Recovery of uranium from uranyl nitrate raffinate. Contributed Paper PE-06

International Nuclear Information System (INIS)

Anilkumar Reddy, A.M.; Shiva Kumar, M.; Varadan, K.M.K.; Babaji, P.; Sairam, S. Sheela; Saibaba, N.

2014-01-01

At New Uranium Oxide Fuel Plant, NUOFP(O) of Nuclear Fuel Complex (NFC), the Uranyl Nitrate Raffinate (UNR) generated during solvent extraction process is washed with Treated Lean Solvent(TLS) to recover residual U. Earlier this UNR consisting of 0.5-1 gm/l and 2.5 FA was neutralised with vapour ammonia. The slurry was then filtered over pre coat drum filter and the resultant Uranyl Nitrate Raffinate cake (UNRC) was stored in polyethylene lined MS drums. The valuable U was thus being locked up in UNRC. Also, the storage of UNRC drums required lot of floor space which have to be repacked frequently to contain the radioactivity. Hence the need has come to avoid the generation of UNRC and the recovery of U from the already generated UNRC. The generation of UNRC was avoided by developing alternate process of UNR treatment with Treated Lean Solvent for the removal of residual U and the resulting Acidic Raffinate Slurry (ARS) is disposed. The Uranium recovery from UNRC is done by dissolving the cake in Uranyl Nitrate Raffinate solution to leach the hexavalent Uranium by utilizing the free acidity in UNR. The leaching time is about six hours and the uranium forms uranyl nitrate. The resulting leach solutions are relatively dilute but complex acidic nitrate solutions containing wide variety of ions. Metallic ions commonly present include uranium, iron, magnesium, aluminium, sodium, calcium etc. The uranium concentration is normally 1-1.5 g/L. This uranium is separated by solvent extraction. The active agent in solvent extraction is Tri Butyl Phosphate in kerosene that can selectively extract uranium into an organic complex which is insoluble in aqueous. The organic used for extraction is Treated Lean Solvent in the quality of freshly prepared solvent and the resulting Acidic Raffinate Slurry is disposed by sale. The leaching of Uranium from UNRC was done in plant scale and about 1200 kgs of UNRC was successfully processed in trial batch. The paper deals with details of

Densities concentrations of aqueous of uranyl nitrate solutions

International Nuclear Information System (INIS)

Rodrigo Otero, A.; Rodriguez Hernandez, B.; Fernandez Rodriguez, L.

1966-01-01

The ratio density-concentration of aqueous uranyl nitrate solutions expressed as U 3 O 8 grams/liter, U grams/liter and hexahydrate uranyl nitrate weight percent at different temperatures, are established. Experimental values are graphically correlated and compared whit some published data. (Author) 2 refs

Photochemical reduction of uranyl nitrate

Energy Technology Data Exchange (ETDEWEB)

Duerksen, W.K.

1993-10-20

The photochemical reduction of uranyl nitrate solutions to tetravalent uranium was investigated as a means of producing uranium dioxide feed for the saltless direct oxide reduction (SDOR) process. At high uranium concentrations, reoxidation of U{sup +4} occurs rapidly. The kinetics of the nitric oxidation of tetravalent uranium depend on the concentrations of hydrogen ion, nitrate ion, nitrous acid, and tetravalent uranium in the same manner as was reported elsewhere for the nitrate oxidation of PU{sup +3}. Reaction rate data were successfully correlated with a mechanism in which nitrogen dioxide is the reactive intermediate. Addition of a nitrous acid scavenger suppresses the reoxidation reaction. An immersion reactor employing a mercury vapor lamp gave reduction times fast enough for routine production usage. Precipitation techniques for conversion of aqueous U(NO{sub 3}){sub 4} to hydrous UO{sub 2} were evaluated. Prolonged dewatering times tended to make the process time consuming. Use of 3- to 4-M aqueous NaOH gave the best dewatering times observed. Reoxidation of the UO{sub 2} by water of hydration was encountered, which required the drying process to be carried out under a reducing atmosphere.

Investigation of uranyl nitrate complexes with trialkylphosphine oxides

International Nuclear Information System (INIS)

Kobets, L.V.; Kopashova, I.M.; Dik, T.A.; Volodin, I.A.; Kovalenko, M.A.; Semenij, V.Ya.

1982-01-01

Using the methods of vibrational spectroscopy and thermal analysis a number of uranyl complexes with trialkylphosphine oxides of the general formula UO 2 (NO 3 ) 2 x2R 3 PO, where R-C 2 H 5 -C 10 H 21 have been studied. Infrared and Raman spectra are interpreted according to vibration types. Comparison of vibrational spectra of the complexes in solid phase and solutions of organic solvents permitted to find the differences in position and amount of acids responsible for complexing. It is detected that in the series of complexes investigated the strength of uranyl bond with phosphoryl group oxygen practically remains stable, whereas degree of covalence of nitrate groups is observed. The pointed out peculiarities are interpreted proceeding from the presence of bridge nitrate groups in the structure of the complexes. Thermal stability of the complexes is studied, chemism of their decomposition being suggested

Study of the extraction mechanisms by TBP saturated by uranyl nitrate; Etude des mecanismes d'extraction du TBP sature par le nitrate d'uranyle

Energy Technology Data Exchange (ETDEWEB)

Meze, F

2004-02-15

This work deals with a particular phenomenon likely to occur in the nuclear waste reprocessing process PUREX. It was shown earlier by Russian works that the extractant molecule, tributyl phosphate (TBP), saturated by uranyl nitrate keeps its extraction capacities for nitric acid and tetravalent actinides. This study is composed of three parts. Firstly, some liquid-liquid extraction experiments were conducted to verify the ability of TBP saturated by uranyl nitrate to conserve its extraction capacities for nitric acid. Then, during these experiments, the UV and infrared spectra of both phases were recorded to obtain the organic phase speciation. At last, the informations gathered during the experimental part were used to build a general species distribution model of the H{sub 2}O/HNO{sub 3}/UO{sub 2}(NO{sub 3}){sub 2}/TBP system. (author)

A study of precipitation from pure solutions of uranyl nitrate; Etude de la precipitaion de solutions pures de nitrate d'uranyle

Energy Technology Data Exchange (ETDEWEB)

Decrop, J; Holder, J; Sauteron, J [Commissariat a l' Energie Atomique, Usine du Bouchet, Service des Lab. de Recherches et de Controle, Saclay (France). Centre d' Etudes Nucleaires

1961-07-01

After its purification by extraction of the uranyl nitrate from the organic solvent, uranium has to be converted into solid form again: uranium trioxide (UO{sub 3}). It can be done either by thermal decomposition of uranyl nitrate or by precipitation of uranium, followed by filtration and calcination. Only the second method has been studied for now at the Bouchet plant. This paper reports the bench-scale and pilot-scale experiments of the studies of the precipitation of pure solutions of uranyl nitrate using ammonia (gaseous or in solution) or ammonium carbonate. These have been carried out at the Bouchet plant. It investigates the chemical aspect (pH, precipitates chemical composition) and the technical aspect of the different ways of precipitation (conditions of precipitation, decantation and filtration of precipitates). (M.P.)

Effect of diluent on extraction of uranyl nitrate from nitric acid solution by tri-n-octylamine

International Nuclear Information System (INIS)

Kojima, Takashi; Ukon, Toshiaki; Fukutomi, Hiroshi

1979-01-01

The distribution ratios in the extraction equilibriums of uranylnitrate from 3 M HNO 3 by tri-n-octylamine (TOA) nitrate salt in nitrobenzene, chlorobenzene, benzene, toluene, cyclohexane, nitrobenzene-benzene and benzene-cylohexane mixtures have been determined in varying the concentrations of uranyl nitrate and TOA nitrate salt. The extraction mechanisms have been discussed in detail based on the law of mass action. It has been concluded that the extractions of uranyl nitrate by TOA nitrate salt in nitrobenzene, 74% nitrobenzene-benzene and 49% nitrobenzene-benzene mixture are represented by the equation TOAHNO 3 (org) + UO 2 2+ (aq) + 2 NO 3 - (aq) = TOAHUO 2 (NO 3 - ) 3 (org), while the extractions of uranyl nitrate by TOA nitrate salt in chlorobenzene, benzene, toluene, cyclohexane, benzene-cyclohexane mixtures and 24% nitrobenzene-benzene mixture are represented by the equation 2 TOAHNO 3 (org) + UO 2 2+ (aq) + 2 NO 3 - (aq) = TOAHUO 2 (NO 3 ) 3 TOAHNO 3 (org). In the latter the extraction equilibrium constants increase in the order of chlorobenzene < benzene < toluene < cyclohexane and with decreasing of the volume fraction of benzene in benzene-cyclohexane mixtures. The effects of diluent have been discussed in detail on the basis of the Hildebrand-Scatchard theory of regular solutions. (author)

Investigations on uranyl nitrate solubility in nitric acid in different concentrations at temperatures of 50C

International Nuclear Information System (INIS)

Deigele, E.

1983-01-01

The solubility of uranyl nitrate was studied in nitric acid solutions of different concentrations at a temperature of 5 0 C. This temperature was chosen with a view to using water as coolant and to facilitate the handling of the strong acid solutions. Accurate curves were established by a multitude of accurate measurements in the high concentration range. Further solubility curves can be derived from this basic curve. Some of the precipitates in the interesting regions of the solubility curve were analyzed. (orig./EF) [de

Criticality parameters for uranyl nitrate or plutonium nitrate systems in tributyl phosphate/kerosine and water

International Nuclear Information System (INIS)

Weber, W.

1985-01-01

This report presents the calculated values of smallest critical masses and volumina and neutron physical parameters for uranyl nitrate (3, 4, 5% U-235) or plutonium nitrate (5% Pu-240), each in a 30 per cent solution of tributyl phosphate (TBP)/kerosine. For the corresponding nitrate-water solutions, newly calculated results are presented together with a revised solution density model. A comparison of the data shows to what extent the criticality of nitrate-TBP/kerosine systems can be assessed on the basis of nitrate-water parameters, revealing that such data can be applied to uranyl nitrate/water systems, taking into account that the smallest critical mass of uranyl nitrate-TBP/kerosine systems, up to a 5 p.c. U-235 enrichment, is by 4.5 p.c. at the most smaller than that of UNH-water solutions. Plutonium nitrate (5% Pu-240) in the TBP/kerosine solution will have a smallest critical mass of up to 7 p.c. smaller, as compared with the water data. The suitability of the computing methods and cross-sections used is verified by recalculating experiments carried out to determine the lowest critical enrichment of uranyl nitrate. The calculated results are well in agreement with experimental data. The lowest critical enrichment is calculated to be 2.10 p.c. in the isotope U-235. (orig.) [de

Kinetic of liquid-liquid extraction for uranyl nitrate and actinides (III) and lanthanides (III) nitrates by amide extractants

International Nuclear Information System (INIS)

Toulemonde, V.; CEA Centre d'Etudes de la Vallee du Rhone, 30 -Marcoule

1995-01-01

The kinetics of liquid-liquid extraction by amide extractants have been investigated for uranyl nitrate (monoamide extractants), actinides (III) and lanthanides (III) nitrates (diamide extractants). The transfer of the metallic species from the aqueous phase to the organic phase was studied using two experimental devices: ARMOLLEX (Argonne Modified Lewis cell for Liquid Liquid Extraction) and RSC (Rotating Stabilized Cell). The main conclusions are: for the extraction of uranyl nitrate by DEHDMBA monoamide, the rate-controlling step is the complexation of the species at the interface of the two liquids. Thus, an absorption-desorption (according to Langmuir theory) reaction mechanism was proposed; for the extraction of actinides (III) and lanthanides (III) nitrates in nitric acid media by DMDBTDMA diamide, the kinetic is also limited by interfacial reactions. The behavior of Americium and Europium is very similar as fare as their reaction kinetics are concerned. (author)

Kinetic of liquid-liquid extraction for uranyl nitrate and actinides (III) and lanthanides (III) nitrates by amide extractants; Cinetique d`extraction liquide-liquide du nitrate d`uranyle et des nitrates d`actinides (III) et de lanthanides (III) par des extractants a fonction amide

Energy Technology Data Exchange (ETDEWEB)

Toulemonde, V [CEA Centre d` Etudes Nucleaires de Saclay, 91 -Gif-sur-Yvette (France); [CEA Centre d` Etudes de la Vallee du Rhone, 30 -Marcoule (France). Dept. d` Exploitation du Retraitement et de Demantelement

1995-12-20

The kinetics of liquid-liquid extraction by amide extractants have been investigated for uranyl nitrate (monoamide extractants), actinides (III) and lanthanides (III) nitrates (diamide extractants). The transfer of the metallic species from the aqueous phase to the organic phase was studied using two experimental devices: ARMOLLEX (Argonne Modified Lewis cell for Liquid Liquid Extraction) and RSC (Rotating Stabilized Cell). The main conclusions are: for the extraction of uranyl nitrate by DEHDMBA monoamide, the rate-controlling step is the complexation of the species at the interface of the two liquids. Thus, an absorption-desorption (according to Langmuir theory) reaction mechanism was proposed; for the extraction of actinides (III) and lanthanides (III) nitrates in nitric acid media by DMDBTDMA diamide, the kinetic is also limited by interfacial reactions. The behavior of Americium and Europium is very similar as fare as their reaction kinetics are concerned. (author). 89 refs.

Formation of the second organic phase during uranyl nitrate extraction from aqueous solution by 30% tributylphosphate solution in paraffin

International Nuclear Information System (INIS)

Yhrkin, V.G.

1996-01-01

For extraction systems aqueous solution of uranyl nitrate-30% solution of tributylphosphate in individual paraffins from C 13 to C 17 the influence of the second organic phase of uranyl nitrate concentration in aqueous and organic phases, the length of hydrocarbon chain of paraffin hydrocarbon and temperature from 25 to 50 deg C on formation conditions has been defected. A special method of achieving the conditions of organic phase stratification from three-phase region, involving definition of equilibrium phases composition by density and refractive index, has been elaborated for more precise definition of organic phase homogeneity region. It has been revealed that without addition of nitric acid to uranyl nitrate solution the organic phase homogeneity limits can be achieved solely on paraffins C 15 , C 16 and C 17 and only under conditions similar to equeous phase saturation in terms of uranyl nitrate. 16 refs., 2 figs

The gas-phase bis-uranyl nitrate complex ((UO2)2(NO3)5)-: infrared spectrum and structure

International Nuclear Information System (INIS)

Groenewold, G.S.; van Stipdonk, Michael J.; Oomens, Jos; De Jong, Wibe A.; McIlwain, Michael E.

2011-01-01

The infrared spectrum of the bis-uranyl nitrate complex ((UO 2 ) 2 (NO 3 ) 5 ) - was measured in the gas phase using multiple photon dissociation (IRMPD). Intense absorptions corresponding to the nitrate symmetric and asymmetric vibrations, and the uranyl asymmetric vibration were observed. The nitrate v 3 vibrations indicate the presence of nitrate in a bridging configuration bound to both uranyl cations, and probably two distinct pendant nitrates in the complex. The coordination environment of the nitrate ligands and the uranyl cations were compared to those in the mono-uranyl complex. Overall, the uranyl cation is more loosely coordinated in the bis-uranyl complex ((UO 2 ) 2 (NO 3 ) 5 ) - compared to the mono-complex (UO 2 (NO 3 ) 3 ) - , as indicated by a higher O-U-O asymmetric stretching (v 3 ) frequency. However, the pendant nitrate ligands are more strongly bound in the bis-complex than they are in the mono-uranyl complex, as indicated by the v 3 frequencies of the pendant nitrate, which are split into nitrosyl and O-N-O vibrations as a result of bidentate coordination. These phenomena are consistent with lower electron density donation per uranyl by the nitrate bridging two uranyl centers compared to that of a pendant nitrate in the mono-uranyl complex. The lowest energy structure predicted by density functional theory (B3LYP functional) calculations was one in which the two uranyl molecules bridged by a single nitrate coordinated in a bis-bidentate fashion. Each uranyl molecule was coordinated by two pendant nitrate ligands. The corresponding vibrational spectrum was in excellent agreement with the IRMPD measurement, confirming the structural assignment.

The gas-phase bis-uranyl nitrate complex ((UO2)2(NO3)5)-: infrared spectrum and structure

International Nuclear Information System (INIS)

Groenewold, Gary S.; van Stipdonk, Michael J.; Oomens, Jos; de Jong, Wibe; McIlwain, Michael E.

2011-01-01

The infrared spectrum of the bis-uranyl nitrate complex ((UO 2 ) 2 (NO 3 ) 5 ) - was measured in the gas phase using multiple photon dissociation (IRMPD). Intense absorptions corresponding to the nitrate symmetric and asymmetric vibrations, and the uranyl asymmetric vibration were observed. The nitrate nu3 vibrations indicate the presence of nitrate in a bridging configuration bound to both uranyl cations, and probably two distinct pendant nitrates in the complex. The coordination environment of the nitrate ligands and the uranyl cations were compared to those in the mono-uranyl complex. Overall, the uranyl cation is more loosely coordinated in the bis-uranyl complex ((UO 2 ) 2 (NO 3 ) 5 ) - compared to the mono-complex (UO 2 (NO 3 ) 3 ) - , as indicated by a higher O-U-O asymmetric stretching (nu3) frequency. However, the pendant nitrate ligands are more strongly bound in the bis-complex than they are in the mono-uranyl complex, as indicated by the ν 3 frequencies of the pendant nitrate, which are split into nitrosyl and O-N-O vibrations as a result of bidentate coordination. These phenomena are consistent with lower electron density donation per uranyl by the nitrate bridging two uranyl centers compared to that of a pendant nitrate in the mono-uranyl complex. The structure was calculated using density functional theory (B3LYP functional), which produced a structure in which the two uranyl molecules bridged by a single nitrate coordinated in a bis-bidentate fashion. Each uranyl molecule was coordinated by two pendant nitrate ligands. The corresponding vibrational spectrum was in excellent agreement with the IRMPD measurement, confirming the structural assignment.

Thermal decomposition of ammonium diuranate, uranyl nitrate hexahydrate and uranyl peroxide

International Nuclear Information System (INIS)

Yulianto, T.; Mutiara, E.

2011-01-01

The behaviors of three types of starting powder had been investigated during their thermal decomposition processes in nitrogen, air, and hydrogen. The powder types were the products of uranyl nitrate precipitation, i.e. ADU (ammonium diuranate), UNH (uranyl nitrate hexahydrate), and UPO (uranyl peroxide). The objective of the investigation was to find out the best atmosphere that would result in good quality powder in a thermal decomposition process with the lowest temperature and the shortest period of time in order to reduce the cost of UO 2 powder preparation. Before the thermal decomposition process was initiated, all powder types were characterized for their crystal structures. The investigation was conducted by TG-DTA instrument at temperature up to 800°C and the heating rate of 10°C/minute. The crystal structures were identified by X-Ray Diffractometer with Cu-Ka radiation. The specific surface area of the powder was also observed using BET method, especially for the powder that underwent the process in hydrogen heated up to 800°C. The Results showed that the process took place faster in hydrogen, and UNH required lower thermal decomposition temperature in relations with other types of powder. (author)

The study of kinetics of uranyl nitrate extraction and reextraction, di-n-butylphosphoric acid reextraction in the flow mixer in the system aqueous solutions - tri-n-butyl phosphate in diluent

International Nuclear Information System (INIS)

Shchepetil'nikov, N.N.; Timofeev, A.N.; Kharitonov, V.V.

1992-01-01

Kinetics of uranyl nitrate and HNO 3 extraction and reextraction in a flow-type mixer for the system 30 vol.% TBP in extractant dearomatized diluent (EDD) was studied. Kinetics of dibutylphosphate acid reextraction was considered and the influence of uranium and zirconium presence on the process was investigated. It is shown that in laboratory mixer of continuous action in case of phase contact duration of 1 min. in system 30 % solution of TBP in EDD extraction sufficiently similar to equilibrium extraction of uranyl nitrate and nitric acid during their extraction and reextraction is achieved

A study of precipitation from pure solutions of uranyl nitrate

International Nuclear Information System (INIS)

Decrop, J.; Holder, J.; Sauteron, J.

1961-01-01

After its purification by extraction of the uranyl nitrate from the organic solvent, uranium has to be converted into solid form again: uranium trioxide (UO 3 ). It can be done either by thermal decomposition of uranyl nitrate or by precipitation of uranium, followed by filtration and calcination. Only the second method has been studied for now at the Bouchet plant. This paper reports the bench-scale and pilot-scale experiments of the studies of the precipitation of pure solutions of uranyl nitrate using ammonia (gaseous or in solution) or ammonium carbonate. These have been carried out at the Bouchet plant. It investigates the chemical aspect (pH, precipitates chemical composition) and the technical aspect of the different ways of precipitation (conditions of precipitation, decantation and filtration of precipitates). (M.P.)

Preparation of working calibration and test materials: uranyl nitrate solution

International Nuclear Information System (INIS)

Yamamura, S.S.; Spraktes, F.W.; Baldwin, J.M.; Hand, R.L.; Lash, R.P.

1977-05-01

Reliable working calibration and test materials (WCTMs) are essential to a meaningful analytical measurements quality assurance program. This report describes recommended methods for the preparation of uranyl nitrate solution WCTMs for testing analytical methods, for calibrating methods, and for testing personnel. Uranyl nitrate solution WCTMs can be synthesized from characterized starting materials or prepared from typical plant materials by thorough characterization with reference to primary or secondary reference calibration and test materials (PRCTMs or SRCTMs). Recommended starting materials are described along with detailed procedures for (a) preparing several widely-used types of uranyl nitrate solution WCTMs, (b) packaging the WCTMs, (c) analyzing the WCTMs to establish the reference values or to confirm the synthesis, and (d) statistically evaluating the analytical data to assign reference values and to assess the accuracy of the WCTMs

Effects of nitrate, fulvate, phosphate, phthalate, salicylate and catechol on the sorption of uranyl onto SiO2. A comparative study

International Nuclear Information System (INIS)

Zhang Hongxia; Wen Chuanxi; Tao Zuyi; Wu Wangsuo

2011-01-01

We have performed a large number of batch sorption experiments of uranyl onto SiO 2 and examined the effects of nitrate or ionic strength, phosphate, fulvic acid(FA), phthalic acid (PH), salicylic acid (SA), and catechol (CA) on the uranyl sorption onto SiO 2 . Three sorption edges and three sorption isotherms at ionic strengths 0.05, 0.1, and 0.5 mol/L KNO 3 were used to investigate the effect of ionic strength or nitrate on the sorption and the Langmuir, Freundlich, and Dubinin-Radushkevich models are used to simulate the sorption isotherms, respectively. Five sorption edges in the presence of phosphate, FA, PH, SA, and CA were compared with that in the absence of complexing ligand. The results suggest that the effect of complexation of uranyl with nitrate on the uranyl sorption can be negligible and the sorption can be described Freundlich and D-R model very well. The positive effect of phosphate on the uranyl sorption was found, though the extent of effect was decreased with increasing pH. The positive effect and the negative effect of FA on the uranyl sorption were found at low pH and high pH ranges, respectively. The sorption edge of uranyl sorption remained unaffected in the presence of PH in the pH 2-10. In the presence of SA, the no effect and the negative effect on the uranyl sorption were, respectively, found at low pH and high pH ranges. The negative effect of CA on the uranyl sorption was found in the pH 2-10. (author)

Thermodynamics of dehydration process of uranyl nitrate pentahydrate of thorium

International Nuclear Information System (INIS)

Khamidov, F.A.; Mirsaidov, I.U.; Nazarov, K.M.; Nasriddinov, S.K.; Badalov, A.B.

2010-01-01

Present article is devoted to thermodynamics of dehydration process of uranyl nitrate pentahydrate of thorium. The results of researches of dehydration process of uranyl nitrate pentahydrate of thorium Th(NO_3)_4·5H_2O were considered. The researches were carried out by means of tensimeter method with membrane zero-manometer under equilibrium conditions and at 300-450 K temperature ranges. The thermodynamic characteristics of dehydration process of initial crystalline hydrate was defined.

Critical experiment study on uranyl nitrate solution experiment facility

International Nuclear Information System (INIS)

Zhu Qingfu; Shi Yongqian; Wang Jinrong

2005-01-01

The Uranyl Nitrate Solution Experiment Facility was constructed for the research on nuclear criticality safety. In this paper, the configuration of the facility is introduced; a series of critical experiments on uranyl nitrate solution is described later, which were performed for various uranium concentrations under different conditions, i.e. with or without neutron absorbers in the core and with or without water-reflector outside the core. Critical volume and the minimum 235U critical mass for different uranium concentrations are presented. Finally, theoretical analysis is made on the experimental results. (authors)

Contribution to the study of the evaporation of aqueous uranyl nitrate solutions; Contribution a l'etude de l'evaporation des solutions aqueuses de nitrate d'uranyle

Energy Technology Data Exchange (ETDEWEB)

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

1967-05-15

This work was carried out with a view to define the conditions under which is affected the concentration of aqueous uranyl nitrate solutions one of the steps in uranium extraction metallurgy. The first port is devoted to the experimental determination of the physical characteristics of aqueous uranyl nitrate solutions, from dilute to concentrated solutions. The second part of this work is devoted to the isothermal evaporation of solution a west ted-wall column; this chemical engineering study has been more particularly devoted to the definition of the influence of the dynamics of the liquid phase on the exchange of matter between the two phases in contact. (author) [French] La concentration par evaporation des solutions aqueuses de nitrate d'uranyle constitue une etape de la metallurgie de l'uranium dont ce travail a voulu preciser la connaissance. Dans ce but, une premiere partie a ete consacree a la determination experimentale de caracteristiques physiques des solutions aqueuses de nitrate d'uranyle, des solutions diluees aux solutions saturees. Dans une deuxieme partie, ce travail a porte sur l'evaporation isotherme des solutions dans une colonne a paroi mouillee; cette etude de genie chimique a ete plus particulierement orientee de facon a preciser l'influence de la dynamique de la phase liquide sur l'echange de matiere entre les deux phases en contact. (auteur)

Electron spectra and mechanism of complexing of uranyl nitrate in water-acetone solutions

International Nuclear Information System (INIS)

Zazhogin, A.A.; Zazhogin, A.P.; Komyak, A.I.; Serafimovich, A.I.

2003-01-01

Based on the analysis of the luminescence and electronic absorption spectra, the processes of complexing in an aqueous solution of UO 2 (NO 3 ) 2 ·6H 2 O with small additions of acetone have been studied. In a pure aqueous solution, uranyl exists as the complex UO 2 ·5H 2 O. It is shown that the addition of acetone to the solution leads to the displacement of some water molecules out of the first coordination sphere of uranyl and the formation of the uranyl nitrate dihydrate complexes UO 2 (NO 3 ) 2 ·2H 2 O. It has been established that the stability of these complexes is determined by the decrease in the water activity and in the degree of hydration of uranyl and nitrate, which is the result of the local increase in the concentration of acetone molecules (due to their hydrophobicity) in the regions of the solution where uranyl and nitrate ions are found. The experimental facts supported the mechanism proposed are presented. (authors)

Determination of uranium in uranium metal, uranium oxides, and uranyl nitrate solutions by potentiometric titration

International Nuclear Information System (INIS)

Tucker, H.L.; McElhaney, R.J.

1983-01-01

A simple, fast method for the determination of uranium in uranium metal, uranium oxides, and uranyl nitrate solutions has been adapted from the Davies-Gray volumetric method to meet the needs of Y-12. One-gram duplicate aliquots of uranium metal or uranium oxide are dissolved in 1:1 HNO 3 and concentrated H 2 SO 4 to sulfur trioxide fumes, and then diluted to 100-mL volume. Duplicate aliquots are then weighed for analysis. For uranyl nitrate samples, duplicate aliquots containing between 50 and 150 mg of U are weighed and analyzed directly. The weighed aliquot is transferred to a Berzelius beaker; 1.5 M sulfamic acid is added, followed in order by concentrated phosphoric acid, 1 M ferrous sulfate, and (after a 30-second interval) the oxidizing reagent. After a timed 3-minute waiting period, 100 mL of the 0.1% vanadyl sulfate-sulfuric acid mixture is added. The sample is then titrated past its endpoint with standard potassium dichromate, and the endpoint is determined by second derivative techniques on a mV/weight basis

Design of one evaporation system for uranyl nitrate solution

International Nuclear Information System (INIS)

Mancilla Romero, R.J.

1975-01-01

The authors propose an instant evaporation system with recirculation of the concentrated solution to raise the concentration from 50 to 1500 g of uranium per litre of solution. The capacity of the plant is to be 14.1 kg of uranium per hour. The main equipment used in the system is as follows: 1. Ring-type heat exchanger, for increasing the temperature of the mixture of fresh and recirculated solution from 80 to 115 0 C; 2. Separation tank, in which instant evaporation is carried out. The absolute pressure inside the tank will be 500 mmHg, with steam separation from a concentrated (78.5 wt.%) uranyl nitrate solution; 3. Desuperheater-condenser of horizontal tubular type for condensing water vapour and recovering any uranyl nitrate that may have been entrained; 4. Storage tank for the concentrate, with a capacity for one day's normal operation, and a heating coil to prevent crystallization of the concentrated solution; 5. Two storage tanks for feed and condensate with capacity for one day's normal operation; 6. Supporting structure for the above components. Virtually all equipment in contact with the uranyl nitrate solution will be made of 304 stainless steel. Saturated steam at 143.3 0 C will be required. The cost of the proposed system is $543 030.00. (author)

Synthesis of microspheres of triuranium octaoxide by simultaneous water and nitrate extraction from ascorbate-uranyl sols

International Nuclear Information System (INIS)

Brykala, M.; Deptula, A.; Rogowski, M.; Lada, W.; Olczak, T.; Wawszczak, D.; Smolinski, T.; Wojtowicz, P.; Modolo, G.

2014-01-01

A new method for synthesis of uranium oxide microspheres (diameter <100 μm) has been developed. It is a variant of our patented Complex Sol-Gel Process, which has been used to synthesize high-quality powders of a wide variety of complex oxides. Starting uranyl-nitrate-ascorbate sols were prepared by addition of ascorbic acid to uranyl nitrate hexahydrate solution and alkalizing by aqueous ammonium hydroxide and then emulsified in 2-ethylhexanol-1 containing 1v/o SPAN-80. Drops of emulsion were firstly gelled by extraction of water by the solvent. Destruction of the microspheres during thermal treatment, owing to highly reactive components in the gels, requires modification of the gelation step by Double Extraction Process-simultaneously extraction of water and nitrates using Primene JMT, which completely eliminates these problem. Final step was calcination in air of obtained microspheres of gels to triuranium octaoxide. (author)

Extraction of rare earth metals (3) from aqueous solutions containing thorium and uranyl nitrates

International Nuclear Information System (INIS)

Pyartman, A.K.; Kopyrin, A.A.; Berinskij, A.E.; Keskinov, V.A.

2000-01-01

Isotherms of extraction of rare earth metals (3) from aqueous solutions containing thorium and uranyl nitrates by solutions of tributylphosphate (TBP) and diisooctylmethylphosphonate (DIOMP) in kerosene at 298.15 Deg C and pH 1 are presented. Equations for description of interphase distribution of components of the systems considered are suggested. These equations describe distribution of components adequately in the systems of thorium nitrate (uranyl nitrate) - rare earth nitrates - (TBP, DIOMP) in the case of wide variation of phase compositions. Dependences of separation factors on composition of aqueous phase are considered [ru

The treatment of uranyl nitrate from the AMOR process for VKTA Rossendorf

International Nuclear Information System (INIS)

Boessert, W.; Krempl, R.; Miller, J.W.

2003-01-01

The blending of uranyl nitrate solutions at VKTA and its subsequent treatment at BNFL-Sellafield is a significant step towards the safe and effective treatment of these enriched uranyl nitrate solutions. Overall the integration of the expertise of the international company BNFL/Westinghouse will lead to the achievement of a successful solution. This success has involved the integration of the project management and operational facilities of BNFL Sellafield with the local planning, design and manufacture capacities of Westinghouse Reaktor GmbH. (orig.)

Standard test method for isotopic analysis of hydrolyzed uranium hexafluoride and uranyl nitrate solutions by thermal ionization mass spectrometry

CERN Document Server

American Society for Testing and Materials. Philadelphia

2005-01-01

1.1 This method applies to the determination of isotopic composition in hydrolyzed nuclear grade uranium hexafluoride. It covers isotopic abundance of 235U between 0.1 and 5.0 % mass fraction, abundance of 234U between 0.0055 and 0.05 % mass fraction, and abundance of 236U between 0.0003 and 0.5 % mass fraction. This test method may be applicable to other isotopic abundance providing that corresponding standards are available. 1.2 This test method can apply to uranyl nitrate solutions. This can be achieved either by transforming the uranyl nitrate solution to a uranyl fluoride solution prior to the deposition on the filaments or directly by depositing the uranyl nitrate solution on the filaments. In the latter case, a calibration with uranyl nitrate standards must be performed. 1.3 This test method can also apply to other nuclear grade matrices (for example, uranium oxides) by providing a chemical transformation to uranyl fluoride or uranyl nitrate solution. 1.4 This standard does not purport to address al...

Complete removal of uranyl nitrate from tissue matrix using supercritical fluid extraction

International Nuclear Information System (INIS)

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

2003-01-01

The removal of uranyl nitrate from tissue matrix has been studied with supercritical carbon dioxide modified with methanol alone as well as complexing reagents dissolved in methanol. A systematic study of various complexing agents led to the development of an extraction procedure for the quantitative recovery of uranium from tissue matrix with supercritical carbon dioxide modified with methanol containing small quantities of acetylacetone. The drying time and temperature employed in loading of uranyl nitrate onto tissue paper were found to influence the extraction efficiency significantly

Skin contamination resulting from an uranyl nitrate burn. An incident study

International Nuclear Information System (INIS)

Quesne, B.; Auriol, B.; Berard, P.; Chalabreysse, J.

1993-01-01

The authors describe the circumstances of a burn incident on hand by a mixture of diluted nitric acid and uranyl nitrate. The burn is located on the left hand fingers. After important washings uranium remains on the fingers. During about ten days, the worker is examined and the therapy is going on till the total radioactivity disappearance. Urine collection of twenty four hours is prescribed during the treatment. The whole activity is kept on the burnt skin. The quick desquamation is the elimination way of the skin retention. 6 refs., 3 figs., 4 tabs

Uranyl nitrate-exposed rat alveolar macrophages cell death: Influence of superoxide anion and TNF α mediators

International Nuclear Information System (INIS)

Orona, N.S.; Tasat, D.R.

2012-01-01

Uranium compounds are widely used in the nuclear fuel cycle, military and many other diverse industrial processes. Health risks associated with uranium exposure include nephrotoxicity, cancer, respiratory, and immune disorders. Macrophages present in body tissues are the main cell type involved in the internalization of uranium particles. To better understand the pathological effects associated with depleted uranium (DU) inhalation, we examined the metabolic activity, phagocytosis, genotoxicity and inflammation on DU-exposed rat alveolar macrophages (12.5–200 μM). Stability and dissolution of DU could differ depending on the dissolvent and in turn alter its biological action. We dissolved DU in sodium bicarbonate (NaHCO 3 100 mM) and in what we consider a more physiological vehicle resembling human internal media: sodium chloride (NaCl 0.9%). We demonstrate that uranyl nitrate in NaCl solubilizes, enters the cell, and elicits its cytotoxic effect similarly to when it is diluted in NaHCO 3 . We show that irrespective of the dissolvent employed, uranyl nitrate impairs cell metabolism, and at low doses induces both phagocytosis and generation of superoxide anion (O 2 − ). At high doses it provokes the secretion of TNFα and through all the range of doses tested, apoptosis. We herein suggest that at DU low doses O 2 − may act as the principal mediator of DNA damage while at higher doses the signaling pathway mediated by O 2 − may be blocked, prevailing damage to DNA by the TNFα route. The study of macrophage functions after uranyl nitrate treatment could provide insights into the pathophysiology of uranium‐related diseases. -- Highlights: ► Uranyl nitrate effect on cultured macrophages is linked to the doses and independent of its solubility. ► At low doses uranyl nitrate induces generation of superoxide anion. ► At high doses uranyl nitrate provokes secretion of TNFα. ► Uranyl nitrate induces apoptosis through all the range of doses tested.

Uranyl nitrate-exposed rat alveolar macrophages cell death: Influence of superoxide anion and TNF α mediators

Energy Technology Data Exchange (ETDEWEB)

Orona, N.S. [School of Science and Technology, National University of General Martín, Avda Gral Paz 5445 (1650) San Martín, Buenos Aires (Argentina); Tasat, D.R., E-mail: deborah.tasat@unsam.edu.ar [School of Science and Technology, National University of General Martín, Avda Gral Paz 5445 (1650) San Martín, Buenos Aires (Argentina); School of Dentistry, University of Buenos Aires, M. T. de Alvear 2142 (1122), Buenos Aires (Argentina)

2012-06-15

Uranium compounds are widely used in the nuclear fuel cycle, military and many other diverse industrial processes. Health risks associated with uranium exposure include nephrotoxicity, cancer, respiratory, and immune disorders. Macrophages present in body tissues are the main cell type involved in the internalization of uranium particles. To better understand the pathological effects associated with depleted uranium (DU) inhalation, we examined the metabolic activity, phagocytosis, genotoxicity and inflammation on DU-exposed rat alveolar macrophages (12.5–200 μM). Stability and dissolution of DU could differ depending on the dissolvent and in turn alter its biological action. We dissolved DU in sodium bicarbonate (NaHCO{sub 3} 100 mM) and in what we consider a more physiological vehicle resembling human internal media: sodium chloride (NaCl 0.9%). We demonstrate that uranyl nitrate in NaCl solubilizes, enters the cell, and elicits its cytotoxic effect similarly to when it is diluted in NaHCO{sub 3}. We show that irrespective of the dissolvent employed, uranyl nitrate impairs cell metabolism, and at low doses induces both phagocytosis and generation of superoxide anion (O{sub 2}{sup −}). At high doses it provokes the secretion of TNFα and through all the range of doses tested, apoptosis. We herein suggest that at DU low doses O{sub 2}{sup −} may act as the principal mediator of DNA damage while at higher doses the signaling pathway mediated by O{sub 2}{sup −} may be blocked, prevailing damage to DNA by the TNFα route. The study of macrophage functions after uranyl nitrate treatment could provide insights into the pathophysiology of uranium‐related diseases. -- Highlights: ► Uranyl nitrate effect on cultured macrophages is linked to the doses and independent of its solubility. ► At low doses uranyl nitrate induces generation of superoxide anion. ► At high doses uranyl nitrate provokes secretion of TNFα. ► Uranyl nitrate induces apoptosis through

Determination of small amounts of nitric acid in the presence of large amounts of uranium (VI) and extraction of nitric acid into TBP solutions highly loaded with uranyl nitrate

International Nuclear Information System (INIS)

Kolarik, Z.; Schuler, R.

1982-10-01

A new method for the determination of small amounts of nitric acid in the presence of large amounts of uranium(VI) was elaborated. The method is based on the precipitation of uranium(VI) as iodate and subsequent alkalimetric titration of the acid in the supernatant. The extraction of nitric acid and uranium(VI) with 30% TBP in dodecane was studied at high loading of the organic phase with uranyl nitrate and at 25, 40 and 60 0 C. The results are compared with available published data on the extraction of nitric acid under similar conditions. (orig.) [de

Liquid-liquid extraction kinetics of uranyl nitrate and actinides (III)-lanthanides nitrates by extractants with amide function

International Nuclear Information System (INIS)

Toulemonde, V.

1995-01-01

Nowadays, the most important part of electric power is generated by fission energy. But spent fuels have then to be reprocessed. The production of these reprocessed materials separately and with a high purity level is done according to a liquid-liquid extraction process (Purex process) with the use of tributyl phosphate as solvent. Optimization studies concerning the extracting agent have been undertaken. This work gives the results obtained for the uranyl nitrate and the actinides (III)-lanthanides (III) nitrates extraction by extractants with amide function (monoamide for U(VI) and diamide for actinides (III) and lanthanides (III)). The extraction kinetics have been studied in the case of a metallic specie transfer from the aqueous phase towards the organic phase. The experiments show that the nitrates extraction kinetics is limited by the complexation chemical reaction of the species at the interface between the two liquids. An adsorption-desorption interfacial reactional mechanism (Langmuir theory) is proposed for the uranyl nitrate. (O.M.)

Renal handling of drugs in renal failure. I: Differential effects of uranyl nitrate- and glycerol-induced acute renal failure on renal excretion of TEAB and PAH in rats

International Nuclear Information System (INIS)

Lin, J.H.; Lin, T.H.

1988-01-01

Two etiologically different models of experimental acute renal failure were induced in rats by administration of either glycerol or uranyl nitrate. Both compounds caused a substantial decrease in the glomerular filtration rate (GFR) and the net tubular secretion of tetraethylammonium bromide (TEAB) and para-aminohippuric acid (PAH). The degree of renal impairment induced by uranyl nitrate and glycerol appeared to be dose related. Deprivation of drinking water 24 hr before the administration of glycerol potentiated the renal damage. In uranyl nitrate-induced renal failure, the decline of the net tubular secretion for TEAB and PAH was not proportional to the decrease in GFR; the secretion process deteriorated faster than the GFR. For example, when 0.5 mg/kg uranyl nitrate was administered, GFR fell to approximately 65% of normal, whereas the net tubular secretion was decreased to 30% of normal. These results suggest that the tubular transport was preferentially affected by uranyl nitrate. In contrast, in glycerol-induced renal failure, the decline of TEAB secretion fell in a parallel fashion with the GFR, suggesting that the glomeruli and the proximal tubules were equally damaged by glycerol. However, in this latter model, the decline of PAH secretion did not parallel the decrease in GFR, contradicting the proposal that glycerol affects equally the glomeruli and the proximal tubules. This discrepancy may be due to the selective competitive inhibition of PAH secretion by the accumulation of naturally occurring organic acids

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

International Nuclear Information System (INIS)

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

2013-01-01

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

First start-up of nuclear criticality safety experiment facility for uranyl nitrate solution

International Nuclear Information System (INIS)

Zhu Qingfu; Shi Yongqian; Shen Leisheng; Hu Dingsheng; Zhao Shouzhi; He Tao; Sun Zheng; Lin Shenghuo; Yao Shigui

2005-01-01

The uranyl nitrate solution experiment facility for the research on nuclear criticality safety is described. The nuclear fuel loading steps in the first start-up for water-reflected core are presented. During the experiments, the critical volume of uranyl nitrate solution was determined as 20479.62 mL with count rate inverse extrapolation method, reactivity interpolation method, and steady power method. By calculation, critical mass of 235 U was derived as 1579.184 g from experimental data. The worth of control rods was also calibrated in the first start-up of the facility. (authors)

Synthesis of microspheres of triuranium octaoxide by simultaneous water and nitrate extraction from ascorbate-uranyl sols.

Science.gov (United States)

Brykala, M; Deptula, A; Rogowski, M; Lada, W; Olczak, T; Wawszczak, D; Smolinski, T; Wojtowicz, P; Modolo, G

A new method for synthesis of uranium oxide microspheres (diameter nitrate-ascorbate sols were prepared by addition of ascorbic acid to uranyl nitrate hexahydrate solution and alkalizing by aqueous ammonium hydroxide and then emulsified in 2-ethylhexanol-1 containing 1v/o SPAN-80. Drops of emulsion were firstly gelled by extraction of water by the solvent. Destruction of the microspheres during thermal treatment, owing to highly reactive components in the gels, requires modification of the gelation step by Double Extraction Process-simultaneously extraction of water and nitrates using Primene JMT, which completely eliminates these problem. Final step was calcination in air of obtained microspheres of gels to triuranium octaoxide.

Tritium distribution ratios between the 30 % tributyl phosphate(TBP)-normal dodecane(nDD) organic phase and uranyl nitrate-nitric acid aqueous phase

International Nuclear Information System (INIS)

Fujine, Sachio; Uchiyama, Gunzou; Sugikawa, Susumu; Maeda, Mitsuru; Tsujino, Takeshi.

1989-10-01

Tritium distribution ratios between the organic and aqueous phases were measured for the system of 30 % tributyl phosphate(TBP)-normal dodecane(nDD)/uranyl nitrate-nitric acid water. It was confirmed that tritium is extracted by TBP into the organic phase in both chemical forms of tritiated water (HTO) and tritiated nitric acid (TNO 3 ). The value of tritium distribution ratio ranged from 0.002 to 0.005 for the conditions of 0-6 mol/L nitric acid, 0.5-800 mCi/L tritium in aqueous phase, and 0-125 g-U/L uranium in organic phase. Isotopic distribution coefficient of tritium between the organic and aqueous phases was observed to be about 0.95. (author)

Determination of uranium in uranyl nitrate solutions of nuclear grade quality - Gravimetric method

International Nuclear Information System (INIS)

1990-01-01

This international Standard specifies a precise and accurate gravimetric method for determining the uranium content in uranyl nitrate product solutions of nuclear grade quality at concentrations above 100 g/l of uranium. Non-volatile impurities influence the accuracy of the method. Uranyl nitrate is converted into uranium octoxide (U 3 O 8 ) by ignition in air to constant mass at 900 deg. C ± 10 deg. C. Calculation of the uranium content in the sample using a gravimetric conversion factor which depends on the isotopic composition of the uranium. The isotopic composition is determined by mass spectrometry

Thermal decomposition of uranyl nitrate hexahydrate. Study of intermediate reaction products; Decomposition thermique du nitrate d'uranyle hexahydrate etude des intermediaires de cette decomposition

Energy Technology Data Exchange (ETDEWEB)

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

1970-07-01

The thermal decomposition of uranyl nitrate hexahydrate has been carried but at constant pressure and constant rate of reaction. The following intermediary products have been shown to exist and isolated: UO{sub 2}(NO{sub 3}){sub 2}.3H{sub 2}O; UO{sub 2}(NO{sub 3}){sub 2}. 2H{sub 2}O; UO{sub 2}(NO{sub 3}){sub 2}. H{sub 2}O; UO{sub 2}(NO{sub 3}){sub 2} and UO{sub 3}. These products, together with the hexahydrate UO{sub 2} (NO{sub 3}){sub 2}.6H{sub 2}O, have been studied by: - X-ray diffraction, using the Debye-Scherrer method.- infra-red spectrography: determination of the type of bonding for the water and the nitrate groups. - nuclear magnetic resonance: study of the mobility of water molecules. The main results concern: - the water molecule bonds in the series of hydrates with 6.3 and 2 H{sub 2}O. - isolation and characterization of uranyl nitrate monohydrate, together with the determination of its molecular structure. - the mobility of the water molecules in the series of the hydrates with 6.3 and 2 H{sub 2}O. An analysis is made of the complementary results given by infra-red spectroscopy and nuclear magnetic resonance; they are interpreted for the whole of the hydrate series. [French] La decomposition thermique du nitrate d'uranyle hexahydrate a ete effectuee en operant a pression et vitesse de decomposition constantes. Les produits intermediaires suivants ont ete mis en evidence et isoles: UO{sub 2}(NO{sub 3}){sub 2}, 3H{sub 2}O; UO{sub 2}(NO{sub 3}){sub 2}, 2H{sub 2}O; UO{sub 2}(NO{sub 3}){sub 2},H{sub 2}O; UO{sub 2}(NO{sub 3}){sub 2} et UO{sub 3}. Ces composes, ainsi que l'hexahydrate UO{sub 2}(NO{sub 3} ){sub 2}, 6H{sub 2}O ont ete etudies par: - diffraction des rayons X, selon la methode Debye-Scherrer.- spectrographie infra-rouge: determination des modes de liaison de l'eau et des groupements nitrate. - resonance magnetique nucleaire: etude de la mobilite des molecules d'eau. Les principaux resultats portent sur: - les liaisons des molecules d'eau dans la

HTGR fuel development: loading of uranium on carboxylic acid cation-exchange resins using solvent extraction of nitrate

International Nuclear Information System (INIS)

Haas, P.A.

1975-09-01

The reference fuel kernel for recycle of 233 U to HTGR's (High-Temperature Gas-Cooled Reactors) is prepared by loading carboxylic acid cation-exchange resins with uranium and carbonizing at controlled conditions. The purified 233 UO 2 (NO 3 ) 2 solution from a fuel reprocessing plant contains excess HNO 3 (NO 3 - /U ratio of approximately 2.2). The reference flowsheet for a 233 U recycle fuel facility at Oak Ridge uses solvent extraction of nitrate by a 0.3 M secondary amine in a hydrocarbon diluent to prepare acid-deficient uranyl nitrate. This nitrate extraction, along with resin loading and amine regeneration steps, was demonstrated in 14 runs. No significant operating difficulties were encountered. The process is controlled via in-line pH measurements for the acid-deficient uranyl nitrate solutions. Information was developed on pH values for uranyl nitrate solution vs NO 3 - /U mole ratios, resin loading kinetics, resin drying requirements, and other resin loading process parameters. Calculations made to estimate the capacities of equipment that is geometrically safe with respect to control of nuclear criticality indicate 100 kg/day or more of uranium for single nitrate extraction lines with one continuous resin loading contactor or four batch loading contactors. (auth)

Establishing the traceability of a uranyl nitrate solution to a standard reference material

International Nuclear Information System (INIS)

Jackson, C.H.; Clark, J.P.

1978-01-01

A uranyl nitrate solution for use as a Working Calibration and Test Material (WCTM) was characterized, using a statistically designed procedure to document traceability to National Bureau of Standards Reference Material (SPM-960). A Reference Calibration and Test Material (PCTM) was prepared from SRM-960 uranium metal to approximate the acid and uranium concentration of the WCTM. This solution was used in the characterization procedure. Details of preparing, handling, and packaging these solutions are covered. Two outside laboratories, each having measurement expertise using a different analytical method, were selected to measure both solutions according to the procedure for characterizing the WCTM. Two different methods were also used for the in-house characterization work. All analytical results were tested for statistical agreement before the WCTM concentration and limit of error values were calculated. A concentration value was determined with a relative limit of error (RLE) of approximately 0.03% which was better than the target RLE of 0.08%. The use of this working material eliminates the expense of using SRMs to fulfill traceability requirements for uranium measurements on this type material. Several years' supply of uranyl nitrate solution with NBS traceability was produced. The cost of this material was less than 10% of an equal quantity of SRM-960 uranium metal

Bases for DOT exemption uranyl nitrate solution shipments

International Nuclear Information System (INIS)

Moyer, R.A.

1982-07-01

Uranyl nitrate solutions from a Savannah River Plant reprocessing facility have been transported in cargo tank trailers for more than 20 years without incident during transit. The solution is shipped to Oak Ridge for further processing and returned to SRP in a solid metal form for recycle. This solution, called uranyl nitrate hexahydrate (UNH) solution in Department of Transportation (DOT) regulations, is currently diluted about 2-fold to comply with DOT concentration limits (10% of low specific activity levels) specified for bulk low specific activity (LSA) liquid shipments. Dilution of the process solution increases the number of shipments, the cost of transportation, the cost of shipper preparations, the cost of further reprocessing in the receiving facility to first evaporate the added water, and the total risk to the population along the route of travel. However, the radiological risk remains about the same. Therefore, obtaining an exemption from DOT regulations to permit shipment of undiluted UNH solution, which is normally about two times the present limit, is prudent and more economical. The radiological and nonradiological risks from shipping a unit load of undiluted solution are summarized for the probable route. Data and calculations are presented on a per load or per shipment basis throughout this memorandum to keep it unclassified

The system uranyl nitrate-dietyl ether-water. Extraction by water in spray and packed columns from uranyl nitrate-either solutions

International Nuclear Information System (INIS)

Perez Luina, A.; Gutierrez Jodra, L.

1960-01-01

This paper is a continuation of the one published in Chemical Engineering Progress. Symposium Series, 50, n. 12, 127 (1954). New runs for spray columns, are given and other concentrations in uranyl nitrate for the packed columns. New correlations for the overall H.T.U. are also given. The individual H.T.U. have been grapycally calculated and show that the film resistances have similar values, being independent of the concentration of the ether phase. (Author) 24 refs

Water-Reflected 233U Uranyl Nitrate Solutions in Simple Geometry

International Nuclear Information System (INIS)

Elam, K.R.

2001-01-01

A number of critical experiments involving 233 U were performed in the Oak Ridge National Laboratory Building 9213 Critical Experiments Facility during the years 1952 and 1953. These experiments, reported in Reference 1, were directed toward determining bounding values for the minimum critical mass, minimum critical volume, and maximum safe pipe size of water-moderated solutions of 233 U. Additional information on the critical experiments was found in the experimental logbooks. Two experiments utilizing uranyl nitrate (UO 2 (NO 3 ) 2 ) solutions in simple geometry are evaluated in this report. Experiment 37 is in a 10.4-inch diameter sphere, and Experiment 39 is in a 10-inch diameter cylinder. The 233 U concentration ranges from 49 to 62 g 233 U/l. Both experiments were reflected by at least 6 inches of water in all directions. Paraffin-reflected uranyl nitrate experiments, also reported in Reference 1, are evaluated elsewhere. Experiments with smaller paraffin reflected 5-, 6-, and 7.5-inch diameter cylinders are evaluated in U233-SOL-THERM-004. Experiments with paraffin reflected 8-, 8.5-, 9-, 10-, and 12-inch diameter cylinders are evaluated in U233-SOL-THERM-002. Later experiments with highly-enriched 235 U uranyl fluoride solution in the same 10.4-inch diameter sphere are reported in HEU-SOL-THERM-010. Both experiments were judged acceptable for use as criticality-safety benchmark experiments

Contribution to the study of uranyl salts in butyl phosphate solutions; Contribution a l'etude des solutions de sels d'uranyle dans les phosphates butyliques

Energy Technology Data Exchange (ETDEWEB)

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

1965-06-01

A spectroscopic study in the normal infrared region and involving the following associations: tri-alkyl phosphates (tri-butyl, tri-ethyl, tri-methyl), uranyl salts (nitrate, chloride, acetate) has confirmed the existence of an interaction between the phosphoryl group and the uranium atom, as shown by a movement of absorption band for the valency P = 0 from {approx} 1270 cm{sup -1} to {approx} 1180 cm{sup -1}. A study of the preparation, analysis and spectroscopy of the solids obtained by the precipitation of uranyl salts by acid butyl phosphates has been carried out. By infrared spectrophotometry it has been shown that the tri-butyl and di-butyl phosphates are associated in non-polar diluents even before the uranium is introduced. The extraction of uranyl salts from acid aqueous solutions by a diluted mixture of tri-butyl and di-butyl phosphates proceeds by different mechanisms according to the nature of the ion (nitrate or chloride). (author) [French] Une etude spectroscopique dans l'infrarouge moyen portant sur les associations: - phosphates trialcoyliques (tributylique - triethylique - trimethylique) - sels d'uranyle (nitrate, chlorure, acetate) a confirme l'existence d'une interaction entre le groupement phosphoryle et l'atome d'uranium, se manifestant par un deplacement de la bande d'absorption de la vibration de valence P = 0 de {approx} 1270 cm{sup -1} a {approx} 1180 cm{sup -1}. Une etude preparative, analytique et spectroscopique des solides obtenus par precipitation de sels d'uranyle par les phosphates butyliques acides a ete effectuee. La spectrophotomerie infrarouge met en evidence l'association, anterieure a toute introduction d'uranium, des phosphates tributylique et dibutylique dans des diluants non polaires. L'extraction de sels d'uranyle, d'une solution aqueuse acide par un melange dilue de phosphates tributylique et dibutylique, s'effectue suivant des processus differents a la nature de l'anion (nitrate ou chlorure). (auteur)

Physico-chemical study of new functionalized surfactants having thermo sensitive de-mixing behaviour: use in extraction of uranyl nitrate

International Nuclear Information System (INIS)

Prevost, S.

2006-04-01

New thermo-sensitive functionalized surfactants with metal-chelating properties have been developed and their physical-chemistry studied. They associate a polyethoxylated nonionic surfactant (CiEj) block and a amino-acid residue as a chelating group. Functionalization preserves both properties of the thermo-sensitive surfactant moiety and the chelating group, a diamide closed to uranyl ionophore.The complexing group participates to the polar head group of the surfactant, increasing the area per molecule. As a result, functionalized surfactants form spherical micelles when diluted in water, and the concentrated part of their phase diagrams exhibits structures having higher curvatures than the nonionic precursor CiEj. The structure of the uranyl - diamide complex has been elucidated by NMR and ESI-MS and is of the type UO 2 (NO 3 ) 2 .L; the associated complexation constant, which is very low, has been evaluated by 1 H NMR.A nitrate salt, LiNO 3 , is added at high concentration to improve complexation. The effect of this salt has been analyzed, and was found to be rather similar to the effect on classical CiEj. When uranyl nitrate complexation occurs, the cloud point decreases dramatically, together with the reduction of the area per head group at micelle/solution interface. This effect can be minimized by using a nonionic precursor having a larger polar head group. The functionalized surfactants have been tested in the cloud point extraction of uranyl nitrate, and have proved their efficiency. Those results demonstrate the viability of the functionalized surfactants design, with a covalent link between a thermo-sensitive surfactant block and a chelating group. (author)

TG/DTA and X ray Diffraction Studies on Ammonium Uranyl Nitrate

International Nuclear Information System (INIS)

Kim, Byung Ho; Lee, Young Bum; Jeong, Ji Young; Choi, Jong Hyun; Kim, Tae Joon; Nam, Ho Yun; Kim, Jong Man

2011-01-01

Ammonium uranyl nitrate (AUN) is an important intermediate product during conversion of a uranyl nitrate[UO 2 (NO 3 ) 2 ] solution to UO 2 powder for the fabrication of nuclear fuels, the so-called modified direct denitration (MDD) process. The MDD process involves the thermal decomposition of AUN double salts, which are prepared from a mixture consisting of a UO 2 (NO 3 ) 2 solution and NH 4 NO 3 . The physical and chemical properties of an oxide powder depend upon its thermal treatment. Three double salts are known for the UO 2 (NO 3 ) 2 - NH 4 NO 3 -H 2 O system, but there have been only a few studies done on thermal decomposition of these salts. Therefore, the objective of this study is to investigate the reaction pathways during a thermal decomposition and reduction of AUN to achieve a better knowledge of the influence of an AUN preparation process and thermal decomposition procedures on uranium oxides under a nitrogen, air, or hydrogen atmosphere

Electrochemical studies on the reduction of uranyl ions in nitric acid-hydrazine media at platinum electrode

International Nuclear Information System (INIS)

Mishra, Satyabrata; Sini, K.; Mallika, C.; Kamachi Mudali, U.; Jagadeeswara Rao, Ch.

2015-01-01

Production of uranous nitrate with good conversion efficiency is one of the major steps in the aqueous reprocessing of spent fuels of nuclear reactors, as U(IV) is used for the separation of Pu from U by the selective reduction of Pu(IV) into practically non-extractable Pu(III) in aqueous streams. Electro-reduction of uranyl ions has the advantage of not introducing corrosive chemicals into the process stream. High current efficiency with maximum conversion of U(VI) to U(IV) can be achieved in continuous as well as batch mode electro-reduction, if the process is voltage-controlled rather than current controlled. As potentiostatic studies reveal the mechanism of reduction of uranyl ions in potential controlled electrolysis, the reduction behavior of uranyl ions (UO 2 2+ ) in nitric acid and nitric acid-hydrazine media were investigated by Cyclic Voltammetric (CV) and Chronopotentiometric (CP) techniques using platinum working electrode at 298 K. Heterogeneous electron transfer rate constant (ks) for uranyl reduction was estimated at a very low concentration of nitric acid (0.05 M) using Klinger and Kochi equation. Values of the diffusion coefficients were determined as a function of acidity with and without hydrazine. Reduction of uranyl ions was found to be under kinetic as well as diffusion control when the concentration of nitric acid was 0.05 M and in the absence of hydrazine. However, as the acidity of the supporting electrolyte increased, the reduction was purely under kinetic control. (author)

Properties and thermal decomposition of the double salts of uranyl nitrate-ammonium nitrate

International Nuclear Information System (INIS)

Notz, K.J.; Haas, R.A.

1989-01-01

The formation of ammonium nitrate-uranyl nitrate double salts has important effects on the thermal denitration process for the preparation of UO 3 and on the physical properties of the resulting product. Analyses were performed, and properties and decomposition behavior were determined for three double salts: NH 4 UO 2 (NO 3 ) 3 , (NH 4 ) 2 UO 2 (NO 3 ) 4 , and (NH 4 ) 2 UO 2 (NO 3 ) 4 ·2H 2 O. The tinitrate salt decomposes without melting at 270-300 C to give a γ-UO 3 powder of ∼3-μm average size, with good ceramic properties for fabrication into UO 2 nuclear fuel pellets. The tetranitrate dihydrate melts at 48 C; it also dehydrates to the anhydrous salt. The anhydrous tetranitrate decomposes exothermically, without melting, at 170-270 C by losing one mole of ammonium nitrate to form the trinitrate salt

High temperature interaction studies on equimolar nitrate mixture of uranyl nitrate hexahydrate and gadolinium nitrate hexahydrate

International Nuclear Information System (INIS)

Kalekar, Bhupesh B.; Raje, Naina; Reddy, A.V.R.

2015-01-01

Rare earths including gadolinium form a sizeable fraction of the fission products in the nuclear fission of fissile material in the reactor. These fission products can interact with uranium dioxide fuel and can form various compounds which can alter the thermal behavior of the fuel. The mixed oxide formed due to the high temperature interactions of mixture of uranyl nitrate hexahydrate (UNH) and gadolinium nitrate hexahydrate (GdNH) has been studied using thermal and X- ray diffraction techniques. The equimolar mixture of UNH and GdNH was prepared by mixing the weighed amount of individual nitrates and grinding gently with mortar and pestle. Thermogravimetry (TG) measurements were carried out by separately heating 100 mg of mixture and individual nitrates at heating rate of 10°C min -1 using Netzsch thermal analyzer (Model No.: STA 409 PC Luxx) in high purity nitrogen atmosphere with a flow rate of 120 mL min -1 . The XRD measurement was carried out on a Philips X-ray diffractometer (Model PW1710) using nickel-filtered Cu-Kα radiation

The research of technology and equipment for a microwave denitration process of the uranyl nitrate solution

International Nuclear Information System (INIS)

Bao Weimin; Wang Xuejun; Ma Xuquan; Shi Miaoyi; Zhang Zhicheng; Bao Zhu Tian.

1991-01-01

In order to improve the present process of converting the plutonium nitrate into oxide powder in the nuclear fuel cycle, a new conversion process for the direct denitration using microwave heating has been developed. Microwave denitration is based on intramolecular polarization of a material in electric field and has no need of a process of heat transfer during microwave heating, so that the whole material can be heated quickly and uniformly. The thermal decomposition reactions of Pu, U, Th and RE nitrate have been analyzed and compared. The uranyl nitrate solution was chosen as imitative plutonium nitrate solution. The performance parameters ε r tanδ of U, Th and RE nitrate and oxide in microwave field were measured. The data obtained show that all of them could absorb microwave energy well and cause heating decomposition reactions. The microwave denitration test unit was designed and made. Denitration tests for rare-earths nitrate and uranyl nitrate solutions were performed. It could be completed in one step that the uranyl nitrate solution was evaporated, dryed and denitrated in a vessel. The denitrated products are a porous lump and easy to scrape off from the denitration vessel. The main forms of the products UO 3 ·0.8H 2 O and U 3 O 8 which have excellent powder properties. The capacity of the denitration unit is 1.3 kg UO 3 /h. According to the experimental results the simplicity, feasibility and good repeatability of the process have been fully proved. The unit operates easily and is adaptable to conversion of nitrate in nuclear fuel cycle. (author)

Studying of the dehydration process of uranyl nitrate hexahydrate (Unh)

International Nuclear Information System (INIS)

Badalov, A.; Kamalov, J.J.; Homidov, B.J.; Mirsaidov, I.U.; Eshbekov, N.R.

2005-01-01

By the tensimeteric method is studying the dehydration process of uranyl nitrate hexahydrate (Unh). It is shown, that the temperature interval 300-400 K in equilibrium conditions the dehydration process of Unh runs in three stages. According to the equations of dependence of saturated steam pressure from temperature, the thermodynamic characteristics of each stage of the dehydration process of Unh are calculated

Calorimetric measurement of the enthalpy of extraction of uranyl nitrate by tri-n-amyl phosphate

International Nuclear Information System (INIS)

Srinivasan, T.G.; Vasudeva Rao, P.R.; Venugopal, V.; Sood, D.D.

2002-01-01

Enthalpy of extraction of uranyl nitrate by tri n-amyl phosphate (TAP) and its solutions in n-dodecane has been directly measured by solution calorimetry for the first time. Measurements have been made at 303±1 K, in both forward as well as the reverse extraction modes. The enthalpies of the accompanying reactions such as the dilution of the uranyl nitrate in the aqueous phase, the hydration of TAP, the mixing of TAP and n-dodecane, the mixing of the metal-solvate (UO 2 (NO 3 ) 2 ·2TAP) and n-dodecane and mixing of the metal-solvate and TAP have also been independently measured and used to derive both the equilibrium state enthalpies and the standard state enthalpies for the extraction. Two distinct standard states have been used for the organic phase, viz., 1) all solutes infinitely diluted in diluent (ΔH*) and 2) all solutes infinitely diluted in the water saturated extractant (ΔH 0 ). The results have been compared with the enthalpies of extraction measured by employing the temperature dependence of the distribution ratio as well as calorimetry reported in the literature for extraction of uranyl nitrate by TAP and TBP. (author)

New thermo-sensitive chelating surfactants for selective solvent-free extraction of uranyl nitrate

International Nuclear Information System (INIS)

Prevost, S.; Larpent, C.; Testard, F.; Coulombeau, H.; Baczko, K.; Berthon, L.; Desvaux, H.; Madic, C.; Zemb, T.

2004-01-01

Functional surfactants were synthesised by grafting a chelating group (amino-acid residue) to the tip of a poly-ethoxylated nonionic surfactant chain (C i E j : C i H 2i +1(OCH 2 CH 2 ) j OH)) or in a branched position. C i E j nonionic surfactants are known to be thermo-reversible and to exhibit a clouding phenomenon associated to phase separation of micelles. The functional surfactants retain both surface-active properties, characteristic thermo-reversible behaviour and have efficient complexing properties toward uranyl. In the presence of uranyl nitrate, small micelles are formed at ambient temperature and the de-mixing leads to a separation of the target ion trapped by the functional surfactant (cloud point extraction). Those surfactants are more efficient than mixture of classical C i E j and complexing agent solubilized in the micelles. This reveals a synergistic effect of the covalent bond between the chelating group and the nonionic surfactant C i E j . This paper presents a systematic study of the extraction and aggregation properties and the influence of the nature of the ions. (authors)

Determination of parameters dissolution of yellow-cake. Production of uranyl nitrate - Gas precipitation of AUC

International Nuclear Information System (INIS)

Mellah, A.

1987-07-01

The different stages of the purification cycle of yellow-cakes have been studied thoroughly in order to obtain an ammonium uranyl carbonate (AUC) as an intermediate product of uranium dioxide (UO 2 ). The optimal parameters of yellow-cake dissolution, filtration, extraction by solvent, scrubbing and stripping were determined. An original program of thermodynamic calculation was developed for the determination of the free energies of yellow-cake dissolution reactions. Different numerical methods were used to determine the kinetic constant, the reaction order and correlation equations of uranyl nitrate density as a function of U and H + concentrations, before and after the extraction cycle. For the first time, Algerian filteraids were used for the filtration of uranyl nitrate solutions with satisfactory results. A laboratory designed installation enabled the precipitation of AUC by injection of ammonia and carbon dioxide gases. Interesting results have been obtained and further investigations should be carried out in order to optimize all the paremeters of the gas precipitation of AUC

Quantification of uranyl in presence of citric acid

International Nuclear Information System (INIS)

Garcia G, N.; Barrera D, C.E.; Ordonez R, E.

2007-01-01

To determine the influence that has the organic matter of the soil on the uranyl sorption on some solids is necessary to have a detection technique and quantification of uranyl that it is reliable and sufficiently quick in the obtaining of results. For that in this work, it intends to carry out the uranyl quantification in presence of citric acid modifying the Fluorescence induced by UV-Vis radiation technique. Since the uranyl ion is very sensitive to the medium that contains it, (speciation, pH, ionic forces, etc.) it was necessary to develop an analysis technique that stands out the fluorescence of uranyl ion avoiding the out one that produce the organic acids. (Author)

Modeling of critical experiments employing Raschig rings in uranyl nitrate solution

International Nuclear Information System (INIS)

Tanner, J.E.

1989-01-01

Four critical experiments employing borated glass rings in concentrated uranyl nitrate solution yielded k eff higher by 0. 04 when modeled with a flux-weighted, homogenized cross section set than when modeled with discrete rings. k eff varied by 0.014 for a 10% boron uncertainty and by up to 0.04 for a 10% packing fraction uncertainty

Cutaneous contamination after a uranyl nitrate skin burn: incident report

International Nuclear Information System (INIS)

Berard, P.; Chalabreysse, J.; Quesne, B.; Auriol, B.

1994-01-01

The authors review the circumstances of a handburn incident by a mixture of dilute nitric acid and uranyl nitrate. The burn was localised on the thumb and three fingers of the left hand. After abundant washing, external direct measurements revealed the presence of uranium on the fingers. The injured employee was maintained under observation for ten days, and therapy was performed until all the activity disappeared. External monitoring with various detectors, and measurements of the bandages and skin showed a rapid decrease of uranium fixation. All urine was collected throughout the duration of the treatment. The study shows that all the activity was retained on the burnt skin, with very little systemic uptake. Rapid peeling eliminated the cutaneous retention. Internal and external dose assessments were calculated and the committed effective dose equivalent and the committed dose equivalent for the skin and bone surfaces were low. (author)

Contribution to the study of uranyl salts in butyl phosphate solutions; Contribution a l'etude des solutions de sels d'uranyle dans les phosphates butyliques

Energy Technology Data Exchange (ETDEWEB)

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

1965-06-01

A spectroscopic study in the normal infrared region and involving the following associations: tri-alkyl phosphates (tri-butyl, tri-ethyl, tri-methyl), uranyl salts (nitrate, chloride, acetate) has confirmed the existence of an interaction between the phosphoryl group and the uranium atom, as shown by a movement of absorption band for the valency P = 0 from {approx} 1270 cm{sup -1} to {approx} 1180 cm{sup -1}. A study of the preparation, analysis and spectroscopy of the solids obtained by the precipitation of uranyl salts by acid butyl phosphates has been carried out. By infrared spectrophotometry it has been shown that the tri-butyl and di-butyl phosphates are associated in non-polar diluents even before the uranium is introduced. The extraction of uranyl salts from acid aqueous solutions by a diluted mixture of tri-butyl and di-butyl phosphates proceeds by different mechanisms according to the nature of the ion (nitrate or chloride). (author) [French] Une etude spectroscopique dans l'infrarouge moyen portant sur les associations: - phosphates trialcoyliques (tributylique - triethylique - trimethylique) - sels d'uranyle (nitrate, chlorure, acetate) a confirme l'existence d'une interaction entre le groupement phosphoryle et l'atome d'uranium, se manifestant par un deplacement de la bande d'absorption de la vibration de valence P = 0 de {approx} 1270 cm{sup -1} a {approx} 1180 cm{sup -1}. Une etude preparative, analytique et spectroscopique des solides obtenus par precipitation de sels d'uranyle par les phosphates butyliques acides a ete effectuee. La spectrophotomerie infrarouge met en evidence l'association, anterieure a toute introduction d'uranium, des phosphates tributylique et dibutylique dans des diluants non polaires. L'extraction de sels d'uranyle, d'une solution aqueuse acide par un melange dilue de phosphates tributylique et dibutylique, s'effectue suivant des processus differents a la

Clinico-biochemical studies on acute toxic nephropathy in goats due to uranyl nitrate

Energy Technology Data Exchange (ETDEWEB)

Dash, P.K.; Joshi, H.C.

1989-02-01

Acute toxic nephropathy was produced in 6 healthy goats by injecting intravenously 1% uranyl nitrate (UN) (15 mg/kg body weight). The early painful clinical signs simulating shock progressed with subnormal temperature, slow-shallow respiration and arrhythmic pulse followed by death due to respiratory failure within 96 to 120 hr. All the affected goats had normocytic normochromic anemia, leucocytosis, neutrophilia with left shift eosinopenia, decreased monocytes and presence of 1-2% reticulocytes in the peripheral blood smears. On blood chemical analysis, a uniform and continuous rise was seen in serum creatinine with a concomitant daily increase of serum urea and uric acid. Simultaneous analysis of urine indicated polyuria leading to oliguria, acidic pH, albuminuria, glycosuria with presence of neutrophils, RBC's, epithelial and fatty casts, increase of triple phosphate, and cystine crystals reflecting acute damage of kidneys in the affected goats.

Clinico-biochemical studies on acute toxic nephropathy in goats due to uranyl nitrate

International Nuclear Information System (INIS)

Dash, P.K.; Joshi, H.C.

1989-01-01

Acute toxic nephropathy was produced in 6 healthy goats by injecting intravenously 1% uranyl nitrate (UN) (15 mg/kg body weight). The early painful clinical signs simulating shock progressed with subnormal temperature, slow-shallow respiration and arrhythmic pulse followed by death due to respiratory failure within 96 to 120 hr. All the affected goats had normocytic normochromic anemia, leucocytosis, neutrophilia with left shift eosinopenia, decreased monocytes and presence of 1-2% reticulocytes in the peripheral blood smears. On blood chemical analysis, a uniform and continuous rise was seen in serum creatinine with a concomitant daily increase of serum urea and uric acid. Simultaneous analysis of urine indicated polyuria leading to oliguria, acidic pH, albuminuria, glycosuria with presence of neutrophils, RBC's, epithelial and fatty casts, increase of triple phosphate, and cystine crystals reflecting acute damage of kidneys in the affected goats

PMR spectra and proton magnetic relaxation in uranyl nitrate-hexamethylenetetramine-urea-water gel forming system

International Nuclear Information System (INIS)

Vashman, A.A.; Pronin, I.S.; Brylkina, T.V.; Makarov, V.M.

1979-01-01

PMR spectra and proton relaxation in the nitrate-hexamethylenetetramine (HMTA)-urea-water gelling system are studied. According to PMR spectra products of HMTA chemical decomposition, which are supposed to be formed in the gelling process, have not been detected. Effect of hydrogen exchange upon PMR spectra of urea and water in the presence of HMTA and uranyl nitrate is studied. Periods of spin-lattice and spin-spin relaxations of water and HMTA protons in gels on the base of uranyl nitrate are found. Data on relaxation permitted to make qualitative conclusions upon the gel structure and HMTA molecule distribution over ''phases''. Nonproducibility of the results of period measurements in gels is the result of nonproducibility of the gel structure in the course of transformation of liquid solution into gel. Temperature dependences of proton relaxation in the gels are impossible yet to interpret on the basis of temperature behaviour of one correlation period, controlling dipole-dipole nuclear magnetic relaxation, and obeying Arrhenius dependence on the temperature

Critical experiments on low enriched uranyl nitrate solution with STACY

International Nuclear Information System (INIS)

Miyoshi, Yoshinori

1996-01-01

As the STACY started steady operations, systematic criticality data on low enriched uranyl nitrate solution system could be accumulated. Main experimental parameters for the cylindrical tank of 60 cm in diameter were uranium concentration and the reflector condition. Basic data on a simple geometry will be helpful for the validation of the standard criticality safety codes, and for evaluating the safety margin included in the criticality designs. Experiments on the reactivity effects of structural materials such as borated concrete and polyethylene are on schedule next year as the second series of experiments using 10 wt% enriched uranyl solution. Furthermore, neutron interacting experiments with two slab tanks will be performed to investigate the fundamental properties of neutron interaction effects between core tanks. These data will be useful for making more reasonable calculation models and for evaluating the safety margin in the criticality designs for the multiple unit system. (J.P.N.)

Obtention of Uo3 by means of denitration of uranyl nitrate in a fluidized-bed

International Nuclear Information System (INIS)

Santos, W.R. dos; Costa, P.A.

1990-01-01

A fluidized-bed pilot unit for the production of UO 3 installed at IPEN-CNEN/SP is described. Its capacity is of 20 kg U/h in a continuous process. The main components of this pilot unit are: a system for the concentration of nuclearly pure uranyl nitrate (≅ 100 g U/L), a system for the denitration of the concentrated uranyl nitrate, an absorption system for NO 2 produced during the denitration reaction and, finally, a system for the dissolution of UO 3 that does not meet the specifications. The operational troubles found during the initial runs are presented. The results of the physical and chemical analysis of the UO 3 produced are discussed and a comparison is made for the UO 3 obtained by both fluidized-bed and wet processes. (author) [pt

Uranyl fluoride luminescence in acidic aqueous solutions

International Nuclear Information System (INIS)

Beitz, J.V.; Williams, C.W.

1996-01-01

Luminescence emission spectra and decay rates are reported for uranyl species in acidic aqueous solutions containing HF or added NaF. The longest luminescence lifetime, 0.269 ± 0.006 ms, was observed from uranyl in 1 M HF + 1 M HClO 4 at 296 K and decreased with increasing temperature. Based on a luminescence dynamics model that assumes equilibrium among electronically excited uranyl fluoride species and free fluoride ion, this long lived uranyl luminescence in aqueous solution is attributed primarily to UO 2 F 2 . Studies on the effect of added LiNO 3 or Na 2 WO 4 ·2H 2 O showed relatively weak quenching of uranyl fluoride luminescence which suggests that high sensitivity determination of the UF 6 content of WF 6 gas should be feasible via uranyl luminescence analysis of hydrolyzed gas samples of impure WF 6

Luminescence enhancement of uranyl ion by benzoic acid in acetonitrile

International Nuclear Information System (INIS)

Satendra Kumar; Maji, S.; Joseph, M.; Sankaran, K.

2014-01-01

Uranyl ion is known for its characteristic green luminescence and therefore luminescence spectroscopy is a suitable technique for characterizing different uranyl species. In aqueous medium, luminescence of uranyl ion is generally weak due to its quenching by water molecules and therefore in order to enhance the luminescence of uranyl ion in aqueous medium, luminescence enhancing reagents such as H 3 PO 4 , H 2 SO 4 , HCIO 4 have been widely used. The other method to enhance the uranyl luminescence is by ligand sensitized luminescence, a method well established for lanthanides. In this work, luminescence of uranyl ion is found to be enhanced by benzoic acid in acetonitrile medium. In aqueous medium benzoic acid does not enhance the uranyl luminescence although it forms 1:1 and 1:2 complexes with uranyl ion. Luminescence spectra of uranyl benzoate revealed that enhancement is due to sensitization of uranyl luminescence by benzoate ions. UV-Vis spectroscopy has been utilized to characterize the specie formed in the in acetonitrile medium. UV-Vis spectroscopy along with luminescence spectra revealed that the specie to be tribenzoate complex of uranyl (UO 2 (C 6 H 5 COO) 3 ) - having D 3 h symmetry. (author)

Thermometric titration of a free acid and of uranyl in spent fuel element solutions

International Nuclear Information System (INIS)

Zamek, M.; Strafelda, F.

1975-01-01

A method was elaborated of determining nitric acid in the presence of uranyl nitrate in both aqueous and non-aqueous solutions using a pyridine aqueous solution as a titration agent, and of determining excess uranyl after a hydrogen peroxide addition by a further titration using the same agent. Even a hundred-fold excess of magnesium did not disturb the titration. The method is used in operating solution analyses in the extraction fuel reprocessing in the presence of a small amount of plutonium and of fission products. The reproducibility and accuracy of the method varied in the order of tens to units per cent depending on the concentration of components to be determined. The procedure is applicable for test volumes ranging between 0.1 and 10 ml in concentrations of 1 to 10 -3 M. (author)

Contribution to the study of uranyl salts in butyl phosphate solutions

International Nuclear Information System (INIS)

Coulon, A.

1965-06-01

A spectroscopic study in the normal infrared region and involving the following associations: tri-alkyl phosphates (tri-butyl, tri-ethyl, tri-methyl), uranyl salts (nitrate, chloride, acetate) has confirmed the existence of an interaction between the phosphoryl group and the uranium atom, as shown by a movement of absorption band for the valency P = 0 from ∼ 1270 cm -1 to ∼ 1180 cm -1 . A study of the preparation, analysis and spectroscopy of the solids obtained by the precipitation of uranyl salts by acid butyl phosphates has been carried out. By infrared spectrophotometry it has been shown that the tri-butyl and di-butyl phosphates are associated in non-polar diluents even before the uranium is introduced. The extraction of uranyl salts from acid aqueous solutions by a diluted mixture of tri-butyl and di-butyl phosphates proceeds by different mechanisms according to the nature of the ion (nitrate or chloride). (author) [fr

Rapid determination of fluoride in uranyl nitrate solution obtained in conversion process of uranium tetrafluoride

International Nuclear Information System (INIS)

Levin, R.; Feldman, R.; Sahar, E.

1976-01-01

In uranium production the conversion of impure uranium tetrafluoride by sodium hydroxide was chosen as a current process. A rapid method for determination of fluoride in uranyl-nitrate solution was developed. The method includes precipitation of uranium as diuranate, separation by centrifugation, and subsequent determination of fluoride in supernate by titration with thorium nitrate. Fluoride can be measured over the range 0.15-2.5 gr/gr U, with accuracy of +-5%, within 15 minutes. (author)

Nuclear fuel technology - Determination of uranium in uranyl nitrate solutions of nuclear grade quality - Gravimetric method

International Nuclear Information System (INIS)

2003-01-01

This International Standard specifies a precise and accurate gravimetric method for determining the mass fraction of uranium in uranyl nitrate solutions of nuclear grade quality containing more than 100 g/kg of uranium. Non-volatile impurities influence the accuracy of the method

Development of processes for pilot plant production of purified uranyl nitrate solutions

Energy Technology Data Exchange (ETDEWEB)

Alfredson, P. G.; Charlton, B. G.; Ryan, R. K.; Vilkaitis, V. K.

1975-01-15

Nuclear purity uranyl nitrate solutions were produced from Rum Jungle yellow cake by dissolution in nitric acid and purification by solvent extraction with 20 vol. per cent tributyl phosphate in kerosene using pump - mix mixer-settler contactors. The design of the equipment, experimental studies and operating experience are described. Dissolution of yellow cake and recycled uranium oxide materials was readily carried out in a 100 l dissolver to give solutions containing 300 gU l{sup -1} and 0.5 to 4 M nitric acid. Filtration of silica from this solution prior to solvent extraction was not necessary in this work for yellow cake containing 0.25 per cent silica. A low acid flowsheet for uranium purification was developed in which the nitric acid consumption was reduced by 76 per cent and the throughput of the mixer-settler units was increased by 67 per cent compared with the initial design flowsheet. Nine extraction and seven scrubbing stages were used with a feed solution containing 300 gU l{sup -1} and 1.0 M nitric acid and with a portion of the product recycled as scrub solution. The loaded organic phase was stripped in 16 stages with 0.05 M nitric acid heated to 60 deg C to give a 120 gU l{sup -1} product. The uranium concentration in the raffinate was < 0.04 g l{sup -1}, corresponding to approximately 0.01 per cent of the feed. (author)

Experience with a uranyl nitrate/uranium dioxide conversion pilot plant

International Nuclear Information System (INIS)

Arcuri, L.; Pietrelli, L.

1984-01-01

A plant for the precipitation of sinterable nuclear grade UO 2 powders is described in this report. The plant has been designed, built and set up by SNIA TECHINT. ENEA has been involved in the job as nuclear consultant. Main process steps are: dissolution of UO 2 powder or sintered UO 2 pellets, adjustment of uranyl nitrate solutions, precipitation of uranium peroxide by means of hydrogen peroxide, centrifugation of the precipitate, drying, calcination and reduction to uranium dioxide. The report is divided in two main section: the process description and the ''hot test'' report. Some laboratory data on precipitation of ammonium diuranate by means of NH 4 OH, are also reported

Process control for a continuous uranyl nitrate evaporator

International Nuclear Information System (INIS)

Peterson, S.F.; MacIntyre, L.P.

1984-07-01

A continuous uranyl nitrate evaporator at the Savannah River Plant (SRP) in Aiken, South Carolina ws the subject of this work. A rigorous mathematical model of the evaporator was developed. A difference equation form of the model was then constructed and used for control studies. Relative gain analysis was done on the system in order to identify any promising multivariable control schemes. Several alternate control schemes were modeled, tuned, and compared against the scheme presently in use at SRP. As the pneumatic specific gravity instrumentation at SRP is very noisy, the noise was simulated and used in the second phase of the control study. In this phase, alternate tuning methods and filters were invesigated and compared. The control studies showed that the control algorithm now in use at SRP is the simplest and best available. 10 references, 53 figures, 22 tables

Fabrication of ceramic grade UO2 by direct conversion of uranyl nitrate hexahydrate

International Nuclear Information System (INIS)

Lainetti, P.E.O.; Riella, H.G.

1992-01-01

A method of direct conversion of uranyl nitrate hexahydrate (UNH) solution to ceramic grade uranium dioxide powders by thermal denitration in a furnace that combines atomization nozzle and a gas stirred bed is described. The main purpose of this work is to show that this alternative process is technically viable, specially if the recovery of the scrap generated in the nuclear fuel pellet production is required, without further generation of new liquid wastes. (author)

Chemical, mass spectrometric, spectrochemical, nuclear, and radiochemical analysis of nuclear-grade uranyl nitrate solutions

International Nuclear Information System (INIS)

Anon.

1981-01-01

The standard covers analytical procedures to determine compliance of nuclear-grade uranyl nitrate solution to specifications. The following methods are described in detail: uranium by ferrous sulfate reduction-potassium dichromate titrimetry and by ignition gravimetry; specific gravity by pycnometry; free acid by oxalate complexation; thorium by the Arsenazo(III) (photometric) method; chromium by the diphenylcarbazide (photometric) method; molybdenum by the thiocyanate (photometric) method; halogens separation by steam distillation; fluorine by specific ion electrode; halogen distillate analysis: chloride, bromide and iodide by amperometric microtitrimetry; bromine by the fluorescein (photometric) method; sulfate sulfur by (photometric) turbidimetry; phosphorus by the molybdenum blue (photometric) method; silicon by the molybdenum blue (photometric) method; carbon by persulfate oxidation-acid titrimetry; nonvolatile impurities by spectrography; volatile impurities by rotating-disk spark spectrography; boron by emission spectrography; impurity elements by spark source mass spectrography; isotopic composition by multiple filament surface-ionization mass spectrometry; uranium-232 by alpha spectrometry; total alpha activity by direct alpha counting; fission product activity by beta and gamma counting; entrained organic matter by infrared spectrophotometry

Evaluation of renal function following administration of ethane-1-hydroxy-1,1-biphosphonate (EHBP) in animals submitted to oral intoxication with uranyl nitrate

International Nuclear Information System (INIS)

Martinez, A.B.; Mandalunis, P.M.; Bozal, C.B.; Cabrini, Romulo L.; Ubios, A.M.

2003-01-01

Workers involved in the processes of extraction, purification and manufacture of uranium of nuclear plants are occupationally exposed to both natural and enriched uranium. Several chelating agents (TIRON, EDTA, BAI, etc.) have been tested in terms of their capacity to sequester uranium before it reaches its target organs. Our laboratory has studied a first generation biphosphonate, ethane-1-hydroxy-1,1-biphosphonate (EHBP). We have shown that treatment with EHBP induces survival rates of 75% and 100% in adult and suckling rats respectively intoxicated with an intraperitoneal injection of uranyl nitrate. There are no data available to date on the renal function following treatment with EBHP to counteract the toxic effects of an oral lethal dose of uranyl nitrate. The aim of the present study was to assay creatininemia and uremia as end-points to assess renal function. The results obtained reveal that the alterations in renal function induced by oral uranyl nitrate intoxication can be reduced at 48 hours and reverted at 14 days by subcutaneous or oral administration of EHBP. (author)

Extraction with tributyl phosphate (TBP) from ferric nitrate solutions

International Nuclear Information System (INIS)

Kolarik, Z.; Grudpan, K.

1985-01-01

Ferric nitrate acts as a strong salting-out agent in the extraction of thorium(IV), uranyl, europium(III), samarium(III) and zirconium(IV) nitrates as well as of nitric acid with tributyl phosphate in dodecane. Nitric acid, if present in the extraction system together with large amounts of ferric nitrate, markedly suppresses the extraction of thorium(IV) and lanthanides(III) but significantly supports the extraction of zirconium(IV). Separation factors of different metal pairs are presented as functions of the concentrations of ferric nitrate and nitric acid

Minimum critical values of uranyl and plutonium nitrate solutions calculated by various routes of the french criticality codes system CRISTAL using the new isopiestic nitrate density law

International Nuclear Information System (INIS)

Anno, Jacques; Rouyer, Veronique; Leclaire, Nicolas

2003-01-01

This paper provides for various cases of 235 U enrichment or Pu isotopic vectors, and different reflectors, new minimum critical values of uranyl nitrate and plutonium nitrate solutions (H + =0) obtained by the standard IRSN calculation route and the new isopiestic density laws. Comparisons are also made with other more accurate routes showing that the standard one's results are most often conservative and usable for criticality safety assessments. (author)

Uranyl complexes as scaffolding or spacers for cucurbit[6]uril molecules in homo- and heterometallic species, including a uranyl-lanthanide complex

Energy Technology Data Exchange (ETDEWEB)

Thuery, Pierre [NIMBE, CEA, CNRS, Universite Paris-Saclay, CEA Saclay, Gif-sur-Yvette (France)

2017-06-16

The reaction of uranyl nitrate with cucurbit[6]uril (CB6) and carboxylic or sulfonic ligands under hydrothermal conditions and in the presence of additional metal cations (K{sup I} or Ce{sup III}) or cosolvents provided four complexes, which were crystallographically characterized. The compound [(UO{sub 2}){sub 2}K{sub 2}(CB6)(adc){sub 2}(NO{sub 3}){sub 2}(H{sub 2}O){sub 2}].5H{sub 2}O (1), where H{sub 2}adc is 1,3-adamantanedicarboxylic acid, crystallizes in the form of a central K{sub 2}(CB6){sup 2+} column surrounded by two one-dimensional (1D) polymeric UO{sub 2}(adc)(NO{sub 3}){sup -} chains attached to the column by nitrate bridges, with a perfect match of the repeat lengths in the two subunits. The longer 1,3-adamantanediacetic acid (H{sub 2}adac) gives the complex [(UO{sub 2}){sub 2}(adac){sub 2}(HCOOH){sub 2}].CB6.6H{sub 2}O (2), in which the 1D uranyl-containing polymer and columns of CB6 molecules form a layered arrangement held by weak CH..O hydrogen bonds. The complex formed with the dipotassium salt of methanedisulfonic acid (K{sub 2}mds), [(UO{sub 2}){sub 2}K{sub 2}(CB6)(mds){sub 2}(OH){sub 2}(H{sub 2}O){sub 8}].4H{sub 2}O (3), is a 1D polymer, in which K{sub 2}(CB6){sup 2+} units are connected to one another by doubly hydroxide-bridged uranyl dimers in which the disulfonates are terminal, chelating ligands; connection between the two subunits is solely through potassium oxo-bonding to uranyl. The complex [(UO{sub 2}){sub 2}Ce{sub 2}(CB6)(C{sub 2}O{sub 4}){sub 3}(NO{sub 3}){sub 4}(H{sub 2}O){sub 6}].2H{sub 2}O (4) is a 1D polymer containing bridging oxalate ligands formed in situ, in which CB6 is coordinated to the lanthanide cations only; one nitrate ligand and one water ligand, hydrogen-bonded to each other, are included in the CB6 cavity, with the possible occurrence of interactions between nitrate oxygen atoms and ureido carbon atoms. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Complexes of uranyl nitrate with 2,6-pyridinedicarboxamides: synthesis, crystal structure, and DFT study

Energy Technology Data Exchange (ETDEWEB)

Alyapyshev, Mikhail; Babain, Vasiliy [ITMO University, 49, Kronverksky pr., 197101, St. Petersburg (Russian Federation); ThreeArc Mining Ltd., 5, Stary Tolmachevskiy per., 115184, Moscow (Russian Federation); Tkachenko, Lyudmila; Lumpov, Alexander [Khlopin Radium Institute, 28, 2nd Murinskiy pr., 194021, St. Petersburg (Russian Federation); Gurzhiy, Vladislav; Zolotarev, Andrey; Dar' in, Dmitriy [St. Petersburg State University, 7-9, Universitetskaya nab., 199034, St. Petersburg (Russian Federation); Ustynyuk, Yuriy; Gloriozov, Igor [M.V. Lomonosov Moscow State University, 119991, Moscow (Russian Federation); Paulenova, Alena [Department of Nuclear Engineering, Oregon State University, Corvallis, OR (United States)

2017-05-04

Two complexes of uranyl nitrate with N,N,N',N'-tetrabutyl-2,6-pyridinedicarboxamide (TBuDPA) and N,N'-diethyl-N,N'-diphenyl-2,6-pyridinedicarboxamide (EtPhDPA) were synthesized and studied. The complex of tetraalkyl-2,6-pyridinedicarboxamide with metal nitrate was synthesized for the first time. XRD analysis revealed the different type of complexation: a 1:1 metal:ligand complex for EtPhDPA and complex with polymeric structure for TBuDPA. The quantum chemical calculations (DFT) confirm that both ligands form the most stable complexes that match the minimal values pre-organization energy of the ligands. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

New insights into the acid mediated disproportionation of pentavalent uranyl

Energy Technology Data Exchange (ETDEWEB)

Mougel, Victor; Biswas, Biplab; Pecaut, Jacques; Mazzanti, Marinella [Laboratoire de Reconnaissance Ionique et Chimie de Coordination, SCIB, UMR-E 3 CEA-UJF FRE 3200 CNRS, INAC, CEA-Grenoble, 17 rue des Martyrs, 38054 Grenoble Cedex 09 (France)

2010-07-01

The reaction of benzoic acid with the uranyl(V) complex [(UO{sub 2}Py{sub 5})(KI{sub 2}Py{sub 2})] in pyridine leads to immediate disproportionation with formation of a hexa-nuclear U(IV) benzoate cluster, a bis-benzoate complex of uranyl(VI) and water. (authors)

Determination of the extractive capacity of para-tert butyl calix[8]arene octa-phosphinoylated towards uranyl ions from an aqueous-acidic-salty medium

International Nuclear Information System (INIS)

Serrano V, E. C.

2011-01-01

The extraction properties of octa-phosphinoylated para-tert butyl calix[8]arene (prepared in the laboratory) in chloroform towards uranyl ions from an aqueous-acidic-salty medium (HNO 3 -3.5 NaNO 3 ) containing uranyl nitrate salt, was investigated. Two spectroscopic techniques UV/Vis and Luminescence were used for this study. The latter permitted analyze the fluorescence from the uranyl ions influenced by the surrounding medium. Both permitted to learn about the power of this calixarene as extractant towards the mentioned ions. Its extraction ability or capability using this calixarene at 5.91 x 10 -4 M towards the uranyl ions was 400% as determined by UV/Vis while fluorescence revealed 100% of uranyl ion extraction. A closed analysis of the results obtained by using these techniques revealed that the stoichiometry of the main extracted species was 1calixarene:2 uranyl ions. The loading capacity of the calixarene ligand towards the uranyl ions was also investigated using both techniques. UV/Vis resulted to be inadequate for quantifying exactly the loading capacity of the calixarene whereas luminescence was excellent indeed, using a 5.91 x 10 -4 M calixarene concentration, its loading capacity was 0.157 M of free uranyl ions from 0.161 M of uranyl ions present in the aqueous-acidic-salty medium. The extracts from the ability and capacity studies were concentrated to dryness, purified and the dried extracts were analyzed by infrared and neutron activation analysis. By these techniques it was demonstrated that during the extraction of the uranyl ions by the calixarene ligand they form thermodynamically and kinetically stable complexes, since in the solid state, the 1:2, calixarene; uranyl ions stoichiometry was kept with the minimum formula: (UO 2 ) 2 B 8 bL 8 (NO 3 ) 4 (H 2 O) 4 CHCl 3 (CH 3 OH) 3 the methanol molecules come from its purification. It is proposed that B 8 bL 8 calixarene in chloroform medium is a good extractant for the treatment of nuclear wastes or

Comprehensive analysis of the renal transcriptional response to acute uranyl nitrate exposure

Directory of Open Access Journals (Sweden)

Argiles Angel

2006-01-01

Full Text Available Abstract Background Chemical and radiological toxicities related to uranium acute exposure have been widely studied in nuclear fuel workers and military personnel. It is well known that uranyl nitrate induces acute renal failure (ARF. However, the mechanisms of this metal-induced injury are not well defined at the molecular level. Results Renal function and histology were assessed in mice receiving uranyl nitrate (UN(+ and controls (UN(-. To identify the genomic response to uranium exposure, serial analysis gene expression (SAGE of the kidney was performed in both groups. Over 43,000 mRNA SAGE tags were sequenced. A selection of the differentially expressed transcripts was confirmed by real-time quantitative PCR and Western blotting. UN(+ animals developed renal failure and displayed the characteristic histological lesions of UN nephropathy. Of the >14,500 unique tags identified in both libraries, 224 had a modified expression level; they are known to participate in inflammation, ion transport, signal transduction, oxidative stress, apoptosis, metabolism, and catabolism. Several genes that were identified had not previously been evaluated within the context of toxic ARF such as translationally controlled tumor protein, insulin like growth factor binding protein 7 and ribosomal protein S29, all apoptosis related genes. Conclusion We report a comprehensive description of the UN induced modifications in gene expression levels, including the identification of genes previously unrelated to ARF. The study of these genes and the metabolisms they control should improve our understanding of toxic ARF and enlighten on the molecular targets for potential therapeutic interventions.

Extraction of uranyl nitrate from aqueous solution by dicyclohexyl-18-crown-6

International Nuclear Information System (INIS)

Kojima, Takashi; Ohno, Fumiaki; Fukutomi, Hiroshi

1981-01-01

The extraction of uranyl nitrate from aqueous solution by dicyclohexyl-18-crown-6(DCC) in cyclohexane, toluene, benzene, chlorobenzene and nitrobenzene has been studied in varying the concentrations of DCC and uranyl nitrate. The extraction equilibria have been discussed in detail based on the law of mass action, and it has been found that the extractions in cyclohexane, toluene and benzene are represented by the equation 2 DCC(org) + UO 2 2+ (aq) + 2 NO 3 - (aq) = (DCC) 2 UO 2 (NO 3 ) 2 (org), and the extraction in chlorobenzene is described by the equations DCC(org) + UO 2 2+ (aq) + 2NO 3 - (aq) = DCC UO 2 (NO 3 ) 2 (org) and 2DCC(org) + UO 2 2+ (aq) + 2NO 3 - (aq) = (DCC) 2 UO 2 (NO 3 ) 2 (org), and the extraction in nitrobenzene is expressed by the equations DCC(org) + UO 2 2+ (aq) + 2NO 3 - (aq) = DCC UO 2 (NO 3 ) 2 (org), 2DCC(org) + UO 2 2+ (aq) + 2NO 3 - (aq) = (DCC) 2 UO 2 (NO 3 ) 2 (org) and DCC UO 2 (NO 3 ) 2 (org) = DCC UO 2 NO 3 + (org) + NO 3 - (org). The equilibrium constants of the reaction 2DCC(org) + UO 2 2+ (aq) + 2NO 3 - (aq) = (DCC) 2 UO 2 (NO 3 ) 2 (org) increase in the order of cyclohexane < toluene < benzene < chlorobenzene < nitrobenzene. The enthalpy and entropy changes for the extraction reactions into benzene and nitrobenzene were determined from the change of the extraction equilibrium constants with temperature. (author)

Sub-critical pulsed neutron experiments with uranyl nitrate solutions in spherical geometry

International Nuclear Information System (INIS)

Gurin, Victor N.; Ryazanov, Boris G.; Sviridov, Victor I.; Volnistov, Vladimir V.

2003-01-01

The pulse source method is used to study homogeneous solution assemblies. Three sets of sub-critical pulse experiments with spherical tanks filled with water solution of uranyl nitrate (90% enrichment) were carried out at the RF-GS facility, Obninsk, Russia. Seven spherical tanks with the volume within the range of 1.29 L to 19.8 L were used in the experiments. Three uranium concentrations were studied, i.e. 20.7, 29.6 and 37.5 g/L. The sub-critical experiments were analyzed with the MCNP 4A code based on the Monte-Carlo method, and with ENDF/B-V library. (author)

Standard test methods for chemical, mass spectrometric, spectrochemical, nuclear, and radiochemical analysis of nuclear-grade uranyl nitrate solutions

CERN Document Server

American Society for Testing and Materials. Philadelphia

1999-01-01

1.1 These test methods cover procedures for the chemical, mass spectrometric, spectrochemical, nuclear, and radiochemical analysis of nuclear-grade uranyl nitrate solution to determine compliance with specifications. 1.2 The analytical procedures appear in the following order: Sections Determination of Uranium 7 Specific Gravity by Pycnometry 15-20 Free Acid by Oxalate Complexation 21-27 Determination of Thorium 28 Determination of Chromium 29 Determination of Molybdenum 30 Halogens Separation by Steam Distillation 31-35 Fluoride by Specific Ion Electrode 36-42 Halogen Distillate Analysis: Chloride, Bromide, and Iodide by Amperometric Microtitrimetry 43 Determination of Chloride and Bromide 44 Determination of Sulfur by X-Ray Fluorescence 45 Sulfate Sulfur by (Photometric) Turbidimetry 46 Phosphorus by the Molybdenum Blue (Photometric) Method 54-61 Silicon by the Molybdenum Blue (Photometric) Method 62-69 Carbon by Persulfate Oxidation-Acid Titrimetry 70 Conversion to U3O8 71-74 Boron by ...

Benchmark calculation for water reflected STACY cores containing low enriched uranyl nitrate solution

International Nuclear Information System (INIS)

Miyoshi, Yoshinori; Yamamoto, Toshihiro; Nakamura, Takemi

2001-01-01

In order to validate the availability of criticality calculation codes and related nuclear data library, a series of fundamental benchmark experiments on low enriched uranyl nitrate solution have been performed with a Static Experiment Criticality Facility, STACY in JAERI. The basic core composed of a single tank with water reflector was used for accumulating the systematic data with well-known experimental uncertainties. This paper presents the outline of the core configurations of STACY, the standard calculation model, and calculation results with a Monte Carlo code and JENDL 3.2 nuclear data library. (author)

Determination of the stability of the uranyl ion sipped in τ-hydrogen phosphate of zirconium in sodic form

International Nuclear Information System (INIS)

Ordonez R, E.; Fernandez V, S.M.; Drot, R.; Simoni, E.

2005-01-01

The stability of the uranyl sipped in the zirconium τ-hydrogen phosphate in sodic form (τ-NaZrP), was carried out characterizing the complexes formed by Laser spectroscopy in the visible region and by X-ray photoelectron spectroscopy. The material was prepared by a new synthesis technique working in nitrogen atmosphere and to low temperatures. The sorption of the uranyl ion was made in acid media with concentrations of 10 -4 and 10 -5 of uranyl nitrate and with ion forces of 0.1 and 0.5 M of NaClO 4 . The spectra of induced fluorescence with laser (TRLFS) show that the uranyl is fixed in very acid media in three well differentiated species, to pH less acid, the specie of long half life disappears and are only those of short half life. The results of the binding energy obtained by XPS indicate that the binding energy of the uranyl confer it a stable character to the complex formed in the τ-NaZP, that makes to this material appropriate to retain to the uranyl in solution to high ion forces and in acid media. (Author)

A comparison of processes for the conversion of uranyl nitrate into ceramic-grade UO/sub 2/

International Nuclear Information System (INIS)

Haas, P.A.

1988-01-01

The preferred processes for converting uranyl nitrate solutions into UO/sub 2/ for the fabrication of nuclear fuel pellets all involve the thermal decomposition of solid compounds into UO/sub 3/ without melting. Criteria for comparisons are given and used to compare eight conversion processes. Costs for the conversion processes are estimated to be 60 to 108% of the costs for the most commonly used ammonium diuranate precipitation/calcination process

Standard test method for gamma energy emission from fission products in uranium hexafluoride and uranyl nitrate solution

CERN Document Server

American Society for Testing and Materials. Philadelphia

2005-01-01

1.1 This test method covers the measurement of gamma energy emitted from fission products in uranium hexafluoride (UF6) and uranyl nitrate solution. It is intended to provide a method for demonstrating compliance with UF6 specifications C 787 and C 996 and uranyl nitrate specification C 788. 1.2 The lower limit of detection is 5000 MeV Bq/kg (MeV/kg per second) of uranium and is the square root of the sum of the squares of the individual reporting limits of the nuclides to be measured. The limit of detection was determined on a pure, aged natural uranium (ANU) solution. The value is dependent upon detector efficiency and background. 1.3 The nuclides to be measured are106Ru/ 106Rh, 103Ru,137Cs, 144Ce, 144Pr, 141Ce, 95Zr, 95Nb, and 125Sb. Other gamma energy-emitting fission nuclides present in the spectrum at detectable levels should be identified and quantified as required by the data quality objectives. 1.4 This standard does not purport to address all of the safety concerns, if any, associated with its us...

Study on the transport behavior of uranyl nitrate in aqueous and non-aqueous systems

International Nuclear Information System (INIS)

Roesel, B.

1985-01-01

The analytical ultracentrifuge has proven itself through diffusion measurements to be well suited for studying radioactive compounds. In the framework of this paper the extent to which the UV and schlieren optics of an analytical ultracentrifuge can be used for extraction-kinetic tests was tested. With this method there is also the possibility of determining the distribution coefficients right at the phase boundary. The results show the good possibility of application of the absorption and schlieren optics to the study of the transport behavior of uranyl nitrate in practice oriented solutions. (orig.) [de

Solid solutions of hydrogen uranyl phosphate and hydrogen uranyl arsenate. A family of luminescent, lamellar hosts

International Nuclear Information System (INIS)

Dorhout, P.K.; Rosenthal, G.L.; Ellis, A.B.

1988-01-01

Hydrogen uranyl phosphate, HUO 2 PO 4 x 4H 2 O (HUP), and hydrogen uranyl arsenate, HUO 2 AsO 4 x 4H 2 O (HUAs), form solid solutions of composition HUO 2 (PO 4 ) 1-x (AsO 4 )x (HUPAs), representing a family of lamellar, luminescent solids that can serve as hosts for intercalation chemistry. The solids are prepared by aqueous precipitation reactions from uranyl nitrate and mixtures of phosphoric and arsenic acids; thermogravimetric analysis indicates that the phases are tetrahydrates, like HUP and HUAs. Powder x-ray diffraction data reveal the HUPAs solids to be single phases whose lattice constants increase with X, in rough accord with Vegard's law Spectral shifts observed for the HUPAs samples. Emission from the solids is efficient (quantum yields of ∼ 0.2) and long-lived (lifetimes of ∼ 150 μs), although the measured values are uniformly smaller than those of HUP and HUAs; unimolecular radiative and nonradiative rate constants for excited-state decay of ∼ 1500 and 5000 s -1 , respectively, have been calculated for the compounds. 18 refs., 5 figs., 2 tabs

Orientational order and dynamics of water in bulk and in aqueous solutions of uranyl ions

International Nuclear Information System (INIS)

Chopra, Manish; Choudhury, Niharendu

2014-01-01

Molecular dynamics simulations in canonical ensemble of aqueous solutions of uranyl nitrate and bulk water at ambient condition have been carried out to investigate orientational order and dynamics of water. The orientational distributions of water around a central water molecule in bulk water and around a uranyl ion in an aqueous uranyl solution have been calculated. Orientational dynamics of water in bulk and in aqueous uranyl nitrate solution have also been analysed. (author)

Laboratory and pilot-plant studies on the conversion of uranyl nitrate hexahydrate to UF6 by fluidized-bed processes

International Nuclear Information System (INIS)

Youngblood, E.L.; Urza, I.J.; Cathers, G.I.

1977-06-01

This report describes laboratory and pilot-plant studies on the conversion of uranyl nitrate hexahydrate (UNH) to UF 6 and on purification of the UF 6 . Experimental laboratory studies on the removal of residual nitrate from uranium trioxide (UO 3 ) calcine and the fluorination of technetium and subsequent sorption on MgF 2 were conducted to support the pilot-plant work. Two engineering-scale pilot plants utilizing fluidized-bed processes were constructed for equipment and process testing of the calcination of UNH to UO 3 and the direct fluorination of UO 3 to UF 6

Quantification of uranyl in presence of citric acid; Cuantificacion de uranilo en presencia de acido citrico

Energy Technology Data Exchange (ETDEWEB)

Garcia G, N.; Barrera D, C.E. [UAEM, Facultad de Quimica, 50000 Toluca, Estado de Mexico (Mexico); Ordonez R, E. [ININ, 52750 La Marquesa, Estado de Mexico (Mexico)]. e-mail: nidgg@yahoo.com.mx

2007-07-01

To determine the influence that has the organic matter of the soil on the uranyl sorption on some solids is necessary to have a detection technique and quantification of uranyl that it is reliable and sufficiently quick in the obtaining of results. For that in this work, it intends to carry out the uranyl quantification in presence of citric acid modifying the Fluorescence induced by UV-Vis radiation technique. Since the uranyl ion is very sensitive to the medium that contains it, (speciation, pH, ionic forces, etc.) it was necessary to develop an analysis technique that stands out the fluorescence of uranyl ion avoiding the out one that produce the organic acids. (Author)

Uranyl ion complexation by the tripodal ligand nitrilo-tri-acetate

Energy Technology Data Exchange (ETDEWEB)

Thuery, P. [CEA Saclay, DSM/DRECAM/SCM, F-91191 Gif Sur Yvette, (France)

2007-07-01

Reaction of uranyl nitrate with N-(2-acetamido)iminodiacetic acid (ADA) under hydrothermal conditions resulted in the hydrolysis of the amide group and the isolation of the complex [(UO{sub 2})(HNTA)(H{sub 2}O){sub 2}], in which each nitrilo-tri-acetate ligand, protonated at the N site, bridges three metal atoms to give rise to infinite ladder-like ribbons built from 2:2 metallacycles. (author)

Supercritical fluid extraction of uranium and neodymium nitrates

International Nuclear Information System (INIS)

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

2011-01-01

Supercritical fluid extraction (SFE) of uranyl nitrate and neodymium nitrate salts from a mixture was investigated in the present study using Sc-CO 2 modified with various ligands such as organophosphorous compounds, amides, and diketones. Preferential extraction of uranyl nitrate over neodymium nitrate was demonstrated using Sc-CO 2 modified with amide, di-(2ethylhexyl) isobutyramide (D2EHIBA). (author)

Photochemistry and exciplex of the uranyl ion in aqueous solution

International Nuclear Information System (INIS)

Marcantonatos, M.D.

1980-01-01

The effects of acidity, temperature, self-quenching and H-donor concentration on the luminescent state of the aqua-uranyl(VI) ion have been studied in aqueous acidic nitrate and perchlorate solution. The detailed results cannot be explained by any single simple mechanism such as radiative, non-radiative or spontaneous collisional quenching, or irreversible hydrogen abstraction from water. Quantitative analysis of the results shows a far more complex mechanism, involving the adiabatic formation of the species *UO 2 H 2+ and *U 2 O 4 H 4+ , as already proposed by the author. This mechanism is supported by state and m.o. correlations. The abstraction of hydrogen from water is shown to take place by H atom transfer in a *uranyl-water complex intermediate, rather than by attack of H + on the fully occupied πsub(u) orbitals of uranium(V) in a well-defined uranyl water complex with strong charge transfer character. A qualitative description of the exciplex *U 2 O 4 H 4+ is shown to be possible in a v.b. formalism and the origin of its radiative properties is discussed on this basis. (author)

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.

Series of mixed uranyl-lanthanide (Ce, Nd) organic coordination polymers with aromatic polycarboxylates linkers.

Science.gov (United States)

Mihalcea, Ionut; Volkringer, Christophe; Henry, Natacha; Loiseau, Thierry

2012-09-17

Three series of mixed uranyl-lanthanide (Ce or Nd) carboxylate coordination polymers have been successfully synthesized by means of a hydrothermal route using either conventional or microwave heating methods. These compounds have been prepared from mixtures of uranyl nitrate, lanthanide nitrate together with phthalic acid (1,2), pyromellitic acid (3,4), or mellitic acid (5,6) in aqueous solution. The X-ray diffraction (XRD) single-crystal revealed that the phthalate complex (UO(2))(4)O(2)Ln(H(2)O)(7)(1,2-bdc)(4)·NH(4)·xH(2)O (Ln = Ce(1), Nd(2); x = 1 for 1, x = 0 for 2), is based on the connection of tetranuclear uranyl-centered building blocks linked to discrete monomeric units LnO(2)(H(2)O)(7) via the organic species to generate infinite chains, intercalated by free ammonium cations. The pyromellitate phase (UO(2))(3)Ln(2)(H(2)O)(12)(btec)(3)·5H(2)O (Ce(3), Nd(4)) contains layers of monomeric uranyl-centered hexagonal and pentagonal bipyramids linked via the carboxylate arms of the organic molecules. The three-dimensionality of the structure is ensured by the connection of remaining free carboxylate groups with isolated monomeric units LnO(2)(H(2)O)(7). The network of the third series (UO(2))(2)(OH)Ln(H(2)O)(7)(mel)·5H(2)O (Ce(5), Nd(6)) is built up from dinuclear uranyl units forming layers through connection with the mellitate ligands, which are further linked to each other through discrete monomers LnO(3)(H(2)O)(6). The thermal decomposition of the various coordination complexes led to the formation of mixed uranium-lanthanide oxide, with the fluorite-type structure at 1500 °C (for 1, 2) or 1400 °C for 3-6. Expected U/Ln ratio from the crystal structures were observed for compounds 1-6.

Cyclic phosphopeptides to rationalize the role of phosphoamino acids in uranyl binding to biological targets

Energy Technology Data Exchange (ETDEWEB)

Starck, Matthieu; Laporte, Fanny A.; Oros, Stephane; Sisommay, Nathalie; Gathu, Vicky; Lebrun, Colette; Delangle, Pascale [INAC/SyMMES, UMR5819, Universite Grenoble Alpes, CEA, CNRS, Grenoble (France); Solari, Pier Lorenzo [Synchrotron SOLEIL, L' orme des Merisiers, Saint-Aubin, Gif-sur-Yvette (France); Creff, Gaelle; Den Auwer, Christophe [Institut de Chimie de Nice, UMR7272, Universite Cote d' Azur, Nice (France); Roques, Jerome [Institut de Physique Nucleaire d' Orsay, CNRS-IN2P3, Univ. Paris-Sud, Universite Paris-Saclay (France)

2017-04-19

The specific molecular interactions responsible for uranium toxicity are not yet understood. The uranyl binding sites in high-affinity target proteins have not been identified yet and the involvement of phosphoamino acids is still an important question. Short cyclic peptide sequences, with three glutamic acids and one phosphoamino acid, are used as simple models to mimic metal binding sites in phosphoproteins and to help understand the mechanisms involved in uranium toxicity. A combination of peptide design and synthesis, analytical chemistry, extended X-ray absorption fine structure (EXAFS) spectroscopy, and DFT calculations demonstrates the involvement of the phosphate group in the uranyl coordination sphere together with the three carboxylates of the glutamate moieties. The affinity constants measured with a reliable analytical competitive approach at physiological pH are significantly enhanced owing to the presence of the phosphorous moiety. These findings corroborate the importance of phosphoamino acids in uranyl binding in proteins and the relevance of considering phosphoproteins as potential uranyl targets in vivo. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Uranyl citrate dimers as guests in a copper-bipyridine framework: a novel hetero-metallic inorganic-organic hybrid compound

International Nuclear Information System (INIS)

Thuery, P.

2007-01-01

Reaction of uranyl nitrate with citric acid (H 4 cit) in the presence of copper(II) bis(tri-fluoro-methane-sulfonate) and 4,4'-bipyridine (bipy) under hydrothermal conditions gave the mixed complex[Cu(bipy) 2 (H 2 O) 2 ][UO 2 (Hcit)(H 2 O)] 2 .5H 2 O, in which di-anionic uranyl citrate dimers are incorporated in the interlayer spaces of the [Cu(bipy) 2 (H 2 O) 2 ] n 2n+ square grid assemblage. An extended hydrogen bonding network links the uranyl complex units together and also to the grid framework, resulting in the formation of a 3-D assemblage held by weak interactions. (author)

Uranous nitrate production using PtO2 catalyst and H2/H2 gas mixtures

International Nuclear Information System (INIS)

Rao, K.S.; Shyamlal, R.; Narayanan, C.V.; Patil, A.R.; Ramanujam, A.; Kansra, V.P.; Balu, K.; Vaidya, V.N.

2001-01-01

The feasibility of producing near 100% uranous nitrate, the partitioning agent used in the spent fuel reprocessing by Purex process, by catalytically reducing uranyl nitrate with H 2 and H 2 gas mixtures was extensively studied. As near quantitative reduction of uranyl nitrate could be easily achieved in laboratory scale studies, pilot plant scale reduction of uranyl nitrate was also carried out and five litres of uranyl nitrate of 100 g/1 could be quantitatively reduced in one hour. (author)

The extraction and effect in the system uranyl nitrate-dietyl ether-water

International Nuclear Information System (INIS)

Perez Luina, A.; Gutierrez Jodra, L.; Rius Miro, A.

1960-01-01

The solute transfer of uranyl nitrate from diethyl ether to water has been studied in a spray column using water as dispersed phase and a direction of extraction from ether to water. The column is 102 cm long and has a diameter of 4,7 cm. The entrances of the phases are 77 cm apart. The rates of flow of both phases have been used as variables and the concentration of the continuous phase has been determined at different heights. The curves of logarithm of concentration of the continuous phase vs. distance to interphase show the present of a drop of concentration in the entrance of the continuous phase. This depends on the rates of flow of the phases. No effect in the entrance of the dispersed phase has been found. (Author) 20 refs

Uranyl ion transport across tri-n-butyl phosphate/n-dodecane liquid membranes

International Nuclear Information System (INIS)

Shukla, J.P.; Misra, S.K.

1991-01-01

Carrier-facilitated transport of uranium (VI) against its concentration gradient from aqueous nitrate acidic solutions across organic bulk liquid membranes (BLM) and supported liquid membranes (SLM) containing TBP as the mobile carrier and n-dodecane as the membrane solvent was investigated. Extremely dilute uranyl nitrate solutions in about 2.5 M nitric acid generally constituted as the source phase. Uranyl transport appreciably increased with both stirring of the receiving phase and the carrier concentration in the organic membrane, while enhanced acidity of the strip side adversely affected the partioning of the cation into this phase. Among the several reagents tested, diluted ammonium carbonate (∼1M) solutions served efficiently as the stripant. Besides Accurel polypropylene (PP) film as the solid support for SLM, some silicon flat-sheet membranes with different inorganic fillers like silica, calcium silicate, calcium carbonate, chromium oxide, zinc oxide etc. and teflon membranes transported about 70% of uranium in nearly 7-8 hr employing 1 M ammonium carbonate as the strippant. Specifically, 30% TBP supported on Accurel flat-sheet supports transfered better than 70% of uranium from moderate acid feeds (2.5M) under similar conditions. Membranes supporting Aliquat-336, TLA, TOPO etc. yielded somewhat poor uranium recoveries. The feed : strip volume ratio showed an inverse relationship to the fraction of cation transported. (author). 9 refs., 2 tab s

Enhancement of uranyl fluorescence using trimesic acid: Ligand sensitization and co-fluorescence

Energy Technology Data Exchange (ETDEWEB)

Maji, S. [Chemistry Group, Materials Chemistry Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India); Viswanathan, K.S., E-mail: vish@igcar.gov.in [Chemistry Group, Materials Chemistry Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India)

2011-09-15

Trimesic acid (TMA) was shown to sensitize and enhance uranyl fluorescence in aqueous medium, with the enhancement being a maximum at pH 5.0. Fluorescence spectra and lifetime data together suggest that TMA complexes with uranyl (UO{sub 2}{sup 2+}). The fluorescence of UO{sub 2}{sup 2+} in its acid complex is further enhanced by more than two orders of magnitude following the addition of Y{sup 3+}; a process referred to as co-fluorescence, leading to the possibility of detecting uranium at sub ng/mL level. The present study demonstrates, for the first time, fluorescence enhancement of the uranyl species due to co-fluorescence. - Highlights: > Trimesic acid was shown to sensitize and enhance the fluorescence of uranium in aqueous medium. > This ligand also exhibited co-fluorescence of uranium with Y{sup 3+}. > To the best of our knowledge this is the first report of co-fluorescence in uranium. > The enhancement of uranium fluorescence, resulted in detection limits in the ng/mL regime.

Laboratory and pilot-plant studies on the conversion of uranyl nitrate hexahydrate to UF/sub 6/ by fluidized-bed processes

Energy Technology Data Exchange (ETDEWEB)

Youngblood, E.L.; Urza, I.J.; Cathers, G.I.

1977-06-01

This report describes laboratory and pilot-plant studies on the conversion of uranyl nitrate hexahydrate (UNH) to UF/sub 6/ and on purification of the UF/sub 6/. Experimental laboratory studies on the removal of residual nitrate from uranium trioxide (UO/sub 3/) calcine and the fluorination of technetium and subsequent sorption on MgF/sub 2/ were conducted to support the pilot-plant work. Two engineering-scale pilot plants utilizing fluidized-bed processes were constructed for equipment and process testing of the calcination of UNH to UO/sub 3/ and the direct fluorination of UO/sub 3/ to UF/sub 6/.

Evaluation of neutronic characteristics of STACY 80-cm-diameter cylindrical core fueled with 6% enriched uranyl nitrate solution

International Nuclear Information System (INIS)

Yanagisawa, Hiroshi; Sono, Hiroki

2003-06-01

For the examination of neutronic safety design of forthcoming experimental core configurations in the Static Experiment Critical Facility (STACY), neutronic characteristics of 80-cm-diameter cylindrical cores fueled with 6% enriched uranyl nitrate solution have been evaluated by computational analyses. In the analyses, the latest nuclear data library, JENDL-3.3, was used as neutron cross section data. The neutron diffusion and transport calculations were performed using a diffusion code, CITATION, in the SRAC code system and a continuous-energy Monte Carlo code, MVP. Critical level heights of the cores were obtained using such parameters as uranium concentration (up to 500 gU/l), free nitric acid concentration (up to 8 mol/l), and concentration of soluble neutron poisons, gadolinium and boron. It has been confirmed from the evaluation that all critical cores comply with safety criteria required in the STACY operation concerning excess reactivity, reactivity addition rates and shutdown margins by safety rods. (author)

Infrared studies on complexes between octaethyltetraamidepyrophosphate (OETAPP) and uranyl salts

International Nuclear Information System (INIS)

Grychowski, P.; Mikulski, J.; Moravets, Ya.; Shara, V.; Shourkova, L.

1981-01-01

Uranyl nitrate and uranyl chloride were extracted from the water phase with CHCl 3 solution of octaethyltetraamidepyrophosphate (OETAPP). Infrared spectra of the organic phases were recorded before and after the extraction. For both systems, the frequency of the P=O stretching mode of OETAPP after the extraction was lowered, which indicates for the formation of OETAPP UO 2 (NO 3 ) 2 and OETAPP UO 2 Cl 2 complexes. If uranyl nitrate was extracted with OETAPP in CCl 4 a precipitate was formed in the solution. From the analysis of the IR spectrum of the precipitate it was concluded that the complex OETAPP UO 2 (NO 3 ) 2 was formed also in this case, however, the complex was insoluble in CCl 4 . (author)

Calculation of concentration profiles and their experimental verification with a pulsed sieve-plate column and the reactive material system of uranyl nitrate, nitric acid/tributyl phosphate, kerosine

International Nuclear Information System (INIS)

Ihle, E.

1985-01-01

The present study is concerned with the calculation of stationary and non-stationary concentration profiles as well as with the starting and disturbance behaviour of a pulsed sieve-plate extraction column. It investigates into the material system HNO 3 /uranyl nitrate in water with 30 per cent by volume of tributyl phosphate in kerosine. During the measurements of the concentration profiles for HNO 3 transition, which were effected in the direction of extraction and reextraction, it was shown that the concentration profiles measured in the mixer-settler range, in spite of a sixfold enlargement of the specific heat transfer area, do not differ essentially from those measured in the dispersion range. During the measurements of concentration profiles for HNO 3 /uranium transition, which were effected in the direction of coextraction and co-reextraction only for mixer-settler range, it was discovered that with increasing phase ratios, there is a depletion of the uranium concentration in the aqueous phase. If the phase ratio is further raised, it is the nitric acid, and not the uranium, that is depleted. (orig./PW) [de

Thermal and X-ray diffraction analysis studies during the decomposition of ammonium uranyl nitrate

OpenAIRE

Kim, B. H.; Lee, Y. B.; Prelas, M. A.; Ghosh, T. K.

2012-01-01

Two types of ammonium uranyl nitrate (NH4)2UO2(NO3)4?2H2O and NH4UO2(NO3)3, were thermally decomposed and reduced in a TG-DTA unit in nitrogen, air, and hydrogen atmospheres. Various intermediate phases produced by the thermal decomposition and reduction process were investigated by an X-ray diffraction analysis and a TG/DTA analysis. Both (NH4)2UO2(NO3)4?2H2O and NH4UO2(NO3)3 decomposed to amorphous UO3 regardless of the atmosphere used. The amorphous UO3 from (NH4)2UO2(NO3)4?2H2O was crysta...

Critical Parameters of Complex Geometry Intersecting Cylinders Containing Uranyl Nitrate Solution

Energy Technology Data Exchange (ETDEWEB)

Rothe, Robert Emil; Briggs, Joseph Blair

1999-06-01

About three dozen previously unreported critical configurations are presented for very complex geometries filled with high concentration enriched uranyl nitrate solution. These geometries resemble a tall, thin Central Column (or trunk of a "tree") having long, thin arms (or "branches") extending up to four directions off the column. Arms are equally spaced from one another in vertical planes; and that spacing ranges from arms in contact to quite wide spacings. Both the Central Column and the many different arms are critically safe by themselves when each, alone, is filled with fissile solution; but, in combination, criticality occurs due to the interactions between arms and the column. Such neutronic interactions formed the principal focus of this study. While these results are fresh to the nuclear criticality safety industry and to those seeking novel experiments against which to validate computer codes, the experiments, themselves, are not recent. Over 100 experiments were performed at the Rocky Flats Critical Mass Laboratory between September, 1967, and February of the following year.

Ions generated from uranyl nitrate solutions by electrospray ionization (ESI) and detected with Fourier transform ion-cyclotron resonance (FT-ICR) mass spectrometry.

Science.gov (United States)

Pasilis, Sofie; Somogyi, Arpád; Herrmann, Kristin; Pemberton, Jeanne E

2006-02-01

Electrospray ionization (ESI) of uranyl nitrate solutions generates a wide variety of positively and negatively charged ions, including complex adducts of uranyl ions with methoxy, hydroxy, and nitrate ligands. In the positive ion mode, ions detected by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry are sensitive to instrumental tuning parameters such as quadrupole operating frequency and trapping time. Positive ions correspond to oligomeric uranyl nitrate species that can be characterized as having a general formula of [(UO(2))(n)(A)(m)(CH(3)OH)(s)](+) or [(UO(2))(n)(O)(A)(m)(CH(3)OH)(s)](+) with n = 1-4, m = 1-7, s = 0 or 1, and A = OH, NO(3), CH(3)O or a combination of these, although the formation of NO(3)-containing species is preferred. In the negative ion mode, complexes of the form [(UO(2))(NO(3))(m)](-) (m = 1-3) are detected, although the formation of the oxo-containing ions [(UO(2))(O)(n)(NO(3))(m)](-) (n = 1-2, m = 1-2) and the hydroxy-containing ions [(UO(2))(OH)(n)(NO(3))(m)](-) (n = 1-2, m = 0-1) are also observed. The extent of coordinative unsaturation of both positive and negative ions can be determined by ligand association/exchange and H/D exchange experiments using D(2)O and CD(3)OD as neutral reaction partners in the gas-phase. Positive ions are of varying stability and reactivity and may fragment extensively upon collision with D(2)O, CD(3)OD and N(2) in sustained off-resonance irradiation/collision-induced dissociation (SORI-CID) experiments. Electron-transfer reactions, presumably occurring during electrospray ionization but also in SORI-CID, can result in reduction of U(VI) to U(V) and perhaps even U(IV).

Electronic structure and properties of uranyl compounds. Problems of electron-donor conception

International Nuclear Information System (INIS)

Glebov, V.A.

1982-01-01

Comparison of the series of the ligand mutual substitution in the uranyl compounds with the ligand series of d-elements and with the uranyl ''covalent model'', is made. The data on ionization potentials of the ligand higher valent levels and on the structure of some uranyl nitrate compounds are considered. It is concluded that the mechanism of the ligand effect on the properties of uranyl grouping is more complex, than it is supposed in the traditional representations on the nature of electron-donor interactions in the uranyl compounds

Processing of uranyl nitrate hexahydrate (UNH) at DOE's Fernald Site: Success and pitfalls

International Nuclear Information System (INIS)

Luken, D.W.; Brettschneider, D.J.; Heck, R.P. III; White, C.A.

1996-01-01

After 36 years of operation, uranium production at the Department of Energy Fernald Environmental Management Project (FEMP) was halted in 1989. Uranyl Nitrate Hexahydrate (UNH) had been produced during the uranium refining. In June 1991, DOE determined the UNH to be a mixed hazardous waste under the Resource Conservation and Recovery Act. A UNH Neutralization Project began processing UNH stored in stainless steel tanks located in various areas within the Fernald Plant 2/3 Complex. It was discovered that the valves, flanges, and other fittings of the UNH storage tanks were leaking. This made processing the UNH a high priority and Comprehensive, Environmental, Response, Compensation, and Liability Act Removal Action No. 20, Stabilization of UNH Inventories, was initiated. This report presents the successes and pitfalls of the cleanup of UNH

The final effect of extraction system in the uranyl nitrate-water-diethyl ether

International Nuclear Information System (INIS)

Perez Luina, A.; Gutierrez Jodra, L.; Miro, A. R.

1957-01-01

The solute transfer of uranyl nitrate from diallylether to water has been studied in a spray column using water as dispersed phase and a direction of extraction from ether to water. The column is 102 cm. long has a diameter of 4. 7 cm. The entrances of the phases are 7 7 cm. apart. The rates of flow of both phases have been used as variables and the concentration of the continuous phase has been determined; at different heights. The curves of logarithm of concentration of the continuous phase vs , distance to interphase show the presence of a drop of concentration in the entrance of the continuous phase. This depends on the rates of flow of the phases. No effect in the entrance of the dispersed phase has been found. (Author)

Thermodynamics of uranium and nitric acid extraction from aqueous solution of TBP/diluent

International Nuclear Information System (INIS)

Souza Freitas, R.F. de.

1982-06-01

A thermodynamically consistent procedure for predicting distribution equilibria for uranyl nitrate and nitric acid between an aqueous solution and 30 vol % tributyl phosphate (TBP) in a hydrocarbon diluent is studied. Experimental work is developed in order to obtain equilibrium data for the system uranyl nitrate, nitric acid, water and 30 vol % TBP in n-dodecane, at 25 0 C and 40 0 C. The theoretical equilibrium data, obtained with the aid of a computer, are compared with the experimental results. (Author) [pt

Partitioning of uranyl between ferrihydrite and humic substances at acidic and circum-neutral pH

Science.gov (United States)

Dublet, Gabrielle; Lezama Pacheco, Juan; Bargar, John R.; Fendorf, Scott; Kumar, Naresh; Lowry, Gregory V.; Brown, Gordon E.

2017-10-01

As part of a larger study of the reactivity and mobility of uranyl (U(VI)O22+) cations in subsurface environments containing natural organic matter (NOM) and hydrous ferric oxides, we have examined the effect of reference humic and fulvic substances on the sorption of uranyl on 2-line ferrihydrite (Fh), a common, naturally occurring nano-Fe(III)-hydroxide. Uranyl was reacted with Fh at pH 4.6 and 7.0 in the presence and absence of Elliott Soil Humic Acid (ESHA) (0-835 ppm) or Suwanee River Fulvic Acid (SRFA) (0-955 ppm). No evidence was found for reduction of uranyl by either form of NOM after 24 h of exposure. The following three size fractions were considered in this study: (1) ≥0.2 μm (Fh-NOM aggregates), (2) 0.02-0.2 μm (dispersed Fh nanoparticles and NOM macro-molecules), and (3) <0.02 μm (dissolved). The extent to which U(VI) is sorbed in aggregates or dispersed as colloids was assessed by comparing U, Fe, and NOM concentrations in these three size fractions. Partitioning of uranyl between Fh and NOM was determined in size fraction (1) using X-ray absorption spectroscopy (XAS). Uranyl sorption on Fh-NOM aggregates was affected by the presence of NOM in different ways depending on pH and type of NOM (ESHA vs. SRFA). The presence of ESHA in the uranyl-Fh-NOM ternary system at pH 4.6 enhanced uranyl uptake more than the presence of SRFA. In contrast, neither form of NOM affected uranyl sorption at pH 7.0 over most of the NOM concentration range examined (0-500 ppm); at the highest NOM concentrations (500-955 ppm) uranyl uptake in the aggregates was slightly inhibited at pH 7.0, which is interpreted as being due to the dispersion of Fh aggregates. XAS at the U LIII-edge was used to characterize molecular-level changes in uranyl complexation as a result of sorption to the Fh-NOM aggregates. In the absence of NOM, uranyl formed dominantly inner-sphere, mononuclear, bidentate sorption complexes on Fh. However, when NOM concentration was increased at pH 4.6, the

Treatment of uranyl nitrate and flouride solutions

International Nuclear Information System (INIS)

Rodrigo Otero, A.; Rodrigo Vilaseca, F.; Morales Calvo, G.

1977-01-01

A theoretical study on the fluoride complexes contained in uranyl and aluminium solutions has been carried out. Likewise concentration limits and Duhring diagrams for those solutions have been experimentally established. As a result, the optimum operation conditions for concentration by evaporation in the treatment plant, have been deduced. (Author) 12 refs

Investigation of Uranyl Nitrate Ion Pairs Complexed with Amide Ligands using Electrospray Ionization Ion Trap Mass Spectrometry and Density Functional Theory

International Nuclear Information System (INIS)

Groenewold, Gary S.; Dinescu, Adriana; Benson, Michael T.; Gresham, Garold L.; van Stipdonk, Michael J.

2011-01-01

Ion populations formed from electrospray of uranyl nitrate solutions containing different amides vary depending on ligand nucleophilicity and steric crowding at the metal center. The most abundant species were ion pair complexes having the general formula (UO2(NO3)(amide)n=2,3)+, and complexes containing the amide conjugate base, reduced uranyl UO2+, and a 2+ charge were also formed. The formamide experiment produced the greatest diversity of species that stems from weaker amide binding leading to dissociation and subsequent solvent coordination or metal reduction. Experiments using methyl formamide, dimethyl formamide, acetamide, and methyl acetamide produced ion pair and doubly charged complexes that were more abundant, and less abundant complexes containing solvent or reduced uranyl. This pattern is reversed in the dimethylacetamide experiment, which displayed reduced doubly charged complexes and augmented reduced uranyl complexes. DFT investigations of the tris-amide ion pair complexes showed that inter-ligand repulsion distorts the amide ligands out of the uranyl equatorial plane, and that complex stabilities do not increase with increasing amide nucleophilicity. Elimination of an amide ligand largely relieves the interligand repulsion, and the remaining amide ligands become closely aligned with the equatorial plane in the structures of the bis-amide ligands. The studies show that the phenomenological distribution of coordination complexes in a metal-ligand electrospray experiment is a function of both ligand nucleophilicity and interligand repulsion, and that the latter factor begins exerting influence even in the case of relatively small ligands like the substituted methyl-formamide and methyl-acetamide ligands.

Solid state interaction studies on binary nitrate mixtures of uranyl nitrate hexahydrate and lanthanum nitrate hexahydrate at elevated temperatures

Energy Technology Data Exchange (ETDEWEB)

Kalekar, Bhupesh; Raje, Naina, E-mail: nraje@barc.gov.in; Reddy, A.V.R.

2017-02-15

Interaction behavior of uranyl nitrate hexahydrate (UNH) and lanthanum nitrate hexahydrate (LaNH) have been investigated on the mixtures in different molar ratios of the two precursors and monitoring the reactions at elevated temperatures with thermoanalytical and X-ray diffraction measurement techniques. During the decomposition of equimolar mixture of LaNH and UNH, formation of lanthanum uranate (U{sub 0.5}La{sub 0.5})O{sub 2}, was seen by the temperature of 500 °C along with lanthanum oxide (La{sub 2}O{sub 3}) and uranium trioxide (UO{sub 3}). By the temperature of 700 °C, the formation of uranium sesquioxide (U{sub 3}O{sub 8}) was observed along with (U{sub 0.5}La{sub 0.5})O{sub 2} as end products in uranium rich mixtures. Lanthanum rich compositions decomposed by the temperature of 700 °C to give (U{sub 0.5}La{sub 0.5})O{sub 2} and La{sub 2}O{sub 3} as end products. - Highlights: • UO{sub 2}(NO{sub 3}){sub 2}.6H{sub 2}O and La(NO{sub 3}){sub 3}.6H{sub 2}O interact through their intermediates. • Formation of (U{sub 0.5}La{sub 0.5})O{sub 2} by 500 °C. • La deficient mixtures decompose to give U{sub 3}O{sub 8} and (U{sub 0.5}La{sub 0.5})O{sub 2} as end products. • La rich mixtures decompose to give La{sub 2}O{sub 3} and (U{sub 0.5}La{sub 0.5})O{sub 2} as end product.

Critical Parameters of Complex Geometries of Intersecting Cylinders Containing Uranyl Nitrate Solution

International Nuclear Information System (INIS)

Rothe, R. E.

1999-01-01

About three dozen previously unreported critical configurations are presented for very complex geometries filled with high concentration enriched uranyl nitrate solution. These geometries resemble a tall, thin Central Column (or trunk of a ''tree'') having long, thin arms (or ''branches'') extending up to four directions off the column. Arms are equally spaced from one another in vertical planes, and that spacing ranges from arms in contact to quite wide spacings. Both the Central Column and the many different arms are critically safe by themselves with each, alone, is filled with fissile solution; but, in combination, criticality occurs due to the interactions between arms and the column. Such neutronic interactions formed the principal focus of this study. While these results are fresh to the nuclear criticality safety industry and to those seeking novel experiments against which to validate computer codes, the experiments, themselves, are not recent. Over 100 experiments were performed at the Rocky Flats Critical Mass Laboratory between September, 1967, and February of the following year

Novel two-dimensional uranyl-organic assemblages in the citrate and D(-)-citramalate families

International Nuclear Information System (INIS)

Thuery, P.

2008-01-01

Uranyl nitrate reacts with D(-)-citramalic acid (H(3)citml) under mild hydrothermal conditions to give the two-dimensional polymer [UO 2 (Hcitml)] 1, in which each ligand chelates one metal atom through its hydroxyl and alpha- carboxylate groups and binds to three others in monodentate fashion. The resulting neutral layers display isolated uranyl pentagonal bipyramidal polyhedra. Whereas citric acid (H(4)cit) has been shown previously to give various three- and mono-dimensional uranyl organic assemblages, complexation under hydrothermal conditions in the presence of either NaOH/NEt 4 Cl or pyridine yields the complexes [NEt 4 ] 2 [(UO 2 ) 3 (cit) 2 (H 2 O) 2 ]· 2H 2 O 2 and [Hpy] 2 )[(UO 2 ) 3 (cit)(Hcit)(OH)] 3, respectively, which both crystallize as two- dimensional frameworks. The layers are either planar and separated by the counter ions in 2 or corrugated and hydrogen bonded to one another in 3. In both 2 and 3, [UO 2 (cit)] 2 4- dimeric subunits with edge-sharing pentagonal bipyramidal uranium coordination polyhedra are present but, in both cases and in contrast with previous structures containing [UO 2 (Hcit)] 2 2- dimers, the carboxylate group not involved in the dimer formation is coordinated to another uranyl unit, which is part of either a centrosymmetric hexagonal bipyramidal bis-aquated group or a different, [(UO 2 ) 2 (Hcit)(OH)] dimer. These examples of two- dimensional assemblages further illustrate the variety of architectures which can be obtained with citric and related acids and the important structure-directing effects of the counter ions. (author)

Removal of uranyl ions by p-hexasulfonated calyx[6]arene acid

Energy Technology Data Exchange (ETDEWEB)

Popescu, Ioana-Carmen [R and D National Institute for Metals and Radioactive Resources–ICPMRR, B-dul Carol I No.70, Sector 2, Bucharest 020917 (Romania); Petru, Filip [“C.D. Nenitescu” Institute of Organic Chemistry, Splaiul Independentei 202B, Sector 6, Bucharest 71141 (Romania); Humelnicu, Ionel [“Al.I. Cuza” University of Iasi, The Faculty of Chemistry, Bd. Carol-I No. 11, Iasi 700506 (Romania); Mateescu, Marina [National R and D Institute for Chemistry and Petrochemistry, Splaiul Independenţei No. 202, Bucharest 060021 (Romania); Militaru, Ecaterina [R and D National Institute for Metals and Radioactive Resources–ICPMRR, B-dul Carol I No.70, Sector 2, Bucharest 020917 (Romania); Humelnicu, Doina, E-mail: doinah@uaic.ro [“Al.I. Cuza” University of Iasi, The Faculty of Chemistry, Bd. Carol-I No. 11, Iasi 700506 (Romania)

2014-10-15

Radioactive pollution is a significant threat for the people’s health. Therefore highly effective radioactive decontamination methods are required. Ion exchange, biotechnologies and phytoremediation in constructed wetlands have been used as radioactive decontamination technologies for uranium contaminated soil and water remediation. Recently, beside those classical methods the calix[n]arenic derivatives’ utilization as radioactive decontaminators has jogged attention. The present work aims to present the preliminary research results of uranyl ion sorption studies on the p-hexasulfonated calyx[6]arenic acid. The effect of temperature, contact time, sorbent amount and uranyl concentration variation on sorption efficiency was investigated. Isotherm models revealed that the sorption process fit better Langmuir isotherm.

The system uranyl nitrate-dietyl ether-water. Extraction by water in spray and packed columns from uranyl nitrate-either solutions; El sistema nitrato de uranilo-eter dietilico-agua, extraccion de nitrato de uranilo con agua a partir de disoluciones etereas en columnas de pulverizacion y de relleno

Energy Technology Data Exchange (ETDEWEB)

Perez Luina, A; Gutierrez Jodra, L

1960-07-01

This paper is a continuation of the one published in Chemical Engineering Progress. Symposium Series, 50, n. 12, 127 (1954). New runs for spray columns, are given and other concentrations in uranyl nitrate for the packed columns. New correlations for the overall H.T.U. are also given. The individual H.T.U. have been grapycally calculated and show that the film resistances have similar values, being independent of the concentration of the ether phase. (Author) 24 refs.

Determination of the stability of the uranyl ion sipped in {tau}-hydrogen phosphate of zirconium in sodic form; Determinacion de la estabilidad del ion uranilo sorbido en {tau}-hidrogenofosfato de zirconio en forma sodica

Energy Technology Data Exchange (ETDEWEB)

Ordonez R, E.; Fernandez V, S.M. [ININ, 52045 Ocoyoacac, Estado de Mexico (Mexico); Drot, R.; Simoni, E. [Universite de Paris-Sud-XI, Institut de Physique Nucleaire d' Orsay, Groupe de radiochimie, Bat. 100, 91406 Orsay (France)]. e-mail: edo@nuclear.inin.mx

2005-07-01

The stability of the uranyl sipped in the zirconium {tau}-hydrogen phosphate in sodic form ({tau}-NaZrP), was carried out characterizing the complexes formed by Laser spectroscopy in the visible region and by X-ray photoelectron spectroscopy. The material was prepared by a new synthesis technique working in nitrogen atmosphere and to low temperatures. The sorption of the uranyl ion was made in acid media with concentrations of 10{sup -4} and 10{sup -5} of uranyl nitrate and with ion forces of 0.1 and 0.5 M of NaClO{sub 4}. The spectra of induced fluorescence with laser (TRLFS) show that the uranyl is fixed in very acid media in three well differentiated species, to pH less acid, the specie of long half life disappears and are only those of short half life. The results of the binding energy obtained by XPS indicate that the binding energy of the uranyl confer it a stable character to the complex formed in the {tau}-NaZP, that makes to this material appropriate to retain to the uranyl in solution to high ion forces and in acid media. (Author)

The interaction of uranyl ions with inorganic pyrophosphatase from baker's yeast

International Nuclear Information System (INIS)

Bienwald, B.; Heitmann, P.

1978-01-01

The interaction of uranyl ions with inorganic pyrophosphatase from baker's yeast was investigated by measurement of their effect on the protein fluorescence. Fluorescence titrations of the native enzyme with uranyl nitrate show that there is a specific binding of uranyl ions to the enzyme. It was deduced that each subunit of the enzyme binds one uranyl ion. The binding constant was estimated to be in the order of 10 7 M -1 . The enzyme which contains a small number of chemically modified carboxyl groups was not able to bind uranyl ions specifically. The modification of carboxyl groups was carried out by use of a water soluble carbodiimide and the nucleophilic reagent N-(2,4-dinitro-phenyl)-hexamethylenediamine. The substrate analogue calcium pyrophosphate displaced the uranyl ions from their binding sites at the enzyme From the results it is concluded that carboxyl groups of the active site are the ligands for the binding of uranyl ions. (author)

The toxicity of uranyl nitrate on primary brain cell culture of L. Hoevenii

International Nuclear Information System (INIS)

Ismail Bahari; Fauziah Mohd Noor

1995-01-01

In Malaysia, uranium is indirectly being concentrated by mining and petroleum industries that have no relevance to its use. Concentration of uranium and the production of TENORM may give rise to radiological risk to workers and the environment. A study was conducted to determine the toxicity of a uranium compound, uranyl nitrate. For this purpose a primary brain cell culture derived from L. hoevenii was used. The nature of uranil nitrate toxicity was determined by comparing with the effects induced by mitomycin C and gamma radiation. The toxicity of these agents were measured by observing changes in Unschedule DNA Synthesis (UDS) and the induction of micronucleus. Result from the study showed that UO sub 2 sup 2+ is UDS positive and is toxic to the primary brain cells of L. hoevenii. It gives a response profile that is almost similar to that induced by gamma radiation and mitomycin C. We believed that a low concentration, UO sub 2 sup 2+ acts as a chemo toxic agent rather than as an ionising radiation. At higher concentration the toxicity of UO sub 2 sup 2+ comes from both its chemo toxic and radiation effects. Results of this study also show the ability of the primary culture to carry out repair on its DNA damaged by the UDS positive agents

Study of the solubility of plutonyl nitrate with a view to its extraction by a solvent; Etude de la solubilite du nitrate de plutonyle en vue de son extraction par solvant

Energy Technology Data Exchange (ETDEWEB)

Vergnaud, G [Commissariat a l' Energie Atomique, Fontenay aux Roses (France). Centre d' Etudes Nucleaires

1965-09-01

The research covers the determination of the partition coefficient of plutonyl nitrate and their application to the industrial treatment of plutonium. The solvent used is a tri-n-butyl phosphate solution diluted to 30 per cent in dodecane. The parameters which have been studied and which can affect the extraction of the plutonyl nitrate are: the plutonyl nitrate concentration; the nitric acid concentration; the uranyl nitrate concentration; the tetravalent plutonium nitrate concentration. The industrial application has been studied using a battery of mixer-separators. The operational conditions are defined in the case of a conventional plutonium separation plant. The results obtained, for a higher plutonyl nitrate concentration than that actually planned, are satisfactory and encouraging as far as the operation is concerned. Only the presence of polymerized tetravalent plutonium can adversely affect the satisfactory extraction of the plutonium. (author) [French] L'etude porte sur les coefficients de partage du nitrate de plutonyle et leur application a l'elaboration industrielle du plutonium. Le solvant utilise est une solution de phosphate de tri-n-butyle, dilue a 30 pour cent dans le dodecane. Les parametres etudies et pouvant influencer l'extraction du nitrate de plutonyle, par ce solvant, sont: concentration du nitrate de plutonyle; concentration de l'acide nitrique; concentration du nitrate d'uranyle; concentration au nitrate de plutonium tetravalent. L'application industrielle est etudiee au moyen d'une batterie de melangeurs-decanteurs. Les conditions operatoires sont definies d'apres un schema classique d'usine de separation de plutonium. Les resultats obtenus, pour une concentration du nitrate de plutonyle superieure a celle reellement prevue, sont satisfaisants et encourageants pour l'exploitation. Seule, la presence de plutonium tetraralent polymerise, peut nuire a une bonne extraction du plutonium. (auteur)

Study of the solubility of plutonyl nitrate with a view to its extraction by a solvent; Etude de la solubilite du nitrate de plutonyle en vue de son extraction par solvant

Energy Technology Data Exchange (ETDEWEB)

Vergnaud, G. [Commissariat a l' Energie Atomique, Fontenay aux Roses (France). Centre d' Etudes Nucleaires

1965-09-01

The research covers the determination of the partition coefficient of plutonyl nitrate and their application to the industrial treatment of plutonium. The solvent used is a tri-n-butyl phosphate solution diluted to 30 per cent in dodecane. The parameters which have been studied and which can affect the extraction of the plutonyl nitrate are: the plutonyl nitrate concentration; the nitric acid concentration; the uranyl nitrate concentration; the tetravalent plutonium nitrate concentration. The industrial application has been studied using a battery of mixer-separators. The operational conditions are defined in the case of a conventional plutonium separation plant. The results obtained, for a higher plutonyl nitrate concentration than that actually planned, are satisfactory and encouraging as far as the operation is concerned. Only the presence of polymerized tetravalent plutonium can adversely affect the satisfactory extraction of the plutonium. (author) [French] L'etude porte sur les coefficients de partage du nitrate de plutonyle et leur application a l'elaboration industrielle du plutonium. Le solvant utilise est une solution de phosphate de tri-n-butyle, dilue a 30 pour cent dans le dodecane. Les parametres etudies et pouvant influencer l'extraction du nitrate de plutonyle, par ce solvant, sont: concentration du nitrate de plutonyle; concentration de l'acide nitrique; concentration du nitrate d'uranyle; concentration au nitrate de plutonium tetravalent. L'application industrielle est etudiee au moyen d'une batterie de melangeurs-decanteurs. Les conditions operatoires sont definies d'apres un schema classique d'usine de separation de plutonium. Les resultats obtenus, pour une concentration du nitrate de plutonyle superieure a celle reellement prevue, sont satisfaisants et encourageants pour l'exploitation. Seule, la presence de plutonium tetraralent polymerise, peut nuire a une bonne extraction du plutonium

Calculational study of benchmark critical experiments on high-enriched uranyl nitrate solution systems

International Nuclear Information System (INIS)

Oh, I.; Rothe, R.E.

1978-01-01

Criticality calculations on minimally reflected, concrete-reflected, and plastic-reflected single tanks and on arrays of cylinders reflected by concrete and plastic have been performed using the KENO-IV code with 16-group Hansen-Roach neutron cross sections. The fissile material was high-enriched (93.17% 235 U) uranyl nitrate [UO 2 (NO 3 ) 2 ] solution. Calculated results are compared with those from a benchmark critical experiments program to provide the best possible verification of the calculational technique. The calculated k/sub eff/'s underestimate the critical condition by an average of 1.28% for the minimally reflected single tanks, 1.09% for the concrete-reflected single tanks, 0.60% for the plastic-reflected single tanks, 0.75% for the concrete-reflected arrays of cylinders, and 0.51% for the plastic-reflected arrays of cylinders. More than half of the present comparisons were within 1% of the experimental values, and the worst calculational and experimental discrepancy was 2.3% in k/sub eff/ for the KENO calculations

Critical Parameters of Complex Geometries of Intersecting Cylinders Containing Uranyl Nitrate Solution

Energy Technology Data Exchange (ETDEWEB)

J. B. Briggs (INEEL POC); R. E. Rothe

1999-06-14

About three dozen previously unreported critical configurations are presented for very complex geometries filled with high concentration enriched uranyl nitrate solution. These geometries resemble a tall, thin Central Column (or trunk of a ''tree'') having long, thin arms (or ''branches'') extending up to four directions off the column. Arms are equally spaced from one another in vertical planes, and that spacing ranges from arms in contact to quite wide spacings. Both the Central Column and the many different arms are critically safe by themselves with each, alone, is filled with fissile solution; but, in combination, criticality occurs due to the interactions between arms and the column. Such neutronic interactions formed the principal focus of this study. While these results are fresh to the nuclear criticality safety industry and to those seeking novel experiments against which to validate computer codes, the experiments, themselves, are not recent. Over 100 experiments were performed at the Rocky Flats Critical Mass Laboratory between September, 1967, and February of the following year.

A thermal analysis - mass spectrometric study of the reactions in the binary nitrate system UO2(NO3)2.6H2O-Ba(NO3)2

International Nuclear Information System (INIS)

Kalekar, B.B.; Rajagopalan, K.V.; Ravindran, P.V.

2008-01-01

Solid state reaction between uranyl nitrate hexahydrate and barium nitrate at elevated temperatures has been studied. Barium nitrate does not react directly with uranyl nitrate hexahydrate (UNH). The decomposition product of the latter, UO 3 , however, reacts with molten barium nitrate to form nitrato complexes which decompose to form barium uranates. The decomposition of the nitrato complex is often attended by a change of oxidation state of uranium. Uranyl-nitrate-rich compositions form uranates with uranium in oxidation state V, whereas barium-nitrate-rich compositions form uranates with uranium in oxidation state VI. The tendency for hydrolysis of uranyl nitrate hexahydrate at elevated temperatures is lowered in presence of barium nitrate and, unlike in the case of dehydration of pure UNH, uranyl nitrate dihydrate is formed as dehydration intermediate. (author)

Development of a reconversion method for uranyl nitrate to oxide in the reconversion step of reprocessing of irradiated fuel

International Nuclear Information System (INIS)

Govindan, P.; Palamalai, A.; Vijayan, K.S.; Subbuthai, S.; Murugesan, S.; Mohan, S.V.; Subba Rao, R.V.

2002-01-01

Ammonium uranyl carbonate (AUC) precipitation is developed for the conversion of uranyl nitrate to oxide in the uranium reconversion step of reprocessing of irradiated fuel by the addition of ammonium carbonate salt. Different precipitation conditions of AUC are studied. The solubility of AUC as a function of uranium concentration in the feed at different temperatures using ammonium carbonate salt as precipitant is studied. This study indicates that 95-99.8% of uranium is recovered as AUC by precipitating 5-125 g/l of uranium with loss of uranium (250-10 ppm) in the filtrate by adding ammonium carbonate salt. It is also observed that the solubility of AUC increased as the concentration of uranium decreased. Thermal decomposition is carried out by thermogravimetry/differential thermal analysis (TG/DTA) and evolved gas analysis-mass spectrometry (EGA-MS) to find out AUC decomposition and gases evolved during decomposition. Studies are also carried out to characterize AUC by using X-ray diffraction (XRD). The data show that AUC obtained by the above conditions is very much consistent with published information. (author)

Efficient uranous nitrate production using membrane electrolysis

International Nuclear Information System (INIS)

Zhongwei Yuan; Taihong Yan; Weifang Zheng; Hongying Shuang; Liang Xian; Xiaoyan Bian; Chen Zuo; Chuanbo Li; Zhi Cao

2013-01-01

Electrochemical reduction of uranyl nitrate is a green, simple way to make uranous ion. In order to improve the ratio of uranous ion to the total uranium and maintain high current efficiency, an electrolyser with very thin cathodic and anodic compartment, which were separated by a cation exchange membrane, was setup, and its performance was tested. The effects of various parameters on the reduction were also evaluated. The results show that the apparatus is quite positive. It runs well with 120 mA/cm 2 current density (72 cm 2 cathode, constant current batch operation). U(IV) yield can achieve 93.1 % (500 mL feed, total uranium 199 g/L) after 180 min electrolysis. It was also shown that when U(IV) yield was below 80 %, very high current efficiency was maintained, and there was almost a linear relationship between uranous ion yield and electrolysis time; under the range of experimental conditions, the concentration of uranyl nitrate, hydrazine, and nitric acid had little effect on the reduction. (author)

Mechanism of acute renal failure after uranyl nitrate

International Nuclear Information System (INIS)

Blantz, R.C.; Konnen, K.

1975-01-01

Administration of 25 mg/kg uranyl nitrate (UN) to rats leads to a brief period of polyuria followed by progressive oliguria with death at 5 days. Factors that determine glomerular filtration rate (GFR) were examined in control Munich--Wistar rats (n = 16) and 2 h after either 15 mg/kg (n = 8) or 25 kg/kg (n = 7) of UN (i.v.) utilizing direct measurements of hydrostatic and oncotic pressures and plasma flow. Total kidney GFR was reduced to 47 percent of control in the low dose group and to 21 percent in the high dose group. The simultaneous nephron filtration rate (sngfr) was 28.6 +- 0.8 nl/min/g kidney wt in control, 29.1 +- 1.0 in the low dose group, and 18.1 +- 1.2 (P less than 0.001) in the higher dose group. Nephron plasma flow was equal to control at both doses of UN. Also directly measured hydrostatic pressure gradient across the glomerular capillary was not changed. The effective filtration pressure achieved equilibrium in control animals but became significantly positive at the efferent end of the capillary at both doses of UN and increased. Total glomerular permeability (L/sub p/A) was progressively reduced from control (0.089 +- 0.005 nl/s/g kidney wt/mm Hg) at low dose UN (0.047 +- 0.013) and high dose (0.024 +- 0.003 nl/s/g kidney wt/mm Hg). Therefore UN decreases GFR by two mechanisms: (a) tubular damage leading to back-diffusion of solutes and (b) a primary reduction in sngfr due to reduced L/sub p/A

Determination of total and extractable hydrogen peroxide in organic and aqueous solutions of uranyl nitrate

International Nuclear Information System (INIS)

Goodall, Ph.

1999-01-01

The development of a spectrophotometric method for the determination of hydrogen peroxide in uranyl nitrate solutions is reported. The method involves the measurement of the absorbance at 520 mm of a vanadyl peroxide species. This species was formed by the addition of a reagent consisting of vanadium (V) (50 mmol x dm -3 ) in dilute sulphuric acid (2 mol x dm -3 H 2 SO 4 ). This reagent, after dilution, was also used as an extractant for organic phase samples. The method is simple and robust and tolerant of nitric acid and U(VI). Specificity and accuracy were improved by the application of solid phase extraction techniques to remove entrained organic solvents and Pu(VI). Reverse phase solid phase extraction was used to clean-up aqueous samples or extracts which were contaminated with entrained solvent. A solid phase extraction system based upon an extraction chromatography system was used to remove Pu(IV). Detection limits of 26 μmol x dm -3 (0.88 μg x cm -3 ) or 7 μmol x dm -3 (0.24 μg x cm -3 ) for, respectively, a 1 and 4 cm path length cell were obtained. Precisions of RSD = 1.4% and 19.5% were obtained at the extremes of the calibration curve (5 mmol x dm -3 and 50 μmol x dm -3 H 2 O 2 , 1 cm cell). The introduction of the extraction and clean-up stages had a negligible effect upon the precision of the determination. The stability of an organic phase sample was tested and no loss of analyte could be discerned over a period of at least 5 days. (author)

The thermal denigration in fluid-bed to make uranyl product

International Nuclear Information System (INIS)

Ma Zhenrong; Cui Yulin; Zhu Changbing; Fan Chuanyong; Liu Yanfeng

2010-01-01

Nuclear fuel reprocessing plant used the thermal denigration to high concentration of uranyl nitrate solution in fluid-bed to make uranyl product. First the uranyl nitrate solution were concentrated in evaporator, into 300 gU/L, 600 gU/L, 750 gU/L and 1000 gU/L.When the fluid-bed was in good fluidity state at 320 degree C, the solution was sprayed all over the surface of the fine crystal seeds through the dual-channel air-blast nozzles to make new crystal seed and to make them grow up. The denigration reaction occurred when the internal temperature of the fluid-bed was kept at about 300 degree C by the outside and inside heat apparatus. The product were transported crossing the valve and spiral transfer to pack. The tail gas was purified and discharged. Through the fluid-bed's running, the variation discipline of temperature and the pressure, the effect curve of the quality of product accumulated to pressure drop were determined. At the same time, the gentrification temperature, the distributed heat and the transfer mode were tested. (authors)

Analysis Ratio of Uranyl/Urea and Uranyl/HMTA on the ComplexesUranyl-Urea and Uranyl-HMTA with Spectrophotometry Method

International Nuclear Information System (INIS)

Simbolon, Sahat

2000-01-01

Reaction between uranyl and urea and uranyl and HMTA was investigated atpH = 4 and room temperature. The result of the reaction was measured withspectrophotometer, each absorbance was pictured between mol fraction andabsorbance for uranyl - urea and uranyl - HMTA. The linear and horizontalcurve was found for reaction uranyl - urea, meanwhile S curve for thereaction uranyl and HMTA. It was found that reaction between uranyl and HMTAon mol fraction value less than 0.25 was complexes meanwhile on the range of0.25 and 0.5 the reaction between uranyl and HMTA was stoichiometries.(author)

Application of the NICADonnan model for proton, copper and uranyl binding to humic acid

NARCIS (Netherlands)

Saito, T.; Nagasaki, S.; Tanaka, S.; Koopal, L.K.

2004-01-01

Humic acids are natural organic materials that play an important role in the migration of heavy metal and actinide ions in aquatic and soil systems. In the present study, the binding of protons, copper ions and uranyl ions to the purified Aldrich humic acid (PAHA) is investigated and the results are

Ligand exchange in uranyl complexes in non-aqueous solutions: equilibrium properties

International Nuclear Information System (INIS)

Egozy, Y.; Weiss, S.

1976-01-01

The systems uranyl nitrate, tributylphosphate and 8-hydroxyquinoline or diphenylcarbazone were studied in chloroform, carbon tetrachloride and 1,2-dichloroethane at a number of temperatures. The nature of the complexes formed was determined and the equilibrium constants and several thermodynamic functions were measured. 8-hydroxyquinoline and diphenylcarbazone will be valuable as indicators for uranyl in kinetic studies. They are also interesting since they participate, along with tributylphosphate, in formation of synergistic complexes. (author)

Precipitation characteristics of uranyl ions at different pHs depending on the presence of carbonate ions and hydrogen peroxide.

Science.gov (United States)

Kim, Kwang-Wook; Kim, Yeon-Hwa; Lee, Se-yoon; Lee, Jae-Won; Joe, Kih-Soo; Lee, Eil-Hee; Kim, Jong-Seung; Song, Kyuseok; Song, Kee-Chan

2009-04-01

This work studied the dissolution of uranium dioxide and precipitation characteristics of uranyl ions in alkaline and acidic solutions depending on the presence of carbonate ions and H2O2 in the solutions at different pHs controlled by adding HNO3 or NaOH in the solution. The chemical structures of the precipitates generated in different conditions were evaluated and compared by using XRD, SEM, TG-DT, and IR analyses together. The sizes and forms of the precipitates in the solutions were evaluated, as well. The uranyl ions were precipitated in the various forms, depending on the solution pH and the presences of hydrogen peroxide and carbonate ions in the solution. In a 0.5 M Na2CO3 solution with H2O2, where the uranyl ions formed mixed uranyl peroxy-carbonato complexes, the uranyl ions were precipitated as a uranium peroxide of UO4(H20)4 at pH 3-4, and precipitated as a clarkeite of Na2U2Ox(OH)y(H2O)z above pH 13. In the same carbonate solution without H2O2, where the uranyl ions formed uranyl tris-carbonato complex, the uranyl ions were observed to be precipitated as a different form of clarkeite above pH 13. The precipitate of uranyl ions in a nitrate solution without carbonate ions and H2O2 at a high pH were studied together to compare the precipitate forms in the carbonate solutions.

Thermal decomposition study of uranyl nitrate and cerium hydroxide in a spray dryer

International Nuclear Information System (INIS)

Silva Wildhagen, G.R. da.

1993-05-01

A study, in a spray dryer system based on drying and thermal decomposition of uranyl nitrate solutions aiming the production of uranium trioxide adequate for the use in posterior steps of reduction and hydro fluorination in nuclear fuel cycle; and cerium hydroxide suspensions for the production of cerium oxide with high surface area is presented. Thus, the project and construction of a countercurrent spray dryer was elaborated for capacity of 10 Kg U O 3 /h and 3,5 k Ce O 2 /h. The methodology used in these experiments consisted in the analysis of several parameters (concentration and flow rate of the feed, atomization pressure and inlet temperature of the dryer) over the physical and chemical properties of the products. Using the obtained results, with the help of a mathematical model, it was developed the project of a continuous pilot unity for the production of uranium trioxide or cerium oxide, with capacity of 20 Kg U O 3 /h or 10 Kg Ce O 2 /h, respectively. (author)

Annual report of STACY operation in F.Y. 1997. 280mm thickness slab core {center_dot} 10% enriched uranyl nitrate solution

Energy Technology Data Exchange (ETDEWEB)

Onodera, Seiji; Sono, Hiroki; Hirose, Hideyuki [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment] [and others

1998-06-01

Fifty-three times critical experiments (run number R0104 to R0156) with STACY in NUCEF, were performed in F.Y. 1997. During these experiments, 10% enriched uranyl nitrate solution was used as fuel, and core configuration was 280mm thickness and 1.5m height slab core tank with various rectangular solid reflectors; ordinary or borated concrete, polyethylene and so on, to measure mainly reactivity worth by changes of reflecting material and its thickness. Operation data of STACY in F.Y. 1997 are summarized in this report. (author)

Determination of the extractive capacity of para-tert butyl calix[8]arene octa-phosphinoylated towards uranyl ions from an aqueous-acidic-salty medium; Determinacion de la capacidad extractiva del p-ter-butilocalix[8]areno octa-fosfinoilado hacia iones uranilo de un medio acuo-acido salino

Energy Technology Data Exchange (ETDEWEB)

Serrano V, E. C.

2011-07-01

The extraction properties of octa-phosphinoylated para-tert butyl calix[8]arene (prepared in the laboratory) in chloroform towards uranyl ions from an aqueous-acidic-salty medium (HNO{sub 3}-3.5 NaNO{sub 3}) containing uranyl nitrate salt, was investigated. Two spectroscopic techniques UV/Vis and Luminescence were used for this study. The latter permitted analyze the fluorescence from the uranyl ions influenced by the surrounding medium. Both permitted to learn about the power of this calixarene as extractant towards the mentioned ions. Its extraction ability or capability using this calixarene at 5.91 x 10{sup -4} M towards the uranyl ions was 400% as determined by UV/Vis while fluorescence revealed 100% of uranyl ion extraction. A closed analysis of the results obtained by using these techniques revealed that the stoichiometry of the main extracted species was 1calixarene:2 uranyl ions. The loading capacity of the calixarene ligand towards the uranyl ions was also investigated using both techniques. UV/Vis resulted to be inadequate for quantifying exactly the loading capacity of the calixarene whereas luminescence was excellent indeed, using a 5.91 x 10{sup -4} M calixarene concentration, its loading capacity was 0.157 M of free uranyl ions from 0.161 M of uranyl ions present in the aqueous-acidic-salty medium. The extracts from the ability and capacity studies were concentrated to dryness, purified and the dried extracts were analyzed by infrared and neutron activation analysis. By these techniques it was demonstrated that during the extraction of the uranyl ions by the calixarene ligand they form thermodynamically and kinetically stable complexes, since in the solid state, the 1:2, calixarene; uranyl ions stoichiometry was kept with the minimum formula: (UO{sub 2}){sub 2}B{sub 8}bL{sup 8}(NO{sub 3}){sub 4}(H{sub 2}O){sub 4}CHCl{sub 3}(CH{sub 3}OH){sub 3} the methanol molecules come from its purification. It is proposed that B{sub 8}bL{sup 8} calixarene in

A Solution-Based Approach for Mo-99 Production: Considerations for Nitrate versus Sulfate Media

Directory of Open Access Journals (Sweden)

Amanda J. Youker

2013-01-01

Full Text Available Molybdenum-99 is the parent of Technetium-99m, which is used in nearly 80% of all nuclear medicine procedures. The medical community has been plagued by Mo-99 shortages due to aging reactors, such as the NRU (National Research Universal reactor in Canada. There are currently no US producers of Mo-99, and NRU is scheduled for shutdown in 2016, which means that another Mo-99 shortage is imminent unless a potential domestic Mo-99 producer fills the void. Argonne National Laboratory is assisting two potential domestic suppliers of Mo-99 by examining the effects of a uranyl nitrate versus a uranyl sulfate target solution configuration on Mo-99 production. Uranyl nitrate solutions are easier to prepare and do not generate detectable amounts of peroxide upon irradiation, but a high radiation field can lead to a large increase in pH, which can lead to the precipitation of fission products and uranyl hydroxides. Uranyl sulfate solutions are more difficult to prepare, and enough peroxide is generated during irradiation to cause precipitation of uranyl peroxide, but this can be prevented by adding a catalyst to the solution. A titania sorbent can be used to recover Mo-99 from a highly concentrated uranyl nitrate or uranyl sulfate solution; however, different approaches must be taken to prevent precipitation during Mo-99 production.

Synthesis of pyrimidine carboxamide derivatives catalyzed by uranyl

African Journals Online (AJOL)

2014-09-02

(Received September 2, 2014; revised January 1, 2016). ABSTRACT. An efficient and simple method was developed for the synthesis pyrimidine-5-carboxamides using. UO2(NO3)2.6H2O catalyst under conventional and microwave irradiation. The synthesis of dihydropyrimidine using uranyl nitrate had shown many ...

Ultrastructural and metabolic changes in osteoblasts exposed to uranyl nitrate

International Nuclear Information System (INIS)

Tasat, D.R.; Orona, N.S.; Mandalunis, P.M.; Cabrini, R.L.; Ubios, A.M.

2007-01-01

Exposure to uranium is an occupational hazard to workers who continually handle uranium and an environmental risk to the population at large. Since the cellular and molecular pathways of uranium toxicity in osteoblast cells are still unknown, the aim of the present work was to evaluate the adverse effects of uranyl nitrate (UN) on osteoblasts both in vivo and in vitro. Herein we studied the osteoblastic ultrastructural changes induced by UN in vivo and analyzed cell proliferation, generation of reactive oxygen species (ROS), apoptosis, and alkaline phosphatase (APh) activity in osteoblasts exposed to various UN concentrations (0.1, 1, 10, and 100 μM) in vitro. Cell proliferation was quantified by means of the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay, ROS was determined using the nitro blue tetrazolium test, apoptosis was morphologically determined using Hoechst 3332 and APh activity was assayed spectrophotometrically. Electron microscopy revealed that the ultrastructure of active and inactive osteoblasts exposed to uranium presented cytoplasmic and nuclear alterations. In vitro, 1-100 μM UN failed to modify cell proliferation ratio and to induce apoptosis. ROS generation increased in a dose-dependent manner in all tested doses. APh activity was found to decrease in 1-100 μM UN-treated cells vs. controls. Our results show that UN modifies osteoblast cell metabolism by increasing ROS generation and reducing APh activity, suggesting that ROS may play a more complex role in cell physiology than simply causing oxidative damage. (orig.)

Critical experiment program of heterogeneous core composed for LWR fuel rods and low enriched uranyl nitrate solution

International Nuclear Information System (INIS)

Miyoshi, Yoshinori; Yamamoto, Toshihiro; Watanabe, Shouichi; Nakamura, Takemi

2003-01-01

In order to stimulate the criticality characteristics of a dissolver in a reprocessing plant, a critical experiment program of heterogeneous cores is under going at a Static Critical Experimental Facility, STACY in Japan Atomic Energy Research Institute, JAERI. The experimental system is composed of 5w/o enriched PWR-type fuel rod array immersed in 6w/o enriched uranyl nitrate solution. First series of experiments are basic benchmark experiments on fundamental critical data in order to validate criticality calculation codes for 'general-form system' classified in the Japanese Criticality Safety Handbook, JCSHB. Second series of experiments are concerning the neutron absorber effects of fission products related to the burn-up credit Level-2. For demonstrating the reactivity effects of fission products, reactivity effects of natural elements such as Sm, Nd, Eu and 103 Rh, 133 Cs, solved in the nitrate solution are to be measured. The objective of third series of experiments is to validate the effect of gadolinium as a soluble neutron poison. Properties of temperature coefficients and kinetic parameters are also studied, since these parameters are important to evaluate the transient behavior of the criticality accident. (author)

Study of the Changes in Composition of Ammonium Diuranate with Progress of Precipitation, and Study of the Properties of Ammonium Diuranate and its Subsequent Products Produced from both Uranyl Nitrate and Uranyl Fluoride Solutions

Directory of Open Access Journals (Sweden)

Subhankar Manna

2017-04-01

Full Text Available Uranium metal used for fabrication of fuel for research reactors in India is generally produced by magnesio-thermic reduction of UF4. Performance of magnesio-thermic reaction and recovery and quality of uranium largely depends on properties of UF4. As ammonium diuranate (ADU is first product in powder form in the process flow-sheet, properties of UF4 depend on properties of ADU. ADU is generally produced from uranyl nitrate solution (UNS for natural uranium metal production and from uranyl fluoride solution (UFS for low enriched uranium metal production. In present paper, ADU has been produced via both the routes. Variation of uranium recovery and crystal structure and composition of ADU with progress in precipitation reaction has been studied with special attention on first appearance of the precipitate Further, ADU produced by two routes have been calcined to UO3, then reduced to UO2 and hydroflorinated to UF4. Effect of two different process routes of ADU precipitation on the characteristics of ADU, UO3, UO2 and UF4 were studied here.

Study of the changes in composition of ammonium diuranate with progress of precipitation, and study of the properties of ammonium diuranate and its subsequent products produced from both uranyl nitrate and uranyl fluoride solutions

International Nuclear Information System (INIS)

Manna, Subhankar; Kumar, Raj; Satpati, Santosh K.; Roy, Saswati B.; Joshi, Jyeshtharaj B.

2017-01-01

Uranium metal used for fabrication of fuel for research reactors in India is generally produced by magnesio-thermic reduction of UF 4 . Performance of magnesio-thermic reaction and recovery and quality of uranium largely depends on properties of UF 4 . As ammonium diuranate (ADU) is first product in powder form in the process flow-sheet, properties of UF 4 depend on properties of ADU. ADU is generally produced from uranyl nitrate solution (UNS) for natural uranium metal production and from uranyl fluoride solution (UFS) for low enriched uranium metal production. In present paper, ADU has been produced via both the routes. Variation of uranium recovery and crystal structure and composition of ADU with progress in precipitation reaction has been studied with special attention on first appearance of the precipitate Further, ADU produced by two routes have been calcined to UO 3 , then reduced to UO 2 and hydroflorinated to UF 4 . Effect of two different process routes of ADU precipitation on the characteristics of ADU, UO 3 , UO 2 and UF 4 were studied here

Ion exchange separation of nitrate from uranium compounds and its determination by spectrophotometry and ion chromatography

International Nuclear Information System (INIS)

Pires, M.A.F.; Atalla, L.T.; Abrao, A.

1985-11-01

A procedure for the separation of nitrate from uranium compounds by retaintion of uranyl ion on a cationic ion exchanger and its determination in the effluent is described. Nitrate is analysed by the spectrometric method with 1-phenol-2,4-dissulphonic acid. This determination covers the 1 to 10 μg NO - 3 /mL range and requires an amount of 10 to 100 μg NO - 3 . The main interference is uranium (VI) due its own intense yellow color. This difficulty is overcome by the complete separation of UO 2 ++ with the cationic resin. Alternatively, the ion chromatography technique is used for the determination of nitrate in the effluent of the cationic resin. The determination was easily made by the comparison of the nitrate peak hights of the analyte and the standard solutions. The ion chromatography method is very sensitive (0,3 μg NO - 3 /mL), reproducible and suitable for routine analysis and permits the determination of fraction of part per million of nitrate in uranium. The results of nitrate determination using both spectrophotometric and ion chromatography techniques are compared. The method is being routinely applied for the quality control of uranium compounds in the fuel cycle, specially uranium oxide, ammonium diuranate, uranium peroxide and ammonium uranyl tricarbonate. (Author) [pt

Conversion and Blending Facility highly enriched uranium to low enriched uranium as uranyl nitrate hexahydrate. Revision 1

Energy Technology Data Exchange (ETDEWEB)

NONE

1995-07-05

This Conversion and Blending Facility (CBF) will have two missions: (1) convert HEU materials to pure HEU uranyl nitrate (UNH) and (2) blend pure HEU UNH with depleted and natural UNH to produce HEU UNH crystals. The primary emphasis of this blending operation will be to destroy the weapons capability of large, surplus stockpiles of HEU. The blended LEU product can only be made weapons capable again by the uranium enrichment process. To the extent practical, the chemical and isotopic concentrations of blended LEU product will be held within the specifications required for LWR fuel. Such blended LEU product will be offered to the United States Enrichment Corporation (USEC) to be sold as feed material to the commercial nuclear industry. Otherwise, blended LEU Will be produced as a waste suitable for storage or disposal.

Evaluation of renal function following administration of ethane-1-hydroxy-1,1-biphosphonate (EHBP) in animals submitted to oral intoxication with uranyl nitrate; Evaluacion de la funcion renal luego de la administracion de etidronato bisodico en animales intoxicados con nitrato de uranilo por via oral

Energy Technology Data Exchange (ETDEWEB)

Martinez, A B; Mandalunis, P M; Bozal, C B; Cabrini, Romulo L; Ubios, A M [Comision Nacional de Energia Atomica, General San Martin (Argentina). Dept. de Radiobiologia

2003-07-01

Workers involved in the processes of extraction, purification and manufacture of uranium of nuclear plants are occupationally exposed to both natural and enriched uranium. Several chelating agents (TIRON, EDTA, BAI, etc.) have been tested in terms of their capacity to sequester uranium before it reaches its target organs. Our laboratory has studied a first generation biphosphonate, ethane-1-hydroxy-1,1-biphosphonate (EHBP). We have shown that treatment with EHBP induces survival rates of 75% and 100% in adult and suckling rats respectively intoxicated with an intraperitoneal injection of uranyl nitrate. There are no data available to date on the renal function following treatment with EBHP to counteract the toxic effects of an oral lethal dose of uranyl nitrate. The aim of the present study was to assay creatininemia and uremia as end-points to assess renal function. The results obtained reveal that the alterations in renal function induced by oral uranyl nitrate intoxication can be reduced at 48 hours and reverted at 14 days by subcutaneous or oral administration of EHBP. (author)

Effect of the temperature and oxalic acid in the uranyl sorption in zircon; Efecto de la temperatura y acido oxalico en la sorcion de uranilo en circon

Energy Technology Data Exchange (ETDEWEB)

Ordonez R, E.; Almazan T, M. G.; Garcia G, N. [ININ, Departamento de Quimica, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico); Hernandez O, R., E-mail: eduardo.ordonez@inin.gob.mx [Instituto Tecnologico de Veracruz, Ingenieria Quimica, Miguel Angel de Quevedo No. 2779, 91860 Veracruz (Mexico)

2012-10-15

In this work the results of the temperature effect study are presented on uranyl solutions adsorbed on zirconium silicate (ZrSiO{sub 4}) and also on the compounds formed in surface with oxalic acid. The adsorption isotherms of uranyl on hydrated zircon with NaClO{sub 4} 0.5 M, show an increase of the uranyl sorption efficiency when increasing the temperature from 20 to 4 C with a sudden descent in this efficiency when changing the temperature at 60 C. The uranyl sorption efficiency increases to hydrate the zircon with a solution of oxalic acid 0.1 M, maintaining the same tendency regarding to the temperatures of the sorption in medium NaClO{sub 4} 0.5 M. The complex formation in the zircon surface with organic acids of low molecular weight increases the fixation of the uranyl in solution due to the formation of ternary systems, in the order Zircon/A. Organic/Uranyl, without altering their response to the temperature. (Author)

Development of the process for production of UO2 powder by atomization of uranyl nitrate

International Nuclear Information System (INIS)

Oliveira Lainetti, P.E. de.

1991-01-01

A method of direct conversion of uranyl nitrate hexahydrate (UNH) solution to ceramic grade uranium dioxide powders by thermal denitration in a furnace that combines atomization nozzle and a gas stirred bed is described. The main purpose of this work is to show that this alternative process is technically viable, specially if the recovery of the scrap generated in the nuclear fuel pellet production is required, without further generation of new liquid wastes. The steps for the development of the denitration unit as well as the characteristics of the final powders are described. Powder production experiments have been carried out for different atomization gas pressures and furnace upper section temperatures. Determination of impurity content, specific surface area, particle size and pore size distribution, density, U content, and O/U rate of uranium dioxide powders have been done; phase identification and morphology studies have also been performed. Sintered pellets have been studied by hydrostatic density determination and microstructure analyses. (author)

Photochemical reduction of uranyl ion by acetonitrile and propionitrile

International Nuclear Information System (INIS)

Brar, A.S.; Chander, R.; Sandhu, S.S.

1979-01-01

The photochemical reduction of uranyl ion by acetonitrile, propionitrile, benzonitrile, phenylacetonitrile, cyanoacetic acid and malononitrile in aqueous or aq. acetone medium using radiations >= 400 nm from a medium pressure mercury vapour lamp has been investigated. Except acetonitrile and propionitrile all other nitriles fail to bring about the reduction of uranyl ion. The reduction with aceto- and propionitriles has been found to obey pseudo-first order kinetics. The magnitude of rate of reduction with propionitrile is higher than that with acetonitrile. The pseudo-first order rate constants and quenching constant have been calculated from the kinetic data. It has been found that physical and chemical quenching compete with each other. The plot of reciprocal of quantum yield versus reciprocal (nitrile) is linear with a small intercept on the ordinate axis. Absorption spectra of uranyl ion in pure water, in the presence of acid and in the presence of acid+nitrile reveal that there is no ground state interaction between uranyl ion and the nitrile. A mechanism of photochemical reduction of uranyl ion based on α-hydrogen abstraction from the nitrile has been proposed. (auth.)

Subcritical multiplication measurements with a BeO reflected 233U uranyl nitrate solution system

International Nuclear Information System (INIS)

Job, P.K.; Srinivasan, M.; Nargundkar, V.R.; Chandramoleshwar, K.; Pasupathy, C.S.; Das, S.; Mayankutty, P.C.

1978-01-01

A series of subcritical multiplication measurements were carried out in PURNIMA with 233 U uranyl nitrate solution contained in all 11 x 11 cm 2 square sectional tank and reflected by 30 cm thickness of BeO on all sides. The objective of these experiments was to determine the 'Minimum critical mass' of the system in rectangular parellelopiped geometry. The rectangular aluminium core tank was attached to the bottom of an alpha tight glove box. BeO reflector was arranged below the glove box outside the core tank. The system multiplication was measured as a function of solution concentration and core volume by means of neutron detectors placed outside the assembly. The extrapolated critical mass was obtained through conventional inverse counts plot. The maximum amount of 233 U used was 120 gms. The rectangular geometry was estimated to be 235 +- 10 gms, in the concentration range of 80 to 120 gms/litre of 233 U. The experimental set up, procedure adopted, method of analysis and the details of the results are described. (author)

Interaction of uranyl ions with snake venom proteins from Lachesis muta muta

International Nuclear Information System (INIS)

MacCordick, H.J.; Taghva, F.

1997-01-01

The reaction product of uranyl nitrate with whole-protein Bushmaster snake venom in nitrate buffer at pH 3.5 has been studied. The maximum uptake of uranium was 291 μmol U x g -1 of venom. The infrared spectrum of the product showed an asymmetric O-U-O vibration at 921 cm -1 typical of complex formation with the uranyl ion. Stability measurements with the UO 2 2+ -protein complex in neutral medium indicated moderate hydrolytic stability, with 14% dissociation after 16 hours at 0 deg C. Neutron irradiation and desorption studies with a 235 U-labelled complex showed that generated fission products such as lanthanides and barium were readily lixiviated at pH 7, whereas Ru and Zr were highly retained by the protein substrate. (author)

Uranous nitrate production for purex process applications using PtO2 catalyst and H2/H2-gas mixtures

International Nuclear Information System (INIS)

Sreenivasa Rao, K.; Shyamali, R.; Narayan, C.V.; Patil, A.R.; Jambunathan, U.; Ramanujam, A.; Kansara, V.P.

2003-04-01

In the Purex process of spent fuel reprocessing. the twin objectives- decontamination and partitioning are achieved by extracting uranium (VI) and plutonium (IV) together in the solvent 30% TBP-dodecane and then selectively reducing Pu (IV) to Pu (III) in which valency it is least extractable in the solvent. Uranous nitrate stabilized with hydrazine nitrate is the widely employed partitioning agent. The conventional method of producing U(IV) is by the electrolytic reduction of uranyl nitrate with hydrazine nitrate as uranous ion stabilizer. Tre percentage conversion of U(VI) to U(IV) obtained in this method is 50 -60 %. The use of this solution as partitioning agent leads not only to the dilution of the plutonium product but also to increase in uranium processing load by each externally fed uranous nitrate batch. Also the oxide coating of the anode, TSIA (Titanium Substrate Insoluble Anode) wears out after a certain period of operation. This necessitates recoating which is quite cumbersome considering the amount of the decontamination involved. An alternative to the conventional electrolytic method of reduction of uranyl nitrate to uranous nitrate was explored at FRD laboratory .The studies have revealed that near 100% uranous nitrate can be produced by reducing uranyl nitrate with H 2 gas or H 2 (8%)- Ar/N 2 gas mixture in presence of PtO 2 catalyst. This report describes the laboratory scale studies carried out to optimize the various parameters. Based on these studies reduction of uranyl nitrate on a pilot plant scale was carried out. The design and operation of the reductor column and also the various studies carried out in the pilot plant studies are discussed. Near 100% conversion of uranyl nitrate to uranous nitrate and also the redundancy of supply of electrical energy make this process a viable alternative to the existing electrolytic method. (author)

Study of the changes in composition of ammonium diuranate with progress of precipitation, and study of the properties of ammonium diuranate and its subsequent products produced from both uranyl nitrate and uranyl fluoride solutions

Energy Technology Data Exchange (ETDEWEB)

Manna, Subhankar; Kumar, Raj; Satpati, Santosh K.; Roy, Saswati B. [Bhabha Atomic Research Centre, Trombay, Mumbai (India); Joshi, Jyeshtharaj B. [Dept. of Chemical Engineering, Institute of Chemical Technology, Mumbai (India)

2017-04-15

Uranium metal used for fabrication of fuel for research reactors in India is generally produced by magnesio-thermic reduction of UF{sub 4}. Performance of magnesio-thermic reaction and recovery and quality of uranium largely depends on properties of UF{sub 4}. As ammonium diuranate (ADU) is first product in powder form in the process flow-sheet, properties of UF{sub 4} depend on properties of ADU. ADU is generally produced from uranyl nitrate solution (UNS) for natural uranium metal production and from uranyl fluoride solution (UFS) for low enriched uranium metal production. In present paper, ADU has been produced via both the routes. Variation of uranium recovery and crystal structure and composition of ADU with progress in precipitation reaction has been studied with special attention on first appearance of the precipitate Further, ADU produced by two routes have been calcined to UO{sub 3}, then reduced to UO{sub 2} and hydroflorinated to UF{sub 4}. Effect of two different process routes of ADU precipitation on the characteristics of ADU, UO{sub 3}, UO{sub 2} and UF{sub 4} were studied here.

Uranyl complexes formed with a para-t-butylcalix[4]arene bearing phosphinoyl pendant arms on the lower rim. Solid and solution studies

Energy Technology Data Exchange (ETDEWEB)

Ramirez, F. de M. [Instituto Nacional de Investigaciones Nucleares, La Marquesa, Ocoyoacac (Mexico). Dept. de Quimica; Varbanov, S. [Bulgarian Academy of Sciences, Sofia (Bulgaria). Inst. of Organic Chemistry with Center of Phytochemistry; Buenzli, J.C.G. [Ecole Polytechnique Federale de Lausanne (EPFL) (Switzerland). Inst. of Chemical Sciences and Engineering; Rivas-Silva, J.F.; Ocana-Bribiesca, M.A. [Instituto de Fisica de la BUAP, Puebla (Mexico); Cortes-Jacome, M.A.; Toledo-Antonio, J.A. [Instituto Mexicano del Petroleo/Programa de Ingenieria Molecular (Mexico)

2012-07-01

The current interest in functionalized calixarenes with phosphorylated pendant arms resides in their coordination ability towards f elements and capability towards actinide/rare earth separation. Uranyl cation forms 1:1 and 1:2 (M:L) complexes with a tetra-phosphinoylated p-tert-butylcalix[4]arene, B{sub 4}bL{sup 4}: UO{sub 2}(NO{sub 3}){sub 2}(B{sub 4}bL{sup 4}){sub n} . xH{sub 2}O (n = 1, x = 2, 1; n = 2, x = 6, 2). Spectroscopic data point to the inner coordination sphere of 1 containing one monodentate nitrate anion, one water molecule and the four phosphinoylated arms bound to UO{sub 2}{sup 2+} while in 2, uranyl is only coordinated to calixarene ligands. In both cases the U(VI) ion is 8-coordinate. Uranyl complexes display enhanced metal-centred luminescence due to energy transfer from the calixarene ligands; the luminescence decays are bi-exponential with associated lifetimes in the ranges 220 {mu}s < {tau}{sub s} < 250 {mu}s and 630 {mu}s < {tau}{sub L} < 640 {mu}s, pointing to the presence of two species with differently coordinated calixarene, as substantiated by a XPS study of U(4f{sub 5/2,7/2}), O(1s) and P(2p) levels on solid state samples. The extraction study of UO{sub 2}{sup 2+} cation and trivalent rare-earth (Y, La, Eu) ions from acidic nitrate media by B{sub 4}bL{sup 4} in chloroform shows the uranyl cation being much more extracted than rare earths. (orig.)

Photochemical reduction of uranyl ion with triphenylphosphine

International Nuclear Information System (INIS)

Brar, A.S.; Sidhu, M.S.; Sandhu, S.S.

1981-01-01

Photochemical reduction of uranyl ion with triphenylphosphine has been studied in acetone-water medium in the presence of sulphuric acid at 346nm, 400nm and 434nm wavelengths. The photochemical reduction is of second order and increases with increase in hydrogen ion concentration. Absorption spectra of uranyl ion in acidic medium and uranyl ion with triphenylphosphine do not show any ground state complex formation. The value of quantum yield increases with the wavelength of the radiation increase from 346 to 434nm. Plots of reciprocal of quantum yield for the formation of U(IV) versus reciprocal [triphenylphosphine] are linear. Products characterized by UV and visible, IR and TLC show the formation of U(IV) and triphenylphosphine oxide. On the basis of above observations mechanism of the photochemical reduction has been proposed. (author)

Uranyl adsorption kinetics within silica gel: dependence on flow velocity and concentration

Science.gov (United States)

Dodd, Brandon M.; Tepper, Gary

2017-09-01

Trace quantities of a uranyl dissolved in water were measured using a simple optical method. A dilute solution of uranium nitrate dissolved in water was forced through nanoporous silica gel at fixed and controlled water flow rates. The uranyl ions deposited and accumulated within the silica gel and the uranyl fluorescence within the silica gel was monitored as a function of time using a light emitting diode as the excitation source and a photomultiplier tube detector. It was shown that the response time of the fluorescence output signal at a particular volumetric flow rate or average liquid velocity through the silica gel can be used to quantify the concentration of uranium in water. The response time as a function of concentration decreased with increasing flow velocity.

Growth of uranyl hydroxide nanowires and nanotubes with electrodeposition method

International Nuclear Information System (INIS)

Wang Lin; Yuan Liyong; Chai Zhifang; Shi Weiqun

2013-01-01

Actinides nanomaterials have great potential applications in fabrication of novel nuclear fuel and spent fuel reprocessing in advanced nuclear energy system. However, the relative research so far still lacks systematic investigation on the synthetic methods for actinides nanomaterials. In this work, we use track-etched membranes as hard templates to synthesize uranium based nanomaterials with novel structures by electrodeposition method. Through electrochemical behavior investigations and subsequent product characterizations such as energy dispersive spectrometer (EDS), fourier transform infrared spectroscopy (FTIR), the chemical composition of deposition products have been confirmed as the uranyl hydroxide. More importantly, accurate control of morphology and structures (nanowires and nanotubes) could be achieved by carefully adjusting the growth parameters such as deposition time and deposition current density. It was found that the preferred morphology of electrodeposition products is nanowire when a low current density was applied, whereas nanotubes could be formed only under conditions of high current density and the short deposition time. The mechanism for the formation of nanowires in track-etched membranes is based on the precipitation of uranyl hydroxide from uranyl nitrate solution, according to the previous researches about obtaining nanostructures of hydroxides from nitrate salt solutions. And we have concluded that the formation of nanotubes is attributed to the hydrogen bubbles generated by water electrolysis under the condition of over-potential electro-reduction. The conveying of hydrogen bubbles plays the role of dynamic template which can prevent the complete filling of uranyl hydroxide in the channels. Additionally, we transform the chemical composition of deposition products from uranyl hydroxide to triuranium octoxide by calcining them at 500 and 800 degree centigrade, respectively, and SEM results show the morphologies of nanowires and

Study of the mechanism and kinetics of the reduction of uranyl ions in phosphoric acid solutions

International Nuclear Information System (INIS)

El Kacemi, K.; Tyburce, B.; Belcadi, S.

1982-01-01

The electrochemical reduction of uranyl ions in 0.1 to 9 M phosphoric acid has been investigated by polarography, cyclic voltammetry, chronopotentiometry and potentiostatic coulometry. In concentrated phosphoric acid solutions (H 3 PO 4 3 PO 4 concentrations. So, when the concentration of U(VI) increases and/or that of H 3 PO 4 reduces, the system becomes reversible. (author)

Criticality safety benchmark experiment on 10% enriched uranyl nitrate solution using a 28-cm-thickness slab core

International Nuclear Information System (INIS)

Yamamoto, Toshihiro; Miyoshi, Yoshinori; Kikuchi, Tsukasa; Watanabe, Shouichi

2002-01-01

The second series of critical experiments with 10% enriched uranyl nitrate solution using 28-cm-thick slab core have been performed with the Static Experiment Critical Facility of the Japan Atomic Energy Research Institute. Systematic critical data were obtained by changing the uranium concentration of the fuel solution from 464 to 300 gU/l under various reflector conditions. In this paper, the thirteen critical configurations for water-reflected cores and unreflected cores are identified and evaluated. The effects of uncertainties in the experimental data on k eff are quantified by sensitivity studies. Benchmark model specifications that are necessary to construct a calculational model are given. The uncertainties of k eff 's included in the benchmark model specifications are approximately 0.1%Δk eff . The thirteen critical configurations are judged to be acceptable benchmark data. Using the benchmark model specifications, sample calculation results are provided with several sets of standard codes and cross section data. (author)

A Nuclear Reactor and Chemical Processing Design for Production of Molybdenum-99 with Crystalline Uranyl Nitrate Hexahydrate Fuel

Science.gov (United States)

Stange, Gary Michael

Medical radioisotopes are used in tens of millions of procedures every year to detect and image a wide variety of maladies and conditions in the human body. The most widely-used diagnostic radioisotope is technetium-99m, a metastable isomer of technetium-99 that is generated by the radioactive decay of molybdenum-99. For a number of reasons, the supply of molybdenum-99 has become unreliable and the techniques used to produce it have become unattractive. This has spurred the investigation of new technologies that avoid the use of highly enriched uranium to produce molybdenum-99 in the United States, where approximately half of the demand originates. The first goal of this research is to develop a critical nuclear reactor design powered by solid, discrete pins of low enriched uranium. Analyses of single-pin heat transfer and whole-core neutronics are performed to determine the required specifications. Molybdenum-99 is produced directly in the fuel of this reactor and then extracted through a series of chemical processing steps. After this extraction, the fuel is left in an aqueous state. The second goal of this research is to describe a process by which the uranium may be recovered from this spent fuel solution and reconstituted into the original fuel form. Fuel recovery is achieved through a crystallization step that generates solid uranyl nitrate hexahydrate while leaving the majority of fission products and transuranic isotopes in solution. This report provides background information on molybdenum-99 production and crystallization chemistry. The previously unknown thermal conductivity of the fuel material is measured. Following this is a description of the modeling and calculations used to develop a reactor concept. The operational characteristics of the reactor core model are analyzed and reported. Uranyl nitrate crystallization experiments have also been conducted, and the results of this work are presented here. Finally, a process flow scheme for uranium

Nitrate and bicarbonate selective CHEMFETs

NARCIS (Netherlands)

Antonisse, M.M.G.; Engbersen, Johannes F.J.; Reinhoudt, David

1995-01-01

The development of durable anion selective CHEMFET micro sensors is described. Selectivity in these sensors is either obtained from differences in hydration energy of the anions (the Hlofmeister series, giving nitrate selectivity) or by introduction of a new class of uranyl salophene ionophores

Uranyl-organic assemblies with the macrocyclic ligand 1, 4, 8, 11-tetra-aza-cyclo-tetradecane-1, 4, 8, 11-tetraacetate (TETA)

International Nuclear Information System (INIS)

Thuery, Pierre

2010-01-01

Three uranyl ion complexes obtained from the reaction of uranyl nitrate hexahydrate and 1, 4, 8, 11-tetra-aza-cyclo-tetradecane-1, 4, 8, 11-tetraacetic acid (H 4 TETA) were characterized by their crystal structure. The centrosymmetric macrocycle, in the [3434] conformation with either carbon or nitrogen atoms as corners, is zwitterionic, with four carboxylate groups and two or four protonated nitrogen atoms. The complexes [(UO 2 ) 2 (H 2 TETA)(C 2 O 4 )(H 2 O) 2 ] (1) and [UO 2 (H 4 TETA)(H 2 O)].NO 3 .Cl (2) were synthesized under hydrothermal conditions and 1 includes additional oxalate ligands generated in situ. Both compounds are two-dimensional polymers in which the four-fold monodentate macrocyclic ligand unites either four uranyl oxalate dinuclear species (1) or isolated uranyl ions (2). Complex 3, [UO 2 (H 2 TETA)(H 2 O)].6H 2 O, was obtained at room temperature and, although it displays the same stoichiometry as 2, it differs from it by being a three-dimensional framework. Both 2 and 3 present channels containing either counter-ions or water molecules. As often observed, the water content of the low-temperature species, 3, is higher than that of the high-temperature one, 2. (author)

Study on removing nitrate from uranium solution by ion-exchange method

International Nuclear Information System (INIS)

Zhou Genmao

2004-01-01

Nitrate of low concentration can interfere with adsorption of uranyl sulfate anion on anion-exchange resins because the anion-exchange resins have a stronger affinity for nitrate in uranium solution. Nitrate can be adsorbed with a high efficiency resin, then desorbed by sodium hydroxide. The nitrate concentration is about 60 g/L in eluate. The research results show that nitrate can be recovered from uranium solution with N-3 anion-exchange resin

Photochemical reduction of uranyl ion with amides

International Nuclear Information System (INIS)

Brar, A.S.; Chander, R.; Sandhu, S.S.

1981-01-01

The photochemical reduction of uranyl ion by formamide, acetamide, propionamide, butyramide, iso butyramids, n-methylformamide, N, N-dimethylformamide and N, N-diethylformamide in aqueous medium using radiation >= 380 nm from a medium pressure mercury vapour lamp has been investigated. The reduction with the said amides has been found to obey pseudo first order kinetics. The magnitude of the rate of reduction for the simple amides has been found to follow the following order formamide > isobutyramide approx. butyramide > propionamide > acetamide while the rate order for N-alkylformamides compared with that of the formamide has been found to be formamide > N-methylformamide > N,N-diethylformamide approx. N,N-dimethylformamide. The pseudo first order rate constants and quenching constants have been found from the kinetic data. It has been found that physical and chemical quenching compete with each other. Plots of reciprocal of quantum yields versus reciprocal [amide] have been found to be linear with intercepts on the ordinate axis. Absorption spectra of uranyl ion in doubly distilled water, in the presence of acid and in the presence of acid and amide reveal that there is no ground state interaction between uranyl ion and the amide. A mechanism of photoreduction of uranyl ion with amides has been proposed. (author)

Complexes of uranyl with N-oxides of heterocyclic amines. Electron-vibrational absorption spectra

International Nuclear Information System (INIS)

Jezowska-Trzebiatowska, B.; Wieczorek, M.

1977-01-01

A number of coordination compounds formed by uranyl chloride and nitrate with N-oxides of heterocyclic amines have been prepared and characterized by spectral measurements in the absorption region 20000-50000 cm -1 . The electrons and vibronic transitions have been determined and discussed. (author)

A relativistic density functional study of uranyl hydrolysis and complexation by carboxylic acids in aqueous solution

International Nuclear Information System (INIS)

Ray, Rupashree Shyama

2009-01-01

In this work, the complexation of uranium in its most stable oxidation state VI in aqueous solution was studied computationally, within the framework of density functional (DF) theory. The thesis is divided into the following parts: Chapter 2 briefly summarizes the relevant general aspects of actinide chemistry and then focuses on actinide environmental chemistry. Experimental results on hydrolysis, actinide complexation by carboxylic acids, and humic substances are presented to establish a background for the subsequent discussion. Chapter 3 describes the computational method used in this work and the relevant features of the parallel quantum chemistry code PARAGAUSS employed. First, the most relevant basics of the applied density functional approach are presented focusing on relativistic effects. Then, the treatment of solvent effects, essential for an adequate modeling of actinide species in aqueous solution, will be introduced. At the end of this chapter, computational parameters and procedures will be summarized. Chapter 4 presents the computational results including a comparison to available experimental data. In the beginning, the mononuclear hydrolysis product of UO_2"2"+, [UO_2OH]"+, will be discussed. The second part deals with actinide complexation by carboxylate ligands. First of all the coordination number for uranylacetate will be discussed with respect to implications for the complexation of actinides by humic substances followed by the uranyl complexation of aromatic carboxylic acids in comparison to earlier results for aliphatic ones. In the end, the ternary uranyl-hydroxo-acetate are discussed, as models of uranyl humate complexation at ambient condition.

Investigation of uranyl-ion hydrolysis in uranyl pertechnetate and uranyl perchlorates solutions by two-phases potentiometric titration method

International Nuclear Information System (INIS)

Volk, V.I.; Belikov, A.D.

1977-01-01

The applicability of the method of two-phase potentiometric titration for studying hydrolysis of multi-charge ions has been shown. Hydrolysis of uranyl-ion has been investigated and hydrolysis constants in the solutions of uranyl pertechnetate and perchlorate have been calculated equal to (6.2+-0.15)x10 -5 and (9.25+-0.5)10 -5 , respectively. Infrared spectra of the initial crystallohydrates of uranyl pertechnetate and perchlorate has been analyzed. The data on hydrolysis of an uranyl-ion and IR spectra of crystallohydrates of the investigated salts have revealed the ability of pertechnetate ion to complexing with an uranyl group

The influence of nitrate concentrations and acidity on the electrocatalytic reduction of nitrate on platinum

NARCIS (Netherlands)

Groot, de M.T.; Koper, M.T.M.

2004-01-01

A study was performed to determine the influence of nitrate concentration and acidity on the reaction rate and selectivity of the electrocatalytic nitrate reduction on platinum. There are two different nitrate reduction mechanisms on platinum: a direct mechanism (0.4–0.1 V vs. SHE) and an indirect

Role of ion transfer membrane in the production of uranous nitrate

International Nuclear Information System (INIS)

Nair, M.K.T.; Singh, R.K.; Bajpai, D.D.; Venugopalan, A.K.; Singh, R.R.; Gurba, P.B.; Thomas, Mathew

1992-01-01

In Purex process, plutonium and uranium are co-extracted into organic phase and these are partitioned by reducing Pu(IV) to Pu(III) using hydrazine stabilized uranous nitrate solution. Usually, uranous nitrate is added in much higher quantity than the stoichiometric requirement to effect complete reduction of plutonium. In conventional electrolytic cells only 60 to 70% of uranyl to uranous conversion is achieved. Use of this solution results in dilution of plutonium product. In addition to this, each externally fed uranous nitrate batch increases uranium processing load and affects the plant throughput. In order to keep the additional uranium processing load to a minimum, it is necessary to increase the uranous content to near cent percent level in the externally fed uranous nitrate solution. The studies carried out at PREFRE (Power Reactor Fuel Reprocessing) laboratory have shown that it is possible to produce concentrated uranous nitrate solution, nearly free from uranyl nitrate, by using a cation exchange membrane. This paper describes the development work carried out at PREFRE plant, Tarapur for production of cent percent uranous nitrate solution. Development of electrolytic cells for uranous production, from laboratory scale to pilot plant scale, has been explained. (author). 24 refs., 8 figs., 8 tabs

A relativistic density functional study of uranyl hydrolysis and complexation by carboxylic acids in aqueous solution

Energy Technology Data Exchange (ETDEWEB)

Ray, Rupashree Shyama

2009-02-10

In this work, the complexation of uranium in its most stable oxidation state VI in aqueous solution was studied computationally, within the framework of density functional (DF) theory. The thesis is divided into the following parts: Chapter 2 briefly summarizes the relevant general aspects of actinide chemistry and then focuses on actinide environmental chemistry. Experimental results on hydrolysis, actinide complexation by carboxylic acids, and humic substances are presented to establish a background for the subsequent discussion. Chapter 3 describes the computational method used in this work and the relevant features of the parallel quantum chemistry code PARAGAUSS employed. First, the most relevant basics of the applied density functional approach are presented focusing on relativistic effects. Then, the treatment of solvent effects, essential for an adequate modeling of actinide species in aqueous solution, will be introduced. At the end of this chapter, computational parameters and procedures will be summarized. Chapter 4 presents the computational results including a comparison to available experimental data. In the beginning, the mononuclear hydrolysis product of UO{sub 2}{sup 2+}, [UO{sub 2}OH]{sup +}, will be discussed. The second part deals with actinide complexation by carboxylate ligands. First of all the coordination number for uranylacetate will be discussed with respect to implications for the complexation of actinides by humic substances followed by the uranyl complexation of aromatic carboxylic acids in comparison to earlier results for aliphatic ones. In the end, the ternary uranyl-hydroxo-acetate are discussed, as models of uranyl humate complexation at ambient condition.

Hygroscopic behavior of atmospheric aerosols containing nitrate salts and water-soluble organic acids

Science.gov (United States)

Jing, Bo; Wang, Zhen; Tan, Fang; Guo, Yucong; Tong, Shengrui; Wang, Weigang; Zhang, Yunhong; Ge, Maofa

2018-04-01

While nitrate salts have critical impacts on environmental effects of atmospheric aerosols, the effects of coexisting species on hygroscopicity of nitrate salts remain uncertain. The hygroscopic behaviors of nitrate salt aerosols (NH4NO3, NaNO3, Ca(NO3)2) and their internal mixtures with water-soluble organic acids were determined using a hygroscopicity tandem differential mobility analyzer (HTDMA). The nitrate salt / organic acid mixed aerosols exhibit varying phase behavior and hygroscopic growth depending upon the type of components in the particles. Whereas pure nitrate salt particles show continuous water uptake with increasing relative humidity (RH), the deliquescence transition is still observed for ammonium nitrate particles internally mixed with organic acids such as oxalic acid and succinic acid with a high deliquescence point. The hygroscopicity of submicron aerosols containing sodium nitrate and an organic acid is also characterized by continuous growth, indicating that sodium nitrate tends to exist in a liquid-like state under dry conditions. It is observed that in contrast to the pure components, the water uptake is hindered at low and moderate RH for calcium nitrate particles containing malonic acid or phthalic acid, suggesting the potential effects of mass transfer limitation in highly viscous mixed systems. Our findings improve fundamental understanding of the phase behavior and water uptake of nitrate-salt-containing aerosols in the atmospheric environment.

Hygroscopic behavior of atmospheric aerosols containing nitrate salts and water-soluble organic acids

Directory of Open Access Journals (Sweden)

B. Jing

2018-04-01

Full Text Available While nitrate salts have critical impacts on environmental effects of atmospheric aerosols, the effects of coexisting species on hygroscopicity of nitrate salts remain uncertain. The hygroscopic behaviors of nitrate salt aerosols (NH4NO3, NaNO3, Ca(NO32 and their internal mixtures with water-soluble organic acids were determined using a hygroscopicity tandem differential mobility analyzer (HTDMA. The nitrate salt ∕ organic acid mixed aerosols exhibit varying phase behavior and hygroscopic growth depending upon the type of components in the particles. Whereas pure nitrate salt particles show continuous water uptake with increasing relative humidity (RH, the deliquescence transition is still observed for ammonium nitrate particles internally mixed with organic acids such as oxalic acid and succinic acid with a high deliquescence point. The hygroscopicity of submicron aerosols containing sodium nitrate and an organic acid is also characterized by continuous growth, indicating that sodium nitrate tends to exist in a liquid-like state under dry conditions. It is observed that in contrast to the pure components, the water uptake is hindered at low and moderate RH for calcium nitrate particles containing malonic acid or phthalic acid, suggesting the potential effects of mass transfer limitation in highly viscous mixed systems. Our findings improve fundamental understanding of the phase behavior and water uptake of nitrate-salt-containing aerosols in the atmospheric environment.

Studies on the reverse osmosis treatment of uranyl nitrate solution

International Nuclear Information System (INIS)

Prabhakar, S.; Panicker, S.T.; Misra, B.M.; Ramani, P.S.

1992-01-01

The aqueous effluent generated in uranium processing, particularly in the nuclear fuel fabrication step, contains mainly uranium nitrate. This requires treatment before discharge into the environment to meet stringent standards. This paper presents the performance of cellulose acetate membranes with regard to rejection of uranium under reverse osmotic conditions for feed concentrations up to 200 mg/l of uranium, which corresponds to the levels normally prevalent in the effluents. The use of additives like the disodium salt of ethylenediaminetetraacetic acid and sodium sulfate for the improvement of reverse osmosis performance of the above membranes was also investigated. In the light of the experimental results, the suitability of reverse osmosis for the decontamination of uranium effluents is discussed

High-affinity uranyl-specific antibodies suitable for cellular imaging

International Nuclear Information System (INIS)

Reisser-Rubrecht, L.; Torne-Celer, C.; Renier, W.; Averseng, O.; Plantevin, S.; Quemeneur, E.; Bellanger, L.; Vidaud, C.

2008-01-01

Monoclonal antibodies (mAbs) have proved to be valuable models for the study of protein-metal interactions, and previous reports have described very specific antibodies to chelated metal ions, including uranyl. We raised specific mAbs against UO 2 2+ -DCP-BSA (DCP, 1, 10-phenanthroline-2,9-dicarboxylic acid) to generate new sets of antibodies that might cross-react with various complexed forms of uranyl in different environments for further application in the field of toxicology. Using counter-screening with UO 2 2+ -DCP-casein, we selected two highly specific mAbs against uranyl-DCP (K D = 10-100 pM): U04S and U08S. Competitive assays in the presence of different metal ions (UO 2 2+ , Fe 3+ , Zn 2+ , Cu 2+ , and Ca 2+ ) showed that uranyl in solution can act as a good competitor, suggesting some antibody ability to cross-react with chelating groups other than DCP in the UO 2 2+ equatorial coordination plane. Interestingly, one of the antibodies could be used for revealing uranyl cations in cell samples. Fluorescence activated cell sorting analyses after immuno-labeling revealed the interaction of uranyl with human kidney cells HK2. The intracellular accumulation of uranyl could be directly visualized by metal-immunostaining using fluorescent-labeled mAb. Our results suggest that U04S mAb epitopes mostly include the uranyl fraction and its para-topes can accommodate a wide variety of chelating groups. (authors)

Component activities in the system thorium nitrate-nitric acid-water at 25oC

International Nuclear Information System (INIS)

Lemire, R.J.; Brown, C.P.

1982-01-01

The equilibrium composition of the vapor above thorium nitrate-nitric acid-water mixtures has been studied as a function of the concentrations of thorium nitrate and nitric acid using a transpiration technique. At 25 o C, the thorium nitrate concentrations m T ranged from 0.1 to 2.5 molal and the nitric acid concentrations m N from 0.3 to 25 molal. The vapor pressure of the nitric acid was found to increase with increasing thorium nitrate concentration for a constant molality of nitric acid in aqueous solution. At constant m T , the nitric acid vapor pressure was particularly enhanced at low nitric acid concentrations. The water vapor pressures decreased regularly with increasing concentrations of both nitric acid and thorium nitrate. The experimental data were fitted to Scatchard's ion-component model, and to empirical multiparameter functions. From the fitting parameters, and available literature data for the nitric acid-water and thorium nitrate-water systems at 25 o C, expressions were calculated for the variation of water and thorium nitrate activities, as functions of the nitric acid and thorium nitrate concentrations, using the Gibbs-Duhem equation. Calculated values for the thorium nitrate activities were strongly dependent on the form of the function originally used to fit the vapor pressure data. (author)

Extraction of uranyl sulfate with primary amine

International Nuclear Information System (INIS)

Mrnka, M.; Bizek, V.; Nekovar, P.; Cizevska, S.; Schroetterova, D.

1984-01-01

PRIMENE JM-T was used for extraction. Its composition was found to approach the general formula C 21 H 43 NH 2 . It was found that the extraction of uranyl sulfate is lower in case of a higher steady-state concentration of sulfuric acid in the aqueous phase. Extraction is accompanied with coextraction of water. The results obtained showed that uranyl sulfate passes into the organic phase by two mechanisms: extraction with amine sulfate and extraction with free amine. A mathematical description of the process was made based on the obtained results. (E.S.)

Charge-density matching in organic-inorganic uranyl compounds

International Nuclear Information System (INIS)

Krivovichev, S.V.; Krivovichev, S.V.; Tananaev, I.G.; Myasoedov, B.F.

2007-01-01

Single crystals of [C 10 H 26 N 2 ][(UO 2 )(SeO 4 ) 2 (H 2 O)](H 2 SeO 4 ) 0.85 (H 2 O) 2 (1), [C 10 H 26 N 2 ][(UO 2 )(SeO 4 ) 2 ] (H 2 SeO 4 ) 0.50 (H 2 O) (2), and [C 8 H 20 N] 2 [(UO 2 )(SeO 4 ) 2 (H 2 O)] (H 2 O) (3) were prepared by evaporation from aqueous solution of uranyl nitrate, selenic acid and the respective amines. The structures of the compounds have been solved by direct methods and structural models have been obtained. The structures of the compounds 1, 2, and 3 contain U and Se atoms in pentagonal bipyramidal and tetrahedral coordinations, respectively. The UO 7 and SeO 4 polyhedra polymerize by sharing common O atoms to form chains (compound 1) or sheets (compounds 2 and 3). In the structure of 1, the layers consisting of hydrogen-bonded [UO 2 (SeO 4 ) 2 (H 2 O)] 2- chains are separated by mixed organic-inorganic layers comprising from [NH 3 (CH 2 ) 10 NH 3 ] 2+ molecules, H 2 O molecules, and disordered electroneutral (H 2 SeO 4 ) groups. The structure of 2 has a similar architecture but a purely inorganic layer is represented by a fully connected [UO 2 (SeO 4 ) 2 ] 2- sheet. The structure of 3 does not contain disordered (H 2 SeO 4 ) groups but is based upon alternating [UO 2 (SeO 4 ) 2 (H 2 O)] 2- sheets and 1.5-nm-thick organic blocks consisting of positively charged protonated octylamine molecules, [NH 3 (CH 2 ) 7 CH 3 ] + . The structures may be considered as composed of anionic inorganic sheets (2D blocks) and cationic organic blocks self-organized according to competing hydrophilic-hydrophobic interactions. Analysis of the structures allows us to conclude that the charge-density matching principle is observed in uranyl compounds. In order to satisfy some basic peculiarities of uranyl (in general, actinyl) chemistry, it requires specific additional mechanisms: (a) in long-chain-amine-templated compounds, protonated amine molecules inter-digitate; (b) in long-chain-diamine-templated compounds, incorporation of acid-water interlayers into

Cyanex based uranyl sensitive polymeric membrane electrodes.

Science.gov (United States)

Badr, Ibrahim H A; Zidan, W I; Akl, Z F

2014-01-01

Novel uranyl selective polymeric membrane electrodes were prepared using three different low-cost and commercially available Cyanex extractants namely, bis(2,4,4-trimethylpentyl) phosphinic acid [L1], bis(2,4,4-trimethylpentyl) monothiophosphinic acid [L2] and bis(2,4,4-trimethylpentyl) dithiophosphinic acid [L3]. Optimization and performance characteristics of the developed Cyanex based polymer membrane electrodes were determined. The influence of membrane composition (e.g., amount and type of ionic sites, as well as type of plasticizer) on potentiometric responses of the prepared membrane electrodes was studied. Optimized Cyanex-based membrane electrodes exhibited Nernstian responses for UO₂(2+) ion over wide concentration ranges with fast response times. The optimized membrane electrodes based on L1, L2 and L3 exhibited Nernstian responses towards uranyl ion with slopes of 29.4, 28.0 and 29.3 mV decade(-1), respectively. The optimized membrane electrodes based on L1-L3 showed detection limits of 8.3 × 10(-5), 3.0 × 10(-5) and 3.3 × 10(-6) mol L(-1), respectively. The selectivity studies showed that the optimized membrane electrodes exhibited high selectivity towards UO₂(2+) ion over large number of other cations. Membrane electrodes based on L3 exhibited superior potentiometric response characteristics compared to those based on L1 and L2 (e.g., widest linear range and lowest detection limit). The analytical utility of uranyl membrane electrodes formulated with Cyanex extractant L3 was demonstrated by the analysis of uranyl ion in different real samples for nuclear safeguards verification purposes. The results obtained using direct potentiometry and flow-injection methods were compared with those measured using the standard UV-visible and inductively coupled plasma spectroscopic methods. © 2013 Published by Elsevier B.V.

High-affinity uranyl-specific antibodies suitable for cellular imaging

Energy Technology Data Exchange (ETDEWEB)

Reisser-Rubrecht, L.; Torne-Celer, C.; Renier, W.; Averseng, O.; Plantevin, S.; Quemeneur, E.; Bellanger, L.; Vidaud, C. [CEA Valrho, DSV, IBEB, Serv Biochim et Toxicol Nucl, F-30207 Bagnols Sur Ceze (France)

2008-07-01

Monoclonal antibodies (mAbs) have proved to be valuable models for the study of protein-metal interactions, and previous reports have described very specific antibodies to chelated metal ions, including uranyl. We raised specific mAbs against UO{sub 2}{sup 2+}-DCP-BSA (DCP, 1, 10-phenanthroline-2,9-dicarboxylic acid) to generate new sets of antibodies that might cross-react with various complexed forms of uranyl in different environments for further application in the field of toxicology. Using counter-screening with UO{sub 2}{sup 2+}-DCP-casein, we selected two highly specific mAbs against uranyl-DCP (K{sub D} = 10-100 pM): U04S and U08S. Competitive assays in the presence of different metal ions (UO{sub 2}{sup 2+}, Fe{sup 3+}, Zn{sup 2+}, Cu{sup 2+}, and Ca{sup 2+}) showed that uranyl in solution can act as a good competitor, suggesting some antibody ability to cross-react with chelating groups other than DCP in the UO{sub 2}{sup 2+} equatorial coordination plane. Interestingly, one of the antibodies could be used for revealing uranyl cations in cell samples. Fluorescence activated cell sorting analyses after immuno-labeling revealed the interaction of uranyl with human kidney cells HK2. The intracellular accumulation of uranyl could be directly visualized by metal-immunostaining using fluorescent-labeled mAb. Our results suggest that U04S mAb epitopes mostly include the uranyl fraction and its para-topes can accommodate a wide variety of chelating groups. (authors)

COGEMA Experience in Uranous Nitrate Preparation

International Nuclear Information System (INIS)

Tison, E.; Bretault, Ph.

2006-01-01

Separation and purification of plutonium by PUREX process is based on a sequence of extraction and back extraction which requires reducing plutonium Pu IV (extractable form) into Pu III (inextractable form) Different reducers can be used to reduce Pu IV into Pu III. Early plants such as that for Magnox fuel at Sellafield used ferrous sulfamate while UP 1 at Marcoule used uranous sulfamate. These reducers are efficient and easy to prepare but generates ferric and/or sulphate ions and so complicates management of the wastes from the plutonium purification cycle. Recent plants such as UP3 and UP2 800 at La Hague, THORP at Sellafield, and RRP at Rokkasho Mura (currently under tests) use uranous nitrate (U IV) stabilized by hydrazinium nitrate (N 2 H 5 NO 3 ) and hydroxyl ammonium nitrate (HAN). In the French plants, uranous nitrate is used in U-Pu separation and alpha barrier and HAN is used in Pu purification. Compared to sulfamate, U IV does not generate extraneous chemical species and uranyl nitrate (U VI) generated by reducing Pu IV follows the main uranium stream. More over uranous nitrate is prepared from reprocessed purified uranyl nitrate taken at the outlet of the reprocessing plant. Hydrazine and HAN offer the advantage to be salt-free reagents. Uranous nitrate can be generated either by electrolysis or by catalytic hydrogenation process. Electrolytic process has been implemented in early plant UP 1 at Marcoule (when changing reducer from uranous sulfamate to uranous nitrate) and was used again in UP2 plant at La Hague. However, the electrolytic process presented several disadvantages such as a low conversion rate and problems associated with the use of mercury. Electrolysis cells with no mercury were developed for the Eurochemic plant in Belgium and then implemented in the first Japanese reprocessing plant in Tokai-Mura. But finally, in 1975, the electrolytic process was abandoned in favor of the catalytic hydrogenation process developed at La Hague. The

Removal of uranyl ions from residual waters using some algae types

International Nuclear Information System (INIS)

Cecal, Al.; Rudic, V.; Gulea, A.; Palamaru, I.; Humelnicu, D.; Salaru, V.V.; Popa, K.

1997-01-01

This paper deals with a study on the bioaccumulation of uranyl ions resulted from residual effluents, by means of some microbiological collectors: Scenedesmus quadricauda, Anabaena karakumica, Calothrix brevissima, Penicillium sp, as well as the Glucide extract of Porphyridium cruentum, in several experimental conditions. The retaining degree of the bioaccumulated uranyl ions, as well as the leaching degree, in HCl and H 2 O media, of the same ions previously retained on algae, were karakumica >Penicillium sp> Calothrix brevissima. The leaching effect of bioaccumulated uranyl ions is higher in hydrochloric acid then in water. (authors)

Analysis of 99Mo Production Capacity in Uranyl Nitrate Aqueous Homogeneous Reactor using ORIGEN and MCNP

Directory of Open Access Journals (Sweden)

A. Isnaeni

2014-04-01

Full Text Available 99mTc is a very useful radioisotope in medical diagnostic procedure. 99mTc is produced from 99Mo decay. Currently, most of 99Mo is produced by irradiating 235U in the nuclear reactor. 99Mo mostly results from the fission reaction of 235U targets with a fission yield about 6.1%. A small additional amount is created from 98Mo neutron activation. Actually 99Mo is also created in the reactor fuel, but usually we do not extract it. The fuel will become spent fuel which is a highly radioactive waste. 99Mo production system in the aqueous homogeneous reactor offers a better method, because all of the 99Mo can be extracted from the fuel solution. Fresh reactor fuel solution consists of uranyl nitrate dissolved in water. There is no separation of target and fuel in an aqueous homogeneous reactor where target and fuel become one liquid solution, and there is no spent fuel generated from this reactor. Simulation of the extraction process is performed while reactor in operation (without reactor shutdown. With an extraction flow rate of 3.6 L/h, after 43 hours of reactor operation the production of 99Mo is relatively constant at about 98.6 curie/hour

The reaction of hydrazine nitrate with nitric acid

International Nuclear Information System (INIS)

Kida, Takashi; Sugikawa, Susumu

2004-03-01

It is known that hydrazine nitrate used in nuclear fuel reprocessing plants is an unstable substance thermochemically like hydroxylamine nitrate. In order to take the basic data regarding the reaction of hydrazine nitrate with nitric acid, initiation temperatures and heats of this reaction, effect of impurity on initiation temperature and self-accelerating reaction when it holds at constant temperature for a long time were measured by the pressure vessel type reaction calorimeter etc. In this paper, the experimental data and evaluation of the safe handling of hydrazine nitrate in nuclear fuel reprocessing plants are described. (author)

Modular Regiospecific Synthesis of Nitrated Fatty Acids

DEFF Research Database (Denmark)

Hock, Katharina J.; Grimmer, Jennifer; Göbel, Dominik

2016-01-01

Endogenous nitrated fatty acids are an important class of signaling molecules. Herein a modular route for the efficient and regiospecific preparation of nitrooleic acids as well as various analogues is described. The approach is based on a simple set of alkyl halides as common building blocks...

The application of time-resolved luminescence spectroscopy to a remote uranyl sensor

International Nuclear Information System (INIS)

Varineau, P.T.; Duesing, R.; Wangen, L.E.

1991-01-01

Time resolved luminescence spectroscopy is an effective method for the determination of a wide range of uranyl concentrations in aqueous samples. We have applied this technique to the development of a remote sensing device using fiber optic cables coupled with a micro flow cell in order to probe for uranyl in aqueous samples. This sensor incorporates a Nafion membrane through which UO 2 2+ can diffuse in to a reaction/analysis chamber which holds phosphoric acid, a reagent which enhances the uranyl luminescence intensity and lifetime. With this device, anionic and fluorescing organic interferences could be eliminated, allowing for the determination of uranyl over a concentration range of 10 4 to 10 -9 M. 17 refs., 5 figs

'Low-acid' sulfide oxidation using nitrate-enriched groundwater

Science.gov (United States)

Donn, Michael; Boxall, Naomi; Reid, Nathan; Meakin, Rebecca; Gray, David; Kaksonen, Anna; Robson, Thomas; Shiers, Denis

2016-04-01

Acid drainage (AMD/ARD) is undoubtedly one of the largest environmental, legislative and economic challenges facing the mining industry. In Australia alone, at least 60m is spent on AMD related issues annually, and the global cost is estimated to be in the order of tens of billions US. Furthermore, the challenge of safely and economically storing or treating sulfidic wastes will likely intensify because of the trend towards larger mines that process increasingly higher volumes of lower grade ores and the associated sulfidic wastes and lower profit margins. While the challenge of managing potentially acid forming (PAF) wastes will likely intensify, the industrial approaches to preventing acid production or ameliorating the effects has stagnated for decades. Conventionally, PAF waste is segregated and encapsulated in non-PAF tips to limit access to atmospheric oxygen. Two key limitations of the 'cap and cover' approach are: 1) the hazard (PAF) is not actually removed; only the pollutant linkage is severed; and, 2) these engineered structures are susceptible to physical failure in short-to-medium term, potentially re-establishing that pollutant linkage. In an effort to address these concerns, CSIRO is investigating a passive, 'low-acid' oxidation mechanism for sulfide treatment, which can potentially produce one quarter as much acidity compared with pyrite oxidation under atmospheric oxygen. This 'low-acid' mechanism relies on nitrate, rather than oxygen, as the primary electron accepter and the activity of specifically cultured chemolithoautotrophic bacteria and archaea communities. This research was prompted by the observation that, in deeply weathered terrains of Australia, shallow (oxic to sub-oxic) groundwater contacting weathering sulfides are commonly inconsistent with the geochemical conditions produced by ARD. One key characteristic of these aquifers is the natural abundance of nitrate on a regional scale, which becomes depleted around the sulfide bodies, and

Lewis Acid Assisted Nitrate Reduction with Biomimetic Molybdenum Oxotransferase Complex.

Science.gov (United States)

Elrod, Lee Taylor; Kim, Eunsuk

2018-03-05

The reduction of nitrate (NO 3 - ) to nitrite (NO 2 - ) is of significant biological and environmental importance. While Mo IV (O) and Mo VI (O) 2 complexes that mimic the active site structure of nitrate reducing enzymes are prevalent, few of these model complexes can reduce nitrate to nitrite through oxygen atom transfer (OAT) chemistry. We present a novel strategy to induce nitrate reduction chemistry of a previously known catalyst Mo IV (O)(SN) 2 (2), where SN = bis(4- tert-butylphenyl)-2-pyridylmethanethiolate, that is otherwise incapable of achieving OAT with nitrate. Addition of nitrate with the Lewis acid Sc(OTf) 3 (OTf = trifluoromethanesulfonate) to 2 results in an immediate and clean conversion of 2 to Mo VI (O) 2 (SN) 2 (1). The Lewis acid additive further reacts with the OAT product, nitrite, to form N 2 O and O 2 . This work highlights the ability of Sc 3+ additives to expand the reactivity scope of an existing Mo IV (O) complex together with which Sc 3+ can convert nitrate to stable gaseous molecules.

Standard test method for determination of bromine and chlorine in UF6 and uranyl nitrate by X-Ray fluorescence (XRF) spectroscopy

CERN Document Server

American Society for Testing and Materials. Philadelphia

2001-01-01

1.1 This method covers the determination of bromine (Br) and chlorine (Cl) in uranium hexafluoride (UF6) and uranyl nitrate solution. The method as written covers the determination of bromine in UF6 over the concentration range of 0.2 to 8 μg/g, uranium basis. The chlorine in UF6 can be determined over the range of 4 to 160 μg/g, uranium basis. Higher concentrations may be covered by appropriate dilutions. The detection limit for Br is 0.2 μg/g uranium basis and for Cl is 4 μg/g uranium basis. 1.2 This standard may involve hazardous materials, operations and equipment. This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

Benchmarking uranyl peroxide capsule chemistry in organic media

Energy Technology Data Exchange (ETDEWEB)

Neal, Harrison A.; Nyman, May [Department of Chemistry, Oregon State University, Corvallis, OR (United States); Szymanowski, Jennifer; Fein, Jeremy B.; Burns, Peter C. [Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame, Notre Dame, IN (United States)

2017-01-03

Uranyl peroxide capsules are a recent addition to polyoxometalate (POM) chemistry. Ten years of development has ensued only in water, while transition metal POMs are commonly exploited in aqueous and organic media, controlled by counterions or ligation to render the clusters hydrophilic or hydrophobic. Here, new uranyl POM behavior is recognized in organic media, including (1) stabilization and immobilization of encapsulated hydrophilic countercations, identified by Li nuclear magnetic resonance (NMR) spectroscopy, (2) formation of new cluster species upon phase transfer, (3) extraction of uranyl clusters from different starting materials including simulated spent nuclear fuel, (4) selective phase transfer of one cluster type from a mixture, and (5) phase transfer of clusters from both acidic and alkaline media. The capsule morphology of the uranyl POMs renders accurate characterization by X-ray scattering, including the distinction of geometrically similar clusters. Compositional analysis of the aqueous phase post-extraction provided a quantitative determination of the ion exchange process that enables transfer of the clusters into the organic phase. Preferential partitioning of uranyl POMs into organic media presents new frontiers in metal ion behavior and chemical reactions in the confined space of the cluster capsules in hydrophobic media, as well as the reactivity of clusters at the organic/aqueous interface. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Benchmarking uranyl peroxide capsule chemistry in organic media

International Nuclear Information System (INIS)

Neal, Harrison A.; Nyman, May; Szymanowski, Jennifer; Fein, Jeremy B.; Burns, Peter C.

2017-01-01

Uranyl peroxide capsules are a recent addition to polyoxometalate (POM) chemistry. Ten years of development has ensued only in water, while transition metal POMs are commonly exploited in aqueous and organic media, controlled by counterions or ligation to render the clusters hydrophilic or hydrophobic. Here, new uranyl POM behavior is recognized in organic media, including (1) stabilization and immobilization of encapsulated hydrophilic countercations, identified by Li nuclear magnetic resonance (NMR) spectroscopy, (2) formation of new cluster species upon phase transfer, (3) extraction of uranyl clusters from different starting materials including simulated spent nuclear fuel, (4) selective phase transfer of one cluster type from a mixture, and (5) phase transfer of clusters from both acidic and alkaline media. The capsule morphology of the uranyl POMs renders accurate characterization by X-ray scattering, including the distinction of geometrically similar clusters. Compositional analysis of the aqueous phase post-extraction provided a quantitative determination of the ion exchange process that enables transfer of the clusters into the organic phase. Preferential partitioning of uranyl POMs into organic media presents new frontiers in metal ion behavior and chemical reactions in the confined space of the cluster capsules in hydrophobic media, as well as the reactivity of clusters at the organic/aqueous interface. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Uranyl sorption onto alumina

International Nuclear Information System (INIS)

Jacobsson, A.M.M.

1997-01-01

The mechanism for the adsorption of uranyl onto alumina from aqueous solution was studied experimentally and the data were modeled using a triple layer surface complexation model. The experiments were carried out at low uranium concentrations (9 x 10 -11 --5 x 10 -8 M) in a CO 2 free environment at varying electrolyte concentrations (0.01--1 M) and pH (4.5--12). The first and second acid dissociation constants, pK a1 and pK a2 , of the alumina surface were determined from potentiometric titrations to be 7.2 ± 0.6 and 11.2 ± 0.4, respectively. The adsorption of uranium was found to be independent of the electrolyte concentration. The authors therefore conclude that the uranium binds as an inner sphere complex. The results were modeled using the code FITEQL. Two reactions of uranium with the surface were needed to fit the data, one forming a uranyl complex with a single surface hydroxyl and the other forming a bridged or bidentate complex reacting with two surface hydroxyls of the alumina. There was no evidence from these experiments of site heterogeneity. The constants used for the reactions were based in part on predictions made utilizing the Hard Soft Acid Base, HSAB, theory, relating the surface complexation constants to the hydrolysis of the sorbing metal ion and the acid dissociation constants of the mineral oxide surface

Removal of uranyl ions from residual waters using some algae types

International Nuclear Information System (INIS)

Cecal, A.; Palamaru, I.; Humelnicu, D.; Popa, K.; Salaru, V.V.; Rudic, V.; Gulea, A.

1999-01-01

This paper deals with a study on the bioaccumulation of uranyl ions resulted from residual effluents by means of some microbiological collectors: Scenedesmus quadricauda, Anabaena karakumica, Calothrix brevissima, Penicillinium sp, as well as the Glucid extract of Porphyridium cruentum, under various experimental conditions. The retaining degree of the bioaccumulated uranyl ions, as well as the leaching degree, in HCl and H 2 O media, of the same ions previously retained on algae were established. The retaining degree decreases in the series: Scenedesmus quadricauda > Anabaena karakumica > Penicillinium sp > Calothrix brevissima. The leaching effect of bioaccumulated uranyl ions is higher in hydrochloric acid than in water. (author)

Nitric acid recycling and copper nitrate recovery from effluent.

Science.gov (United States)

Jô, L F; Marcus, R; Marcelin, O

2014-01-01

The recycling of nitric acid and copper nitrate contained in an industrial effluent was studied. The experiments conducted on such a medium showed that the presence of copper nitrate significantly improves nitric acid-water separation during distillation in an azeotropic medium. At the temperature of the azeotrope, however, this metal salt starts to precipitate, making the medium pasty, thus inhibiting the nitric acid extraction process. The optimisation of parameters such as column efficiency and adding water to the boiler at the azeotrope temperature are recommended in this protocol in order to collect the various components while avoiding the formation of by-products: NOx compounds. Thus, the absence of column, along with the addition of a small volume of water at a temperature of 118 °C, significantly increases the yield, allowing 94 % nitric acid to be recovered at the end of the process, along with the residual copper nitrate. The resulting distillate, however, is sufficiently dilute to not be used as is. Rectification is required to obtain concentrated nitric acid at 15 mol·l(-1), along with a weakly acidic distillate from the distillation front. This latter is quenched using potassium hydroxide and is used as a fertiliser solution for horticulture or sheltered market gardening. This process thus allows complete recycling of all the medium's components, including that of the distillate resulting from the nitric acid rectification operation.

Energy transfer and quenching processes of excited uranyl ion and lanthanide ions in solutions

International Nuclear Information System (INIS)

Yamamura, Tomoo; Tomiyasu, Hiroshi

1995-01-01

Deactivation processes of photoexcited uranyl ion by various lanthanide ions in aqueous solution were studied. Each lanthanide ions show different interaction with excited uranyl ion depending on its lowest excited energy level, the number of 4f electrons and the acid concentration of the solution. (author)

Crystallization characteristics of ammonium uranyl carbonate (AUC) in ammonium carbonate solutions

International Nuclear Information System (INIS)

Kim, T.J.; Jeong, K.C.; Park, J.H.; Chang, I.S.; Choi, C.S.

1994-01-01

Ammonium carbonate solutions with an excessive amount of NH 3 were produced in a commercial AUC (ammonium uranyl carbonate) conversion plant. In this study the AUC crystals, precipitated with uranyl nitrate and ammonium carbonate solutions prepared in the laboratory, were characterized to determine the feasibility of recycling ammonium carbonate solution. The AUC crystals were easily agglomerated with the increasing concentration of CO 3 2- and mole ratio of NH 4 + /CO 3 2- in ammonium carbonate solution. Effects of a mixing system for the solution in the AUC crystallizer and the feed location of the solution onthe agglomeration of AUC crystals were also studied along with the effects of agglomerated AUC powders on UO 2 powders. Finally, the feasibility of manufacturing UO 2 fuel with a sintered pellet density of 10.52 g/cm 3 , using the AUC powders generated in this experiment, was demonstrated. (orig.)

Electrochemical behavior of uranyl in anhydrous polar organic media

Energy Technology Data Exchange (ETDEWEB)

Burn, Adam G.; Nash, Kenneth L. [Washington State Univ., Pullmann, WA (United States). Dept. of Chemistry

2017-09-01

Weak complexes between pentavalent and hexavalent actinyl cations have been reported to exist in acidic, non-complexing high ionic strength aqueous media. Such ''cation-cation complexes'' were first identified in the context of actinide-actinide redox reactions in acidic aqueous media relevant to solvent extraction-based separation systems, hence their characterization is of potential interest for advanced nuclear fuel reprocessing. This chemistry could be relevant to efforts to develop advanced actinide separations based on the upper oxidation states of americium, which are of current interest. In the present study, the chemical behavior of pentavalent uranyl was examined in non-aqueous, aprotic polar organic solvents (propylene carbonate and acetonitrile) to determine whether UO{sub 2}{sup +} cations generated at the reducing working electrode surface would interact with the UO{sub 2}{sup 2+} cations in the bulk phase to form cation-cation complexes in such media. In magnesium perchlorate media, the electrolyte adsorbed onto the working electrode surface and interfered with the uranyl reduction/diffusion process through an ECE (electron transfer/chemical reaction/electron transfer) mechanism. In parallel studies of uranyl redox behavior in tetrabutylammonium hexafluorophosphate solutions, an EC (electron transfer/chemical reaction) mechanism was observed in the cyclic voltammograms. Ultimately, no conclusive electrochemical evidence demonstrated uranyl cation-cation interactions in the non-aqueous, aprotic polar organic solvent solutions, though the results reported do not completely rule out the presence of UO{sub 2}{sup +}.UO{sub 2}{sup 2+} complexes.

Engaging the Terminal: Promoting Halogen Bonding Interactions with Uranyl Oxo Atoms.

Science.gov (United States)

Carter, Korey P; Kalaj, Mark; Surbella, Robert G; Ducati, Lucas C; Autschbach, Jochen; Cahill, Christopher L

2017-11-02

Engaging the nominally terminal oxo atoms of the linear uranyl (UO 2 2+ ) cation in non-covalent interactions represents both a significant challenge and opportunity within the field of actinide hybrid materials. An approach has been developed for promoting oxo atom participation in a range of non-covalent interactions, through judicious choice of electron donating equatorial ligands and appropriately polarizable halogen-donor atoms. As such, a family of uranyl hybrid materials was generated based on a combination of 2,5-dihalobenzoic acid and aromatic, chelating N-donor ligands. Delineation of criteria for oxo participation in halogen bonding interactions has been achieved by preparing materials containing 2,5-dichloro- (25diClBA) and 2,5-dibromobenzoic acid (25diBrBA) coupled with 2,2'-bipyridine (bipy) (1 and 2), 1,10-phenanthroline (phen) (3-5), 2,2':6',2''-terpyridine (terpy) (6-8), or 4'-chloro-2,2':6',2''-terpyridine (Cl-terpy) (9-10), which have been characterized through single crystal X-ray diffraction, Raman, Infrared (IR), and luminescence spectroscopy, as well as through density functional calculations of electrostatic potentials. Looking comprehensively, these results are compared with recently published analogues featuring 2,5-diiodobenzoic acid which indicate that although inclusion of a capping ligand in the uranyl first coordination sphere is important, it is the polarizability of the selected halogen atom that ultimately drives halogen bonding interactions with the uranyl oxo atoms. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Distribution of iron during full loading of amberlite IRC-72 resin with uranium from nitrate solutions at 300C

International Nuclear Information System (INIS)

Shaffer, J.H.; Greene, C.W.

1979-01-01

The integrity of resin-based fuel kernels used in the fabrication of fuel elements for a high-temperature gas-cooled reactor will depend, in part, on the concentration of iron incorporated in the resin particles during their loading with uranium. Consequently, assessment of chemical specifications for iron as an impurity in uranyl nitrate solution should be based on its distribution during the resin loading operation. For this purpose, the behavior of iron, as an impurity in uranyl nitrate solutions, was investigated under equilibrium conditions at 30 0 C during full loading of Amberlite IRC-72 cation exchange reaction were derived from calculations based on complex coordination of ferric ion with the resin over the nitrate ion concentration range of approx. 0.5 to 2 N

Use of the ion exchange method for determination of stability constants of uranyl ions with three soil humic acids

International Nuclear Information System (INIS)

Tao Zuyi; Du Jinzhou

1994-01-01

The ion exchange equilibrium method proposed by Ardakani and Stevenson has not been widely used to determine the stability constants of metal-soil organic matter complexes. In this paper the Ardakani-Stevenson's method has been modified and the stability constants of uranyl ion complexes with three soil humic acids were determined by using the modified Ardakani-Stevenson's method. (orig.)

Study of the influence of the citric and oxalic acid in the uranyl sorption in ZrP2O7 for their use in contention barriers

International Nuclear Information System (INIS)

Garcia G, N.

2009-01-01

Countries which produce electricity by nuclear means, such as Mexico, need to develop a technology for that at long term safe containment of nuclear waste that are produced in nuclear power plants, for now, the arrangement of these is made by international companies, as which is extremely expensive. The most accepted proposal for the containment of radioactive waste is the Deep Geological Repository (DGR), which consists of a number of natural barriers and of engineering barriers. Currently, barriers to engineering and materials that the make up are still under study, because must meet a series of structural criteria and chemical such as high insolubility, thermal and chemical stability with ionizing radiation. The surface must have adsorbed features of ions and organic compounds dissolved in infiltration water that could penetrate for a crack in the DGR. This study focuses, as first stage, is the uranyl sorption on zirconium diphosphate in various conditions of time, concentration and ph, then evaluates the influence of citric acid and oxalic acid on the sorption of uranyl on ZrP 2 O 7 , in order to model the behaviour of alpha emitters that are dissolved by percolating water laden with salts and organic matter, that infiltrates might during catastrophic events in the DGR. It was confirmed the purity of the zirconium diphosphate because it was synthesized from sea sand with the physicochemical characterization and superficial. The proposed methodology included elemental analysis by neutron activation and X-ray emission induced by charged particles, functional group analysis with infrared spectroscopy, morphology with scanning electron microscopy, crystallinity with transmission electron microscopy and X-ray diffraction. For properties surface was determined, the specific area using Bet multipoint technique, acidity constants in the FITEQL 4.0 program, the hydration time was obtained from literature, the point of zero charge was identified with a mass titration and

Fluid bed direct denitration process for plutonium nitrate to oxide conversion

International Nuclear Information System (INIS)

Souply, K.R.; Neal, D.H.

1977-01-01

The fluid bed direct-denitration process appears feasible for reprocessing Light Water Reactor fuel. Considerable experience with the fluid bed process exists in the denitration of uranyl nitrate and it shows promise for use in the denitration of plutonium nitrate. The process will require some development work before it can be used in a production-size facility. This report describes a fluid bed direct-denitration process for converting plutonium nitrate to plutonium oxide, and the information should be used when making comparisons of alternative processes or as a basis for further detailed studies

Vapor-liquid equilibria for nitric acid-water and plutonium nitrate-nitric acid-water solutions

International Nuclear Information System (INIS)

Maimoni, A.

1980-01-01

The liquid-vapor equilibrium data for nitric acid and nitric acid-plutnonium nitrate-water solutions were examined to develop correlations covering the range of conditions encountered in nuclear fuel reprocessing. The scanty available data for plutonium nitrate solutions are of poor quality but allow an order of magnitude estimate to be made. A formal thermodynamic analysis was attempted initially but was not successful due to the poor quality of the data as well as the complex chemical equilibria involved in the nitric acid and in the plutonium nitrate solutions. Thus, while there was no difficulty in correlating activity coefficients for nitric acid solutions over relatively narrow temperature ranges, attempts to extend the correlations over the range 25 0 C to the boiling point were not successful. The available data were then analyzed using empirical correlations from which normal boiling points and relative volatilities can be obtained over the concentration ranges 0 to 700 g/l Pu, 0 to 13 M nitric acid. Activity coefficients are required, however, if estimates of individual component vapor pressures are needed. The required ternary activity coefficients can be approximated from the correlations

Determination of uranyl nitrate diffusion coefficients in organic and aqueous media using the porous diaphragm method

International Nuclear Information System (INIS)

Chierice, G.O.

1974-01-01

The diffusion coefficient is one of the parameters necessary for the obtention of the extraction exponential coefficients, that are contained within the H.T.U. (height of transfer unity) calculation expression, when operating with continuous organic phase. The organic phase used was tri-n-butyl-phosphate (TBP) and varsol in the 35% and 65% proportions respectively. After each experiment, the uranium content present in each compartment was spectrophotometrically determined and the quantities contained in the aqueous phases were determined by means of volumetric titration. It was found out that the uranyl ion diffusion coefficient is two and one half times less in organic phase, this just being attributed to the greater interactions of the uranyl ions in organic than in aqueous medium

Synthesis and complexation properties towards uranyl cation of carboxylic acid derivatives of p-tert-butyl-calix[6]arene

International Nuclear Information System (INIS)

Souane, R.

2005-03-01

In the fuel reprocessing plants radioactive metals, and more particularly, uranium in UO 2 2+ form in the various installations, have many varied physico-chemical forms and there is a risk of exposure and internal contamination in the nuclear industry. It is necessary to exert a medical control to ensure the protection of the health of the workers. This medical control is done by dosing uranyl cation in the urine of the exposed people. This work forms part of this context. Indeed, we prepared a ligand able to complex the ion uranyl and which is also to be grafted on a solid support. In the family of calixarenes, the calix[6]arenes functionalized by three or four carboxylic functions were selected like chelating molecules of the ion uranyl. The properties of complexation of these calixarenes were studied by potentiometry in methanol, under these conditions balances of protonation and complexation were determined and the constant partners were obtained using the Hyperquad program. We synthesized tri-carboxylic calix[6]arenes comprising of the groupings nitro (NO 2 ) in para position of phenol in order to see the influence of a substitution in para position on the complexation. We also synthesized calix[6]arenes tetra-carboxylic in order to show the role of an additional carboxylic acid grouping. The potentiometric study determined thermodynamic parameters of protonation and complexation of carboxylic calix[6]arenes. The results of the complexation highlighted which complex UO 2 L corresponding to the ligand para-tert-butyl-calix[6]arene tetra-acid is more stable than that corresponding to the ligand mono-nitro calix[6]arene tri-acid (ΔlogΒ110 = 4.3), and than the effect of the groupings nitro in para position has low influence on the complexation of UO 2 2+ . This makes it possible to consider as possible the grafting of the calix[6]arenes which one knows the behaviour of trapping. To this end we synthesized the ligand 23. (author)

Liquids - vapor and liquids - solids equilibria in the system Th(NO3)4 - UO2(NO3)2 - HNO3 - H2O

International Nuclear Information System (INIS)

Volk, V.I.; Vakhrushin, A.Yu.; Mamaev, S.L.; Zhirnov, Yu.P.

1999-01-01

Liquids - vapor and liquids - solids equilibria in the system Th(NO 3 ) 4 - UO 2 (NO 3 ) 2 - HNO 3 - H 2 O were investigated. It was established that in this system thorium nitrate hexahydrate and uranyl nitrate hexa- and trihydrate are formed. Empiric equations of solubility isotherm at 25 deg C were found. Densities of liquid phases of the system were determined. It was established that uranyl nitrates and thorium nitrates salt out nitric acid in vapor phase just as separately so in the case of mutual presence. Empiric equation fixing relationship between nitric acid concentration in condensed phase and concentrations of all components in liquid phase was found

Method of separation of uranium from contaminating ions in an aqueous feed liquid containing uranyl ions

International Nuclear Information System (INIS)

Sundar, P.S.; Elikan, L.; Lyon, W.L.

1975-01-01

A coupled cationic/anionic method for the separation of uranium from contaminated aqueous solutions which contain uranyl ions is proposed. The fluid is extracted using an organic solvent containing a reagent which, together with the uranyl ions, forms a soluble aggregate in that solvent. As an example, 0.1 - 1 Mol/l Di-2-ethyl-hexyl-phosphorous acid in kerosene is mentioned. The organic solvent is then treated with a sealing liquid (volume ratio 20 - 35). For separation, an aqueous carbonate solution or a sulfuric acid solution can be used; the most favorable pH-values and concentrations for both cases are mentioned. The U +4 -ion at the sulfuric acid separation is subsequently oxidized to the uranyl ion with air. In each case, an extraction with an amine follows; after that, the amine is separated using an ammonium-carbonate solution and the uranium aggregate is precipitated, for example as ammonium uranyl tricarbonate, and then further processed to uranium oxide. The solvents and fluids used are led back in closed circuit; a flow diagram is given. (UWI) [de

1H chemically induced dynamic nuclear polarization in the photodecomposition of uranyl carboxylates

International Nuclear Information System (INIS)

Rykov, S.V.; Khudyakov, I.V.; Skakovsky, E.D.; Burrows, H.D.; Formosinho, S.J.; Miguel, M. da G.M.

1991-01-01

Chemically induced dynamic nuclear polarization ( 1 H CIDNP) has been observed during photolysis of uranyl salts of pivalic, propionic, and acetic acids in D 2 O solution, [ 2 H 6 ]acetone, [ 2 H 4 ]methanol, or in some other solvent. The multiplet polarization of isobutene and isobutane protons has been found under photolysis of deoxygenated pivalate solution. The polarized compounds are formed in the triplet pairs of tert-butyl free radicals. 1 H Emission of the tert-butylperoxyl group and emission of 1 H from isobutene have been recorded under photolysis of air-saturated pivalate solutions. The CIDNP of butane protons stays as a multiplet. Such changes in the presence of air/oxygen have arisen apparently because of the formation of tert-butylperoxyl free radical and its reaction with tert-butyl radical products, i.e. hydroperoxide (peroxide) and isobutene. Isobutene probably forms a complex with molecular oxygen which has a very short proton relaxation time. During the photolysis of uranyl pivalate in the presence of p-benzoquinone (5 x 10 -2 -0.1 mol dm -3 ) we have not observed any CIDNP, whereas under p-benzoquinone concentrations of 10 -3 -10 -2 mol dm -3 the CIDNP from both hydroquinone and p-benzoquinone has been followed. Photolysis of uranyl propionate has led to CIDNP from butane protons. An emission from methyl group protons of a compound with an ethylperoxyl fragment in the presence of air/oxygen has been observed. The same polarization picture has arisen under interaction of photoexcited uranyl with propionic acid. During the photolysis of uranyl acetate at relatively low concentrations (10 -2 mol dm -3 ) a CIDNP very similar to that registered for uranyl propionate was recorded. The ethyl fragment is probably obtained in reactions for two methyl radicals formed from acetate with the parent uranyl acetate, namely hydrogen-atom abstraction and addition reactions. (author)

Investigation of uranyl phosphite interaction with some amides

International Nuclear Information System (INIS)

Avduevskaya, K.A.; Ragulina, N.B.; Rozanov, I.A.; Mukhajlov, Yu.N.; Kanishcheva, A.S.; Grevtseva, T.G.

1981-01-01

Uranyl (amide) phosphitocomplexes of [UO 2 HPO 3 H 2 OAA]xH 2 O, [UO 2 HPO 3 (AA) 2 ], [UO 2 HPO 3 H 2 O DMC], [UO 2 HPO 3 H 2 ODMFA], [UO 2 HPO 3 DAMA] and UO 2 HPO 3 x2FAxH 2 O compositions, where AA-acetamide; DMC-N, N-dimetyl carbamide, DMFA-dimetyl formamide; DAMA-diamide of malonic acid; FA-formamide, are separated, identified and investigated. Derivatives of mono substituted uranyl phosphite of UO 2 (H 2 PO 3 ) 2 x2FA and [UO 2 (H 2 PO 3 ) 2 H 2 O]x2TMC composition (where TMC-tetramethyl carbamide), are synthesized. Structures of complexes with DAMA, TMC, DMFA and acid dimethyl-ammonium diphosphitouranylate-(CH 3 ] 2 NH 2 x[UO 2 (HPO 3 ) 3 (H 2 PO 3 )] are investigated [ru

Recovery of uranium from an irradiated solid target after removal of molybdenum-99 produced from the irradiated target

Science.gov (United States)

Reilly, Sean Douglas; May, Iain; Copping, Roy; Dale, Gregory Edward

2017-10-17

A process for minimizing waste and maximizing utilization of uranium involves recovering uranium from an irradiated solid target after separating the medical isotope product, molybdenum-99, produced from the irradiated target. The process includes irradiating a solid target comprising uranium to produce fission products comprising molybdenum-99, and thereafter dissolving the target and conditioning the solution to prepare an aqueous nitric acid solution containing irradiated uranium. The acidic solution is then contacted with a solid sorbent whereby molybdenum-99 remains adsorbed to the sorbent for subsequent recovery. The uranium passes through the sorbent. The concentrations of acid and uranium are then adjusted to concentrations suitable for crystallization of uranyl nitrate hydrates. After inducing the crystallization, the uranyl nitrate hydrates are separated from a supernatant. The process results in the purification of uranyl nitrate hydrates from fission products and other contaminants. The uranium is therefore available for reuse, storage, or disposal.

Potential New Ligand Systems for Binding Uranyl Ions in Seawater Environments

Energy Technology Data Exchange (ETDEWEB)

Arnold, John [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

2014-12-13

Work began this quarter on a new project involving a combined computational and biosynthetic approach to selective recognition of uranyl ion in aqueous solution. This project exploits the results of computational studies to discover new ligand classes. Synthetic studies will follow to generate target systems for uranyl binding and determination of binding constants. The process will be iterative, with results from computation informing synthesis, and vice versa. The theme of the ligand classes to be examined initially will be biologically based. New phosphonate-containing α-amino acid N-carboxyanhydride (NCA) monomers were used recently to prepare well-defined phosphonate-containing poly-peptides and block copolypeptides. Our first approach is to utilize these phosphate- and phosphonate-containing NCAs for the coordination of uranyl. The work includes the laboratory-scale preparation of a series of NCAs and the full thermodynamic and spectroscopic characterization of the resulting uranyl complexes. We are also evaluating the sequestering activity in different physiological and environmental conditions of these copolymers as well as their biodegradability.

Luminescence of uranyl ion complexed with 2,6-pyridine dicarboxylic acid as ligand in acetonitrile medium. Observation of co-luminescence

Energy Technology Data Exchange (ETDEWEB)

Maji, Siuli; Kumar, Satendra; Sankaran, Kannan [Indira Ghandi Centre for Atomic Research, Tamil Nadu (India). Materials Chemistry Div.

2017-10-01

Luminescence from UO{sub 2}{sup 2+} (uranyl ion) complexed with 2,6-pyridine dicarboxylic acid (PDA) has been studied using acetonitrile (MeCN) as solvent between pH 1.0 and 6.0. The enhancement in luminescence intensity because of sensitization by PDA in the non-aqueous environment provided by the MeCN is found to be one order better than in aqueous medium. The luminescence is further enhanced by about four times following the addition of Y{sup 3+}; a process known as co-luminescence. This is the first study on co-luminescence of uranyl ion in its PDA complex. Lifetime studies indicate the presence of two species having different micro-environments. Formations of both intra and inter molecular complexes are believed to be responsible for enhancement due to co-luminescence.

Luminescence of uranyl ion complexed with 2,6-pyridine dicarboxylic acid as ligand in acetonitrile medium. Observation of co-luminescence

International Nuclear Information System (INIS)

Maji, Siuli; Kumar, Satendra; Sankaran, Kannan

2017-01-01

Luminescence from UO_2"2"+ (uranyl ion) complexed with 2,6-pyridine dicarboxylic acid (PDA) has been studied using acetonitrile (MeCN) as solvent between pH 1.0 and 6.0. The enhancement in luminescence intensity because of sensitization by PDA in the non-aqueous environment provided by the MeCN is found to be one order better than in aqueous medium. The luminescence is further enhanced by about four times following the addition of Y"3"+; a process known as co-luminescence. This is the first study on co-luminescence of uranyl ion in its PDA complex. Lifetime studies indicate the presence of two species having different micro-environments. Formations of both intra and inter molecular complexes are believed to be responsible for enhancement due to co-luminescence.

Charge-density matching in organic-inorganic uranyl compounds

Energy Technology Data Exchange (ETDEWEB)

Krivovichev, S.V. [Saint Petersburg State Univ., Dept. of Crystallography, Faculty of Geology (Russian Federation); Krivovichev, S.V.; Tananaev, I.G.; Myasoedov, B.F. [Russian Academy of Sciences, A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Moscow (Russian Federation)

2007-10-15

Single crystals of [C{sub 10}H{sub 26}N{sub 2}][(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)](H{sub 2}SeO{sub 4}){sub 0.85}(H{sub 2}O){sub 2} (1), [C{sub 10}H{sub 26}N{sub 2}][(UO{sub 2})(SeO{sub 4}){sub 2}] (H{sub 2}SeO{sub 4}){sub 0.50}(H{sub 2}O) (2), and [C{sub 8}H{sub 20}N]{sub 2}[(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)] (H{sub 2}O) (3) were prepared by evaporation from aqueous solution of uranyl nitrate, selenic acid and the respective amines. The structures of the compounds have been solved by direct methods and structural models have been obtained. The structures of the compounds 1, 2, and 3 contain U and Se atoms in pentagonal bipyramidal and tetrahedral coordinations, respectively. The UO{sub 7} and SeO{sub 4} polyhedra polymerize by sharing common O atoms to form chains (compound 1) or sheets (compounds 2 and 3). In the structure of 1, the layers consisting of hydrogen-bonded [UO{sub 2}(SeO{sub 4}){sub 2}(H{sub 2}O)]{sup 2-} chains are separated by mixed organic-inorganic layers comprising from [NH{sub 3}(CH{sub 2}){sub 10}NH{sub 3}]{sup 2+} molecules, H{sub 2}O molecules, and disordered electroneutral (H{sub 2}SeO{sub 4}) groups. The structure of 2 has a similar architecture but a purely inorganic layer is represented by a fully connected [UO{sub 2}(SeO{sub 4}){sub 2}]{sup 2-} sheet. The structure of 3 does not contain disordered (H{sub 2}SeO{sub 4}) groups but is based upon alternating [UO{sub 2}(SeO{sub 4}){sub 2}(H{sub 2}O)]{sup 2-} sheets and 1.5-nm-thick organic blocks consisting of positively charged protonated octylamine molecules, [NH{sub 3}(CH{sub 2}){sub 7}CH{sub 3}]{sup +}. The structures may be considered as composed of anionic inorganic sheets (2D blocks) and cationic organic blocks self-organized according to competing hydrophilic-hydrophobic interactions. Analysis of the structures allows us to conclude that the charge-density matching principle is observed in uranyl compounds. In order to satisfy some basic peculiarities of uranyl (in

Studies on supercritical fluid extraction behaviour of uranium and thorium nitrates using amides

International Nuclear Information System (INIS)

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

2007-01-01

Supercritical fluid extraction studies of uranyl nitrate and thorium nitrate in mixture were carried out using various amides such as N,N-di(2-ethylhexyl) isobutyramide (D2EHIBA),N,N-dihexyl octanamide (DHOA) and Diisooctyl Butanamide (DiOBA). These studies established a preferential extraction of uranium over thorium. Among the various amides studied, D2EHIBA offered the best rate of preferential extraction of uranium over thorium. (author)

Nitric acid adduct formation during crystallization of barium and strontium nitrates and their co-precipitation from nitric acid media

International Nuclear Information System (INIS)

Mishina, N.E.; Zilberman, B.Ya.; Lumpov, A.A.; Koltsova, T.I.; Puzikov, E.A.; Ryabkov, D.V.

2015-01-01

The molar solubilities of Ba, Sr and Pb nitrates in nitric acid as a function of total nitrate concentration is presented and described by the mass action law, indicating on formation of the adducts with nitric acid. Precipitates of Ba(NO 3 ) 2 and Sr(NO 3 ) 2 crystallized from nitric acid were studied by ISP OES and IR spectroscopy. The data obtained confirmed formation of metastable adducts with nitric acid. IR and X-ray diffraction studies of the mixed salt systems indicated conversion of the mixed salts into (Ba,Sr)(NO 3 ) 2 solid solution of discrete structure in range of total nitrate ion concentration ∼6 mol/L. (author)

Spectroscopic characterization of alkaline earth uranyl carbonates

International Nuclear Information System (INIS)

Amayri, Samer; Reich, Tobias; Arnold, Thuro; Geipel, Gerhard; Bernhard, Gert

2005-01-01

A series of alkaline uranyl carbonates, M[UO 2 (CO 3 ) 3 ].nH 2 O (M=Mg 2 , Ca 2 , Sr 2 , Ba 2 , Na 2 Ca, and CaMg) was synthesized and characterized by inductively coupled plasma mass spectrometry (ICP-MS) and atomic absorption spectrometry (AAS) after nitric acid digestion, X-ray powder diffraction (XRD), and thermal analysis (TGA/DTA). The molecular structure of these compounds was characterized by extended X-ray absorption fine-structure (EXAFS) spectroscopy and X-ray photoelectron spectroscopy (XPS). Crystalline Ba 2 [UO 2 (CO 3 ) 3 ].6H 2 O was obtained for the first time. The EXAFS analysis showed that this compound consists of (UO 2 )(CO 3 ) 3 clusters similar to the other alkaline earth uranyl carbonates. The average U-Ba distance is 3.90+/-0.02A.Fluorescence wavelengths and life times were measured using time-resolved laser-induced fluorescence spectroscopy (TRLFS). The U-O bond distances determined by EXAFS, TRLFS, XPS, and Raman spectroscopy agree within the experimental uncertainties. The spectroscopic signatures observed could be useful for identifying uranyl carbonate species adsorbed on mineral surfaces

Annual report of STACY operation in FY.2000. Experiments on neutron-interacting systems with two slab-shaped core tanks and 10% enriched uranyl nitrate solution. 2. Contract research

Energy Technology Data Exchange (ETDEWEB)

Onodera, Seiji; Hirose, Hideyuki; Izawa, Kazuhiko [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment] [and others

2001-09-01

Criticality experiments on neutron-interacting systems have been performed since FY.1999 at STACY (Static Experiment Critical Facility) in NUCEF (Nuclear Fuel Cycle Safety Engineering Research Facility). In the experiments two slab-shaped core tanks and 10% enriched uranyl nitrate solution were used. The dimension of the core tanks is 35 cm in thickness, 70 cm in width and 150 cm in height. In FY.2000, the reactivity effect of neutron-isolating materials, such as polyethylene and concrete, and neutron absorbers made of hafnium and cadmium, which were placed between those two core tanks, was determined by the experiments. This report summarizes the data on the operation and the fuel management for the 57 experiments conducted in FY.2000. (author)

Validation of nitrogen-nitrate analysis by the chromotropic acid method

Energy Technology Data Exchange (ETDEWEB)

Santos, Ana Claudia O.; Matoso, Erika, E-mail: anaclaudia.oliveira@marinha.mil.br [Centro Tecnológico da Marinha em São Paulo (CTMSP/CEA), Iperó, SP (Brazil). Centro Experimental ARAMAR

2017-07-01

The problems caused by contamination of water bodies demand strict control of disposal in rivers, seas and oceans. Nitrate ion is present in agricultural inputs, which are applied to the soil to boost plant growth. However, excess or indiscriminate use of these products contaminates water bodies, triggering eutrophication of the aquatic ecosystems. Furthermore, due to diseases that can be caused by the ingestion of high levels of nitrate, such as methaemoglobinaemia, nitrate levels should be controlled in drinking waters and effluents. There are several methods for the determination of nitrate, being the chromotropic acid method a simple and low-cost solution. This method consists of acid addition into the sample in the presence of H{sub 2}SO{sub 4}. The absorbance related to the produced yellow color can be measured by a UV-Vis spectrophotometer at 410 nm. In a modified form, this method can be applied to different aqueous matrices by use of other reagents that eliminate interferences. The aim of this study was to validate the nitrate determination method in waters using chromotropic acid. This method is used in Laboratório Radioecológico (LARE) to analyze effluent to comply with Wastewater Controlling Program of Centro Tecnológico da Marinha em São Paulo – Centro Experimental ARAMAR (CTMSP-CEA). The correlation coefficient for the linearity test was 0.9997. The evaluated detection limit was relatively high (LD = 0.045 mgN/L), if compared to ion chromatography, for example, but enough to determine the presence of this ion, considering the maximum limit proposed by the current legislation. The chromotropic acid method showed to be a robust, accurate and precise method, according the parameters used in this work. (author)

Validation of nitrogen-nitrate analysis by the chromotropic acid method

International Nuclear Information System (INIS)

Santos, Ana Claudia O.; Matoso, Erika

2017-01-01

The problems caused by contamination of water bodies demand strict control of disposal in rivers, seas and oceans. Nitrate ion is present in agricultural inputs, which are applied to the soil to boost plant growth. However, excess or indiscriminate use of these products contaminates water bodies, triggering eutrophication of the aquatic ecosystems. Furthermore, due to diseases that can be caused by the ingestion of high levels of nitrate, such as methaemoglobinaemia, nitrate levels should be controlled in drinking waters and effluents. There are several methods for the determination of nitrate, being the chromotropic acid method a simple and low-cost solution. This method consists of acid addition into the sample in the presence of H 2 SO 4 . The absorbance related to the produced yellow color can be measured by a UV-Vis spectrophotometer at 410 nm. In a modified form, this method can be applied to different aqueous matrices by use of other reagents that eliminate interferences. The aim of this study was to validate the nitrate determination method in waters using chromotropic acid. This method is used in Laboratório Radioecológico (LARE) to analyze effluent to comply with Wastewater Controlling Program of Centro Tecnológico da Marinha em São Paulo – Centro Experimental ARAMAR (CTMSP-CEA). The correlation coefficient for the linearity test was 0.9997. The evaluated detection limit was relatively high (LD = 0.045 mgN/L), if compared to ion chromatography, for example, but enough to determine the presence of this ion, considering the maximum limit proposed by the current legislation. The chromotropic acid method showed to be a robust, accurate and precise method, according the parameters used in this work. (author)

DFT study of uranyl peroxo complexes with H2O, F-, OH-, CO3(2-), and NO3(-).

Science.gov (United States)

Odoh, Samuel O; Schreckenbach, Georg

2013-05-06

The structural and electronic properties of monoperoxo and diperoxo uranyl complexes with aquo, fluoride, hydroxo, carbonate, and nitrate ligands have been studied using scalar relativistic density functional theory (DFT). Only the complexes in which the peroxo ligands are coordinated to the uranyl moiety in a bidentate mode were considered. The calculated binding energies confirm that the affinity of the peroxo ligand for the uranyl group far exceeds that of the F(-), OH(-), CO3(2-), NO3(-), and H2O ligands. The formation of the monoperoxo complexes from UO2(H2O)5(2+) and HO2(-) were found to be exothermic in solution. In contrast, the formation of the monouranyl-diperoxo, UO2(O2)2X2(4-) or UO2(O2)2X(4-/3-) (where X is any of F(-), OH(-), CO3(2-), or NO3(-)), complexes were all found to be endothermic in aqueous solution. This suggests that the monoperoxo species are the terminal monouranyl peroxo complexes in solution, in agreement with recent experimental work. Overall, we find that the properties of the uranyl-peroxo complexes conform to well-known trends: the coordination of the peroxo ligand weakens the U-O(yl) bonds, stabilizes the σ(d) orbitals and causes a mixing between the uranyl π- and peroxo σ- and π-orbitals. The weakening of the U-O(yl) bonds upon peroxide coordination results in uranyl stretching vibrational frequencies that are much lower than those obtained after the coordination of carbonato or hydroxo ligands.

Differential changes in functional activity of organic cation transporters in rats with uranyl nitrate-induced acute renal failure.

Science.gov (United States)

Maeng, Han-Joo; Shim, Won-Sik; Ahn, Sun-Joo; Yu, Sang-Soo; Kim, Dae-Duk; Shim, Chang-Koo; Chung, Suk-Jae

2012-08-01

We studied the impact of experimental kidney failure on the pharmacokinetics of a model organic cation and investigated the underlying mechanism(s) of the organic cation transporters. The systemic pharmacokinetics and tissue distribution of triethylmethylammonium (TEMA), a model organic cation, were characterized after intravenous doses of 0.3-30 μmol/kg in rats with or without uranyl nitrate-induced acute renal failure (UN-ARF). To study the effect of endogenous substrates in plasma from UN-ARF rats on organic cation transport, rOCT- or rOCT2-dependent uptake of tetraethylammonium (TEA) was studied in rOCT1-transfected or rOCT2-transfected LLC-PK1 cells, respectively. As a result, the AUC for TEMA was increased, probably because of decreased total clearance, and the tissue-to-plasma concentration ratio (T/P ratio) of TEMA was unchanged in the liver but decreased significantly in the kidneys of UN-ARF rats. In vitro, the uptake of TEA was decreased significantly by adding UN-ARF plasma, compared with control plasma, in rOCT2-overexpressing LLC-PK1 cells, but not in rOCT1-overexpressing LLC-PK1 cells. These observations suggest that the induction of UN-ARF leads to an accumulation of endogenous organic cation(s), probably rOCT2 substrate(s), in the plasma, thereby affecting the TEMA pharmacokinetics and distribution to the kidneys in rats.

Boric acid - ammonium rhodanide (nitrate, sulfate) - water system at 25 deg C

Energy Technology Data Exchange (ETDEWEB)

Skvortsov, V G; Molodkin, A K; Tsekhanskij, R S; Sadetdinov, Sh V; Nikonov, F V [Chuvashskij Gosudarstvennyj Pedagogicheskij Inst., Cheboksary (USSR); Universitet Druzhby Narodov, Moscow (USSR))

1985-03-01

Methods of isothermal solubility and refractometry have been used to establish that boric acid-ammonium rhodanite (nitrate, sulfate) - water systems are of a simple eutonic type. Rhodanide salts out boric acid, while nitrate and sulfate salt it in. The lyotropic effect referred to the volumetric share of both anion and cation increases in the series SCN/sup -/ < NO/sub 3//sup -/ < SO/sub 4//sup 2 -/.

The final effect ef extraction system in the uranyl nitrate-water-diethyl ether; El efecto final de la extraccion en el sistema nitro de uranilo-eter dietilico-agua

Energy Technology Data Exchange (ETDEWEB)

Perez Luina, A; Gutierrez Jodra, L; Miro, A R

1957-07-01

The solute transfer of uranyl nitrate from diallylether to water has been studied in a spray column using water as dispersed phase and a direction of extraction from ether to water. The column is 102 cm. long has a diameter of 4. 7 cm. The entrances of the phases are 7 7 cm. apart. The rates of flow of both phases have been used as variables and the concentration of the continuous phase has been determined; at different heights. The curves of logarithm of concentration of the continuous phase vs , distance to interphase show the presence of a drop of concentration in the entrance of the continuous phase. This depends on the rates of flow of the phases. No effect in the entrance of the dispersed phase has been found. (Author)

The boric acid - ammonium rhodanide (nitrate, sulfate) - water system at 25 deg C

International Nuclear Information System (INIS)

Skvortsov, V.G.; Molodkin, A.K.; Tsekhanskij, R.S.; Sadetdinov, Sh.V.; Nikonov, F.V.

1985-01-01

Methods of isothermal solubility and refractometry have been used to establish that boric acid-ammonium rhodanite (nitrate, sulfate) - water systems are of a simple eutonic type. Rhodanide salts out boric acid, while nitrate and sulfate salt it in. The lyotropic effect referred to the volumetric share of both anion and cation increases in the series SCN - 3 - 4 2-

Effects of Calcium Lignosulfonate and Silicic Acid on Ammonium Nitrate Degradation

Directory of Open Access Journals (Sweden)

Ahmet Ozan Gezerman

2014-01-01

Full Text Available Ammonium nitrate salts are the most commonly used nitrogenous fertilizers in industry. However, storage of ammonium nitrate is problematic, since its initial properties can decline because of environmental factors, leading to large economic losses. In this study, in order to prevent the caking and degradation of ammonium nitrate, an alternative composition with additional calcium lignosulfonate and silicic acid was studied. The resulting fertilizer was analyzed by screening analysis, ion chromatography, and electron microscopy methods.

Nitrosation and Nitration of Fulvic Acid, Peat and Coal with Nitric Acid.

Directory of Open Access Journals (Sweden)

Kevin A Thorn

Full Text Available Nitrohumic acids, produced from base extraction of coals and peats oxidized with nitric acid, have received considerable attention as soil ammendments in agriculture. The nitration chemistry however is incompletely understood. Moreover, there is a need to understand the reaction of nitric acid with natural organic matter (NOM in general, in the context of a variety of environmental and biogeochemical processes. Suwannee River NOM, Suwannee River fulvic acid, and Pahokee Peat fulvic acid were treated with 15N-labeled nitric acid at concentrations ranging from 15% to 22% and analyzed by liquid and solid state 15N NMR spectroscopy. Bulk Pahokee peat and Illinois #6 coal were also treated with nitric acid, at 29% and 40% respectively, and analyzed by solid state 15N NMR spectroscopy. In addition to nitro groups from nitration of aromatic carbon, the 15N NMR spectra of all five samples exhibited peaks attributable to nitrosation reactions. These include nitrosophenol peaks in the peat fulvic acid and Suwannee River samples, from nitrosation of phenolic rings, and N-nitroso groups in the peat samples, from nitrosation of secondary amides or amines, the latter consistent with the peat samples having the highest naturally abundant nitrogen contents. Peaks attributable to Beckmann and secondary reactions of the initially formed oximes were present in all spectra, including primary amide, secondary amide, lactam, and nitrile nitrogens. The degree of secondary reaction product formation resulting from nitrosation reactions appeared to correlate inversely with the 13C aromaticities of the samples. The nitrosation reactions are most plausibly effected by nitrous acid formed from the reduction of nitric acid by oxidizable substrates in the NOM and coal samples.

Uranyl(VI) luminescence spectroscopy at elevated temperatures

Energy Technology Data Exchange (ETDEWEB)

Steudtner, Robin; Franzen, Carola; Brendler, Vinzenz [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Div. Surface Processes; Haubitz, Toni [Brandenburg Univ. of Technology, Cottbus-Senftenberg (Germany)

2016-07-01

We studied the influence of temperature and ionic strength on the luminescence characteristics (band position, decay time and intensity) of the free uranyl ion (UO{sub 2}{sup 2+}) in acidic aqueous solution. Under the chosen conditions an increasing temperature reduced both intensity and luminescence decay time of the UO{sub 2}{sup 2+} luminescence, but the individual U(VI) emission bands did not change.

Diluent and extractant effects on the enthalpy of extraction of uranium(VI) and americium(III) nitrates by trialkyl phosphates

International Nuclear Information System (INIS)

Srinivasan, T.G.; Vasudeva Rao, P.R.; Sood, D.D.

1998-01-01

The effect of various diluents such as n-hexane, n-heptane n-octane, isooctane, n-decane, n-undecane, n-dodecane, n-tetradecane, n-hexadecane, cyclohexane, benzene, toluene, p-xylene, mesitylene and o-dichlorobenzene on the enthalpy of extraction of uranyl nitrate by tri-n-amyl phosphate (TAP) over the temperature range 283 K--333 K has been studied. The results indicate that the enthalpy of extraction does not vary significantly with the diluents studied. Also enthalpies of extraction of uranyl nitrate and americium(III) nitrate by neutral organo phosphorous extractants such as tri-n-butyl phosphate (TBP), tri-n-amyl phosphate (TAP), tri-sec-butyl phosphate (TsBP), tri-isoamyl phosphate (TiAP) and tri-n-hexyl phosphate (THP) have been studied. An attempt has been made to explain the trends, on the basis of the nature of the solvate formed and the different terms which contribute to the overall enthalpy change

Synthesis of phosphorylated calix[4]arene derivatives for the design of solid phases immobilizing uranyl cations

International Nuclear Information System (INIS)

Maroun, E.B.; Hagege, A.; Asfari, Z.; Basset, CH.; Quemeneur, E.; Vidaud, C.

2009-01-01

With the aim of developing supports for uranyl cations immobilisation, new 1, 3-alternate calix[4]arenes bearing both phosphonic acid functions as chelating sites and N-succinimide-4-oxa-butyrate as the anchoring arm were synthesised in good yields. The coupling of such calixarenes to a gel was performed and a successful immobilisation of uranyl cations was obtained. (authors)

Synthesis of phosphorylated calix[4]arene derivatives for the design of solid phases immobilizing uranyl cations

Energy Technology Data Exchange (ETDEWEB)

Maroun, E.B.; Hagege, A.; Asfari, Z. [Laboratoire de Chimie Analytique et Minerale, UMR 7178 ULP/CNRS/IN2P3 LC4, ECPM, Strasbourg Cedex (France); Basset, CH.; Quemeneur, E.; Vidaud, C. [CEA IBEB, SBTN, Centre de Marcoule, Bagnols-sur-Ceze (France)

2009-07-01

With the aim of developing supports for uranyl cations immobilisation, new 1, 3-alternate calix[4]arenes bearing both phosphonic acid functions as chelating sites and N-succinimide-4-oxa-butyrate as the anchoring arm were synthesised in good yields. The coupling of such calixarenes to a gel was performed and a successful immobilisation of uranyl cations was obtained. (authors)

Annual report of STACY operation in FY.1999. Experiments on two unit neutron-interacting system with slab-shaped core tanks and 10% enriched uranyl nitrate solution (1). (contract research)

Energy Technology Data Exchange (ETDEWEB)

Onodera, Seiji; Sono, Hiroki; Hirose, Hideyuki [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment] [and others

2000-11-01

A new series of experiments on two unit neutron-interacting system started in the last half of FY.1999 at STACY (Static Experiment Critical Facility) in NUCEF (Nuclear Fuel Cycle Safety Engineering Research Facility). The experiments were conducted with two slab-shaped core tanks and 10% enriched uranyl nitrate solution. The dimensions of the core tanks are 35 cm in thickness, 70 cm in width and 150 cm in height. In the experiments, critical level heights were measured varying the distance between the two core tanks under the non-reflected condition in order to evaluate reactivity effects on the neutron interaction between the two core tanks. This report summarizes the data on the operation and the fuel management for the 25 experiments conducted in the last half of FY.1999. (author)

Selective Se-for-S substitution in Cs-bearing uranyl compounds

Energy Technology Data Exchange (ETDEWEB)

Gurzhiy, Vladislav V., E-mail: vladgeo17@mail.ru [Department of Crystallography, St. Petersburg State University, University Emb. 7/9, 199034 St. Petersburg, Russia Federation (Russian Federation); Tyumentseva, Olga S.; Krivovichev, Sergey V. [Department of Crystallography, St. Petersburg State University, University Emb. 7/9, 199034 St. Petersburg, Russia Federation (Russian Federation); Tananaev, Ivan G. [Far Eastern Federal University, Suhanova st. 8, Vladivostok 690950 (Russian Federation)

2017-04-15

Phase formation in the mixed sulfate-selenate aqueous system of uranyl nitrate and cesium nitrate has been investigated. Two types of crystalline compounds have been obtained and characterized using a number of experimental (single crystal XRD, FTIR, SEM) and theoretical (information-based complexity calculations, topological analysis) techniques. No miscibility gaps have been observed for Cs{sub 2}[(UO{sub 2}){sub 2}(TO{sub 4}){sub 3}] (T= S, Se), which crystallizes in tetragonal system, P-42{sub 1}m, a =9.616(1)–9.856(2), c =8.105(1)–8.159(1) Å, V =749.6(2)–792.5(3) Å{sup 3}. Nine phases with variable amount of S and Se have been structurally characterized. The structures of the Cs{sub 2}[(UO{sub 2}){sub 2}(TO{sub 4}){sub 3}] (T= S, Se) compounds are based upon the [(UO{sub 2}){sub 2}(TO{sub 4}){sub 3}]{sup 2-} layers of corner-sharing uranyl pentagonal bipyramids and TO{sub 4} tetrahedra. The layers contain two types of tetrahedral sites: T1 (3-connected, i.e. having three O atoms shared by adjacent uranyl polyhedra) and T2 (4-connected). The Se-for-S substitution in tetrahedral sites is highly selective with smaller S{sup 6+} cation showing a strong preference for the more tightly bonded T2 site. Crystallization in the pure Se system starts with the formation of Cs{sub 2}[(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)](H{sub 2}O) crystals, its subsequent dissolution and formation of Cs{sub 2}[(UO{sub 2}){sub 2}(SeO{sub 4}){sub 3}]. The information-based structural complexity calculations for these two phases support the rule that more topologically complex structures form at the latest stages of crystallization. - Graphical abstract: Nine phases representing the Cs{sub 2}[(UO{sub 2}){sub 2}(TO{sub 4}){sub 3}] (T= S, Se) solid solution series with variable amount of S and Se have been prepared by isothermal evaporation from aqueous solutions and characterized using a number of experimental and theoretical techniques. No immiscibility is observed between the

Microporous uranyl chromates successively formed by evaporation from acidic solution

Energy Technology Data Exchange (ETDEWEB)

Siidra, Oleg I.; Nazarchuk, Evgeny V.; Bocharov, Sergey N.; Kayukov, Roman A. [St. Petersburg State Univ. (Russian Federation). Dept. of Crystallography; Depmeier, Wulf [Kiel Univ. (Germany). Inst. fuer Geowissenschaften

2018-04-01

The first microporous framework structures containing uranium and chromium have been synthesized and characterized. Rb{sub 2}[(UO{sub 2}){sub 2}(CrO{sub 4}){sub 3}(H{sub 2}O){sub 2}](H{sub 2}O){sub 3} (1) was crystallized from uranyl chromate solution by evaporation. Further evaporation led to increased viscosity of the solution and overgrowing of Rb{sub 2}[(UO{sub 2}){sub 2}(CrO{sub 4}){sub 3}(H{sub 2}O)](H{sub 2}O) (2) on the crystals of 1. With respect to 1, the framework of 2 is partially dehydrated. Both frameworks differ compositionally by only one water molecule, but this seemingly small difference affects significantly the pore size and overall structural topology of the frameworks, which present very different flexibility of the U-O-Cr links. These are rigid in the pillared framework of 1, in contrast to 2 where the U-O-Cr angles range from 126.3 to 168.2 , reflecting the substantial flexibility of Cr-O-U connections which make them comparable to the corresponding Mo-O-U links in uranyl molybdates.

Response of humic acid formation to elevated nitrate during chicken manure composting.

Science.gov (United States)

Shi, Mingzi; Wei, Zimin; Wang, Liqin; Wu, Junqiu; Zhang, Duoying; Wei, Dan; Tang, Yu; Zhao, Yue

2018-06-01

Nitrate can stimulate microbes to degrade aromatic compounds, whereas humic acid (HA) as a high molecular weight aromatic compound, its formation may be affected by elevated nitrate during composting. Therefore, this study is conducted to determine the effect of elevated nitrate on HA formation. Five tests were executed by adding different nitrate concentrations to chicken manure composting. Results demonstrate that the concentration of HA in treatment group is significantly decreased compared with control group (p < 0.05), especially in the highest nitrate concentration group. RDA indicates that the microbes associated with HA and environmental parameters are influenced by elevated nitrate. Furthermore, structural equation model reveals that elevated nitrate reduces HA formation by mediating microbes directly, or by affecting ammonia and pH as the indirect drivers to regulate microbial community structure. Copyright © 2018 Elsevier Ltd. All rights reserved.

Preparation of the pur uranium-metal; La preparation de l'uranium-metal pur

Energy Technology Data Exchange (ETDEWEB)

Goldschmidt, B; Vertes, P [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1955-07-01

A detailed description of the chemical processes used to prepare in the factory of Bouchet of the CEA (Seine-Et-Oise) pur metal uranium with either relatively rich ores, or extracts coming of physical or chemical treatment of poor ores. The nitric treatment of ores succeeds to the production of uranate of impure sodium carbonate. This last last product is dissolved in nitric acid and the uranyl nitrate is extracted by tributyl-phosphate diluted in an inert solvent. The uranyl nitrate pure is re-extracted and successively transformed in uranium peroxide, in orange oxide then in brown oxide which is transformed in fluoride by the anhydrous hydrofluoric acid. Uranate fluoride is then reduced in metal by the pure calcium with an yield superior to 99%. (authors) [French] Description detaillee des procedes chimiques mis en jeu pour preparer a l'Usine du Bouchet du Commissariat a l'Energie Atomique (Seine-et-Oise) l'uranium metal pur a partir soit de minerais relativement riches, soit de concentres provenant de traitement physique ou chimique de minerais pauvres. Le traitement nitrique des minerais aboutit a la production d'uranate de soude impur. Ce dernier est a son tour dissous dans l'acide nitrique et le nitrate d'uranyle est extrait par du tributyl-phosphate dilue par un solvant inerte. Le nitrate d'uranyle pur reextrait est transforme successivement en peroxyde d'uranium, en oxyde orange puis en oxyde brun qui est transforme en fluorure par l'acide fluorhydrique anhydre. Le fluorure uraneux est reduit en metal par le calcium pur avec un rendement superieur a 99 %. (auteurs)

Resin-based preparation of HTGR fuels: operation of an engineering-scale uranium loading system

International Nuclear Information System (INIS)

Haas, P.A.

1977-10-01

The fuel particles for recycle of 233 U to High-Temperature Gas-Cooled Reactors are prepared from uranium-loaded carboxylic acid ion exchange resins which are subsequently carbonized, converted, and refabricated. The development and operation of individual items of equipment and of an integrated system are described for the resin-loading part of the process. This engineering-scale system was full scale with respect to a hot demonstration facility, but was operated with natural uranium. The feed uranium, which consisted of uranyl nitrate solution containing excess nitric acid, was loaded by exchange with resin in the hydrogen form. In order to obtain high loadings, the uranyl nitrate must be acid deficient; therefore, nitric acid was extracted by a liquid organic amine which was regenerated to discharge a NaNO 3 or NH 4 NO 3 solution waste. Water was removed from the uranyl nitrate solution by an evaporator that yielded condensate containing less than 0.5 ppM of uranium. The uranium-loaded resin was washed with condensate and dried to a controlled water content via microwave heating. The loading process was controlled via in-line measurements of the pH and density of the uranyl nitrate. The demonstrated capacity was 1 kg of uranium per hour for either batch loading contractors or a continuous column as the resin loading contractor. Fifty-four batch loading runs were made without a single failure of the process outlined in the chemical flowsheet or any evidence of inability to control the conditions dictated by the flowsheet

Potentiometric determination of free nitric-acid in trilaurylamine solutions containing plutonium nitrate

International Nuclear Information System (INIS)

Perez, J.J.; Saey, J.C.

1965-01-01

A potentiometric method of determination of the free nitric acid in trilaurylamine solutions containing plutonium or thorium nitrates is described. The potentiometric titration is carried out in a mixture of benzene and 1,2-dichloro ethane with a standard solution of trilaurylamine as the titrant. When thorium nitrate is present the metal complex is not dissociated then the titration has a single end-point. In the case of plutonium nitrate the partial dissociation of the plutonium complex corresponds to a second point. The experimental error in duplicate analyses of 50 samples is about 1 per cent for free acid concentrations in the range of 0,03 to 0,1 N and plutonium concentrations between 1 to 5 g/l. (authors) [fr

Uranyl tris-beta-diketonate complexes

International Nuclear Information System (INIS)

Sidorenko, G.V.; Adamov, V.M.; Shcherbakova, L.L.; Suglubov, D.N.

1986-01-01

Uranyl tris-pivaloyltrifluoroacetonates (M/IOTA/UO 2 L 3 ; M/IOTA/ = Na, K, Cs, 1/2Ba, NR 4 ; R = C 8 H 17 ) and tris-dipivaloylmethanate (M/IOTA/UO 2 L/IOTA/ 3 , M/IOTA/ = K) have been synthesized for the first time. The compounds were characterized by chemical analysis and IR, NMR, and mass spectra. NaUO 2 L 3 , KUO 2 L 3 , CsUO 2 L 3 and Ba(UO 2 ) 2 L 6 sublime in high vacuum with partial decomposition. Specifically, decomposition gives UL 4 , identified by mass spectrometry. All the tris-complexes except those with outer-sphere NR 4 cation are characterized by an asymmetric structure of the uranyl group, recorded by IR spectroscopy using isotopic substitution of 18 O in uranyl. NMR spectra of the tris-complexes indicate the equivalence of all beta-diketonate groups, i.e., a coordination number of six for uranyl

Production and Characterization of Desmalonichrome Relative Binding Affinity for Uranyl Ions in Relation to Other Siderophores

Energy Technology Data Exchange (ETDEWEB)

Mo, Kai-For; Dai, Ziyu; Wunschel, David S.

2016-06-24

Siderophores are Fe binding secondary metabolites that have been investigated for their uranium binding properties. Much of the previous work has focused on characterizing hydroxamate types of siderophores, such as desferrioxamine B, for their uranyl binding affinity. Carboxylate forms of these metabolites hold potential to be more efficient chelators of uranyl, yet they have not been widely studied and are more difficult to obtain. Desmalonichrome is a carboxylate siderophore which is not commercially available and so was obtained from the ascomycete fungus Fusarium oxysporum cultivated under Fe depleted conditions. The relative affinity for uranyl binding of desmalonichrome was investigated using a competitive analysis of binding affinities between uranyl acetate and different concentrations of iron(III) chloride using electrospray ionization mass spectrometry (ESI-MS). In addition to desmalonichrome, three other siderophores, including two hydroxamates (desferrioxamine B and desferrichrome) and one carboxylate (desferrichrome A) were studied to understand their relative affinities for the uranyl ion at two pH values. The binding affinities of hydroxymate siderophores to uranyl ion were found to decrease to a greater degree at lower pH as the concentration of Fe (III) ion increases. On the other hand, lowering pH has little impact on the binding affinities between carboxylate siderophores and uranyl ion. Desmalonichrome was shown to have the greatest relative affinity for uranyl at any pH and Fe(III) concentration. These results suggest that acidic functional groups in the ligands are critical for strong chelation with uranium at lower pH.

Electrospray ionization of uranyl-citrate complexes

Science.gov (United States)

Somogyi, Árpád; Pasilis, Sofie P.; Pemberton, Jeanne E.

2007-09-01

Results presented here demonstrate the usefulness of electrospray ionization and gas-phase ion-molecule reactions to predict structural and electronic differences in complex inorganic ions. Electrospray ionization of uranyl citrate solutions generates positively and negatively charged ions that participate in further ion-molecule reactions in 3D ion trap and FT-ICR mass analyzers. Most ions observed are derived from the major solution uranyl-citrate complexes and involve species of {(UO2)2Cit2}2-, (UO2)3Cit2, and {(UO2)3Cit3}3-, where Cit indicates the citrate trianion, C6H5O73-. In a 3D ion trap operated at relatively high pressure, complex adducts containing solvent molecules, alkali and ammonium cations, and nitrate or chloride anions are dominant, and proton/alkali cation (Na+, K+) exchange is observed for up to six exchangeable protons in an excess of alkali cations. Adduct formation in a FT-ICR cell that is operated at lower pressures is less dominant, and direct detection of positive and negative ions of the major solution complexes is possible. Multiply charged ions are also detected, suggesting the presence of uranium in different oxidation states. Changes in uranium oxidation state are detected by He-CID and SORI-CID fragmentation, and certain fragments undergo association reactions in trapping analyzers, forming "exotic" species such as [(UO2)4O3]-, [(UO2)4O4]-, and [(UO2)4O5]-. Ion-molecule reactions with D2O in the FT-ICR cell indicate substantial differences in H/D exchange rate and D2O accommodation for different ion structures and charge states. Most notably, the positively charged ions [H2(UO2)2Cit2(H)]+ and [(UO2)2(Cit)]+ accommodate two and three D2O molecules, respectively, which reflects well the structural differences, i.e., tighter uranyl-citrate coordination in the former ion than in the latter. The corresponding negatively charged ions accommodate zero or two D2O molecules, which can be rationalized using suggested solution phase structures

Preparation and thermogravimetric study of some uranyl phosphates

International Nuclear Information System (INIS)

Schaekers, J.M.

1970-10-01

The preparation of uranyl ammonium phosphate trihydrate (UAP = UO 2 NH 4 PO 4 .3H 2 O), acid uranyl phosphate tetrahydrate(AUP = UO 2 HPO 4 .4H 2 O) and neutral uranyl phosphate tetrahydrate (NUPT = (UO 2 ) 3 (PO 4 ) 2 .4H 2 O) was investigated during the data from the literature. The thermal decomposition in different atmospheres, such as air, oxygen, nitrogen and argon, was studied in the temperature range 25-1000 0 C. It was found that the pyrophosphate U 2 O 3 P 2 O 7 is a stable decomposition product of UAP as well as of AUP. A mixture of U 3 O 8 and U 2 O 3 P 2 O 7 is obtained when the NUPT is decomposed in an oxygen-free atmosphere. NUPT however is stable in an oxidising atmosphere. Hydrogen and carbon reductions were also carried out, and UO 2 or (UO) 2 P 2 O 7 as well as mixtures of these two products can be obtained, depending on the starting material and the reduction temperature. The different reduction and decomposition reactions were studied by means of thermogravimetric analysis, and activation energies were calculated where possible. I.R. spectral analysis was also used to identify various products with the same composition [af

Theoretical treatment of equilibrium data and evaluation of diffusion coefficients in extraction of uranium

Energy Technology Data Exchange (ETDEWEB)

Manohar, Smitha; Theyyunni, T K [Process Engineering and Systems Development Division, Bhabha Atomic Research Centre, Mumbai (India); Ragunathan, T S [Department of Chemical Engineering, Indian Inst. of Tech., Mumbai (India)

1994-06-01

A meaningful approach to the calculation of the performance of solvent extraction contactors in the PUREX process requires a good understanding of the equilibrium distribution of the important constituents, namely uranyl nitrate and nitric acid. Published literature refers to the empirical correlation of the distribution data, generally in the form of polynomials. Attempts are made to describe the distribution data in a form which is specially convenient for numerical computations along with its theoretical significance. Attempts are also made to derive suitable equations which would aid in estimation of diffusion coefficients in the uranyl nitrate-nitric acid-TBP/diluent system. (author). 2 tabs.

The mechanism of the transient depression of the erythropoietic rate induced in the rat by a single injection of uranyl nitrate

International Nuclear Information System (INIS)

Giglio, M.J.; Brandan, N.; Leal, T.L.; Bozzini, C.E.

1989-01-01

With the purpose of assessing the effect of uranyl nitrate (UN) on the rate of erythropoiesis, 1 mg/kg of the compound was injected iv to adult female Wistar rats. The dosing vehicle was injected into control animals. A single injection of UN induced a transient depression of the rate of red cell volume 59 Fe uptake, which reached its lowest value (68% depression) by the seventh postinjection day. By 14 days, 59 Fe incorporation had returned to normal. The amount of iron going to erythroid tissue per hour, reticulocyte count, and immunoreactive erythropoietin concentration in both plasma and kidney extracts were also significantly depressed in UN-treated rats in relation to these values in vehicle-injected rats by the seventh postinjection day. Dose-response curves for exogenous erythropoietin (Epo) performed in polycythemic intact and UN-treated rats 7 days after drug injection revealed a significant depression of the response in UN-injected animals. Moreover, bone marrow cells obtained from rats pretreated with UN formed a reduced number of erythroid colonies in vitro in response to Epo. Therefore, possible mechanisms for the observed transient depression in the rate of erythropoiesis associated with acute UN treatment include decreased Epo production and direct or indirect damage of erythroid progenitor cells

Effect of nitrate on corrosion of austenitic stainless steel in boiling nitric acid solution containing chromium ions

International Nuclear Information System (INIS)

Hasegawa, Satoshi; Kim, Seong-Yun; Ebina, Tetsunari; Ito, Tatsuya; Nagano, Nobumichi; Hitomi, Keitaro; Ishii, Keizo; Tokuda, Haruaki

2016-01-01

The oxidation behavior of chromium and the corrosion behavior of austenitic stainless steel in boiling nitric acid solution containing highly concentrated nitrates were investigated using UV-visible spectroscopic measurements, Raman spectral measurements, immersion tests, and potentiodynamic polarization measurements. The oxidation rate measurement of chromium from Cr(III) to Cr(VI) was performed by 1 M boiling nitric acid solution containing each highly concentrated nitrates: Al(NO_3)_3, Nd(NO_3)_3, Ca(NO_3)_2, Mg(NO_3)_2, and NaNO_3 as a simulant of uranium nitrate in uranium concentrator in reprocessing plants. As a result, the rate of chromium oxidation was different depending on the added nitrates even at the same nitric acid concentration. In addition, the oxidation rate of chromium was increased with increasing the calculated partial pressure of nitric acid in consideration of the hydration of cation of nitrates. Furthermore, the corrosion rate of type 310 stainless steel was accelerated by the solution having a high chromium oxidation rate containing nitrates. These results indicated that the acceleration of the corrosion rate in the solutions depending on the oxidation rate of chromium, and the rate is affected by the salt-effect of nitrates. (author)

Treatment of uranyl nitrate and flouride solutions; Tratamiento de soluciones que contienen nitrato de uranilo y fluoruros

Energy Technology Data Exchange (ETDEWEB)

Rodrigo Otero, A; Rodrigo Vilaseca, F; Morales Calvo, G

1977-07-01

A theoretical study on the fluoride complexes contained in uranyl and aluminium solutions has been carried out. Likewise concentration limits and Duhring diagrams for those solutions have been experimentally established. As a result, the optimum operation conditions for concentration by evaporation in the treatment plant, have been deduced. (Author) 12 refs.

Uranium (VI) chemistry at the interface solution/minerals (quartz and aluminium hydroxide): experiments and spectroscopic investigations of the uranyl surface species

International Nuclear Information System (INIS)

Froideval, A.

2004-09-01

This study deals with the understanding of the uranyl chemistry at the 0.1 M NaNO 3 solution/mineral (quartz and aluminium hydroxide) interface. The aims are:(i) to identify and to characterize the different uranyl surface species (mononuclear, polynuclear complexes and/or precipitates...), i.e. the coordination environments of sorbed/precipitated uranyl ions, by using X-ray photoelectron spectroscopy (XPS), extended X-ray absorption fine structure (EXAFS) and time-resolved laser-induced fluorescence spectroscopy (TRLFS), and;(ii) to investigate the influence of pH, initial uranyl aqueous concentration and hydroxyl ligand concentration on the uranyl surface speciation. Our study on the speciation of uranyl ions at the quartz surface (i) confirms the formation of uranyl polynuclear/oligomers on quartz from moderate (1 μmol/m 2 ) to high (26 μmol/m 2 ) uranyl surface concentrations and (ii) show that theses polynuclear species coexist with uranyl mononuclear surface species over a pH range ≅ 5-8.5 and a wide range of initial uranyl concentration o f the solutions (10-100 μM). The uranyl concentration of these surface species depends on pH and on the initial uranyl aqueous concentration. Hydrate (surface-) precipitates and/or adsorbed polynuclear species and monomeric uranyl surface complexes are formed on aluminium hydroxide. Uranyl mononuclear complexes are predominant at acidic pH, as well as uranyl in solution or on the surface. Besides mononuclear species, precipitates and/or adsorbed polynuclear species are predominantly formed at neutral pH values on aluminium hydroxide. A main contribution of our investigations is that precipitation and/or adsorption of polynuclear species seem to occur at low uranyl surface concentrations (0.01-0.4 μmol/m 2 ). The uranyl surface speciation is mainly dependent on the pH and the aluminol ligand concentration. (author)

Analytical resolution of the mixture TBP-HDBP-H2MBP-H3PO4

International Nuclear Information System (INIS)

Pires, M.A.F.

1983-01-01

Several schemes for the separation of dibutylphosphoric acid (HDBP), main degradation product of tributylphosphate (TBP), in TBP/diluent, TBP/diluent-uranyl nitrate and TBP/diluent-thorium nitrate mixture were studied. For the resolution of HDBP-TBP/diluent-heavy metal nitrates (U-VI,Th-IV) systems, techniques such as: in exchange chromatography, ion chromatography using common ion exchangers and chromatographic separation with alumina column were investigated. For the identification, determination and analytical resolution following up the several systems studied, techniques such as refraction index measurement, electrical conductivity measurement, molecular absorption spectrophotometry, gas chromatography and ion chromatography, were applied. The separation of HDBP component was achieved using an alumina column where it was adsorbed from the TBP/diluent-uranyl nitrate and selectively eluted. Several modifications of this procedure for samples from the Uranium Purification Pilot Plant at Instituto de Pesquisas Energeticas e Nucleares (Sao Paulo, Brazil) were made. Special emphasis was given to the determination of HDBP using the ion chromatography technique. HDBP along with any monobutylphosphate acid (H 2 MBP) and phosphoric acid (H 3 PO 4 ) were stripped from the organic phase into dilute sodium hydroxide. HDBP is separated from H 2 MBP and H 3 PO 4 by ion chromatography and determined by its peak height. The determination of degradation products from TBP in TBP/diluent-uranyl nitrate and TBP/diluent-thorium nitrate systems was then performed. The detection limit for dibutylphosphate is 1.0μg HDBP/ml of analyte solution. (Author) [pt

Sorption of uranyl ions on hydrous oxides

International Nuclear Information System (INIS)

Gupta, A.R.; Venkataramani, B.

1988-01-01

Sorption of uranyl ions on hydrous titanium oxide (HTiO), magnetite (MAG), and hydrous thorium oxide (HThO) has been studied as a function of pH. Hydrous oxides have been characterized by their pH-titration curves, intrinsic dissociation constants (pK ai * ) and point of zero charge (pH pzc ). The fraction of protonated surface hydroxyl groups as well as the surface pH (pH surf ) as a function of solution pH have been computed. The distribution of various hydrolyzed species of uranyl ions with solution pH have been compared with uranyl sorption isotherm on these oxides. Sorption edge in all the cases occurs when free hydroxyl groups are available on the surface and pH surf is sufficiently high to favor the formation of dimer-like species on the surface. A new model for the sorption process, called surface hydrolysis model, which explains these and other features of uranyl sorption on hydrous oxides has been proposed. The model visualizes the sorption process as linking of uranyl ions with two adjacent free surface hydroxyl groups without deprotonation (provided the surface pH is high for the hydrolysis of uranyl ions) and formation of dimer-like structures on the surface. The new model has been successfully applied to the present and other available data on uranyl ion sorption on hydrous oxides. (author)

The clearance of uranium after deposition of the nitrate and bicarbonate in different regions of the rat lung

International Nuclear Information System (INIS)

Ellender, M.

1987-01-01

This study investigated the tissue distribution and excretion of uranium after its deposition as either the nitrate or bicarbonate in the three regions of the respiratory system of the rat. Results confirm the recommendations of ICRP that uranyl nitrate and bicarbonate should be treated as class D compounds; but imply that some of the parameters used in the ICRP lung model are not applicable to soluble uranium compounds. (author)

Feeding nitrate and docosahexaenoic acid affects enteric methane production and milk fatty acid composition in lactating dairy cows.

Science.gov (United States)

Klop, G; Hatew, B; Bannink, A; Dijkstra, J

2016-02-01

An experiment was conducted to study potential interaction between the effects of feeding nitrate and docosahexaenoic acid (DHA; C22:6 n-3) on enteric CH4 production and performance of lactating dairy cows. Twenty-eight lactating Holstein dairy cows were grouped into 7 blocks of 4 cows. Within blocks, cows were randomly assigned to 1 of 4 treatments: control (CON; urea as alternative nonprotein N source to nitrate), NO3 [21 g of nitrate/kg of dry matter (DM)], DHA (3 g of DHA/kg of DM and urea as alternative nonprotein N source to nitrate), or NO3 + DHA (21 g of nitrate/kg of DM and 3 g of DHA/kg of DM, respectively). Cows were fed a total mixed ration consisting of 21% grass silage, 49% corn silage, and 30% concentrates on a DM basis. Feed additives were included in the concentrates. Cows assigned to a treatment including nitrate were gradually adapted to the treatment dose of nitrate over a period of 21 d during which no DHA was fed. The experimental period lasted 17 d, and CH4 production was measured during the last 5d in climate respiration chambers. Cows produced on average 363, 263, 369, and 298 g of CH4/d on CON, NO3, DHA, and NO3 + DHA treatments, respectively, and a tendency for a nitrate × DHA interaction effect was found where the CH4-mitigating effect of nitrate decreased when combined with DHA. This tendency was not obtained for CH4 production relative to dry matter intake (DMI) or to fat- and protein corrected milk (FPCM). The NO3 treatment decreased CH4 production irrespective of the unit in which it was expressed, whereas DHA did not affect CH4 production per kilogram of DMI, but resulted in a higher CH4 production per kilogram of fat- and protein-corrected milk (FPCM) production. The FPCM production (27.9, 24.7, 24.2, and 23. 8 kg/d for CON, NO3, DHA, and NO3 + DHA, respectively) was lower for DHA-fed cows because of decreased milk fat concentration. The proportion of saturated fatty acids in milk fat was decreased by DHA, and the proportion of

Thermal and x-ray crystallographic features of the binary system UO2(NO3)2.6H2O-Ni(NO3)2.6H2O at elevated temperatures

International Nuclear Information System (INIS)

Kalekar, B.B.; Rajagopalan, K.V.; Ravindran, P.V.

2007-01-01

Solid state reaction between uranyl nitrate hexahydrate and nickel nitrate hexahydrate of different compositions has been studied at higher temperatures. The binary system containing uranyl nitrate hexahydrate (UNH) and nickel nitrate hexahydrate is found to form eutectic corresponding to 53 mol% of uranyl nitrate hexahydrate at 40 degC. The overlap of evolution of nitric oxide and water vapour above 230 degC confirmed the presence of hydroxynitrates of uranium and nickel. Both the nitrates decomposed independently. NiO formed by the decomposition of nickel nitrate hexahydrate reacted with UO 3 formed by the initial decomposition of uranyl nitrate hexahydrate to form a double oxide, NiU 3 O 10 , in the case of mixtures containing 70 mol% uranyl nitrate hexahydrate. The compositions richer than 70 mol% in uranyl nitrate hexahydrate formed U 3 O 8 along with nickel uranate. With mixtures leaner in uranyl nitrate hexahydrate, NiO was observed along with NiU 3 O 10 and, further, the formation of NiU 3 O 10 was completed at a lower temperature. (author)

Reactivity of nitrate and organic acids at the concrete–bitumen interface of a nuclear waste repository cell

Energy Technology Data Exchange (ETDEWEB)

Bertron, A., E-mail: bertron@insa-toulouse.fr [Université de Toulouse (France); UPS, INSA (France); LMDC (Laboratoire Matériaux et Durabilité des Constructions), 135, avenue de Rangueil, F-31 077, Toulouse Cedex 04 (France); Jacquemet, N. [Université de Toulouse (France); UPS, INSA (France); LMDC (Laboratoire Matériaux et Durabilité des Constructions), 135, avenue de Rangueil, F-31 077, Toulouse Cedex 04 (France); Erable, B. [Université de Toulouse (France); INPT, UPS (France); CNRS, Laboratoire de Génie Chimique, 4, Allée Emile Monso, F-31030 Toulouse (France); Sablayrolles, C. [Université de Toulouse (France); INP (France); LCA (Laboratoire de Chimie Agro-Industrielle), ENSIACET, 4 allée Emile Monso, BP 44 362, 31432 Toulouse Cedex 4 (France); INRA (France); LCA (Laboratoire de Chimie Agro-Industrielle), F-31029 Toulouse (France); Escadeillas, G. [Université de Toulouse (France); UPS, INSA (France); LMDC (Laboratoire Matériaux et Durabilité des Constructions), 135, avenue de Rangueil, F-31 077, Toulouse Cedex 04 (France); Albrecht, A. [Andra, 1-7, rue Jean-Monnet, 92298 Châtenay-Malabry (France)

2014-03-01

Highlights: • Interactions of cement paste and organic acid–nitrate solutions were investigated. • Cement leaching imposed alkaline pH (>10) very rapidly in the liquid media. • Acetic acid action on cement paste was similar to that of classical leaching. • Oxalic acid attack formed Ca-oxalate salts; organic matter in solution decreased. • Nitrate was stable under abiotic conditions and with organic matter. - Abstract: This study investigates the fate of nitrate and organic acids at the bitumen–concrete interface within repository cell for long-lived, intermediate-level, radioactive wastes. The interface was simulated by a multiphase system in which cementitious matrices (CEM V cement paste specimens) were exposed to bitumen model leachates consisting of nitrates and acetic acid with and without oxalic acid, chemical compounds likely to be released by bitumen. Leaching experiments were conducted with daily renewal of the solutions in order to accelerate reactions. The concentrations of anions (acetate, oxalate, nitrate, and nitrite) and cations (calcium, potassium) and the pH were monitored over time. Mineralogical changes of the cementitious matrices were analysed by XRD. The results confirmed the stability of nitrates in the abiotic conditions of the experiments. The action of acetic acid on the cementitious matrix was similar to that of ordinary leaching in the absence of organic acids (i.e. carried out with water or strong acids); no specific interaction was detected between acetate and cementitious cations. The reaction of oxalic acid with the cementitious phases led to the precipitation of calcium oxalate salts in the outer layer of the matrix. The concentration of oxalate was reduced by 65% inside the leaching medium.

Method of manufacturing ceramic oxide nuclear fuels and intermediate products thereof

International Nuclear Information System (INIS)

Matous, V.; Pecak, V.; Baran, V.

1978-01-01

Uranyl nitrate or uranyl sulphate is extracted as a tributyl phosphate solvate into an organic solvent from aqueous solutions of uranium in sulphuric or nitric acid obtained from ore treatment or from wet reprocessing. Uranyl fluorides obtained from dry reprocessing should be hydrolysed and converted to uranyl sulphate or uranyl nitrate for such extraction. The tributyl phosphate solvate of the compound in the organic solvent (in a higher petrol fraction or in a chlorinated hydrocarbon) is directly precipitated using an aqueous solution of a hydroxide, preferably ammonium hydroxide as a hydrated oxide. Stoichiometric and overstoichiometric amounts of hydroxides lead to the formation of amorphous diuranates. Substoichiometric amounts of hydroxides used and of hydroxylamine solutions only lead to hydrolysis in which heavy macroscopic yellow crystalline precipitates are formed of the hydrated uranium oxide. Drying and annealing may result in UO 3 and UO 2 , respectively. (B.S.)

Preparation of the pur uranium-metal; La preparation de l'uranium-metal pur

Energy Technology Data Exchange (ETDEWEB)

Goldschmidt, B.; Vertes, P. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1955-07-01

A detailed description of the chemical processes used to prepare in the factory of Bouchet of the CEA (Seine-Et-Oise) pur metal uranium with either relatively rich ores, or extracts coming of physical or chemical treatment of poor ores. The nitric treatment of ores succeeds to the production of uranate of impure sodium carbonate. This last last product is dissolved in nitric acid and the uranyl nitrate is extracted by tributyl-phosphate diluted in an inert solvent. The uranyl nitrate pure is re-extracted and successively transformed in uranium peroxide, in orange oxide then in brown oxide which is transformed in fluoride by the anhydrous hydrofluoric acid. Uranate fluoride is then reduced in metal by the pure calcium with an yield superior to 99%. (authors) [French] Description detaillee des procedes chimiques mis en jeu pour preparer a l'Usine du Bouchet du Commissariat a l'Energie Atomique (Seine-et-Oise) l'uranium metal pur a partir soit de minerais relativement riches, soit de concentres provenant de traitement physique ou chimique de minerais pauvres. Le traitement nitrique des minerais aboutit a la production d'uranate de soude impur. Ce dernier est a son tour dissous dans l'acide nitrique et le nitrate d'uranyle est extrait par du tributyl-phosphate dilue par un solvant inerte. Le nitrate d'uranyle pur reextrait est transforme successivement en peroxyde d'uranium, en oxyde orange puis en oxyde brun qui est transforme en fluorure par l'acide fluorhydrique anhydre. Le fluorure uraneux est reduit en metal par le calcium pur avec un rendement superieur a 99 %. (auteurs)

Synthesis and complexation properties towards uranyl cation of carboxylic acid derivatives of p-tert-butyl-calix[6]arene; Synthese et proprietes complexantes vis-a-vis de l'ion uranyle de derives carboxyliques du p-tert-butyl-calix[6]arene

Energy Technology Data Exchange (ETDEWEB)

Souane, R

2005-03-15

In the fuel reprocessing plants radioactive metals, and more particularly, uranium in UO{sub 2}{sup 2+} form in the various installations, have many varied physico-chemical forms and there is a risk of exposure and internal contamination in the nuclear industry. It is necessary to exert a medical control to ensure the protection of the health of the workers. This medical control is done by dosing uranyl cation in the urine of the exposed people. This work forms part of this context. Indeed, we prepared a ligand able to complex the ion uranyl and which is also to be grafted on a solid support. In the family of calixarenes, the calix[6]arenes functionalized by three or four carboxylic functions were selected like chelating molecules of the ion uranyl. The properties of complexation of these calixarenes were studied by potentiometry in methanol, under these conditions balances of protonation and complexation were determined and the constant partners were obtained using the Hyperquad program. We synthesized tri-carboxylic calix[6]arenes comprising of the groupings nitro (NO{sub 2}) in para position of phenol in order to see the influence of a substitution in para position on the complexation. We also synthesized calix[6]arenes tetra-carboxylic in order to show the role of an additional carboxylic acid grouping. The potentiometric study determined thermodynamic parameters of protonation and complexation of carboxylic calix[6]arenes. The results of the complexation highlighted which complex UO{sub 2}L corresponding to the ligand para-tert-butyl-calix[6]arene tetra-acid is more stable than that corresponding to the ligand mono-nitro calix[6]arene tri-acid ({delta}log{beta}110 = 4.3), and than the effect of the groupings nitro in para position has low influence on the complexation of UO{sub 2}{sup 2+}. This makes it possible to consider as possible the grafting of the calix[6]arenes which one knows the behaviour of trapping. To this end we synthesized the ligand 23

Metal complex derivatives of hydrogen uranyl phosphate

International Nuclear Information System (INIS)

Grohol, D.; Blinn, E.L.

1994-01-01

Derivatives of hydrogen uranyl phosphate were prepared by incorporating transition metal complexes into the uranyl phosphate matrix. The transition metal complexes employed include bis(ethylenediamine)copper(II), bis(1,3-propanediamine)copper(II) chloride, (triethylenetetramine)copper(II), (1,4,8,11-tetraazacyclotetradecane)copper(II), (1,4,8,12-tetraazacyclopentadecane)copper(II), (1,4,8,11-tetraazacyclotetradecane)nickel(II) chloride, (triethylenetetramine)nickel(II) and others. The chemical analyses of these derivatives indicated that the incorporation of the transition metal complexes into the uranyl phosphate matrix via ion exchange was not stoichiometric. The extent of ion exchange is dependent on the size and structure of the transition metal complex. All complexes were characterized by X-ray powder diffractometry, electronic and infrared spectra, thermal analyses and chemical analysis. An attempt was made to correlate the degree of quenching of the luminescence of the uranyl ion to the spacing between the uranyl phosphate layers in the derivatives

The acid-catalyzed hydrolysis of an α-pinene-derived organic nitrate: kinetics, products, reaction mechanisms, and atmospheric impact

Science.gov (United States)

Rindelaub, Joel D.; Borca, Carlos H.; Hostetler, Matthew A.; Slade, Jonathan H.; Lipton, Mark A.; Slipchenko, Lyudmila V.; Shepson, Paul B.

2016-12-01

The production of atmospheric organic nitrates (RONO2) has a large impact on air quality and climate due to their contribution to secondary organic aerosol and influence on tropospheric ozone concentrations. Since organic nitrates control the fate of gas phase NOx (NO + NO2), a byproduct of anthropogenic combustion processes, their atmospheric production and reactivity is of great interest. While the atmospheric reactivity of many relevant organic nitrates is still uncertain, one significant reactive pathway, condensed phase hydrolysis, has recently been identified as a potential sink for organic nitrate species. The partitioning of gas phase organic nitrates to aerosol particles and subsequent hydrolysis likely removes the oxidized nitrogen from further atmospheric processing, due to large organic nitrate uptake to aerosols and proposed hydrolysis lifetimes, which may impact long-range transport of NOx, a tropospheric ozone precursor. Despite the atmospheric importance, the hydrolysis rates and reaction mechanisms for atmospherically derived organic nitrates are almost completely unknown, including those derived from α-pinene, a biogenic volatile organic compound (BVOC) that is one of the most significant precursors to biogenic secondary organic aerosol (BSOA). To better understand the chemistry that governs the fate of particle phase organic nitrates, the hydrolysis mechanism and rate constants were elucidated for several organic nitrates, including an α-pinene-derived organic nitrate (APN). A positive trend in hydrolysis rate constants was observed with increasing solution acidity for all organic nitrates studied, with the tertiary APN lifetime ranging from 8.3 min at acidic pH (0.25) to 8.8 h at neutral pH (6.9). Since ambient fine aerosol pH values are observed to be acidic, the reported lifetimes, which are much shorter than that of atmospheric fine aerosol, provide important insight into the fate of particle phase organic nitrates. Along with rate constant

Mechanistic study of the interaction of uranyl ions with zirconium oxide and zirconium silicate; Etude mecanistique de l'interaction des ions uranyle avec l'oxyde et le silicate de zirconium

Energy Technology Data Exchange (ETDEWEB)

Lomenech, C

2002-04-01

This work deals with structural and thermodynamic studies of the sorption of uranyl species on zircon and zirconia. After determination of the specific areas, of the pH of the isoelectric points, and of the sorption site numbers, thermodynamic data were obtained using alpha spectrometry, for different uranyl concentrations, different background electrolytes (NaClO{sub 4} or KNO{sub 3}) and different ionic strengths. The structural identification of the surface complexes and sorption sites was carried out using several spectroscopies: XPS spectroscopy allowed a determination of the nature of the sorption sites ({identical_to}Zr-O- on zirconia and {identical_to}Si-O- on zircon). Whereas fluorescence decay measurements gave the number of surface species, the combined use of XPS spectroscopy and laser spectro-fluorimetry enabled us to correlate differences in bonding energies and emission wavelengths with differences in the nature of the background electrolyte or in the pH of sorption; DRIFT spectroscopy was a powerful tool for the determination of the presence of sorbed uranyl nitrate species. EXAFS results clearly showed a splitting of the equatorial oxygen atoms in two shells, corresponding to a polydentate, inner-sphere complex. EXAFS results also indicated strong similarities between dry samples and in situ experiments, which confirms the validity of all the spectroscopic measurements. Macroscopic thermodynamic data were then modeled using a surface complexation model (2 pK and constant capacitance models), the results of the structural study being used as constraints for the simulation code FITEQL. (author)

Micro-SHINE Uranyl Sulfate Irradiations at the Linac

Energy Technology Data Exchange (ETDEWEB)

Youker, Amanda J. [Argonne National Lab. (ANL), Argonne, IL (United States); Kalensky, Michael [Argonne National Lab. (ANL), Argonne, IL (United States); Chemerisov, Sergey [Argonne National Lab. (ANL), Argonne, IL (United States); Schneider, John [Argonne National Lab. (ANL), Argonne, IL (United States); Byrnes, James [Argonne National Lab. (ANL), Argonne, IL (United States); Vandegrift, George F. [Argonne National Lab. (ANL), Argonne, IL (United States)

2016-08-01

Peroxide formation due to water radiolysis in a uranyl sulfate solution is a concern for the SHINE Medical Technologies process in which Mo-99 is generated from the fission of dissolved low enriched uranium. To investigate the effects of power density and fission on peroxide formation and uranyl-peroxide precipitation, uranyl sulfate solutions were irradiated using a 50-MeV electron linac as part of the micro-SHINE experimental setup. Results are given for uranyl sulfate solutions with both high and low enriched uranium irradiated at different linac powers.

Development of mathematical model of H{sub 2}O-HNO{sub 3}-UO{sub 2}(NO{sub 3}){sub 2}-TBP-Diluent System

Energy Technology Data Exchange (ETDEWEB)

Ochkin, A.; Gladilov, D.; Nekhaevskiy, S.; Merkushkin, A. [D. Mendeleev University of Chemical Technology of Russia, 9 Miusskay Sqr., Moscow, 125047 (Russian Federation)

2016-07-01

The nuclear fuel reprocessing is based on the PUREX process. Usually 30% TBP in hydrocarbon diluents is applied, then the composition of the organic phase can be expressed as H{sub 2}O-HNO{sub 3}-UO{sub 2}(NO{sub 3}){sub 2}-Pu(NO{sub 3}){sub 4}-TBP-diluent. The mathematical model of H{sub 2}O-HNO{sub 3}-UO{sub 2}(NO{sub 3}){sub 2}-TBP-dodecane system has been elaborated. Mole fractions and volume ones and rational activity coefficients have been used in order to create the system of equations on the base of mass action law. The method for calculating activity coefficients was provided. The formation constants of uranyl nitrate di-solvate and mono-solvate and di-solvate of acid have been determined. Interaction between uranyl nitrate di-solvate and dodecane and between TBP and dodecane was taken into account. Activity coefficients of nitric acid and uranyl nitrate in mixed solutions were considered. Errors of adequacy have been determined for the systems containing 30% and 12% TBP concentrations.

The uranyl cation as a visible-light photocatalyst for C(sp{sup 3})-H fluorination

Energy Technology Data Exchange (ETDEWEB)

West, Julian G.; Bedell, T. Aaron; Sorensen, Erik J. [Department of Chemistry, Princeton University, Princeton, NJ (United States)

2016-07-25

The fluorination of unactivated C(sp{sup 3})-H bonds remains a desirable and challenging transformation for pharmaceutical, agricultural, and materials scientists. Previous methods for this transformation have used bench-stable fluorine atom sources; however, many still rely on the use of UV-active photocatalysts for the requisite high-energy hydrogen atom abstraction event. Uranyl nitrate hexahydrate is described as a convenient, hydrogen atom abstraction catalyst that can mediate fluorinations of certain alkanes upon activation with visible light. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Structural investigation of the complexation of uranyl and lanthanide ions by CMPO-functionalized calixarenes

International Nuclear Information System (INIS)

Cherfa, S.

1998-12-01

A way to reduce the volume of nuclear wastes is to make a simultaneous extraction of actinides and lanthanides for their ulterior separation. Historically, the two first series of extractants used for the reprocessing of these wastes are the phosphine oxides and the CMPO (carbamoyl methyl phosphine oxide). In order to better know the type of complexes formed during the extraction, have been carried out structural studies concerning these two series (uranyl complexes and lanthanide nitrates). These studies have been carried out by X-ray diffraction on monocrystals. More recently, a new series of extracting molecules of lanthanides (III) and actinides (III) have been developed. It has been shown that in functionalizing an organic macrocycle of calixarene type (cyclic oligomer resulting of the poly-condensation of phenolic units) by a ligand of CMPO type, the extracting power of these molecules in terms of yield and selectivity towards the lighter lanthanides was superior to those of the CMPO alone. This study, carried out by X-ray diffraction on monocrystals of complexes formed between these ligands calix[4]arenes-CMPO (with 4 phenolic units) with uranyl and lanthanides nitrates, has allowed to define the type of the formed complexes, that is to say to establish the stoichiometry and the coordination mode (monodentate or bidentate) of the CMPO functions. These different steps of characterization have allowed too to determine the correlations existing between the complexes structures in the one hand and the selectivity and the exacerbation of the extracting power measured in liquid phase on the other hand. (O.M.)

Mechanistic study of the interaction of uranyl ions with zirconium oxide and zirconium silicate

International Nuclear Information System (INIS)

Lomenech, C.

2002-04-01

This work deals with structural and thermodynamic studies of the sorption of uranyl species on zircon and zirconia. After determination of the specific areas, of the pH of the isoelectric points, and of the sorption site numbers, thermodynamic data were obtained using alpha spectrometry, for different uranyl concentrations, different background electrolytes (NaClO 4 or KNO 3 ) and different ionic strengths. The structural identification of the surface complexes and sorption sites was carried out using several spectroscopies: XPS spectroscopy allowed a determination of the nature of the sorption sites (≡Zr-O- on zirconia and ≡Si-O- on zircon). Whereas fluorescence decay measurements gave the number of surface species, the combined use of XPS spectroscopy and laser spectro-fluorimetry enabled us to correlate differences in bonding energies and emission wavelengths with differences in the nature of the background electrolyte or in the pH of sorption; DRIFT spectroscopy was a powerful tool for the determination of the presence of sorbed uranyl nitrate species. EXAFS results clearly showed a splitting of the equatorial oxygen atoms in two shells, corresponding to a polydentate, inner-sphere complex. EXAFS results also indicated strong similarities between dry samples and in situ experiments, which confirms the validity of all the spectroscopic measurements. Macroscopic thermodynamic data were then modeled using a surface complexation model (2 pK and constant capacitance models), the results of the structural study being used as constraints for the simulation code FITEQL. (author)

Supercritical fluid extraction of uranium from tissue paper matrix using organic extractants

International Nuclear Information System (INIS)

Kanekar, A.S.; Bhattacharyya, A.; Pathak, P.N.; Mohapatra, P.K.; Manchanda, V.K.

2009-01-01

Direct extraction of dried uranyl nitrate from tissue paper matrix was carried out using supercritical carbon dioxide modified with methanol solutions of extractants such as tri-n-butyl phosphate (TBP) and di-n-hexyl octanamide (DHOA)). The effects of temperature, pressure, extractant and nitric acid concentration on the extraction of uranyl ion were investigated. (author)

Investigation of the process of co-crystallization of barium and strontium nitrates from the system acetic acid-water

International Nuclear Information System (INIS)

Hubicki, W.; Piskorek, M.

1976-01-01

Co-crystallization of barium nitrate and strontium nitrate from the system CH 3 COOH-H 2 O was investigated by using radioactive tracer Ba 133 . The authors have found that during the crystallization of strontium nitrate from acetic acid solution at 25 0 C, one can obtain a 67-fold lowering of the content of barium in strontium nitrate, a 40-fold lowering of the content of barium in strontium nitrate is at 35 0 C. Strontium nitrate went to the solid phase with 70% efficiency. Acetic acid solutions of 24.5-24.3 per cent weight were used. Attention was paid to the franctionation of barium admixtures during crystallization of strontium nitrate from acetic acid solutions (so called ''isothermic salting out crystallization process'') is in agreement with the logarithmic law of Doerner-Hoskins. Process is characterized by a constant coefficient of surface co-crystallization lambda = 18. The results of investigations show that it is possible to obtain spectrally pure non-barium strontium nitrate as the result of its crystallization from the system CH 3 COOH-H 2 O at a temperature of 25 0 and 35 0 C. (author)

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.

Barium uranyl diphosphonates

Energy Technology Data Exchange (ETDEWEB)

Nelson, Anna-Gay D., E-mail: nelsoa@umich.edu [Department of Civil Engineering and Geological Sciences and Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556 (United States); Department of Earth and Environmental Sciences, University of Michigan, Ann Arbor, MI 48109-1005 (United States); Alekseev, Evgeny V. [Institute of Energy and Climate Research (IEK-6), Forschungszentrum Juelich Wilhelm-Johnen-Strasse, Juelich 52428 (Germany); Ewing, Rodney C. [Department of Earth and Environmental Sciences, University of Michigan, Ann Arbor, MI 48109-1005 (United States); Albrecht-Schmitt, Thomas E. [Department of Civil Engineering and Geological Sciences and Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556 (United States)

2012-08-15

Three Ba{sup 2+}/UO{sub 2}{sup 2+} methylenediphosphonates have been prepared from mild hydrothermal treatment of uranium trioxide, methylendiphosphonic acid (C1P2) with barium hydroxide octahydrate, barium iodate monohydrate, and small aliquots of HF at 200 Degree-Sign C. These compounds, Ba[UO{sub 2}[CH{sub 2}(PO{sub 3}){sub 2}]{center_dot}1.4H{sub 2}O (Ba-1), Ba{sub 3}[(UO{sub 2}){sub 4}(CH{sub 2}(PO{sub 3}){sub 2}){sub 2}F{sub 6}]{center_dot}6H{sub 2}O (Ba-2), and Ba{sub 2}[(UO{sub 2}){sub 2}(CH{sub 2}(PO{sub 3}){sub 2})F{sub 4}]{center_dot}5.75H{sub 2}O (Ba-3) all adopt layered structures based upon linear uranyl groups and disphosphonate molecules. Ba-2 and Ba-3 are similar in that they both have UO{sub 5}F{sub 2} pentagonal bipyramids that are bridged and chelated by the diphosphonate moiety into a two-dimensional zigzag anionic sheet (Ba-2) and a one-dimensional ribbon anionic chain (Ba-3). Ba-1, has a single crystallographically unique uranium metal center where the C1P2 ligand solely bridges to form [UO{sub 2}[CH{sub 2}(PO{sub 3}){sub 2}]{sup 2-} sheets. The interlayer space of the structures is occupied by Ba{sup 2+}, which, along with the fluoride ion, mediates the structure formed and maintains overall charge balance. - Graphical abstract: Illustration of the stacking of the layers in Ba{sub 3}[(UO{sub 2}){sub 4}(CH{sub 2}(PO{sub 3}){sub 2}){sub 2})F{sub 6}]{center_dot}6H{sub 2}O viewed along the c-axis. The structure is constructed from UO{sub 7} pentagonal bipyramidal units, U(1)O{sub 7}=gray, U(2)O{sub 7}=yellow, barium=blue, phosphorus=magenta, fluorine=green, oxygen=red, carbon=black, and hydrogen=light peach. Highlights: Black-Right-Pointing-Pointer The polymerization of the UO{sub 2}{sup 2+} sites to form uranyl dimers leads to structural variations in compounds. Black-Right-Pointing-Pointer Barium cations stitch uranyl diphosphonate anionic layers together, and help mediate structure formation. Black-Right-Pointing-Pointer HF acts as both a

Resolution of TBP-H/sub 2/MBP-HDBP-H/sub 3/PO/sub 4/. Application to UO/sub 2/(NO/sub 3/)/sub 2/-TBP, Th(NO/sub 3/)/sub 4/-TBP, and ZrO(NO/sub 3/)/sub 2/-TBP systems. [Separation of dibutyl phosphoric acid, monobutylphosphoric acid and orthophosphoric acid from tri-butylphosphate

Energy Technology Data Exchange (ETDEWEB)

Pires, M A.F.; Abrao, A

1981-04-01

Several schemes for the separation of dibutylphosphoric acid (HDBP), monobutylphosphoric acid (H/sub 2/MBP) and orthophosphoric acid (H/sub 3/PO/sub 4/) as hydrolytic and radiolytic degradation products from tri-n-butylphosphate (TBP) were studied. For the resolution of a HDBP, H/sub 2/MPB and H/sub 3/PO/sub 4/ mixture in TBP-diluent, or in TBP-diluent-heavy metal nitrate (U-VI, Th-IV or Zr-IV), techniques such as ion exchange chromatography, ion chromatography and separation onto a chromatographic alumina column were investigated. For the identification, determination and analytical resolution following up for the several systems studied, techniques such as refraction index measurement, electrical conductivity measurement, molecular spectrophotometry and gas chromatography were applied. Special emphasis was given to the separation using alumina column where the HDBP acid was retained and eluted selectively for its separation from TBP-varsol-uranyl nitrate mixtures. This analytical procedure was applied to the samples coming from the Uranium Purification Pilot Plant in operation at the Centro de Engenharia Quimica (IPEN).

Splitting of the luminescent excited state of the uranyl ion

International Nuclear Information System (INIS)

Flint, C.D.; Sharma, P.; Tanner, P.A.

1982-01-01

The luminescence spectra of some uranyl compounds has been studied. It has been proposed that the splitting of the luminescent excited state of the uranyl ion is due to a descent in symmetry experienced by the uranyl ion when it is placed in a crystal field. In recent years there has been developed a highly successful model of the electronic structure of the uranyl ion. In this paper the authors use this model to interpret the luminescence spectra of a variety of uranyl compounds

On uranyl phosphites

International Nuclear Information System (INIS)

Avduevskaya, K.A.; Ragulina, N.B.; Rozanov, I.A.; Koval', E.M.

1978-01-01

The medium and single-substituted uranyl phosphites of the UO 2 HPO 3 x 3H 2 O and UO 2 (H 2 PO 3 ) 2 x3H 2 O composition were separated in crystal state for the first time. The medium phosphite is fully dehydrated above H 2 SO 4 , intermediate hydrates not being formed. Waterless phosphite decomposes at the temperature above 360 deg C into the mixture of uranium and uranyl phosphates, hydrogen being liberated. The thermal decomposition of single-substituted phosphite starts at the temperature above 150 deg C and is accompanied by the full reduction of uranium up to U(4). The product of calcination is identified as cubic UP 2 O 7

Research on the conversion of highly enriched uranium (HEU) nitrate by using the microwave denitration

International Nuclear Information System (INIS)

Bao Weimin; Song Chongli

1998-08-01

In order to simplify the denitration process by microwave heating, the uranyl nitrate is firstly denitrated and converted into UO 3 . The produced UO 3 was then further heated in the microwave field to transfer UO 3 to U 3 O 8 and to form a single product of U 3 O 8 . When the phase transfer from UO 3 to U 3 O 8 occurs, the temperature of the product increases 200∼300 degree C in two minutes. The phase-transfer temperature can be controlled by the input power of microwave. High quality U 3 O 8 can be obtained at a denitration temperature about 500 degree C. It contains no residual NO x and has a specific surface area great than 3 m 2 /g. The denitration temperature is measured with an IR-thermometer and checked with an optic fiber thermometer. The working curve and process parameter were studied in a microwave denitration unit for high enriched uranyl nitrate solution (90 g(U)/L, 4 mol/L HNO 3 and 1.2 L per batch)

Cloning and nitrate induction of nitrate reductase mRNA

OpenAIRE

Cheng, Chi-Lien; Dewdney, Julia; Kleinhofs, Andris; Goodman, Howard M.

1986-01-01

Nitrate is the major source of nitrogen taken from the soil by higher plants but requires reduction to ammonia prior to incorporation into amino acids. The first enzyme in the reducing pathway is a nitrate-inducible enzyme, nitrate reductase (EC 1.6.6.1). A specific polyclonal antiserum raised against purified barley nitrate reductase has been used to immunoprecipitate in vivo labeled protein and in vitro translation products, demonstrating that nitrate induction increases nitrate reductase p...

A protein engineered to bind uranyl selectively and with femtomolar affinity

Science.gov (United States)

Zhou, Lu; Bosscher, Mike; Zhang, Changsheng; Özçubukçu, Salih; Zhang, Liang; Zhang, Wen; Li, Charles J.; Liu, Jianzhao; Jensen, Mark P.; Lai, Luhua; He, Chuan

2014-03-01

Uranyl (UO22+), the predominant aerobic form of uranium, is present in the ocean at a concentration of ~3.2 parts per 109 (13.7 nM) however, the successful enrichment of uranyl from this vast resource has been limited by the high concentrations of metal ions of similar size and charge, which makes it difficult to design a binding motif that is selective for uranyl. Here we report the design and rational development of a uranyl-binding protein using a computational screening process in the initial search for potential uranyl-binding sites. The engineered protein is thermally stable and offers very high affinity and selectivity for uranyl with a Kd of 7.4 femtomolar (fM) and >10,000-fold selectivity over other metal ions. We also demonstrated that the uranyl-binding protein can repeatedly sequester 30-60% of the uranyl in synthetic sea water. The chemical strategy employed here may be applied to engineer other selective metal-binding proteins for biotechnology and remediation applications.

Complexes of vanadyl and uranyl ions with the chelating groups of humic matter

International Nuclear Information System (INIS)

Goncalves, M.L.S.; Mota, A.M.

1987-01-01

The uranyl and vanadyl complexes formed with salicylic, phthalic and 3,4-dihydroxybenzoic acids have been studied by potentiometry in order to determine the stability constants of the Msub(m) Lsub(n) species formed in solution, and the constants for hydrolysis and polymeric complexes, at 25.0 0 , in 0.10, 0.40 and 0.70M sodium perchlorate. MINIQUAD was used in process the data to find the best models for the species in solution, and calculate the formation constants. The uranyl-salicylic acid sytem was also studied by spectrophotometry and the program SQUAD used to process the data obtained. The best models for these systems show that co-ordination of the uranyl ion by carboxylate groups is easier than for the vanadyl ion, whereas the vanadyl ion seems to form more stable complexes with phenolate groups. Both oxo-cations seem to tend to hydrolyse rather than form complexes when the L:M ratios are greater than unity. Although the change in the constants with ionic strength is small, the activity coefficients of the salicylate and phthalate species have been calculated at ionic strengths 0.40 and 0.70M, along with the interaction parameters with Na + , from the stability constants found for the species ML and H 2 L, according to the Bronsted-Guggenheim expression. (author)

Effect of gibberellic acid and potassium nitrate on seed germination ...

African Journals Online (AJOL)

Ramonda serbica and Ramonda nathaliae are rare resurrection plants, endemic and relict species from Balkan Peninsula. The effect of gibberellic acid (GA3) and potassium nitrate (KNO3) were conducted to determine the seed germination response for these two species. An experiment was conducted with four ...

Quasirelativistic pseudopotential study of species isoelectronic to uranyl and the equatorial coordination of uranyl

International Nuclear Information System (INIS)

Pyykkoe, P.; Li, J.; Runeberg, N.

1994-01-01

The calculated trends of geometries and vibrational frequencies of several uranyl isoelectronic species, like the known NUN and CUO, and the unknown CUN - , NUO + , and NUF 2+ , are reported. The NUN and CUO results support the matrix spectroscopic assignments. The simplest example of equatorial coordination to uranyl is the C 2d species UO 3 . Its calculated vibrational frequencies also support matrix spectroscopic ones. We earlier suggested that the large range of uranyl bond lengths in UO 6 6- -type systems could be interpreted in terms of a open-quotes frozen, soft e g vibrational modeclose quotes. Further studies on UF 6 , U(OH) 6 , [(OUO)(F eq ) n ] (n-2) -, [(OUO)(NO 3 ) 3 ] - , and [(OUO)(CO 3 ) 3 ] 4- show only small variation of R ax as function of R eq . Thus, the all-oxide case is a special one, where all ligands are capable of single and multiple bonding. 44 refs., 10 figs., 7 tabs

Determination of uranyl ion by potentiometric titration using an uranyl-selective electrode

International Nuclear Information System (INIS)

Nassory, N.S.

1990-01-01

A potentiometric titration of uranyl ion is described using an uranyl selective electrode based on a membrane containing a complex of UO 2 -bis[di-4-(1,1,3,3-tetramethylbutyl)phenyl phosphate] as an ion-exchanger and tritolyl phosphate as a solvent mediator. The titrations were carried out with various titrants: Sodium hydroxide, potassium fluoride and sodium salts of acetate, oxalate and citrate. The equivalence points were determined by Gran's method. Good results were obtained by using sodium oxalate as a titrant for the determination of uranium in several samples of ammonium diuranate. The results were quite comparable with those obtained by X-ray fluorescence spectrometry. (orig.)

Raman spectroscopic study of the aging and nitration of actinide processing anion-exchange resins in concentrated nitric acid

International Nuclear Information System (INIS)

Buscher, C. T.; Donohoe, R. J.; Mecklenburg, S. L.; Berg, J. M.; Tait, C. D.; Huchton, K. M.; Morris, D. E.

1999-01-01

Degradation of two types of anion exchange resins, Dowex 11 and Reillex HPQ, from the action of concentrated nitric acid (4 to 12 M) and radiolysis [from depleted uranium as UO 2 2+ nitrate species and 239 Pu as Pu(IV) nitrate species] was followed as a function of time with Raman vibrational spectroscopy. Elevated temperatures (∼50 degree sign C) were used in the absence of actinide metal loading to simulate longer exposures of the resin to a HNO 3 process stream and waste storage conditions. In the absence of actinide loading, only minor changes in the Dowex resin at acid concentrations ≤10 M were observed, while at 12 M acid concentration, the emergence of a Raman peak at 1345 cm-1 indicates the addition of nitro functional groups to the resin. Similar studies with the Reillex resin show it to be more resistant to nitric acid attack at all acid concentrations. Incorporation of weakly radioactive depleted uranium as the UO 2 2+ nitrate species to the ion-exchange sites of Dowex 11 under differing nitric acid concentrations (6 to 12 M) at room temperature showed no Raman evidence of resin degradation or nitration, even after several hundred days of contact. In contrast, Raman spectra for Dowex 11 in the presence of 239 Pu as Pu(IV) nitrate species reveal numerous changes indicating resin alterations, including a new mode at 1345 cm-1 consistent with a Pu(IV)-nitrate catalyzed addition of nitro groups to the resin backbone. (c) 2000 Society for Applied Spectroscopy

Determination of solubility isotherms of barium and strontium nitrates in the system acetic acid-water at 250 C

International Nuclear Information System (INIS)

Hubicki, W.; Piskorek, M.

1976-01-01

Investigastions of the solubility of barium and strontium nitrates were carried out in the system: acetic acid - water at 25 0 C. When one compares the isotherms of solubility of barium and strontium nitrates, one can observe that it is possible to separate the admixtures of barium from strontium nitrates as a result of fractional crystallization of these nitrates from actic acid solution at the temperatures lower than 31.3 0 C, i.e. below the temperature of transformation: Sr(NO 3 ) 2 . 4H 2 O reversible to Sr(NO 3 ) 2 + 4H 2 O for aqueous solution. (author)

Potentiometric study on the complex equilibria between uranyl ions and 3,5-disulfosalicyclic acid in 0. 5 M NaCl0/sub 4/ medium

Energy Technology Data Exchange (ETDEWEB)

Lajunen, L H.J.; Parhi, S [Oulu Univ. (Finland)

1979-01-01

In the preceding papers on the complex equilibria between metal ions and aromatic o-hydroxycarboxylic acids, a report was presented on the equilibrium system of uranyl ions and 3-hydroxy-5,7-disulfo-2-naphthoic acid. The computer analysis showed that the data (obtained by means of emf titrations) were well explicable with two successive complexes. The present investigation was made to evaluate the formation of the U0/sub 2//sup 2 +/ complexes of 3,5-disulfosalicyclic acid in 0.5 M NaCl0/sub 4/ solution at 25/sup 0/C. In this case the computer analysis revealed the formation of more stable complexes: experimental details are given and discussed.

Ruthenium release from thermally overheated nitric acid solution containing ruthenium nitrosyl nitrate and sodium nitrate to solidify

Energy Technology Data Exchange (ETDEWEB)

Sawada, Kayo; Ueda, Yasuyuki; Enokida, Youichi [Nuclear Chemical Engineering Laboratory, Nagoya University, Nagoya 4648603 (Japan)

2016-07-01

Radioactive ruthenium (Ru) is one of the dominant elemental species released into the environment from a fuel reprocessing plant in a hypothetical design accident due to its relatively higher fission yield and longer half-life. After the hypothetical accident assuming the loss of all electric power and cooling functions, high-level liquid waste (HLLW) may be overheated by the energetic decays of many fission products in it, and Ru may be oxidized to the volatile tetroxide, RuO{sub 4}, which is released through the off-gas pathway. At a reprocessing plant in Japan, alkaline solution from the solvent scrubbing stream is sometimes mixed with the HLLW followed by vitrification, which can be influenced by the addition of sodium nitrate to a simulated HLLW containing ruthenium nitrosyl nitrate that was experimentally evaluated on a small scale using the overheated nitric acid solution of 2 mol/dm{sup 3}, which was kept at 180 Celsius degrees in a glass evaporator placed in a thermostatic bath. The release fraction of Ru increased by approximately 30% by the addition of sodium nitrate. This may be partially explained by the existence of relatively highly concentrated nitrate ions in the liquid phase that oxidize the ruthenium species to RuO{sub 4} during the drying process. (authors)

Selectivity in ligand binding to uranyl compounds: A synthetic, structural, thermodynamic and computational study

Energy Technology Data Exchange (ETDEWEB)

Arnold, John [Univ. of California, Berkeley, CA (United States)

2015-01-21

The uranyl cation (UO₂²⁺) is the most abundant form of uranium on the planet. It is estimated that 4.5 billion tons of uranium in this form exist in sea water. The ability to bind and extract the uranyl cation from aqueous solution while separating it from other elements would provide a limitless source of nuclear fuel. A large body of research concerns the selective recognition and extraction of uranyl. A stable molecule, the cation has a linear O=U=O geometry. The short U-O bonds (1.78 Å) arise from the combination of uranium 5f/6d and oxygen 2p orbitals. Due to the oxygen moieties being multiply bonded, these sites were not thought to be basic enough for Lewis acidic coordination to be a viable approach to sequestration. The goal of this research is thus to broaden the coordination chemistry of the uranyl ion by studying new ligand systems via synthetic, structural, thermodynamic and computational methods. It is anticipated that this fundamental science will find use beyond actinide separation technologies in areas such as nuclear waste remediation and nuclear materials. The focus of this study is to synthesize uranyl complexes incorporating amidinate and guanidinate ligands. Both synthetic and computational methods are used to investigate novel equatorial ligand coordination and how this affects the basicity of the oxo ligands. Such an understanding will later apply to designing ligands incorporating functionalities that can bind uranyl both equatorially and axially for highly selective sequestration. Efficient and durable chromatography supports for lanthanide separation will be generated by (1) identifying robust peptoid-based ligands capable of binding different lanthanides with variable affinities, and (2) developing practical synthetic methods for the attachment of these ligands to Dowex ion exchange resins.

Selectivity in ligand binding to uranyl compounds: A synthetic, structural, thermodynamic and computational study

International Nuclear Information System (INIS)

Arnold, John

2015-01-01

The uranyl cation (UO 2 2+ ) is the most abundant form of uranium on the planet. It is estimated that 4.5 billion tons of uranium in this form exist in sea water. The ability to bind and extract the uranyl cation from aqueous solution while separating it from other elements would provide a limitless source of nuclear fuel. A large body of research concerns the selective recognition and extraction of uranyl. A stable molecule, the cation has a linear O=U=O geometry. The short U-O bonds (1.78 Å) arise from the combination of uranium 5f/6d and oxygen 2p orbitals. Due to the oxygen moieties being multiply bonded, these sites were not thought to be basic enough for Lewis acidic coordination to be a viable approach to sequestration. The goal of this research is thus to broaden the coordination chemistry of the uranyl ion by studying new ligand systems via synthetic, structural, thermodynamic and computational methods. It is anticipated that this fundamental science will find use beyond actinide separation technologies in areas such as nuclear waste remediation and nuclear materials. The focus of this study is to synthesize uranyl complexes incorporating amidinate and guanidinate ligands. Both synthetic and computational methods are used to investigate novel equatorial ligand coordination and how this affects the basicity of the oxo ligands. Such an understanding will later apply to designing ligands incorporating functionalities that can bind uranyl both equatorially and axially for highly selective sequestration. Efficient and durable chromatography supports for lanthanide separation will be generated by (1) identifying robust peptoid-based ligands capable of binding different lanthanides with variable affinities, and (2) developing practical synthetic methods for the attachment of these ligands to Dowex ion exchange resins.

Zirconia silicate modified with phytic acid (IP6) and its effect on uranyl sorption

International Nuclear Information System (INIS)

Escalante G, D. C.

2016-01-01

In this work the sorption capacity of uranyl ions on zirconium silicate (ZrSiO_4) extracted from sea sand of Baja California Sur was studied, the effect of phytic acid (IP6) accompanied by a perchlorate salt of sodium (NaClO_4) on the surface of the mineral. In the first stage, ZrSiO_4 was obtained from sea sand by extraction using hydrofluoric acid, the purified and hydrated material was later characterized by instrumental techniques such as X-ray diffraction to determine its purity and crystallinity. The ZrSiO_4-purified, ZrSiO_4/NaClO_4 and ZrSiO_4/IP6 were studied by physicochemical and surface characterization. By scanning electron microscopy was observed that ZrSiO_4 initially is formed by flat structures, however, when it is hydrated with NaClO_4 the formation of particles on the material exists, whereas when the IP6 is added the crystals on the surface are elongated forming structures geometric shapes. This modification on the surface of the ZrSiO_4 was corroborated by atomic force microscopy where significant changes were observed in the topography of the purified and hydrated material. By Fourier transform infrared spectroscopy is identifies the presence of functional groups from hydration with IP6 and NaClO_4 on the surface of SrSiO_4. Characterization of surface properties was performed by determining the surface area of the purified ZrSiO_4, SrSiO_4/NaClO_4 and ZrSiO_4/IP6 systems using the Bet multipoint and fractal dimension technique; the hydration time, zero loading point was evaluated by means of a bulk titration and surface site density (Ds). The fluorescence and phosphorescence techniques allowed determining the optimum hydration point and the uranium species sorbed on the surface of the ZrSiO_4 as in the systems hydrated with IP6 and with NaClO_4. This technique provided relevant information about the speciation and complex formation of IP6 with uranyl ions on the surface of ZrSiO_4. Sorption isotherms and kinetics were prepared by the liquid

Development and optimisation of process parameters for recovery of uranium from calcia slag and lining material (SLM) by leaching process and subsequent recovery of uranium from the leach liquor generated

International Nuclear Information System (INIS)

Verma, Dinesh Kumar; Srivastava, Praveen Kumar; Das, Santanu; Kumar, Raj; Roy, S.B.

2014-01-01

Presently uranium value is recovered by nitric acid dissolution of the SLM, to get uranyl nitrate solution (UNS) and subsequent solvent extraction process. UNS generated After SLM dissolution is very lean in uranium content and create difficulty in solvent extraction. Moreover, NO X is also generated during SLM dissolution in nitric acid. An alternate process was developed where nitric acid is not being used and uranium is being recovered by leaching out the SLM using acetic acid. The process was also optimised for recovery and overall economics of the process by using process effluent AALL (Acetic Acid Leach Liquor) as a leaching agent. The uranium value in the leach liquor was precipitated by using sodium hydroxide. The precipitate was dissolved in nitric acid and the Uranyl Nitrate Solution generated was having Uranium concentration of 15-30 g/l. The alternate process developed will have less effluent generation, less NO X generation and will produce more concentrated UNS in comparison to the nitric acid dissolution process

Impact of uranyl-calcium-carbonato complexes on uranium(VI) adsorption to synthetic and natural sediments.

Science.gov (United States)

Stewart, Brandy D; Mayes, Melanie A; Fendorf, Scott

2010-02-01

Adsorption on soil and sediment solids may decrease aqueous uranium concentrations and limit its propensity for migration in natural and contaminated settings. Uranium adsorption will be controlled in large part by its aqueous speciation, with a particular dependence on the presence of dissolved calcium and carbonate. Here we quantify the impact of uranyl speciation on adsorption to both goethite and sediments from the Hanford Clastic Dike and Oak Ridge Melton Branch Ridgetop formations. Hanford sediments were preconditioned with sodium acetate and acetic acid to remove carbonate grains, and Ca and carbonate were reintroduced at defined levels to provide a range of aqueous uranyl species. U(VI) adsorption is directly linked to UO(2)(2+) speciation, with the extent of retention decreasing with formation of ternary uranyl-calcium-carbonato species. Adsorption isotherms under the conditions studied are linear, and K(d) values decrease from 48 to 17 L kg(-1) for goethite, from 64 to 29 L kg (-1) for Hanford sediments, and from 95 to 51 L kg(-1) for Melton Branch sediments as the Ca concentration increases from 0 to 1 mM at pH 7. Our observations reveal that, in carbonate-bearing waters, neutral to slightly acidic pH values ( approximately 5) and limited dissolved calcium are optimal for uranium adsorption.

Infrared Spectroscopy of Discrete Uranyl Anion Complexes

International Nuclear Information System (INIS)

Groenewold, G. S.; Gianotto, Anita K.; McIIwain, Michael E.; Van Stipdonk, Michael J.; Kullman, Michael; Moore, David T.; Polfer, Nick; Oomens, Jos; Infante, Ivan A.; Visscher, Lucas; Siboulet, Bertrand; De Jong, Wibe A.

2008-01-01

The Free-Electron Laser for Infrared Experiments (FELIX) w 1 as used to study the wavelength-resolved multiple photon photodissociation of discrete, gas phase uranyl (UO2 2 2+) complexes containing a single anionic ligand (A), with or without ligated solvent molecules (S). The uranyl antisymmetric and symmetric stretching frequencies were measured for complexes with general formula [UO2A(S)n]+, where A was either hydroxide, methoxide, or acetate; S was water, ammonia, acetone, or acetonitrile; and n = 0-3. The values for the antisymmetric stretching frequency for uranyl ligated with only an anion ([UO2A]+) were as low or lower than measurements for [UO2]2+ ligated with as many as five strong neutral donor ligands, and are comparable to solution phase values. This result was surprising because initial DFT calculations predicted values that were 30-40 cm-1 higher, consistent with intuition but not with the data. Modification of the basis sets and use of alternative functionals improved computational accuracy for the methoxide and acetate complexes, but calculated values for the hydroxide were greater than the measurement regardless of the computational method used. Attachment of a neutral donor ligand S to [UO2A]+ produced [UO2AS]+, which produced only very modest changes to the uranyl antisymmetric stretch frequency, and did not universally shift the frequency to lower values. DFT calculations for [UO2AS]+ were in accord with trends in the data, and showed that attachment of the solvent was accommodated by weakening of the U-anion bond as well as the uranyl. When uranyl frequencies were compared for [UO2AS]+ species having different solvent neutrals, values decreased with increasing neutral nucleophilicity

Thermal analysis studies of ammonium uranyl carbonate

International Nuclear Information System (INIS)

Cao Xinsheng; Ma Xuezhong; Wang Fapin; Liu Naixin; Ji Changhong

1988-01-01

The simultaneous thermogravimetry and differential thermal analysis of the ammonium uranyl carbonate powder were performed with heat balance in the following atmosphers: Air, Ar and Ar-8%H 2 . The thermogravimetry and differential thermal analysis curves of the ammonium uranyl carbonate powder obtained from different source were reported and discussed

Infrared spectra of volatile adduct of uranyl pivaloyltrifluoroacetonate with hexamethylphosphorotriamide

International Nuclear Information System (INIS)

Bukhmarina, V.N.; Dushin, R.B.; Sidorenko, G.V.; Suglobov, D.N.

1983-01-01

Adduct of uranyl pivaloyltrifluoroacetonate with hexamethylphosphortriamide (1), sublimated without decomposition and characterized by a high thermal stability, has been synthesized, as well as adducts of uranyl dipivaloylmethanate with hexamethylphosphortriamide (2) and dimethyl sulfoxide (3), sublimated with partial dissociation. IR spectra of crystalline adducts 1-3, their solutions in benzene; gaseous and matrix-isolated adduct 1 have been measured. It is shown that in gaseous phase 1 exists practically completely in non-dissociated form. It is detected that uranyl group in crystalline 1 and 2 and in matrix-isolated 1 in contrast to crystalline 3 and previously studied adducts of uranyl β-diketonates has an asymmetric structure. Strength constants of uranyl group in crystalline 1-3 and matrix-isolated 1 are determined

Thermochemical investigations on uranyl phosphates and arsenates

International Nuclear Information System (INIS)

Barten, H.

1986-11-01

The results are described of a study of the thermochemical stability of anhydrous uranyl phosphates and arsenates. A number of aspects of chemical technological importance are indicated in detail. The synthesized anhydrous uranyl phosphates and arsenates were very hygroscopic, so that experiments on these compounds had to be carried out under moisture-free conditions. Further characterisation of these compounds are given, including a study of their thermal stabilities and phase relations. The uranyl phosphates reduced reversibly at temperatures of the order of 1100 to 1600 0 C. This makes it possible to express their relative stabilities quantitatively, in terms of the oxygen pressures of the reduction reactions. The thermal decomposition of uranyl arsenates did not occur by reduction, as for the phosphates, but by giving off arsenic oxide vapour. The results of measurements of enthalpies of solution led to the determination of the enthalpies of formation, heat capacity and the standard entropies of the uranyl arsenates. The thermochemical functions at high-temperatures could consequently be calculated. Attention is paid to the possible formation of uranium arsenates, whose uranium has a valency lower than six, hitherto not reported in literature. It was not possible to prepare arsenates of tetravalent uranium. However, three new compounds were observed, one of these, UAsO 5 , was studied in some detail. (Auth.)

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)

Preparation of the pur uranium-metal

International Nuclear Information System (INIS)

Goldschmidt, B.; Vertes, P.

1955-01-01

A detailed description of the chemical processes used to prepare in the factory of Bouchet of the CEA (Seine-Et-Oise) pur metal uranium with either relatively rich ores, or extracts coming of physical or chemical treatment of poor ores. The nitric treatment of ores succeeds to the production of uranate of impure sodium carbonate. This last last product is dissolved in nitric acid and the uranyl nitrate is extracted by tributyl-phosphate diluted in an inert solvent. The uranyl nitrate pure is re-extracted and successively transformed in uranium peroxide, in orange oxide then in brown oxide which is transformed in fluoride by the anhydrous hydrofluoric acid. Uranate fluoride is then reduced in metal by the pure calcium with an yield superior to 99%. (authors) [fr

Absorption infrared spectra of interaction products of cyclic polyethers 18-crown-6 and dibenzo-18-crown-6 with uranyl dinitrate hexahydrate

International Nuclear Information System (INIS)

Chumaevskij, N.A.; Belomestnykh, V.I.; Razgonyaeva, G.A.; Shabel'nik, K.S.; Afanas'eva, E.E.

1988-01-01

Using the method of IR spectroscopy it is established that during interaction of uranyl nitrate hexahydrate (UNH) with crown-ethers under investigation macrocycles adhere to UO 2 2+ via hydrogen bonds between water molecules and oxygen of polyethers. Interaction of UNH with the above-mentioned crowns leads to conformational rearrangement of cycles of polyethers and improvement of their symmetry, reflecting in noticeable simplification of IR spectra of interaction products as compared to spectra of initial cyclic polyethers

Complexation of uranyl ion with sulfonates. One- to three-dimensional assemblies with 1,5- and 2,7-naphthalenedisulfonates

Energy Technology Data Exchange (ETDEWEB)

Thuery, Pierre [NIMBE, CEA, CNRS, Universite Paris-Saclay, CEA Saclay, Gif-sur-Yvette (France); Harrowfield, Jack [ISIS, Universite de Strasbourg (France)

2017-02-03

Uranyl nitrate was treated with the sodium salt of either 1,5- or 2,7-naphthalenedisulfonate (1,5-ndsNa{sub 2} or 2,7-ndsNa{sub 2}, respectively) under (solvo)-hydrothermal conditions, in the presence of additional coligands and/or metal cations, to give six new complexes, which were characterized by determination of their crystal structures. Complex [UO{sub 2}(1,5-nds)(H{sub 2}O)] (1) crystallizes as a three-dimensional (3D) framework, with both sulfonate groups coordinated in the O,O{sup '}-bridging mode. In the presence of the N-chelating species 2,2{sup '}-bipyridine (bipy) or 1,10-phenanthroline (phen), the three complexes [(UO{sub 2}){sub 2}(1,5-nds)(OH){sub 2}(bipy){sub 2}].H{sub 2}O (2), [(UO{sub 2}){sub 2}(1,5-nds)(OH){sub 2}(bipy){sub 2}].bipy (3) and [(UO{sub 2}){sub 2}(1,5-nds)(OH){sub 2}(phen){sub 2}] (4) were obtained, in which doubly hydroxide-bridged uranyl dimers are assembled into one-dimensional (1D) chains by bis(unidentate) disulfonate ligands. Complex [Cu(bipy){sub 2}Cl][UO{sub 2}(2,7-nds)(OH)].H{sub 2}O (5) displays anionic, two-dimensional (2D) sheets in which unidentate/O,O{sup '}-bridging disulfonate ligands link hydroxide-bridged uranyl dimers. In the additional presence of cucurbit[6]uril (CB6), complex [(UO{sub 2}){sub 4}Na{sub 4}(2,7-nds){sub 2}(CB6)Cl{sub 4}O{sub 2}(H{sub 2}O){sub 10}].5H{sub 2}O (6) crystallizes as a 3D framework of intricate architecture, with bis(μ{sub 3}-oxo)-bridged uranyl tetranuclear moieties connected to CB6-bound sodium cations by doubly O,O{sup '}-bridging disulfonates. Complexes 2 and 4 display intense and well-resolved uranyl emission in the solid state, while nearly complete quenching is observed in 3 and 5. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Uranyl soaps - thermal, electronic and infrared spectral study

International Nuclear Information System (INIS)

Solanki, A.K.; Bhandari, A.M.

1981-01-01

The electronic and infrared spectra and TGA thermogram of uranyl soaps (laurate, mystrate, palmitate and stearate) have been studied. The environment about the UO 2+ 2 ion would comprise two 'short bite' bidentate carboxylate groups and oxygen atoms bridging from adjacent carboxylic molecules. The uranyl soaps have UO 2+ 2 vibronic absorption (approx. equal to 22730 cm -1 ) in the range found for eight coordinate uranyl complexes. The greater resistance to thermal degradation (approx. equal to 300 0 C) of these soaps and their stepwise thermal degradation infer strong metal-ligand interaction. (orig.) [de

Can uranyl complexes encapsulate to carbon nanotubes? A ...

Indian Academy of Sciences (India)

K SRINIVASU

We find that uranyl-aqua complex ([UO2(H2O)5]2+) binds stronger as compared to uranyl-hydroxo-complex .... until the maximum Hellmann–Feynman force on each atom ..... porters and near-infrared agents for selective cancer cell.

Processing of Sierra Albarrana uranium ores

International Nuclear Information System (INIS)

Gutierrez Jodra, L.; Perez Luina, A.; Perarnau, M.

1960-01-01

Uranium recovery by hydrometallurgy from brannerite, found in Hornachuelos (Cordoba) is described. It has been studied the acid and alkaline leaching and salt roasting, proving as more satisfactory the acid leaching. Besides the uranium solubilization by acid leaching, is described the further process to obtain pure uranyl nitrate. (Author)

Processing of Sierra Albarrana uranium ores; Tratamiento de los minerales de uranio de Sierra Albarrana

Energy Technology Data Exchange (ETDEWEB)

Gutierrez Jodra, L; Perez Luina, A; Perarnau, M

1960-07-01

Uranium recovery by hydrometallurgy from brannerite, found in Hornachuelos (Cordoba) is described. It has been studied the acid and alkaline leaching and salt roasting, proving as more satisfactory the acid leaching. Besides the uranium solubilization by acid leaching, is described the further process to obtain pure uranyl nitrate. (Author)

Uranyl sulfate irradiations at the Van de Graaff: A means to combat uranyl peroxide precipitation

Energy Technology Data Exchange (ETDEWEB)

Youker, Amanda J. [Argonne National Lab. (ANL), Argonne, IL (United States); Kalensky, Michael [Argonne National Lab. (ANL), Argonne, IL (United States); Quigley, Kevin J. [Argonne National Lab. (ANL), Argonne, IL (United States); Brossard, Thomas [Argonne National Lab. (ANL), Argonne, IL (United States); Chemerisov, Sergey D. [Argonne National Lab. (ANL), Argonne, IL (United States); Vandegrift, George F. [Argonne National Lab. (ANL), Argonne, IL (United States)

2017-05-01

As part of an effort to support SHINE Medical Technologies in developing a process to produce Mo-99 by neutron-induced fission, a series of irradiation experiments was performed with a 3 MeV Van de Graaff accelerator to generate high radiation doses in 0.5–2 mL uranyl sulfate solutions. The purpose was to determine what conditions result in uranyl peroxide precipitation and what can be done to prevent its formation. The effects of temperature, dose rate, uranium concentration, and the addition of known catalysts for the destruction of peroxide were determined.

Temperature and pH driven association in uranyl aqueous solutions

Directory of Open Access Journals (Sweden)

M. Druchok

2012-12-01

Full Text Available An association behavior of uranyl ions in aqueous solutions is explored. For this purpose a set of all-atom molecular dynamics simulations is performed. During the simulation, the fractions of uranyl ions involved in dimer and trimer formations were monitored. To accompany the fraction statistics one also collected distributions characterizing average times of the dimer and trimer associates. Two factors effecting the uranyl association were considered: temperature and pH. As one can expect, an increase of the temperature decreases an uranyl capability of forming the associates, thus lowering bound fractions/times and vice versa. The effect of pH was modeled by adding H+ or OH- ions to a "neutral" solution. The addition of hydroxide ions OH- favors the formation of the associates, thus increasing bound times and fractions. The extra H+ ions in a solution produce an opposite effect, thus lowering the uranyl association capability. We also made a structural analysis for all the observed associates to reveal the mutual orientation of the uranyl ions.

Photobehavior of aqueous uranyl ion and photo-oxygenation of isobutane using light from the visible region

International Nuclear Information System (INIS)

Bergfeldt, T.M.; Waltz, W.L.; Xu, X; Sedlak, P.; Dreyer, U.; Mockel, H.; Lilie, J.; Stephenson, J.W.

2003-01-01

The photochemical and photophysical behavior of the aqueous uranyl ion [UO 2 (H 2 O) 5 ] 2+ has been studied under the influence of visible light and with added perchloric acid over the range of 0.01-4 M. In the presence of 2-methylpropane (isobutane), photo-oxygenation of isobutane occurs to yield, as the major product, 2-methyl-2-propanol (tert-butyl alcohol) along with lesser amounts of 2-methyl-2-propene (isobutene) and other C1-C8 products. The quantum yield for formation of tert-butyl alcohol is independent of light intensity at the irradiation wavelength of 415 nm and of uranyl concentration, but it increases from 0.016 ± 0.001 at 0.01 M HC1O 4 (pH 2) to 0.13 ± 0.01 at 4 M HC1O 4 . The emission spectrum from the electronically excited uranyl ion and the associated quantum yields have been measured in the presence and absence of isobutane, as a function of added perchloric acid. While in both cases the shape of the spectrum remains invariant, the quantum yields increase with increasing perchloric acid concentration. The strong dependence on added perchloric acid is interpreted within the context of the presence and interconversion of two electronically excited species, an acid form, *[UO 2 (H 2 O) 5 ] 2+ , and a base form, *[UO 2 (H 2 O) n (OH)] + . It is proposed that both forms react with isobutane to give a tert-butyl radical, and that oxidation of coordinated aqua ligands occur, the latter generating a hydroxyl radical whose reaction with isobutane rapidly leads also to a tert-butyl radical. The reaction of this alkyl radical with ground-state [UO 2 (H 2 O) 5 ] 2+ then gives rise to the stable tert-butyl alcohol product and reduced forms of uranyl ion. Based upon the values of the quantum yields and of excited-state lifetime measurements reported in the literature, a comprehensive mechanism has been developed in a quantitative manner to provide calculated values of the rate constants for the individual mechanistic steps. The calculated rate constants

IR spectra and structure of uranyl pivaloyltrifluoroacetylacetonate isolated in argon matrix

International Nuclear Information System (INIS)

Belyaeva, A.A.; Dushin, R.B.; Sidorenko, G.V.; Suglobov, D.N.

1985-01-01

When studying IR absorption spectra of a number of isotopomers of uranyl pivaloyl trifluoroacetonate (UPTFA), isolated in the matrix of argon and dissolved in benzene, and comparing them with the spectra of uranyl hexafluoroacetylacetonate (UHFA) vapours, it has been ascertained, that UPTFA vapours consist of monomers and dimers, and UPTFA solution in benzene - of dimers.It is shown, that the dimers have T-shaped structure, at that, the bond inside the dimer is realized by yl-atom of oxygen of an uranyl ion, included in the equatorial coordination sphere of another uranyl ion. Proofs of the dimer T-like structure distortion in gaseous or matrix-isolated state, as a result of which the difference of the angles between uranyl axes from 90 deg is observed, are given. In the framework of approximated model of isolated uranyl-ion the force constants for all the compounds investigated are calaculted

Specific capture of uranyl protein targets by metal affinity chromatography

International Nuclear Information System (INIS)

Basset, C.; Dedieu, A.; Guerin, P.; Quemeneur, E.; Meyer, D.; Vidaud, C.

2008-01-01

To improve general understanding of biochemical mechanisms in the field of uranium toxicology, the identification of protein targets needs to be intensified. Immobilized metal affinity chromatography (IMAC) has been widely developed as a powerful tool for capturing metal binding proteins from biological extracts. However uranyl cations (UO 2 2+ ) have particular physico-chemical characteristics which prevent them from being immobilized on classical metal chelating supports. We report here on the first development of an immobilized uranyl affinity chromatography method, based on the cation-exchange properties of amino-phosphonate groups for uranyl binding. The cation distribution coefficient and loading capacity on the support were determined. Then the stability of the uranyl-bonded phase under our chromatographic conditions was optimized to promote affinity mechanisms. The successful enrichment of uranyl binding proteins from human serum was then proven using proteomic and mass spectral analysis. (authors)

Structural variability in uranyl-lanthanide hetero-metallic complexes with DOTA and oxalato ligands

International Nuclear Information System (INIS)

Thuery, P.

2009-01-01

Four novel 4f-5f hetero-metallic complexes could be obtained from the reaction of uranyl and lanthanide nitrates with DOTA (H 4 L) under hydrothermal conditions. In all cases, as in the previous examples reported, additional oxalato ligands are formed in situ. Variations in the stoichiometry of the final products and the presence of hydroxo ions in some cases appear to result in a large structural variability. In the two isomorphous complexes [(UO 2 ) 2 Ln 2 (L) 2 (C 2 O 4 )] with Ln = Sm(1) or Eu(2), the lanthanide ion is located in the N 4 O 4 site and is also bound to a carboxylate oxygen atom from a neighbouring unit, to give zigzag chains which are further linked to one another by [(UO 2 ) 2 (C 2 O 4 )] 2+ di-cations, resulting in the formation of a 3D framework. In [(UO 2 ) 4 Gd 2 (L) 2 (C 2 O 4 ) 3 (H 2 O) 6 ].2H 2 O (3), 2D bilayer subunits of the 'double floor' type with uranyl oxalate pillars are assembled into a 3D framework by other, disordered uranyl ions. [(UO 2 ) 2 Gd(L)(C 2 O 4 )(OH)].H 2 O (4) is a 2D assembly in which cationic {[(UO 2 ) 2 (C 2 O 4 )(OH)] + } n chains are linked to one another by the [Gd(L)] - groups. The most notable feature of this compound is the environment of the 4f ion, which is eight-coordinate and twisted square anti-prismatic (TSA'), instead of nine-coordinate mono-capped square anti-prismatic (SA), as generally observed in DOTA complexes of gadolinium(III) and similarly-sized ions. (author)

Effect of inhibitors on acid production by baker's yeast.

Science.gov (United States)

Sigler, K; Knotková, A; Kotyk, A

1978-01-01

Glucose-induced acid extrusion, respiration and anaerobic fermentation in baker's yeast was studied with the aid of sixteen inhibitors. Uranyl(2+) nitrate affected the acid extrusion more anaerobically than aerobically; the complexing of Mg2+ and Ca2+ by EDTA at the membrane had no effect. Inhibitors of glycolysis (iodoacetamide, N-ethylmaleimide, fluoride) suppressed acid production markedly, and so did the phosphorylation-blocking arsenate. Fluoroacetate, inhibiting the citric-acid cycle, had no effect. Inhibition by uncouplers depended on their pKa values: 2,4,6-trinitrophenol (pKa 0.4) less than 2,4-dinitrophenol (4.1) less than azide (4.7) less than 3-chlorophenylhydrazonomalononitrile (6.0). Inhibition by trinitrophenol was only slightly increased by its acetylation. Cyanide and nonpermeant oligomycin showed practically no effect; inhibition by dicyclohexylcarbodiimide was delayed but potent. The concentration profiles of inhibition of acid production differed from those of respiration and fermentation. Thus, though the acid production is a metabolically dependent process, it does not reflect the intensity of metabolism, except partly in the first half of glycolysis.

A family of uranyl-aromatic dicarboxylate (pht-, ipa-, tpa-) framework hybrid materials: photoluminescence, surface photovoltage and dye adsorption.

Science.gov (United States)

Gao, Xue; Wang, Che; Shi, Zhong-Feng; Song, Jian; Bai, Feng-Ying; Wang, Ji-Xiao; Xing, Yong-Heng

2015-07-07

Four uranyl complexes [(UO2)(pht)H2O]·H2O (pht = phthalic acid) (1), (UO2)2(Hipa)4(H2O)2 (Hipa = isophthalic acid) (2), (UO2)(tpa)(DMF)2 (tpa = terephthalic acid) (3) and (UO2)(box)2 (box = benzoic acid) (4) were synthesized by the reaction of UO2(CH3COO)2·2H2O as the metal source and phthalic acid, isophthalic acid, terephthalic acid or benzoic acid as the ligand. They were characterized by elemental analyses, IR, UV-Vis, XRD, single crystal X-ray diffraction analysis and thermal gravimetric analysis. The structural analysis reveals that complex 1 exhibits a one-dimensional chain structure constructed by the building unit [(UO2)2(pht)4(H2O)2] and further extends the chain into a 2D supramolecular architecture by hydrogen bonding interactions. Complex 2 is a discrete [(UO2)2(Hipa)4(H2O)2] structure, and by the hydrogen bonding interaction, forms a 3D supramolecular structure. In complexes 3 and 4, adjacent uranyl polyhedra form a 1D chain through bridging terephthalic acid and benzoic acid, respectively. In order to extend their functional properties, their photoluminescence, surface photovoltage and dye adsorption properties have been studied.

The ytterbium nitrate-quinoline (piperidine) nitrate-water system

International Nuclear Information System (INIS)

Khisaeva, D.A.; Boeva, M.K.; Zhuravlev, E.F.

1985-01-01

Using the method of cross sections the solubility of solid phases in the ytterbium nitrate-quinoline nitrate - water (1) and ytterbium nitrate-piperidine nitrate-water (2) systems is studied at 25 and 50 deg C. It is established, that in system 1 congruently melting compound of the composition Yb(NO 3 ) 3 x2C 9 H 7 NxHNO 3 x3H 2 O is formed. The new solid phase has been isolated as a preparation and subjected to chemical X-ray diffraction, differential thermal and IR spectroscopic analyses. Isotherms of system 2 in the studied range of concentrations and temperatures consist of two branches, corresponding to crystallization of tetruaqueous ytterbi um nitrate and nitric acid piperidine

Synthesis and characterization of heterometallic uranyl pyridinedicarboxylate compounds

Science.gov (United States)

Jayasinghe, Ashini S.; Payne, Maurice K.; Forbes, Tori Z.

2017-10-01

The incorporation of transition metals into hybrid uranyl materials can result in more diverse structural topologies and variations in physical and chemical properties. To explore the impact of transition metals on the uranyl cation, five uranium containing bimetallic chain compounds, [(UO2)M(PDC)2(H2O)4]·4(H2O) (PDC = 2,6 pyridinedicarboxylate; M = Ni2+, Co2+, Fe2+, Zn2+, and Cu2+) were synthesized by evaporation of aqueous solutions at room temperature. The uranyl cation is complex by two PDC ligands and the transition metal cations bond to the complex to form a one-dimensional chain topology. The presence of the transition metal leads to the presence of a stronger uranyl oxo bonds as shown by the single-crystal X-ray diffraction data and the Raman spectra. Solid state diffuse reflectance UV/Visible spectra confirmed the presence of the transition metals in the structure by the broad bands that appeared at relevant wavelengths.

Multi-scale modelling of uranyl chloride solutions

Energy Technology Data Exchange (ETDEWEB)

Nguyen, Thanh-Nghi; Duvail, Magali, E-mail: magali.duvail@icsm.fr; Villard, Arnaud; Dufrêche, Jean-François, E-mail: jean-francois.dufreche@univ-montp2.fr [Institut de Chimie Séparative de Marcoule (ICSM), UMR 5257, CEA-CNRS-Université Montpellier 2-ENSCM, Site de Marcoule, Bâtiment 426, BP 17171, F-30207 Bagnols-sur-Cèze Cedex (France); Molina, John Jairo [Fukui Institute for Fundamental Chemistry, Kyoto University, Takano-Nishihiraki-cho 34-4, Sakyo-ku, Kyoto 606-8103 (Japan); Guilbaud, Philippe [CEA/DEN/DRCP/SMCS/LILA, Marcoule, F-30207 Bagnols-sur-Cèze Cedex (France)

2015-01-14

Classical molecular dynamics simulations with explicit polarization have been successfully used to determine the structural and thermodynamic properties of binary aqueous solutions of uranyl chloride (UO{sub 2}Cl{sub 2}). Concentrated aqueous solutions of uranyl chloride have been studied to determine the hydration properties and the ion-ion interactions. The bond distances and the coordination number of the hydrated uranyl are in good agreement with available experimental data. Two stable positions of chloride in the second hydration shell of uranyl have been identified. The UO{sub 2}{sup 2+}-Cl{sup −} association constants have also been calculated using a multi-scale approach. First, the ion-ion potential averaged over the solvent configurations at infinite dilution (McMillan-Mayer potential) was calculated to establish the dissociation/association processes of UO{sub 2}{sup 2+}-Cl{sup −} ion pairs in aqueous solution. Then, the association constant was calculated from this potential. The value we obtained for the association constant is in good agreement with the experimental result (K{sub UO{sub 2Cl{sup +}}} = 1.48 l mol{sup −1}), but the resulting activity coefficient appears to be too low at molar concentration.

Spectropolarimetric analysis. Communication 14. Determination of uranyl with d-tartaric acid

Energy Technology Data Exchange (ETDEWEB)

Bakalov, V D; Dunina, V V; Potapov, V M [Moskovskij Gosudarstvennyj Univ. (USSR)

1982-02-01

The possibility has been shown of improving the sensitivity and precision of determination of uranium (6) in the form of its tartrate complex by using spectropolarimetry instead of polarimetry and circular dichroism instead of optical rotatory dispersion. The method makes it possible to reduce reagent consumption, to expand a range of uranium(6) concentration, which could be determined, due to changes of the cell length and reading range. On the basis of the circular dichroism spectrum of the uranyl-tartrate complex, its symmetry has been estimated to be Dsub(4h) with the coordination number of four on the equatorial plane.

Uranyl Sulfate Nanotubules Templated by N-phenylglycine

Directory of Open Access Journals (Sweden)

Oleg I. Siidra

2018-04-01

Full Text Available The synthesis, structure, and infrared spectroscopy properties of the new organically templated uranyl sulfate Na(phgH+7[(UO26(SO410](H2O3.5 (1, obtained at room temperature by evaporation from aqueous solution, are reported. Its structure contains unique uranyl sulfate [(UO26(SO410]8− nanotubules templated by protonated N-phenylglycine (C6H5NH2CH2COOH+. Their internal diameter is 1.4 nm. Each of the nanotubules is built from uranyl sulfate rings sharing common SO4 tetrahedra. The template plays an important role in the formation of the complex structure of 1. The aromatic rings are stacked parallel to each other due to the effect of π–π interaction with their side chains extending into the gaps between the nanotubules.

Catalyzed reduction of nitrate in aqueous solutions

International Nuclear Information System (INIS)

Haas, P.A.

1994-08-01

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

Determination of Cl in the Uranium by mean of voltametry

International Nuclear Information System (INIS)

Saryati; Supardi

1996-01-01

The determination of Cl in uranium by mean of voltametry in the nitric acid media has been studied. Hanging mercury droop electrode (HMDE) is used as a working electrode, calomel electrode standard (SCE) is used as a reference electrode and Pt wire as counter electrode. To draw a voltamogram, a Square Wave Voltametry (SWV) technique by using pulse height of 20 mV, frequency of 100 hz, scan increment of 2 mv/sec and initial potential of 0.33 V Vs SCE was used. Uranyl nitrate concentration must not be more than 100 mg/10 ml. CI concentration in uranyl nitrate was (16.81 ± 0.32) μg/g

Determination of solubility isotherms of barium and strontium nitrates in the system acetic acid-water at 25/sup 0/ C

Energy Technology Data Exchange (ETDEWEB)

Hubicki, W.; Piskorek, M. (Uniwersytet Marii Curie-Sklodowskiej, Lublin (Poland))

1976-01-01

Investigations of the solubility of barium and strontium nitrates were carried out in the system: acetic acid - water at 25/sup 0/ C. When one compares the isotherms of solubility of barium and strontium nitrates, one can observe that it is possible to separate the admixtures of barium from strontium nitrates as a result of fractional crystallization of these nitrates from actic acid solution at the temperatures lower than 31.3/sup 0/ C, i.e. below the temperature of transformation: Sr(NO/sub 3/)/sub 2/ . 4H/sub 2/O reversible to Sr(NO/sub 3/)/sub 2/ + 4H/sub 2/O for aqueous solution.

Aggregation-induced emission active tetraphenylethene-based sensor for uranyl ion detection

Energy Technology Data Exchange (ETDEWEB)

Wen, Jun; Huang, Zeng; Hu, Sheng [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang, 621900, Sichuan Province (China); Li, Shuo, E-mail: lishuo@cqut.edu.cn [School of Chemical Engineering, Chongqing University of Technology, Chongqing 400054 (China); Li, Weiyi, E-mail: weiyili@mail.xhu.edu.cn [School of Science, Xihua University, Chengdu, Sichuan, 610065 (China); Wang, Xiaolin, E-mail: xlwang@caep.cn [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang, 621900, Sichuan Province (China)

2016-11-15

Highlights: • A novel AIE fluorescent sensor for the detection of uranyl has been developed. • TPE-T is capable of visually distinguish UO{sub 2}{sup 2+} among many metals owing to the AIE phenomenon. • TPE-T showed a wide effective pH range, high selectivity and good anti-interference qualities. • TPE-T showed good accuracy in the determination of uranyl in river water. - Abstract: A novel tetraphenylethene-based fluorescent sensor, TPE-T, was developed for the detection of uranyl ions. The selective binding of TPE-T to uranyl ions resulted in a detectable signal owing to the quenching of its aggregation-induced emission. The developed sensor could be used to visually distinguish UO{sub 2}{sup 2+} from lanthanides, transition metals, and alkali metals under UV light; the presence of other metal ions did not interfere with the detection of uranyl ions. In addition, TPE-T was successfully used for the detection of uranyl ions in river water, illustrating its potential applications in environmental systems.

Luminescent properties of Europium(III) nitrate with 1,10-phenantroline and cinnamic acid in light - Transforming polymer materials

Science.gov (United States)

Kalinovskaya, I. V.; Zadorozhnaya, A. N.

2018-04-01

Influence of cinnamic acid on the luminescent properties of the europium(III) nitrate with 1,10-phenantroline in a polymer materials was studied. It was shown that combined use of these rare earth complexes leads to intense luminescence in the 400-700 nm region. Samples containing polymer europium nitrate with 1,10-phenantroline and cinnamic acid at a molar ratio of 1:2,0 had the maximum luminescence intensity and photostability.

Drying of residue and separation of nitrate salts in the sludge waste for the lagoon sludge treatment

International Nuclear Information System (INIS)

Hwang, D. S.; Lee, K. I.; Choi, Y. D.; Hwang, S. T.; Park, J. H.

2003-01-01

This study investigated the dissolution property of nitrate salts in the dissolution process by water and the drying property of residue after separating nitrates in a series of the processes for the sludge treatment. Desalination was carried out with the adding ratio of water and drying property was analyzed by TG/DTA, FTIR, and XRD. Nitrate salts involved in the sludge were separated over 97% at the water adding ratio of 2.5. But a small quantity of calcium and sodium nitrate remained in the residue These were decomposed over 600 .deg. C and calcium carbonate, which was consisted mainly of residue, was decomposed into calcium oxide over 750 .deg. C. The residue have to be decomposed over 800 .deg. C to converse uranyl nitrate of six value into the stable U 3 O 8 of four value. As a result of removing the nitrates at the water adding ratio of 2.5 and drying the residue over 900 .deg. C, volume of the sludge waste decreased over 80%

Evaluation of the stability of uranyl peroxo-carbonato complex ions in carbonate media at different temperatures

International Nuclear Information System (INIS)

Kim, Kwang-Wook; Lee, Keun-Young; Chung, Dong-Yong; Lee, Eil-Hee; Moon, Jei-Kwon; Shin, Dong-Woo

2012-01-01

Highlights: ► The stability of peroxide in uranyl peroxo carbonato complex solutions with different temperatures was characterized. ► The decomposition rate of uranyl peroxo carbonato complex ion to uranyl tris-carbonato complex ion was observed to increase with temperature ► The decomposition kinetics of uranyl peroxo carbonato complex ions was evaluated by absorption and Raman spectroscopies. ► A precipitate of uranyl peroxo carbonato complex solution was evaluated with XRD. - Abstract: This work studied the stability of peroxide in uranyl peroxo carbonato complex ions in a carbonate solution with hydrogen peroxide using absorption and Raman spectroscopies, and evaluated the temperature dependence of the decomposition characteristics of uranyl peroxo carbonato complex ions in the solution. The uranyl peroxo carbonato complex ions self-decomposed more rapidly into uranyl tris-carbonato complex ions in higher temperature carbonate solutions. The concentration of peroxide in the solution without free hydrogen peroxide represents the concentration of uranyl peroxo carbonato complex ions in a mixture of uranyl peroxo carbonato complex and uranyl tris-carbonato complex ions. The self-decomposition of the uranyl peroxo carbonato complex ions was a first order reaction, and its activation energy was evaluated to be 7.144 × 10 3 J mol −1 . The precipitation of sodium uranium oxide hydroxide occurred when the amount of uranyl tris-carbonato complex ions generated from the decomposition of the uranyl peroxo carbonato complex ions exceeded the solubility of uranyl tris-carbonato ions in the solution at the solution temperature.

Sorption of uranyl ions on hydrous silicon dioxide

International Nuclear Information System (INIS)

Lieser, K.H.; Quandt-Klenk, S.; Thybusch, B.

1992-01-01

Sorption of uranyl ions on SiO 2 .χH 2 O (silica gel) is investigated in absence and in presence of carbonate as function of pH. The curves obtained are very similar to those observed for sorption of uranyl ion on TiO 2 .χH 2 O, indicating the dominating influence of the uranium species in solution. Between pH 2 and 5 the sorption ratio R s increases with hydrolysis of uranyl ions (formation of UO 2 OH + ), around pH 7 it is nearly independent of pH, and at higher pH it decreases again. The equilibrium constants are calculated for these ranges. In presence of carbonate R s decreases drastically above pH 6, due to the formation of carbonato complexes in solution. Sorption of uranyl ions on SiO 2 .χH 2 O, on TiO 2 .χH 2 O, and on cryst. SiO 2 and Al 2 O 3 is compared. The problems of 'surface complexation' modelling are discussed. (orig.)

Evaluation of the stability of uranyl peroxo-carbonato complex ions in carbonate media at different temperatures

Energy Technology Data Exchange (ETDEWEB)

Kim, Kwang-Wook, E-mail: nkwkim@kaeri.re.kr [Korea Atomic Energy Research Institute, 1045 Daedeok daero, Yuseong, Daejeon 305-353 (Korea, Republic of); Lee, Keun-Young; Chung, Dong-Yong; Lee, Eil-Hee; Moon, Jei-Kwon [Korea Atomic Energy Research Institute, 1045 Daedeok daero, Yuseong, Daejeon 305-353 (Korea, Republic of); Shin, Dong-Woo [Gyeongsang National University, 900 Gajwa, Jinju 660-701 (Korea, Republic of)

2012-09-30

Highlights: Black-Right-Pointing-Pointer The stability of peroxide in uranyl peroxo carbonato complex solutions with different temperatures was characterized. Black-Right-Pointing-Pointer The decomposition rate of uranyl peroxo carbonato complex ion to uranyl tris-carbonato complex ion was observed to increase with temperature Black-Right-Pointing-Pointer The decomposition kinetics of uranyl peroxo carbonato complex ions was evaluated by absorption and Raman spectroscopies. Black-Right-Pointing-Pointer A precipitate of uranyl peroxo carbonato complex solution was evaluated with XRD. - Abstract: This work studied the stability of peroxide in uranyl peroxo carbonato complex ions in a carbonate solution with hydrogen peroxide using absorption and Raman spectroscopies, and evaluated the temperature dependence of the decomposition characteristics of uranyl peroxo carbonato complex ions in the solution. The uranyl peroxo carbonato complex ions self-decomposed more rapidly into uranyl tris-carbonato complex ions in higher temperature carbonate solutions. The concentration of peroxide in the solution without free hydrogen peroxide represents the concentration of uranyl peroxo carbonato complex ions in a mixture of uranyl peroxo carbonato complex and uranyl tris-carbonato complex ions. The self-decomposition of the uranyl peroxo carbonato complex ions was a first order reaction, and its activation energy was evaluated to be 7.144 Multiplication-Sign 10{sup 3} J mol{sup -1}. The precipitation of sodium uranium oxide hydroxide occurred when the amount of uranyl tris-carbonato complex ions generated from the decomposition of the uranyl peroxo carbonato complex ions exceeded the solubility of uranyl tris-carbonato ions in the solution at the solution temperature.

Probing the influence of N-donor capping ligands on supramolecular assembly in molecular uranyl materials

Energy Technology Data Exchange (ETDEWEB)

Carter, Korey P.; Kalaj, Mark; Cahill, Christopher L. [Department of Chemistry, The George Washington University, Washington, DC (United States)

2016-01-15

The syntheses and crystal structures of six new compounds containing the UO{sub 2}{sup 2+} cation, 3,5-dichlorobenzoic acid, and a chelating N-donor [2,2'-bipyridine (bipy), 1,10-phenanthroline (phen), 4,7-dimethyl-1,10-phenanthroline (dimethylphen), 2,2{sup '}:6{sup '},2''-terpyridine (terpy), 4{sup '}-chloro-2,2{sup '}:6{sup '},2''-terpyridine (Cl-terpy), or 2,4,6-tris(2-pyridyl)-s-triazine (TPTZ)] are reported. Single-crystal X-ray diffraction analysis of these materials enabled the exploration of the structural relationship between the benzoic acids and the chelating N-donor as well as providing a platform to evaluate the effects of ligand choice on uranyl hydrolysis and subsequent oligomerization. At an unadjusted pH (ca. 3), a mix of uranyl monomers and dimers are observed, dimer formation resulting from both bridging carboxylate linkers and hydroxo bridges. Assembly by halogen- and hydrogen-bonding interactions as well as π-π interactions was observed depending on the experimental conditions utilized. Further, spectroscopic characterization (both vibrational and luminescence) of complexes 1, 4, and 5 to explore the effects of the electron-donating ability of the capping ligand on the corresponding uranyl luminescence and vibrational spectra suggests that there is a relationship between the observed bathochromic shifts and the electron-donating ability of the capping ligands. (Copyright copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Probing the influence of N-donor capping ligands on supramolecular assembly in molecular uranyl materials

International Nuclear Information System (INIS)

Carter, Korey P.; Kalaj, Mark; Cahill, Christopher L.

2016-01-01

The syntheses and crystal structures of six new compounds containing the UO 2 2+ cation, 3,5-dichlorobenzoic acid, and a chelating N-donor [2,2'-bipyridine (bipy), 1,10-phenanthroline (phen), 4,7-dimethyl-1,10-phenanthroline (dimethylphen), 2,2 ' :6 ' ,2''-terpyridine (terpy), 4 ' -chloro-2,2 ' :6 ' ,2''-terpyridine (Cl-terpy), or 2,4,6-tris(2-pyridyl)-s-triazine (TPTZ)] are reported. Single-crystal X-ray diffraction analysis of these materials enabled the exploration of the structural relationship between the benzoic acids and the chelating N-donor as well as providing a platform to evaluate the effects of ligand choice on uranyl hydrolysis and subsequent oligomerization. At an unadjusted pH (ca. 3), a mix of uranyl monomers and dimers are observed, dimer formation resulting from both bridging carboxylate linkers and hydroxo bridges. Assembly by halogen- and hydrogen-bonding interactions as well as π-π interactions was observed depending on the experimental conditions utilized. Further, spectroscopic characterization (both vibrational and luminescence) of complexes 1, 4, and 5 to explore the effects of the electron-donating ability of the capping ligand on the corresponding uranyl luminescence and vibrational spectra suggests that there is a relationship between the observed bathochromic shifts and the electron-donating ability of the capping ligands. (Copyright copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Radiation-induced nitration of organic compounds in aqueous solutions

International Nuclear Information System (INIS)

Ershov, B.G.; Gordeev, A.V.; Bykov, G.L.; Moisy, P.

2012-01-01

Radiolysis in aqueous nitrate and acetic acid solutions and nitrate/nitric acid and phenol was studied. The radiolysis of these solutes occurs with circle NO 2 radical, which is the active nitrating agent. Accumulation of nitromethane and nitrite was determined during γ-irradiation of aqueous solutions containing acetic and nitrate solutions. Irradiation of aqueous phenol-nitrate/nitric acid solutions results in the formation of 2- and 4-nitrophenols.

Radiation-induced nitration of organic compounds in aqueous solutions

Energy Technology Data Exchange (ETDEWEB)

Ershov, B.G.; Gordeev, A.V.; Bykov, G.L. [Russian Academy of Sciences, Moscow (Russian Federation). Frumkin Inst. of Physical Chemistry and Electrochemistry; Moisy, P. [CEA, Bagnols sur Ceze (France). Nuclear Energy Div.

2012-07-01

Radiolysis in aqueous nitrate and acetic acid solutions and nitrate/nitric acid and phenol was studied. The radiolysis of these solutes occurs with {sup circle} NO{sup 2} radical, which is the active nitrating agent. Accumulation of nitromethane and nitrite was determined during {gamma}-irradiation of aqueous solutions containing acetic and nitrate solutions. Irradiation of aqueous phenol-nitrate/nitric acid solutions results in the formation of 2- and 4-nitrophenols.

Method for loading resin beds

International Nuclear Information System (INIS)

Notz, K.J.; Rainey, R.H.; Greene, C.W.; Shockley, W.E.

1978-01-01

An improved method of preparing nuclear reactor fuel by carbonizing a uranium loaded cation exchange resin provided by contacting a H+ loaded resin with a uranyl nitrate solution deficient in nitrate, comprises providing the nitrate deficient solution by a method comprising the steps of reacting in a reaction zone maintained between about 145 to 200 0 C, a first aqueous component comprising a uranyl nitrate solution having a boiling point of at least 145 0 C with a second aqueous component to provide a gaseous phase containing HNO 3 and a reaction product comprising an aqueous uranyl nitrate solution deficient in nitrate

Aggregation-induced emission active tetraphenylethene-based sensor for uranyl ion detection.

Science.gov (United States)

Wen, Jun; Huang, Zeng; Hu, Sheng; Li, Shuo; Li, Weiyi; Wang, Xiaolin

2016-11-15

A novel tetraphenylethene-based fluorescent sensor, TPE-T, was developed for the detection of uranyl ions. The selective binding of TPE-T to uranyl ions resulted in a detectable signal owing to the quenching of its aggregation-induced emission. The developed sensor could be used to visually distinguish UO2(2+) from lanthanides, transition metals, and alkali metals under UV light; the presence of other metal ions did not interfere with the detection of uranyl ions. In addition, TPE-T was successfully used for the detection of uranyl ions in river water, illustrating its potential applications in environmental systems. Copyright © 2016 Elsevier B.V. All rights reserved.

The state of uranyl ions in water-dioxane solvent mixtures

International Nuclear Information System (INIS)

Geipel, G.; Nebel, D.; Baraniak, L.

1985-01-01

A comparison of the spectra of uranyl ions in HCl and dioxane solutions leads to the conclusion that dioxane promotes complex formation. The investigation of spectra showed that taking into account the hydrolysis of uranyl ions in dioxane containing solutions, two successive equilibrium reactions take place. The formation constants were determined. Conductivity measurements confirmed the spectrophotometrically determined equilibria. In solutions containing up to 60 % dioxane there is no incorporation of dioxane in the solvating envelope of the uranyl ion. (author)

A novel stable 3D luminescent uranyl complex for highly efficient and sensitive recognition of Ru3+ and biomolecules

Science.gov (United States)

Tian, Hong-Hong; Chen, Liang-Ting; Zhang, Rong-Lan; Zhao, Jian-She; Liu, Chi-Yang; Weng, Ng Seik

2018-02-01

A novel highly stable 3D luminescent uranyl coordination polymer, namely {[UO2(L)]·DMA}n (1), was assembled with uranyl salt and a glycine-derivative ligand [6-(carboxymethyl-amino)-4-oxo-4,5-dihydro-[1,3,5]triazin-2-ylamino]-acetic acid (H2L) under solvothermal reaction. Besides, It was found that complex 1 possesses excellent luminescent properties, particularly the efficient selectivity and sensitivity in the recognition of Ru3+, biomacromolecule bovine serum albumin (BSA), biological small molecules dopamine (DA), ascorbic acid (AA) and uric acid (UA) in the water solution based on a "turn-off" mechanism. Accordingly, the luminescent explorations also demonstrated that complex 1 could be acted as an efficient luminescent probe with high quenching efficiency and low detection limit for selectively detecting Ru3+ and biomolecules (DA, AA, UA and BSA). It was noted that the framework structure of complex 1 still remains highly stable after quenching, which was verified by powder X-ray diffraction (PXRD).

Evaluation of the stability of uranyl peroxo-carbonato complex ions in carbonate media at different temperatures.

Science.gov (United States)

Kim, Kwang-Wook; Lee, Keun-Young; Chung, Dong-Yong; Lee, Eil-Hee; Moon, Jei-Kwon; Shin, Dong-Woo

2012-09-30

This work studied the stability of peroxide in uranyl peroxo carbonato complex ions in a carbonate solution with hydrogen peroxide using absorption and Raman spectroscopies, and evaluated the temperature dependence of the decomposition characteristics of uranyl peroxo carbonato complex ions in the solution. The uranyl peroxo carbonato complex ions self-decomposed more rapidly into uranyl tris-carbonato complex ions in higher temperature carbonate solutions. The concentration of peroxide in the solution without free hydrogen peroxide represents the concentration of uranyl peroxo carbonato complex ions in a mixture of uranyl peroxo carbonato complex and uranyl tris-carbonato complex ions. The self-decomposition of the uranyl peroxo carbonato complex ions was a first order reaction, and its activation energy was evaluated to be 7.144×10(3) J mol(-1). The precipitation of sodium uranium oxide hydroxide occurred when the amount of uranyl tris-carbonato complex ions generated from the decomposition of the uranyl peroxo carbonato complex ions exceeded the solubility of uranyl tris-carbonato ions in the solution at the solution temperature. Copyright © 2012 Elsevier B.V. All rights reserved.

Structure and dynamics of aqueous solution of uranyl ions

International Nuclear Information System (INIS)

Chopra, Manish; Choudhury, Niharendu

2014-01-01

The present work describes a molecular dynamics simulation study of structure and dynamics of aqueous solution of uranyl ions in water. Structural properties of the system in terms of radial distribution functions and dynamical characteristics as obtained through velocity autocorrelation function and mean square displacements have been analyzed. The results for radial distribution functions show the oxygen of water to form the first solvation shell at 2.4 Å around the uranium atom, whereas the hydrogen atoms of water are distributed around the uranium atom with the major peak at around 3.0 Å. Analyses of transport behaviors of ions and water through MSD indicates that the diffusion of the uranyl ion is much less as compared to that of the water molecules. It is also observed that the dynamical behavior of water molecules gets modified due to the presence of uranyl ion. The effect of increase in concentration of uranyl ions on the structure and dynamics of water molecules is also studied

Loading ion exchange resins with uranium for HTGR fuel kernels

International Nuclear Information System (INIS)

Notz, K.J.; Greene, C.W.

1976-12-01

Uranium-loaded ion exchange beads provide an excellent starting material in the production of uranium carbide microspheres for nuclear fuel applications. Both strong-acid (sulfonate) and weak-acid (carboxylate) resins can be fully loaded with uranium from a uranyl nitrate solution utilizing either a batch method or a continuous column technique

Activation of Graphene Oxide with Hydrochloric Acid for Nitrate Removal from Aqueous Solutions

Directory of Open Access Journals (Sweden)

Abolghasem Alighardashi

2017-11-01

Full Text Available Long-term drinking of nitrate-contaminated water poses a serious risk to human health. The present study explores the possibility of enhancing the adsorption capacity of graphene oxide via activation with hydrochloric acid for nitrate removal from aqueous solutions. Experiments were performed in a batch reactor in which such major factors as pH, reaction time, and concentrations of both graphene oxide (GO and activated graphene oxide (AGO were used as variables. Nitrate removal efficiency was investigated using the One-Way ANOVA statistical test and SPSS-16 software. The chemical composition and solid structure of the synthesized AGO were analyzed using FE-SEM coupled with energy dispersive spectrometry (EDS. The micropore volumes of the samples were determined using the BET and BJH. The predominant composition (52% of the synthesized AGO was C and its mean pore diameter was 26.896 nm. The maximum adsorption capacity of AGO was estimated at 3333.33 mg/g. Based on the results, the AGO nano-structure may be recomended as a new means for nitrate removal from aqueous solutions.

Comparative study of uranyl(VI) and -(V) carbonato complexes in an aqueous solution.

Science.gov (United States)

Ikeda, Atsushi; Hennig, Christoph; Tsushima, Satoru; Takao, Koichiro; Ikeda, Yasuhisa; Scheinost, Andreas C; Bernhard, Gert

2007-05-14

Electrochemical, complexation, and electronic properties of uranyl(VI) and -(V) carbonato complexes in an aqueous Na2CO3 solution have been investigated to define the appropriate conditions for preparing pure uranyl(V) samples and to understand the difference in coordination character between UO22+ and UO2+. Cyclic voltammetry using three different working electrodes of platinum, gold, and glassy carbon has suggested that the electrochemical reaction of uranyl(VI) carbonate species proceeds quasi-reversibly. Electrolysis of UO22+ has been performed in Na2CO3 solutions of more than 0.8 M with a limited pH range of 11.7 < pH < 12.0 using a platinum mesh electrode. It produces a high purity of the uranyl(V) carbonate solution, which has been confirmed to be stable for at least 2 weeks in a sealed glass cuvette. Extended X-ray absorption fine structure (EXAFS) measurements revealed the structural arrangement of uranyl(VI) and -(V) tricarbonato complexes, [UO2(CO3)3]n- [n = 4 for uranyl(VI), 5 for uranyl(V)]. The bond distances of U-Oax, U-Oeq, U-C, and U-Odist are determined to be 1.81, 2.44, 2.92, and 4.17 A for the uranyl(VI) complex and 1.91, 2.50, 2.93, and 4.23 A for the uranyl(V) complex, respectively. The validity of the structural parameters obtained from EXAFS has been supported by quantum chemical calculations for the uranyl(VI) complex. The uranium LI- and LIII-edge X-ray absorption near-edge structure spectra have been interpreted in terms of electron transitions and multiple-scattering features.

Selectivity in Ligand Binding to Uranyl Compounds: A Synthetic, Structural, Thermodynamic and Computational Study

Energy Technology Data Exchange (ETDEWEB)

Arnold, John [Univ. of California, Berkeley, CA (United States)

2017-12-06

The uranyl cation (UO₂²⁺) is the most abundant form of uranium on the planet. It is estimated that 4.5 billion tons of uranium in this form exist in sea water. The ability to bind and extract the uranyl cation from aqueous solution while separating it from other elements would provide a limitless source of nuclear fuel. A large body of research concerns the selective recognition and extraction of uranyl. A stable molecule, the cation has a linear O=U=O geometry. The short U-O bonds (1.78 Å) arise from the combination of uranium 5f/6d and oxygen 2p orbitals. Due to the oxygen moieties being multiply bonded, these sites were not thought to be basic enough for Lewis acidic coordination to be a viable approach to sequestration. We believe that the goal of developing a practical system for uranium separation from seawater will not be attained without new insights into our existing fundamental knowledge of actinide chemistry. We posit that detailed studies of the kinetic and thermodynamic factors that influence interactions between f-elements and ligands with a range of donor atoms is essential to any major advance in this important area. The goal of this research is thus to broaden the coordination chemistry of the uranyl ion by studying new ligand systems via synthetic, structural, thermodynamic and computational methods. We anticipate that this fundamental science will find use beyond actinide separation technologies in areas such as nuclear waste remediation and nuclear materials.

Thermal decomposition of uranyl sulphate hydrate

International Nuclear Information System (INIS)

Sato, T.; Ozawa, F.; Ikoma, S.

1980-01-01

The thermal decomposition of uranyl sulphate hydrate (UO 2 SO 4 .3H 2 O) has been investigated by thermogravimetry, differential thermal analysis, X-ray diffraction and infrared spectrophotometry. As a result, it is concluded that uranyl sulphate hydrate decomposes thermally: UO 2 SO 4 .3H 2 O → UO 2 SO 4 .xH 2 O(2.5 = 2 SO 4 . 2H 2 O → UO 2 SO 4 .H 2 O → UO 2 SO 4 → α-UO 2 SO 4 → β-UO 2 SO 4 → U 3 O 8 . (author)

Electronic spectra of plutonium ions in nitric acid and in lithium nitrate solutions

International Nuclear Information System (INIS)

Mekhail, F.M.

1987-01-01

The absorption spectra of plutonium ions in nitric acid have been described. There is a characteristic change in the absorption spectra of Pu v in lithium nitrate solutions. In 2 M-lithium nitrate a new peak at 969 nm and high absorption at 1200 nm are noticed. A decrease in the absorption by about 20% and the appearance of a new shoulder at 1120 nm in 6 M-lithium nitrate are found. There is no change in the spectrum in 4 M-lithium nitrate. The absorption spectra of plutonium ions in the spectral range 200 - 400 nm are interesting. All plutonium ions have an intense band in the region 250 - 260 nm as well as a less intense and rather diffuse band at 320 - 330 nm in lithium nitrate solutions the sharp band at 250 - 260 nm has disappeared. This suggests that this band is very sensitive to the environmental field. The band is probably produced by 5 F q → 5 f q-1 6 d transition as well as electron transfer. It is believed that the spectrum of Pu V at pH 6.5 represents the hydrolysis product Pu O 2 (O H). 9 fig., 4 tab

Nitrate Activation of Cytosolic Protein Kinases Diverts Photosynthetic Carbon from Sucrose to Amino Acid Biosynthesis

Science.gov (United States)

Champigny, Marie-Louise; Foyer, Christine

1992-01-01

The regulation of carbon partitioning between carbohydrates (principally sucrose) and amino acids has been only poorly characterized in higher plants. The hypothesis that the pathway of sucrose and amino acid biosynthesis compete for carbon skeletons and energy is widely accepted. In this review, we suggest a mechanism involving the regulation of cytosolic protein kinases whereby the flow of carbon is regulated at the level of partitioning between the pathways of carbohydrate and nitrogen metabolism via the covalent modulation of component enzymes. The addition of nitrate to wheat seedlings (Triticum aestivum) grown in the absence of exogenous nitrogen has a dramatic, if transient, impact on sucrose formation and on the activities of sucrose phosphate synthase (which is inactivated) and phosphoenolpyruvate carboxylase (which is activated). The activities of these two enzymes are modulated by protein phosphorylation in response to the addition of nitrate, but they respond in an inverse fashion. Sucrose phosphate synthase in inactivated and phosphoenolpyruvate carboxylase is activated. Nitrate functions as a signal metabolite activating the cytosolic protein kinase, thereby modulating the activities of at least two of the key enzymes in assimilate partitioning and redirecting the flow of carbon away from sucrose biosynthesis toward amino acid synthesis. PMID:16653003

Structural study of the uranyl and rare earth complexation functionalized by the CMPO; Etude structurale de la complexation de l'uranyle et des ions lanthanides par des calixarenes fonctionnalises par le CMPO

Energy Technology Data Exchange (ETDEWEB)

Cherfa, S

1998-12-10

In view of reducing the volume of nuclear waste solutions, a possible way is to extract simultaneously actinide and lanthanide ions prior to their ulterior separation.. Historically, the two extractant families used for nuclear waste reprocessing are the phosphine oxides and the CMPO (Carbamoyl Methyl Phosphine Oxide). For a better understanding of the complexes formed during extraction, we undertook structural studies of the complexes formed between uranyl and lanthanide (III) ions and the two classes of ligands cited above. These studies have been performed by X-ray diffraction on single crystals. Recently, a new type of extractants of lanthanide (III) and actinide (III) ions has been developed. When the Organic macrocycle called calixarene (an oligomeric compound resulting from the poly-condensation of phenolic units) is functionalized by a CMPO ligand, the extracting power, in terms of yield and selectivity towards lightest lanthanides, is greatly enhanced compared to the one measured for the single CMPO. Our X-ray diffraction studies allowed us to characterise, in terms of stoichiometry and monodentate or bidentate coordination mode of the CMPO functions, the complexes of calix[4]arene-CMPO (with four phenolic units) with lanthanide nitrates and uranyl. These different steps of characterisation enabled us to determine the correlation between the structures of the complexes and both selectivity and exacerbation of the extracting power measured in the liquid phase. (author)

Complex formation between uranyl and various thiosemicarbazide derivatives

International Nuclear Information System (INIS)

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

1987-01-01

Complex formation between hexavalent uranium and salicylaldehyde thiosemicarbazone (H 2 L), salicylaldehyde S-methyl-isothiosemicarbazone (H 2 Q), S-methyl-N 1 ,N 4 -bis(salicylidene)isothiosemicarbazide(H 2 Z), and thiosemicarbazidodiacetic acid (H 2 R) has been studied spectrophotometrically in solution. Stability constants for complexes having the composition UO 2 A have been calculated. Solid uranyl derivatives having the composition UO 2 L x 2H 2 O, UO 2 Q x 2H 2 O, UO 2 Z x 2H 2 O, and UO 2 R x 2H 2 O have been obtained. These derivatives were isolated and their IR spectroscopic behavior and thermal properties were investigated

Structural contributions to the third-law entropy of uranyl phases

International Nuclear Information System (INIS)

Chen, F.; Ewing, R.C.

1999-01-01

Entropies that are used in geochemical calculations are usually based on calorimetric measurements. However, because of the contributions of neglected residual entropies which cannot be determined by calorimetric measurements, the true third-law entropies for many phases may be quite different from those derived from thermal data. The residual entropies are caused by site-mixing, structural disorder and magnetic spin disorder and may result in a considerable contribution to the third-law entropy of solid phases. Magnetic spin-configurational entropy is not expected to be significant in uranyl phases. However, because most uranyl phases are based on sheet or chain structures and usually contain several molecular water groups, site-mixing, vacancies, as well as disorder in the orientation of hydrogen bonds and the polar H 2 O molecules may occur. Calculations of the ideal site-mixing configurational entropy for some uranyl phases indicate that the residual contributions that arise from substitution and vacancies to the third-law entropies of uranyl phases may be large. A brief examination of the crystal chemistry of water molecules in uranyl phases suggests that considerable residual entropy may be caused by the disorder of hydrogen bonds associated with interstitial H 2 O groups

Catalytic effects of inorganic acids on the decomposition of ammonium nitrate.

Science.gov (United States)

Sun, Jinhua; Sun, Zhanhui; Wang, Qingsong; Ding, Hui; Wang, Tong; Jiang, Chuansheng

2005-12-09

In order to evaluate the catalytic effects of inorganic acids on the decomposition of ammonium nitrate (AN), the heat releases of decomposition or reaction of pure AN and its mixtures with inorganic acids were analyzed by a heat flux calorimeter C80. Through the experiments, the different reaction mechanisms of AN and its mixtures were analyzed. The chemical reaction kinetic parameters such as reaction order, activation energy and frequency factor were calculated with the C80 experimental results for different samples. Based on these parameters and the thermal runaway models (Semenov and Frank-Kamenestkii model), the self-accelerating decomposition temperatures (SADTs) of AN and its mixtures were calculated and compared. The results show that the mixtures of AN with acid are more unsteady than pure AN. The AN decomposition reaction is catalyzed by acid. The calculated SADTs of AN mixtures with acid are much lower than that of pure AN.

Feeding nitrate and docosahexaenoic acid affects enteric methane production and milk fatty acid composition in lactating dairy cows

NARCIS (Netherlands)

Klop, G.; Hatew, B.; Bannink, A.; Dijkstra, Jan

2016-01-01

An experiment was conducted to study potential interaction between the effects of feeding nitrate and docosahexaenoic acid (DHA; C22:6 n-3) on enteric CH₄ production and performance of lactating dairy cows. Twenty-eight lactating Holstein dairy cows were grouped into 7 blocks of 4

Hydrothermal Phase Relations Among Uranyl Minerals at the Nopal I Analog Site

International Nuclear Information System (INIS)

Murphy, William M.

2007-01-01

Uranyl mineral paragenesis at Nopal I is an analog of spent fuel alteration at Yucca Mountain. Petrographic studies suggest a variety of possible hydrothermal conditions for uranium mineralization at Nopal I. Calculated equilibrium phase relations among uranyl minerals show uranophane stability over a broad range of realistic conditions and indicate that uranyl mineral variety reflects persistent chemical potential heterogeneity. (author)

Headspace Analysis of Ammonium Nitrate

Science.gov (United States)

2017-01-25

explosive ammonium nitrate produces ammonia and nitric acid in the gaseous headspace above bulk solids, but the concentrations of the products have been...and NO2-, a product of nitrate fragmentation (Figure 7). Brief spikes in the background and dips in oxalic acid signal were observed at the time of...either filtered air or experimental nitric acid vapor sources so that analyte signal could be measured directly opposite background. With oxalic

Syntheses and crystal structures of two novel alkaline uranyl chromates A2(UO2)(CrO4)2 (A=Rb, Cs) with bidentate coordination mode of uranyl ions by chromate anions

International Nuclear Information System (INIS)

Siidra, Oleg I.; Nazarchuk, Evgeny V.; Krivovichev, Sergey V.

2012-01-01

Single crystals of Cs 2 (UO 2 )(CrO 4 ) 2 and Rb 2 (UO 2 )(CrO 4 ) 2 were prepared by solid state reactions. The structures are based upon the [(UO 2 )(CrO 4 ) 2 ] 2− chains. Within the chains, UrO 5 pentagonal bipyramids (Ur=uranyl) form Ur 2 O 8 dimers, which are linked via CrO 4 tetrahedra into one-dimensional chains. The CrO 4 tetrahedra coordinate uranyl ions in both mono- and bidentate fashion, which is unusual for uranyl chromates. The bidentate coordination has a strong influence upon geometrical parameters of both U and Cr coordination polyhedra. The conformation of the chains in 1 and 2 is different due to the different size of the Cs + and Rb + cations. - Graphical abstract: Uranyl chromate chain with monodentate and bidentate coordination mode of uranyl cations by CrO 4 tetrahedra in Cs 2 (UO 2 )(CrO 4 ) 2 . Highlights: ► Single crystals of novel uranyl chromates were prepared by solid state reactions. ► The CrO 4 tetrahedra coordinate uranyl ions in both mono- and bidentate fashion. ►The bidentate coordination has a strong influence upon geometrical parameters.

Density functional study of uranyl (VI) amidoxime complexes

International Nuclear Information System (INIS)

Chi Fang-Ting; Xiong Jie; Hu Sheng; Xia Xiu-Long; Wang Xiao-Lin; Li Peng; Gao Tao

2012-01-01

Uranyl (VI) amidoxime complexes are investigated using relativistic density functional theory. The equilibrium structures, bond orders, and Mulliken populations of the complexes have been systematically investigated under a generalized gradient approximation (GGA). Comparison of (acet) uranyl amidoxime complexes ([UO 2 (AO) n ] 2−n , 1 ≤ n ≤ 4) with available experimental data shows an excellent agreement. In addition, the U−O(1), U−O(3), C(1)−N(2), and C(3)−N(4) bond lengths of [UO 2 (CH 3 AO) 4 ] 2− are longer than experimental data by about 0.088, 0.05, 0.1, and 0.056 Å. The angles of N(3)−O(3)−U, O(2)−N(1)−C(1), N(3)−C(3)−N(4), N(4)−C(3)−C(4), and C(4)−C(3)−N(3) are different from each other, which is due to existing interaction between oxygen in uranyl and hydrogen in amino group. This interaction is found to be intra-molecular hydrogen bond. Studies on the bond orders, Mulliken charges, and Mulliken populations demonstrate that uranyl oxo group functions as hydrogen-bond acceptors and H atoms in ligands act as hydrogen-bond donors forming hydrogen bonds within the complex

Theoretical insights into the uranyl adsorption behavior on vanadium carbide MXene

Science.gov (United States)

Zhang, Yu-Juan; Zhou, Zhang-Jian; Lan, Jian-Hui; Ge, Chang-Chun; Chai, Zhi-Fang; Zhang, Peihong; Shi, Wei-Qun

2017-12-01

Remediation of the contamination by long-lived actinide wastes is extremely important but also challenging. Adsorption based techniques have attracted much research attention for their potential as low-cost and effective methods to reduce the radioactive waste from solution. In this work, we have investigated the adsorption behavior of uranyl species [with the general form UO2(L1)x(L2)y(L3)z, where L1, L2 and L3 stand for ligands H2O, OH and CO3, respectively] on hydroxylated vanadium carbide V2C(OH)2 MXene nanosheets using density functional theory based simulation methods We find that all studied uranyl species can stably bond to hydroxylated MXene with binding energies ranging from -3.3 to -4.6 eV, suggesting that MXenes could be effective adsorbers for uranyl ions. The strong adsorption is achieved by forming two Usbnd O bonds with the hydroxylated Mxene. In addition, the axial oxygen atoms from the uranyl ions form hydrogen bonds with the hydroxylated V2C, further strengthening the adsorption. We have also investigated the effects of F termination on the uranyl adsorption properties of V2C nanosheets. Usbnd F bonds are in general weaker than Usbnd O bonds on the adsorption site, suggesting that F terminated Mexne is less favorable for uranyl adsorption applications.

Probing uranyl(VI) speciation in the presence of amidoxime ligands using electrospray ionization mass spectrometry.

Science.gov (United States)

Mustapha, Adetayo M; Pasilis, Sofie P

2013-10-15

Extraction processes using poly(acrylamidoxime) resins are being developed to extract uranium from seawater. The main complexing agents in these resins are thought to be 2,6-dihydroxyiminopiperidine (DHIP) and N(1),N(5)-dihydroxypentanediimidamide (DHPD), which form strong complexes with uranyl(VI) at the pH of seawater. It is important to understand uranyl(VI) speciation in the presence of these and similar amidoxime ligands to understand factors affecting uranyl(VI) adsorption to the poly(acrylamidoxime) resins. Experiments were carried out in positive ion mode on a quadrupole ion trap mass spectrometer equipped with an electrospray ionization source. The ligands investigated were DHIP, DHPD, and N(1),N(2)-dihydroxyethanediimidamide (DHED). DHED and DHPD differ only in the number of carbons separating the oxime groups. The effects on the mass spectra of changes in uranyl(VI):ligand ratio, pH, and ligand type were examined. DHIP binds uranyl(VI) more effectively than DHPD or DHED in the pH range investigated, forming ions derived from solution-phase species with uranyl(VI):DHIP stoichiometries of 1:1, 1:2, and 2:3. The 2:3 uranyl(VI):DHIP complex appears to be a previously undescribed solution species. Ions related to uranyl(VI):DHPD complexes were detected in very low abundance. DHED is a more effective complexing agent for uranyl(VI) than DHPD, forming ions having uranyl(VI):DHED stoichiometries of 1:1, 1:2, 1:3, and 2:3. This study presents a first look at the solution chemistry of uranyl(VI)-amidoxime complexes using electrospray ionization mass spectrometry. The appearance of previously undescribed solution species suggests that the uranyl-amidoxime system is a rich and relatively complex one, requiring a more in-depth investigation. Copyright © 2013 John Wiley & Sons, Ltd.

Efficient tetracycline adsorption and photocatalytic degradation of rhodamine B by uranyl coordination polymer

Science.gov (United States)

Ren, Ya-Nan; Xu, Wei; Zhou, Lin-Xia; Zheng, Yue-Qing

2017-07-01

Two mixed uranyl-cadmium malonate coordination polymers [(UO2)2Cd(H-bipy)2(mal)4(H2O)2]·4H2O 1 and [(UO2)Cd(bipy)(mal)2]·H2O 2 (H2mal = malonic acid, bipy =4,4‧-bipyridine) have been synthesized in room temperature. Compound 1 represents a one-dimensional (1D) chain assembly of Cd(II) ions, uranyl centers and malonate ligands. Compound 2 exhibits a two-dimensional (2D) 2D +2D → 3D polycatenated framework based on inclined interlocked 2D 44 sql grids. The two compounds have been characterized by elemental analysis, IR and UV-vis spectroscopy, thermal analysis, powder X-ray diffraction and photoluminescence spectroscopy. And the ferroelectric property of 2 also has been studied. Moreover, compound 2 exhibits good photocatalytic activity for dye degradation under UV light and is excellent adsorbent for removing tetracycline antibiotics in the aqueous solution.

Uranyl ion recovery from waste waters by microbiological collectors

International Nuclear Information System (INIS)

Cecal, Alexandru; Palamaru, Iliana; Navrotescu, Tinca

1995-01-01

This study deals with the bioaccumulation of uranyl ions from radioactive effluents by Scenedesmus quadricauda alga. From the experimental data one can observe a greater retaining capacity of uranyl ions after four days of contact time. Filtered uranium and alga content was determined by the arsenazo III spectrophotometric method. The colored compound was determined by using wavelength λ=665 nm. (authors)

Hydrothermal syntheses and characterization of uranyl tungstates with electro-neutral structural units

Energy Technology Data Exchange (ETDEWEB)

Balboni, Enrica; Burns, Peter C. [Univ. of Notre Dame, IN (United States). Dept. of Civil and Enviromental Engineering and Earth Sciences; Univ. of Notre Dame, IN (United States). Dept. of Chemistry and Biochemistry

2015-11-01

Two uranyl tungstates, (UO{sub 2})(W{sub 2}O{sub 7})(H{sub 2}O){sub 3} (1) and (UO{sub 2}){sub 3}(W{sub 2}O{sub 8})F{sub 2}(H{sub 2}O){sub 3} (2), were synthesized under hydrothermal conditions at 220 C and were structurally, chemically, and spectroscopically characterized. 1 Crystallizes in space group Pbcm, a = 6.673(5) Aa, b = 12.601(11) Aa, c = 11.552 Aa; 2 is in C2/m, a = 13.648(1) Aa, b = 16.852(1) Aa, c = 9.832(1) Aa, β = 125.980(1) {sup circle}. In 1 the U(VI) cations are present as (UO{sub 2}){sup 2+} uranyl ions that are coordinated by five oxygen atoms to give pentagonal bipyramids. These share two edges with two tungstate octahedra and single vertices with four additional octahedra, resulting in a sheet with the iriginite-type anion topology. Only water molecules are located in the interlayer. The structural units of 2 consist of (UO{sub 2}){sup 2+} uranyl oxy-fluoride pentagonal bipyramids present as either [UO{sub 2}F{sub 2}O{sub 3}]{sup -6} or [UO{sub 2}FO{sub 4}]{sup -5}, and strongly distorted tungstate octahedra. The linkage of uranyl pentagonal bipyramids and tungstate octahedra gives a unique sheet anion topology consisting of pentagons, squares and triangles. In 2, the uranyl tungstates sheets are connected into a novel electro-neutral three-dimensional framework through dimers of uranyl pentagonal bipyramids. These dimers connecting the sheets share an edge defined by F anions. 2 is the first example of a uranyl tungstate oxy-fluoride, and 1 and 2 are rare examples of uranyl compounds containing electro-neutral structural units.

Nephrotoxicity of uranyl acetate: effect on rat kidney brush border membrane vesicles

International Nuclear Information System (INIS)

Goldman, M.; Yaari, A.; Moran, A.; Doshnitzki, Z.; Cohen-Luria, R.

2006-01-01

Since the Gulf war exposure to depleted uranium, a known nephrotoxic agent, there is a renewed interest in the toxic effects of uranium in general and its mechanism of nephrotoxicity which is still largely unknown in particular. In order to investigate the mechanism responsible for uranium nephrotoxicity and the therapeutic effect of urine alkalization, we utilized rat renal brush border membrane vesicles (BBMV). Uranyl acetate (UA) caused a decrease in glucose transport in BBMV. The apparent K i of uranyl was 139±30 μg uranyl/mg protein of BBMV. Uranyl at 140 μg/mg protein of BBMV reduced the maximal capacity of the system to transport glucose [V max 2.2±0.2 and 0.96±0.16 nmol/mg protein for control and uranyl treated BBMV (P m (1.54±0.33 and 1.54±0.51 mM for control, and uranyl treated BBMV, respectively). This reduction in V max is at least partially due to a decrease in the number of sodium-coupled glucose transporters as apparent from the reduction in phlorizin binding to the uranyl treated membranes, V max was reduced from 247±13 pmol/mg protein in control BBMV to 119±3 pmol/mg protein in treated vesicles (P<0.001). The pH of the medium has a profound effect on the toxicity of UA on sodium-coupled glucose transport in BBMV: higher toxicity at neutral pH (around pH 7.0), and practically no toxicity at alkaline pH (7.6). This is the first report showing a direct inhibitory dose and pH dependent effect of uranyl on the glucose transport system in isolated apical membrane from kidney cortex. (orig.)

Thermochemical investigations on uranyl phosphates and arsenates

International Nuclear Information System (INIS)

Barten, H.

1986-01-01

Results are described of a study of the thermochemical stability of anhydrous phosphates and arsenates. The results of phase studies deal with compound formation and characterization, coexisting phases and limiting physical or chemical properties. The uranyl phosphates evolve oxygen at higher temperatures and the arsenates lose arsenic oxide vapour. These phenomena give the possibility to describe their thermodynamic stabilities. Thus oxygen pressures of uranyl phosphates have been measured using a static, non-isothermal method. Having made available the pure anhydrous compounds in the course of this investigation, molar thermodynamic quantities have been measured as well. These include standard enthalpies of formation from solution calorimetry and high-temperature heat-capacity functions derived from enthalpy increments measured. Some attention is given to compounds with uranium in valencies lower than six which have been met during the investigation. An evaluation is made of the thermodynamics of the compounds studied, to result in tabulized high-temperature thermodynamic functions. Relative stabilities within the systems are discussed and comparisons of the uranyl phosphates and the arsenates are made. (Auth.)

Synthesis of uranyl ion imprinted polymer and its application in analysis

International Nuclear Information System (INIS)

Xiao Jingshui; Liu Huijun; Xiao Xilin; Huang Shengli

2011-01-01

Uranyl ion imprinted polymer beads were prepared by the copolymerization of styrene monomer and divinyl benzene as crosslinking agent in methanol solution,with the UO 2 2+ -o-dihydroxybenzene-4-vinyl pyridine ternary complex as template, the 2, 2'-azo-bis-isobutyronitrile as initiator and UO 2 2+ as the imprinting ion. The uranyl ions were removed from the polymer beads by treating with 6 mol/L HCl, leaving behind cavities that match uranyl ion in size. The treated polymer beads can preconcentrate uranyl ions from dilute aqueous solutions. The adsorption efficiency can reach 99% or above with good selectivity when pH is in the range of 5-7 and the adsorption time is more than 20 min. The elution rate can reach above 99% under the conditions of concentration of HCl being above 1.0 mol/L, elution time more than 20 min and the elution Janume more than 5 times the Janume of ion imprinted polymer. The uranyl ion imprinted polymer beads have been successfully applied to determine micro-uranium in brine samples. The results are satisfactory compared with NBS method.(authors)

Structural observations of heterometallic uranyl copper(II) carboxylates and their solid-state topotactic transformation upon dehydration.

Science.gov (United States)

Olchowka, Jakub; Falaise, Clément; Volkringer, Christophe; Henry, Natacha; Loiseau, Thierry

2013-02-04

The hydrothermal reactions of uranyl nitrate and metallic copper with aromatic polycarboxylic acids gave rise to the formation of five heterometallic UO(2)(2+)-Cu(2+) coordination polymers: (UO(2))Cu(H(2)O)(2)(1,2-bdc)(2) (1; 1,2-bdc = phthalate), (UO(2))Cu(H(2)O)(2)(btec)⋅4 H(2)O (2) and (UO(2))Cu(btec) (2'; btec = pyromellitate), (UO(2))(2)Cu(H(2)O)(4)(mel) (3; mel = mellitate), and (UO(2))(2)O(OH)(2)Cu(H(2)O)(2)(1,3-bdc)⋅H(2)O (4; 1,3-bdc = isophthlalate). Single-crystal X-ray diffraction (XRD) analysis of compound 1 revealed 2D layers of chains of UO(8) and CuO(4)(H(2)O)(2) units that were connected through the phthalate ligands. In compound 2, these sheets were connected to each other through the two additional carboxylate arms of the pyromellitate, thus resulting in a 3D open-framework with 1D channels that trapped water molecules. Upon heating, free and bonded water species (from Cu-OH(2)) were evacuated from the structure. This thermal transition was followed by in situ XRD and IR spectroscopy. Heating induced a solid-state topotactic transformation with the formation of a new set of Cu-O interactions in the crystalline anhydrous structure (2'), in order to keep the square-planar environment around the copper centers. The structure of compound 3 was built up from trinuclear motifs, in which one copper center, CuO(4)(OH(2))(2), was linked to two uranium units, UO(5)(H(2)O)(2). The assembly of this trimer, "U(2)Cu", with the mellitate generated a 3D network. Complex 4 contained a tetranuclear uranyl core of UO(5)(OH)(2) and UO(6)(OH) units that were linked to two copper centers, CuO(OH)(2)(H(2)O)(2), which were then connected to each other through isophthalate ligands and U=O-Cu interactions to create a 3D structure. The common structural feature of these different compounds is a bridging oxo group of U=O-Cu type, which is reflected by apical Cu-O distances in the range 2.350(3)-2.745(5) Å. In the case of a shorter Cu-O distance, a slight lengthening

Structural observations of heterometallic uranyl copper(II) carboxylates and their solid-state topotactic transformation upon dehydration

International Nuclear Information System (INIS)

Olchowka, Jakub; Falaise, Clement; Volkringer, Christophe; Henry, Natacha; Loiseau, Thierry

2013-01-01

The hydrothermal reactions of uranyl nitrate and metallic copper with aromatic polycarboxylic acids gave rise to the formation of five heterometallic UO 2 2+ -Cu 2+ coordination polymers: (UO 2 )Cu(H 2 O) 2 (1,2-bdc) 2 (1; 1,2-bdc=phthalate), (UO 2 )Cu(H 2 O) 2 (btec).4 H 2 O (2) and (UO 2 )Cu(btec) (2'; btec=pyromellitate), (UO 2 ) 2 Cu(H 2 O) 4 (mel) (3; mel=mellitate), and (UO 2 ) 2 O(OH) 2 Cu(H 2 O) 2 (1,3-bdc).H 2 O (4; 1,3-bdc=isophthlalate). Single-crystal X-ray diffraction (XRD) analysis of compound 1 revealed 2D layers of chains of UO 8 and CuO 4 (H 2 O) 2 units that were connected through the phthalate ligands. In compound 2, these sheets were connected to each other through the two additional carboxylate arms of the pyromellitate, thus resulting in a 3D open-framework with 1D channels that trapped water molecules. Upon heating, free and bonded water species (from Cu-OH 2 ) were evacuated from the structure. This thermal transition was followed by in situ XRD and IR spectroscopy. Heating induced a solid-state topotactic transformation with the formation of a new set of Cu-O interactions in the crystalline anhydrous structure (2'), in order to keep the square-planar environment around the copper centers. The structure of compound 3 was built up from trinuclear motifs, in which one copper center, CuO 4 (OH 2 ) 2 , was linked to two uranium units, UO 5 (H 2 O) 2 . The assembly of this trimer, ''U 2 Cu'', with the mellitate generated a 3D network. Complex 4 contained a tetranuclear uranyl core of UO 5 (OH) 2 and UO 6 (OH) units that were linked to two copper centers, CuO(OH) 2 (H 2 O) 2 , which were then connected to each other through isophthalate ligands and U=O-Cu interactions to create a 3D structure. The common structural feature of these different compounds is a bridging oxo group of U=O-Cu type, which is reflected by apical Cu-O distances in the range 2.350(3)-2.745(5) Aa. In the case of a shorter Cu-O distance, a slight

Role of contaminants in the fluorination of β-UO3 to UF4 by freon-12

International Nuclear Information System (INIS)

Girgis, B.S.; Rofail, N.H.

1992-01-01

Ammonium uranate was precipitated from uranyl nitrate or sulphate by NH 3 gas or urea, and decomposed to β-UO 3 by calcination at 623 or 773 K. Oxides contaminated by high contents of nitrates (non-washed uranate) displayed higher conversion to UF 4 in comparison to the respective pre-washed uranate. Products of thermal treatment at 623 K were also more reactive towards fluorination, which was ascribed to the highly-disordered, loosely bound, high surface area products. The presence of residual nitrate, and probably ammonium, ions help in the partial reduction to lower oxides and in preventing recrystallization of the reaction solids. Ammonium uranate precipitated from uranyl sulphate and decomposed at 623 K is more easily fluorinated than the product decomposed at 773 K; it is also better product for fluorination than the uranate precipitated from uranyl nitrate. The complete conversion to UF 4 i attained after 45 min with the uranate precipitated from uranyl sulphate and treated at 623 K, but it needs 120 min with the product formed from uranyl nitrate and decomposed at the same temperature. (orig.)

Enhanced Adsorption and Recovery of Uranyl Ions by NikR Mutant-Displaying Yeast

Directory of Open Access Journals (Sweden)

Kouichi Kuroda

2014-04-01

Full Text Available Uranium is one of the most important metal resources, and the technology for the recovery of uranyl ions (UO22+ from aqueous solutions is required to ensure a semi-permanent supply of uranium. The NikR protein is a Ni2+-dependent transcriptional repressor of the nickel-ion uptake system in Escherichia coli, but its mutant protein (NikRm is able to selectively bind uranyl ions in the interface of the two monomers. In this study, NikRm protein with ability to adsorb uranyl ions was displayed on the cell surface of Saccharomyces cerevisiae. To perform the binding of metal ions in the interface of the two monomers, two metal-binding domains (MBDs of NikRm were tandemly fused via linker peptides and displayed on the yeast cell surface by fusion with the cell wall-anchoring domain of yeast α-agglutinin. The NikRm-MBD-displaying yeast cells with particular linker lengths showed the enhanced adsorption of uranyl ions in comparison to the control strain. By treating cells with citrate buffer (pH 4.3, the uranyl ions adsorbed on the cell surface were recovered. Our results indicate that the adsorption system by yeast cells displaying tandemly fused MBDs of NikRm is effective for simple and concentrated recovery of uranyl ions, as well as adsorption of uranyl ions.

Comparison of numerical and physico-chemical models for on-line spectrophotometric control of uranium

International Nuclear Information System (INIS)

Corriou, J.P.; Boisde, G.

1986-04-01

In view of on-line spectrophotometric control of fuel reprocessing streams, a physico-chemical model able to predict uranium and nitric acid concentrations in an uranyl nitrate-nitric acid system has been searched. Thus the influences of the following parameters: uranium, nitrate, hydrogen ion concentrations, ionic strength, on the equilibria of complexation of uranium (VI) nitrate have been evaluated. Extinction coefficients for the uranium mononitrate and uranium dinitrate complexes are given between 410 and 440 nm. The apparent equilibrium constants are determined as a function of the ionic strength. The limitations of this predictive model are emphasized and comparisons with numerical models are discussed. (16 refs)

Sorption of uranyl species on zircon and zirconia

International Nuclear Information System (INIS)

Lomenech, C.; Drot, R.; Simoni, E.; Ehrhardt, J.J.; Mielczarski, J.

2002-01-01

few samples, because of the weak signals obtained), X-ray electron spectroscopy enabled us to show differences in the bonding energies between uranyl species sorbed either on zircon or on zirconia, or for the same sorbent for different pH or in different media (nitrate or perchlorate), this last point being confirmed by diffuse reflectance infrared spectroscopy. EXAFS measurements were then performed on well-characterised samples, on zircon and zirconia at different pH and in different media, for either dry or in situ samples. The results clearly show that the sorbed species are inner sphere complexes, and they seem to indicate strong similarities between our dry samples and the in situ experiments, which confirms the validity of other spectroscopic measurements. Moreover, differences between samples prepared at different pH were observed, which could possibly be explained by the formation of a surface precipitate. (authors)

Colorimetric peroxidase mimetic assay for uranyl detection in sea water

KAUST Repository

Zhang, Dingyuan

2015-03-04

Uranyl (UO2 2+) is a form of uranium in aqueous solution that represents the greatest risk to human health because of its bioavailability. Different sensing techniques have been used with very sensitive detection limits especially the recently reported uranyl-specific DNAzymes systems. However, to the best of our knowledge, few efficient detection methods have been reported for uranyl sensing in seawater. Herein, gold nanoclusters (AuNCs) are employed in an efficient spectroscopic method to detect uranyl ion (UO2 2+) with a detection limit of 1.86 ÎM. In the absence of UO2 2+, the BSA-stabilized AuNCs (BSA-AuNCs) showed an intrinsic peroxidase-like activity. In the presence of UO2 2+, this activity can be efficiently restrained. The preliminary quenching mechanism and selectivity of UO2 2+ was also investigated and compared with other ions. This design strategy could be useful in understanding the binding affinity of protein-stabilized AuNCs to UO2 2+ and consequently prompt the recycling of UO2 2+ from seawater.

Nitration Study of Cyclic Ladder Polyphenylsilsesquioxane

Directory of Open Access Journals (Sweden)

LIANG Jia-xiang

2017-05-01

Full Text Available Several nitration reagents including fuming nitric acid, HNO3-H2SO4, KNO3-H2SO4, HNO3-KNO3, CH3COOH-KNO3, (CH3CO2O-HNO3 were used to nitrate cyclic ladder polyphenylsilsesquioxane (CL-PPSQ in different conditions in order to enhance the compatibility of the CL-PPSQ in polymers, the NO2-PPSQ was obtained. FTIR, element analysis, GPC, TGA and 1H NMR were used to characterize the structures of the nitrated products. The results show that the nitrating abilities of the fuming nitric acid, HNO3-H2SO4 and KNO3-H2SO4 are very strong. Many nitro groups can be linked with phenyl groups in CL-PPSQ, but with low molecular mass, fracture occurs in siloxane segment. However, the Mn of the product NO2-PPSQ sharply drops by 50% compared with that of CL-PPSQ, so the nitration reagents can break the cyclic structure of CL-PPSQ. The nitrating reagents of HNO3-KNO3 and CH3COOH-KNO3 have no nitration effects on CL-PPSQ. At last, NO2-CL-PPSQ was prepared using (CH3CO2O-HNO3 because of the moderate nitration process and ability. The cyclic structure of PPSQ is remained, although the number of —NO2 group is not too much. At the same time, the nitration mechanism using different nitration reagents was analyzed. A certain amount of NO2+, which is a kind of activator owning strong nitration ability, can be found in the fuming nitric acid and H2SO4-HNO3(KNO3 systems. As to the (CH3CO2O-HNO3 system, the main activator is CH3COONO2.

Thermochemical nitrate reduction

International Nuclear Information System (INIS)

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

1992-09-01

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

Chemistry of the uranyl group

International Nuclear Information System (INIS)

Zarli, B.; Dall'olio, G.; Sindellari, L.

1976-01-01

Some uranyl complexes with hexamethylphosphoramide (HMPA) and urea were prepared and characterized. The compounds with the former ligand have the general formula UO 2 X 2 .HMPA (where X = (C 2 H 5 ) 2 NCSe 2 - , (C 2 H 5 ) 2 NCS 2 - or CH 3 COO - ). For the acetato derivatives a dimeric acetato-bridged structure is suggested. Some properties of UO 2 (NO 3 ) 2 .2(HMPA) are also described. With the latter ligand, in addition to the complexes UO 2 (NO 3 ) 2 .2urea and [UO 2 (urea) 4 (H 2 0)](NO 3 ) 2 already known, the novel complexes UO 2 (pycrate) 2 .4urea and [UO 2 (CH 3 COO) 2 .urea]sub(n) (where n is probably 2) have been prepared. All attempts to obtain urea complexes of uranyl diethyldithio- or diethyldiselenocarbamate failed and only adducts of unsatisfactory stoichiometry were isolated. (author)

Design and synthesis of new poly-phosphorylated upper-rim modified calix[4]arenes as potential and selective chelating agents of uranyl ion

International Nuclear Information System (INIS)

Migianu-Griffoni, E.; Mbemba, C.; Burgada, R.; Lecouvey, M.; Lecercle, D.; Taran, F.

2009-01-01

New upper-rim poly-phosphorylated calix[4]arenes were designed for decorporation of uranium in case of nuclear contamination. A ligand system containing four pre-organized 1-hydroxymethylene-1, 1-bisphosphonic acid moieties anchored onto a calix[4]arene platform has been developed. Three calix[4]-arene-bis-phosphonates were efficiently prepared in multi-step syntheses with a variable carbon chain length between the bis-phosphonate and the calix[4]arene. Affinity constants towards uranyl ion were determined and compared with those of bis(HEDP) and tris(HEDP) phosphonates, known as efficient ligands for uranyl. (authors)

Luminescent properties of [UO{sub 2}(TFA){sub 2}(DMSO){sub 3}], a promising material for sensing and monitoring the uranyl ion

Energy Technology Data Exchange (ETDEWEB)

Martin-Ramos, Pablo; Silva, Manuela Ramos; Silva, Pedro S. Pereira da [Centro de Fisica da Universidade de Coimbra (CFisUC), Department of Physics, Universidade de Coimbra (Portugal); Costa, Ana L.; Melo, J. Sergio Seixas de [Centro de Quimica de Coimbra, Department of Chemistry, Universidade de Coimbra (Portugal); Pereira, Laura C.J. [Centro de Ciencias e Tecnologias Nucleares, Instituto Superior Tecnico, Universidade de Lisboa, Bobadela LRS (Portugal); Martin-Gil, Jesus, E-mail: pmr@unizar.es [Advanced Materials Laboratory, Escuela Tecnica Superior de Ingenierias Agrarias, University of Valladolid, Palencia (Spain)

2016-03-15

An uranyl complex [UO{sub 2}(TFA){sub 2}(DMSO){sub 3}] (TFA=deprotonated trifluoroacetic acid; DMSO=dimethyl sulfoxide) has been successfully synthesized by reacting UO{sub 2}(CH{sub 3}COO){sub 2} ·H{sub 2} O with one equivalent of (CF{sub 3} CO){sub 2} O and DMSO. The complex has been characterized by single-crystal X-ray diffraction, X-ray powder diffraction, elemental analysis, FTIR spectroscopy, thermal analysis and absorption and emission spectroscopies. The spectroscopic properties of the material make it suitable for its application in the sensing and monitoring of uranyl in the PUREX process. (author)

Chemistry of the uranyl group. VI. Complexes of uranyl with hexamethylphosphoramide and urea

Energy Technology Data Exchange (ETDEWEB)

Zarli, B; Dall' olio, G; Sindellari, L [Consiglio Nazionale delle Ricerche, Padua (Italy). Lab. di Chimica e Tecnologia dei Radioelementi

1976-01-01

Some uranyl complexes with hexamethylphosphoramide (HMPA) and urea were prepared and characterized. The compounds with the former ligand have the general formula UO/sub 2/X/sub 2/.HMPA (where X = (C/sub 2/H/sub 5/)/sub 2/NCSe/sub 2//sup -/, (C/sub 2/H/sub 5/)/sub 2/NCS/sub 2//sup -/ or CH/sub 3/COO/sup -/). For the acetato derivatives a dimeric acetato-bridged structure is suggested. Some properties of UO/sub 2/(NO/sub 3/)/sub 2/.2(HMPA) are also described. With the latter ligand, in addition to the complexes UO/sub 2/(NO/sub 3/)/sub 2/.2urea and (UO/sub 2/(urea)/sub 4/(H/sub 2/0))(NO/sub 3/)/sub 2/ already known, the novel complexes UO/sub 2/(pycrate)/sub 2/.4urea and (UO/sub 2/(CH/sub 3/COO)/sub 2/.urea)sub(n) (where n is probably 2) have been prepared. All attempts to obtain urea complexes of uranyl diethyldithio- or diethyldiselenocarbamate failed and only adducts of unsatisfactory stoichiometry were isolated.

Unusual case of a polar copper(II) uranyl phosphonate that fluoresces

Energy Technology Data Exchange (ETDEWEB)

Nelson, A.G.D.; Albrecht-Schmitt, Th.E. [Department of Civil Engineering and Geological Sciences and Department of Chemistry and Biochemistry, 156 Fitzpatrick Hall, University of Notre Dame, Notre Dame, Indiana (United States)

2010-06-15

A polar Cu(II) uranyl diphosphonate, Cu(H{sub 2}O){sub 4}(UO{sub 2}){sub 3}(H{sub 2}O){sub 2}[CH{sub 2}(PO{sub 3}){sub 2}]{sub 2}.5H{sub 2}O, has been prepared under mild hydrothermal conditions. This compound has direct linkages between the oxo atoms of the uranyl moieties and the Cu(II) centers. Despite the presence of Cu(II) in the structure, vibronically-coupled emission is still observed, most likely because there are two crystallographically unique uranyl moieties, only one of which bonds to Cu(II). (authors)

Mass-spectrometric study of volatile uranyl β-diketonates and their adducts

International Nuclear Information System (INIS)

Adamov, V.M.; Belyaev, B.N.; Berezinskij, S.O.; Sidorenko, G.V.; Suglobov, D.N.

1985-01-01

The mass spectra of a number of uranyl β-diketonates containing methyl, trifluoromethyl and tert-butyl substituents in β-diketonate anion, and their adducts are measured. The form of the unsolvated β-diketonates and their adducts in gas phase is studied. The ways of fragmentation of uranyl β-diketonates and their adducts are investigated. The data concerning the thermal and chemical side reactions proceeding with uranyl β-diketonates and their addicts in an ion source are obtained. The mass spectra of the samples of neptunyl and plutonyl β-diketonate adducts synthesized for the first time are measured

Time-resolved luminescence studies in hydrogen uranyl phosphate intercalated with amines

Energy Technology Data Exchange (ETDEWEB)

Novo, Joao Batista Marques [Departamento de Quimica, Universidade Federal do Parana, CP 19081, 81531-990 Curitiba-PR (Brazil)]. E-mail: jbmnovo@quimica.ufpr.br; Batista, Fabio Roberto [Departamento de Quimica, Universidade Federal do Parana, CP 19081, 81531-990 Curitiba-PR (Brazil); Cunha, Carlos Jorge da [Departamento de Quimica, Universidade Federal do Parana, CP 19081, 81531-990 Curitiba-PR (Brazil); Dias, Lauro Camargo Jr. [Departamento de Quimica, Universidade Federal do Parana, CP 19081, 81531-990 Curitiba-PR (Brazil); Teixeira Pessine, Francisco Benedito [Instituto de Quimica, Universidade Estadual de Campinas, CP 6154, 13084-971 Campinas-SP (Brazil)

2007-05-15

Time-resolved luminescence decays of intercalated compounds of hydrogen uranyl phosphate (HUP) with p-toluidinium (HUPPT), benzylaminium (HUPBZ), {alpha}-methylbenzylaminium (HUPMBZ) and hydroxylaminium (HUPHAM) were studied. The prepared compounds belong to the tetragonal P4/ncc space group and showed 00 l reflections shifted to lower angles relative to HUP, indicating that the intercalation increases the c parameter of the unit cell. The luminescence decays of the compounds with 100% of intercalation ratio (HUPHAM and HUPBZ) were analyzed by Global Analysis, assuming Lianos' stretched exponential as the model function, which can be applied to compounds with restricted geometry and mobile donor and quencher molecules. It was remarkable that the luminescence decays showed that the quenching of the emission of the uranyl ions by the intercalated protonated amines is not restricted by low dimensionality of the host uranyl phosphate, and that a diffusion mechanism occurs. Benzylaminium cation efficiently quenches the excited energy of the uranyl ions at close distance, but the long-range and long-lifetime quenching is hindered. A different situation is found in the case of the small hydroxylaminium cation, where the long distance diffusion of the species is fast, playing an important role in the quenching of the excited uranyl ions at longer times.

Time-resolved luminescence studies in hydrogen uranyl phosphate intercalated with amines

International Nuclear Information System (INIS)

Novo, Joao Batista Marques; Batista, Fabio Roberto; Cunha, Carlos Jorge da; Dias, Lauro Camargo Jr.; Teixeira Pessine, Francisco Benedito

2007-01-01

Time-resolved luminescence decays of intercalated compounds of hydrogen uranyl phosphate (HUP) with p-toluidinium (HUPPT), benzylaminium (HUPBZ), α-methylbenzylaminium (HUPMBZ) and hydroxylaminium (HUPHAM) were studied. The prepared compounds belong to the tetragonal P4/ncc space group and showed 00 l reflections shifted to lower angles relative to HUP, indicating that the intercalation increases the c parameter of the unit cell. The luminescence decays of the compounds with 100% of intercalation ratio (HUPHAM and HUPBZ) were analyzed by Global Analysis, assuming Lianos' stretched exponential as the model function, which can be applied to compounds with restricted geometry and mobile donor and quencher molecules. It was remarkable that the luminescence decays showed that the quenching of the emission of the uranyl ions by the intercalated protonated amines is not restricted by low dimensionality of the host uranyl phosphate, and that a diffusion mechanism occurs. Benzylaminium cation efficiently quenches the excited energy of the uranyl ions at close distance, but the long-range and long-lifetime quenching is hindered. A different situation is found in the case of the small hydroxylaminium cation, where the long distance diffusion of the species is fast, playing an important role in the quenching of the excited uranyl ions at longer times

Measurement of uranium concentration by molecular absorption spectrophotometry by means optical fibers; Medicion continua de concentracion de uranio por espectrofotometria de absorcion molecular mediante fibras opticas

Energy Technology Data Exchange (ETDEWEB)

Gauna, Alberto C.; Pascale, Ariel A. [Comision Nacional de Energia Atomica, Buenos Aires (Argentina). Centro Atomico Ezeiza. Agencia Minipost

1996-07-01

An on-line method for measuring the concentration of uranium in uranyl nitrate-nitric acid aqueous solutions is described. The method is based on molecular absorption spectrophotometry with transmission of light by means of optical fibers. It is ideally suited for control and processes development applications. (author)

Measurement of uranium concentration by molecular absorption spectrophotometry by means optical fibers

International Nuclear Information System (INIS)

Gauna, Alberto C.; Pascale, Ariel A.

1996-01-01

An on-line method for measuring the concentration of uranium in uranyl nitrate-nitric acid aqueous solutions is described. The method is based on molecular absorption spectrophotometry with transmission of light by means of optical fibers. It is ideally suited for control and processes development applications. (author)

Thermal and X-ray diffraction analysis studies during the decomposition of ammonium uranyl nitrate.

Science.gov (United States)

Kim, B H; Lee, Y B; Prelas, M A; Ghosh, T K

Two types of ammonium uranyl nitrate (NH 4 ) 2 UO 2 (NO 3 ) 4 ·2H 2 O and NH 4 UO 2 (NO 3 ) 3 , were thermally decomposed and reduced in a TG-DTA unit in nitrogen, air, and hydrogen atmospheres. Various intermediate phases produced by the thermal decomposition and reduction process were investigated by an X-ray diffraction analysis and a TG/DTA analysis. Both (NH 4 ) 2 UO 2 (NO 3 ) 4 ·2H 2 O and NH 4 UO 2 (NO 3 ) 3 decomposed to amorphous UO 3 regardless of the atmosphere used. The amorphous UO 3 from (NH 4 ) 2 UO 2 (NO 3 ) 4 ·2H 2 O was crystallized to γ-UO 3 regardless of the atmosphere used without a change in weight. The amorphous UO 3 obtained from decomposition of NH 4 UO 2 (NO 3 ) 3 was crystallized to α-UO 3 under a nitrogen and air atmosphere, and to β-UO 3 under a hydrogen atmosphere without a change in weight. Under each atmosphere, the reaction paths of (NH 4 ) 2 UO 2 (NO 3 ) 4 ·2H 2 O and NH 4 UO 2 (NO 3 ) 3 were as follows: under a nitrogen atmosphere: (NH 4 ) 2 UO 2 (NO 3 ) 4 ·2H 2 O → (NH 4 ) 2 UO 2 (NO 3 ) 4 ·H 2 O → (NH 4 ) 2 UO 2 (NO 3 ) 4  → NH 4 UO 2 (NO 3 ) 3  → A-UO 3  → γ-UO 3  → U 3 O 8 , NH 4 UO 2 (NO 3 ) 3  → A-UO 3  → α-UO 3  → U 3 O 8 ; under an air atmosphere: (NH 4 ) 2 UO 2 (NO 3 ) 4 ·2H 2 O → (NH 4 ) 2 UO 2 (NO 3 ) 4 ·H 2 O → (NH 4 ) 2 UO 2 (NO 3 ) 4  → NH 4 UO 2 (NO 3 ) 3  → A-UO 3  → γ-UO 3  → U 3 O 8 , NH 4 UO 2 (NO 3 ) 3  → A-UO 3  → α-UO 3  → U 3 O 8 ; and under a hydrogen atmosphere: (NH 4 ) 2 UO 2 (NO 3 ) 4 ·2H 2 O → (NH 4 ) 2 UO 2 (NO 3 ) 4 ·H 2 O → (NH 4 ) 2 UO 2 (NO 3 ) 4  → NH 4 UO 2 (NO 3 ) 3  → A-UO 3  → γ-UO 3  → α-U 3 O 8  → UO 2 , NH 4 UO 2 (NO 3 ) 3  → A-UO 3  → β-UO 3  → α-U 3 O 8  → UO 2 .

Organophosphorous complexones. Pt. 4. Spectrophotometric titration of beryllium(2) with (N,N,N',N-ethylenediamine) tetramethanephosphonic acid

International Nuclear Information System (INIS)

Szczepaniak, W.; Staniewska, M.

1976-01-01

Spectrophotometric titration of Be 2+ with (N,N,N'-ethylenediamine) tetramethanephosphonic acid (EDTP) using Chromazurol S as indicator was carried out. Using a TiMi attachment of a Specol colorimeter it is possible to determine 1.6 μg - 14 μg Be in 2 ml of solution. Alkali metals, alkaline earth metals as well as common anions as chlorides, nitrates, sulphates and acetates do not interfere. Using EDTA as masking agent it is possible to determine beryllium in the presence of divalent cations of the transition metals (Zn 2+ , Cd 2+ , Cu 2+ , Ni 2+ , Co 2+ , Pb 2+ ) Al 3+ , Fe 3+ and lanthanides. Uranyl ion and tetravalent cations e.g. Th 4+ interfere. (author)

Volatile uranyl hexafluoroacetoacetonate complexes

International Nuclear Information System (INIS)

Dines, M.B.; Hall, R.B.; Kaldor, A.; Kramer, G.M.; Maas, E.T. Jr.

1980-01-01

A composition of matter is described, characterized by the formula UO 2 (CF 3 COCHCOCF 3 ).L where L is a ligand selected from isopropanol, ethanol, isobutanol, tert-butanol, methanol, tetrahydrofuran, acetone, dimethylformamide, n-propanol and ethyl acetate. A process for producing the complex comprises reacting uranyl chloride with a hexafluoroacetylacetonate dissolved in a ligand L: experimental details are given. (U.K.)

Correlation between citric acid and nitrate metabolisms during CAM cycle in the atmospheric bromeliad Tillandsia pohliana.

Science.gov (United States)

Freschi, Luciano; Rodrigues, Maria Aurineide; Tiné, Marco Aurélio Silva; Mercier, Helenice

2010-12-15

Crassulacean acid metabolism (CAM) confers crucial adaptations for plants living under frequent environmental stresses. A wide metabolic plasticity can be found among CAM species regarding the type of storage carbohydrate, organic acid accumulated at night and decarboxylating system. Consequently, many aspects of the CAM pathway control are still elusive while the impact of this photosynthetic adaptation on nitrogen metabolism has remained largely unexplored. In this study, we investigated a possible link between the CAM cycle and the nitrogen assimilation in the atmospheric bromeliad Tillandsia pohliana by simultaneously characterizing the diel changes in key enzyme activities and metabolite levels of both organic acid and nitrate metabolisms. The results revealed that T. pohliana performed a typical CAM cycle in which phosphoenolpyruvate carboxylase and phosphoenolpyruvate carboxykinase phosphorylation seemed to play a crucial role to avoid futile cycles of carboxylation and decarboxylation. Unlike all other bromeliads previously investigated, almost equimolar concentrations of malate and citrate were accumulated at night. Moreover, a marked nocturnal depletion in the starch reservoirs and an atypical pattern of nitrate reduction restricted to the nighttime were also observed. Since reduction and assimilation of nitrate requires a massive supply of reducing power and energy and considering that T. pohliana lives overexposed to the sunlight, we hypothesize that citrate decarboxylation might be an accessory mechanism to increase internal CO₂ concentration during the day while its biosynthesis could provide NADH and ATP for nocturnal assimilation of nitrate. Therefore, besides delivering photoprotection during the day, citrate might represent a key component connecting both CAM pathway and nitrogen metabolism in T. pohliana; a scenario that certainly deserves further study not only in this species but also in other CAM plants that nocturnally accumulate citrate

Effect of temperature on the mechanisms of interaction between uranyl ion and zirconium oxo-phosphate

International Nuclear Information System (INIS)

Almazan Torres, Maria Guadalupe

2007-01-01

Uranium sorption onto Zr 2 O(PO 4 ) 2 has been studied between 298 K and 363 K, in 0.1 M NaClO 4 medium. Potentiometric titrations were realized to determine temperature dependency of the acid-base properties (pH pcn , acidity constants). Classical batch experiments were performed at different temperatures. The sorption experiments revealed that the uranium sorption onto Zr 2 O(PO 4 ) 2 is favoured with the temperature. Structural characterization of the surface complexes was performed by both Time-Resolved Laser-Induced Fluorescence (TRLIF) and EXAFS spectroscopy. The TRLIF measurements vs. temperature revealed two uranyl surface complexes. No influence of the temperature onto the nature surface complex was observed. The EXAFS analysis showed a splitting of the equatorial oxygen atoms in two shells, corresponding to uranyl bidentate, inner-sphere complexes. The obtained structural uranyl surface complex information was used to simulate (using a constant capacitance model) the sorption edges. The proposed complexes equilibrium model consists of the following surface complexes: (≡ZrOH) 2 UO 2 2+ and (≡PO) 2 UO 2 . Besides the stability constants for the surface complexes, the thermodynamic parameters ΔH 0 and ΔS 0 were determined using the van't Hoff equation. The enthalpy values associated to the U(VI) retention onto Zr 2 O(PO 4 ) 2 , determined by the temperature dependence of the stability constants, testify that the formation of the complex (≡PO) 2 UO 2 (55 kJ/mol) is endothermic, while no influence of the temperature was observed for the formation of the complex (≡ZrOH) 2 UO 2 2+ . The adsorption reaction of the last complex is then driven by entropy. In addition, calorimetric measurements of uranium sorption onto Zr 2 O(PO 4 ) 2 were carried out to directly quantify the enthalpy associated to the retention processes. (author)

Process for manufacturing (U/Pu)O2 mixed crystals

International Nuclear Information System (INIS)

Druckenbrodt, W.G.; Baumann, S.; Krause, R.; Stoll, W.

1980-01-01

A mixture of uranyl nitrate and plutonium nitrate is used as starting material. Oxidation to valency VI is carried out by overheating and concentrating nitric acid solutions at 135-150 0 C. The deposit formed can be stored at room temperature. Its calcination produces a homogeneous powder which can be sintered. The powder is soluble in HNO 3 . The powder is used for making pellets for thermal reactors and fast breeder reactors. (RW) [de

Electrodialytic removal of nitrate from pineapple juice: effect on selected physicochemical properties, amino acids, and aroma components of the juice.

Science.gov (United States)

Ackarabanpojoue, Yuwadee; Chindapan, Nathamol; Yoovidhya, Tipaporn; Devahastin, Sakamon

2015-05-01

This study aimed at investigating the effect of nitrate removal from pineapple juice by electrodialysis (ED) on selected properties of the ED-treated juice. Single-strength pineapple juice with reduced pulp content was treated by ED to reduce the nitrate concentration to 15, 10, or 5 ppm. After ED, the removed pulp was added to the ED-treated juice and its properties, including electrical conductivity, acidity, pH, total soluble solids (TSS), color, amino acids, and selected aroma compounds, were determined and compared with those of the untreated juice. ED could reduce the nitrate content of 1 L of pineapple juice from an initial value of 50 ppm to less than 5 ppm within 30 min. A significant decrease in the electrical conductivity, acidity, pH, TSS, and yellowness, but a significant increase in the lightness, of the juice was observed upon ED. Concentrations of almost all amino acids of the ED-treated juice significantly decreased. The concentrations of 8 major compound contributors to the pineapple aroma also significantly decreased. Adding the pulp back to the ED-treated juice increased the amino acids concentrations; however, it led to a significant decrease in the concentrations of the aroma compounds. © 2015 Institute of Food Technologists®

Application of salting-out effect equation to modelling of liquid-liquid distribution systems

International Nuclear Information System (INIS)

Pitsch, H.K.

1986-03-01

Physicochemical interpretation of salting-out is reviewed and effects of the medium on liquid-liquid distribution equilibria are described by two non-specific parameters of salting-out agents: total concentration of species in the aqueous phase and water activity. Thus extraction of a given constituent in various media can be forecasted with few data. Different uranyl and technetium (VII) extraction systems are analyzed to show the potentiality of the method. Coextraction of nitric acid and uranyl nitrate by tributyl phosphate is used to show the possibility of modelling complex distribution systems in industrial conditions [fr

New chemistry of the uranyl ion in non aqueous media

International Nuclear Information System (INIS)

Siffredi, G.

2008-12-01

This work deals with new aspects of the chemistry of the uranyl(VI) ion {UO 2 } 2+ in anhydrous polar organic solvents such as the activation of the reputedly inert U-O yl bond and the controlled reduction of this species which represent a particularly active field of research that attracts much attention for both its fundamental aspects and applications. Treatment of uranyl(VI) compounds UO 2 X' 2 (X' = I, OTf, Cl) with Me 3 SiX (X = Cl, Br, I) reagents, in various anhydrous polar organic solvents, has been first considered. In most cases, reduction into tetravalent species with complete de-oxygenation of the uranyl {UO 2 } 2+ ion is observed. The reaction is particularly efficient in acetonitrile where the tetravalent [UX 4 (MeCN) 4 ] complexes, which are useful precursors in uranium chemistry, are isolated. In the course of these reactions, the influence of the solvent, the nature of X' and X in the UO 2 X' 2 precursor and the Me 3 SiX reagent are pointed out. Reaction of the uranyl(VI) UO 2 X 2 (X = I, Cl, OTf, NO 3 ) precursors with the anionic MC 5 R 5 (M = K, R = H, Me; M= Li, R = Me; M= Tl, R = H) reagents did not lead to the organometallic [(η 5 -C 5 R 5 ) n UO 2 X 2-n ] species (n = 1, 2) but to pentavalent uranyl(V) complexes. This method is a facile and rapid route towards the formation of stable pentavalent uranyl which offers promising sources for further U(V) chemical developments and for fundamental and applied interests. Their structure is strongly dependent on the nature of the solvent, the additional ligands X and of the M + cation. In pyridine, the {UO 2 (py) 5 } + ion appears to be an ubiquitous and a quite stable entity. The coordinating properties of the basic oxo groups, which coordinate easily to M + ions (M= Li, K, Tl), favour structural diversity with formation of hetero-polymetallic complexes such as [{UO 2 (py) 5 }{MX(py) 2 }] (M= Li, X I), [{UO 2 (py) 5 }{MX 2 (py) 2 }] ∞ (M= K, Tl, X= OTf; M= K, X= I), [{UO 2 (py) 5 }(M 2 X 3 )]�

Surface complexation modeling of uranyl adsorption on corrensite from the Waste Isolation Pilot Plant Site

Energy Technology Data Exchange (ETDEWEB)

Park, Sang-Won; Leckie, J.O. [Stanford Univ., CA (United States); Siegel, M.D. [Sandia National Labs., Albuquerque, NM (United States)

1995-09-01

Corrensite is the dominant clay mineral in the Culebra Dolomite at the Waste Isolation Pilot Plant. The surface characteristics of corrensite, a mixed chlorite/smectite clay mineral, have been studied. Zeta potential measurements and titration experiments suggest that the corrensite surface contains a mixture of permanent charge sites on the basal plane and SiOH and AlOH sites with a net pH-dependent charge at the edge of the clay platelets. Triple-layer model parameters were determined by the double extrapolation technique for use in chemical speciation calculations of adsorption reactions using the computer program HYDRAQL. Batch adsorption studies showed that corrensite is an effective adsorbent for uranyl. The pH-dependent adsorption behavior indicates that adsorption occurs at the edge sites. Adsorption studies were also conducted in the presence of competing cations and complexing ligands. The cations did not affect uranyl adsorption in the range studied. This observation lends support to the hypothesis that uranyl adsorption occurs at the edge sites. Uranyl adsorption was significantly hindered by carbonate. It is proposed that the formation of carbonate uranyl complexes inhibits uranyl adsorption and that only the carbonate-free species adsorb to the corrensite surface. The presence of the organic complexing agents EDTA and oxine also inhibits uranyl sorption.

Surface complexation modeling of uranyl adsorption on corrensite from the Waste Isolation Pilot Plant Site

International Nuclear Information System (INIS)

Park, Sang-Won; Leckie, J.O.; Siegel, M.D.

1995-09-01

Corrensite is the dominant clay mineral in the Culebra Dolomite at the Waste Isolation Pilot Plant. The surface characteristics of corrensite, a mixed chlorite/smectite clay mineral, have been studied. Zeta potential measurements and titration experiments suggest that the corrensite surface contains a mixture of permanent charge sites on the basal plane and SiOH and AlOH sites with a net pH-dependent charge at the edge of the clay platelets. Triple-layer model parameters were determined by the double extrapolation technique for use in chemical speciation calculations of adsorption reactions using the computer program HYDRAQL. Batch adsorption studies showed that corrensite is an effective adsorbent for uranyl. The pH-dependent adsorption behavior indicates that adsorption occurs at the edge sites. Adsorption studies were also conducted in the presence of competing cations and complexing ligands. The cations did not affect uranyl adsorption in the range studied. This observation lends support to the hypothesis that uranyl adsorption occurs at the edge sites. Uranyl adsorption was significantly hindered by carbonate. It is proposed that the formation of carbonate uranyl complexes inhibits uranyl adsorption and that only the carbonate-free species adsorb to the corrensite surface. The presence of the organic complexing agents EDTA and oxine also inhibits uranyl sorption

Quantification of naphazoline nitrate by UV-spectrophoto-metry

Directory of Open Access Journals (Sweden)

O. I. Panasenko

2013-12-01

Full Text Available One of the main tasks of pharmaceutical chemistry – medical drugs study. Spectrophotometry is widely used in studying of the structure and composition (complexes, dyes, analytical reagents, etc. of various compounds. It widely used for qualitative and quantitative determination of substances (determination of elements traces in metals, alloys, technical facilities. The dependence between substance structure and its electronic spectrum is being studied by many researchers till nowadays. The aim of this work was to highlight the issues of naphazoline quantify definition techniques by the UV-spectrophotometry. According to the existing methods of quality control (MQC, naphazoline nitrate is a substance quantitatively determined by acid-base titration among a mixture of anhydrous acetic acid and acetic anhydride. Titration is carried out with a solution of 0,1 M perchloric acid (indicator - crystal violet. To check the quality of nasal drops nafazoline nitrate MQC is recommended UV-spectrophotometry: drug is dissolved in boric acid solution (20 g/l as the reference solution used solution pharmacopoeia standard sample substance nafazoline nitrate. The character of UV-spectra of the nafazoline nitrate in solvents of different polarity (water, 95% ethanol, 0,1 M NaOH, 0,1 M HCl, 5M H2SO4, was defined and studied. Standard sample of nafazoline nitrate was obtained from the State Enterprise "Scientific and Expert Pharmacopoeia Centre Ukraine". In order to study UV-spectra nafazoline nitrate spectrophotometer SPECORD 200-222U214 (Germany was used. UV-spectrum of nafazoline nitrate in water and 95% ethanol are characterized by two maxima at 270 and 280 nm. Absorption band of nafazoline nitrate in 0, 1 M sodium hydroxide has two maxima at 271 and 280 nm, and in 0, 1 M solution of hydrochloric acid and 5 M solution of sulfuric acid maxima coincide with the maxima spectrum of the drug in water, 95% ethanol. In order to avoid errors associated with

Magnetic biosorbent for removal of uranyl ions

International Nuclear Information System (INIS)

Yamamura, Amanda P.G.; Yamaura, Mitiko; Costa, Caroline H.

2009-01-01

In this work magnetic biosorbent, which consisted of sugarcane bagasse as polymeric matrix with magnetite nanoparticles, was prepared. This magnetic composite has the purpose to remove uranyl ions from aqueous effluents. The magnetite was synthetized by simultaneous precipitation by addition a solution of NaOH to the aqueous solution containing Fe2+ and Fe3+. This magnetic bagasse biosorbent have presented superparamagnetic properties, that is, it have showed a high magnetization of saturation without hysteresis. The magnetic biosorbent was utilized to remove uranyl ions from water. Radioactive uranium waste is generated in hospitals, universities and it is used as fuel for nuclear power plants. Variables of adsorption process of uranyl ions by magnetic biosorbent in nitric solutions were investigated, such as, time required for the uranium-magnetic bagasse biosorbent equilibrium in the interval from 20 to 90 min, pH in the intervals from 2 to 5 and 10, stirring speed from 240 to 500 r.p.m. and biosorbent dose from 2 to 25 g.L-1 were investigated. Equilibrium isotherm was verified according to the Langmuir and Freundlich adsorption isotherm models. The highest adsorption capacity reached 17 mg.g-1. The Gibbs free energy indicated to be spontaneous adsorption. This work updates the paper was presented on the 2007 INAC.

DNA conformational analysis in solution by uranyl mediated photocleavage

DEFF Research Database (Denmark)

Nielsen, Peter E.; Møllegaard, N E; Jeppesen, C

1990-01-01

Uranyl mediated photocleavage of double stranded DNA is proposed as a general probing for DNA helix conformation in terms of minor groove width/electronegative potential. Specifically, it is found that A/T-tracts known to constitute strong distamycin binding sites are preferentially photocleaved ......, uranyl photocleavage of the internal control region (ICR) of the 5S-RNA gene yields a cleavage modulation pattern fully compatible with that obtained by DNase I which also--in a more complex way--senses DNA minor groove width....

Thermodynamics of Uranyl Minerals: Enthalpies of Formation of Uranyl Oxide Hydrates

International Nuclear Information System (INIS)

Kubatko, K.; Helean, K.; Navrotsky, A.; Burns, P.C.

2005-01-01

The enthalpies of formation of seven uranyl oxide hydrate phases and one uranate have been determined using high-temperature oxide melt solution calorimetry: [(UO 2 ) 4 O(OH) 6 ](H 2 O) 5 , metaschoepite; β-UO 2 (OH) 2 ; CaUO 4 ; Ca(UO 2 ) 6 O 4 (OH) 6 (H 2 O) 8 , becquerelite; Ca(UO 2 ) 4 O 3 (OH) 4 (H 2 O) 2 ; Na(UO 2 )O(OH), clarkeite; Na 2 (UO 2 ) 6 O 4 (OH) 6 (H 2 O) 7 , the sodium analogue of compreignacite and Pb 3 (UO 2 ) 8 O 8 (OH) 6 (H 2 O) 2 , curite. The enthalpy of formation from the binary oxides, ΔH f-ox , at 298 K was calculated for each compound from the respective drop solution enthalpy, ΔH ds . The standard enthalpies of formation from the elements, ΔH f o , at 298 K are -1791.0 ± 3.2, -1536.2 ± 2.8, -2002.0 ± 3.2, -11389.2 ± 13.5, -6653.1 ± 13.8, -1724.7 ± 5.1, -10936.4 ± 14.5 and -13163.2 ± 34.4 kJ mol -1 , respectively. These values are useful in exploring the stability of uranyl oxide hydrates in auxiliary chemical systems, such as those expected in U-contaminated environments

Molecular approach of uranyl/mineral surfaces: theoretical approach

International Nuclear Information System (INIS)

Roques, J.

2009-01-01

As migration of radio-toxic elements through the geosphere is one of the processes which may affect the safety of a radioactive waste storage site, the author shows that numerical modelling is a support to experimental result exploitation, and allows the development of new interpretation and prediction codes. He shows that molecular modelling can be used to study processes of interaction between an actinide ion (notably a uranyl ion) and a mineral surface (a TiO 2 substrate). He also reports the predictive theoretical study of the interaction between an uranyl ion and a gibbsite substrate

Uranyl peroxide enhanced nuclear fuel corrosion in seawater.

Science.gov (United States)

Armstrong, Christopher R; Nyman, May; Shvareva, Tatiana; Sigmon, Ginger E; Burns, Peter C; Navrotsky, Alexandra

2012-02-07

The Fukushima-Daiichi nuclear accident brought together compromised irradiated fuel and large amounts of seawater in a high radiation field. Based on newly acquired thermochemical data for a series of uranyl peroxide compounds containing charge-balancing alkali cations, here we show that nanoscale cage clusters containing as many as 60 uranyl ions, bonded through peroxide and hydroxide bridges, are likely to form in solution or as precipitates under such conditions. These species will enhance the corrosion of the damaged fuel and, being thermodynamically stable and kinetically persistent in the absence of peroxide, they can potentially transport uranium over long distances.

Influence of uranyl dibutylphosphate on the UV/VIS spectrophotometric online monitoring of uranium in tributylphosphate/hydrocarbon solvent

International Nuclear Information System (INIS)

Creech, E.T.; Rutenberg, A.C.; Smithwick, R.W.; Seals, R.D.

1984-01-01

In the uranium recovery process at the Y-12 Plant uranium is recovered from aqueous uranyl solutions by extraction into a solvent consisting of 30% tributylphosphate (TBP) and 70% hydrocarbon solvent. Within this process the uranium is continuously monitored by a UV/VIS absorbance measurement of the uranyl/tributylphosphate complex in the organic phase. The uranium is then further extracted from the organic phase to a final water phase. Dibutylphosphate (DBP), which is a decomposition product of TBP, builds up in the organic solvent. A very strong complex of uranyl/dibutylphosphate is formed which cannot be extracted into the aqueous phase. Prior to this work the uranyl/dibutylphosphate complex absorbance was assumed to be the same as the uranyl tributylphosphate complex. To determine the effect of the presence of uranyl/dibutylphosphate on the continuous UV/VIS monitor required (a) the purification of commercial dibutylphosphate, (b) the synthesis, and (c) the characterization of uranyl/dibutylphosphate

Study on the effect of free acidity and entrained TBP in UNPS on the quality of ADU powder

International Nuclear Information System (INIS)

Prudhvi Raju, P.V.S.N.; Mandal, D.

2015-01-01

Graphical abstract: From the experimental study it was found that mean particle size of precipitated Ammonium Di-Uranate (ADU) depends on the free acidity content and entrained TBP in Uranyl Nitrate Pure Solution (UNPS). It was found that as the free acidity as well as the entrained TBP content in UNPS increases, mean particle size of precipitated ADU decreases. Based on the experimental results two correlations were developed as shown in below figures. - Highlights: • The mean particle size of precipitated ADU depends on the free acidity in UNPS. • The mean particle size of precipitated ADU also depends on the entrained TBP in UNPS. • As free acidity in UNPS increases, mean particle size of precipitated ADU decreases. • As entrained TBP in UNPS increases, particle size of precipitated ADU decreases. • Based on the experimental results two correlations were developed to find d p of ADU. - Abstract: The mean particle size and size distribution of Ammonium Di-Uranate (ADU) particles, precipitated during the precipitation reaction of Uranyl Nitrate Pure Solution (UNPS) with ammonia play an important role on the sintered density of UO 2 pellets. The quality of precipitated ADU depends on number of process parameters viz., pH of UNPS, concentration of uranium in UNPS, flow rate of ammonium hydroxide, temperature etc. However, the effects of the presence of free acid and entrained Tri-Butyl-Phosphate (TBP) in UNPS on the quality of ADU powder were not studied till date. Experiments were conducted to study the effect of free acidity and the presence of entrained TBP on the quality of precipitated ADU particles. It was found that as the concentration of free acid as well as the concentration of entrained TBP in UNPS increases, the particle size of precipitated ADU decreases. Based on the experimental results two correlations were developed to determine the mean particle size of ADU; one is based on the free acid content of UNPS and the other is based on the

Study on the effect of free acidity and entrained TBP in UNPS on the quality of ADU powder

Energy Technology Data Exchange (ETDEWEB)

Prudhvi Raju, P.V.S.N. [Nuclear Fuel Complex, Hyderabad 500 062 (India); Mandal, D., E-mail: dmandal@barc.gov.in [Chemical Engineering Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085 (India)

2015-09-15

Graphical abstract: From the experimental study it was found that mean particle size of precipitated Ammonium Di-Uranate (ADU) depends on the free acidity content and entrained TBP in Uranyl Nitrate Pure Solution (UNPS). It was found that as the free acidity as well as the entrained TBP content in UNPS increases, mean particle size of precipitated ADU decreases. Based on the experimental results two correlations were developed as shown in below figures. - Highlights: • The mean particle size of precipitated ADU depends on the free acidity in UNPS. • The mean particle size of precipitated ADU also depends on the entrained TBP in UNPS. • As free acidity in UNPS increases, mean particle size of precipitated ADU decreases. • As entrained TBP in UNPS increases, particle size of precipitated ADU decreases. • Based on the experimental results two correlations were developed to find d{sub p} of ADU. - Abstract: The mean particle size and size distribution of Ammonium Di-Uranate (ADU) particles, precipitated during the precipitation reaction of Uranyl Nitrate Pure Solution (UNPS) with ammonia play an important role on the sintered density of UO{sub 2} pellets. The quality of precipitated ADU depends on number of process parameters viz., pH of UNPS, concentration of uranium in UNPS, flow rate of ammonium hydroxide, temperature etc. However, the effects of the presence of free acid and entrained Tri-Butyl-Phosphate (TBP) in UNPS on the quality of ADU powder were not studied till date. Experiments were conducted to study the effect of free acidity and the presence of entrained TBP on the quality of precipitated ADU particles. It was found that as the concentration of free acid as well as the concentration of entrained TBP in UNPS increases, the particle size of precipitated ADU decreases. Based on the experimental results two correlations were developed to determine the mean particle size of ADU; one is based on the free acid content of UNPS and the other is based on

Separation of uranyl ion using polyaniline

International Nuclear Information System (INIS)

Jayshree Ramkumar; Chandramouleeswaran, S.

2013-01-01

Polyaniline (Pani) was synthesized by the chemical oxidation of aniline. The use of persulphate instead of dichromate was desired in order to avoid the incorporation of chromium in the polymer matrix. The presence of chromium in the matrix, when dichromate was used as an oxidant, was confirmed by various techniques. The batch mode experiments showed that Pani could be used for separation of different metal ions. These ions were converted into their anionic complexes using suitable complexing agents. It was found that EDTA was used as a suitable reagent for the separation of Cu 2+ from Zn 2+ whereas the uranyl ion uptake could be increased to about 95 % when carbonate was used instead of EDTA as complexing agent. A possible application of the above exchange system to preconcentration of uranyl ion from seawater has also been examined. (author)

Spectroscopic studies of 2-thenoyltrifluoro acetonate of uranyl salts doped with europium

International Nuclear Information System (INIS)

Nakagawa, F.T.; Luiz, J.E.M. de Sa; Felinto, M.C.F.C.; Brito, H.F.; Teotonio, E.E.S.

2006-01-01

Uranyl compounds present a great potential as luminescence materials. Some examples of applications are: in laser technology, cathode ray tube, X-rays diagnostic. In this work it was studied the synthesis, characterization and spectroscopic properties study of uranyl 2-thenoyl trifluoroacetonate and uranyl 2- thenoyl trifluoroacetonate doped with europium. The compounds were synthesized and characterized by infrared absorption spectroscopy, thermal analysis, scanning electronic microscopy, and electronic spectroscopy of emission and excitation. The Eu 3+ ion acted as an effective luminescent probe, however the process of energy transfer from UO 2 2+ to Eu 3+ ion has not been efficient. (author)

Decomposition of uranyl peroxo-carbonato complex ion in the presence of metal oxides in carbonate media

International Nuclear Information System (INIS)

Dong-Yong Chung; Min-Sung Park; Keun-Young Lee; Eil-Hee Lee; Kwang-Wook Kim; Jei-Kwon Moon

2015-01-01

Uranium oxide was dissolved in the form of the uranyl peroxo-carbonato complex ion, UO 2 (O 2 )(CO 3 ) 2 4- in carbonate solutions with hydrogen peroxide. When UO 2 (O 2 )(CO 3 ) 2 4- ions lose their peroxide component, they become a stable species of uranyl tricarbonato complex ion, UO 2 (O 2 )(CO 3 ) 2 4- . The uranyl peroxo-carbonato complex self-decomposed more rapidly into the uranyl tricarbonato complex ion in the presence of a metal oxide in the carbonate solution. In this study, decomposition of the uranyl peroxo-carbonato complex in a carbonate solution was investigated in the presence of several metal oxides using absorption spectroscopy. (author)