profile with varying pH. Initially, there was an enhancement in the sorption with increased pH followed by a plateau and finally a decrease thereafter due to the formation of aqueous U(VI)-humate complexes. Spectroscopic studies such as UV spectrophotometry, luminescence and extended X-ray absorption fine structure (EXAFS) measurements were also performed to understand the changes in aqueous speciation of U(VI) ion. The luminescence yields of different aqueous U(VI) species followed the order: U(VI){sub Hydroxy} > U(VI){sub HumicAcid} > U(VI){sub carbonate} > U(VI){sub citrate}. The lower luminescence yield of U(VI)carbonate complex can be attributed to the strong dynamic quenching by carbonate at room temperature. The U(VI) samples shows two distinct life-time suggesting the presence of the different luminescent U(VI) species. Similar trend was observed for U(VI)-bentonite suspension in presence/absence of the complexing ligands. There was luminescence quenching for the sorbed U(VI) due to surface complexation. These observations were further supported by spectrophotometric measurements. EXAFS spectra of U(VI) samples were recorded in luminescence mode at the U L{sub 3

Partitioning of plutonium and uranium in aqueous medium using hydroxyurea as reducing agent

International Nuclear Information System (INIS)

Sivakumar, P.; Subba Rao, R.V.; Meenakshi, S.

2012-01-01

A new process for the partitioning of plutonium and uranium during the reprocessing of spent fuel discharged from fast reactor was optimised using hydroxyurea (HU) as a reductant. Stoichiometric ratio of HU required for the reduction of Pu(IV) was studied. The effect of concentration of uranium, plutonium and acidity on the distribution ratio (Kd) of Pu in the presence of HU was studied. The effect of HU in further purification of Pu such as solvent extraction and precipitation of plutonium as oxalate was also studied. The results of the study indicate that Pu and U can be separated from each other using HU as reductant. (author)

Chemical thermodynamics of uranium

International Nuclear Information System (INIS)

Grenthe, I.; Fuger, J.; Lemire, R.J.; Muller, A.B.; Nguyen-Trung Cregu, C.; Wanner, H.

1992-01-01

A comprehensive overview on the chemical thermodynamics of those elements that are of particular importance in the safety assessment of radioactive waste disposal systems is provided. This is the first volume in a series of critical reviews to be published on this subject. The book provides an extensive compilation of chemical thermodynamic data for uranium. A description of procedures for activity corrections and uncertainty estimates is given. A critical discussion of data needed for nuclear waste management assessments, including areas where significant gaps of knowledge exist is presented. A detailed inventory of chemical thermodynamic data for inorganic compounds and complexes of uranium is listed. Data and their uncertainty limits are recommended for 74 aqueous complexes and 199 solid and 31 gaseous compounds containing uranium, and on 52 aqueous and 17 solid auxiliary species containing no uranium. The data are internally consistent and compatible with the CODATA Key Values. The book contains a detailed discussion of procedures used for activity factor corrections in aqueous solution, as well as including methods for making uncertainty estimates. The recommended data have been prepared for use in environmental geochemistry. Containing contributions written by experts the chapters cover various subject areas such a s: oxide and hydroxide compounds and complexes, the uranium nitrides, the solid uranium nitrates and the arsenic-containing uranium compounds, uranates, procedures for consistent estimation of entropies, gaseous and solid uranium halides, gaseous uranium oxides, solid phosphorous-containing uranium compounds, alkali metal uranates, uncertainties, standards and conventions, aqueous complexes, uranium minerals dealing with solubility products and ionic strength corrections. The book is intended for nuclear research establishments and consulting firms dealing with uranium mining and nuclear waste disposal, as well as academic and research institutes

Enhancement of Extraction of Uranium from Seawater – Final Report

Energy Technology Data Exchange (ETDEWEB)

Dietz, Travis Cameron [Univ. of Maryland, College Park, MD (United States); Tsinas, Zois [Univ. of Maryland, College Park, MD (United States); Tomaszewski, Claire [Univ. of Maryland, College Park, MD (United States); Pazos, Ileana [Univ. of Maryland, College Park, MD (United States); Nigliazzo, Olga [University of Palermo, Palermo (Italy); Li, Weixing [Univ. of Maryland, College Park, MD (United States); Adel-Hadadi, Mohammad [Univ. of Maryland, College Park, MD (United States); Barkatt, Aaron [The Catholic Univ. of America, Washington, DC (United States); Al-Sheikhly, Mohamad [Univ. of Maryland, College Park, MD (United States)

2016-05-16

Even at a concentration of 3 μg/L, the world’s oceans contain a thousand times more uranium than currently know terrestrial sources. In order to take advantage of this stockpile, methods and materials must be developed to extract it efficiently, a difficult task considering the very low concentration of the element and the competition for extraction by other atoms in seawater such as sodium, calcium, and vanadium. The majority of current research on methods to extract uranium from seawater are vertical explorations of the grafting of amidoxime ligand, which was originally discovered and promoted by Japanese studies in the late 1980s. Our study expands on this research horizontally by exploring the effectiveness of novel uranium extraction ligands grafted to the surface of polymer substrates using radiation. Through this expansion, a greater understanding of uranium binding chemistry and radiation grafting effects on polymers has been obtained. While amidoxime-functionalized fabrics have been shown to have the greatest extraction efficiency so far, they suffer from an extensive chemical processing step which involves treatment with powerful basic solutions. Not only does this add to the chemical waste produced in the extraction process and add to the method’s complexity, but it also significantly impacts the regenerability of the amidoxime fabric. The approach of this project has been to utilize alternative, commercially available monomers capable of extracting uranium and containing a carbon-carbon double bond to allow it to be grafted using radiation, specifically phosphate, oxalate, and azo monomers. The use of commercially available monomers and radiation grafting with electron beam or gamma irradiation will allow for an easily scalable fabrication process once the technology has been optimized. The need to develop a cheap and reliable method for extracting uranium from seawater is extremely valuable to energy independence, and will extend the quantity of

Oxalate molecule as the trap for gamma-irradiation energy in the amorphous aluminosilicate Al2(OH)6H4SiO4

International Nuclear Information System (INIS)

Nothig-Laslo, V.; Horvath, L.; Bilinski, H.

1990-01-01

Paramagnetic species which were the products of gamma irradiation at 77 K and at room temperature were studied by ESR spectroscopy in the amorphous aluminosilicate, Al2(OH)6H4SiO4, prepared in the presence and in the absence of oxalate ion. The aluminosilicate precipitated from the solution containing the oxalate ion in 10(-4) mol dm-3 concentration contained the oxalate only in trace amounts. When gamma-irradiated at 77 K and at room temperature, this compound gave the stable paramagnetic species represented by the single ESR line centered at g = 2.000. We ascribe this spectrum to the CO2- radical formed from the oxalate ion. The same aluminosilicate prepared in the absence of the oxalate either produced no stable paramagnetic product after gamma irradiation at room temperature or resulted in composite ESR spectra, indicating the presence of several paramagnetic species if irradiated at 77 K. Complex ESR spectra were transformed by heating to the stable paramagnetic centers which differed from the one obtained from oxalate ion. We conclude that in Al2(OH)6H4SiO4 oxalate acts as a trap for the gamma-radiation energy

The promotion effect of coexisting hygroscopic composition on the reaction between oxalic acid and calcite during humidifying process

Science.gov (United States)

Ma, Q.; He, H.

2012-12-01

Internally mixed oxalic acid with mineral dust has been frequently detected in field measurements (Sullivan and Prather, 2007; Wang et al., 2012; Yang et al., 2009). Meanwhile, Furukawa and Takahashi (Furukawa and Takahashi, 2011) found that most of the oxalic acid in mineral mixture is present as metal oxalate complexes in the aerosols, however, the formation mechanism of these complexes is not well known. It was reported that cloud process of H2C2O4/CaCO3 mixture could lead to the formation of calcium oxalate (Gierlus et al., 2012). Recently, we used Raman spectroscopy to investigate the hygroscopic behavior of H2C2O4/CaCO3 mixture below saturation condition as well as the effect of coexisting hygroscopic compositions, e.g. Ca(NO3)2, NaCl, NH4NO3, and (NH4)2SO4. It was found that there was no interaction between H2C2O4 and calcite without third component during humidifying process under ambient condition. In contrast, the presence of coexisting Ca(NO)3, NaCl, or NH4NO3 could promote the reaction between H2C2O4 and calcite by providing an aqueous circumstance after deliquescence, resulting in the formation of calcium oxalate hydrates. Moreover, substitution of strong acid (HNO3) by medium acid (H2C2O4) occurred when water vapor was absorbed in Ca(NO3)2/H2C2O4 mixture (Ma and He, 2012). As for (NH4)2SO4, there existed a competition effect between (NH4)2SO4 and H2C2O4 for the reaction with CaCO3. CaCO3 was preferentially reacted with (NH4)2SO4 to form gypsum in the solution, while the residual NH4+ and C2O42- ions were bonded to (NH4)2C2O4 after efflorescence. These results implies a potential formation pathway of metal oxalate complexes in the atmosphere and also suggests that synergistic effect between different constituents in humidifying process of mixed particles should be considered in future hygroscopic behavior studies.

Oxalic acid biosynthesis and oxalacetate acetylhydrolase activity in Streptomyces cattleya

International Nuclear Information System (INIS)

Houck, D.R.; Inamine, E.

1987-01-01

In addition to producing the antibiotic thienamycin, Streptomyces cattleya accumulates large amounts of oxalic acid during the course of a fermentation. Washed cell suspensions were utilized to determine the specific incorporation of carbon-14 into oxalate from a number of labeled organic and amino acids. L-[U- 14 C]aspartate proved to be the best precursor, whereas only a small percentage of label from [1,5- 14 C]citrate was found in oxalate. Cell-free extracts catalyzed the formation of [ 14 C]oxalate and [ 14 C]acetate from L-[U- 14 C]aspartate. When L-[4- 14 C]aspartate was the substrate only [ 14 C]acetate was formed. The cell-free extracts were found to contain oxalacetate acetylhydrolase, the enzyme that catalyzes the hydrolysis of oxalacetate to oxalate and acetate. The enzyme is constitutive and is analogous to enzymes in fungi that produce oxalate from oxalacetate. Properties of the crude enzyme were examined

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.)

Isolation and some characteristics of anaerobic oxalate-degrading bacteria from the rumen.

OpenAIRE

Dawson, K A; Allison, M J; Hartman, P A

1980-01-01

Obligately anaerobic oxalate-degrading bacteria were isolated from an enriched population of rumen bacteria in an oxalate-containing medium that had been depleted of other readily metabolized substrates. These organisms, which are the first reported anaerobic oxalate degraders isolated from the rumen, were gram negative, nonmotile rods. They grew in a medium containing sodium oxalate, yeast extract, cysteine, and minerals. The only substrate that supported growth was oxalate. Growth was direc...

TDPAC studies on metal-complex ferrimagnets

Energy Technology Data Exchange (ETDEWEB)

Ohkubo, Yoshitaka [Kyoto Univ., Kumatori, Osaka (Japan). Research Reactor Inst.; Abe, Shizuko; Okada, Takuya [and others

1997-03-01

TDPAC spectra of {sup 117}In (left-arrow {sup 117}Cd) and {sup 111}Cd (left-arrow {sup 111m}Cd) in the mixed metal complex N(C{sub 4}H{sub 9}){sub 4}(M(II)Fe(III)(C{sub 2}O{sub 4}){sub 3})(M=Fe,Ni), the related substraces and LiNbO{sub 3} have been studied. In this paper, pure potassium iron (III) oxalate was prepared and mixed metal complexes were synthesized by changing amount of reagents and the order added, then observed by TDPAC. 2 mol%Cd was dispersed throughout potassium iron oxalate and potassium nickel oxalate, formulating M(II){sub 0.98}Cd(II){sub 0.02}C{sub 2}O{sub 4}{center_dot}2H{sub 2}O (M=Fe, Ni) with the same crystal structure. The formation reaction of mixed metal complex-Fe(II) was faster than that of iron oxalate. Its mixed metal complex-Ni(II) was slower than that of iron oxalate. The rate of quadrupole oscillation was obtained by {omega}{sub Q}({sup 117}In)=67.3 Mrad/s and {omega}{sub Q}({sup 111}Cd)=29.7 Mrad/s of which values were determined by TDPAC spectra of {sup 117}In and {sup 111}Cd in LiNbO{sub 3} at 4K. The value showed pure ion bond of oxygen coordinated with {sup 117}In and {sup 111}Cd. 0.08 {eta} was determined by TDPAC spectrum of {sup 111}Cd(left-arrow {sup 111m}Cd). The rate of {omega}{sub Q} of mixed metal oxalate complex was larger than 2.3, indicating 5s and 5p orbital electron took part in bond of oxygen of oxalic acid or approaching oxygen ion to In nucleus depend on the structual relaxation in decaying of {sup 117}In(left-arrow {sup 117}Cd). (S.Y.)

Microbial growth on oxalate by a route not involving glyoxylate carboligase

Science.gov (United States)

Blackmore, Maureen A.; Quayle, J. R.

1970-01-01

1. The metabolism of oxalate by the pink-pigmented organisms, Pseudomonas AM1, Pseudomonas AM2, Protaminobacter ruber and Pseudomonas extorquens has been compared with that of the non-pigmented Pseudomonas oxalaticus. 2. During growth on oxalate, all the organisms contain oxalyl-CoA decarboxylase, formate dehydrogenase and oxalyl-CoA reductase. This is consistent with oxidation of oxalate to carbon dioxide taking place via oxalyl-CoA, formyl-CoA and formate as intermediates, and also reduction of oxalate to glyoxylate taking place via oxalyl-CoA. 3. The pink-pigmented organisms, when grown on oxalate, contain l-serine–glyoxylate aminotransferase and hydroxypyruvate reductase but do not contain glyoxylate carboligase. The converse of this obtains in oxalate-grown Ps. oxalaticus. This indicates that, in contrast with Ps. oxalaticus, synthesis of C3 compounds from oxalate by the pink-pigmented organisms occurs by a variant of the `serine pathway' used by Pseudomonas AM1 during growth on C1 compounds. 4. Evidence in favour of this scheme is provided by the finding that a mutant of Pseudomonas AM1 that lacks hydroxypyruvate reductase is not able to grow on oxalate. PMID:5472155

Spectroscopic properties of Pr -doped erbium oxalate crystals

Indian Academy of Sciences (India)

Spectroscopic properties of praseodymium ions-doped erbium oxalate ... solution with specific gravity 1.04 g/cm3 was mixed homogeneously with 0.5 M oxalic ... of concentrated nitric acid were transferred carefully and gently through the wall ...

Interaction of Celestine Concentrate and Reagent Grade SrSO4 with Oxalate Solutions

Directory of Open Access Journals (Sweden)

Abdullah Obut

2012-12-01

Full Text Available The interaction of reagent grade strontium sulphate and celestine concentrate with aqueous solutions of oxalic acid, sodiumoxalate and ammonium oxalate for the production of strontium carbonate were investigated for different oxalate compound:SrSO4 moleratios and reaction times using x-ray diffraction analysis and dissolution tests. Under the same experimental conditions, it was foundthat aqueous oxalic acid and sodium oxalate solutions had no or little effect on reagent grade strontium sulphate or celestineconcentrate, but aqueous ammonium oxalate solution converted them into strontium oxalate hydrate. Strontium carbonate was obtainedat conversion ratios of 74.7% for the celestine concentrate and 84.6 % for the reagent grade strontium sulphate by the decompositionof the obtained strontium oxalate hydrate at 600 °C under air atmosphere.

ROLE OF THE MICROFLORA IN DISTAL INTESTINAL TRACT BY MAINTAINING OXALATE HOMEOSTASIS

Directory of Open Access Journals (Sweden)

Osolodchenko T.P.

2015-05-01

Full Text Available Human intestinal microflora is part of the human body and performs numerous function. Considerable research interest is in the field of probiotics for the prevention of kidney stones, which is one of the most common urological diseases.Urolithiasis is one of the most common urological diseases. This is polyetiological disease congenital and acquired character with complex physical and chemical processes that occur not only in the urinary system, but also the whole body. None of the treatments does not guarantee full recovery of the patient and often leads to relapse. The open methods of removal stones yield news minimally invasive the technologys. Development of stone formation depends on the presence of many factors, metabolic disorders, chronic urinary tract infections, genetic disorders and more. Most have the following metabolic disorders as hypercalciuria, hiperurikuria, hipotsytraturia , hyperoxaluria and hipomahniuria. Among all types of urolithiasis kaltsiyoksalatnyy ranked first in the prevalence rate - about 75.0 - 85.0 % of cases. Dietary restriction by oxalates іs the unreliable method of preventing disease. Although there is evidence for the growth inhibition normobiocenosis representatives, which in turn enhances the absorption of salts of oxalic acid oxalate in the application of sodium , magnesium and cobalt in their intragastric administration. Recently published many papers on the impact on the level of oxalate intestinal microflora. The first publications appeared on the influence of gram-negative obligate anaerobes O. formigenes the concentration of oxalate in the urine. This anaerobic bacteria living in the colon, its prevalence - 46.0 % - 77.0 % of the adult population. O. formigenes reveals the symbiotic interaction with the human body by reducing absorption of oxalate in the intestinal cavity with subsequent decrease in their concentration in plasma and urine. O. formigenes has two key enzymes - oksalyl

Decontamination of Uranium-Contaminated Soil Sand Using Supercritical CO2 with a TBP–HNO3 Complex

Directory of Open Access Journals (Sweden)

Kwangheon Park

2015-09-01

Full Text Available An environmentally friendly decontamination process for uranium-contaminated soil sand is proposed. The process uses supercritical CO2 as the cleaning solvent and a TBP–HNO3 complex as the reagent. Four types of samples (sea sand and coarse, medium, and fine soil sand were artificially contaminated with uranium. The effects of the amount of the reagent, sand type, and elapsed time after the preparation of the samples on decontamination were examined. The extraction ratios of uranium in all of the four types of sand samples were very high when the time that elapsed after preparation was less than a few days. The extraction ratio of uranium decreased in the soil sand with a higher surface area as the elapsed time increased, indicating the possible formation of chemisorbed uranium on the surface of the samples. The solvent of supercritical CO2 seemed to be very effective in the decontamination of soil sand. However, the extraction of chemisorbed uranium in soil sand may need additional processes, such as the application of mechanical vibration and the addition of bond-breaking reagents.

Study of uranium +4 stabilization by the formation of a complex with a heteropolyanion ligand, for its off-lines analysis

International Nuclear Information System (INIS)

Bion, L.

1995-01-01

The study of the behaviour of uranium in oxidation state +4, during uranium/plutonium separation step of the PUREX process for reprocessing nuclear fuels, requires the availability of an efficient analytical method allowing the stabilization and off-line analysis of sample of aqueous and organic solutions containing this reagent. It was accordingly decided to develop a stabilization method using the heteropolyanion P 2 W 17 O 61 10- (PWO ' ) as a selective ligand. Besides the stabilization effect, the complexation of uranium +4 results in the appearance of an intense and specific band on the visible absorption spectrum of the formed U(PWO) 2 16- complex. This property made it possible to consider the sensitive spectrophotometric analysis of the sample. The work presented first helped to determine, in the presence of PWO, the characteristic thermodynamic data of the reaction involving uranium +4 and +6, plutonium +3 and +4, nitrous and nitric acids, and hydrazine. In the light of these results, it was possible to plan the development of the stabilisation method. The use of PWO thus helped (1) to design a method capable of stopping any reaction involving the uranium +4 / uranium +6 pair, and (2) to perform the simple analysis of uranium +4. The study presented in the second part uses the example of the U 4+ cation to understand the reasons for the selectivity of the complexation of actinides +4 by PWO. Owing to the remarkable spectroscopic and magnetic properties of this cation, ti was possible to acquire data concerning the structure of the U(PWO) 2 16- complex, both in solution and in the solid state. It was thus demonstrated that the geometry of the environment of U 4+ (eight oxygen forming a cubic anti-prism), which is perfectly complementary to that of the 5f electron wave functions of the actinide, helps to explain the selectivity of the complexation of actinides +4. (author). refs., 46 figs., 40 tabs

Influence of additives on the structure and microstructure of lanthanides and actinides oxalates

International Nuclear Information System (INIS)

Haidon, Blaise; Vitart, Anne-Lise; Rivenet, Murielle; Arab-Chapelet, Benedicte; Roussel, Pascal; Delahaye, Thibaud; Grandjean, Stephane; Abraham, Francis

2015-07-01

Oxalic conversion is a well-known process in the nuclear industry where it is used for precipitating plutonium as an oxalate thereafter calcinated into an oxide. As there is a strong relationship between the morphology of the oxalate precursor and that of the resulting oxide, it is of interest to control the oxalate structure and microstructure during the precipitation step. The influence of additives on the precipitation of neodymium (III) oxalates, non-radioactive analogs of actinides (III) oxalates, was explored. With the use of nitrilotri-methylphosphonic acid (NTMP), the structure and microstructure of the neodymium oxalates are different from that obtained without additive. (authors)

Foreign research reactor uranium supply program: The Y-12 national security complex process

International Nuclear Information System (INIS)

Nelson, T.; Eddy, B.G.

2010-01-01

The Foreign Research Reactor (FRR) Uranium Supply Program at the Y-12 National Security Complex supports the nonproliferation objectives of the HEU Disposition Program, the Reduced Enrichment Research and Test Reactors (RERTR) Program, and the United States FRR Spent Nuclear Fuel (SNF) Acceptance Program. The Y-12 National Nuclear Security Administration (NNSA) Y-12 Site Office maintains the prime contracts with foreign governments for the supply of Low-Enriched Uranium (LEU) for their research reactors. The LEU is produced by down blending Highly Enriched Uranium (HEU) that has been declared surplus to the U.S. national defense needs. The down blending and sale of the LEU supports the Surplus HEU Disposition Program Record of Decision to make the HEU non-weapons usable and to recover the economic value of the uranium to the extent feasible. This program supports the important U.S. government and nuclear nonproliferation commitment to serve as a reliable and cost-effective uranium supplier for those foreign research reactors that are converting or have converted to LEU fuel under the guidance of the NNSA RERTR Program. In conjunction with the FRR SNF Acceptance Program which supports the global nonproliferation efforts to disposition U.S.-origin HEU, the Y-12 FRR Uranium Supply Program can provide the LEU for the replacement fuel fabrication. In addition to feedstock for fuel fabrication, Y-12 supplies LEU for target fabrication for medical isotope production. The Y-12 process uses supply forecasting tools, production improvements and efficient delivery preparations to successfully support the global research reactor community

A non-acid-assisted and non-hydroxyl-radical-related catalytic ozonation with ceria supported copper oxide in efficient oxalate degradation in water

KAUST Repository

Zhang, Tao

2012-06-01

Oxalate is usually used as a refractory model compound that cannot be effectively removed by ozone and hydroxyl radical oxidation in water. In this study, we found that ceria supported CuO significantly improved oxalate degradation in reaction with ozone. The optimum CuO loading amount was 12%. The molar ratio of oxalate removed/ozone consumption reached 0.84. The catalytic ozonation was most effective in a neutral pH range (6.7-7.9) and became ineffective when the water solution was acidic or alkaline. Moreover, bicarbonate, a ubiquitous hydroxyl radical scavenger in natural waters, significantly improved the catalytic degradation of oxalate. Therefore, the degradation relies on neither hydroxyl radical oxidation nor acid assistance, two pathways usually proposed for catalytic ozonation. These special characters of the catalyst make it suitable to be potentially used for practical degradation of refractory hydrophilic organic matter and compounds in water and wastewater. With in situ characterization, the new surface Cu(II) formed from ozone oxidation of the trace Cu(I) of the catalyst was found to be an active site in coordination with oxalate forming multi-dentate surface complex. It is proposed that the complex can be further oxidized by molecular ozone and then decomposes through intra-molecular electron transfer. The ceria support enhanced the activity of the surface Cu(I)/Cu(II) in this process. © 2012 Elsevier B.V.

Oxaloacetate hydrolase, the C-C bond lyase of oxalate secreting fungi

NARCIS (Netherlands)

Han, Y.; Joosten, H.J.; Niu, W.; Zhao, Z.; Mariano, P.S.; McCalman, M.; Kan, van J.; Schaap, P.J.; Dunaway-Mariano, D.

2007-01-01

Oxalate secretion by fungi is known to be associated with fungal pathogenesis. In addition, oxalate toxicity is a concern for the commercial application of fungi in the food and drug industries. Although oxalate is generated through several different biochemical pathways, oxaloacetate

Evidence for a cytoplasmic pathway of oxalate biosynthesis in Aspergillus niger

International Nuclear Information System (INIS)

Kubicek, C.P.; Schreferl-Kunar, G.; Woehrer, W.; Roehr, M.

1988-01-01

Oxalate accumulation of up to 8 g/liter was induced in Aspergillus niger by shifting the pH from 6 to 8. This required the presence of P/sub i/ and a nitrogen source and was inhibited by the protein synthesis inhibitor cycloheximide. Exogenously added 14 CO 2 was not incorporated into oxalate, but was incorporated into acetate and malate, thus indicating the biosynthesis of oxalate by hydrolytic cleavage of oxaloacetate. Inhibition of mitochondrial citrate metabolism by fluorocitrate did not significantly decrease the oxalate yield. The putative enzyme that was responsible for this oxaloacetate hydrolase (EC 3.7.1.1), which was induced de novo during the pH shift. Subcellular fractionation of oxalic acid-forming mycelia of A. niger showed that this enzyme is located in the cytoplasm of A. niger. The results are consistent with a cytoplasmic pathway of oxalate formation which does not involve the tricarboxylic acid cycle

Study of aqueous complexes of uranium (IV) in an acid medium by nuclear magnetic resonance

International Nuclear Information System (INIS)

Kiener, C.; Folcher, G.; Rigny, P.; Virlet, J.

1976-01-01

The hydration of tetravalent uranium in acid solutions has been studied by proton magnetic resonance. Longitudinal and transversal relaxation rates of water are reported as a function of temperature, acidity, and added ions. The relaxation rates observed in perchloric solutions at high temperature are governed by the exchange process of water molecules between the inner coordination sphere of uranium(IV) and the bulk water. The bound proton's lifetime lies between 10 ms and 1 s. At pH > 0, the exchange rate depends upon acidity according to a simple expression. At high concentrations of diamagnetic ions the exchange rate depends linearly upon water activity. At low temperature, the proton relaxation rates are dominated by an outer sphere effect and the electronic relaxation time of uranium(IV) is found to be about 10 -13 s. No signal is observed from protons of the water molecules in the first sphere, firmly bound to uranium(IV), which undergo rapid relaxation. The chemical shift of the proton absorption signal in hydrochloric solutions arise from tightly bound water molecules in paramagnetic interaction with uranium(IV) in a second sphere, and in fast exchange with the bulk water. Above a chlorine concentration of 6 M, the monochloro complex of uranium(IV) contributes to the chemical shift. (author)

Vaal Reefs South uranium plant

International Nuclear Information System (INIS)

Anon.

1979-01-01

The Vaal Reefs mining complex, part of the Anglo American Corporation, is the largest gold and uranium producing complex in the world, being South Africa's principal producer, accounting for about a quarter of the country's uranium production. Vaal Reefs South uranium plant in the Orkney district was recently officially opened by Dr AJA Roux, the retiring president of the Atomic Energy Board and chairman of the Uranium Enrichment Corporation and will increase the country's uranium production. In the field of technology, and particularly processing technology, South Africa has shown the world unprecedented technology achievement in the field of uranium extraction from low grade ores and the development of the unique uranium enrichment process. New technical innovations that have been incorporated in this new plant are discussed

Decontamination effectiveness of mixtures of citric acid, oxalic acid and EDTA

International Nuclear Information System (INIS)

Speranzini, R.A.

1990-01-01

An experimental study of the decontamination effectiveness of citric acid, oxalic acid and EDTA mixtures was conducted to assess whether oxalic acid could be removed from decontamination solutions to minimize corrosion. In loop experiments, radioactive specimens from two boiling water reactors and one pressurized water reactor were suspended in solutions of single acids or in mixtures of reagents at total reagent concentrations of less than 0.1 wt% under conditions similar to those used to decontaminate reactor systems. Rate constants for dissolution of oxides and decontamination factors were measured. Based on the results, it was concluded that under certain conditions, oxalic acid was the most effective reagent for the dissolution of oxides. It was also found, however, that conditions under which effective dissolution occurred in solutions of oxalic acid and/or citric acid were difficult to define and control. EDTA was found to be an effective reagent for dissolution of oxides such that rates of dissolution in EDTA containing solutions at 117 degrees Celsius were comparable to rates in oxalic acid containing solutions. At 90 degrees Celsius, EDTA acted synergistically with oxalic acid such that the rate of dissolution of oxides in citric-acid/oxalic-acid/EDTA solutions was higher than in citric-acid/EDTA solutions. The rates of dissolution of oxides were significantly reduced when 60 mg/kg of ferric ion was added to the citric-acid/oxalic-acid, citric-acid/EDTA and citric-acid/oxalic-acid/EDTA solutions. It was concluded that effective decontaminations of BWR and PWR systems could be achieved with mixtures of citric acid and EDTA

Complex formation between uranium(VI) and α-D-glucose 1-phosphate

International Nuclear Information System (INIS)

Koban, A.; Geipel, G.; Bernhard, G.

2003-01-01

The complex formation of uranium(VI) with α-D-glucose 1-phosphate (C 6 H 11 O 6 PO 3 2- , G1P) was determined by time-resolved laser-induced fluorescence spectroscopy (TRLFS) at pH 4 and potentiometric titration in the pH range from 3 to 10. Both measurements show the formation of a 1 : 1 complex at lower pH values. The formation constant of UO 2 (C 6 H 11 O 6 PO 3 ) was calculated from TRLFS measurements to be log β 11 = 5.72±0.12, and from potentiometric titration log β 11 = 5.40±0.25, respectively. It was found by potentiometric titration that at higher pH values the complexation changes to a 1 : 2 complex. The stability constant for this complex was calculated to be log β 12 = 8.96±0.18. (orig.)

Distribution of radium and chemical toxins in the environment of a uranium complex

International Nuclear Information System (INIS)

Markose, P.M.; Eapen, K.P.; Venkataraman, S.; Kamath, P.R.

1978-01-01

The discharge of waste effluents from mining and milling of uranium ore brings into the aquatic environment radioactive pollutants and chemical toxins. The radioactive element of primary concern is radium and the nonactive pollutants are manganese, chlorides, sulphates and water hardness. In the Uranium Complex, Bihar (India), the low grade ore is mined and processed for recovery of uranium. The waste slurries from the process are neutralised and discharged into the tailings pond(TP) where the solids settle and the effluents flow out into a natural stream, Jurianala. The TP effluent mixes with mine water and floor washings from the mill in the canal on its down stream course to the river, R. Subarnarekha. This study was conducted to assess the total pollution from the liquid discharges in the environment and the impact of discharge on water quality. The results of the study of movement of pollutants in the biosphere and laboratory investigations on containment are presented. (author)

Complexes of uranium tetrachlorides and thorium tetrachloride with N-methylpiperazine, 2-methylpiperazine, N-phenylpiperazine, N,N'-dimethylpiperazine and pyrazine

Energy Technology Data Exchange (ETDEWEB)

Manhas, B S; Trikha, A K [Punjabi Univ., Patiala (India). Dept. of Chemistry; Singh, M

1979-01-01

Stable complexes of uranium tetrachloride and thorium tetrachloride with the title ligands have been synthesised and characterised on the basis of elemental analyses, IR and electronic reflectance spectral studies and magnetic susceptibility measurements. The ligands probably coordinate in the chair conformation bridging the metal ions as indicated by IR spectral studies and insolubility of these complexes in common organic solvents. A coordination number of six for uranium (IV) is suggested by the electronic reflectance spectral and magnetic susceptibility data.

MRP-1 and BCRP Promote the Externalization of Phosphatidylserine in Oxalate-treated Renal Epithelial Cells: Implications for Calcium Oxalate Urolithiasis.

Science.gov (United States)

Li, YiFu; Yu, ShiLiang; Gan, XiuGuo; Zhang, Ze; Wang, Yan; Wang, YingWei; An, RuiHua

2017-09-01

To investigate the possible involvement of multidrug resistance-associated protein 1 (MRP-1) and breast cancer resistance protein (BCRP) in the oxalate-induced redistribution of phosphatidylserine (PS) in renal epithelial cell membranes. A western blot analysis was used to examine the MRP-1 and BCRP expression levels. Surface-expressed PS was detected by the annexin V-binding assay. The cell-permeable fluorogenic probe 2,7-dichlorofluorescein diacetate was used to measure the intracellular reactive oxygen species (ROS) level. A rat model of hyperoxaluria was obtained using 0.5% ethylene glycol and 1.0% ammonium chloride. In addition, certain animals received verapamil (50 mg/kg body weight), which is a common inhibitor of MRP-1 and BCRP. The degree of nephrolithiasis was assessed histomorphometrically using sections stained by Pizzolato method and by measuring the calcium oxalate crystal content in the renal tissue. Oxalate produced a concentration-dependent increase in the synthesis of MRP-1 and BCRP. Treatment with MK571 and Ko143 (MRP-1- and BCRP-specific inhibitors, respectively) significantly attenuated the oxalate-induced PS externalization. Adding the antioxidant N-acetyl-l-cysteine significantly reduced MRP-1 and BCRP expression. In vivo, markedly decreased nephrocalcinosis was observed compared with that in the rat model of hyperoxaluria without verapamil treatment. Oxalate induces the upregulation of MRP-1 and BCRP, which act as phospholipid floppases causing PS externalization in the renal epithelial cell membrane. The process is mediated by intracellular ROS production. The ROS-mediated increase in the synthesis of MRP-1 and BCRP can play an important role in hyperoxaluria-promoted calcium oxalate urolithiasis by facilitating phosphatidylserine redistribution in renal epithelial cells. Copyright © 2017 Elsevier Inc. All rights reserved.

Putative Aspergillus niger-induced oxalate nephrosis in sheep : clinical communication

Directory of Open Access Journals (Sweden)

C.J. Botha

2009-05-01

Full Text Available A sheep farmer provided a maize-based brewer's grain (mieliemaroek and bales of Eragrostis curvula hay to ewes and their lambs, kept on zero-grazing in pens. The 'mieliemaroek' was visibly mouldy. After 14 days in the feedlot, clinical signs, including generalised weakness, ataxia of the hind limbs, tremors and recumbency, were noticed. Six ewes died within a period of 7 days. A post mortem examination was performed on 1 ewe. The carcass appeared to be cachectic with mild effusions into the body cavities; mild lung congestion and pallor of the kidneys were observed. Microscopical evaluation revealed nephrosis and birefringent oxalate crystals in the renal tubules when viewed under polarised light. A provisional diagnosis of oxalate nephrosis with subsequent kidney failure was made. Amongst other fungi, Aspergillus niger was isolated from 'mieliemaroek' samples submitted for fungal culture and identification. As A. niger is known to synthesise oxalates, a qualitative screen to detect oxalic acid in the mieliemaroek and purified A. niger isolates was performed using high-performance liquid chromatography (HPLC. Oxalic acid was detected, which supported a diagnosis of soluble oxalate-induced nephropathy.

Conductometric and pH metric investigations of the oxalic acid and NaAsO2 reaction

Directory of Open Access Journals (Sweden)

MIRJANA V. OBRADOVIC

2008-10-01

Full Text Available The reaction between NaAsO2 and oxalic acid was studied by pH-metric and conductometric measurements, applying the methods of continual variation and pH-metric and conductometric titration. It was found that oxalic acid forms a complex anion of the type [AsOC2O4]-. The relative stability constant of the complex at ionic strengths, I, of 0.10 (log Kr = 4.70, 0.20 (log Kr = 4.51, 0.50 (log Kr = 4.24 and 0 (log K0r = 5.05 and thermodynamic para¬meters were calculated using the data obtained by pH-metric measurements at 25.0±0.1 °C (DH = 10.5 kJ mol-1, DG = –29.0 kJ mol-1, DS = 133 J mol-1 K-1.

Evidence for a cytoplasmic pathway of oxalate biosynthesis in Aspergillus niger

Energy Technology Data Exchange (ETDEWEB)

Kubicek, C.P.; Schreferl-Kunar, G.; Woehrer, W.; Roehr, M.

1988-03-01

Oxalate accumulation of up to 8 g/liter was induced in Aspergillus niger by shifting the pH from 6 to 8. This required the presence of P/sub i/ and a nitrogen source and was inhibited by the protein synthesis inhibitor cycloheximide. Exogenously added /sup 14/CO/sub 2/ was not incorporated into oxalate, but was incorporated into acetate and malate, thus indicating the biosynthesis of oxalate by hydrolytic cleavage of oxaloacetate. Inhibition of mitochondrial citrate metabolism by fluorocitrate did not significantly decrease the oxalate yield. The putative enzyme that was responsible for this oxaloacetate hydrolase (EC 3.7.1.1), which was induced de novo during the pH shift. Subcellular fractionation of oxalic acid-forming mycelia of A. niger showed that this enzyme is located in the cytoplasm of A. niger. The results are consistent with a cytoplasmic pathway of oxalate formation which does not involve the tricarboxylic acid cycle.

Morphological control of strontium oxalate particles by PSMA-mediated precipitation reaction

Energy Technology Data Exchange (ETDEWEB)

Yu Jiaguo [State Key Laboratory of Advanced Technology for Material Synthesis and Processing, Wuhan University of Technology, Wuhan 430070 (China)]. E-mail: jiaguoyu@yahoo.com; Tang Hua [State Key Laboratory of Advanced Technology for Material Synthesis and Processing, Wuhan University of Technology, Wuhan 430070 (China); Cheng Bei [State Key Laboratory of Advanced Technology for Material Synthesis and Processing, Wuhan University of Technology, Wuhan 430070 (China)

2005-05-15

In this paper, strontium oxalate particles with different morphologies could be easily obtained by a precipitation reaction of sodium oxalate with strontium chloride in the absence and presence of poly-(styrene-alt-maleic acid) (PSMA). The as-prepared products were characterized with scanning electron microscopy and X-ray diffraction. The effects of pH, aging time and concentration of PSMA on the phase structures and morphologies of the as-prepared strontium oxalate particles were investigated and discussed. The results showed that strontium oxalate particles with various morphologies, such as, bi-pyramids, rods, peanuts, and spherical particles, etc., could be obtained by varying the experimental conditions. PSMA promoted the formation of strontium oxalate dihydrate (SOD) phase. Suitable pH values (pH 7 and 8) favor the formation of the peanut-shaped SrC{sub 2}O{sub 4} particles. This research may provide new insight into the control of morphologies and phase structures of strontium oxalate particles and the biomimetic synthesis of novel inorganic materials.

Dissolution of Simulated and Radioactive Savannah River Site High-Level Waste Sludges with Oxalic Acid & Citric Acid Solutions

International Nuclear Information System (INIS)

STALLINGS, MARY

2004-01-01

sludge solids. We recommend that these results be evaluated further to determine if these solutions contain sufficient neutron poisons. We observed low general corrosion rates in tests in which carbon steel coupons were contacted with solutions of oxalic acid, citric acid and mixtures of oxalic and citric acids. Wall thinning can be minimized by maintaining short contact times with these acid solutions. We recommend additional testing with oxalic and oxalic/citric acid mixtures to measure dissolution performance of sludges that have not been previously dried. This testing should include tests to clearly ascertain the effects of total acid strength and metal complexation on dissolution performance. Further work should also evaluate the downstream impacts of citric acid on the SRS High-Level Waste System (e.g., radiochemical separations in the Salt Waste Processing Facility and addition of organic carbon in the Saltstone and Defense Waste Processing facilities)

Study of new complexes of uranium and comba radical. II-Complexes formed in the presence of OH-, CO3H, CH3-COO-, and B4O7

International Nuclear Information System (INIS)

Vera Palomino, V.; Galiano Sedano, J. A.; Parellada Bellod, R.; Bellido Gonzalez, A.

1975-01-01

Several complexes extracted with CDMBAC organic solutions from uranium aqueous solutions, in presence of sodium and ammonium hydroxides, are studied. These complexes fit to the general formula: U0 2 (OH) n (C[DMBA) n -2 . The uranium extraction in presence of an excess of sodium bicarbonate is also studied. From aqueous solutions of uranyl acetate we have isolated the complex U0 2 (CH 3 -C00) n (CDMBA) n -2. In presence of boric acid and sodium tetraborate an U-CDMBA compound containing boron in its molecule has being obtained by precipitation and liquid-liquid extraction. (Author) 5 refs

Synthesis and reduction of uranium(V) imido complexes with redox-active substituents

Energy Technology Data Exchange (ETDEWEB)

Mullane, Kimberly C.; Carroll, Patrick J.; Schelter, Eric J. [P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, PA (United States)

2017-04-27

Organic azides that contain naphthyl functional groups were used to prepare uranium(V) imido complexes U{sup V}[=NC(2-naph)Ph{sub 2}][N(SiMe{sub 3}){sub 2}]{sub 3} (2), U{sup V}[=NC(2-naph){sub 3}][N(SiMe{sub 3}){sub 2}]{sub 3} (3), and U{sup V}[=N(2-naph)][N(SiMe{sub 3}){sub 2}]{sub 3} (4), and their properties were compared with U{sup V}[=NCPh{sub 3}][N(SiMe{sub 3}){sub 2}]{sub 3} (1). The electronic structures of these compounds were investigated by solution electrochemistry studies, which revealed accessible U{sup V/VI}, U{sup IV/V}, and naphthalene{sup 0}/naphthalene{sup -1} couples. The uranium(V) naphthylimido complexes were reduced by potassium graphite to yield their uranium(IV) congeners K[U{sup IV}[=NC(2-naph)Ph{sub 2}][N(SiMe{sub 3}){sub 2}]{sub 3}] (2-K), K[U{sup IV}[=NC(2-naph){sub 3}][N(SiMe{sub 3}){sub 2}]{sub 3}] (3-K), and K[U{sup IV}[=N(2-naph)][N(SiMe{sub 3}){sub 2}]{sub 3}] (4-K). The electronic structure of the dianionic compounds were investigated by DFT calculations, and this revealed that the second reduction was ligand-based, which opens the possibility of accomplishing multi-electron redox chemistry by using a tailored multiply-bonded ligand. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Synthesis and characterization of thorium(IV) and uranium(IV) complexes with Schiff bases

Energy Technology Data Exchange (ETDEWEB)

Radoske, Thomas; Maerz, Juliane; Kaden, Peter; Patzschke, Michael; Ikeda-Ohno, Atsushi [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Chemistry of the F-Elements

2017-06-01

We report herein the synthesis and characterization of several imine complexes of tetravalent thorium (Th(IV)) and uranium (U(IV)). The ligands investigated in this study are a Schiff base type, including the well-known salen ligand (H{sub 2}Le, Fig. 1). The complexation in solution was investigated by NMR measurements indicating paramagnetic effects of unpaired f-electrons of U(IV) on the ligand molecule. We also determined the solid-state molecular structures of the synthesized complexes by single crystal X-ray diffraction. The synthesized complexes show an eight-fold coordination geometry around the actinide center surrounded by two tetradentate ligands with 2N- and 2O-donor atoms.

Two-stage precipitation of neptunium (IV) oxalate

International Nuclear Information System (INIS)

Luerkens, D.W.

1983-07-01

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

Preparation, characterization and catalytic effects of copper oxalate nanocrystals

International Nuclear Information System (INIS)

Singh, Gurdip; Kapoor, Inder Pal Singh; Dubey, Reena; Srivastava, Pratibha

2012-01-01

Graphical abstract: Prepared copper oxalate nanocrystals were characterized by FE-SEM and bright field TEM micrographs. Its catalytic activity was evaluated on the thermal decomposition of ammonium perchlorate using TG and TG-DSC techniques. Highlights: ► Preparation of nanocrystals (∼9.0 nm) of copper oxalate using Cu(NO 3 ) 2 ·2H 2 O, oxalic acid and acetone under thermal conditions. ► Method is simple and novel. ► Characterization using XRD, SEM, TEM, HRTEM and ED pattern. ► Catalytic activity of copper oxalate nanocrystals on AP thermal decomposition using thermal techniques (TG, TG-DSC and ignition delay). ► Kinetics of thermal decomposition of AP + CONs using isoconversional and model fitting kinetic approaches. - Abstract: Recent work has described the preparation and characterization of copper oxalate nanocrystals (CONs). It was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM) and electron diffraction pattern (ED). The catalytic activity of CONs on the thermal decomposition of ammonium perchlorate (AP) and composite solid propellants (CSPs) has been done by thermogravimetry (TG), differential scanning calorimetry (DSC) and ignition delay measurements. Burning rate of CSPs was also found to be enhanced in presence of copper oxalate nanocrystals. Kinetics of thermal decomposition of AP with and without CONs has also been investigated. The model free (isoconversional) and model-fitting kinetic approaches have been applied to data for isothermal TG decomposition.

Two-stage fungal leaching of vanadium from uranium ore residue of the leaching stage using statistical experimental design

International Nuclear Information System (INIS)

Gharehbagheri, Hassan; Safdari, Jaber; Roostaazad, Reza; Rashidi, Abbas

2013-01-01

Highlights: ► In this work, the percent of vanadium recovery from uranium mine waste was 44.8. ► Unlike autotrophs, Aspergillus niger is a suitable microorganism to deal with such a resource. ► In the first step of the present work, citric acid was produced more than the other acids. ► When sterilization of uranium ore waste is not economic, two-step bioleaching is an appropriate method. - Abstract: In this investigation, bioleaching of vanadium from uranium ore residue of the leaching stage was studied by Aspergillus niger in a two-step process at 30 °C and 150 rpm. The first step was initiated by growth of fungi in the absence of mine waste. Using response surface methodology, three factors were surveyed for fungal growth: initial pH, sucrose concentration and spore population. Also concentrations of oxalic, citric, and gluconic acids were measured as response in this step. During 30 days, maximum productions of these acids were 3265, 11578, and 7988 mg/l, respectively. Initial pH and sucrose concentration were significant factors for oxalic and citric acid production; however, for gluconic acid production sucrose concentration and spore population were significant. Then, the content of each flask was filtered and mine waste was added to liquor with pulp density of 3%. During 3 days, in the second step, vanadium recovered about 44.8% in the liquor

Features of atopic dermatitis in children with oxalic acid dysmetabolism

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T.V. Stoieva

2018-03-01

Full Text Available The article presents the features of atopic dermatitis in children with concomitant metabolic disturbances of oxalic acid. The influence of metabolic shifts was evaluated by clinical presentation, morphofunctional parameters of the skin and the features of oxalic acid metabolites excretion. In this study, a high incidence of dysmetabolic changes was identified, their significance was determined by the involvement of different systems for oxalic acid products excretion. The increased concentration of oxalate in the urine and in the exhaled air condensate had irritant effect and is associated with the hereditary metabolic disorders, early manifestation of atopy symptoms and the intensity of skin itching, with moderate increase of immunoglobulin E level.

Novel Inorganic Coordination Polymers Based on Cadmium Oxalates

Science.gov (United States)

Prasad, P. A.; Neeraj, S.; Vaidhyanathan, R.; Natarajan, Srinivasan

2002-06-01

Three new cadmium oxalate coordination polymers, I-III, with extended layered structures have been synthesized in the presence of imidazole. While I was prepared by the reaction between imidazolium oxalate and Cd, II and III were synthesized from their constituents using hydrothermal methods. [Cd(C2O4)(C3N2H4)]∞ (I): monoclinic, space group P21/c (no. 14), a=8.7093(1) Å, b=9.9477(3) Å, c=8.4352 Å, β=93.796(1)°, Z=4; [Cd(C2O4)2(C3N2H4)3(H2O)]∞ (II): monoclinic, space group P21/c (no. 14), a=7.8614(2) Å, b=14.9332(3) Å, c=15.9153(4) Å β=94.587(1)°, Z=4; [Cd(C2O4)2(C3N2H4)3(H2O)]∞ (III): monoclinic, space group P21/c (no. 14), a=11.844(2) Å, b=9.066(1) Å, c=18.583(2) Å, β=103.84(2)°, Z=4. While the structure of I is made from CdO5N distorted octahedra linked with oxalate, II and III are built-up from CdO6N, CdO5N2 distorted pentagonal bi-pyramids connected to oxalate units. The framework formulas of II and III are identical and their structures closely related. In all the cases, the networking between the Cd-O/N polyhedra and oxalates give rise to layered architectures with the amine molecules pointing in a direction perpendicular to the layers (in the inter-lamellar region). The difference in the linkages between the oxalates and the Cd atoms in I-III, produces unusual Cd-O-Cd one-dimensional chains, which have been observed for the first time.

Analytical method of uranium (IV) and uranium (VI) in uranium ores and uranium-bearing rocks

International Nuclear Information System (INIS)

Shen Zhuqin; Zheng Yongfeng; Li Qingzhen; Zhong Miaolan; Gu Dingxiang

1995-11-01

The best conditions for keeping the original valences of uranium during the dissolution and separation procedure of geological samples (especially those micro uranium-bearing rock) were studied. With the exist of high concentration protectants, the sample was decomposed with concentration HF at 40 +- 5 degree C. The U(VI) was dissolved completely and formed stable complex UO 2 F 2 , the U(IV) was precipitated rapidly and carried by carrier. Quantitative separation was carried out immediately with suction. The decomposition of sample and separation of solid/liquid phases was completed within two minutes. After separation, the U(IV) and U(VI) were determined quantitatively with laser fluorescence or voltametry respectively according to the uranium content. The limit of detection for this method is 0.7 μg/g, RSD is 10.5%, the determinate range of uranium is 2 x 10 -6 ∼10 -1 g/g. The uranium contents and their valence state ratio were measured for more than one hundred samples of sand stone and granite, the accuracy and precision of these results are satisfactory for uranium geological research. (12 tabs.; 11 refs.)

Total, Soluble and Insoluble Oxalate Contents of Ripe Green and Golden Kiwifruit.

Science.gov (United States)

Nguyễn, Hà Vũ Hồng; Savage, Geoffrey P

2013-03-05

Three bulk samples of two different cultivars of kiwifruit, green ( Actinidia deliciosa L . ) and golden ( Actinidia chinensis L . ) were bought ripe, ready to eat from a local market. The aim of the study was to determine the oxalate composition of each of the three fractions of kiwifruit, namely skin, pulp and seeds. The pulp consisted of 90.4% of the edible portion of the two cultivars while the skin and seeds made up a mean of 8.0% and 1.6% respectively. Total oxalate was extracted with 2.0 M HCL at 21 °C for 15 min and soluble oxalates extracted at 21 °C in water for 15 min from each fraction. The total and soluble oxalate compositions of each fraction were determined using ion exchange HPLC chromatography. The pulp of golden kiwifruit contained lower amounts of total oxalates (15.7 vs. 19.3 mg/100 g FW) and higher amounts of soluble oxalates (8.5 vs. 7.6 mg/100 g FW) when compared to the green cultivar. The skin of the green cultivar contained lower levels of insoluble oxalates (36.9 vs. 43.6 mg/100 g FW), while the seeds of the green cultivar contained higher levels of insoluble oxalates 106.7 vs. 84.7 mg/100 g FW.

Extraction of uranium from simulated ore by the supercritical carbon dioxide fluid extraction method with nitric acid-TBP complex

International Nuclear Information System (INIS)

Dung, Le Thi Kim; Imai, Tomoki; Tomioka, Osamu; Nakashima, Mikio; Takahashi, Kuniaki; Meguro, Yoshihiro

2006-01-01

The supercritical fluid extraction (SFE) method using CO 2 as a medium with an extractant of HNO 3 -tri-n-butyl phosphate (TBP) complex was applied to extract uranium from several uranyl phosphate compounds and simulated uranium ores. An extraction method consisting of a static extraction process and a dynamic one was established, and the effects of the experimental conditions, such as pressure, temperature, and extraction time, on the extraction of uranium were ascertained. It was found that uranium could be efficiently extracted from both the uranyl phosphates and simulated ores by the SFE method using CO 2 . It was thus demonstrated that the SFE method using CO 2 is useful as a pretreatment method for the analysis of uranium in ores. (author)

Uranium mill tailings neutralization: contaminant complexation and tailings leaching studies

International Nuclear Information System (INIS)

Opitz, B.E.; Dodson, M.E.; Serne, R.J.

1985-05-01

Laboratory experiments were performed to compare the effectiveness of limestone (CaCO 3 ) and hydrated lime [Ca(OH) 2 ] for improving waste water quality through the neutralization of acidic uranium mill tailings liquor. The experiments were designed to also assess the effects of three proposed mechanisms - carbonate complexation, elevated pH, and colloidal particle adsorption - on the solubility of toxic contaminants found in a typical uranium mill waste solution. Of special interest were the effects each of these possible mechanisms had on the solution concentrations of trace metals such as Cd, Co, Mo, Zn, and U after neutralization. Results indicated that the neutralization of acidic tailings to a pH of 7.3 using hydrated lime provided the highest overall waste water quality. Both the presence of a carbonate source or elevating solution pH beyond pH = 7.3 resulted in a lowering of previously achieved water quality, while adsorption of contaminants onto colloidal particles was not found to affect the solution concentration of any constituent investigated. 24 refs., 8 figs., 19 tabs

Urinary oxalate excretion, as determined by isotope dilution and indirect colorimetry

International Nuclear Information System (INIS)

Prenen, J.A.C.; Boer, P.; Leersum, L. van; Oldenburg, S.J.; Endeman, H.J.

1983-01-01

A simple and reliable method for the determination of urinary oxalate excretion is described. Urinary oxalate is precipitated with calcium chloride, and the oxalate content of the precipitate is measured by an indirect colorimetric method developed by Neas and Guyon in 1972. For single urine samples, a correction is made for the incompleteness of the precipitation of calcium oxalate by isotope dilution. The range of normal values (5% limits) determined in 52 normal subjects was 0.121-0.325 mmol.24 h - 1 .m - 2 for a 1-day collection period and 0.145-0.301 mmol. 24 h - 1 .m - 2 for a 3-day collection period. The within-assay CV of a control urine with a low oxalate concentration was 9% (n=7) and the between-assay CV for the same control urine was 12% (n=6). When the values obtained for oxalate excretion were normalized to body surface area, there was no significant difference between males and females; the main source of variation was the intra-individual variation. (Auth.)

Multisensor system for determination of iron(II), iron(III), uranium(VI) and uranium(IV) in complex solutions

International Nuclear Information System (INIS)

Legin, A.V.; Seleznev, B.L.; Rudnitskaya, A.M.; Vlasov, Yu.G.; Tverdokhlebov, S.V.; Mack, B.; Abraham, A.; Arnold, T.; Baraniak, L.; Nitsche, H.

1999-01-01

Development and analytical evaluation of a multisensor system based on the principles of 'electronic tongue' for the determination of low contents of uranium(VI), uranium(IV), iron(II) and iron(III) in complex aqueous media have been carried out. A set of 29 different chemical sensors on the basis of all- solid-state crystalline and vitreous materials with enhanced electronic conductivity and redox and ionic cross-sensitivity have been incorporated into the sensor array. Multidimensional data have been processed by pattern recognition methods such as artificial neural networks and partial least squares. It has been demonstrated that Fe(II) and Fe(III) contents in the range from 10 -7 to 10 -4 mol L -1 of total iron concentration can be determined with the average precision of about 25 %. U(VI) and U(IV) contents can been determined with the average precision of 10-40% depending on the concentration. The developed multisensor system can be applied in future for the analysis of mining and borehole waters as well other contaminated natural media, including on-site measurements. (author)

Availability of calcium from chemically pure potassium oxalate to the buffalo (Bubalus bubalis)

International Nuclear Information System (INIS)

Singh, Sudarshan; Sareen, V.K.; Marwah, S.R.; Sharma, K.C.; Bhatia, I.S.

1978-01-01

Three experiments were conducted to determine the true dige'stibility of calcium in the buffalo calves fed chemically pure potassium oxalate. In each experiments 6 calves were divided into two groups, viz. control and oxalate-fed. The control group was given basal ration consisting of wheat straw, mustard-cake and maize grains. The oxalate-fed group was fed the basal ration supplemented with 60, 100 and 140 g potassium oxalate per day in experiments 1,2, and 3 respectively. The percent true digestibility of calcium was 51.7 and 52.5 in experiment 1, 60.5 and 44.1 in experiment 2, and 59.3 and 44.1 in experiment 3 in the control and oxalate-fed groups respectively. In all the experiments the oxalate was completely broken down in the rumen. The volume of water intake and urine excretion was more in the oxalate-fed groups. The daily alkali output in the urine in terms of N-acid was 0.7 and 1.3 in experiment 1, 1.5 and 2.5 in experiment 2, and 2.1 and 3.8 in experiment 3 in control and oxalate-fed groups respectively. The daily bicarbonate concentration in the urine (in g) was 26.5 and 53.4 in experiment 1, 83.2 and 146.2 in experiment 2, and 132.6 and 222.8 in experiment 3 in control and oxalate-fed groups respectively. Likewise the excretion of oxalate in the urine was more in oxalate-fed groups. On the basis of the results obtained, the reason for the somewhat low true digestibility of calcium in the calves consuming more than 60 g of potassium oxalate/day are discussed. Isotope-dilution technique using 45 CaCl 2 was employed in the study. (auth.)

Hydrothermal synthesis of uranyl squarates and squarate-oxalates: hydrolysis trends and in situ oxalate formation.

Science.gov (United States)

Rowland, Clare E; Cahill, Christopher L

2010-07-19

We report the synthesis of two uranyl squarates and two mixed-ligand uranyl squarate-oxalates from aqueous solutions under hydrothermal conditions. These products exhibit a range of uranyl building units from squarates with monomers in (UO(2))(2)(C(4)O(4))(5).6NH(4).4H(2)O (1; a = 16.731(17) A, b = 7.280(8) A, c = 15.872(16) A, beta = 113.294(16) degrees , monoclinic, P2(1)/c) and chains in (UO(2))(2)(OH)(2)(H(2)O)(2)(C(4)O(4)) (2; a = 12.909(5) A, b = 8.400(3) A, c = 10.322(4) A, beta = 100.056(7) degrees , monoclinic, C2/c) to two squarate-oxalate polymorphs with dimers in (UO(2))(2)(OH)(C(4)O(4))(C(2)O(4)).NH(4).H(2)O (3; a = 9.0601(7) A, b = 15.7299(12) A, c = 10.5108(8) A, beta = 106.394(1) degrees , monoclinic, P2(1)/n; and 4; a = 8.4469(6) A, b = 7.7589(5) A, c = 10.5257(7) A, beta = 105.696(1) degrees , monoclinic, P2(1)/m). The dominance at low pH of monomeric species and the increasing occurrence of oligomeric species with increasing pH suggests that uranyl hydrolysis, mUO(2)(2+) + nH(2)O right harpoon over left harpoon [(UO(2))(m)(OH)(n)](2m-n) + nH(+), has a significant role in the identity of the inorganic building unit. Additional factors that influence product assembly include in situ hydrolysis of squaric acid to oxalic acid, dynamic metal to ligand concentration, and additional binding modes resulting from the introduction of oxalate anions. These points and the effects of uranyl hydrolysis with changing pH are discussed in the context of the compounds presented herein.

Unusual calcium oxalate crystals in ethylene glycol poisoning.

Science.gov (United States)

Godolphin, W; Meagher, E P; Sanders, H D; Frohlich, J

1980-06-01

A patient poisoned with ethylene glycol exhibited the symptoms of (1) hysteria, (2) metabolic acidosis with both a large anion gap and osmolal gap, and (3) crystalluria. However, the shape of the urinary crystals was prismatic and resembled hippurate rather than the expected dipyramidal calcium oxalate dihydrate. X-ray crystallography positively identified them as calcium oxalate monohydrate.

Electrochemical investigation of uranium β-diketonates for all-uranium redox flow battery

International Nuclear Information System (INIS)

Yamamura, Tomoo; Shiokawa, Yoshinobu; Yamana, Hajimu; Moriyama, Hirotake

2002-01-01

The redox flow battery using uranium as the negative and the positive active materials in polar aprotic solvents was proposed. In order to establish the guiding principle for the uranium compounds as the active materials, the investigation of uranium β-diketonate complexes was conducted on (i) the solubility of active materials, (ii) the electrode reaction of U(VI) and U(IV) β-diketonate complexes and (iii) the estimation of the open circuit voltage of the battery. The solubilities of higher than 0.8 mol dm -3 of U(VI) complexes and higher than 0.4 mol dm -3 of a U(IV) complex were obtained in the solvents. The electrode reactions of U(pta) 4 , UO 2 (dpm) 2 , UO 2 (fod) 2 and UO 2 (pta) 2 were first studied and the redox potentials of uranium β-diketonates were thermodynamically discussed. The open circuit voltage is estimated more than 1 V by using Hacac or Hdpm. The larger open circuit voltage is expected when a ligand with the larger basicity is used

The uranium in the environment; L'uranium dans l'environnement

Energy Technology Data Exchange (ETDEWEB)

NONE

2001-07-01

The uranium is a natural element omnipresent in the environment, with a complex chemistry more and more understood. Many studies are always today devoted to this element to better improve the uranium behavior in the environment. To illustrate this knowledge and for the public information the CEA published this paper. It gathers in four chapters: historical aspects and properties of the uranium, the uranium in the environment and the impacts, the metrology of the uranium and its migration. (A.L.B.)

Complexation of vanadium with amidoxime and carboxyl groups. Uncovering the competitive role of vanadium in uranium extraction from seawater

Energy Technology Data Exchange (ETDEWEB)

Wang, Cong-Zhi; Wu, Qun-Yan; Lan, Jian-Hui; Shi, Wei-Qun [Chinese Academy of Sciences, Beijing (China). Inst. of High Energy Physics; Chai, Zhi-Fang [Chinese Academy of Sciences, Beijing (China). Inst. of High Energy Physics; Soochow Univ., Suzhou (China). School of Radiological and Interdisciplinary Sciences (RAD-X); Wu, Guo-Zhong [Chinese Academy of Sciences, Shanghai (China). Shanghai Inst. of Applied Physics

2017-09-01

At present, amidoxime-based adsorbents are considered to be the most promising materials for extraction of uranium from seawater. However, the high concentrations of transition metals especially vanadium strongly compete with uranium in the sequestration process, which is extremely limited the commercial use of amidoxime-based adsorbents. In this work, the coordination modes, bonding nature, and stabilities of possible vanadium(IV) (VO{sup 2+}) and (V) (VO{sub 2}{sup +}, VO{sup 3+}, V{sup 5+}) complexes with amidoximate (AO{sup -}), carboxyl (Ac{sup -}), glutarimidedioximate (HA{sup -}) and deprotonated glutarimidedioximate (A{sup 2-}) on single and double alkyl chains (R=C{sub 13}H{sub 26}) are systematically explored by quantum chemical calculations. Different from the uranyl (UO{sub 2}{sup 2+}) complexes, the AO{sup -} groups of the vanadium(IV) and (V) complexes prefer to coordinate as monodentate and chelate ligands, while few species with AO{sup -} groups in η{sup 2}-binding mode have been observed in the vanadium complexes. Besides, the vanadium complexes are predicted to have obvious covalent metal-ligand bonds. According to thermodynamic stability analysis, all the vanadium complexes with AO{sup -}, Ac{sup -}, HA{sup -} and A{sup 2-} ligands on double alkyl chains are found to be more stable than corresponding complexes with ligands on a single chain. The synergistic effect of the amidoxime and carboxyl groups can be observed in most of VO{sub 2}{sup +} and VO{sup 3+} complexes with mixed ligands (AO{sup -}/Ac{sup -}). The vanadium(IV) and (V) complexes are more stable than the corresponding uranyl complexes, and the adsorption capability of the amidoxime-based adsorbents toward vanadium(V) ions decrease in the order of VO{sub 2}{sup +}>VO{sup 3+}> V{sup 5+}. The dioxovanadium cation VO{sub 2}{sup +} is predicted to form multinuclear vanadium complex in the sequestration process, possibly resulting in higher stable VO{sub 2}{sup +} complexes. Therefore

Crystallization of calcium oxalate in minimally diluted urine

Science.gov (United States)

Bretherton, T.; Rodgers, A.

1998-09-01

Crystallization of calcium oxalate was studied in minimally diluted (92%) urine using a mixed suspension mixed product crystallizer in series with a Malvern particle sizer. The crystallization was initiated by constant flow of aqueous sodium oxalate and urine into the reaction vessel via two independent feed lines. Because the Malvern cell was in series with the reaction vessel, noninvasive measurement of particle sizes could be effected. In addition, aliquots of the mixed suspension were withdrawn and transferred to a Coulter counter for crystal counting and sizing. Steady-state particle size distributions were used to determine nucleation and growth kinetics while scanning electron microscopy was used to examine deposited crystals. Two sets of experiments were performed. In the first, the effect of the concentration of the exogenous sodium oxalate was investigated while in the second, the effect of temperature was studied. Calcium oxalate nucleation and growth rates were found to be dependent on supersaturation levels inside the crystallizer. However, while growth rate increased with increasing temperature, nucleation rates decreased. The favored phases were the trihydrate at 18°C, the dihydrate at 38° and the monohydrate at 58°C. The results of both experiments are in agreement with those obtained in other studies that have been conducted in synthetic and in maximally diluted urine and which have employed invasive crystal counting and sizing techniques. As such, the present study lends confidence to the models of urinary calcium oxalate crystallization processes which currently prevail in the literature.

Inherently safe in situ uranium recovery

Science.gov (United States)

Krumhansl, James L; Brady, Patrick V

2014-04-29

An in situ recovery of uranium operation involves circulating reactive fluids through an underground uranium deposit. These fluids contain chemicals that dissolve the uranium ore. Uranium is recovered from the fluids after they are pumped back to the surface. Chemicals used to accomplish this include complexing agents that are organic, readily degradable, and/or have a predictable lifetime in an aquifer. Efficiency is increased through development of organic agents targeted to complexing tetravalent uranium rather than hexavalent uranium. The operation provides for in situ immobilization of some oxy-anion pollutants under oxidizing conditions as well as reducing conditions. The operation also artificially reestablishes reducing conditions on the aquifer after uranium recovery is completed. With the ability to have the impacted aquifer reliably remediated, the uranium recovery operation can be considered inherently safe.

Heterogeneous nucleation of calcium oxalate on native oxide surfaces

International Nuclear Information System (INIS)

Song, L.; Pattillo, M.J.; Graff, G.L.; Campbell, A.A.; Bunker, B.C.

1994-04-01

The aqueous deposition of calcium oxalate onto colloidal oxides has been studied as a model system for understanding heterogeneous nucleation processes of importance in biomimetic synthesis of ceramic thin films. Calcium oxalate nucleation has been monitored by measuring induction times for nucleation using Constant Composition techniques and by measuring nucleation densities on extended oxide surfaces using an atomic force microscope. Results show that the dependence of calcium oxalate nucleation on solution supersaturation fits the functional form predicted by classical nucleation theories. Anionic surfaces appear to promote nucleation better than cationic surfaces, lowering the effective energy barrier to heterogeneous nucleation

Total, Soluble and Insoluble Oxalate Contents of Ripe Green and Golden Kiwifruit

Directory of Open Access Journals (Sweden)

Hà Vũ Hồng Nguyễn

2013-03-01

Full Text Available Three bulk samples of two different cultivars of kiwifruit, green (Actinidia deliciosa L. and golden (Actinidia chinensis L. were bought ripe, ready to eat from a local market. The aim of the study was to determine the oxalate composition of each of the three fractions of kiwifruit, namely skin, pulp and seeds. The pulp consisted of 90.4% of the edible portion of the two cultivars while the skin and seeds made up a mean of 8.0% and 1.6% respectively. Total oxalate was extracted with 2.0 M HCL at 21 °C for 15 min and soluble oxalates extracted at 21 °C in water for 15 min from each fraction. The total and soluble oxalate compositions of each fraction were determined using ion exchange HPLC chromatography. The pulp of golden kiwifruit contained lower amounts of total oxalates (15.7 vs. 19.3 mg/100 g FW and higher amounts of soluble oxalates (8.5 vs. 7.6 mg/100 g FW when compared to the green cultivar. The skin of the green cultivar contained lower levels of insoluble oxalates (36.9 vs. 43.6 mg/100 g FW, while the seeds of the green cultivar contained higher levels of insoluble oxalates 106.7 vs. 84.7 mg/100 g FW.

Correlation between oxalic acid production and copper tolerance in Wolfiporia cocos

Science.gov (United States)

C. A. Clausen; Frederick Green; B. M. Woodward; J. W. Evans; R. C. DeGroot

2000-01-01

The increased interest in copper-based wood preservatives has hastened the need for understanding why some fungi are able to attack copper-treated wood. Due in part to accumulation of oxalic acid by brown-rot fungi and visualization of copper oxalate crystals in wood decayed by known copper-tolerant decay fungi, oxalic acid has been implicated in copper tolerance by...

Steric control of redox events in organo-uranium chemistry: synthesis and characterisation of U(V) oxo and nitrido complexes

OpenAIRE

Tsoureas, Nikolaos; Kilpatrick, Alexander; Inman, Christopher; Cloke, Frederick Geoffrey

2016-01-01

The synthesis and molecular structures of a U(V) neutral terminal oxo complex and a U(V) sodium uranium nitride contact ion pair are described. The synthesis of the former is achieved by the use of tBuNCO as a mild oxygen transfer reagent, whilst that of the latter is via the reduction of NaN3. Both mono-uranium complexes are stabilised by the presence of bulky silyl substituents on the ligand framework that facilitate a 2e- oxidation of a single U(III) centre. In contrast, when steric hindra...

Sources and atmospheric processes impacting oxalate at a suburban coastal site in Hong Kong: Insights inferred from 1 year hourly measurements

Science.gov (United States)

Zhou, Yang; Huang, Xiaohui Hilda; Bian, Qijing; Griffith, Stephen M.; Louie, Peter K. K.; Yu, Jian Zhen

2015-09-01

Oxalic acid is one of the most abundant dicarboxylic acids in the atmosphere, receiving a great deal of attention due to its potential influence on cloud condensation nucleus activities. In this work, we report 10 months of hourly oxalate measurements in particulate matter of less than 2.5 µm in aerodynamic diameter (PM2.5) by a Monitor for Aerosols and Gases in ambient Air at a suburban coastal site in Hong Kong from April 2012 to February 2013. A total of more than 6000 sets of oxalate and inorganic ion data were obtained. The mean (±SD) oxalate concentration was 0.34 (±0.18) µg m-3, accounting for 2.8% of the total ion mass and 1.5% of the PM2.5 mass. Seasonal variation showed higher concentrations in fall and winter (0.54 and 0.36 µg m-3, respectively) and lower concentrations in spring and summer (~0.26 µg m-3). Different from the inorganic ions, a shallow dip in the oxalate concentration consistently occurred in the morning after sunrise (around 9:00 A.M.) throughout all seasons. Our analysis suggests that this was likely due to photolysis of oxalate-Fe (III) complex under sunlight. In summer, a small daytime peak was discernable for oxalate and nitrate. This characteristic, together with a more evident diurnal variation of O3, indicates comparatively more active photochemical oxidation in summer than other seasons. High correlations were observed between oxalate and non-sea-salt SO42- (NSS) (R2 = 0.63) and Ox (O3 + NO2) (R2 = 0.48), indicating significant commonality in their secondary formation. Positive matrix factorization analysis of oxalate and other real-time gas and particle-phase component data estimates that secondary formation processes, including secondary gas or aqueous oxidation processes (49%), oxidation processes of biomass burning emissions (37%), accounted for the majority of PM2.5 oxalate. A backward trajectories cluster analysis found that higher oxalate/NSS ratios were associated with low pollution samples under the influence of

Zircon U-Pb geochronology and geochemistry of granites in the Zhuguangshan complex, South China: Implications for uranium mineralization

Science.gov (United States)

Zhang, Long; Chen, Zhenyu; Li, Xiaofeng; Li, Shengrong; Santosh, M.; Huang, Guolong

2018-05-01

The Zhuguangshan complex, composed of Caledonian, Indosinian, and Yanshanian granites, and Cretaceous mafic dykes, is one of the most important granite-hosted uranium producers in South China. Here we present LA-ICP-MS zircon U-Pb and hornblende 40Ar/39Ar geochronology and whole-rock and biotite geochemistry for the granites in this complex to evaluate the magmatism and its constraints on uranium mineralization. Samples collected from the Fuxi, Youdong, Longhuashan, Chikeng, Qiling, and Sanjiangkou intrusions yield zircon weighted 206Pb/238U ages of 426.7 ± 5.4 Ma, 226.4 ± 3.5 Ma, 225.0 ± 2.7 Ma, 152.2 ± 3.0 Ma, 153.9 ± 2.1 Ma, and 155.2 ± 2.1 Ma, respectively. A new Ar-Ar dating of the hornblende of the diabase from the Changjiang uranium ore field yields a plateau age of 145.1 ± 1.5 Ma. These results coupled with published geochronological data indicate that six major magmatic events occurred in the study area at 420-435 Ma, 225-240 Ma, 150-165 Ma, 140 Ma, 105 Ma, and 90 Ma. Both U-bearing and barren granites occur in this complex, and they display differences in whole-rock and biotite geochemistry. The barren granites show higher Al2O3, CaO, TFMM, Rb, Zr, Ba, SI, Mg#, (La/Yb)N, and Eu/Eu*, but lower SiO2, ALK, Rb, DI, Rb/Sr, and TiO2/MgO than those of the U-bearing granites. Biotites in the U-bearing granites are close to the Fe-rich siderophyllite-annite end member with Fe/(Fe + Mg) ratios higher than 0.66, whereas those in the barren granites are relatively close to the Mg-rich eastonite-phlogopite end member with Fe/(Fe + Mg) ratios uranium ore potential of the granites in the Zhuguangshan complex. The geochemical variations of U-bearing and barren granites can serve as a potential detector for granite-hosted uranium deposits.

Effects of Juice Processing on Oxalate Contents in Carambola Juice Products.

Science.gov (United States)

Huynh, Nha K; Nguyen, Ha V H

2017-09-01

Effects of processing methods including pressing, enzyme-assisted extraction, lactic acid fermentation by Lactobacillus acidophilus, and alcohol fermentation by Saccharomyces cerevisiae on total and soluble oxalate contents of carambola juices were studied. In comparison with pressing, the use of enzyme increased juice yields (15.89-17.29%), but resulted in higher total oxalate (1.60-1.73 times) and soluble oxalate contents (1.16-1.49 times). In addition, extension of enzyme incubation periods led to an increase in soluble oxalate contents in the products (p carambola juices. These results suggested that carambola juice products should only be consumed moderately, and that alcohol fermentation could be a potential method to reduce oxalate contents in foods in order to prevent the risks of forming kidney stones.

Reaction of Hydrazine Hydrate with Oxalic Acid: Synthesis and ...

African Journals Online (AJOL)

NICO

2013-11-28

Nov 28, 2013 ... The title compound is a molecular salt containing two discrete hydrazinium cations and an oxalate anion. The oxalate ... RESEARCH ARTICLE ... Scheme and reaction showing the simple experimental procedure for the preparation of .... 7 A.I. Vogel, A Text Book of Quantitative Inorganic Analysis, 4th edn.,.

Studies on the decomposition of oxalic acid by nitric acid in presence of catalysts

International Nuclear Information System (INIS)

Noronha, D.M.; Pius, I.C.; Chaudhury, S.

2015-01-01

Impure Plutonium oxalate generated from the recovery of plutonium from waste solutions may require further purification via anion exchange. Conventionally, plutonium oxalate is converted to oxide in a furnace and the oxide is dissolved in Conc. HNO 3 containing HF and purified by anion exchange route. Studies initiated on the decomposition of oxalic acid with Conc. HNO 3 to facilitate direct dissolution of plutonium oxalate and quantitative destruction of oxalate are discussed in this paper. (author)

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

Optimization of precipitation conditions of thorium oxalate precipitate

International Nuclear Information System (INIS)

Pazukhin, Eh.M.; Smirnova, E.A.; Krivokhatskij, A.S.; Pazukhina, Yu.L.; Kiselev, P.P.

1986-01-01

Thorium precipitation in the form of difficultly soluble oxalate has been investigated. The equation binding the concentration of metal with the nitric acid in the initial solution and quantity of a precipitator necessary for minimization of desired product losses is derived. The graphical solution of this equation for a case, when the oxalic acid with 0.78 mol/l concentration is the precipitator, is presented

Uranium(iii) complexes supported by hydrobis(mercaptoimidazolyl)borates: synthesis and oxidation chemistry.

Science.gov (United States)

Maria, Leonor; Santos, Isabel C; Santos, Isabel

2018-05-23

The reaction of [UI3(thf)4] with the sodium or lithium salts of hydrobis(2-mercapto-1-methylimidazolyl)borate ligands ([H(R)B(timMe)2]-) in a 1 : 2 ratio, in tetrahydrofuran, gave the U(iii) complexes [UI{κ3-H,S,S'-H(R)B(timMe)2}2(thf)2] (R = H (1), Ph (2)) in good yields. Crystals of [UI{κ3-H,S,S'-H(Ph)B(timMe)2}2(thf)2] (2) were obtained by recrystallization from a tetrahydrofuran/acetonitrile solution, and the ion-separated uranium complex [U{κ3-H,S,S'-H(Ph)B(timMe)2}2(CH3CN)3][I] (3-I) was obtained by dissolution of 2 in acetonitrile followed by recrystallization. One-electron oxidation of 2 with AgBPh4 or I2 resulted in the formation of the cationic U(iv) complexes [U{κ3-H,S,S'-H(Ph)B(timMe)2}3][X] (X = BPh4 (6-BPh4), I (6-I)), due to a ligand redistribution process. These complexes are the first examples of homoleptic poly(azolyl)borate U(iv) complexes. Treatment of complex 2 with azobenzene led to the isolation of crystals of the U(iv) compound [UI{κ3-H(Ph)B(timMe)2}2(κ2-timMe)] (7). Treatment of 2 with pyridine-N oxide (pyNO) led to the formation of the uranyl complex [UO2{κ2-S,S'-H(Ph)B(timMe)2}2] (8) and of complex 6-I, while from the reaction of [U{κ3-H(Ph)B(timMe)2}2(thf)3][BPh4] (5) with pyNO, the oxo-bridged U(iv) complex [{U{κ3-H(Ph)B(timMe)2}2(pyNO)}2(μ-O)][BPh4]2 (9) was also obtained. In the U(iii) and U(iv) complexes, the bis(azolyl)borate ligands bind to the uranium center in a κ3-H,S,S' coordination mode, while in the U(vi) complex the ligands bind to the metal in a κ2-S,S' mode. The presence of UH-B interactions in the solid-state, for the nine-coordinate complexes 1, 2, 3, 6 and 7 and for the eight-coordinate complex 9, was supported by IR spectroscopy and/or X-ray diffraction analysis.

U{sub x}Th{sub 1-x}(C{sub 2}O{sub 4}){sub 2} solide characterisation studies

Energy Technology Data Exchange (ETDEWEB)

Carrigan, C.; Taylor, R.; Sarsfield, M. [National Nuclear Laboratory, Sellafield, Seascale, Cumbria, CA20 1PG (United Kingdom)

2016-07-01

Many advanced reprocessing schemes under development are aimed at co-processing and co-conversion of actinides, unlike current reprocessing plants that produce separate uranium and plutonium products. The most well developed option for the co-conversion stage is probably oxalate co-precipitation, followed by the thermal co-conversion to a mixed oxide product. It is thus envisaged that future processes will avoid separation of plutonium from uranium and instead allow part of the uranium to flow with the plutonium, resulting in co-precipitation as the oxalate, and finally co-conversion to a mixed uranium-plutonium oxide (MOX), which can be fabricated into recycled nuclear fuel for further energy generation. The co-crystallisation of uranium (IV) and plutonium (III) into a single oxalate structure ensures the homogenous distribution of the 2 actinides at the molecular scale. The joint conversion of uranium and plutonium to the oxide form makes it possible to remove the complicated step of blending and grinding the 2 distinct oxide powders, as currently employed for the purposes of MOX fuel fabrication. This concept can also be extended to other actinides, including minor actinides from partitioning processes such as SANEX (Selective Actinide Extraction) and GANEX (Grouped Actinide Extraction) processes or even a thorium containing product from recycle of thorium based fuels. A selection of U{sub x}Th{sub 1-x}(C{sub 2}O{sub 4}){sub 2} solids at varying concentrations of uranium and thorium were prepared by oxalate co-precipitation. Uranium (VI) was conditioned electrochemically at -0.7 V to uranium (IV), in the presence of hydrazine. The reduced uranium (IV) in nitric acid was mixed with thorium nitrate solutions at different concentration ratios with oxalic acid. The mixed tetravalent uranium-thorium oxalate solid products have been characterised by Raman and IR spectroscopies. The influence of thorium substituted into the uranium oxalate structure was evaluated

U_xTh_1_-_x(C_2O_4)_2 solide characterisation studies

International Nuclear Information System (INIS)

Carrigan, C.; Taylor, R.; Sarsfield, M.

2016-01-01

Many advanced reprocessing schemes under development are aimed at co-processing and co-conversion of actinides, unlike current reprocessing plants that produce separate uranium and plutonium products. The most well developed option for the co-conversion stage is probably oxalate co-precipitation, followed by the thermal co-conversion to a mixed oxide product. It is thus envisaged that future processes will avoid separation of plutonium from uranium and instead allow part of the uranium to flow with the plutonium, resulting in co-precipitation as the oxalate, and finally co-conversion to a mixed uranium-plutonium oxide (MOX), which can be fabricated into recycled nuclear fuel for further energy generation. The co-crystallisation of uranium (IV) and plutonium (III) into a single oxalate structure ensures the homogenous distribution of the 2 actinides at the molecular scale. The joint conversion of uranium and plutonium to the oxide form makes it possible to remove the complicated step of blending and grinding the 2 distinct oxide powders, as currently employed for the purposes of MOX fuel fabrication. This concept can also be extended to other actinides, including minor actinides from partitioning processes such as SANEX (Selective Actinide Extraction) and GANEX (Grouped Actinide Extraction) processes or even a thorium containing product from recycle of thorium based fuels. A selection of U_xTh_1_-_x(C_2O_4)_2 solids at varying concentrations of uranium and thorium were prepared by oxalate co-precipitation. Uranium (VI) was conditioned electrochemically at -0.7 V to uranium (IV), in the presence of hydrazine. The reduced uranium (IV) in nitric acid was mixed with thorium nitrate solutions at different concentration ratios with oxalic acid. The mixed tetravalent uranium-thorium oxalate solid products have been characterised by Raman and IR spectroscopies. The influence of thorium substituted into the uranium oxalate structure was evaluated. Several vibrational modes

Effect of mineral constituents in the bioleaching of uranium from uraniferous sedimentary rock samples, Southwestern Sinai, Egypt.

Science.gov (United States)

Amin, Maisa M; Elaassy, Ibrahim E; El-Feky, Mohamed G; Sallam, Abdel Sattar M; Talaat, Mona S; Kawady, Nilly A

2014-08-01

Bioleaching, like Biotechnology uses microorganisms to extract metals from their ore materials, whereas microbial activity has an appreciable effect on the dissolution of toxic metals and radionuclides. Bioleaching of uranium was carried out with isolated fungi from uraniferous sedimentary rocks from Southwestern Sinai, Egypt. Eight fungal species were isolated from different grades of uraniferous samples. The bio-dissolution experiments showed that Aspergillus niger and Aspergillus terreus exhibited the highest leaching efficiencies of uranium from the studied samples. Through monitoring the bio-dissolution process, the uranium grade and mineralogic constituents of the ore material proved to play an important role in the bioleaching process. The tested samples asserted that the optimum conditions of uranium leaching are: 7 days incubation time, 3% pulp density, 30 °C incubation temperature and pH 3. Both fungi produced the organic acids, namely; oxalic, acetic, citric, formic, malonic, galic and ascorbic in the culture filtrate, indicating an important role in the bioleaching processes. Copyright © 2014 Elsevier Ltd. All rights reserved.

Effect of pH and uranium concentration on interaction of uranium(VI) and uranium(IV) with organic ligands in aqueous solutions

International Nuclear Information System (INIS)

Li, W.C.; Victor, D.M.; Chakrabarti, C.L.

1980-01-01

The effect of pH and uranium concentration on the interactions of uranium(VI) and uranium(IV) with organic ligands was studied by employing dialysis and ultrafiltration techniques. The interactions of U(VI) and U(IV) with organic ligands in nitrate or chloride aqueous solution have been found to be pH-dependent. The stability constants of uranium-organic complexes decrease in the order: fulvic acid>humic acid>tannic acid for U(VI) and humic acid>tannic acid>fulvic acid for U(IV). Scatchard plots for the uranium-organic acid systems indicate two types of binding sites with a difference in stability constants of about 10 2 . Ultrafiltration of uranium-humic acid complexes indicates that U(VI) and U(IV) ions are concentrated in larger molecular size fractions (>5.1 nm) at pH less than or equal to 3 and in smaller molecular size fractions (in the range 5.1 to 3.1 nm and 2.4 to 1.9 nm) at pH greater than or equal to 5. 7 figures, 4 tables

Aspects of calcium oxalate crystallization: theory, in vitro studies, and in vivo implementation.

Science.gov (United States)

Rodgers, A

1999-11-01

There are three main approaches to urolithiasis research: theory, basic science, and clinical implementation. Although each approach has yielded meaningful results, there does not appear to be complete synergy between them. This article examines these approaches as they pertain to urinary calcium oxalate crystallization processes. Theoretical calculations were performed to examine the role of oxalate concentration on calcium oxalate supersaturation. The effects of magnesium, citrate, and combinations thereof on calcium oxalate crystallization kinetics were examined in a mixed suspension, mixed product removal crystallizer. Finally, male volunteers were given supplements of calcium alone and binary combinations of calcium, magnesium, and citrate to investigate their effects on the urinary supersaturation of calcium oxalate. Calculations showed that oxalate is 23 times more potent than calcium in its effect on the supersaturation of calcium oxalate. In the in vitro experiments, magnesium and citrate reduced the growth and nucleation kinetics as well as the supersaturation. In combination, these two components were more effective than the individual components in reducing the growth rate and the supersaturation. All of the supplements favorably altered the kinetic and thermodynamic risk factors. Calcium was the most effective in reducing the urinary excretion of oxalate. Articulation of these three approaches is essential for the meaningful investigation and understanding of urolithiasis.

Preparation of High-purity Indium Oxalate Salt from Indium Scrap by Organic Acids

International Nuclear Information System (INIS)

Koo, Su-Jin; Ju, Chang-Sik

2013-01-01

Effect of organic acid on the preparation of indium-oxalate salt from indium scraps generated from ITO glass manufacturing process was studied. Effects of parameters, such as type and concentration of organic acids, pH of reactant, temperature, reaction time on indium-oxalate salt preparation were examined. The impurity removal efficiency was similar for both oxalic acid and citric acid, but citric acid did not make organic acid salt with indium. The optimum conditions were 1.5 M oxalic acid, pH 7, 80 .deg. C, and 6 hours. On the other hand, the recoveries increased with pH, but the purity decreased. The indium-oxalate salt purity prepared by two cycles was 99.995% (4N5). The indium-oxalate salt could be converted to indium oxide and indium metal by substitution reaction and calcination

Directed synthesis of crystalline plutonium (III) and (IV) oxalates: accessing redox-controlled separations in acidic solutions

International Nuclear Information System (INIS)

Runde, Wolfgang; Brodnax, Lia F.; Goff, George S.; Bean, Amanda C.; Scott, Brian L.

2009-01-01

Both binary and ternary solid complexes of Pu(III) and Pu(IV) oxalates have been previously reported in the literature. However, uncertainties regarding the coordination chemistry and the extent of hydration of some compounds remain mainly because of the absence of any crystallographic characterization. Single crystals of hydrated oxalates of Pu(III), Pu 2 (C 2 O 4 ) 3 (H 2 O) 6 ·3H 2 O (I) and Pu(IV), KPu(C 2 O 4 ) 2 (OH)·2.5H 2 O (II), were synthesized under moderate hydrothermal conditions and characterized by single crystal X-ray diffraction studies. Compounds I and II are the first plutonium(III) or (IV) oxalate compounds to be structurally characterized via single crystal X-ray diffraction studies. Crystallographic data for I: monoclinic, space group P21/c, a = 11.246(3) A, b = 9.610(3) A, c = 10.315(3) A, Z = 4 and II: monoclinic, space group C2/c, a = 23.234(14) A, b = 7.502(4) A, c = 13.029(7) A, Z = 8.

Extraction of uranium and lead from mixed waste debris using a variety of metal/ligand complexes

International Nuclear Information System (INIS)

Needham, D.A.; Duran, B.L.; Ehler, D.S.; Sauer, N.N.

1997-01-01

To ensure the safety of our Nation's nuclear stockpile, Los Alamos National Laboratory is in the process of constructing the DARHT (Dual Axis Radiographic Hydrodynamic Test) facility. DARHT will examine the effects of aging and the stability of our stockpile. Contained testing will be phased in to reduce the impact of these tests, which contain depleted uranium, on our environment. The main focus of this research is to develop a treatment scheme for the recovery of depleted uranium and lead from shot debris that will result from these tests. The goals of this research are to optimize the conditions on a bench scale using a commercially available water soluble polymer to bind the lead and a variety of metal/ligand complexes such as 4,5-dihydroxy-1,3-benzene-disulfonic acid, dithionite, sodium carbonate/bicarbonate, and sodium hypochlorite to bind the uranium. Studies were conducted on a mixture of debris, such as wood, cable, paper towels, and tubing that contained both uranium and lead ranging in concentration from 10-1000's of ppm of contaminants. Experiments were done varying combinations and successions of extractant solutions as well as a number of sequential extractions. Studies show that a mixture of sodium hypochlorite and carbonate removed 90+% of both uranium and lead. We then focused on a separation scheme for the lead and uranium

Uranium leaching analysis (IAEA method) and total uranium determination in caldasite by the fluorometric method

International Nuclear Information System (INIS)

Sardela, I.A.; Fujimori, K.

1980-10-01

Caldasite is a radioactive mineral known mostly for its high radioactive content (U and Th). It is found only at the Pocos de Caldas Alkaline Complex, States of Minas Gerais. Samples colected at Campos do Serrote, Taquari and Brigrada located in the alkaline complex were submitted to the fluorometric method of uranium analysis. The results show a good precision and close agreement with those obtained with gamma ray spectroscopy. IAEA uranium leaching analysis has also been applied to this mineral, but only 0,4% of the total content was dissolved. The uranium leaching was more intense on the samples that have smaller equivalent uranium than total uranium and it may be attributed to a higher range Rn gas escape from this mineral. (Author) [pt

Wu-Ling-San formula prophylaxis against recurrent calcium oxalate ...

African Journals Online (AJOL)

Wu-Ling-San (WLS) formula has been proved to prevent calcium oxalate nephrolithiasis both in vitro and in vivo. This is the first prospective, randomized and placebo-controlled clinical trial of WLS in calcium oxalate nephrolithiasis prevention. All patients who enrolled were asked to drink enough fluid to urinate at least 2 L ...

Complexes carbéniques nucléophiles de l'uranium

OpenAIRE

Tourneux , Jean-Christophe

2012-01-01

The only stable f-metal carbene complexes (excluding NHC) metals f present R2C(2-) groups having one or two phosphorus atoms in the central carbon in alpha position. The objective of this work was to develop the chemistry of carbenes for uranium (metal 5f) with the dianion C{Ph2P(=S)}2(2-) (SCS(2-)) to extend the organometallic chemistry of this element in its various oxidation states (+3-6), and to reveal the influence of the 5f orbitals on the nature and reactivity of the double bond C=U.We...

Synthesis of unsymmetrical dimethylhydrazine oxalate from rejected liquid rocket propellant

Science.gov (United States)

Mu, Xiaogang; Yang, Jingjing; Zhang, Youzhi

2018-02-01

The rejected liquid propellant unsymmetrical dimethylhydrazine (UDMH) was converted to UDMH oxalate, which has commercial value. The UDMH oxalate structure and stability were investigated by the Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, differential scanning calorimetry, and ultraviolet-visible spectrophotometric analysis. The results indicate that UDMH oxalate has good thermal and aqueous solution stability, a melting point of 144 °C, an initial decomposition temperature of 180 °C, and a peak wavelength of UV in aqueous solution at λ = 204 nm. This disposal method of rejected UDMH is highly efficient and environmentally safe.

A coupled mass transfer and surface complexation model for uranium (VI) removal from wastewaters

International Nuclear Information System (INIS)

Lenhart, J.; Figueroa, L.A.; Honeyman, B.D.

1994-01-01

A remediation technique has been developed for removing uranium (VI) from complex contaminated groundwater using flake chitin as a biosorbent in batch and continuous flow configurations. With this system, U(VI) removal efficiency can be predicted using a model that integrates surface complexation models, mass transport limitations and sorption kinetics. This integration allows the reactor model to predict removal efficiencies for complex groundwaters with variable U(VI) concentrations and other constituents. The system has been validated using laboratory-derived kinetic data in batch and CSTR systems to verify the model predictions of U(VI) uptake from simulated contaminated groundwater

Investigation and analytical application of thorium and uranium complexes with amino acids

International Nuclear Information System (INIS)

Korenman, I.M.; Sergeev, G.M.

1979-01-01

The coordination is investigated of thorium (4) and uranium (6) with aminoacids, particularly, with aspartic acid. With the latter the metals form chelates, which have a particular structure and a stationary inner sphere. A description is made of the composition, conditions of formation (gr H), and a stability of some asparaginate complexes of actinoids, the coordination methods of aspartic acid. An asparaginatometric method is proposed for a direct complexometric titration of microgram amounts of thorium in the presence of uranium, zirconium and rare earth elements with photometric indication. As metal-chromic indicators the sulfophthaleins are applied. The given procedure allows measurement of impurities of accompanying elements, viz., beryllium (up to 1%) in thorium preparations. Application of aspartic acid and arsenazo 1 indicator permits us to define Be(2) with a relative error not higher than 5% in thorium compounds, which exclude the analysis by other methods

Oxalate Encapsulation in Aqueous Medium by Tripodal Urea ...

Indian Academy of Sciences (India)

1H-NMR titration studies: All 1H-NMR titration experiments for L1 and L2 were conducted on a Bruker 300 MHz spectrometer at 298 K respectively. Potassium oxalate dihydrate (K2C2O4.2H2O) was used to prepare the stock solution of anion in DMSO-d6:D2O (1:1.1) solvent system. Lower solubility of potassium oxalate in ...

Plasma biochemistry and urinalysis variables of koalas (Phascolarctos cinereus) with and without oxalate nephrosis.

Science.gov (United States)

Speight, K Natasha; Haynes, Julie I; Boardman, Wayne; Breed, William G; Taggart, David A; Rich, Brian; Woolford, Lucy

2014-06-01

Oxalate nephrosis is a highly prevalent disease in the Mount Lofty Ranges koala population in South Australia, but associated clinicopathologic findings remain undescribed. The aims of this study were to determine plasma biochemical and urinalysis variables, particularly for renal function and urinary crystal morphology and composition, in koalas with oxalate nephrosis. Blood and urine samples from Mount Lofty Ranges koalas with oxalate nephrosis were compared with those unaffected by renal oxalate crystal deposition from Mount Lofty and Kangaroo Island, South Australia and Moggill, Queensland. Plasma and urine biochemistry variables were analyzed using a Cobas Bio analyzer, and urinary oxalate by high-performance liquid chromatography. Urinary crystal composition was determined by infrared spectroscopy and energy dispersive X-ray analysis. Azotemia (urea > 6.6 mmol/L, creatinine > 150 μmol/L) was found in 93% of koalas with oxalate nephrosis (n = 15). All azotemic animals had renal insufficiency (urine specific gravity [USG] < 1.035), and in 83%, USG was < 1.030. Koalas with oxalate nephrosis were hyperoxaluric compared with Queensland koalas (P < .01). Urinary crystals from koalas with oxalate nephrosis had atypical morphology and were composed of calcium oxalate. Mount Lofty Ranges koalas unaffected by renal oxalate crystal deposition had renal insufficiency (43%), although only 14% had USG < 1.030 (n = 7). Unaffected Mount Lofty Ranges and Kangaroo Island koalas were hyperoxaluric compared with Queensland koalas (P < .01). Koalas with oxalate nephrosis from the Mount Lofty Ranges had renal insufficiency, hyperoxaluria, and pathognomonic urinary crystals. The findings of this study will aid veterinary diagnosis of this disease. © 2014 American Society for Veterinary Clinical Pathology and European Society for Veterinary Clinical Pathology.

Sorption of uranium (VI) on homoionic sodium smectite experimental study and surface complexation modeling.

Science.gov (United States)

Korichi, Smain; Bensmaili, Aicha

2009-09-30

This paper is an extension of a previous paper where the natural and purified clay in the homoionic Na form were physico-chemically characterized (doi:10.1016/j.clay.2008.04.014). In this study, the adsorption behavior of U (VI) on a purified Na-smectite suspension is studied using batch adsorption experiments and surface complexation modeling (double layer model). The sorption of uranium was investigated as a function of pH, uranium concentration, solid to liquid ratio, effect of natural organic matter (NOM) and NaNO(3) background electrolyte concentration. Using the MINTEQA2 program, the speciation of uranium was calculated as a function of pH and uranium concentration. Model predicted U (VI) aqueous speciation suggests that important aqueous species in the [U (VI)]=1mg/L and pH range 3-7 including UO(2)(2+), UO(2)OH(+), and (UO(2))(3)(OH)(5)(+). The concentration of UO(2)(2+) decreased and that of (UO(2))(3)(OH)(5)(+) increased with increasing pH. The potentiometric titration values and uptake of uranium in the sodium smectite suspension were simulated by FITEQL 4.0 program using a two sites model, which is composed of silicate and aluminum reaction sites. We compare the acidity constants values obtained by potentiometric titration from the purified sodium smectite with those obtained from single oxides (quartz and alpha-alumina), taking into account the surface heterogeneity and the complex nature of natural colloids. We investigate the uranium sorption onto purified Na-smectite assuming low, intermediate and high edge site surfaces which are estimated from specific surface area percentage. The sorption data is interpreted and modeled as a function of edge site surfaces. A relationship between uranium sorption and total site concentration was confirmed and explained through variation in estimated edge site surface value. The modeling study shows that, the convergence during DLM modeling is related to the best estimation of the edge site surface from the N(2

NDA technique for the assay of wet plutonium oxalate

International Nuclear Information System (INIS)

Marshall, R.S.; Canada, T.R.

1980-01-01

A method has been developed to quantitatively measure batches of wet plutonium oxalate. The method is based on a count of coincidence neutrons to which a correction is applied for the effects of neutron moderation by water. A therma-neutron coincidence counter (TNC) with two concentric rings of 3 He detectors provides the signal needed for the water correction. The signal is the ratio of neutron counts between the detector rings that changes with the percent of water in plutonium oxalate. To evaluate the measurement technique, 26 batches of plutonium oxalate were measured in an in-line TNC. The evaluation showed the measurements to be essentially unbiased and precise to 2.2%

Exploration of Bernabe Montano complex of uranium deposits, New Mexico, USA

International Nuclear Information System (INIS)

Porter, D.A.

1981-01-01

The Bernabe Montano discovery is a significant eastern extension of the Grants Mineral Belt, consisting of two nearly parallel mineralized trends with a combined strike length of about 14.5 km. One deposit with approximately 10 6 lb of uranium oxide has been blocked out and several km of mineralized trend require additional delineation drilling. The mineralization exhibits many similarities to Westwater Canyon Member ore deposits in other parts of the Grants Mineral Belt; one of the most significant is the continuation of the south-easterly trend that has persisted, with some breaks, for a length of over 175 km. As with other Grants Mineral Belt deposits, the mineralization is associated with multilevel humate masses that are roughly parallel to the bedding of the Westwater Canyon Member host sandstone beds. These humate masses and the associated uranium deposits show a marked preference for the margins of the thicker, more laterally continuous, channelways. The discovery of the Bernabe Montano complex of deposits is significant for several reasons. First, it opened up exploration in the distal fan facies where many geologists thought the uranium potential was relatively low. The discovery is potentially more significant in that it demonstrates the ability of detailed subsurface geologic mapping to suggest the location of high potential geologic trends in partially explored but favourable regions where the more traditional surface geologic and radiometric techniques are no longer effective in finding new deposits. (author)

Interaction Studies of Dilute Aqueous Oxalic Acid

Directory of Open Access Journals (Sweden)

Kiran Kandpal

2007-01-01

Full Text Available Molecular conductance λm, relative viscosity and density of oxalicacid at different concentration in dilute aqueous solution were measured at 293 K.The conductance data were used to calculate the value association constant.Viscosity and density data were used to calculate the A and B coefficient ofJone-Dole equation and apparent molar volume respectively. The viscosityresults were utilized for the applicability of Modified Jone-Dole equation andStaurdinger equations. Mono oxalate anion acts, as structure maker and thesolute-solvent interaction were present in the dilute aqueous oxalic acid.

Cation-mediated conversion of the state of charge in uranium arene inverted-sandwich complexes

Energy Technology Data Exchange (ETDEWEB)

Camp, Clement; Mougel, Victor; Pecaut, Jacques; Mazzanti, Marinella [Laboratoire de Reconnaissance Ionique et Chimie de Coordination, SCIB, UMR-E3 CEA-UJF, INAC, CEA-Grenoble (France); Maron, Laurent [LCPNO, CNRS and INSA, UPS, Universite de Toulouse (France)

2013-12-16

Two new arene inverted-sandwich complexes of uranium supported by siloxide ancillary ligands [K{U(OSi(OtBu)_3)_3}{sub 2}(μ-η{sup 6}:η{sup 6}-C{sub 7}H{sub 8})] (3) and [K{sub 2}{U(OSi(OtBu)_3)_3}{sub 2}(μ-η{sup 6}:η{sup 6}-C{sub 7}H{sub 8})] (4) were synthesized by the reduction of the parent arene-bridged complex [{U(OSi(OtBu)_3)_3}{sub 2}(μ-η{sup 6}:η{sup 6}-C{sub 7}H{sub 8})] (2) with stoichiometric amounts of KC{sub 8} yielding a rare family of inverted-sandwich complexes in three states of charge. The structural data and computational studies of the electronic structure are in agreement with the presence of high-valent uranium centers bridged by a reduced tetra-anionic toluene with the best formulation being U{sup V}-(arene{sup 4-})-U{sup V}, KU{sup IV}-(arene{sup 4-})-U{sup V}, and K{sub 2}U{sup IV}-(arene{sup 4-})-U{sup IV} for complexes 2, 3, and 4 respectively. The potassium cations in complexes 3 and 4 are coordinated to the siloxide ligands both in the solid state and in solution. The addition of KOTf (OTf=triflate) to the neutral compound 2 promotes its disproportionation to yield complexes 3 and 4 (depending on the stoichiometry) and the U{sup IV} mononuclear complex [U(OSi(OtBu){sub 3}){sub 3}(OTf)(thf){sub 2}] (5). This unprecedented reactivity demonstrates the key role of potassium for the stability of these complexes. (Copyright copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Estimation of rare earth elements in uranium matrix after solvent extraction of uranium as uranium-antipyrine-anion complex using chloroform as solvent

International Nuclear Information System (INIS)

Bose, Roopa; Murthy, D.S.R.; Malhotra, R.K.

1999-01-01

The neutron economy in a nuclear reactor dictates the occurrence of neutron absorbers at very low levels. Hence the determination of lanthanides especially Sm, Eu, Gd and Dy is one of the most difficult and complicated analytical tasks particularly in high uranium matrix. Solvent extraction is a potent and versatile technique for the separation of lanthanides. The systems generally used for lanthanide extraction are TBP-nitrate, TBP-chloride, TBP-thiocyanate TOPO, DEHPA-nitrate etc. However, these methods of extraction of lanthanides fail to give a clear cut separation for their determination from uranium matrix. Hence analytical procedures have been standardised for extraction of uranium matrix into the organic phase leaving lanthanides unextracted in the aqueous phase. In this direction Cyanex-923 a mixture of 4 trialkyl phosphine oxides, TBP- TOPO and trioctylamine in xylene have been used for extraction of uranium and consequent determination of lanthanides by ICP-AES in the aqueous phase. In this paper the authors have investigated uranium -antipyrine -anion, a different combination other than the well known phosphine oxides and tertiary amines for extraction of uranium

Dynamic process model of a plutonium oxalate precipitator. Final report

Energy Technology Data Exchange (ETDEWEB)

Miller, C.L.; Hammelman, J.E.; Borgonovi, G.M.

1977-11-01

In support of LLL material safeguards program, a dynamic process model was developed which simulates the performance of a plutonium (IV) oxalate precipitator. The plutonium oxalate precipitator is a component in the plutonium oxalate process for making plutonium oxide powder from plutonium nitrate. The model is based on state-of-the-art crystallization descriptive equations, the parameters of which are quantified through the use of batch experimental data. The dynamic model predicts performance very similar to general Hanford oxalate process experience. The utilization of such a process model in an actual plant operation could promote both process control and material safeguards control by serving as a baseline predictor which could give early warning of process upsets or material diversion. The model has been incorporated into a FORTRAN computer program and is also compatible with the DYNSYS 2 computer code which is being used at LLL for process modeling efforts.

Dynamic process model of a plutonium oxalate precipitator. Final report

International Nuclear Information System (INIS)

Miller, C.L.; Hammelman, J.E.; Borgonovi, G.M.

1977-11-01

In support of LLL material safeguards program, a dynamic process model was developed which simulates the performance of a plutonium (IV) oxalate precipitator. The plutonium oxalate precipitator is a component in the plutonium oxalate process for making plutonium oxide powder from plutonium nitrate. The model is based on state-of-the-art crystallization descriptive equations, the parameters of which are quantified through the use of batch experimental data. The dynamic model predicts performance very similar to general Hanford oxalate process experience. The utilization of such a process model in an actual plant operation could promote both process control and material safeguards control by serving as a baseline predictor which could give early warning of process upsets or material diversion. The model has been incorporated into a FORTRAN computer program and is also compatible with the DYNSYS 2 computer code which is being used at LLL for process modeling efforts

Characterization of oxalate-based 237NpO2 powder

International Nuclear Information System (INIS)

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

1976-01-01

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

Redox reactivity and coordination chemistry of uranium

International Nuclear Information System (INIS)

Nocton, G.

2009-09-01

The study and the understanding of actinides chemistry have important implications in the nuclear field both for the development of new actinides materials and the retreatment of the nuclear wastes. One of the major issues in that chemistry is that the actinides elements are known to undergo redox reaction and to form assemblies of different size and different topologies. In that context uranium can be a good model of the heavier radioelement because it is much less radioactive. So, this work concerns the synthesis and the study of the spectroscopy and the magnetic properties of several uranium based polymetallic assemblies synthesized by taking advantage of the redox properties and the coordination chemistry of uranium. The hydrolysis reactivity of trivalent uranium has been studied in absence of sterically hindered ligands and led to the synthesis of oxo/hydroxo uranium assemblies with different sizes by changing the starting complex or the reaction conditions. By following the same strategy, the controlled oxidation of trivalent uranium complexes led to an original azido/nitrido uranium complex. The coordination chemistry of the pentavalent uranyl polymer {[UO 2 py 5 ][KI 2 py 3 ]} n has also been studied with different ligand and in different conditions and led to several cation-cation complexes for which the stability is sufficient for studying there dismutation by proton NMR. By changing the ancillary ligands stable monomeric complexes of pentavalent uranyl complexes were also obtained. The magnetic properties of all the complexes, monomers and polymetallic complexes were studied and an antiferromagnetic coupling was observed for the cation-cation pentavalent uranyl dimer [UO 2 (dbm) 2 (K 18 C 6 )] 2 . (author)

Uranium speciation in plants

International Nuclear Information System (INIS)

Guenther, A.; Bernhard, G.; Geipel, G.; Reich, T.; Rossberg, A.; Nitsche, H.

2003-01-01

Detailed knowledge of the nature of uranium complexes formed after the uptake by plants is an essential prerequisite to describe the migration behavior of uranium in the environment. This study focuses on the determination of uranium speciation after uptake of uranium by lupine plants. For the first time, time-resolved laser-induced fluorescence spectroscopy and X-ray absorption spectroscopy were used to determine the chemical speciation of uranium in plants. Differences were detected between the uranium speciation in the initial solution (hydroponic solution and pore water of soil) and inside the lupine plants. The oxidation state of uranium did not change and remained hexavalent after it was taken up by the lupine plants. The chemical speciation of uranium was identical in the roots, shoot axis, and leaves and was independent of the uranium speciation in the uptake solution. The results indicate that the uranium is predominantly bound as uranyl(VI) phosphate to the phosphoryl groups. Dandelions and lamb's lettuce showed uranium speciation identical to lupine plants. (orig.)

Mixed complexes of uranium(IV) and thorium(IV) with N,N'-ethylenebis(salicylideneimine) and N,N'-propylenebis(salicylideneimine)

Energy Technology Data Exchange (ETDEWEB)

Doretti, L; Madalosso, F; Sitran, S; Faleschini, S [Consiglio Nazionale delle Ricerche, Padua (Italy). Lab. di Chimica e Tecnologia dei Radioelementi

1976-01-01

Recently some uranium tetrachloride adducts with N-(hydroxyphenyl)-salicylaldimine and N-(methoxyphenyl)salicylaldimine have been prepared (Doretti et al., J. Inorg. Nucl. Chem., (in press)): the study has now extended to the complexes of Uranium(IV) and Thorium(IV) with N,N'-Ethylenebis(salicylideneimine), H/sub 2/salen, and N,N'-Propylenebis(salicylideneimine), H/sub 2/salpropen, with the aim to prepare fully substituted complexes, mixed complexes containing both chloride and Schiff base groups and adducts of tetrachlorides with free Schiff bases. This paper reports the preparation and properties of the compounds MCl/sub 4/(H/sub 2/salen), MCl/sub 4/(H/sub 2/salpropen), M(salen)Cl/sub 2/, M(salen)/sub 2/ and M(salpropen)/sub 2/, where M = U or Th. These compounds have been characterized by elemental analyses and their IR spectra are reported and discussed.

Ultrastructural and biochemical studies on formation of calcium oxalate in plants

International Nuclear Information System (INIS)

Abdelmottaleb, A.M.

1989-01-01

Plant calcium oxalate crystals occur within cells called crystal idioblasts. Important aspects of this calcification phenomenon have not been characterized. This dissertation examines some of the aspects of this ubiquitous type of calcification including (1) characterization of ultrastructural features of developing crystal idioblasts, (2) determination of the relationship of specialized ultrastructural features of the idioblasts to transport of compounds and mechanisms of crystal deposition, and (3) the biochemical relationship between ascorbic acid metabolism and production of oxalic acid used for crystal formation. Structural and cytochemical studies revealed that crystal idioblasts have dense cytoplasm, modified plastids, enlarged nuclei, extensive endoplasmic reticulum, numerous dictyosomes and vesicles, and a bundle of raphide crystals in their vacuoles. A mechanism for Ca transport and crystal precipitation is proposed, based on these results. There is a strong and dynamic relationship between Ca concentration and oxalic acid produced for crystal formation, where increasing Ca level in the growth medium lead to increased total and insoluble oxalate in the plant. Calmodulin antagonists reduced oxalic acid production

Corrosion and impedance studies on magnesium alloy in oxalate solution

International Nuclear Information System (INIS)

Fekry, A.M.; Tammam, Riham H.

2011-01-01

Highlights: → Corrosion behavior of AZ91E alloy was investigated in 0.1 M Na 2 C 2 O 4 containing different additives as Br - , Cl - or Silicate. → The corrosion rate of 0.1 M oxalate solution containing silicate ion is lower than the blank (0.1 M Na 2 C 2 O 4 ). This was confirmed by scanning electron microscope (SEM) observations. → For the other added ions Br - or Cl - , the corrosion rate is higher than the blank. - Abstract: Corrosion behavior of AZ91E alloy was investigated in oxalate solution using potentiodynamic polarization and electrochemical impedance measurements (EIS). The effect of oxalate concentration was studied, where the corrosion rate increases with increasing oxalate concentration. The effect of added ions (Br - , Cl - or SiO 3 2- ) on the electrochemical behavior of magnesium alloy in 0.1 M Na 2 C 2 O 4 solution at 298 K, was investigated. It was found that the corrosion rate of 0.1 M oxalate solution containing silicate ion is lower than the blank (0.1 M Na 2 C 2 O 4 ). This was confirmed by scanning electron microscope (SEM) observations. However, for the other added ions Br - or Cl - , the corrosion rate is higher than the blank.

Uranium

International Nuclear Information System (INIS)

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

2010-01-01

concentration in peat bogs, deposits combined with marine phosphates, with coal and lignite, with black shales, with carbonate rocks, deposits in Precambrian quartz pebble conglomerates, basal-type deposits, deposits in sandstones (tabular, roll-type and tectono-lithologic deposits), breccia chimney filling deposits, deposits in metamorphic rocks, metasomatic deposits, deposits in intrusive rocks, deposits associated with hematite breccia complexes, deposits in granitic rocks, deposits in volcanic rocks, deposits in proterozoic discordances (Athabasca basin, Pine Creek geo-syncline); 4 - French uranium bearing areas and deposits: history of the French uranium mining industry, geological characteristics of French deposits (black shales, sandstones, granites), abroad success of French mining companies (Africa, North America, South America, Australia, Asia); 5 - exploration and exploitation; 6 - uranium economy: perspectives of uranium demand, present day production status, secondary resources, possible resources, market balances, prices and trends, future availability and nuclear perspectives. (J.S.)

Studies on removal of plutonium from oxalic acid containing hydrochloric acid solutions

Energy Technology Data Exchange (ETDEWEB)

Ghadse, D R; Noronha, D M; Joshi, A R [Fuel Chemistry Division, Bhabha Atomic Research Centre, Mumbai (India)

1994-06-01

Solution containing hydrochloric acid, oxalic acid and considerable quantities of plutonium may be generated while recycling of scrap produced during the metallic fuel fabrication. Plutonium from such waste is normally recovered by anion exchange method after the destruction of oxalic acid using suitable oxidising agent. Solvent extraction and ion exchange methods are being explored in this laboratory for recovery of Pu from oxalic acid containing HCl solutions without prior destruction of oxalic acid. This paper describes the results on the determination of distribution ratios for extraction of Pu(IV) from hydrochloric acid using Aliquot-336 or HDEHP under varying experimental conditions. (author). 5 refs., 5 tabs.

Influence of nutrition on feline calcium oxalate urolithiasis with emphasis on endogenous oxalate synthesis

NARCIS (Netherlands)

Dijcker, J.C.; Plantinga, E.A.; Baal, van J.; Hendriks, W.H.

2011-01-01

The prevalence of calcium oxalate (CaOx) uroliths detected in cats with lower urinary tract disease has shown a sharp increase over the last decades with a concomitant reciprocal decrease in the occurrence of struvite (magnesium ammonium phosphate) uroliths. CaOx stone-preventative diets are

Turning sunlight into stone: the oxalate-carbonate pathway in a tropical tree ecosystem

Directory of Open Access Journals (Sweden)

G. Cailleau

2011-07-01

Full Text Available An African oxalogenic tree, the iroko tree (Milicia excelsa, has the property to enhance carbonate precipitation in tropical oxisols, where such accumulations are not expected due to the acidic conditions in these types of soils. This uncommon process is linked to the oxalate-carbonate pathway, which increases soil pH through oxalate oxidation. In order to investigate the oxalate-carbonate pathway in the iroko system, fluxes of matter have been identified, described, and evaluated from field to microscopic scales. In the first centimeters of the soil profile, decaying of the organic matter allows the release of whewellite crystals, mainly due to the action of termites and saprophytic fungi. In addition, a concomitant flux of carbonate formed in wood tissues contributes to the carbonate flux and is identified as a direct consequence of wood feeding by termites. Nevertheless, calcite biomineralization of the tree is not a consequence of in situ oxalate consumption, but rather related to the oxalate oxidation inside the upper part of the soil. The consequence of this oxidation is the presence of carbonate ions in the soil solution pumped through the roots, leading to preferential mineralization of the roots and the trunk base. An ideal scenario for the iroko biomineralization and soil carbonate accumulation starts with oxalatization: as the iroko tree grows, the organic matter flux to the soil constitutes the litter, and an oxalate pool is formed on the forest ground. Then, wood rotting agents (mainly termites, saprophytic fungi, and bacteria release significant amounts of oxalate crystals from decaying plant tissues. In addition, some of these agents are themselves producers of oxalate (e.g. fungi. Both processes contribute to a soil pool of "available" oxalate crystals. Oxalate consumption by oxalotrophic bacteria can then start. Carbonate and calcium ions present in the soil solution represent the end products of the oxalate

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.)

Oxalate Mass Balance During Chemical Cleaning in Tank 5F

Energy Technology Data Exchange (ETDEWEB)

Poirier, M.; Fink, S.

2011-07-08

The Savannah River Site (SRS) is preparing Tank 5F for closure. The first step in preparing the tank for closure is mechanical sludge removal. Following mechanical sludge removal, SRS performed chemical cleaning with oxalic acid to remove the sludge heel. Personnel are currently assessing the effectiveness of the chemical cleaning to determine whether the tank is ready for closure. SRS personnel collected liquid samples during chemical cleaning and submitted them to Savannah River National Laboratory (SRNL) for analysis. Following chemical cleaning, they collected a solid sample (also known as 'process sample') and submitted it to SRNL for analysis. The authors analyzed these samples to assess the effectiveness of the chemical cleaning process. Analysis of the anions showed the measured oxalate removed from Tank 5F to be approximately 50% of the amount added in the oxalic acid. To close the oxalate mass balance, the author collected solid samples, leached them with nitric acid, and measured the concentration of cations and anions in the leachate.

Uranium extraction from underground deposits

International Nuclear Information System (INIS)

Wolfe, C.R.

1982-01-01

Uranium is extracted from underground deposits by passing an aqueous oxidizing solution of carbon dioxide over the ore in the presence of calcium ions. Complex uranium carbonate or bicarbonate ions are formed which enter the solution. The solution is forced to the surface and the uranium removed from it

Reversible dihydrogen activation and hydride transfer by a uranium nitride complex

Energy Technology Data Exchange (ETDEWEB)

Falcone, Marta; Poon, Lok Nga; Fadaei Tirani, Farzaneh; Mazzanti, Marinella [Institut des Sciences et Ingenierie Chimiques, Ecole Polytechnique Federale de Lausanne (EPFL), Lausanne (Switzerland)

2018-03-26

Cleavage of dihydrogen is an important step in the industrial and enzymatic transformation of N{sub 2} into ammonia. The reversible cleavage of dihydrogen was achieved under mild conditions (room temperature and 1 atmosphere of H{sub 2}) by the molecular uranium nitride complex, [Cs{U(OSi(O"tBu)_3)_3}{sub 2}(μ-N)], leading to a rare hydride-imide bridged diuranium(IV) complex, [Cs{U(OSi(O"tBu)_3)_3}{sub 2}(μ-H)(μ-NH)], that slowly releases H{sub 2} under vacuum. This complex is highly reactive and quickly transfers hydride to acetonitrile and carbon dioxide at room temperature, affording the ketimide- and formate-bridged U{sup IV} species [Cs{U(OSi(O"tBu)_3)_3}{sub 2}(μ-NH)(μ-CH{sub 3}CHN)] and [Cs{U(OSi(O"tBu)_3)_3}{sub 2}(μ-HCOO)(μ-NHCOO)]. (copyright 2018 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Evaluation of the uranium potential of the Bushveld Complex

International Nuclear Information System (INIS)

Cheney, E.S.

1986-04-01

The poor quality of the airborne radiometric surveys and the lack of exploration geochemical data in the public domain prevent a satisfactory assessment of the uranium potential of the Bushveld area. Undue reliance must be placed upon fitting models of uranium ore deposits to the geology of the Bushveld area. Although the Bushveld granites have an unusually high background of uranium (20 to 40 ppm), they probably only host small vein-type deposits. The vein at the Albert Silver mine should be investigated as a type example to determine if it is only economic in the narrow interval of supergene enrichment. The Rooiberg Group has considerable potential for caldera-related deposits and for uranium-bearing sulphide deposits (including Olympic Dam-type deposits) in sedimentary interbeds. The Loskop Formation appears to be correlative with the Glentig and lower Swaershoek Formations of the Waterberg area. The Waterberg Group is the logical host to investigate for giant uncomformity/vein-type uranium deposits like those in Canada and Australia. Because the Waterberg consists of four uncomformity-bounded sequences, it is rarely more than 3 km thick; all of the sequences could be younger than 1770 Ma

METHOD OF RECOVERING TRANSURANIC ELEMENTS OF AN ATOMIC NUMBER BELOW 95

Science.gov (United States)

Seaborg, G.T.; James, R.A.

1959-12-15

The concentration of neptanium or plutonium by two carrier precipitation steps with identical carriers but using (after dissolution of the first carrier in nitric acid) a reduced quantity of carrier for the second precipitation is discussed. Carriers suitable are uranium(IV) hypophosphate, uranium(IV) pyrophosphate, uranium(IV) oxalate, thorium oxalate, thorium citrate, thorium tartrate, thorium sulfide, and uranium(IV) sulfide.

Solvothermal synthesis of uranium(VI) phases with aromatic carboxylate ligands: A dinuclear complex with 4-hydroxybenzoic acid and a 3D framework with terephthalic acid

Energy Technology Data Exchange (ETDEWEB)

Zhang, Yingjie, E-mail: yzx@ansto.gov.au [Australian Nuclear Science and Technology Organisation, Locked Bag 2001, Kirrawee DC, NSW 2232 (Australia); Karatchevtseva, Inna [Australian Nuclear Science and Technology Organisation, Locked Bag 2001, Kirrawee DC, NSW 2232 (Australia); Bhadbhade, Mohan [Mark Wainwright Analytical Centre, University of New South Wales, Kensington, NSW 2052 (Australia); Tran, Toan Trong; Aharonovich, Igor [School of Physics and Advanced Materials, University of Technology Sydney, Ultimo, NSW 2007 (Australia); Fanna, Daniel J.; Shepherd, Nicholas D. [School of Science and Health, Western Sydney University, Locked Bag 1797, Penrith, NSW 2751 (Australia); Lu, Kim [Australian Nuclear Science and Technology Organisation, Locked Bag 2001, Kirrawee DC, NSW 2232 (Australia); Li, Feng [School of Science and Health, Western Sydney University, Locked Bag 1797, Penrith, NSW 2751 (Australia); Lumpkin, Gregory R. [Australian Nuclear Science and Technology Organisation, Locked Bag 2001, Kirrawee DC, NSW 2232 (Australia)

2016-02-15

With the coordination of dimethylformamide (DMF), two new uranium(VI) complexes with either 4-hydroxybenzoic acid (H{sub 2}phb) or terephthalic acid (H{sub 2}tph) have been synthesized under solvothermal conditions and structurally characterized. [(UO{sub 2}){sub 2}(Hphb){sub 2}(phb)(DMF)(H{sub 2}O){sub 3}]·4H{sub 2}O (1) has a dinuclear structure constructed with both pentagonal and hexagonal bipyramidal uranium polyhedra linked through a µ{sub 2}-bridging ligand via both chelating carboxylate arm and alcohol oxygen bonding, first observation of such a coordination mode of 4-hydroxybenzoate for 5 f ions. [(UO{sub 2})(tph)(DMF)] (2) has a three-dimensional (3D) framework built with pentagonal bipyramidal uranium polyhedra linked with µ{sub 4}-terephthalate ligands. The 3D channeled structure is facilitated by the unique carboxylate bonding with nearly linear C–O–U angles and the coordination of DMF molecules. The presence of phb ligands in different coordination modes, uranyl ions in diverse environments and DMF in complex 1, and tph ligand, DMF and uranyl ion in complex 2 has been confirmed by Raman spectroscopy. In addition, their thermal stability and photoluminescence properties have been investigated. - Graphical abstract: With the coordination of dimethylformamide, two new uranyl complexes with either 4-hydroxybenzoate or terephthalate have been synthesized under solvothermal conditions and structurally characterized. - Highlights: • Solvent facilitates the synthesis of two new uranium(VI) complexes. • A dinuclear complex with both penta- and hexagonal bipyramidal uranium polyhedral. • A unique µ{sub 2}-bridging mode of 4-hydroxybenzoate via alcohol oxygen for 5 f ions. • A 3D framework with uranium polyhedra and µ{sub 4}-terephthalate ligands. • Vibration modes and photoluminescence properties are reported.

Probable functions of calcium oxalate crystals in different tissues of ...

African Journals Online (AJOL)

Representatives of seven major edible aroid accessions were screened for calcium oxalate using standard histochemical methods. All the accessions were noted to contain calcium oxalate in the forms of raphide bundles and intra-amylar crystals. The crystals were widely present in all parts of the plants including spongy ...

(Di­methyl­phosphor­yl)methanaminium hydrogen oxalate–oxalic acid (2/1)

OpenAIRE

Bialek, Sebastian; Clemens, Rebecca; Reiss, Guido J.

2014-01-01

The reaction of (di­methyl­phosphor­yl)methanamine (dpma) with oxalic acid in ethanol yielded the title solvated salt, C3H11NOP+·C2HO4 −·0.5C2H2O4. Its asymmetric unit consists of one dpmaH+ cation, one hydrogen oxalate anion and a half-mol­ecule of oxalic acid located around a twofold rotation axis. The H atom of the hydrogen oxalate anion is statistically disordered over two positions that are trans to each other. The hydrogen oxalate monoanion is not planar (bend angle ∼16°) whereas the ox...

Successful treatment of sodium oxalate induced urolithiasis with Helichrysum flowers.

Science.gov (United States)

Onaran, Metin; Orhan, Nilüfer; Farahvash, Amirali; Ekin, Hasya Nazlı; Kocabıyık, Murat; Gönül, İpek Işık; Şen, İlker; Aslan, Mustafa

2016-06-20

Helichrysum (Asteraceae) flowers, known as "altın otu, yayla çiçeği, kudama çiçeği" , are widely used to remove kidney stones and for their diuretic properties in Turkey. To determine the curative effect of infusions prepared from capitulums of Helichrysum graveolens (M. Bieb.) Sweet (HG) and H. stoechas ssp. barellieri (Ten.) Nyman (HS) on sodium oxalate induced kidney stones. Infusions prepared from the capitulums of HG and HS were tested for their curative effect on calcium oxalate deposition induced by sodium oxalate (70mg/kg i.p.). Following the injection of sodium oxalate for 5 days, plant extracts were administered to rats at two different doses. Potassium citrate was used as positive control. Water intake, urine volume, body, liver and kidney weights were measured; biochemical and hematological analyses were conducted on urine and blood samples. Additionally, histopathological examinations were done on kidney samples. H. stoechas extract showed prominent effect at 156mg/kg dose (stone formation score: 0.33), whereas number of kidney stones was maximum in sodium oxalate group (stone formation score: 2.33). The reduction in the uric acid and oxalate levels of urine samples and the elevation in the urine citrate levels are significant and promising in extract groups. Some hematological, biochemical and enzymatic markers are also ameliorated by the extracts. This is the first report on the curative effect of immortal flowers. Our preliminary study indicated that Helichrysum extracts may be used for treatment of urolithiasis and Helichrysum extracts are an alternative therapy to potassium citrate for patients suffering from kidney stones. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Synthesis and characterization of new oxalate ester-polymer composites for practical applications

Energy Technology Data Exchange (ETDEWEB)

Petre, Razvan [Scientific Research Centre for CBRN Defense and Ecology, 225 Sos. Oltenitei, Bucharest 041309 (Romania); University POLITEHNICA of Bucharest, 149 Calea Victoriei, Bucharest 010072 (Romania); Zecheru, Teodora, E-mail: teodora.zecheru@yahoo.com [Scientific Research Centre for CBRN Defense and Ecology, 225 Sos. Oltenitei, Bucharest 041309 (Romania)

2013-03-15

The present study focused on the synthesis of high purity oxalate esters: bis(2,4,6-trichlorophenyl) oxalate (TCPO) and bis(2,4,5-trichloro-6-carbobutoxyphenyl) oxalate (TCCBPO), and further on their incorporation into potentially applicative polymer composites. The organic compounds were characterized through NMR and the composites obtained were evaluated for light capacity availability at room temperature and low temperatures. The concentrations of the peroxide, fluorescer, catalyst, and polymer additives were optimized. The chemiluminescent composites' performances were evaluated after 360 days and returned satisfactory results. - Highlights: Black-Right-Pointing-Pointer bis(2,4,6-Trichlorophenyl)-oxalate (TCPO) was synthesized. Black-Right-Pointing-Pointer bis(2,4,5-Trichloro-6-carbobutoxiphenyl)-oxalate (TCCBPO) was synthesized. Black-Right-Pointing-Pointer TCPO and TCCBPO-based composites were obtained. Black-Right-Pointing-Pointer The composites light emission was evaluated versus scotopic visual sensitivity. Black-Right-Pointing-Pointer The new compositions present superior performances within extensive emission time.

Enhanced nitrogen availability in karst ecosystems by oxalic acid release in the rhizosphere

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Fujing ePan

2016-05-01

Full Text Available In karst ecosystems, a high level of CaCO3 enhances the stabilization of soil organic matter (SOM and causes nitrogen (N and/or phosphorus (P limitation in plants. Oxalic acid has been suggested to be involved in the nutrient-acquisition strategy of plants because its addition can temporarily relieve nutrient limitation. Therefore, understanding how oxalic acid drives N availability may help support successful vegetation restoration in the karst ecosystems of southwest China. We tested a model suggested by Clarholm et al. (2015 where oxalate reacts with Ca bridges in SOM, thus exposing previously protected areas to enzymatic attacks in a way that releases N for local uptake. We studied the effects of oxalic acid, microbial biomass C (MBC, and β-1,4-N-acetylglucosaminidase (NAG on potential N mineralization rates in rhizosphere soils of four plant species (two shrubs and two trees in karst areas. The results showed that rhizosphere soils of shrubs grown on formerly deforested land had significantly lower oxalic acid concentrations and NAG activity than that of trees in a 200-year-old forest. The levels of MBC in rhizosphere soils of shrubs were significantly lower than those of trees in the growing season, but the measure of shrubs and trees were similar in the non-growing season; the potential N mineralization rates showed a reverse pattern. Positive relationships were found among oxalic acid, MBC, NAG activity, and potential N mineralization rates for both shrubs and trees. This indicated that oxalic acid, microbes, and NAG may enhance N availability for acquisition by plants. Path analysis showed that oxalic acid enhanced potential N mineralization rates indirectly through inducing microbes and NAG activities. We found that the exudation of oxalic acid clearly provides an important mechanism that allows plants to enhance nutrient acquisition in karst ecosystems.

Enhanced Chemical Cleaning: Effectiveness Of The UV Lamp To Decompose Oxalates

International Nuclear Information System (INIS)

Ketusky, E.; Huff, T.; Sudduth, C.

2010-01-01

Enhanced Chemical Cleaning is a new process scheduled to begin cleaning Savannah River Site High Level Waste Tanks in 2012. It is an improvement over the current chemical cleaning method, in that it minimizes downstream impacts on the High Level Waste System. It is based on a state of the art scale removal process used on the secondary side of nuclear power plants, with modifications to accommodate the unique constraints created by the tanks. Both Enhanced Chemical Cleaning and the scale removal process are founded on dissolving metal oxides/hydroxides using oxalic acid, with subsequent oxalate decomposition via hydroxylation using ozone or peroxide, and UV light as a catalyst. A divergence Enhanced Chemical Cleaning has from nuclear power scale removal is the significantly increased solids concentration during oxalate decomposition. These solids can limit the ability of the UV light to create hydroxyl radicals, either by limiting the ability of the light to penetrate through the solution, or by increasing the fouling rate on the UV light. Both will decrease the overall catalytic effectiveness, thereby decreasing the concentration of formed hydroxyl radicals. The hydroxyl radicals are the driving force behind the oxalate decomposition. To understand the impact of increased solids, testing was performed using a medium pressure UV light inside an ozone supplied Oxalate Decomposition Reactor. Using a dissolved metal sludge simulant with an initial oxalate concentration greater than 12,000 ppm, and an initial pH of about 2.0, the spent acid solution was recirculated through the reactor, while the UV light was allowed to foul. For the first few hours, the oxalate decomposition rate was about 1,300 ppm/hour. After about 3 hours, enough time for the UV lamp to foul, the oxalate decomposition rate decreased to about 500 ppm/hour. The decomposition rate then remained roughly constant for the next 16 hours. Overall, testing showed that the oxalate destruction rate decreased

Measurement of plutonium oxalate in thermal neutron coincidence counters

International Nuclear Information System (INIS)

Marshall, R.S.; Erkkila, B.H.

1979-01-01

A coincidence neutron counting method has been developed for assaying batches of plutonium oxalate. Using counting data from two concentric rings of 3 He detectors, corrections are made for the effects that water has on the coincidence neutron count rate. Batches of plutonium oxalate varying from 750 to 1000 g of plutonium and from 34 to 54% water are assayed with an average accuracy of +-3%

Inhibition of crystallization of calcium oxalate by the extraction of Tamarix gallica L.

Science.gov (United States)

Bensatal, Ahmed; Ouahrani, M R

2008-12-01

The main objective is to study the inhibitor effect of acid fraction of the extract of Tamarix gallica L on the crystallization of calcium oxalate. The extract of Tamarix gallica L is very rich by acid compounds that are used as an inhibitor of nephrolithiasis (calcium oxalate). Our study of the calcium oxalate crystallization is based on the model of turbidimetry by means of a spectrophotometer. The calcium oxalate formation is induced by the addition of oxalate solutions of sodium and of calcium chloride. The addition of inhibitor with various concentrations enabled us to give information on the percentage of inhibition. The comparison between the turbidimetric slopes with and without inhibitor gives the effectiveness of inhibitor for the acid fraction. By comparing the photographs of with and without inhibitor, we concluded that the extract of Tamarix gallica L acts at the stage of growth. The acid fraction of the extract of Tamarix gallica L gives an activity remarkable in the formation of urinary lithiasis (calcium oxalate); this effectiveness is due to the presence of functions of acid.

New french uranium mineral species

International Nuclear Information System (INIS)

Branche, G.; Chervet, J.; Guillemin, C.

1952-01-01

In this work, the authors study the french new uranium minerals: parsonsite and renardite, hydrated phosphates of lead and uranium; kasolite: silicate hydrated of uranium and lead uranopilite: sulphate of uranium hydrated; bayleyite: carbonate of uranium and of hydrated magnesium; β uranolite: silicate of uranium and of calcium hydrated. For all these minerals, the authors give the crystallographic, optic characters, and the quantitative chemical analyses. On the other hand, the following species, very rare in the french lodgings, didn't permit to do quantitative analyses. These are: the lanthinite: hydrated uranate oxide; the α uranotile: silicate of uranium and of calcium hydrated; the bassetite: uranium phosphate and of hydrated iron; the hosphuranylite: hydrated uranium phosphate; the becquerelite: hydrated uranium oxide; the curite: oxide of uranium and lead hydrated. Finally, the authors present at the end of this survey a primary mineral: the brannerite, complex of uranium titanate. (author) [fr

Analysis on uranium metallogenetic conditions of granite pluton in Ulan Uzhur

International Nuclear Information System (INIS)

Lu Yaozu

2014-01-01

Qimantage area in Qinghai province is one of the important exploration areas in the present China, Ulan Uzhur complex pluton, located in the compound tectonic magmatic belt of Qimantage, is the main cluster area with uranium mineralization. This paper describes the petrochemical, geochemical, petrophysical and Heishan uranium deposit mineralization characteristics of rocks formed at the different tectonic-magmatic cycles in Ulan Uzhur complex pluton. Uranium metallogenic conditions in Ulan Uzhur complex pluton were analyzed from uranium source, magmatic activity and structure. The research shew that the Ulan Uzhur complex pluton has the petrochemical characteristics of uranium rock and Cisuralian monzonitic granite has the most significant relationship to uranium mineralization, it has the characteristics of high background radiation, many anomalies and pronounced ore-control structure, Heishan uranium deposit was controlled by factors such as pronounced northeast and the northwest structure and alteration. To conclude, Ulan Uzhur complex pluton possesses good uranium metallogenic prospect. (author)

Separation of rubidium from irradiated aluminum-encapsulated uranium

International Nuclear Information System (INIS)

Horwitz, E.P.; Schmitz, F.J.; Rokop, D.J.

1982-01-01

A procedure was developed for separating rubidium from irradiated aluminum encapsulated uranium. The separations procedure produces a final ultra-high purity RbCl product for subsequent high performance mass spectrometric analysis. The procedure involves first removing most of the macro-components and fission products by strong base anion exchange using, first, concentrated HCl, then oxalic acid media and second, selectively separating rubidium from alkaline-earth ions and other alkali-metal ions, including cesium, using Bio-Rex-40 cation-exchange resin. The resultant RbCl is then put through a final vacuum sublimation step. Ultra-pure reagents and specially clean glassware are used throughout the procedure to minimize contamination by naturally-occurring rubidium

Growth and characterization of Sm3+ doped cerium oxalate single crystals

Directory of Open Access Journals (Sweden)

Minu Mary C

2016-07-01

Full Text Available Single crystals of Sm3+ doped cerium oxalate decahydrate were synthesized using single diffusion gel technique and the conditions influencing the size, morphology, nucleation density and quality of the crystals were optimized. Highly transparent single crystals of average size 3 mm × 2 mm × 1 mm with well-defined hexagonal morphology were grown during a time period of two weeks. X-ray powder diffraction analysis revealed that the grown crystals crystallize in the monoclinic system with space group P21/c as identical with the pure cerium oxalate. The various functional groups of the oxalate ligand and the water of crystallization were identified by Fourier transform infrared spectroscopy. The photoluminescence spectrum of the Sm3+ doped cerium oxalate indicated that the Sm3+ ions are optically active in the cerium oxalate matrix. The crystal has a strong and efficient orange red emission with a wavelength peak at 595 nm and hence can be effectively used for optical amplification. Microhardness measurements of the crystal revealed that they belong to the soft material category.

Corrosion and impedance studies on magnesium alloy in oxalate solution

Energy Technology Data Exchange (ETDEWEB)

Fekry, A.M., E-mail: hham4@hotmail.com [Chemistry Department, Faculty of Science, Cairo University, Gamaa Street, Giza 12613 (Egypt); Tammam, Riham H. [Chemistry Department, Faculty of Science, Cairo University, Gamaa Street, Giza 12613 (Egypt)

2011-06-15

Highlights: > Corrosion behavior of AZ91E alloy was investigated in 0.1 M Na{sub 2}C{sub 2}O{sub 4} containing different additives as Br{sup -}, Cl{sup -} or Silicate. > The corrosion rate of 0.1 M oxalate solution containing silicate ion is lower than the blank (0.1 M Na{sub 2}C{sub 2}O{sub 4}). This was confirmed by scanning electron microscope (SEM) observations. > For the other added ions Br{sup -} or Cl{sup -}, the corrosion rate is higher than the blank. - Abstract: Corrosion behavior of AZ91E alloy was investigated in oxalate solution using potentiodynamic polarization and electrochemical impedance measurements (EIS). The effect of oxalate concentration was studied, where the corrosion rate increases with increasing oxalate concentration. The effect of added ions (Br{sup -}, Cl{sup -} or SiO{sub 3}{sup 2-}) on the electrochemical behavior of magnesium alloy in 0.1 M Na{sub 2}C{sub 2}O{sub 4} solution at 298 K, was investigated. It was found that the corrosion rate of 0.1 M oxalate solution containing silicate ion is lower than the blank (0.1 M Na{sub 2}C{sub 2}O{sub 4}). This was confirmed by scanning electron microscope (SEM) observations. However, for the other added ions Br{sup -} or Cl{sup -}, the corrosion rate is higher than the blank.

Precipitation of plutonium (III) oxalate and calcination to plutonium oxide

International Nuclear Information System (INIS)

Esteban, A.; Orosco, E.H.; Cassaniti, P.; Greco, L.; Adelfang, P.

1989-01-01

The plutonium based fuel fabrication requires the conversion of the plutonium nitrate solution from nuclear fuel reprocessing into pure PuO2. The conversion method based on the precipitation of plutonium (III) oxalate and subsequent calcination has been studied in detail. In this procedure, plutonium (III) oxalate is precipitated, at room temperature, by the slow addition of 1M oxalic acid to the feed solution, containing from 5-100 g/l of plutonium in 1M nitric acid. Before precipitation, the plutonium is adjusted to trivalent state by addition of 1M ascorbic acid in the presence of an oxidation inhibitor such as hydrazine. Finally, the precipitate is calcinated at 700 deg C to obtain PuO2. A flowsheet is proposed in this paper including: a) A study about the conditions to adjust the plutonium valence. b) Solubility data of plutonium (III) oxalate and measurements of plutonium losses to the filtrate and wash solution. c) Characterization of the obtained products. Plutonium (III) oxalate has several potential advantages over similar conversion processes. These include: 1) Formation of small particle sizes powder with good pellets fabrication characteristics. 2) The process is rather insensitive to most process variables, except nitric acid concentration. 3) Ambient temperature operations. 4) The losses of plutonium to the filtrate are less than in other conversion processes. (Author) [es

Geochemistry of the uranium mineralized Achala granitic complex, Argentina: Comparison with Hercynian peraluminous leucogranites of western Europe

International Nuclear Information System (INIS)

Cuney, M.; Leroy, J.; Valdiviezo, P.A.; Daziano, C.; Gamba, M.; Zarco, A.J.; Morello, O.; Ninci, C.; Molina, P.

1989-01-01

The Achala granitic complex belongs to the Sierras Pampeanas Hercynian belt, located west of the city of Cordoba, Argentina. This complex is very large (about 100 km N-S and 40 km E-W) and is composed of biotite, biotite with muscovite and muscovite with tourmaline granites intruded in amphibolite grade metamorphic rocks, along a main N 20 deg. E structural direction. Numerous uranium mineralizations are located within the granitic massif and tungsten mineralizations are present both in the enclosing metamorphic rocks and in the granite. The geochemistry of the granite has been studied in four test areas (Southern, Copina, Median and Don Vincente). Two test areas (Median and Don Vicente) present clear evidence of hydrothermal alteration: albitization and dequartzification similar to the French 'episyenites', silicification and argillic alteration. Potassic alteration is rare and weakly developed. The two test areas with hydrothermal alteration present a high uranium geochemical background (5-30 ppm). High thorium contents (up to 65 ppm) are essentially observed in the less differentiated granites of the Copina and Median areas. Thorium/uranium ratios are highly variable (1-10). Uranium minerals are related to different environments - (1) apatite-biotite enclave mineralized with uraninite and uranothorite, (2) gneiss from the contact metamorphism rim, (3) granite with incipient dequartzification, (4) granite associated with albitic episyenites and (5) silicified granite - but are all located in the two test areas presenting clear evidence of hydrothermal alteration. The three petrogenetic events are clearly related to very different mechanisms, separated from each other by several tens of millions of years in the west European Hercynian chain. In the same period the same succession of events leading to uranium deposits is observed in Argentina. 34 refs, 10 figs, 1 tab

Arthritis associated with calcium oxalate crystals in an anephric patient treated with peritoneal dialysis

International Nuclear Information System (INIS)

Rosenthal, A.; Ryan, L.M.; McCarty, D.J.

1988-01-01

The authors report a case of calcium oxalate arthropathy in a woman undergoing intermittent peritoneal dialysis who was not receiving pharmacologic doses of ascorbic acid. She developed acute arthritis, with calcium oxalate crystals in Heberden's and Bouchard's nodes, a phenomenon previously described in gout. Intermittent peritoneal dialysis may be less efficient than hemodialysis in clearing oxalate, and physicians should now consider calcium oxalate-associated arthritis in patients undergoing peritoneal dialysis who are not receiving large doses of ascorbic acid

Uranium removal from soils: An overview from the Uranium in Soils Integrated Demonstration program

International Nuclear Information System (INIS)

Francis, C.W.; Brainard, J.R.; York, D.A.; Chaiko, D.J.; Matthern, G.

1994-01-01

An integrated approach to remove uranium from uranium-contaminated soils is being conducted by four of the US Department of Energy national laboratories. In this approach, managed through the Uranium in Soils Integrated Demonstration program at the Fernald Environmental Management Project, Fernald, Ohio, these laboratories are developing processes that selectively remove uranium from soil without seriously degrading the soil's physicochemical characteristics or generating waste that is difficult to manage or dispose of. These processes include traditional uranium extractions that use carbonate as well as some nontraditional extraction techniques that use citric acid and complex organic chelating agents such as naturally occurring microbial siderophores. A bench-scale engineering design for heap leaching; a process that uses carbonate leaching media shows that >90% of the uranium can be removed from the Fernald soils. Other work involves amending soils with cultures of sulfur and ferrous oxidizing microbes or cultures of fungi whose role is to generate mycorrhiza that excrete strong complexers for uranium. Aqueous biphasic extraction, a physical separation technology, is also being evaluated because of its ability to segregate fine particulate, a fundamental requirement for soils containing high levels of silt and clay. Interactions among participating scientists have produced some significant progress not only in evaluating the feasibility of uranium removal but also in understanding some important technical aspects of the task

Determination of UO2F2, UO2 and UF4 in tetrafluoride of uranium samples

International Nuclear Information System (INIS)

Contreras Guzman, Ariel; Arlegui Hormazabal, Oscar

2003-01-01

The combustible elements for investigation reactors that at the present are manufacturing by the Chilean Nuclear Energy Commission (CCHEN) they are based on aluminum and silicide uranium powdered which is obtained from metallic uranium. At the present the Conversion Units, is developing the technology of transformation UF 6 in metallic Uranium, reason for which is necessary that the Chemical Analysis Laboratory have a methodology that allows to quantify the presence of UO 2 F 2 , UO 2 and UF 4 in the samples obtained in this transformation process. For this reason we are implements the methodology of sequential analysis that had been developed previously, for the Institute of Energy and Nuclear Investigations, IPEN Brasil, and to adapt it to the present conditions in the Laboratory of Chemical Analysis of the CCHEN. This method is based on the different solubilities that present those sample in front of solvents as ethanol and solutions of ammonium oxalate, what allows the separation of these compounds for a later analysis by means of the method of Davies and Gray. This method is based on the reduction of the uranium (VI) to uranium (IV) with ferrous ion amid phosphoric acid, quantifying the present uranium in the samples by means of titration with potassium dicromate. With the purpose of checking the efficiency of the method, the sum of all values of uranium coming from each compound and compares it with the total uranium of the sample (author)

Enzymatic oxalic acid regulation correlated with wood degradation in four brown-rot fungi

Science.gov (United States)

Anne Christine Steenkjær Hastrup; Frederick Green III; Patricia K. Lebow; Bo Jensen

2012-01-01

Oxalic acid is a key component in the initiation of brown-rot decay and it has been suggested that it plays multiple roles during the degradation process. Oxalic acid is accumulated to varying degrees among brown-rot fungi; however, details on active regulation are scarce. The accumulation of oxalic acid was measured in this study from wood degraded by the four brown-...

(Di­methyl­phosphor­yl)methanaminium hydrogen oxalate–oxalic acid (2/1)

Science.gov (United States)

Bialek, Sebastian; Clemens, Rebecca; Reiss, Guido J.

2014-01-01

The reaction of (di­methyl­phosphor­yl)methanamine (dpma) with oxalic acid in ethanol yielded the title solvated salt, C3H11NOP+·C2HO4 −·0.5C2H2O4. Its asymmetric unit consists of one dpmaH+ cation, one hydrogen oxalate anion and a half-mol­ecule of oxalic acid located around a twofold rotation axis. The H atom of the hydrogen oxalate anion is statistically disordered over two positions that are trans to each other. The hydrogen oxalate monoanion is not planar (bend angle ∼16°) whereas the oxalic acid molecule shows a significantly smaller bend angle (∼7°). In the crystal, the components are connected by strong O—H⋯O and much weaker N—H⋯O hydrogen bonds, leading to the formation of layers extending parallel to (001). The structure was refined from a racemically twinned crystal with twin components in an approximate 1:1 ratio. PMID:24765013

Studying inhibition of calcium oxalate stone formation: an in vitro approach for screening hydrogen sulfide and its metabolites

Directory of Open Access Journals (Sweden)

S. Vaitheeswari

2015-06-01

Full Text Available ABSTRACTPurpose:Calcium oxalate urolithiasis is one of the most common urinary tract diseases and is of high prevalence. The present study proposes to evaluate the antilithiatic property of hydrogen sulfide and its metabolites like thiosulfate & sulfate in an in vitro model.Materials and Methods:The antilithiatic activity of sodium hydrogen sulfide (NaSH, sodium thiosulfate (Na2S2O3 and sodium sulfate (Na2SO4 on the kinetics of calcium oxalate crystal formation was investigated both in physiological buffer and in urine from normal and recurrent stone forming volunteers. The stones were characterized by optical and spectroscopic techniques.Results:The stones were characterized to be monoclinic, prismatic and bipyramidal habit which is of calcium monohydrate and dihydrate nature. The FTIR displayed fingerprint corresponding to calcium oxalate in the control while in NaSH treated, S=O vibrations were visible in the spectrum. The order of percentage inhibition was NaSH>Na2S2O3>Na2SO4.Conclusion:Our study indicates that sodium hydrogen sulfide and its metabolite thiosulfate are inhibitors of calcium oxalate stone agglomeration which makes them unstable both in physiological buffer and in urine. This effect is attributed to pH changes and complexing of calcium by S2O32-and SO42- moiety produced by the test compounds.

A Novel Method for Fabricating Double Layers Porous Anodic Alumina in Phosphoric/Oxalic Acid Solution and Oxalic Acid Solution

Directory of Open Access Journals (Sweden)

Yanfang Xu

2016-01-01

Full Text Available A novel method for fabricating ordered double layers porous anodic alumina (DL-PAA with controllable nanopore size was presented. Highly ordered large pore layer with interpore distance of 480 nm was fabricated in phosphoric acid solution with oxalic acid addition at the potential of 195 V and the small pore layer was fabricated in oxalic acid solution at the potential from 60 to 100 V. Experimental results show that the thickness of large pore layer is linearly correlative with anodizing time, and pore diameter is linearly correlative with pore widening time. When the anodizing potential in oxalic acid solution was adjusted from 60 to 100 V, the small pore layers with continuously tunable interpore distance from 142 to 241 nm and pore density from 1.94×109 to 4.89×109 cm−2 were obtained. And the interpore distance and the pore density of small pore layers are closely correlative with the anodizing potential. The fabricated DL-PAA templates can be widely utilized for fabrication of ordered nanomaterials, such as superhydrophobic or gecko-inspired adhesive materials and metal or semiconductor nanowires.

Optimization of air-sparged plutonium oxalate/hydroxide precipitators

International Nuclear Information System (INIS)

VanderHeyden, W.B.; Yarbro, S.L.; Fife, K.W.

1997-04-01

The high cost of waste management and experimental work makes numerical modeling an inexpensive and attractive tool for optimizing and understanding complex chemical processes. Multiphase open-quotes bubbleclose quotes columns are used extensively at the Los Alamos Plutonium Facility for a variety of different applications. No moving parts and efficient mixing characteristics allow them to be used in glovebox operations. Initially, a bubble column for oxalate precipitations is being modeled to identify the effect of various design parameters such as, draft tube location, air sparge rate and vessel geometry. Two-dimensional planar and axisymmetric models have been completed and successfully compared to literature data. Also, a preliminary three-dimensional model has been completed. These results are discussed in this report along with future work

Solubility measurement of uranium in uranium-contaminated soils

International Nuclear Information System (INIS)

Lee, S.Y.; Elless, M.; Hoffman, F.

1993-08-01

A short-term equilibration study involving two uranium-contaminated soils at the Fernald site was conducted as part of the In Situ Remediation Integrated Program. The goal of this study is to predict the behavior of uranium during on-site remediation of these soils. Geochemical modeling was performed on the aqueous species dissolved from these soils following the equilibration study to predict the on-site uranium leaching and transport processes. The soluble levels of total uranium, calcium, magnesium, and carbonate increased continually for the first four weeks. After the first four weeks, these components either reached a steady-state equilibrium or continued linearity throughout the study. Aluminum, potassium, and iron, reached a steady-state concentration within three days. Silica levels approximated the predicted solubility of quartz throughout the study. A much higher level of dissolved uranium was observed in the soil contaminated from spillage of uranium-laden solvents and process effluents than in the soil contaminated from settling of airborne uranium particles ejected from the nearby incinerator. The high levels observed for soluble calcium, magnesium, and bicarbonate are probably the result of magnesium and/or calcium carbonate minerals dissolving in these soils. Geochemical modeling confirms that the uranyl-carbonate complexes are the most stable and dominant in these solutions. The use of carbonate minerals on these soils for erosion control and road construction activities contributes to the leaching of uranium from contaminated soil particles. Dissolved carbonates promote uranium solubility, forming highly mobile anionic species. Mobile uranium species are contaminating the groundwater underlying these soils. The development of a site-specific remediation technology is urgently needed for the FEMP site

Influence of oxalic acid on the dissolution kinetics of manganese oxide

Science.gov (United States)

Godunov, E. B.; Artamonova, I. V.; Gorichev, I. G.; Lainer, Yu. A.

2012-11-01

The kinetics and electrochemical processes of the dissolution of manganese oxides with various oxidation states in sulfuric acid solutions containing oxalate ion additives is studied under variable conditions (concentration, pH, temperature). The parameters favoring a higher degree of the dissolution of manganese oxides in acidic media are determined. The optimal conditions are found for the dissolution of manganese oxides in acidic media in the presence of oxalate ions. The mechanism proposed for the dissolution of manganese oxides in sulfuric acid solutions containing oxalic acid is based on the results of kinetic and electrochemical studies. The steps of the dissolution mechanism are discussed.

ENHANCED CHEMICAL CLEANING: EFFECTIVENESS OF THE UV LAMP TO DECOMPOSE OXALATES

Energy Technology Data Exchange (ETDEWEB)

Ketusky, E.; Huff, T.; Sudduth, C.

2010-01-19

Enhanced Chemical Cleaning is a new process scheduled to begin cleaning Savannah River Site High Level Waste Tanks in 2012. It is an improvement over the current chemical cleaning method, in that it minimizes downstream impacts on the High Level Waste System. It is based on a state of the art scale removal process used on the secondary side of nuclear power plants, with modifications to accommodate the unique constraints created by the tanks. Both Enhanced Chemical Cleaning and the scale removal process are founded on dissolving metal oxides/hydroxides using oxalic acid, with subsequent oxalate decomposition via hydroxylation using ozone or peroxide, and UV light as a catalyst. A divergence Enhanced Chemical Cleaning has from nuclear power scale removal is the significantly increased solids concentration during oxalate decomposition. These solids can limit the ability of the UV light to create hydroxyl radicals, either by limiting the ability of the light to penetrate through the solution, or by increasing the fouling rate on the UV light. Both will decrease the overall catalytic effectiveness, thereby decreasing the concentration of formed hydroxyl radicals. The hydroxyl radicals are the driving force behind the oxalate decomposition. To understand the impact of increased solids, testing was performed using a medium pressure UV light inside an ozone supplied Oxalate Decomposition Reactor. Using a dissolved metal sludge simulant with an initial oxalate concentration greater than 12,000 ppm, and an initial pH of about 2.0, the spent acid solution was recirculated through the reactor, while the UV light was allowed to foul. For the first few hours, the oxalate decomposition rate was about 1,300 ppm/hour. After about 3 hours, enough time for the UV lamp to foul, the oxalate decomposition rate decreased to about 500 ppm/hour. The decomposition rate then remained roughly constant for the next 16 hours. Overall, testing showed that the oxalate destruction rate decreased

Uranium-mediated electrocatalytic dihydrogen production from water

Science.gov (United States)

Halter, Dominik P.; Heinemann, Frank W.; Bachmann, Julien; Meyer, Karsten

2016-02-01

Depleted uranium is a mildly radioactive waste product that is stockpiled worldwide. The chemical reactivity of uranium complexes is well documented, including the stoichiometric activation of small molecules of biological and industrial interest such as H2O, CO2, CO, or N2 (refs 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11), but catalytic transformations with actinides remain underexplored in comparison to transition-metal catalysis. For reduction of water to H2, complexes of low-valent uranium show the highest potential, but are known to react violently and uncontrollably forming stable bridging oxo or uranyl species. As a result, only a few oxidations of uranium with water have been reported so far; all stoichiometric. Catalytic H2 production, however, requires the reductive recovery of the catalyst via a challenging cleavage of the uranium-bound oxygen-containing ligand. Here we report the electrocatalytic water reduction observed with a trisaryloxide U(III) complex [((Ad,MeArO)3mes)U] (refs 18 and 19)—the first homogeneous uranium catalyst for H2 production from H2O. The catalytic cycle involves rare terminal U(IV)-OH and U(V)=O complexes, which have been isolated, characterized, and proven to be integral parts of the catalytic mechanism. The recognition of uranium compounds as potentially useful catalysts suggests new applications for such light actinides. The development of uranium-based catalysts provides new perspectives on nuclear waste management strategies, by suggesting that mildly radioactive depleted uranium—an abundant waste product of the nuclear power industry—could be a valuable resource.

Synthesis, characterization, thermogravimetry, and structural study of uranium complexes derived from dibasic S-alkylated thiosemicarbazone ligands

Czech Academy of Sciences Publication Activity Database

Fasihizad, A.; Barak, T.; Ahmadi, M.; Dušek, Michal; Pojarová, Michaela

2014-01-01

Roč. 67, č. 12 (2014), s. 2160-2170 ISSN 0095-8972 R&D Projects: GA ČR(CZ) GA14-03276S Institutional support: RVO:68378271 Keywords : uranium complex * isothiosemicarbazone * crystallography * spectra * thermal stability Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.012, year: 2014

Uranium(VI) transport modeling: geochemical data and submodels

International Nuclear Information System (INIS)

Tripathi, V.S.

1984-01-01

Understanding the geochemical mobility of U(VI) and modeling its transport is important in several contexts including ore genesis, uranium exploration, nuclear and mill-tailings waste management, and solution mining of uranium ores. Adsorption is a major control on partitioning of solutes at the mineral/solution interface. The effect of carbonate, fluoride, and phosphate complexing on adsorption of uranium was investigated. A critical compilation of stability constants of inorganic complexes and solid compounds of U(VI) necessary for proper design of experiment and for modeling transport of uranium was prepared. The general features of U(VI) adsorption in ligand-free systems are similar to those characteristic of other hydrolyzable metal ions. The adsorption processes studied were found to be reversible. The adsorption model developed in ligand-free systems, when solution complexing is taken into account, proved remarkably successful in describing adsorption of uranium in the presence of carbonate and fluoride. The presence of phosphate caused a much smaller decrease in the extent of adsorption than expected; however, a critical reassessment of the stability of UO 2 2+ .HPO 4 2- complexes, showed that phosphato complexes, if any, are extremely weak under experimental conditions. Removal of uranium may have occurred due to precipitation of sodium uranyl phosphates in addition to adsorption

Precipitation stripping of neodymium from carboxylate extractant with aqueous oxalic acid solutions

International Nuclear Information System (INIS)

Konishi, Yasuhiro; Asai, Satoru; Murai, Tetuya

1993-01-01

This paper describes a precipitation stripping method in which neodymium ions are stripped from carboxylate extractant in organic solvent and simultaneously precipitated with aqueous oxalic acid solution. For the single-stage process, a quantitative criterion for precipitating oxalate powders was derived theoretically, and stripping experiments were done under the precipitation conditions. The resultant precipitates were neodymium oxalate, which is completely free from contamination by the carboxylate extractant and the organic solvent. The overall rate of stripping was controlled by the transfer of neodymium carboxylate in the organic solution, indicating that the presence of oxalic acid in the aqueous phase has no effect on the stripping rate. These findings demonstrate the feasibility of combining the conventional stripping and precipitation stages in a solvent extraction process for separation and purification of rare earths

Radiological and environmental safety aspects of uranium fuel fabrication plants at Nuclear Fuel Complex, Hyderabad

International Nuclear Information System (INIS)

Viswanathan, S.; Surya Rao, B.; Lakshmanan, A.R.; Krishna Rao, T.

1991-01-01

Nuclear Fuel Complex, Hyderabad manufactures uranium dioxide fuel assemblies for PHWRs and BWRs operating in India. Starting materials are magnesium diuranate received from UCIL, Jaduguda and imported UF. Both of these are converted to UO 2 pellets by identical chemical processes and mechanical compacting. Since the uranium handled here is free of daughter product activities, external radiation is not a problem. Inhalation of airborne U compounds is one of the main source of exposure. Engineered protective measures like enclosures around U bearing powder handling equipment and local exhausts reduce worker's exposure. Installation of pre-filters, wet rotoclones and electrostatic precipitators in the ventillation system reduces the release of U into the environment. The criticality hazard in handling slightly enriched uranium is very low due to the built-in control based on geometry and inventory. Where airborne uranium is significant, workers are provided with protective respirators. The workers are regularly monitored for external exposure and also for internal exposure. The environmental releases from the NFC facility is well controlled. Soil, water and air from the NFC environment are routinely collected and analysed for all the possible pollutants. The paper describes the Health Physics experience during the last five years on occupational exposures and on environmental surveillance which reveals the high quality of safety observed in our nuclear fuel fabricating installations. (author). 4 refs., 6 tabs

Elucidating Bioreductive Transformations within Physically Complex Media: Impact on the Fate and Transport of Uranium and Chromium

International Nuclear Information System (INIS)

Fendorf, Scott; Francis, Chris; Jardine, Phil; Benner, Shawn

2009-01-01

In situ stabilization (inclusive of natural attenuation) of toxic metals and radionuclides is an attractive approach for remediating many contaminated DOE sites. By immobilizing toxic metals and radionuclides in place, the removal of contaminated water to the surface for treatment as well as the associated disposal costs are avoided. To enhance in situ remediaton, microbiological reductive stabilization of contaminant metals has been, and continues to be, actively explored. It is likely that surface and subsurface microbial activity can alter the redox state of toxic metals and radionuclides, either directly or indirectly, so they are rendered immobile. Furthermore, anaerobic bacterial metabolic products will help to buffer pulses of oxidation, typically from fluxes of nitrate or molecular oxygen, and thus may stabilize reduced contaminants from oxidative mobilization. Uranium and chromium are two elements of particular concern within the DOE complex that, owing to their abundance and toxicity, appear well suited for biologically mediated reductive stabilization. Subsurface microbial activity can alter the redox state of toxic metals and radionuclides, rending them immobile. Imparting an important criterion on the probability that contaminants will undergo reductive stabilization, however, is the chemical and physical heterogeneity of the media. Our research first examined microbially induced transformation of iron (hydr)oxide minerals and their impact on contaminant attenuation. We revealed that in intricate cascade of geochemical reactions is induced by microbially produced Fe(II), and that during transformation contaminants such as U(VI) can be incorporated into the structure, and a set of Fe(II) bearing solids capable of reducing Cr(VI) and stabilizing resulting Cr(III). We also note, however, that common subsurface constituents such as phosphate can modify iron oxide transformation pathways and thus impact contaminant sequestration - affecting both Cr and U

Structural diversity of the lanthanide oxalates: Condensation of neodymium oxygen polyhedra under hydrothermal conditions

International Nuclear Information System (INIS)

Mer, A.; Rivenet, M.; Abraham, F.; De Almeida, L.; Grandjean, S.

2013-01-01

New neodymium hydroxo-oxalate and oxalate [Nd 6 (H 2 O) 6 (C 2 O 4 ) 7 (OH) 4 ].4H 2 O (1) and [Nd 2 (H 2 O) 4 (C 2 O 4 ) 3 ].2H 2 O (2) were synthesized by hydrothermal reaction at 150 C between neodymium nitrate and oxalic acid solutions at pH = 10-11 obtained by adding various monoamines. The structures were determined from single-crystal X-ray diffraction data. The two compounds crystallize in the monoclinic system with space group P21/c and a = 17.4384 (11), b = 8.1717 (5), c = 12.9929 (7), β = 94.66 (1) degrees, V = 1845.38 (19) (Angstroms) 3 , Z = 2 for 1 and a = 9.8249 (2) Angstroms, b = 8.2487 (2) Angstroms, c = 10.1911 (3) Angstroms, β = 99.09 (1), V = 815.53 (4) (Angstroms) 3 , Z = 2 for 2. Full matrix least-squares refinement yielded R1 = 0.0365 and 0.0267 for 6033 and 3382 independent reflections for 1 and 2 respectively. In 2, the three-dimensional neodymium oxalate arrangement results from dimeric units of edge shared NdO 9 polyhedra connected through oxalate ions acting as bis-bidentate. In 1, the neodymium atoms are connected through μ2-OH and μ3-OH ions to form a hexa-nuclear inorganic core [Nd 6 (OH) 4 (H 2 O) 6 ] with an un-precedently reported geometry leading to a hexa-nuclear polyhedra block. The blocks are connected through an O-O bridge involving two oxygen atoms of two oxalate ions to build a centipede-like ribbon. The ribbons are further connected through oxalate ions to form a three dimensional neodymium oxalate arrangement. In 1, oxalates adopt four distinct bridging modes of coordination, μ2, μ3, μ4 and μ5. (authors)

Removal of plutonium from nitric acid-oxalic acid solutions using anion exchange method

International Nuclear Information System (INIS)

Kasar, U.M.; Pawar, S.M.; Joshi, A.R.

1999-01-01

An anion exchange method using Amberlyst A-26 (MP) resin was developed for removal of Pu from nitric acid-oxalic acid solutions without destroying oxalate. The method consists of sorption of Pu(IV) on Amberlyst A-26, a macroporous anion exchange resin, from nitric acid-oxalic acid medium in the presence of Al(NO 3 ) 3 . Pu(IV) breakthrough capacity of Amberlyst A-26 using synthetic feed solution was determined. (author)

In-cloud oxalate formation in the global troposphere: a 3-D modeling study