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Sample records for paidarie complex-haye uraniumvi

  1. Uranium(VI) speciation by spectroscopy

    International Nuclear Information System (INIS)

    Meinrath, G.

    1997-01-01

    The application of UV-Vis and time-resolved laser-induced fluorescence (TRLF) spectroscopies to direct of uranium(VI) in environmental samples offers various prospects that have, however, serious limitations. While UV-Vis spectroscopy is probably not sensitive enough to detect uranium(VI) species in the majority of environmental samples, TRLFS is principially able to speciate uranium(VI) at very low concentration levels in the nanomol range. Speciation by TRLFS can be based on three parameters: excitation spectrum, emission spectrum and lifetime of the fluorescence emission process. Due to quenching effects, the lifetime may not be expected to be as characteristics as, e.g., the emission spectrum. Quenching of U(VI) fluorescence by reaction with organic substances, inorganic ions and formation of carbonate radicals is one important limiting factor in the application of U(VI) fluorescence spectroscopy. Fundamental photophysical criteria are illustrated using UV-Vis and fluorescence spectra of U(VI) hydrolysis and carbonato species as examples. (author)

  2. Extraction behavior of uranium(VI) with polyurethane foam

    International Nuclear Information System (INIS)

    Tingchia Huang; Donghwang Chen; Muchang Shieh; Chingtsven Huang

    1992-01-01

    The extraction of uranium(VI) from aqueous solution with polyether-based polyurethane (PU) foam was studied. The effects of the kinds and concentrations of nitrate salts, uranium(VI) concentration, temperature, nitric acid concentration, pH, the content of poly(ethylene oxide) in the polyurethane foam, and the ratio of PU foam weight and solution volume on the extraction of uranium(VI) were investigated. The interferences of fluoride and carbonate ions on the extraction of uranium(VI) were also examined, and methods to overcome both interferences were suggested. It was found that no uranium was extracted in the absence of a nitrate salting-out agent, and the extraction behaviors of uranium(IV) with polyurethane foam could be explained in terms of an etherlike solvent extraction mechanism. In addition, the percentage extraction of a multiple stage was also estimated theoretically

  3. Uranium(VI) adsorption properties of a chelating resin containing polyamine-substituted methylphosphonic acid moiety

    International Nuclear Information System (INIS)

    Matsuda, Masaaki; Akiyoshi, Yoshirou

    1991-01-01

    Uranium(VI) adsorption and desorption properties of a chelating resin containing polyamine-substituted methylphosphonic acid moiety of 2.29 mmol/g-resin (APA) were examined. Uranium(VI) adsorption properties of several ion exchange resins and extractant agents which were known as excellent adsorbents for uranium(VI), were examined together for a comparison with those of APA. Uranium(VI) adsorption capacity of APA at the concentration of 100 mg·dm -3 -uranium(VI) in 100 g·dm -3 -H 2 SO 4 aq. soln., 190 g·dm -3 -H 3 PO 4 aq. soln. and uranium enriched sea water, was 0.2, 0.05 and 0.05 mmol·g -1 respectively. The adsorption capacity of APA for uranium(VI) in these solutions was larger than that of another adsorbents, except the adsorption of uranium(VI) in enriched sea water on ion exchange resin containing phosphoric acid moiety (adsorption capacity ; 0.2 mmol·g -1 ). Uranium(VI) adsorption rate on APA was high and the relation between treatment time (t : min) and uranium(VI) concentration (y : mg·dm -3 ) in 100 g·dm -3 H 2 SO 4 aq. soln. after treatment, was shown as following equation, y=20 0.048t+1.90 (0≤t≤30). The adsorbed uranium(VI) on APA was able to be eluted with a mixed aq. soln. of hydrogen peroxide and sodium hydroxide and also was able to be eluted with an aq. alkaline soln. dissolved reduction agents such as sodium sulfite and hydrazine. From these results, it was thought that uranium(VI) adsorbed on APA was eluted due to the reduction to uranium(VI) by these eluents. (author)

  4. A spectroscopic study of uranium(VI) interaction with magnetite

    International Nuclear Information System (INIS)

    El Aamrani, S.; Gimenez, J.; Rovira, M.; Seco, F.; Grive, M.; Bruno, J.; Duro, L.; Pablo, J. de

    2007-01-01

    The uranium sorbed onto commercial magnetite has been characterized by using two different spectroscopic techniques such as X-ray photoelectron spectroscopy (XPS), and extended X-ray absorption fine structure (EXAFS). Magnetite samples have been put in contact with uranium(VI) solutions in conditions in which a high uranium uptake is expected. After several days, the magnetite surface has been analysed by XPS and EXAFS. The XPS results obtained are not conclusive regarding the uranium oxidation state in the magnetite surface. On the other hand, the results obtained with the EXAFS technique show that the uranium-magnetite sample spectrum has characteristics from both the UO 2 and schoepite spectra, e.g. a relatively high coordination number of equatorial oxygens and two axial oxygens, respectively. These results would indicate that the uranium sorbed onto magnetite would be a mixture of uranium(IV) and uranium(VI)

  5. Ion-exchanger ultraviolet spectrophotometry for uranium(VI)

    International Nuclear Information System (INIS)

    Waki, H.; Korkisch, J.

    1983-01-01

    A sensitive method based on solid-phase spectrophotometry has been developed for the microdetermination of uranium(VI) in water samples. Uranium is sorbed on the anion-exchanger QAE-Sephadex from thiocyanate solution and the absorbance of the exchanger is measured at 300 nm. This method is about 30 times more sensitive than solution spectrophotometry. Absorption spectra of various metals in the anion-exchanger phase are presented and their interferences discussed. A procedure for the cation-exchange separation of uranium from accompanying elements before spectral measurement of uranium is proposed. (author)

  6. Extraction separation studies of uranium(VI) by amine oxides

    International Nuclear Information System (INIS)

    Ejaz, M.

    1975-01-01

    The extraction of uranium(VI) by two amine oxides, 4-(5-nonyl)pyridine oxide and trioctylamine oxide has been studied. The extraction behavior of these two N-oxides is compared. The dependence of extraction on the type of amine oxide and acid, nature of organic diluent, and amine oxide concentration has been investigated. The influence of the concentration of the metal and salting-out agents is described. The possible mechanism of extraction is discussed in the light of the results of extraction isotherms, loading radiodata, and log-log plots of amine oxide concentration vs distribution ratio. The separation factors for a number of metal ions are reported, and the separation of uranium from some fission elements has also been achieved

  7. Application of Calixarenes as Macrocyclic Ligands for Uranium(VI: A Review

    Directory of Open Access Journals (Sweden)

    Katarzyna Kiegiel

    2013-01-01

    Full Text Available Calixarenes represent a well-known family of macrocyclic molecules with broad range of potential applications in chemical, analytical, and engineering materials fields. This paper covers the use of calixarenes as complexing agents for uranium(VI. The high effectiveness of calix[6]arenes in comparison to other calixarenes in uranium(VI separation process is also presented. Processes such as liquid-liquid extraction (LLE, liquid membrane (LM separation, and ion exchange are considered as potential fields for application of calixarenes as useful agents for binding UO22+ for effective separation from aqueous solutions containing other metal components.

  8. Thermochemistry of uranium(VI), arsenic, and alkali metal triple oxides

    International Nuclear Information System (INIS)

    Karyakin, N.V.; Chernorukov, G.N.

    1994-01-01

    The standard enthalpies of reactions of stoichiometric mixtures of potassium dyhydrogen orthoarsenate, uranium(VI) oxide, alkali metal nitrates, and of mixtures of triple oxides with the general formula M I AsUO 6 (M I =Li, Na, K, Rb, and Cs) and potassium nitrate with aqueous solution of hydrofluoric acid were determined an an adiabatic calorimeter at 298.15 K. The standard enthalpies of formation of uranium(VI), arsenic, and alkali metal triple oxides at 298.15 K were calculated form the data obtained. 8 refs., 1 tab

  9. The determination of uranium(VI) by flow-injection analysis

    International Nuclear Information System (INIS)

    Jones, E.A.

    1985-01-01

    A method is described for the direct determination of uranium(VI) in waste waters and acid leach liquors by use of a flow-injection procedure and spectrophotometric measurement with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (bromo-PADAP). The interference effects of several commonly occurring elements were studied. The calibration curve is linear over concentrations of uranium(VI) from 0,5 to 20 mg/1, and the precision obtained on a synthetic leach liquor was 0,019 (relative standard deviation). The procedure is rapid and convenient, and up to 40 samples can be analysed in an hour

  10. Solid phase extraction of uranium(VI) onto benzoylthiourea-anchored activated carbon

    International Nuclear Information System (INIS)

    Zhao Yongsheng; Liu Chunxia; Feng Miao; Chen Zhen; Li Shuqiong; Tian Gan; Wang Li; Huang Jingbo; Li Shoujian

    2010-01-01

    A new solid phase extractant selective for uranium(VI) based on benzoylthiourea anchored to activated carbon was developed via hydroxylation, amidation and reaction with benzoyl isothiocyanate in sequence. Fourier transform infrared spectroscopy and total element analysis proved that benzoylthiourea had been successfully grafted to the surface of the activated carbon, with a loading capacity of 1.2 mmol benzoylthiourea per gram of activated carbon. The parameters that affect the uranium(VI) sorption, such as contact time, solution pH, initial uranium(VI) concentration, adsorbent dose and temperature, have been investigated. Results have been analyzed by Langmuir and Freundlich isotherm; the former was more suitable to describe the sorption process. The maximum sorption capacity (82 mg/g) for uranium(VI) was obtained at experimental conditions. The rate constant for the uranium sorption by the as-synthesized extractant was 0.441 min -1 from the first order rate equation. Thermodynamic parameters (ΔH 0 = -46.2 kJ/mol; ΔS 0 = -98.0 J/mol K; ΔG 0 = -17.5 kJ/mol) showed the adsorption of an exothermic process and spontaneous nature, respectively. Additional studies indicated that the benzoylthiourea-anchored activated carbon (BT-AC) selectively sorbed uranyl ions in the presence of competing ions, Na + , Co 2+ , Sr 2+ , Cs + and La 3+ .

  11. Solid phase extraction of uranium(VI) onto benzoylthiourea-anchored activated carbon

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    Zhao Yongsheng; Liu Chunxia; Feng Miao; Chen Zhen; Li Shuqiong; Tian Gan; Wang Li; Huang Jingbo [College of Chemistry, Sichuan University, 29 Wangjiang Lu, Chengdu, 610064, Sichuan (China); Li Shoujian, E-mail: sjli000616@scu.edu.cn [College of Chemistry, Sichuan University, 29 Wangjiang Lu, Chengdu, 610064, Sichuan (China)

    2010-04-15

    A new solid phase extractant selective for uranium(VI) based on benzoylthiourea anchored to activated carbon was developed via hydroxylation, amidation and reaction with benzoyl isothiocyanate in sequence. Fourier transform infrared spectroscopy and total element analysis proved that benzoylthiourea had been successfully grafted to the surface of the activated carbon, with a loading capacity of 1.2 mmol benzoylthiourea per gram of activated carbon. The parameters that affect the uranium(VI) sorption, such as contact time, solution pH, initial uranium(VI) concentration, adsorbent dose and temperature, have been investigated. Results have been analyzed by Langmuir and Freundlich isotherm; the former was more suitable to describe the sorption process. The maximum sorption capacity (82 mg/g) for uranium(VI) was obtained at experimental conditions. The rate constant for the uranium sorption by the as-synthesized extractant was 0.441 min{sup -1} from the first order rate equation. Thermodynamic parameters ({Delta}H{sup 0} = -46.2 kJ/mol; {Delta}S{sup 0} = -98.0 J/mol K; {Delta}G{sup 0} = -17.5 kJ/mol) showed the adsorption of an exothermic process and spontaneous nature, respectively. Additional studies indicated that the benzoylthiourea-anchored activated carbon (BT-AC) selectively sorbed uranyl ions in the presence of competing ions, Na{sup +}, Co{sup 2+}, Sr{sup 2+}, Cs{sup +} and La{sup 3+}.

  12. Extraction chromatographic method of uranium(VI) with high molecular mass amine (ALIQUAT - 336)

    International Nuclear Information System (INIS)

    Roy, Uday Sankar; Dutta, Keshab Kumar

    1999-01-01

    A selective method has been developed for reversed phase extraction chromatographic studies of uranium(VI) with Aliquat - 336 (liquid anion exchanger) coated on silica gel as stationary phase. Quantitative extraction of uranium has been achieved in HCl - medium from 1.25(M)-4(M). The effect of different acids with various concentrations stripping agents, flow rate on extraction and elution have been investigated. The exchange capacity of the prepared exchanger has been determined. Uranium(VI) has been separated quantitatively from Th, Ce, Zr, Pb, Ga, Hg, Fe, La, Pr, Nd, Sm and Cr from a binary mixture by controlling the extraction and elution conditions. The separation of U(VI) from ternary and quarternary mixtures of various metal ions has also been achieved. (author)

  13. Sorption of Uranium(VI and Thorium(IV by Jordanian Bentonite

    Directory of Open Access Journals (Sweden)

    Fawwaz I. Khalili

    2013-01-01

    Full Text Available Purification of raw bentonite was done to remove quartz. This includes mixing the raw bentonite with water and then centrifuge it at 750 rpm; this process is repeated until white purified bentonite is obtained. XRD, XRF, FTIR, and SEM techniques will be used for the characterization of purified bentonite. The sorption behavior of purified Jordanian bentonite towards and Th4+ metal ions in aqueous solutions was studied by batch experiment as a function of pH, contact time, temperature, and column techniques at 25.0∘C and . The highest rate of metal ions uptake was observed after 18 h of shaking, and the uptake has increased with increasing pH and reached a maximum at . Bentonite has shown high metal ion uptake capacity toward uranium(VI than thorium(IV. Sorption data were evaluated according to the pseudo- second-order reaction kinetic. Sorption isotherms were studied at temperatures 25.0∘C, 35.0∘C, and 45.0∘C. The Langmuir, Freundlich, and Dubinin-Radushkevich (D-R sorption models equations were applied and the proper constants were derived. It was found that the sorption process is enthalpy driven for uranium(VI and thorium(IV. Recovery of uranium(VI and thorium(IV ions after sorption was carried out by treatment of the loaded bentonite with different concentrations of HNO3 1.0 M, 0.5 M, 0.1 M, and 0.01 M. The best percent recovery for uranium(VI and thorium(IV was obtained when 1.0 M HNO3 was used.

  14. Catechol functionalized aminopropyl silica gel: synthesis, characterization and preconcentrative separation of uranium(VI) from thorium(IV)

    International Nuclear Information System (INIS)

    Metilda, P.; Mary Gladis, J.; Prasada Rao, T.P.

    2005-01-01

    A novel solid phase extractant is prepared by chemically immobilizing catechol with diazotized aminopropyl silica gel. The resulting catechol functionalized silica gel (CASG) was characterized by FTIR, and microanalysis and was used for selective enrichment of uranium(VI) from other inorganic ions. The optimum pH range for maximum sorption of uranium(VI) and thorium(IV) was found to be in the range 3.5-6.0. The above actinides were eluted with 10 cm 3 of 1.0 mol dm -3 HCl and determined by using an Arsenazo III spectrophotometric procedure. The calibration graph was rectilinear over the uranium(VI) concentration in the range 2-100 μg dm -3 with a relative standard deviation of 2.15% (for 25 μg of uranium(VI) present in 1.0 dm 3 of sample). The validation of the developed preconcentration procedure was carried out by analyzing marine sediment (MESS-3, NRC, Canada) and soil (IAEA soil-7, Austria) reference materials. The developed preconcentration method enables a simple instruments like a spectrophotometer gave comparable values of uranium(VI) to that of standard inductively coupled plasma-mass spectrometric values during the analysis of real soil and sediment samples. (orig.)

  15. Catechol functionalized aminopropyl silica gel: synthesis, characterization and preconcentrative separation of uranium(VI) from thorium(IV)

    Energy Technology Data Exchange (ETDEWEB)

    Metilda, P.; Mary Gladis, J.; Prasada Rao, T.P. [Regional Research Lab. (CSIR), Trivandrum (India)

    2005-07-01

    A novel solid phase extractant is prepared by chemically immobilizing catechol with diazotized aminopropyl silica gel. The resulting catechol functionalized silica gel (CASG) was characterized by FTIR, and microanalysis and was used for selective enrichment of uranium(VI) from other inorganic ions. The optimum pH range for maximum sorption of uranium(VI) and thorium(IV) was found to be in the range 3.5-6.0. The above actinides were eluted with 10 cm{sup 3} of 1.0 mol dm{sup -3} HCl and determined by using an Arsenazo III spectrophotometric procedure. The calibration graph was rectilinear over the uranium(VI) concentration in the range 2-100 {mu}g dm{sup -3} with a relative standard deviation of 2.15% (for 25 {mu}g of uranium(VI) present in 1.0 dm{sup 3} of sample). The validation of the developed preconcentration procedure was carried out by analyzing marine sediment (MESS-3, NRC, Canada) and soil (IAEA soil-7, Austria) reference materials. The developed preconcentration method enables a simple instruments like a spectrophotometer gave comparable values of uranium(VI) to that of standard inductively coupled plasma-mass spectrometric values during the analysis of real soil and sediment samples. (orig.)

  16. Liquid-liquid extraction of uranium(VI) using Cyanex 272 in toluene from sodium salicylate medium

    International Nuclear Information System (INIS)

    Madane, Namdev S.; Nikam, Gurunath H.; Jadhav, Deepali V.; Mohite, Baburao S.

    2011-01-01

    Liquid-liquid extraction of U(VI) from sodium salicylate media using Cyanex 272 in toluene has been carried out. Uranium(VI) was quantitatively extracted from 1 x 10 -3 M sodium salicylate with 5 x 10 -4 M Cyanex 272 in toluene. It was stripped quantitatively from the organic phase with 1M HCl and determined spectrophotometrically with arsenazo(III) at 660 nm. The effect of concentrations of sodium salicylate, extractant, diluents, metal ion and strippants have been studied. Separation of uranium(VI) from other elements was achieved from binary as well as from multicomponent mixtures. The method was extended to determination of uranium(VI) in geological samples. The method is simple, rapid and selective with good reproducibility (approximately ± 2%). (author)

  17. Solvent extraction of uranium(VI) with benzoylacetanilide and its nitro derivatives

    International Nuclear Information System (INIS)

    Mukherjee, Gautam Kumar; Das, Jyotirmoy

    1984-01-01

    The extraction behaviour of uranium(VI) chelates of benzoylacetanilide and four of its mononitro derivatives, viz., benzoyl-o-nitroacetanilide, benzoyl-m-nitroacetanilide, benzoyl-p-nitro-acetanilide and p-nitrobenzoylacetanilide from aqueous solution into carbon tetrachloride has been studied. The extractions have also been carried out in the presence of pyridine, α-picoline, β-picoline and γ-picoline. The extraction constants, and the two phase formation constants of the chelates and adducts have been determined. The effects of the nitro substituent in benzoylacetanilide and formation of syngergistic adducts have been discussed. (author)

  18. Liquid-liquid extraction and separation studies of uranium(VI)

    International Nuclear Information System (INIS)

    Langade, A.D.; Shinde, V.M.

    1980-01-01

    Separation of uranium(VI) from iron(III), molybdenum(VI), vanadium(V), bismuth(III), zirconium(IV) and thorium(IV) is achieved by liquid-liquid extraction with 4-methyl-3-pentene-2-one (mesityl oxide; MeO) from sodium salicylate media (0.1M, pH 6.0). The extracted species is UO 2 (HO.C 6 H 4 COO) 2 .2MeO. A procedure for separating 50 μg of uranium from mg amounts of the other metals is described. (author)

  19. Enhancement of uranium(VI) biosorption by chemically modified marine-derived mangrove endophytic fungus Fusarium sp. ZZF51

    International Nuclear Information System (INIS)

    Chen, F.; Tan, N.; Long, W.; Yang, S.K.; She, Z.G.; Lin, Y.C.

    2014-01-01

    Fusarium sp. ZZF51, mangrove endophytic fungus originated from South China Sea coast, was chemically modified by formaldehyde, methanol and acetic acid to enhance its affinity of uranium(VI) from waste water. The influencing factors about uranium(VI) adsorption such as contact time, solution pH, the ratio of solid/liquid (S/L) and initial uranium(VI) concentration were investigated, and the suitable adsorption isotherm and kinetic models were determined. In addition, the biosorption mechanism was also discussed by FTIR analysis. Experimental results show that the maximum biosorption capacity of formaldehyde-treated biomass for uranium(VI) at the optimized condition of pH 6.0, S/L 0.6 and equilibrium time 90 min is 318.04 mg g -1 , and those of methanol-treated and HAc-treated biomass are 311.95 and 351.67 mg g -1 at the same pH and S/L values but different equilibrium time of 60 and 90 min, respectively. Thus the maximum biosorption capacity of the three kind of modified biomass have greatly surpassed that of the raw biomass (21.42 mg g -1 ). The study of kinetic exhibits a high level of compliance with the Lagergren's pseudo-second-order kinetic models. Langumir and Freundlich models have proved to be well able to explain the sorption equilibrium with the satisfactory correlation coefficients higher than 0.96. FTIR analysis reveals that the carboxyl, amino and hydroxyl groups on the cell wall of Fusarium sp. ZZF51 play an important role in uranium(VI) biosorption process. (author)

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

    International Nuclear Information System (INIS)

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

    2003-01-01

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

  1. Interaction of uranium(VI) with bioligands present in human biological fluids. The case study of urea and uric acid

    International Nuclear Information System (INIS)

    Osman, A.A.A.; Geipel, G.; Bernhard, G.

    2013-01-01

    The complexation of uranium(VI) with bioligands found in human biological fluids, viz, urea and uric acid in aqueous solutions, has been investigated using time-resolved laser-induced fluorescence spectroscopy (TRLFS) at room temperature, I = 0.1 M (NaClO4) and pH (3 for uric acid; 4 for urea). In both complex systems a static quench effect with increasing ligand concentration and no peaks shift upon complexation were observed. With uranium(VI) both ligands formed a fairly weak 1:1 complex with average stability constants of log β 110 = 4.67 ± 0.29 for uric acid and log β 110 = 3.79 ± 0.15 and 2.12 ± 0.18 for relatively low and relatively high urea concentrations, respectively. Application of the newly generated data on the U(VI) speciation modelling in biofluids, e.g., human urine was also discussed.

  2. Interaction of uranium(VI) with bioligands present in human biological fluids. The case study of urea and uric acid

    Energy Technology Data Exchange (ETDEWEB)

    Osman, A.A.A.; Geipel, G.; Bernhard, G. [Helmholtz-Zentrum Dresden-Rossendorf, Dresden (Germany). Inst. of Resource Ecology

    2013-05-01

    The complexation of uranium(VI) with bioligands found in human biological fluids, viz, urea and uric acid in aqueous solutions, has been investigated using time-resolved laser-induced fluorescence spectroscopy (TRLFS) at room temperature, I = 0.1 M (NaClO4) and pH (3 for uric acid; 4 for urea). In both complex systems a static quench effect with increasing ligand concentration and no peaks shift upon complexation were observed. With uranium(VI) both ligands formed a fairly weak 1:1 complex with average stability constants of log {beta}{sub 110} = 4.67 {+-} 0.29 for uric acid and log {beta}{sub 110} = 3.79 {+-} 0.15 and 2.12 {+-} 0.18 for relatively low and relatively high urea concentrations, respectively. Application of the newly generated data on the U(VI) speciation modelling in biofluids, e.g., human urine was also discussed.

  3. Extraction of uranium(VI) by emulsion liquid membrane containing 5,8-diethyl-7-hydroxy-6-dodecanone oxime

    International Nuclear Information System (INIS)

    Akiba, Kenichi; Takahashi, Toshihiko; Kanno, Takuji

    1984-01-01

    Extraction of uranium(VI) by a liquid surfactant membrane has been studied. The stability of water-in-oil (w/o) emulsion dispersed in the continuous aqueous phase increased with an increase in surfactant concentrations and in the fraction of the organic phase in emulsion globules. Uranium(VI) in dilute acid solutions was extracted into (w/o) emulsions containing 5,8-diethyl-7-hydroxy-6-dodecanone oxime (LIX 63) as a mobile carrier and its concentration decreased according to [U]sub(t)=[U]sub(o)exp(-ksub(obsd)t). The apparent rate constants (ksub(obsd)) increased with an increase in carrier concentrations and in external pH values, while they were slightly dependent on the stripping acid concentrations. Uranium was transported and concentrated into the internal aqueous droplets. The final concentration of uranium in the external aqueous phase dropped to about 10 -3 of its initial value. (author)

  4. Liquid-liquid extraction of uranium(VI) with cryptand-222 and Eosin as the counter ion

    International Nuclear Information System (INIS)

    Viji Jacob Mathew; Khopkar, S.M.

    1995-01-01

    Uranium(VI), (5 μg) was quantitatively extracted at pH 6.0 with 0.01M cryptand-222 in chloroform in the presence of 0.005M Eosin as the counter ion. The metal from the organic phase was stripped with 0.1M perchloric acid. Uranium(VI) from the aqueous phase was determined spectrophotometrically at 430 nm as its complex with oxine. The extraction was quantitative between pH 5.5-6.5. Nitrobenzene, chloroform and dichloromethane were the best diluents. The optimum extractant concentration was 0.01M, while that of Eosin was 0.005M. Except for perchloric acid (0.01M), other acids could not strip uranium. Uranium was separated from manganese, cadmium, lead, thallium and nickel, etc., in the multicomponent mixtures. The relative standard deviation was ±1%. (author). 18 refs., 1 fig., 6 tabs

  5. Uranium(VI) coordination polymers with pyromellitate ligand: Unique 1D channel structures and diverse fluorescence

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yingjie, E-mail: yzx@ansto.gov.au [Australian Nuclear Science and Technology Organization, Locked Bag 2001, Kirrawee DC, NSW 2232 (Australia); Bhadbhade, Mohan [Mark Wainwright Analytical Centre, University of New South Wales, Kensington, NSW 2052 (Australia); Karatchevtseva, Inna [Australian Nuclear Science and Technology Organization, Locked Bag 2001, Kirrawee DC, NSW 2232 (Australia); Price, Jason R. [Australian Synchrotron, 800 Blackburn Road, Clayton, VIC 3168 (Australia); Liu, Hao [Centre for Clean Energy Technology, School of Chemistry and Forensic Science, University of Technology Sydney, PO Box 123, Broadway, Sydney, NSW 2007 (Australia); Zhang, Zhaoming; Kong, Linggen [Australian Nuclear Science and Technology Organization, Locked Bag 2001, Kirrawee DC, NSW 2232 (Australia); Čejka, Jiří [Department of Mineralogy, National Museum, Václavské náměstí, 68, Prague 1, 115 79-CZ (Czech Republic); Lu, Kim; Lumpkin, Gregory R. [Australian Nuclear Science and Technology Organization, Locked Bag 2001, Kirrawee DC, NSW 2232 (Australia)

    2015-03-15

    Three new coordination polymers of uranium(VI) with pyromellitic acid (H{sub 4}btca) have been synthesized and structurally characterized. (ED)[(UO{sub 2})(btca)]·(DMSO)·3H{sub 2}O (1) (ED=ethylenediammonium; DMSO=dimethylsulfoxide) has a lamellar structure with intercalation of ED and DMSO. (NH{sub 4}){sub 2}[(UO{sub 2}){sub 6}O{sub 2}(OH){sub 6}(btca)]·~6H{sub 2}O (2) has a 3D framework built from 7-fold coordinated uranyl trinuclear units and btca ligands with 1D diamond-shaped channels (~8.5 Å×~8.6 Å). [(UO{sub 2}){sub 2}(H{sub 2}O)(btca)]·4H{sub 2}O (3) has a 3D network constructed by two types of 7-fold coordinated uranium polyhedron. The unique μ{sub 5}-coordination mode of btca in 3 enables the formation of 1D olive-shaped large channels (~4.5 Å×~19 Å). Vibrational modes, thermal stabilities and fluorescence properties have been investigated. - Graphical abstract: Table of content: three new uranium(VI) coordination polymers with pyromellitic acid (H{sub 4}btca) have been synthesized via room temperature and hydrothermal synthesis methods, and structurally characterized. Two to three dimensional (3D) frameworks are revealed. All 3D frameworks have unique 1D large channels. Their vibrational modes, thermal stabilities and photoluminescence properties have been investigated. - Highlights: • Three new coordination polymers of U(VI) with pyromellitic acid (H{sub 4}btca). • Structures from a 2D layer to 3D frameworks with unique 1D channels. • Unusual µ{sub 5}-(η{sub 1}:η{sub 2}:η{sub 1}:η{sub 2:}η{sub 1}) coordination mode of btca ligand. • Vibrational modes, thermal stabilities and luminescent properties reported.

  6. Determination of submicromolar amounts of uranium(VI) by compleximetric titration with pyridine-2,6-dicarboxylic acid

    International Nuclear Information System (INIS)

    Marsh, S.F.; Betts, M.R.; Rein, J.E.

    1980-01-01

    Uranium(VI) is selectively determined by a compleximetric titration with pyridine-2,6-dicarboxylic acid, using arsenazo-I indicator and hexamethylenetetramine buffer at pH 4.9. Cyclohexanediaminetetraacetic acid and diethylenetriaminepentaacetic acid provide masking of interfering metal ions. A probe colorimeter apparatus is recommended for end-point detection. The relative standard deviation is 0.6% for 0.17-0.76 μmol of uranium. (Auth.)

  7. Determination of submicromolar amounts of uranium(VI) by compleximetric titration with pyridine-2,6-dicarboxylic acid

    Energy Technology Data Exchange (ETDEWEB)

    Marsh, S F; Betts, M R; Rein, J E [Los Alamos Scientific Lab., NM (USA)

    1980-10-01

    Uranium(VI) is selectively determined by a compleximetric titration with pyridine-2,6-dicarboxylic acid, using arsenazo-I indicator and hexamethylenetetramine buffer at pH 4.9. Cyclohexanediaminetetraacetic acid and diethylenetriaminepentaacetic acid provide masking of interfering metal ions. A probe colorimeter apparatus is recommended for end-point detection. The relative standard deviation is 0.6% for 0.17-0.76 ..mu..mol of uranium.

  8. Antagonism in the extraction of uranium(VI) by the binary mixture of PC88A and benzimidazole

    International Nuclear Information System (INIS)

    Mukherjee, A.; Kamila, S.; Chakravortty, V.

    1999-01-01

    Extraction studies of uranium(VI) by the binary mixture of PC88A and benzimidazole show an antagonistic behavior in the concentration range 10 -5 -10 -6 M of PC88A and 0.005M of benzimidazole. Antagonism is observed due to the deprotonation of PC88A by benzimidazole forming an adduct resulting in the virtual removal of PC88A from the system. (author)

  9. Study of uranium(VI) speciation in phosphoric acid solutions and of its recovery by solvent extraction

    International Nuclear Information System (INIS)

    Dartiguelongue, Adrien

    2014-01-01

    Because small amounts of uranium are present in phosphate rocks, wet phosphoric acids may contain up to 300 ppm of uranium(VI). Therefore, such acids are a cost-effective unconventional source of this metal. Its recovery is a challenge for metallurgical firms which must develop reliable and selective solvent extraction processes. Such processes need to know the chemical equilibria involved in the extraction process, the speciation of uranium and its thermodynamics in solution. These two last points have been investigated in this work. Firstly, the most probable species of uranium(VI) in phosphoric acid solutions have been selected thanks to a detailed review of the literature. Then, a thermodynamic model founded on an equation of state for electrolytes has been built according these hypotheses. It has been validated with speciation data coming from original ATR-IR spectroscopy measurements. Finally, the composition of the aqueous phosphoric acid solutions and the activity coefficients obtained have been combined with a chemical model of uranium(VI) extraction into an organic phase containing a synergistic mixture of bis(2-ethylhexyl)phosphoric acid (D2EHPA) and tri-n-octylphosphine oxide (TOPO) in order to represent the variation of the distribution coefficient of uranium(VI) with H 3 PO 4 concentration. This model had been previously developed at Chimie ParisTech at a given concentration of H 3 PO 4 (i.e., 5,3 mol/L), but in the present study we have tested its validity in an extended range of phosphoric acid concentrations (i.e., 1-7 mol/L) and improved it. (author)

  10. Preparation of 1-(2-pyridylazo)-2-naphthol functionalized benzophenone/naphthalene and their uses in solid phase extractive preconcentration/separation of uranium(VI)

    International Nuclear Information System (INIS)

    Preetha, C.R.; Prasada Rao, T.

    2003-01-01

    The preparation of solid reagent 1-(2-pyridylazo)-2-naphthol functionalized benzophenone/naphthalene for preconcentration/separation of uranium(VI) is described. These reagents enriches uranium(VI) quantitatively from dilute aqueous solutions in the pH range 10.5-11.0. The solid mixture consisting of the enriched metal ion along with solid phase extractant were dissolved in 2 ml of acetone and uranium(VI) content was established spectrophotometrically by using Arsenazo III procedure. Calibration graphs were rectilinear over the uranium(VI) concentration in the range 0.002-0.1 μg cm -3 . Five replicate determinations of 40 μg of uranium present in 1 dm 3 of sample solution gave a mean absorbance of 0.185 with a relative standard deviation of 1.4%. The detection limit (corresponding to 3 times the standard deviation of the blank) and the enrichment factor were found to be 2 μg dm -3 and 500 respectively. Further the possible separation of uranium(VI) from several bivalent, trivalent and tetravalent elements was also established. In addition to validating the developed method by successfully analysing marine sediment reference material (MESS-3), uranium content was established in soil, river and marine sediment samples by the developed method and compared with standard inductively coupled plasma mass spectrometry (ICP-MS) values. (orig.)

  11. Uranium(VI) speciation: modelling, uncertainty and relevance to bioavailability models. Application to uranium uptake by the gills of a freshwater bivalve

    International Nuclear Information System (INIS)

    Denison, F.H.

    2004-07-01

    The effects of varying solution composition on the interactions between uranium(VI) and excised gills of the freshwater bivalve Corbicula fluminea have been investigated in well defined solution media. A significant reduction in the uptake of uranium was observed on increasing the concentrations of the uranium complexing ligands citrate and carbonate. Saturation kinetics as a function of uranium concentration at a pH value of 5.0 were observed, indicating that the uptake of uranium is a facilitated process, probably involving one or several trans-membrane transport systems. A relatively small change in the uptake of uranium was found as a function of pH (factor of ca. 2), despite the extremely large changes to the solution speciation of uranium within the range of pH investigated (5.0 - 7.5). A comprehensive review of the thermodynamic data relevant to the solution composition domain employed for this study was performed. Estimates of the uncertainties for the formation constants of aqueous uranium(VI) species were integrated into a thermodynamic database. A computer program was written to predict the equilibrium distribution of uranium(VI) in simple aqueous systems, using thermodynamic parameter mean-values. The program was extended to perform Monte Carlo and Quasi Monte Carlo uncertainty analyses, incorporating the thermodynamic database uncertainty estimates, to quantitatively predict the uncertainties inherent in predicting the solution speciation of uranium. The use of thermodynamic equilibrium modelling as a tool for interpreting the bioavailability of uranium(VI) was investigated. Observed uranium(VI) uptake behaviour was interpreted as a function of the predicted changes to the solution speciation of uranium. Different steady-state or pre-equilibrium approaches to modelling uranium uptake were tested. Alternative modelling approaches were also tested, considering the potential changes to membrane transport system activity or sorption characteristics on

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-06-23

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-06-23

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

  14. Kinetic and equilibrium study of uranium(VI) adsorption by Bacillus licheniformis

    International Nuclear Information System (INIS)

    Zheng-ji Yi; University of Science and Technology Beijing, Beijing; Jun Yao

    2012-01-01

    Uranium pollution is a severe problem worldwide. Biosorption has been proposed as one of the most promising technologies for the removal of uranyl cations. Here we report on the adsorption behavior of uranium(VI) [U(VI)] on Bacillus licheniformis biomass to explore the potentiality of its application in uranium contamination control. The adsorption equilibrium, adsorption kinetics, and effects of temperature, pH and initial biosorbent dosage on the adsorption equilibrium were investigated in detail through batch experiments. The adsorption process is pronouncedly affected by the solution pH and the optimum pH range should be 4.5-5.0.Temperature range from 25 to 45 deg C has a certain effect on the rate of biosorption, but little effect on the equilibrium adsorption capacity. The U(VI) percentage removal increased concurrently with increasing biomass dosage, whereas the adsorption capacity decreased. The process follows the Langmuir isotherm model. The adsorption kinetics data were fitted very well by the pseudo-first-order rate model. Finally, the calculation results of thermodynamic constant (ΔG a = 9.98 kJ/mol) reveal that the adsorption process can be identified as a spontaneous chemical process. The present results suggest that B. licheniformis has considerable potential for the removal of uranyl from aqueous solution. (author)

  15. Gravimetric determination of uranium(VI) and thorium(IV) with substituted pyrazolones

    International Nuclear Information System (INIS)

    Arora, H.C.; Rao, G.N.

    1981-01-01

    4-Acylpyrazolones like 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (PMBP), 1-phenyl-3-methyl-4-p-nitrobenzoyl-5-pyrazolone (PMNP) and 1-phenyl-3-methyl-4-(3,5 dinitrobenzoyl)-5-pyrazolone (PMDP) have been synthesized and developed as gravimetric reagents for the determination of U(VI) and Th(IV). Uranium(VI) is almost quantitatively precipitated with PMBP, PMNP, and PMDP at pH 2.20, 1.85 and 1.70 respectively. The pH values for the complete precipitation of thorium(IV) with PMBP, PMNP and PMDP are 2.90, 2.75 and 2.50 respectively. PMBP has proved to be an efficient ligand for gravimetric determination of U(VI) by direct weighing method after drying at 100 +- 10 deg C. The percentage relative error varies from 0.4 to 1.6 in the determination of U(VI) by this method. The effect of a number of interfering ions on the precipitation of U(VI) by PMBP has been reported. (author)

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

    International Nuclear Information System (INIS)

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

    2003-01-01

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

  17. Towards a consistent geochemical model for prediction of uranium(VI) removal from groundwater by ferrihydrite

    International Nuclear Information System (INIS)

    Gustafsson, Jon Petter; Daessman, Ellinor; Baeckstroem, Mattias

    2009-01-01

    Uranium(VI), which is often elevated in granitoidic groundwaters, is known to adsorb strongly to Fe (hydr)oxides under certain conditions. This process can be used in water treatment to remove U(VI). To develop a consistent geochemical model for U(VI) adsorption to ferrihydrite, batch experiments were performed and previous data sets reviewed to optimize a set of surface complexation constants using the 3-plane CD-MUSIC model. To consider the effect of dissolved organic matter (DOM) on U(VI) speciation, new parameters for the Stockholm Humic Model (SHM) were optimized using previously published data. The model, which was constrained from available X-ray absorption fine structure (EXAFS) spectroscopy evidence, fitted the data well when the surface sites were divided into low- and high-affinity binding sites. Application of the model concept to other published data sets revealed differences in the reactivity of different ferrihydrites towards U(VI). Use of the optimized SHM parameters for U(VI)-DOM complexation showed that this process is important for U(VI) speciation at low pH. However in neutral to alkaline waters with substantial carbonate present, Ca-U-CO 3 complexes predominate. The calibrated geochemical model was used to simulate U(VI) adsorption to ferrihydrite for a hypothetical groundwater in the presence of several competitive ions. The results showed that U(VI) adsorption was strong between pH 5 and 8. Also near the calcite saturation limit, where U(VI) adsorption was weakest according to the model, the adsorption percentage was predicted to be >80%. Hence U(VI) adsorption to ferrihydrite-containing sorbents may be used as a method to bring down U(VI) concentrations to acceptable levels in groundwater

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2003-08-01

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

  19. Extraction equilibrium of uranium(VI) with dicyclohexano-18-crown-6 and its application for separating uranium and thorium

    International Nuclear Information System (INIS)

    Wang Wenji; Sun Quing; Chen Bozhong

    1986-01-01

    The extraction of uranium with dicyclohexano-18-crown-6 (mixed isomers) is described. The extraction equilibrium of uranium(VI) from aqueous hydrochloric acid solution with dicyclohexano-18-crown-6 isomer A (Isub(a)) and isomer B (Isub(b)) in 1,2-dichloroethane is presented. The extracted species were found to be 1:2 (metal/crown) for Isub(a) and 2:3 for Isub(b) from slope analysis and direct determination of extracted complexes. The extraction equilibrium constants (Ksub(ex)) were determined at 25 deg C and are equal to 29.5 and 0.208, respectively. It is concluded that Isub(a) has a stronger coordination ability for uranium than Isub(b). The different orientation of lone pairs of the oxygen atoms in both isomers has to be taken into account for interpereting the above results. (author)

  20. Effect of porosity and surface chemistry on the adsorption-desorption of uranium(VI) from aqueous solution and groundwater

    International Nuclear Information System (INIS)

    Yakout, S.M.

    2016-01-01

    Rice straw-based biochars modified with different chemical regents were used as an adsorbent for uranium(VI). Effect of pyrolysis temperature and nature of modifying agent's as well as surface chemistry, surface charge, and pore structure on U(VI) removal was investigated. Amount and nature of the surface groups has, in general, more influence than its porosity on U(VI) adsorption. The adsorption was maximum for the initial pH of 5.5. Rice straw derived biochars had comparable U(VI) adsorption as compared to other adsorbents. The U(VI) removal was 90 % from groundwater. NaHCO 3 was found to be the most efficient desorbent eluent for U(VI). (author)

  1. Effect of denaturants on the speciation of uranium(VI) complexes of malonic acid in micellar media

    International Nuclear Information System (INIS)

    Sailaja, B.B.V.; Kebede, Tesfahun; Nageswara Rao, G.; Prasada Rao, M.S.

    2001-01-01

    A computer assisted investigation has been made on the nature of complexes of uranium(VI) with malonic acid. The formation constants have been determined experimentally by monitoring hydrogen ion concentration. The distribution of the metal ion amongst the complexes formed with the above carboxylic acid has also been computed. The formation constants have been refined with the computer program, MINIQUAD75 using the primary alkalimetric data. The predominant complexes formed are UO 2 (H 2 C 3 O 4 ) 2 ) 2- , UO 2 (H 2 C 3 O 4 ) and UO 2 (H 2 C 3 O 4 )(H 2 C 3 O 4 H) - . The distribution pattern of different species varies with the relative concentrations of the metal ion and the ligand. The variation of stability with surfactant concentrations is found to be the cumulative effect of various factors like electrostatic interactions. dilution effect and competition for hydrogen ion associated with the nature of micelles. (author)

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

    International Nuclear Information System (INIS)

    Legin, A.V.; Seleznev, B.L.; Rudnitskaya, A.M.; Vlasov, Yu.G.

    1998-01-01

    The aim of the present paper is the development and analytical evaluation of a multisensor system for determination of low content of iron(II), iron(III) and uranium(VI) in complex aqueous media. Sensor array included sensors on the basis of chalcogenide vitreous materials with redox and ionic cross-sensitivities, crystalline silver sulphide electrode, noble metal electrodes Pt, Au, Ag and redox sensor on the basis of oxide glass. Potentiometric measurements have been taken in a conventional electrochemical cell vs. a standard Ag/AgCl reference electrode. All measurements have been taken at room temperature. Calibration solutions contained UO 2 (NO 3 ) 2 in concentration range 10 -6 -1,610 -5 mol/L, K 3 Fe(CN) 6 and K 4 Fe(CN) 6 or FeSO 4 (NH 4 ) 2 SO 4 and FeCl 3 , with the ratio of Fe(II)/Fe(III) concentration from 100:1 to 1:100, the total concentration of Fe was 10 -4 and 10 -5 mol/L. All solutions have been made on the background electrolyte of calcium and magnesium chlorides and sulphates with the fixed content of 5-27 mmol/L of each component which is a typical one for groundwater or mining water. Sensor potentials have been processed by a back-propagation artificial neural net. Average error of determination of Fe(II) and Fe(III) is about 20 %, of uranium(VI) - 40 %. It was found that sensitivity of the sensor array to iron and uranium is irrespective of the chemical form of these species

  3. Approaches to surface complexation modeling of Uranium(VI) adsorption on aquifer sediments

    Science.gov (United States)

    Davis, J.A.; Meece, D.E.; Kohler, M.; Curtis, G.P.

    2004-01-01

    Uranium(VI) adsorption onto aquifer sediments was studied in batch experiments as a function of pH and U(VI) and dissolved carbonate concentrations in artificial groundwater solutions. The sediments were collected from an alluvial aquifer at a location upgradient of contamination from a former uranium mill operation at Naturita, Colorado (USA). The ranges of aqueous chemical conditions used in the U(VI) adsorption experiments (pH 6.9 to 7.9; U(VI) concentration 2.5 ?? 10-8 to 1 ?? 10-5 M; partial pressure of carbon dioxide gas 0.05 to 6.8%) were based on the spatial variation in chemical conditions observed in 1999-2000 in the Naturita alluvial aquifer. The major minerals in the sediments were quartz, feldspars, and calcite, with minor amounts of magnetite and clay minerals. Quartz grains commonly exhibited coatings that were greater than 10 nm in thickness and composed of an illite-smectite clay with occluded ferrihydrite and goethite nanoparticles. Chemical extractions of quartz grains removed from the sediments were used to estimate the masses of iron and aluminum present in the coatings. Various surface complexation modeling approaches were compared in terms of the ability to describe the U(VI) experimental data and the data requirements for model application to the sediments. Published models for U(VI) adsorption on reference minerals were applied to predict U(VI) adsorption based on assumptions about the sediment surface composition and physical properties (e.g., surface area and electrical double layer). Predictions from these models were highly variable, with results overpredicting or underpredicting the experimental data, depending on the assumptions used to apply the model. Although the models for reference minerals are supported by detailed experimental studies (and in ideal cases, surface spectroscopy), the results suggest that errors are caused in applying the models directly to the sediments by uncertain knowledge of: 1) the proportion and types of

  4. Spectrophotometric Microdetermination of Thorium(IV and Uranium(VI with Chrome Azurol-S in Presence of Cationic Surfactant

    Directory of Open Access Journals (Sweden)

    A. B. Upase

    2011-01-01

    Full Text Available Cationic surfactant, cetyldimethylethylammonium bromide (CDMEAB, sensitize the color reactions of Th(IV and U(VI with chrome azurol-S(CRAS. Formation of water soluble deeply colored ternary complexes of metal ions show large bathochromic shift. Same stoichiometric composition of ternary complexes with 1:2:4 molar ratio (M-CRAS-CDMEAB have been observed for both the metal ions and are responsible for enhancement in molar absorptivities and sensitivities at shifted wavelength. The ternary complexes of thorium(IV and uranium(VI exhibit absorption maxima at 640 and 620 nm with molar absorptivities 85500 and 69600 L.mol-1.cm-2 respectively. Beer’s law were obeyed in concentration range 0.12-0.185 ppm for Th(IV and 0.13-0.162 ppm for U(VI in presence of CDMEAB. Conditional formation constants and various analytical parameters have been evaluated and compared the results of binary and ternary complexes. Enhancement in the molar absorptivities in presence of CDMEAB clearly indicated the usefulness of these colored reactions for microdetermination.

  5. Hazelnut shell activated carbon. A potential adsorbent material for the decontamination of uranium(VI) from aqueous solutions

    International Nuclear Information System (INIS)

    Mijia Zhu; Hankui Chai; Jun Yao; China University of Geosciences; Yunpeng Chen; Zhengji Yi

    2016-01-01

    Batch experiments were conducted to study the ability of hazelnut shell activated carbon (HSAC) to remove uranium(VI) ions from aqueous solutions. The effects of various operational parameters, such as contact time (0-200 min), pH (2.0-7.0), initial U(VI) concentration (20-240 mg/L) and adsorbent dosage (4.0-50 g/L) were examined. Results showed that the adsorption process was rapid within the first 100 min and then achieved equilibrium at 140 min. The kinetics followed a pseudo-second-order rate equation, and the adsorption process was well fit with the Langmuir model. HSAC exhibited good uranium adsorption capacity (16.3 mg/g) at pH 6.0, 140 min contact time and 8.0 g/L adsorbent dosage. Furthermore, the regeneration efficiency was 96.3 % over five cycles under the optimum operational conditions. These properties revealed that HSAC can be a suitable adsorbent for the fast and convenient removal of U(VI) from contaminated water. (author)

  6. Solvent extraction of uranium(VI) and thorium(IV) from nitrate media by carboxylic acid amides

    International Nuclear Information System (INIS)

    Preston, J.S.; Preez, A.C. du

    1995-01-01

    A series of nineteen N-alkyl carboxylic acid amides (R.CO.NHR') has been prepared, in which the alkyl groups R and R' have been varied in order to introduce different degrees of steric complexity into the compounds. A smaller number of N,N-dialkyl amides (R.CO.NR 2 ') and non-substituted amides (R.CO.NH 2 ) has also been prepared for comparison purposes. These amides were characterized by measurement of their boiling points, melting points, refractive indices and densities. The solvent extraction of uranium(VI) and thorium(IV) from sodium nitrate media by solutions of the amides in toluene was studied. Increasing steric bulk of the alkyl groups R and R' was found to cause a marked decrease in the extraction of thorium, with a much smaller effect on the extraction of uranium, thus considerably enhancing the separation between these metals. Vapour pressure osmometry studies indicate that the N-alkyl amides are self-associated in toluene solution, with aggregation numbers up to about 2.5 for 0.6 M solutions at 35 degree C. In contrast, the N,N-dialkyl amides behave as monomers under these conditions. The distribution ratios for the extraction of uranium and thorium show second- and third-order dependences, respectively, on the extractant concentration for both the N-alkyl and N,N-dialkyl amides. 15 refs., 8 figs., 8 tabs

  7. Adsorption of uranium(VI) from sulphate solutions using Amberlite IRA-402 resin: Equilibrium, kinetics and thermodynamics study

    International Nuclear Information System (INIS)

    Solgy, Mostafa; Taghizadeh, Majid; Ghoddocynejad, Davood

    2015-01-01

    Highlights: • Adsorption of uranium from sulphate solutions by an anion exchange resin. • The effects of pH, contact time and adsorbent dosage were investigated. • The adsorption equilibrium is well described by the Freundlich isotherm model. • The adsorption kinetics can be predicted by the pseudo second-order model. • The adsorption is a physical, spontaneous and endothermic process. - Abstract: In the present study, adsorption of uranium from sulphate solutions was evaluated using Amberlite IRA-402 resin. The variation of adsorption process was investigated in batch sorption mode. The parameters studied were pH, contact time and adsorbent dosage. Langmuir and Freundlich isotherm models were used in order to present a mathematical description of the equilibrium data at three different temperatures (25 °C, 35 °C and 45 °C). The final results confirmed that the equilibrium data tend to follow Freundlich isotherm model. The maximum adsorption capacity of Amberlite IRA-402 for uranium(VI) was evaluated to be 213 mg/g for the Langmuir model at 25 °C. The adsorption of uranium on the mentioned anion exchange resin was found to follow the pseudo-second order kinetic model, indicating that chemical adsorption was the rate limiting-step. The values of thermodynamic parameters proved that adsorption process of uranium onto Amberlite IRA-402 resin could be considered endothermic (ΔH > 0) and spontaneous (ΔG < 0)

  8. Complexation study of a tert-butyl-calix[4]arene-based 2-hydroxynaphthalene ligand with uranium(VI) in non-aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Bauer, Anne; Schmeide, Katja [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Surface Processes

    2017-06-01

    The actinide uranium, well known from nuclear power cycle, plays also a role in rare earth production as it is an undesired constituent of the respective ores. To facilitate the production of rare earth elements, uranium has to be removed. Due to their modifiable selectivity and solubility calix[n]arenes are interesting compounds for the extraction of actinides and lanthanides. The mechanism of uranium(VI) interaction with a tert-butyl-calix[4]arene-based 2-hydroxynaphthalene ligand (L1) was studied by TRLFS, UV-vis spectroscopy and isothermal calorimetry.

  9. Interaction of uranium(VI) towards glutathione. An example to study different functional groups in one molecule

    International Nuclear Information System (INIS)

    Frost, L.; Geipel, G.; Viehweger, K.; Bernhard, G.

    2011-01-01

    Glutathione, the most abundant thiol compound of the cell, has a great binding potential towards heavy metal ions. Hence it might influence the distribution of actinides on a cellular level. The unknown strength of the interaction of uranium(VI) with glutathione at physiologically relevant pH is subject of this paper and was studied with UV-vis spectroscopy and time-resolved laserinduced fluorescence spectroscopy (TRLFS). The complex stability constant of UO 2 H 2 GS + , logβ 121 0 , was calculated to be 39.09±0.15 and 39.04±0.02 in case of UV-vis spectroscopy and TRLFS respectively. Therefore the average formation constant for UO 2 2+ +H 2 GS - = UO 2 H 2 GS + can be assigned to be log K 0 11 = 19.83±0.15. Furthermore it was demonstrated that derivatization of the ligand associated with an enhancement of the ligand's spectroscopic properties can be used for the determination of complex stability constants and to assess the coordination chemistry in more detail. Using UV-vis spectroscopy, the stability constant of the complex between UO 2 2+ and glutathione pyruvate S-conjugate, a well absorbing ligand in contrast to glutathione, was calculated to be > 39.24±0.08. Furthermore the interaction of UO 2 2+ with glutathione derivatized with the fluorescent label monobromobimane was examined with femtosecond laser fluorescence spectroscopy. Thereby the stability constant of the 1: 1 complex was determined to be > 39.35±0.02. Although the thiol group of glutathione was blocked a strong coordination was found. Thus a significant involvement of the thiol group in the coordination of U(VI) can be excluded. (orig.)

  10. Removal of uranium(VI) from the aqueous phase by iron(II) minerals in presence of bicarbonate

    Energy Technology Data Exchange (ETDEWEB)

    Regenspurg, Simona, E-mail: regens@gfz-potsdam.de [Industrial Ecology, Royal Institute of Technology (KTH), SE 10044 Stockholm (Sweden); Schild, Dieter; Schaefer, Thorsten; Huber, Florian [Institut fuer Nukleare Entsorgung (INE), Forschungszentrum Karlsruhe, 76344 Eggenstein-Leopoldshafen (Germany); Malmstroem, Maria E. [Industrial Ecology, Royal Institute of Technology (KTH), SE 10044 Stockholm (Sweden)

    2009-09-15

    Uranium(VI) mobility in groundwater is strongly affected by sorption of mobile U(VI) species (e.g. uranyl, UO{sub 2}{sup 2+}) to mineral surfaces, precipitation of U(VI) compounds, such as schoepite (UO{sub 2}){sub 4}O(OH){sub 6}.6H{sub 2}O), and by reduction to U(IV), forming sparingly soluble phases (uraninite; UO{sub 2}). The latter pathway, in particular, would be very efficient for long-term immobilization of U. In nature, Fe(II) is an important reducing agent for U(VI) because it frequently occurs either dissolved in natural waters, sorbed to matrix minerals, or structurally bound in many minerals. Redox reactions between U(VI) and Fe(II) depend not only on the availability of Fe(II) in the environment, but also on the chemical conditions in the aqueous solution. Under natural groundwater condition U(VI) forms complexes with many anionic ligands, which strongly affect its speciation. Carbonate, in particular, is known to form stable complexes with U, raising the question, if U(VI), when complexed by carbonate, can be reduced to UO{sub 2}. The goal of this study was to find out if Fe(II) when structurally bound in a mineral (as magnetite, Fe{sub 3}O{sub 4}) or sorbed to a mineral surface (as corundum, Al{sub 2}O{sub 3}) can reduce U(VI) to U(IV) in the presence of HCO{sub 3}{sup -}. Batch experiments were conducted under anaerobic conditions to observe U removal from the aqueous phase by the two minerals depending on HCO{sub 3}{sup -} addition (1 mM), U concentration (0.01-30 {mu}M) and pH value (6-10). Immediately after the experiments, the mineral surfaces were analyzed by X-ray photoelectron spectroscopy (XPS) to obtain information on the redox state of U bound to the solid surfaces. XPS results gave evidence that U(VI) can be reduced both by magnetite and by corundum amended with Fe(II). In the presence of HCO{sub 3}{sup -} the amount of reduced U on the mineral surfaces increased compared to carbonate-free solutions. This can be explained by the formation

  11. Further study of extraction equilibrium of uranium(VI) with dicyclohexano-18-crown-6 and its application to separating uranium and thorium

    International Nuclear Information System (INIS)

    Wang Wenji; Sun Qing; Chen Bozhong

    1987-01-01

    The extraction equilibrium of uranium(VI) from aqueous hydrochloric acid solution with dicyclohexano-18-crown-6 isomer A (Ia) and isomer B (Ib) in 1,2-dichloroethane is presented. The extracted species are found to be 1:2 (metal/crown) for Ia and 2:3 for Ib from slope analysis and direct determination of extracted complexes. The extraction equilibrium constants (Kex) were determined at 25 deg C, and were equal to 29.5 for the former and 0.208 for the latter. It is concluded that Ia has stronger coordinate ability for uranium than Ib. The method is effective and selective. The results can be used for the separation of uranium and thorium. (author)

  12. Synthesis of xanthate functionalized silica gel and its application for the preconcentration and separation of uranium(VI) from inorganic components

    International Nuclear Information System (INIS)

    Gopi Krishna, P.; Naidu, G.R.K.; Rao, K.S.

    2005-01-01

    A new chelating solid extractant prepared by the chemical immobilization of xanthate on silica gel was characterized by Fourier transform infra red spectrometry (FTIR), thermogravimetric analysis (TGA) and microanalysis and used for the preconcentration and separation of uranyl ion prior to its determination by Arsenazo-III. The effect of pH, weight of the solid extractant, volume of the aqueous phase and the interference of neutral electrolytes, cations and anions on the determination of uranium, have been studied in detail to optimize the conditions for trace determination of uranium(VI). The accuracy of the developed procedure was tested by analyzing marine sediment (MESS-3) and soil (IAEA-SOIL-7) reference materials. The results obtained on analysis of soil and sediment samples are comparable to standard ICP-MS values. (author)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-02-15

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

  14. Study on selective separation of uranium(VI) by new N,N-dialkyl carboxy-amides

    International Nuclear Information System (INIS)

    Suzuki, Shinichi; Sugo, Yumi; Kimura, Takaumi; Yaita, Tsuyoshi

    2007-01-01

    The Feasibility study (FS) on commercialized FR cycle systems has been carried out in Japan. In this Feasibility study, 'Advanced Aqueous' reprocessing was designed as a new reprocessing concept to enhance nuclear non-proliferation by recycling U, Pu and minor actinides (MA) with some fission products (FP). The crystallization and U(VI)/TRU(transuranics) co-extraction technique have been selected as candidate technique in the 'Advanced Aqueous' reprocessing. In JAEA, the result of Feasibility study was received and Fast Reactor Cycle Technology Development Project (FaCT) was started. In the nuclear spent fuel reprocessing, FBR spent fuels will coexist with LWR spent fuels for several decades until FBR cycle begins to operate. For the treatment of LWR spent fuels, high decontamination factor for FP was required for U(VI) storage, and solvent extraction technique was selected in the nuclear fuel treatment. In our laboratory, N,N-di-alkyl carboxy-amides have been developed as extractant based on solvent extraction technique for one of a back-up technology of 'Advanced Aqueous' reprocessing in FBR spent fuel treatments. N,N-di-alkyl carboxy-amides were noted as one of the alternative extractant of tri-butylphosphate (TBP) in the field of nuclear fuel reprocessing. Extraction behavior of U(VI) and Pu(IV) with N,N-di-alkyl carboxy-amides was almost similar to those with TBP. N,N-di-alkyl carboxy-amides have some advantages, namely, their complete incinerability (CHON principle) and high stability for hydrolysis and radiolysis. Their main degradation products are carboxylic acids and secondary amines which hardly affect the separation of U(VI) and Pu(IV) from fission products. Further, the synthesis of N,N-di-alkyl carboxy-amides was relatively easy with reaction of carboxylic chloride and secondary amine. The main purpose of this solvent extraction technique using N,N-di-alkyl carboxy-amides is selective separation of Uranium(VI) with branched N,N-di-alkyl carboxy

  15. Peroxo complexes of molybdenum(VI), tungsten(VI), uranium(VI), zirconium(IV) and thorium(IV) ions containing tridentate Schiff bases derived from salicylaldehyde and amino acids

    International Nuclear Information System (INIS)

    Tarafder, M.T.H.; Khan, A.R.

    1997-01-01

    The synthesis of peroxo complexes of molybdenum(VI), tungsten(VI), uranium(VI), zirconium(IV), thorium(IV) and their possible oxygen transfer reactions is presented. An attempt has also been made to study the size of the metal ions and the electronic effect derived from the tridentate Schiff bases on the v 1 (O-O) mode of the complexes in their IR spectra

  16. Uranium(VI) speciation: modelling, uncertainty and relevance to bioavailability models. Application to uranium uptake by the gills of a freshwater bivalve; Speciation de l'uranium(6), modelisation, incertitude et implication pour les modeles de biodisponibilite. Application a l'accumulation dans les branchies d'un bivalve d'eau douce

    Energy Technology Data Exchange (ETDEWEB)

    Denison, F.H

    2004-07-01

    The effects of varying solution composition on the interactions between uranium(VI) and excised gills of the freshwater bivalve Corbicula fluminea have been investigated in well defined solution media. A significant reduction in the uptake of uranium was observed on increasing the concentrations of the uranium complexing ligands citrate and carbonate. Saturation kinetics as a function of uranium concentration at a pH value of 5.0 were observed, indicating that the uptake of uranium is a facilitated process, probably involving one or several trans-membrane transport systems. A relatively small change in the uptake of uranium was found as a function of pH (factor of ca. 2), despite the extremely large changes to the solution speciation of uranium within the range of pH investigated (5.0 - 7.5). A comprehensive review of the thermodynamic data relevant to the solution composition domain employed for this study was performed. Estimates of the uncertainties for the formation constants of aqueous uranium(VI) species were integrated into a thermodynamic database. A computer program was written to predict the equilibrium distribution of uranium(VI) in simple aqueous systems, using thermodynamic parameter mean-values. The program was extended to perform Monte Carlo and Quasi Monte Carlo uncertainty analyses, incorporating the thermodynamic database uncertainty estimates, to quantitatively predict the uncertainties inherent in predicting the solution speciation of uranium. The use of thermodynamic equilibrium modelling as a tool for interpreting the bioavailability of uranium(VI) was investigated. Observed uranium(VI) uptake behaviour was interpreted as a function of the predicted changes to the solution speciation of uranium. Different steady-state or pre-equilibrium approaches to modelling uranium uptake were tested. Alternative modelling approaches were also tested, considering the potential changes to membrane transport system activity or sorption characteristics on

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

    International Nuclear Information System (INIS)

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

    1999-01-01

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

  18. Sorption of Uranium(VI) and Thorium(IV) ions from aqueous solutions by nano particle of ion exchanger SnO2

    International Nuclear Information System (INIS)

    Nilchi, A.; Rasouli Garmarodi, S.; Shariati Dehaghan, T.

    2012-01-01

    Due to the extensive use of nuclear energy and its replacement for fossil fuels in recent decades, the radioactive waste production has increased enormously. The vast majority of the radioactive wastes products, are in the liquid form and consequently their treatment is of great importance. In this paper, tin oxide with nano-structure has been synthesized as an absorbent by the homogenous sedimentation method in the presence of urea, so as to adsorb uranium(VI) and thorium(IV) ions. The results obtained from the XRD, Scanning Electron Microscopy and nitrogen adsorption/ desorption analyses on the tin oxide sample showed the cassiterite structure with an average particle size of 30 nanometer and a specific surface area of 27.5 m 2 /g. The distribution coefficients of uranium and thorium were studied by means of batch method. The effects of different variables such as pH and time of contact between the exchanger and solution were investigated and the optimum conditions for sorption of these ions were determined.

  19. Highly Efficient Interception and Precipitation of Uranium(VI) from Aqueous Solution by Iron-Electrocoagulation Combined with Cooperative Chelation by Organic Ligands.

    Science.gov (United States)

    Li, Peng; Zhun, Bao; Wang, Xuegang; Liao, PingPing; Wang, Guanghui; Wang, Lizhang; Guo, Yadan; Zhang, Weimin

    2017-12-19

    A new strategy combining iron-electrocoagulation and organic ligands (OGLs) cooperative chelation was proposed to screen and precipitate low concentrations (0-18.52 μmol/L) of uranium contaminant in aqueous solution. We hypothesized that OGLs with amino, hydroxyl, and carboxyl groups hydrophobically/hydrophilically would realize precuring of uranyl ion at pH electrocoagulation would achieve faster and more efficient uranium precipitation. Experimentally, the strategy demonstrated highly efficient uranium(VI) precipitation efficiency, especially with hydrophilic macromolecular OGLs. The uranium removal efficiency at optimized experimental condition reached 99.65%. The decrease of zeta potential and the lattice enwrapping between U-OGLs chelates and flocculation precursor were ascribed to the enhanced uranium precipitation activity. Uranium was precipitated as oxides of U(VI) or higher valences that were easily captured in aggregated micelles under low operation current potential. The actual uranium tailing wastewater was treated, and a satisfied uranium removal efficiency of 99.02% was discovered. After elution of the precipitated flocs, a concentrated uranium solution (up to 106.52 μmol/L) with very few other metallic impurities was obtained. Therefore, the proposed strategy could remove uranium and concentrate it concurrently. This work could provide new insights into the purification and recovery of uranium from aqueous solutions in a cost-effective and environmentally friendly process.

  20. Potentiometric titration in a low volume of solution for rapid assay of uranium. Application to quantitative electro-reduction of uranium(VI)

    International Nuclear Information System (INIS)

    Sahoo, P.; Ananthanarayanan, R.; Murali, N.; Mallika, C.; Falix Lawrence; Kamachi Mudali, U.

    2012-01-01

    A simple, inexpensive PC based potentiometric titration technique for the assay of uranium using low volumes of sample aliquot (25-100 μL) along with all reagents (total volume of solution being less than 2.5 mL) is presented. The technique involves modification of the well known Davies and Gray Method recommended for assay of uranium(VI) in nuclear materials by introducing an innovative potentiometric titration device with a mini cell developed in-house. After appropriate chemical conditioning the titration is completed within a couple of minutes with display of online titration plot showing the progress of titration. The first derivative plot generated immediately after titration provides information of end point. The main advantage of using this technique is to carry out titration with minimum volumes of sample and reagents generating minimum volume of wastes after titration. The validity of the technique was evaluated using standard certified samples. This technique was applied for assay of uranium in a typical sample collected from fuel reprocessing laboratory. Further, the present technique was deployed in investigating the optimum conditions for efficient in situ production of U(IV). The precision in the estimation of uranium is highly satisfactory (RSD less than 1.0%). (author)

  1. Extractive separation of uranium(VI) as perchlorate/chloroacetate complexes with 1-phenyl-2,3 dimethyl-5-pyrazolone and its applications

    International Nuclear Information System (INIS)

    Bose, R.; Murty, D.S.R.

    2003-01-01

    The extraction of U(VI) with 1-phenyl 2,3 dimethyl-5-pyrazolone, at a pH of 2.5, in the presence of common anions, like perchlorate and tri-, di-, and monochloroacetates has been investigated. The optimum experimental conditions have been evaluated by studying various parameters such as pH, equilibration period, reagent concentration, metal concentration, and solvents. Effect of diverse anions and cations on the extraction has also been studied. The extracted species, determined by log D - log R plots are represented as, [UO 2 (Apy) 4 (ClO 4 ) 2 ], [UO 2 (Apy) 2 (TCA) 2 ], [UO 2 (Apy) 2 (DCA) 2 ], [UO 2 (Apy)(H 2 O)(MCA) 2 ]. The conditional stability constants of the quantitatively extracted complexes are calculated. The proposed method allows the selective separation of uranium(VI) from multicomponent mixtures and geological matrices and is also applied for the separation and chemical characterization of impurities at trace and ultratrace levels. (author)

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

    International Nuclear Information System (INIS)

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

    1980-01-01

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

  3. Combined use of flow cytometry and microscopy to study the interactions between the gram-negative betaproteobacterium Acidovorax facilis and uranium(VI)

    Energy Technology Data Exchange (ETDEWEB)

    Gerber, U., E-mail: u.gerber@hzdr.de [Helmholtz-Zentrum Dresden-Rossendorf, Institute of Resource Ecology, P.O. Box 510119, 01314 Dresden (Germany); Zirnstein, I. [Research Institute of Leather and Plastic Sheeting (FILK) gGmbH, Meissner Ring 1-5, 09599 Freiberg (Germany); Krawczyk-Bärsch, E. [Helmholtz-Zentrum Dresden-Rossendorf, Institute of Resource Ecology, P.O. Box 510119, 01314 Dresden (Germany); Lünsdorf, H. [Helmholtz Centre for Infection Research, Central Facility for Microscopy, Inhoffenstr. 7, D-38124 Braunschweig (Germany); Arnold, T. [Helmholtz-Zentrum Dresden-Rossendorf, Institute of Resource Ecology, P.O. Box 510119, 01314 Dresden (Germany); Merroun, M.L. [University of Granada, Department of Microbiology, Campus Fuentenueva, E-18071 Granada (Spain)

    2016-11-05

    Highlights: • Acidovorax facilis is able to remove 130 mg U/g dry biomass from solution. • Kinetically temperature-dependent uranium removal was studied. • Cell viability and metabolic activity was tested by flow cytometry. • Uranium was removed by active biosorption and passive bioaccumulation. - Abstract: The former uranium mine Königstein (Saxony, Germany) is currently in the process of remediation by means of controlled underground flooding. Nevertheless, the flooding water has to be cleaned up by a conventional wastewater treatment plant. In this study, the uranium(VI) removal and tolerance mechanisms of the gram-negative betaproteobacterium Acidovorax facilis were investigated by a multidisciplinary approach combining wet chemistry, flow cytometry, and microscopy. The kinetics of uranium removal and the corresponding mechanisms were investigated. The results showed a biphasic process of uranium removal characterized by a first phase where 95% of uranium was removed within the first 8 h followed by a second phase that reached equilibrium after 24 h. The bacterial cells displayed a total uranium removal capacity of 130 mg U/g dry biomass. The removal of uranium was also temperature-dependent, indicating that metabolic activity heavily influenced bacterial interactions with uranium. TEM analyses showed biosorption on the cell surface and intracellular accumulation of uranium. Uranium tolerance tests showed that A. facilis was able to withstand concentrations up to 0.1 mM. This work demonstrates that A. facilis is a suitable candidate for in situ bioremediation of flooding water in Königstein as well as for other contaminated waste waters.

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

    International Nuclear Information System (INIS)

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

    2002-01-01

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

  5. Phosphorus-modified poly(styrene-co-divinylbenzene)–PAMAM chelating resin for the adsorption of uranium(VI) in aqueous

    Energy Technology Data Exchange (ETDEWEB)

    Cao, Qiong [College of Chemistry and Chemical Engineering, Central South University, Changsha 410083 (China); Liu, Yaochi, E-mail: liuyaochi72@163.com [College of Chemistry and Chemical Engineering, Central South University, Changsha 410083 (China); Wang, Chunzhi [Baling Company, China Petroleum and Chemical Corporation (China); Cheng, Jiashun [College of Chemistry and Chemical Engineering, Central South University, Changsha 410083 (China)

    2013-12-15

    Highlights: • A series of phosphorus-modified poly(styrene-co-divinylbenzene)–PAMAM chelating resins were synthesized. • The materials were commercially available and economic. • The new resins were high effective and selective adsorbents. • U(VI) adsorption is fitted with pseudo-second-order equation and Langmuir model. • The new resins can be regenerated. -- Abstract: Polyamidoamine (PAMAM) modified poly(styrene-co-divinylbenzene) absorbents carrying phosphorus functional groups (PS-PAMAM-PPA) were prepared and used as adsorbents for the adsorption of uranium(VI) from aqueous solution. Different generations of PAMAM were used for obtaining different chelating resins, PS-PPA, PS-1.0G PAMAM-PPA, PS-2.0G PAMAM-PPA, PS-3.0G PAMAM-PPA and PS-4.0G PAMAM-PPA. The synthesized resins were characterized by FTIR and XPS. The effects of many physio-chemical properties on metal ion adsorption to adsorbent phase, such as solution pH, kinetic studies, initial uranium concentration, temperature, were investigated using batch method. The results showed that the maximum adsorption capacity (99.89 mg/g) was observed at the pH 5.0 and 25 °C with initial U(VI) concentration 100 mg/L and adsorbent dose 1 g/L. PS-1.0G PAMAM-PPA had the largest adsorption capacity for U(VI) compared with other prepared adsorbents. The adsorption kinetics of U(VI) onto PS-1.0G PAMAM-PPA followed the mechanism of the pseudo-second-order equation, indicating that the chemical adsorption was a rate-limiting step. The calculated thermodynamic parameters (ΔG, ΔH, ΔS) stated that the adsorption of U(VI) onto PS-1.0G PAMAM-PPA were spontaneous, endothermic and feasible. The adsorption isotherms obeyed the Langmuir isotherm models. The desorption studies showed that PS-1.0G PAMAM-PPA could be used repeatedly and adsorption and desorption percentage did not have any noticeable loss after 27 cycles in a fixed bed.

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

    International Nuclear Information System (INIS)

    Mueller, Katharina

    2010-05-01

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

  7. Contribution to the study of the redox couple Np(VI)/Np(V) in the presence of uranium(VI) in solutions of nitric acid and nitrous acid; Contribution a l'etude du comportement redox du couple Np(VI)/Np(V) en presence d'uranium VI dans les solutions constituees d'acide nitrique et d'acide nitreux

    Energy Technology Data Exchange (ETDEWEB)

    Arpigny, S. [CEA Marcoule, Dept. de Radiochimie et Procedes, DRP, 30 (France)

    2001-07-01

    The redox behavior of the Np(VI)/Np(V) couple was the subject of a spectrometric study of the Np(VI) reduction reaction in nitric acid solutions (4 to 5 M) containing variable concentrations (1.5 to 3.5 x 10{sup -3} M) of nitrous acid. A low nitrous acid concentration and a high nitric acid concentration were found to favor the stabilization of Np(VI). The stoichiometric coefficients of nitrous acid and nitric acid in the Np(VI) reduction reaction were determined thermodynamically, although only the reaction order with respect to HNO{sub 2} could be calculated from a kinetic analysis. Adding nitrate ions to a HNO{sub 3}/HNO{sub 2} solution enhanced the stability of neptunium at oxidation state +VI, but also increased the reduction rate. When uranium(VI) was added to the HNO{sub 3}/HNO{sub 2} solutions, the total quantity of neptunium at oxidation state +V (either free or as a Np(V)-U(VI) complex) remained practically unchanged, as did the Np(VI) reduction rate. The electrochemical behavior of the Np(VI)/Np(V) couple was investigated in a weak acidic medium by voltammetry with an ultra-micro-electrode (UME). The oxidation wave limiting current variation was a linear function of the Np(V) concentration when a gold UME was used, but not with a platinum UME; the reduction wave limiting current variation versus the Np(V) concentration was linear with either gold or platinum UMEs. The presence of the Np(V)-U(VI) complex in the neptunium solutions was characterized by a shift in the normal apparent potential of the Np(VI)/Np(V) couple toward anodic potentials consistent with the previously determined values of the complexation constants. (author)

  8. Uranium(VI) transport modeling: geochemical data and submodels

    International Nuclear Information System (INIS)

    Tripathi, V.S.

    1984-01-01

    Understanding the geochemical mobility of U(VI) and modeling its transport is important in several contexts including ore genesis, uranium exploration, nuclear and mill-tailings waste management, and solution mining of uranium ores. Adsorption is a major control on partitioning of solutes at the mineral/solution interface. The effect of carbonate, fluoride, and phosphate complexing on adsorption of uranium was investigated. A critical compilation of stability constants of inorganic complexes and solid compounds of U(VI) necessary for proper design of experiment and for modeling transport of uranium was prepared. The general features of U(VI) adsorption in ligand-free systems are similar to those characteristic of other hydrolyzable metal ions. The adsorption processes studied were found to be reversible. The adsorption model developed in ligand-free systems, when solution complexing is taken into account, proved remarkably successful in describing adsorption of uranium in the presence of carbonate and fluoride. The presence of phosphate caused a much smaller decrease in the extent of adsorption than expected; however, a critical reassessment of the stability of UO 2 2+ .HPO 4 2- complexes, showed that phosphato complexes, if any, are extremely weak under experimental conditions. Removal of uranium may have occurred due to precipitation of sodium uranyl phosphates in addition to adsorption

  9. The uranium(VI) oxoazides [UO{sub 2}(N{sub 3}){sub 2}.CH{sub 3}CN], [(bipy){sub 2}(UO{sub 2}){sub 2}(N{sub 3}){sub 4}], [(bipy)UO{sub 2}(N{sub 3}){sub 3}]{sup -}, [UO{sub 2}(N{sub 3}){sub 4}]{sup 2-}, and [(UO{sub 2}){sub 2}(N{sub 3}){sub 8}]{sup 4-}

    Energy Technology Data Exchange (ETDEWEB)

    Haiges, Ralf; Christe, Karl O. [Loker Hydrocarbon Research Institute and Department of Chemistry, University of Southern California, Los Angeles, CA (United States); Vasiliu, Monica; Dixon, David A. [Department of Chemistry, The University of Alabama, Tuscaloosa, AL (United States)

    2017-01-12

    The reaction between [UO{sub 2}F{sub 2}] and an excess of Me{sub 3}SiN{sub 3} in acetonitrile solution results in fluoride-azide exchange and the uranium(VI) dioxodiazide adduct [UO{sub 2}(N{sub 3}){sub 2}.CH{sub 3}CN] was isolated in quantitative yield. The subsequent reaction of [UO{sub 2}(N{sub 3}){sub 2}.CH{sub 3}CN] with 2,2{sup '}-bipyridine (bipy) resulted in the formation of the azido-bridged binuclear complex [(bipy){sub 2}(UO{sub 2}){sub 2}(N{sub 3}){sub 4}]. The triazido anion [(bipy)UO{sub 2}(N{sub 3}){sub 3}]{sup -} was obtained by the reaction of [UO{sub 2}(N{sub 3}){sub 2}.CH{sub 3}CN] with stoichiometric amounts of bipy and the ionic azide [PPh{sub 4}][N{sub 3}]. The reaction of [UO{sub 2}(N{sub 3}){sub 2}] with two equivalents of the [PPh{sub 4}][N{sub 3}] resulted in the formation of the mononuclear tetraazido anion [UO{sub 2}(N{sub 3}){sub 4}]{sup 2-} as well as the azido-bridged binuclear anion [(UO{sub 2}){sub 2}(N{sub 3}){sub 8}]{sup 4-}. The novel uranium oxoazides were characterized by their vibrational spectra and in the case of [(bipy){sub 2}(UO{sub 2}){sub 2}(N{sub 3}){sub 4}].CH{sub 3}CN, [PPh{sub 4}][(bipy)UO{sub 2}(N{sub 3}){sub 3}], [PPh{sub 4}]{sub 2}[UO{sub 2}(N{sub 3}){sub 4}], [PPh{sub 4}]{sub 2}[UO{sub 2}(N{sub 3}){sub 4}].2CH{sub 3}CN, and [PPh{sub 4}]{sub 4}[(UO{sub 2}){sub 2}(N{sub 3}){sub 8}].4CH{sub 3}CN by their X-ray crystal structures. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  10. Spectrophotometric study of the complexation equilibria of uranium(VI) with 1,4-bis(4'-methylanilino)anthraquinone and determination of uranium(VI)

    International Nuclear Information System (INIS)

    Idriss, K.A.; Seleim, M.M.; Abu-Bakr, M.S.; Sedaira, H.

    1985-01-01

    The reaction of U(VI) with 1,4-bis(4'-methylanilino)anthraquinone (quinizarin green) in water-dimethylformamide medium was investigated spectrophotometrically. The complexation equilibria in solution were demonstrated. The study of the reaction in presence of equimolar concentrations or in solutions containing metal or ligand excess gave evidence for the formation of complexes with stoichiometric ratios of UO 2 :L = 1:1 and 1:2 in dependence on the pH of the medium. Their thermodynamic stabilities and the values of their molar absorption coefficients were determined. The optimum conditions for spectrophotometric determination of U(VI) with this reagent were found. (author)

  11. Formation of stable uranium(VI) colloidal nanoparticles in conditions relevant to radioactive waste disposal.

    Science.gov (United States)

    Bots, Pieter; Morris, Katherine; Hibberd, Rosemary; Law, Gareth T W; Mosselmans, J Frederick W; Brown, Andy P; Doutch, James; Smith, Andrew J; Shaw, Samuel

    2014-12-09

    The favored pathway for disposal of higher activity radioactive wastes is via deep geological disposal. Many geological disposal facility designs include cement in their engineering design. Over the long term, interaction of groundwater with the cement and waste will form a plume of a hyperalkaline leachate (pH 10-13), and the behavior of radionuclides needs to be constrained under these extreme conditions to minimize the environmental hazard from the wastes. For uranium, a key component of many radioactive wastes, thermodynamic modeling predicts that, at high pH, U(VI) solubility will be very low (nM or lower) and controlled by equilibrium with solid phase alkali and alkaline-earth uranates. However, the formation of U(VI) colloids could potentially enhance the mobility of U(VI) under these conditions, and characterizing the potential for formation and medium-term stability of U(VI) colloids is important in underpinning our understanding of U behavior in waste disposal. Reflecting this, we applied conventional geochemical and microscopy techniques combined with synchrotron based in situ and ex situ X-ray techniques (small-angle X-ray scattering and X-ray adsorption spectroscopy (XAS)) to characterize colloidal U(VI) nanoparticles in a synthetic cement leachate (pH > 13) containing 4.2-252 μM U(VI). The results show that in cement leachates with 42 μM U(VI), colloids formed within hours and remained stable for several years. The colloids consisted of 1.5-1.8 nm nanoparticles with a proportion forming 20-60 nm aggregates. Using XAS and electron microscopy, we were able to determine that the colloidal nanoparticles had a clarkeite (sodium-uranate)-type crystallographic structure. The presented results have clear and hitherto unrecognized implications for the mobility of U(VI) in cementitious environments, in particular those associated with the geological disposal of nuclear waste.

  12. Microbial reduction of uranium(VI) in sediments of different lithologies collected from Sellafield

    International Nuclear Information System (INIS)

    Newsome, Laura; Morris, Katherine; Trivedi, Divyesh; Atherton, Nick; Lloyd, Jonathan R.

    2014-01-01

    Highlights: • U(VI) (aq) mobility can be controlled by stimulating biogeochemical interactions. • Indigenous microbes in varied sediments reduced U(VI) to insoluble U(IV). • Sediment cell numbers and amount of bioavailable Fe(III) could limit this process. - Abstract: The presence of uranium in groundwater at nuclear sites can be controlled by microbial processes. Here we describe the results from stimulating microbial reduction of U(VI) in sediment samples obtained from a nuclear-licensed site in the UK. A variety of different lithology sediments were selected to represent the heterogeneity of the subsurface at a site underlain by glacial outwash deposits and sandstone. The natural sediment microbial communities were stimulated via the addition of an acetate/lactate electron donor mix and were monitored for changes in geochemistry and molecular ecology. Most sediments facilitated the removal of 12 ppm U(VI) during the onset of Fe(III)-reducing conditions; this was reflected by an increase in the proportion of known Fe(III)- and U(VI)-reducing species. However U(VI) remained in solution in two sediments and Fe(III)-reducing conditions did not develop. Sequential extractions, addition of an Fe(III)-enrichment culture and most probable number enumerations revealed that a lack of bioavailable iron or low cell numbers of Fe(III)-reducing bacteria may be responsible. These results highlight the potential for stimulation of microbial U(VI)-reduction to be used as a bioremediation strategy at UK nuclear sites, and they emphasise the importance of both site-specific and borehole-specific investigations to be completed prior to implementation

  13. Selectivity enhancement of phosphate based functional polymeric gels towards Uranium(VI) using ion imprinting

    International Nuclear Information System (INIS)

    Chappa, Sankararao; Agarwal, Chhavi; Pandey, A.K.

    2015-01-01

    The imprinting of gel containing polymer chains of ethylene glycol methacrylate phosphate (EGMP) for U(VI) ions were carried out. The U(VI) imprinting has been carried out in pure EGMP and in EGMP: poly(ethylene glycol) methacrylate (PEGMA) = 1:9 composition. Complexation of the monomer with template (U(VI)) followed by polymerization have been used to imprint the U(VI) onto the polymer chains. The comparison of uptake studies of U(VI) and Pu(IV) at 3 M HNO 3 shows increased selectivity of U(VI) relative to Pu(IV) for both the gel compositions. The less uptake of U(VI) for imprinted EGMP:PEGMA gel relative to pure imprinted EGMP gel at tracer level can be possibly due to the requirement of two EGMP units in the vicinity for U(VI) complexation. (author)

  14. Uranium(VI) and ruthenium extraction by dialkyldithio-phosphoric acids

    International Nuclear Information System (INIS)

    Fitoussi, R.; Musikas, C.

    1980-01-01

    Oxygen donors like dialkylphosphoric acids are good extractants for actinide ions, but little is known about their sulfur homologs. Investigations of U(VI) and Ru extraction from various aqueous media are reported. This includes extraction of U(VI) from nitric, perchloric, and phosphoric acids by solutions of dialkyldithiophosphoric acids in dodecane or benzene. Extraction of U(VI) by synergistic mixtures, of which at least one of the components is a sulfur donor, has been investigated. The extracted species have been identified, and a comparison with the complexes obtained by extraction with the homologous oxygen donors is made. The sulfur-actinide bond is weaker than the oxygen-actinide one, but in some synergistic extractions the dialkyldithiophosphonates are more efficient than the oxygen donors. In addition to size effects, this behavior could be attributed to the weakness of the hydrogen bonds of the SH groups, which allows a greater variety of the ligands to enter the coordination sphere of the metal. Ruthenium, like the d-transition elements, gives strong bonds with the sulfur donors. However, its extraction from nitric acid is slow. We investigated the influence of several parameters on the distribution coefficients and found that the presence of a reagent which destroys nitrous ions is necessary to achieve quantitative extraction. The role of RuNO groups is also discussed

  15. Selective extraction of metals from acidic uranium(VI) solutions using neo-tridecano-hydroxamic acid

    International Nuclear Information System (INIS)

    Bardoncelli, F.; Grossi, G.

    1975-01-01

    According to this invention neo-alkyl-hydroxamic acids are employed as ion-exchanging agents in processes for liquid-liquid extraction with the aim of separating, purifying dissolved metals and of converting a metal salt solution into a solution of a salt of the same metal but with different anion. In particular it is an objective of this invention to provide a method whereby a molecular pure uranium solution is obtained by selective extraction from a uranium solution delivered by irradiated fuel reprocessing plants and containing plutonium, fission products and other unwanted metals, in which method neo-tridecane-hydroxamic acid is employed as ion exchanger. (Official Gazette)

  16. Laser enhanced reductions of uranium(VI) ion in aqueous phosphoric acid solutions

    International Nuclear Information System (INIS)

    Park, Y.Y.; Harada, M.; Tomiyasu, H.; Ikeda, Y.; Takashima, Y.

    1991-01-01

    Photochemical reactions of U(VI) ions with inorganic anions (I - , Br - , Cl - , NCS - ) and organic compounds (1-hexene, cyclohexene, pyridine) in phosphoric acid were studied for the purpose of finding an efficient method of adjusting the oxidation states of uranium ions in nuclear fuel reprocessing. The formation of U(IV) was observed in the photoreactions with I - , Br - and NCS - , but not with Cl - . The yield of U(VI) increased in the order, Br - - - . This order was the same as the quenching rate constants of the excited U(VI) ions with these anions, and the reverse of their standard redox potentials. The rates of the formation of U(IV) in the presence of Br - were measured spectrophotometrically. It was found that the rate equation was first order in both [U(VI)] and [Br - ]. The results were reasonably interpreted by a series of reaction processes involving U(V) and Br radical. With organic molecules, 1-hexene, cyclohexene, and pyridine, the formation of U(IV) were observed. The yield of U(IV) increased in the order pyridine < 1-hexene < cyclohexene. This order is the reverse of their vertical ionization potentials, suggesting an electron transfer mechanism between these organic molecules and excited U(VI). (author)

  17. Stability of uranium(VI) doped CSH phases in high saline water

    Energy Technology Data Exchange (ETDEWEB)

    Wolter, Jan-Martin; Schmeide, Katja [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Surface Processes

    2017-06-01

    To evaluate the long-term stability of U(VI) doped calcium silicate hydrate (CSH) phases at high saline conditions, leaching experiments with NaCl, NaCl/Na{sub 2}SO{sub 4} and NaCl/NaHCO{sub 3} containing solutions were performed. Time-resolved laser-induced fluorescence spectroscopy (TRLFS), infrared spectroscopy (IR) and X-ray powder diffraction (XRD) were applied to study the U(VI) binding onto the CSH phases and to get a deeper understanding of structural changes due to leaching. Results indicate that neither NaCl nor Na{sub 2}SO{sub 4} affect the structural stability of CSH phases and their retention potential for U(VI). However, carbonate containing solutions lead to a decomposition of CSH phases and thus, to a release of incorporated uranium.

  18. Molecular interactions of Leucoagaricus naucinus with uranium(VI) and europium(III)

    Energy Technology Data Exchange (ETDEWEB)

    Wollenberg, Anne; Raff, Johannes [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Biogeochemistry; Guenther, A. [Helmholtz Institute Freiberg for Resource Technology, Freiberg (Germany)

    2017-06-01

    With regard to a molecular understanding of the interaction of fungal mycelium with radionuclides and its possible application for precautionary radiation protection and bio-remediation, the binding mechanism of the radionuclide uranium and the metal europium, as surrogate for trivalent actinides, where investigated with different starting conditions by the living fungal cells of Leucoagaricus naucinus.

  19. Microbial reduction of uranium(VI) by anaerobic microorganisms isolated from a former uranium mine

    Energy Technology Data Exchange (ETDEWEB)

    Gerber, Ulrike; Krawczyk-Baersch, Evelyn [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Biogeochemistry; Arnold, Thuro [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Inst. of Resource Ecology; Scheinost, Andreas C. [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Molecular Structures

    2017-06-01

    The former uranium mine Koenigstein (Germany) is currently in the process of controlled flooding by reason of remediation purposes. However, the flooding water still contains high concentrations of uranium and other heavy metals. For that reason the water has to be cleaned up by a conventional waste water treatment plant. The aim of this study was to investigate the interactions between anaerobic microorganisms and uranium for possible bioremediation approaches, which could be an great alternative for the intensive and expensive waste water treatment. EXAFS (extended X-ray absorption fine structure) and XANES (X-ray absorption near edge structure) measurements were performed and revealed a complete reduction of U(VI) to U(IV) only by adding 10 mM glycerol.

  20. Uranium(VI) retention by Ca-bentonite under (hyper)alkaline conditions

    Energy Technology Data Exchange (ETDEWEB)

    Philipp, Thimo; Schmeide, Katja [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Surface Processes

    2017-06-01

    The sorption behavior of U(VI) on Ca-bentonite was studied in saline, (hyper)alkaline solution via batch experiments. At pH 8.5-9.5 sorption is low in the presence of CO{sub 2} due to the formation of weakly sorbing uranyl carbonate species, which have been observed to dominate speciation up to pH 10 by time-resolved laser-induced fluorescence spectroscopy (TRLFS). In the pH region 10-12, U(VI) retention is almost complete. The retention can either be attributed to strongly sorbing uranyl hydroxo complexes or to a partial precipitation of uranium due to an altered solubility of U(VI) induced by ions leached out of the bentonite.

  1. Retention of uranium(VI) by laumontite, a fracture-filling material of granite

    International Nuclear Information System (INIS)

    Baik, M.H.; Lee, S.Y.; Shon, W.J.

    2009-01-01

    Retention of U(VI) by laumontite, a fracture-filling material of granite as investigated by conducting dynamic and batch sorption experiments in a love-box using a granite core with a natural fracture. The hydrodynamic properties of the granite core were obtained from the elution curve of a on-sorbing tracer, Br - . The elution curve of U(VI) showed a similar behavior to Br - . This reveals that the retention of U(VI) by the fracture-filling material was not significant when migrating through the fracture at a given condition. From the dynamic sorption experiment, the retardation factor R a and the distribution coefficient K a of U(VI) were obtained as about 2.9 and 0.16 cm, respectively. The distribution coefficient K d ) of U(VI) onto laumontite obtained by conducting a batch sorption experiment resulted in a small value of 2.3±0.5 mL/g. This low K d value greed with the result of the dynamic sorption experiment. For the distribution of uranium on the granite surface investigated by an X-ray image mapping, the fracture region filled with laumontite showed a relatively lower content of uranium compared to the surrounding granite surface. Thus, the low retention of U(VI) by the fracture-filling material can be explained by following two mechanisms. One is that U(VI) exists as anionic uranyl hydroxides or uranyl carbonates at a given groundwater condition and the other is the remarkably low sorption capacity of the laumontite for U(VI). author)

  2. The study of complex equilibria of uranium(VI) with selenate

    International Nuclear Information System (INIS)

    Lubal, P.; Havel, J.

    1997-01-01

    Uranyl (M)-selenate (L) complex equilibria in solution were investigated by spectrophotometry in visible range and potentiometry by means of uranyl ion selective electrode. The formation ML and ML 2 species was proved and the corresponding stability constants calculated were: log β 1 = 1.57 6 ± 0.01 6 , log β 2 = 2.42 3 ± 0.01 3 (I 3.0 mol 1 -1 Na(ClO 4 , SeO 4 ) (spectrophotometry) at 298.2 K. Using potentiometry the values for infinite dilution (I → 0 mol 1 -1 ) were: log β 1 = 2.64 ± 0.01, log β 2 ≤ 3.4 at 298.2 K. Absorption spectra of the complexes were calculated and analysed by deconvolution technique. Derivative spectrophotometry for the chemical model determination has also been successfully applied. (author)

  3. Surface complexation modeling of the effects of phosphate on uranium(VI) adsorption

    Energy Technology Data Exchange (ETDEWEB)

    Romero-Gonzalez, M.R.; Cheng, T.; Barnett, M.O. [Auburn Univ., AL (United States). Dept. of Civil Engeneering; Roden, E.E. [Wisconsin Univ., Madison, WI (United States). Dept. of Geology and Geophysics

    2007-07-01

    Previous published data for the adsorption of U(VI) and/or phosphate onto amorphous Fe(III) oxides (hydrous ferric oxide, HFO) and crystalline Fe(III) oxides (goethite) was examined. These data were then used to test the ability of a commonly-used surface complexation model (SCM) to describe the adsorption of U(VI) and phosphate onto pure amorphous and crystalline Fe(III) oxides and synthetic goethite-coated sand, a surrogate for a natural Fe(III)-coated material, using the component additivity (CA) approach. Our modeling results show that this model was able to describe U(VI) adsorption onto both amorphous and crystalline Fe(III) oxides and also goethite-coated sand quite well in the absence of phosphate. However, because phosphate adsorption exhibits a stronger dependence on Fe(III) oxide type than U(VI) adsorption, we could not use this model to consistently describe phosphate adsorption onto both amorphous and crystalline Fe(III) oxides and goethite-coated sand. However, the effects of phosphate on U(VI) adsorption could be incorporated into the model to describe U(VI) adsorption to both amorphous and crystalline Fe(III) oxides and goethite-coated sand, at least for an initial approximation. These results illustrate both the potential and limitations of using surface complexation models developed from pure systems to describe metal/radionuclide adsorption under more complex conditions. (orig.)

  4. Surface complexation modeling of the effects of phosphate on uranium(VI) adsorption

    International Nuclear Information System (INIS)

    Romero-Gonzalez, M.R.; Cheng, T.; Barnett, M.O.; Roden, E.E.

    2007-01-01

    Previous published data for the adsorption of U(VI) and/or phosphate onto amorphous Fe(III) oxides (hydrous ferric oxide, HFO) and crystalline Fe(III) oxides (goethite) was examined. These data were then used to test the ability of a commonly-used surface complexation model (SCM) to describe the adsorption of U(VI) and phosphate onto pure amorphous and crystalline Fe(III) oxides and synthetic goethite-coated sand, a surrogate for a natural Fe(III)-coated material, using the component additivity (CA) approach. Our modeling results show that this model was able to describe U(VI) adsorption onto both amorphous and crystalline Fe(III) oxides and also goethite-coated sand quite well in the absence of phosphate. However, because phosphate adsorption exhibits a stronger dependence on Fe(III) oxide type than U(VI) adsorption, we could not use this model to consistently describe phosphate adsorption onto both amorphous and crystalline Fe(III) oxides and goethite-coated sand. However, the effects of phosphate on U(VI) adsorption could be incorporated into the model to describe U(VI) adsorption to both amorphous and crystalline Fe(III) oxides and goethite-coated sand, at least for an initial approximation. These results illustrate both the potential and limitations of using surface complexation models developed from pure systems to describe metal/radionuclide adsorption under more complex conditions. (orig.)

  5. Examination of Uranium(VI) Leaching During Ligand Promoted Dissolution of Waste Tank Sludge Surrogates

    Energy Technology Data Exchange (ETDEWEB)

    Powell, Brian; Powell, Brian A.; Rao, Linfeng; Nash, Kenneth. L.

    2008-06-10

    The dissolution of synthetic boehmite (?-AlOOH) by 1-hydroxyethane-1,1-diphosphonic acid (HEDPA) was examined in a series of batch adsorption/dissolution experiments. Additionally, the leaching behavior of {sup 233}U(VI) from boehmite was examined as a function of pH and HEDPA concentration. The results are discussed in terms of sludge washing procedures that may be utilized during underground tank waste remediation. In the pH range 4 to 10, complexation of Al(III) by HEDPA significantly enhanced dissolution of boehmite. This phenomenon was especially pronounced in the neutral pH region where the solubility of aluminum, in the absence of complexants, is limited by the formation of sparsely soluble aluminum hydroxides. At pH higher than 10, dissolution of synthetic boehmite was inhibited by HEDPA, likely due to sorption of Al(III):HEDPA complexes. Addition of HEDPA to equilibrated U(VI)-synthetic boehmite suspensions yielded an increase in the aqueous phase uranium concentration. Partitioning of uranium between the solid and aqueous phase is described in terms of U(VI):HEDPA speciation and dissolution of the boehmite solid phase.

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

    International Nuclear Information System (INIS)

    Francis, A.; Dodge, C.

    2008-01-01

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

  7. Polarographic behaviour and determination of uranium(VI) in alcoholic solutions from organic extraction phases

    International Nuclear Information System (INIS)

    Degueldre, C.; Taibi, K.

    1996-01-01

    The determination of U(VI) in organic extraction phases: hydrocarbon-diethyl-2-hexyl phosphoric acid-trioctylphosphine oxide and hydrocarbon-tri-n-octylamine, diluted by an alcohol has been studied by direct current polarography, as well as by differential pulse polarography (DPP). In order to optimise the analytical procedure, miscibility and conductivity studies of the mixtures hydrocarbon-alcohol (ethanol, n- and isopropanol and n- and isobutanol) were made after addition of sulphuric acid as a supporting electrolyte. In the solutions of sulphuric acid in the alcohol-extractant-hydrocarbon phases, U(VI) gives rise to well defined polarograms. Its electroreduction involves a single electron step in all cases. The DPP peak height is proportional to the U(VI) concentration between 2x10 -6 and 2x10 -3 M, and the 3σ detection limit is ca. 10 -6 M

  8. Ternary uranium(VI) carbonato humate complex studied by cryo-TRLFS

    International Nuclear Information System (INIS)

    Steudtner, R.; Sachs, S.; Schmeide, K.; Brendler, V.; Bernhard, G.

    2011-01-01

    The complex formation of U(VI) with humic acid (HA) in the presence of carbonate was studied by time-resolved laser-induced fluorescence spectroscopy at low temperature (cryo-TRLFS) at pH 8.5. In the presence of HA, a decrease of the luminescence intensity of U(VI) and no shift of the emission band maxima in comparison to the luminescence spectrum of the UO 2 (CO 3 ) 3 4- complex, the dominating U(VI) species under the applied experimental conditions in the absence of HA, was observed. The formation of a ternary U(VI) carbonato humate complex of the type UO 2 (CO 3 ) 2 HA(II) 4- starting from UO 2 (CO 3 ) 3 4- was concluded from the luminescence data. For this complex a complex stability constant of log K=2.83 ± 0.17 was determined. Slope analysis resulted in a slope of 1.12 ± 0.11, which verifies the postulated complexation reaction. The results agree very well with literature data. Speciation calculations show that the formation of the ternary U(VI) carbonato humate complex can significantly influence the U(VI) speciation under environmental conditions. (orig.)

  9. Ternary uranium(VI) carbonato humate complex studied by cryo-TRLFS

    Energy Technology Data Exchange (ETDEWEB)

    Steudtner, R.; Sachs, S.; Schmeide, K.; Brendler, V.; Bernhard, G. [Helmholtz-Zentrum Dresden-Rossendorf, Dresden (Germany). Inst. of Radiochemistry

    2011-07-01

    The complex formation of U(VI) with humic acid (HA) in the presence of carbonate was studied by time-resolved laser-induced fluorescence spectroscopy at low temperature (cryo-TRLFS) at pH 8.5. In the presence of HA, a decrease of the luminescence intensity of U(VI) and no shift of the emission band maxima in comparison to the luminescence spectrum of the UO{sub 2}(CO{sub 3}){sub 3}{sup 4-} complex, the dominating U(VI) species under the applied experimental conditions in the absence of HA, was observed. The formation of a ternary U(VI) carbonato humate complex of the type UO{sub 2}(CO{sub 3}){sub 2}HA(II){sup 4-} starting from UO{sub 2}(CO{sub 3}){sub 3}{sup 4-} was concluded from the luminescence data. For this complex a complex stability constant of log K=2.83 {+-} 0.17 was determined. Slope analysis resulted in a slope of 1.12 {+-} 0.11, which verifies the postulated complexation reaction. The results agree very well with literature data. Speciation calculations show that the formation of the ternary U(VI) carbonato humate complex can significantly influence the U(VI) speciation under environmental conditions. (orig.)

  10. Comparative EXAFS study of uranium(VI) and neptunium(V) sorption onto kaolinite

    International Nuclear Information System (INIS)

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

    2005-01-01

    Full text of publication follows: We investigated the surface sorption process of U(VI) and Np(V) on kaolinite by extended X-ray absorption fine structure (EXAFS) spectroscopy in the 10 μM concentration range. Batch experiments with kaolinite in CO 2 -equilibrated systems showed that the adsorption edge of U(VI) occurs at pH 5.5, i.e., near the pH PZC of kaolinite. The adsorption edge of Np(V) occurs well above the pH PZC value at pH 8.5. This may indicate that the bonds between Np(V) and the surface functional groups of kaolinite are not as strong as in the case of U(VI). U(VI) and Np(V) have in common that the amount which is adsorbed decreases when the pH is increased beyond the absorption maximum. This behavior can be attributed to the formation of U(VI) and Np(V) carbonato complexes in the aqueous solutions. The aim of this comparative EXAFS study was to investigate the reason for the different affinities of U(VI) and Np(V) for kaolinite by measuring their local environments at the clay surface. Samples were prepared from 4 g/L kaolinite, 0.1 M NaClO 4 , pH 3.0 - 10.5, presence and absence of ambient CO 2 . The U L 3 - and Np L 2 -edge EXAFS spectra of the wet paste samples were measured at room temperature in fluorescence mode at the Rossendorf Beamline (ROBL) at the European Synchrotron Radiation Facility. The measured U-O and U-Al/Si distances indicate inner-sphere sorption of U(VI) on kaolinite. There was no evidence of uranium neighbors in the EXAFS spectra, suggesting that the adsorbed U(VI) complexes were predominantly monomeric. The average distance between uranium and its equatorial oxygen atoms, O eq , increased from 2.32 to 2.38 Angstrom in the presence of atmospheric CO 2 when the pH was increased from 5.0 to 8.5. In the CO 2 -free system, the U-O eq distance was independent from pH and equal to 2.32 Angstrom. The lengthening of the average U-O eq distance in the presence of carbonate (or bicarbonate) suggests the formation of ternary U(VI)-carbonato complexes with kaolinite. In contrast to U(VI), Np(V) samples prepared at pH 9.0 and ambient CO 2 did not show any indication of an inner-sphere sorption. The measured distances of 1.85, 2.55, 4.24 (all Np-O), 2.94 (Np-C), and 4.86 Angstrom (Np-Np) are consistent with the precipitation of a Np(V) carbonato species at the kaolinite surface. (authors)

  11. Speciation of bioaccumulated uranium(VI) by Euglena mutabilis cells obtained by laser fluorescence spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Brockmann, Sina; Bernhard, Gert [Technical Univ. Dresden (Germany). Radiochemistry; Helmholtz-Zentrum Dresden-Rossendorf (HZDR) e.V., Dresden (Germany). Inst. of Resource Ecology; Arnold, Thuro [Helmholtz-Zentrum Dresden-Rossendorf (HZDR) e.V., Dresden (Germany). Inst. of Resource Ecology

    2014-07-01

    The ability of Euglena mutabilis cells - a unicellular protozoan with a flexible pellicle, which is typically found in acid mine drainage (AMD) environments - to bioaccumulate uranium under acid conditions was studied in batch sorption experiments at pH 3 and 4 using Na{sub 2}SO{sub 4} and NaClO{sub 4} as background media. It was found that axenic cultures of Euglena mutabilis Schmitz were able to bioaccumulate in 5 days 94.9 to 99.2% of uranium from a 1 x 10{sup -5} mol/L uranium solution in perchlorate medium and 95.1 to 95.9% in sodium sulfate medium, respectively. The speciation of uranium in solution and uranium bioaccumulated by Euglena mutabilis cells, were studied by laser induced fluorescence spectroscopy (LIFS). The LIFS investigations showed that the uranium speciation in the NaClO{sub 4} systems was dominated by free uranyl(VI) species and that the UO{sub 2}SO{sub 4} species was dominating in the Na{sub 2}SO{sub 4} medium. Fluorescence spectra of the bioaccumulated uranium revealed that aqueous uranium binds to carboxylic and/or (organo)phosphate groups located on the euglenid pellicle or inside the Euglena mutabilis cells. Reduced uranium immobilization rates of 0.93-1.43 mg uranium per g Euglena mutabilis biomass were observed in similar experiments, using sterile filtrated AMD waters containing, 4.4 x 10{sup -5} mol/L uranium. These lower rates were attributed to competition with other cations for available sorption sites. Additional LIFS measurements, however, showed that the speciation of the bioaccumulated uranium by the Euglena mutabilis cells was found to be identical with the uranium speciation found in the bioaccumulation experiments carried out in Na{sub 2}SO{sub 4} and NaClO{sub 4} media. The results indicate that Euglena mutabilis has the potential to immobilize aqueous uranium under acid condition and thus may be used in future as promising agent for immobilizing uranium in low pH waste water environments. (orig.)

  12. Reduction of neptunium(V) and uranium(VI) in bicarbonate solutions by iron(II)

    International Nuclear Information System (INIS)

    Gogolev, A.V.; Zakharova, E.V.; Rodygina, N.I.; Fedoseev, A.M.; Shilov, V.P.

    2006-01-01

    Interaction of Np(VI) and Fe(II) compounds in bicarbonate solutions is investigated. Interaction of Np(V) with Fe(II) in the presence of phthalate-ions is studied briefly. Fe(II) compounds reduce Np(V) compounds in saturated with Ar or CO 2 solutions with any bicarbonate-ion concentrations. Chemical reaction kinetics is studied. Reduction of U(VI) by Fe(II) compounds takes place in the case of diluted bicarbonate solutions. UO 2 and FeOOH are products of reaction at raised temperatures [ru

  13. Uranium(VI) Reduction by Nanoscale Zerovalent Iron in Anoxic Batch Systems

    International Nuclear Information System (INIS)

    Yan, Sen; Hua, Bin; Bao, Zhengyu; Yang, John; Liu, Chongxuan; Deng, Baolin

    2010-01-01

    This study investigated the influences of pH, bicarbonate, and calcium on U(VI) adsorption and reduction by synthetic nanosize zero valent iron (nano Fe 0 ) particles under an anoxic condition. The results showed that about 87.1%, 82.7% and 78.3% of U(VI) could be reduced within 96 hours in the presence of 10 mM bicarbonate at pHs 6.92, 8.03 and 9.03, respectively. The rates of U(VI) reduction and adsorption by nano Fe 0 , however, varied significantly with increasing pH and concentrations of bicarbonate and/or calcium. Solid phase analysis by X-ray photoelectron spectroscopy confirmed the formation of UO 2 and iron (hydr)oxides as a result of the redox interactions between adsorbed U(VI) and nano Fe 0 . This study highlights the potential important role of groundwater chemical composition in controlling the rates of U(VI) reductive immobilization using nano Fe 0 in subsurface environments.

  14. Influence of Calcite and Dissolved Calcium on Uranium(VI) Sorption to a Hanford Subsurface Sediment

    International Nuclear Information System (INIS)

    Dong, Wenming; Ball, William P.; Liu, Chongxuan; Wang, Zheming; Stone, Alan T.; Bai, Jing; Zachara, John M.

    2005-01-01

    The influence of calcite and dissolved calcium on U(VI) adsorption was investigated using a calcite-containing sandy silt/clay sediment from the U. S. Department of Energy Hanford site. U(VI) adsorption to sediment, treated sediment, and sediment size fractions was studied in solutions that both had and had not been preequilibrated with calcite, at initial [U(VI)] ) 10-7-10-5 mol/L and final pH ) 6.0- 10.0. Kinetic and reversibility studies (pH 8.4) showed rapid sorption (30 min), with reasonable reversibility in the 3-day reaction time. Sorption from solutions equilibrated with calcite showed maximum U(VI) adsorption at pH 8.4 (0.1. In contrast, calcium-free systems showed the greatest adsorption at pH 6.0-7.2. At pH > 8.4, U(VI) adsorption was identical from calcium-free and calcium-containing solutions. For calcite-presaturated systems, both speciation calculations and laser-induced fluorescence spectroscopic analyses indicated that aqueous U(VI) was increasingly dominated by Ca2UO2(CO3)3 0(aq) at pH<8.4 and that formation of Ca2UO2(CO3)3 0(aq) is what suppresses U(VI) adsorption. Above pH 8.4, aqueous U(VI) speciation was dominated by UO2(CO3)3 4- in all solutions. Finally, results also showed that U(VI) adsorption was additive in regard to size fraction but not in regard to mineral mass: Carbonate minerals may have blocked U(VI) access to surfaces of higher sorption affinity

  15. Kinetics of Uranium(VI) Desorption from Contaminated Sediments: Effect of Geochemical Conditions and Model Evaluation

    International Nuclear Information System (INIS)

    Liu, Chongxuan; Shi, Zhenqing; Zachara, John M.

    2009-01-01

    Stirred-flow cell experiments were performed to investigate the kinetics of uranyl (U(VI)) desorption from a contaminated sediment collected from the Hanford 300 Area at the US Department of Energy (DOE) Hanford Site, Washington. Three influent solutions of variable pH, Ca and carbonate concentrations that affected U(VI) aqueous and surface speciation were used under dynamic flow conditions to evaluate the effect of geochemical conditions on the rate of U(VI) desorption. The measured rate of U(VI) desorption varied with solution chemical composition that evolved as a result of thermodynamic and kinetic interactions between the influent solutions and sediment. The solution chemical composition that led to a lower equilibrium U(VI) sorption to the solid phase yielded a faster desorption rate. The experimental results were used to evaluate a multi-rate, surface complexation model (SCM) that has been proposed to describe U(VI) desorption kinetics in the Hanford sediment that contained complex sorbed U(VI) species in mass transfer limited domains. The model was modified and supplemented by including multi-rate, ion exchange reactions to describe the geochemical interactions between the solutions and sediment. With the same set of model parameters, the modified model reasonably well described the evolution of major ions and the rates of U(VI) desorption under variable geochemical and flow conditions, implying that the multi-rate SCM is an effective way to describe U(VI) desorption kinetics in subsurface sediments

  16. Molecular interactions of Leucoagaricus naucinus with uranium(VI) and europium(III)

    International Nuclear Information System (INIS)

    Wollenberg, Anne; Raff, Johannes

    2017-01-01

    With regard to a molecular understanding of the interaction of fungal mycelium with radionuclides and its possible application for precautionary radiation protection and bio-remediation, the binding mechanism of the radionuclide uranium and the metal europium, as surrogate for trivalent actinides, where investigated with different starting conditions by the living fungal cells of Leucoagaricus naucinus.

  17. Solid-phase extraction-spectrophotometric determination of uranium(VI) in natural waters

    Energy Technology Data Exchange (ETDEWEB)

    Sadeghi, Susan; Mohammadzadeh, Darush [Department of Chemistry, University of Birjand, Birjand (Iran); Yamini, Yadollah [Department of Chemistry, Tarbiat Moddars University, Tehran (Iran)

    2003-03-01

    A method for the extraction and determination of uranyl ion in natural waters using octadecyl bonded silica membrane disks modified with piroxicam and spectrophotometry with arsenazo(III) is proposed. The perconcentration step was studied with regard to experimental parameters such as amount of extractant, type and amount of eluent, pH, flow rates and tolerance limit of diverse ions on the recovery of uranyl ion. The limit of detection of the proposed method is 0.4 {mu}g L{sup -1} of uranyl. The method was applied to the recovery of uranyl from different water samples. (orig.)

  18. Solid-phase extraction-spectrophotometric determination of uranium(VI) in natural waters

    International Nuclear Information System (INIS)

    Sadeghi, Susan; Mohammadzadeh, Darush; Yamini, Yadollah

    2003-01-01

    A method for the extraction and determination of uranyl ion in natural waters using octadecyl bonded silica membrane disks modified with piroxicam and spectrophotometry with arsenazo(III) is proposed. The perconcentration step was studied with regard to experimental parameters such as amount of extractant, type and amount of eluent, pH, flow rates and tolerance limit of diverse ions on the recovery of uranyl ion. The limit of detection of the proposed method is 0.4 μg L -1 of uranyl. The method was applied to the recovery of uranyl from different water samples. (orig.)

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

    International Nuclear Information System (INIS)

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

    2002-01-01

    The uptake of heavy metals into plants is commonly quantified by the soil-plant transfer factor. Up to now little is known about the chemical speciation of actinides in plants. To compare the obtained spectroscopic data of uranium complexes in plants with model compounds, we investigate the complexation of uranium with relevant bioligands of various functionalities. A very important class of ligands consists of phosphate esters, which serve as phosphate group and energy transmitters as well as energy storage media in biological systems. Heavy metal ions bound to the phosphate esters can be transported into living cells and then deposited. Therefore, in our study we present the results of uranium complexation with glucose-6-phosphate (G6P), and fructose-6-phosphate (F6P) obtained by time-resolved laser-induced fluorescence spectroscopy (TRLFS). The experiments were performed at a fixed uranyl concentration (10 -5 M) as a function of the ligand concentrations (10 -5 to 10 -3 M) in a pH range from 2 to 4.5. For the glucose phosphate system we observed, using increasing ligand concentrations, a decrease in the fluorescence intensity and a small red shift of the emission bands. From this we conclude that the complexed uranyl glucose phosphate species show only minor or no fluorescence properties. The TRLFS spectra of the glucose phosphate samples indicated the presence of a single species with fluorescence properties. This species has a lifetime of approximately 1.5 μs and was identified as the free uranyl ion. An opposite phenomenon was observed for the fructose phosphate system: there was no decrease in fluorescence intensity. However, a strong red shift of the spectra was observed, illustrating the fluorescence properties of the uranyl fructose phosphate complex. The TRLFS spectra of the fructose phosphate system showed a second lifetime ( 2 2+ UO 2 (lig) x (2-y)+ + y H + (lig = sugar phosphate). Applying the mass action law and transformation to the logarithmic scale, we obtain: log [UO 2 (lig) x (2-y)+ ]/ [UO 2 2+ ] = x log [lig(noncomplexed)] - y log [H + ] + log K. From this we conclude that the 1:1 uranyl sugar phosphate species UO 2 (ROPO 3 ) (R is either glucose or fructose) has formed. Using these data, the complex formation constants for the complexes were calculated to lie in the range of log K=3.7 for G6P and 3.2 for F6P. (author)

  20. Microbial reduction of uranium(VI) by anaerobic microorganisms isolated from a former uranium mine

    International Nuclear Information System (INIS)

    Gerber, Ulrike; Krawczyk-Baersch, Evelyn; Arnold, Thuro; Scheinost, Andreas C.

    2017-01-01

    The former uranium mine Koenigstein (Germany) is currently in the process of controlled flooding by reason of remediation purposes. However, the flooding water still contains high concentrations of uranium and other heavy metals. For that reason the water has to be cleaned up by a conventional waste water treatment plant. The aim of this study was to investigate the interactions between anaerobic microorganisms and uranium for possible bioremediation approaches, which could be an great alternative for the intensive and expensive waste water treatment. EXAFS (extended X-ray absorption fine structure) and XANES (X-ray absorption near edge structure) measurements were performed and revealed a complete reduction of U(VI) to U(IV) only by adding 10 mM glycerol.

  1. Effect of high ionic strength on the extraction of uranium(VI ions

    Directory of Open Access Journals (Sweden)

    M.K. Nazal

    2014-01-01

    Full Text Available Preparation and characterization of didodecylphosphoric acid (HDDPA as an extractant in toluene was carried. Mass spectroscopy showed that the monomer peak at 457.4 amu [M–Na+] is double that of the dimer at 891.9 amu [M–M–Na+] and the monomer molecules concentration dominate the dimer molecules in toluene. HDDPA was used as an extractant for the extraction of U(VI ion from perchlorate and nitrate media that have ionic strength (1.00, 3.00, 5.00, 7.00 M. The effect of HDDPA concentration, pcH, ionic strength of supporting electrolytes, and temperature in the range 15–45 °C on the extraction process have been studied. The stoichiometry of the extraction of U(VI ion, the free energy change (ΔG, the enthalpy change (ΔH, the entropy change (ΔS, and Kex at different ionic strength have been calculated. The formula of the complexes, which were formed has been established to be UO2(X(R2(HR2 at pcH equal 2.00 and UO2(X(R2(HR2 and UO2(X(R2 at pcH = 1.00, where (X isClO4- orNO3- and (HR2 is didodecylphosphoric acid monomer, (R2 is the deprotonated didodecylphosphoric acid, where R is the dodecyl group.

  2. Uranium(VI) retention on quartz and kaolinite. Experiments and modelling

    International Nuclear Information System (INIS)

    Mignot, G.

    2001-01-01

    The behaviour of uranium in the geosphere is an important issue for safety performance assessment of nuclear waste repositories, or in the context of contaminated sites due to mining activity related to nuclear field. Under aerobic conditions, the fate of uranium is mainly governed by the ability of minerals to sorb U(VI) aqueous species. Hence, a thorough understanding of U(VI) sorption processes on minerals is required to provide a valuable prediction of U(VI) migration in the environment. In this study, we performed sorption/desorption experiments of U(VI) on quartz and kaolinite, for systems favouring the formation in solution (i) of UO 2 2+ and monomeric hydrolysis products or (ii) of di-/tri-meric uranyl aqueous species, and / or U(VI)-colloids or UO 2 (OH) 2 precipitates, or (iii) of uranyl-carbonate complexes. Particular attention was paid to determine the surface characteristics of the solids and their modification due to dissolution/precipitation processes during experiments. A double layer surface complexation model was applied to our experimental data in order to derive surface complexation equilibria and intrinsic constants which allow a valuable description of U(VI) retention over a wide range of pH, ionic strength, initial concentration of uranium [0.1-10μM] and solid - solution equilibration time. U(VI) sorption on quartz was successfully modeled by using two sets of adsorption equilibria, assuming (i) the formation of the surface complexes SiOUO 2 + , SiOUO 2 OH and SiO(UO 2 ) 3 (OH) 5 , or (ii) the formation of the mono-dentate complex SiO(UO 2 ) 3 (OH) 5 and of the bidentate complex (SiO) 2 UO 2 . Assumptions on the density of each type of surface sites of kaolinite and on their acid-base properties were made from potentiometric titrations of kaolinite suspensions. We proposed on such a basis a set of surface complexation equilibria which accounts for U(VI) uptake on kaolinite over a wide range of chemical conditions, with aluminol edge sites as predominant surface ligands. (author) [fr

  3. Extraction and separation studies of uranium(VI) with tris-(2-ethyl hexyl) phosphate

    International Nuclear Information System (INIS)

    Sundaramurthi, N.M.; Desai, G.S.; Shinde, V.M.

    1990-01-01

    A solvent extraction method is proposed for the extraction and separation of uranium from salicylate media using tris-(2-ethyl hexyl) phosphate dissolved in xylene as an extractant. The optimum conditions were evaluated from a critical study of pH, salicylate concentration, extractant concentration, period of equilibration and diluent. The method permits the separation of uranium from thorium, cerium, titanium, zirconium, hafnium, copper, vanadium and chromium from binary mixtures and is applicable to the analysis of uranium in synthetic samples. The method is precise, accurate, fast and selective. (author) 5 refs.; 2 tabs

  4. The effect of symmetry on the U L3 NEXAFS of octahedral coordinated uranium(vi)

    Energy Technology Data Exchange (ETDEWEB)

    Bagus, Paul S. [Department of Chemistry, University of North Texas, Denton, Texas 76203-5017, USA; Nelin, Connie J. [Consultant, Austin, Texas 78730, USA; Ilton, Eugene S. [Pacific Northwest National Laboratory, Richland, Washington 99352, USA

    2017-03-21

    We describe a detailed theoretical analysis of how distortions from ideal cubic or Oh symmetry affect the shape, in particular the width, of the U L3-edge NEXAFS for U(VI) in octahedral coordination. The full-width-half-maximum (FWHM) of the L3-edge white line decreases with increasing distortion from Oh symmetry due to the mixing of symmetry broken t2g and eg components of the excited state U(6d) orbitals. The mixing is allowed because of spin-orbit splitting of the ligand field split 6d orbitals. Especially for higher distortions, it is possible to identify a mixing between one of the t2g and one of the eg components, allowed in the double group representation when the spin-orbit interaction is taken into account. This mixing strongly reduces the ligand field splitting, which, in turn, leads to a narrowing of the U L3 white line. However, the effect of this mixing is partially offset by an increase in the covalent anti-bonding character of the highest energy spin-orbit split eg orbital. At higher distortions, mixing overwhelms the increasing anti-bonding character of this orbital which leads to an accelerated decrease in the FWHM with increasing distortion. Additional evidence for the effect of mixing of t2g and eg components is that the FWHM of the white line narrows whether the two axial U-O bond distances shorten or lengthen. Our ab initio theory uses relativistic wavefunctions for cluster models of the structures; empirical or semi-empirical parameters were not used to adjust prediction to experiment. A major advantage is that it provides a transparent approach for determining how the character and extent of the covalent mixing of the relevant U and O orbitals affect the U L3-edge white line.

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

    International Nuclear Information System (INIS)

    Tan Hongbin; Li Yuxiang

    2005-01-01

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

  6. Speciation of bioaccumulated uranium(VI) by Euglena mutabilis cells obtained by laser fluorescence spectroscopy

    International Nuclear Information System (INIS)

    Brockmann, Sina; Bernhard, Gert; Helmholtz-Zentrum Dresden-Rossendorf; Arnold, Thuro

    2014-01-01

    The ability of Euglena mutabilis cells - a unicellular protozoan with a flexible pellicle, which is typically found in acid mine drainage (AMD) environments - to bioaccumulate uranium under acid conditions was studied in batch sorption experiments at pH 3 and 4 using Na 2 SO 4 and NaClO 4 as background media. It was found that axenic cultures of Euglena mutabilis Schmitz were able to bioaccumulate in 5 days 94.9 to 99.2% of uranium from a 1 x 10 -5 mol/L uranium solution in perchlorate medium and 95.1 to 95.9% in sodium sulfate medium, respectively. The speciation of uranium in solution and uranium bioaccumulated by Euglena mutabilis cells, were studied by laser induced fluorescence spectroscopy (LIFS). The LIFS investigations showed that the uranium speciation in the NaClO 4 systems was dominated by free uranyl(VI) species and that the UO 2 SO 4 species was dominating in the Na 2 SO 4 medium. Fluorescence spectra of the bioaccumulated uranium revealed that aqueous uranium binds to carboxylic and/or (organo)phosphate groups located on the euglenid pellicle or inside the Euglena mutabilis cells. Reduced uranium immobilization rates of 0.93-1.43 mg uranium per g Euglena mutabilis biomass were observed in similar experiments, using sterile filtrated AMD waters containing, 4.4 x 10 -5 mol/L uranium. These lower rates were attributed to competition with other cations for available sorption sites. Additional LIFS measurements, however, showed that the speciation of the bioaccumulated uranium by the Euglena mutabilis cells was found to be identical with the uranium speciation found in the bioaccumulation experiments carried out in Na 2 SO 4 and NaClO 4 media. The results indicate that Euglena mutabilis has the potential to immobilize aqueous uranium under acid condition and thus may be used in future as promising agent for immobilizing uranium in low pH waste water environments. (orig.)

  7. Kinetics and equilibrium modeling of uranium(VI) sorption by bituminous shale from aqueous solution

    International Nuclear Information System (INIS)

    Ortaboy, Sinem; Atun, Gülten

    2014-01-01

    Highlights: • Oil shales are sedimentary rocks containing a polymeric matter in a mineral matrix. • Sorption potential of bituminous shale (BS) for uranium recovery was investigated. • U(VI) sorption increased with decreasing pH and increasing temperature. • Kinetic data were analyzed based on single and two resistance diffusion models. • The results fit well to the McKay equation assuming film and intraparticle diffusion. - Abstract: Sorption of U(VI) onto a bituminous shale (BS) from a nuclear power plant project site in Black Sea region was investigated for potential risk assessment when it releases into the environment with contaminated ground and surface water. The sorption characteristics of the BS for U(VI) recovery were evaluated as a function of contact time, adsorbent dosage, initial concentration, pH and temperature. Kinetic results fit better with pseudo-second-order model rather than pseudo-first-order. The possibility of diffusion process was analyzed based on Weber–Morris intra-particle diffusion model. The McKay equation assuming film- and intraparticle diffusion better predicted the data than the Vermeulen approximation presuming surface diffusion. Equilibrium sorption data were modeled according to the Langmuir, Dubinin–Radushkevich (D–R) and Freundlich isotherm equations. Sorption capacity increased from 0.10 to 0.15 mmol g −1 in 298–318 K temperature range. FT-IR analysis and pH dependent sorption studies conducted in hydroxide and carbonate media revealed that U(VI) species were sorbed in uranyl and its hydroxo forms on the BS. Desorption studies showed that U(VI) leaching with Black Sea water was negligible from the loaded BS. The activation parameters (E a , ΔH ∗ and ΔG ∗ ) estimated from diffusion coefficients indicated the presence of an energy barrier in the sorption system. However, thermodynamic functions derived from sorption equilibrium constants showed that overall sorption process was spontaneous in nature and entropy controlled

  8. Characterizing particle-scale equilibrium adsorption and kinetics of uranium(VI) desorption from U-contaminated sediments

    Science.gov (United States)

    Stoliker, Deborah L.; Liu, Chongxuan; Kent, Douglas B.; Zachara, John M.

    2013-01-01

    Rates of U(VI) release from individual dry-sieved size fractions of a field-aggregated, field-contaminated composite sediment from the seasonally saturated lower vadose zone of the Hanford 300-Area were examined in flow-through reactors to maintain quasi-constant chemical conditions. The principal source of variability in equilibrium U(VI) adsorption properties of the various size fractions was the impact of variable chemistry on adsorption. This source of variability was represented using surface complexation models (SCMs) with different stoichiometric coefficients with respect to hydrogen ion and carbonate concentrations for the different size fractions. A reactive transport model incorporating equilibrium expressions for cation exchange and calcite dissolution, along with rate expressions for aerobic respiration and silica dissolution, described the temporal evolution of solute concentrations observed during the flow-through reactor experiments. Kinetic U(VI) desorption was well described using a multirate SCM with an assumed lognormal distribution for the mass-transfer rate coefficients. The estimated mean and standard deviation of the rate coefficients were the same for all Micropore volumes, assessed using t-plots to analyze N2 desorption data, were also the same for all dry-sieved micropore volumes and mass-transfer rate properties. Pore volumes for dry-sieved size fractions exceeded values for the corresponding wet-sieved fractions. We hypothesize that repeated field wetting and drying cycles lead to the formation of aggregates and/or coatings containing (micro)pore networks which provided an additional mass-transfer resistance over that associated with individual particles. The 2–8 mm fraction exhibited a larger average and standard deviation in the distribution of mass-transfer rate coefficients, possibly caused by the abundance of microporous basaltic rock fragments.

  9. Quantifying differences in the impact of variable chemistry on equilibrium Uranium(VI) adsorption properties of aquifer sediments.

    Science.gov (United States)

    Stoliker, Deborah L; Kent, Douglas B; Zachara, John M

    2011-10-15

    Uranium adsorption-desorption on sediment samples collected from the Hanford 300-Area, Richland, WA varied extensively over a range of field-relevant chemical conditions, complicating assessment of possible differences in equilibrium adsorption properties. Adsorption equilibrium was achieved in 500-1000 h although dissolved uranium concentrations increased over thousands of hours owing to changes in aqueous chemical composition driven by sediment-water reactions. A nonelectrostatic surface complexation reaction, >SOH + UO₂²⁺ + 2CO₃²⁻ = >SOUO₂(CO₃HCO₃)²⁻, provided the best fit to experimental data for each sediment sample resulting in a range of conditional equilibrium constants (logK(c)) from 21.49 to 21.76. Potential differences in uranium adsorption properties could be assessed in plots based on the generalized mass-action expressions yielding linear trends displaced vertically by differences in logK(c) values. Using this approach, logK(c) values for seven sediment samples were not significantly different. However, a significant difference in adsorption properties between one sediment sample and the fines (< 0.063 mm) of another could be demonstrated despite the fines requiring a different reaction stoichiometry. Estimates of logK(c) uncertainty were improved by capturing all data points within experimental errors. The mass-action expression plots demonstrate that applying models outside the range of conditions used in model calibration greatly increases potential errors.

  10. Uranium(VI) sorption onto magnetite. Increasing confidence in surface complexation models using chemically evident surface chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Bok, Frank [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Surface Processes

    2017-06-01

    Surface complexation models have made great efforts in describing the sorption of various radionuclides on naturally occurring mineral phases. Unfortunately, many of the published sorption parameter sets are built upon unrealistic or even wrong surface chemistry. This work describes the benefit of combining spectroscopic and batch sorption experimental data to create a reliable and consistent surface complexation parameter set.

  11. Studies of layered uranium(VI) compounds. I. High proton conductivity in polycrystalline hydrogen uranyl phosphate tetrahydrate

    International Nuclear Information System (INIS)

    Howe, A.T.; Shilton, M.G.

    1979-01-01

    Hydrogen uranyl phosphate tetrahydrate HUO 2 PO 4 .4H 2 O has a high proton conductivity. The ac conductivity was 0.4 ohm -1 m -1 at 290 0 K measured parallel to the faces of sintered disks of the compound. The activation energy was found to be 31 +- 3 kJ mole -1 . The values of conductivity were between 3 and 10 times lower when measured perpendicular to the disk faces due to preferred orientation of the plate-like crystals. Both the powder and sintered disks are stable in air and insoluble in phosphoric acid solution of pH 2.5. Experiments are described which enable possible grain boundary contributions to the conductivity to be determined in such hydrates. The extrinsic grain boundary contribution to the conductivity was found to be small from experiments in which the pH in a solution cell was varied. The abnormally high bulk H + conductivity thus inferred is attributed primarily to the high concentration of H + , which exists as H 3 O + in the interlamellar hydrogen-bounded network. A Grotthus-type mechanism of conduction is proposed which involves intermolecular transfer steps (hopping) and intramolecular transfer steps, in comparable numbers, the former facilitated by the high concentration of H 3 O + ions in the structure, and the latter most likely facilitated by the high concentration of H-bond vacancies. 8 figures, 1 table

  12. Study on the electrolytic reduction of Uranium-VI to Uranium-IV in a nitrate system

    International Nuclear Information System (INIS)

    Araujo, B.F. de; Almeida, S.G. de; Forbicini, S.; Matsuda, H.T.; Araujo, J.A. de.

    1981-05-01

    The determination of the best conditions to prepare hydrazine stabilized uranium (IV) nitrate solutions for utilization in Purex flowsheets is dealt with. Electrolytic reduction of U(VI) has been selected as the basic method, using an open electrolytic cell with titanum and platinum electrodes. The hydrazine concentration, the current density, acidity, U(VI) concentration and reduction time were the parameters studied and U(IV)/U(VI) ratio was used to evaluate the degree of reduction. From the results it could be concluded that the technique is reliable. The U(IV) solutions remains constant for at least two weeks and can be used in the chemical processing of irradiated uranium fuels. (Author) [pt

  13. Effect of flavin compounds on uranium(VI) reduction- kinetic study using electrochemical methods with UV-vis spectroscopy

    International Nuclear Information System (INIS)

    Yamasaki, Shinya; Tanaka, Kazuya; Kozai, Naofumi; Ohnuki, Toshihiko

    2017-01-01

    The reduction of uranium hexavalent (U(VI)) to tetravalent (U(IV)) is an important reaction because of the change in its mobility in the natural environment. Although the flavin mononucleotide (FMN) has acted as an electron shuttle for the U(VI) reduction in vivo system, which is called an electron mediator, only the rate constant for the electron transfer from FMN to U(VI) has been determined. This study examined the rate constant for the U(VI) reduction process by three flavin analogues (riboflavin, flavin mononucleotide, flavin adenine dinucleotide) to elucidate their substituent group effect on the U(VI) reduction rate by electrochemical methods. The formation of the U(IV) was monitored by UV-vis spectrometry at 660 nm during the constant potential electrolysis of the U(VI) solution in the presence of the mediator. The cyclic voltammograms indicated that the three flavin analogues behaved as electron mediator to reduce U(VI). The logarithmic rate constant for the U(VI) reduction was related to the standard redox potential of the mediators. This linear relationship indicated that the redox-active group of the mediator and the substituent group of the mediator dominate capability of the U(VI) reduction and its rate, respectively. The apparent reduction potential of U(VI) increased about 0.2 V in the presence of the mediators, which strongly suggests that the biological electron mediator makes the U(VI) reduction possible even under more oxidative conditions. - Highlights: • The rate constant for the U(VI) reduction by flavin analogues was determined. • The flavins showed a mediator effect on the U(VI) reduction. • The logarithmic rate constants for the U(VI) reduction was proportional to redox potential of the mediator. • The presence of the mediator increased about 0.2 V apparent redox potential of U(VI) to U(IV).

  14. 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.

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

    Science.gov (United States)

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

    2013-01-15

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

  16. Investigation of the binding of tiron to uranium(IV) and uranium(VI) found in soil

    International Nuclear Information System (INIS)

    Birnbaum, E.R.; Iams, H.D.; del Rio Garcia, M.; Ford, D.K.; Smith, P.H.; Strietelmeier, B.; Brainard, J.

    1993-01-01

    The authors are investigating the utility of a chelate-reductant system to extract uranium from 2 million yards of contaminated soil at the Fernald uranium reprocessing plant near Cincinnati, Ohio. It has been found that reduction of the uranyl contaminants using Tiron as the ligand. Of concern is whether the increased mobilization is simply a result of the higher affinity of Tiron to U(IV), or whether reduction of amorphous iron oxides contained in the soil is exposing greater amounts of uranyl ions to the ligand. It is important to establish if the latter mechanism is occurring, since a removal process which does not damage the soil is desired. Potentiometric and spectrophotometric studies of Tiron binding to soluble uranyl and U(V) salts will be presented as models to help understand the soil studies. Extraction behavior of UO 2 (OH) 2 will also be presented

  17. Mechanism of uranium(VI) uptake by Saccharomyces cerevisiae under environmentally relevant conditions: Batch, HRTEM, and FTIR studies

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Xia, E-mail: lux2009@lzu.edu.cn; Zhou, Xiao-jiao; Wang, Tie-shan, E-mail: tswang@lzu.edu.cn

    2013-11-15

    Highlights: • Equilibrium reaches very rapid within 15 min. • pH shift towards neutral indicates release of hydroxyl ions. • High ionic strength inhabits biosorption capacity. • Uptake capacity of heat-killed cells is an order of magnitude higher than live one. • Electrostatic interaction, precipitation, and complexation are the main mechanisms. -- Abstract: Biosorption is of significance for the safety evaluation of high-level nuclear wastes repositories and remediation of radioactive contamination places. Quantitive study and structural characterization of uranium uptake by both live and heat-killed Saccharomyces cerevisiae at environmentally relevant uranium concentration and with different ionic strengths were carried out. Kinetic investigation showed the equilibrium reached within 15 min. In equilibrium studies, pH shift towards neutral indicated release of hydroxyl ions. pH was the most important factor, which partly affected electrostatic interaction between uranyl ions and S. cerevisiae surface. The high ionic strength inhibited biosorption capacity, which can be explained by a competitive reaction between sodium ions and uranyl ions. Heat killing process significantly enhanced biosorption capacity, showing an order of magnitude higher than that of live cells. High resolution transmission electron microscopy (HRTEM) coupled with energy dispersive X-ray (EDX) showed needle-like uranium-phosphate precipitation formed on the cell walls for both live and heat-killed cells. Besides, dark-field micrographs displayed considerable similar uranium-phosphate precipitation presented outside the heat-killed cells. The phosphate released during heat-killing process. FTIR illustrated function groups hydroxyl, carboxyl, phosphate, and amino groups played important role in complexation with uranium.

  18. Uranium(VI) sorption on iron oxides in Hanford Site sediment: Application of a surface complexation model

    International Nuclear Information System (INIS)

    Um, Wooyong; Serne, R. Jeffrey; Brown, Christopher F.; Rod, Kenton A.

    2008-01-01

    Sorption of U(VI) on Hanford fine sand (HFS) with varying Fe-oxide (especially ferrihydrite) contents showed that U(VI) sorption increased with the incremental addition of synthetic ferrihydrite into HFS, consistent with ferrihydrite being one of the most reactive U(VI) sorbents present in natural sediments. Surface complexation model (SCM) calculations for U(VI) sorption, using only U(VI) surface-reaction constants obtained from U(VI) sorption data on freshly synthesized ferrihydrite at different pHs, were similar to the measured U(VI) sorption results on pure synthetic ferrihydrite and on HFS with high contents of ferrihydrite (5 wt%) added. However, the SCM prediction using only U(VI) sorption reactions and constants for synthetic ferrihydrite overestimated U(VI) sorption on the natural HFS or HFS with addition of low amounts of added ferrihydrite (1 wt% added). Over-predicted U(VI) sorption was attributed to reduced reactivity of natural ferrihydrite present in Hanford Site sediments, compared to freshly prepared synthetic ferrihydrite. Even though the SCM general composite (GC) approach is considered to be a semi-quantitative estimation technique for contaminant sorption, which requires systematic experimental data on the sorbent-sorbate system being studied to obtain credible SCM parameters, the general composite SCM model was still found to be a useful technique for describing U(VI) sorption on natural sediments. Based on U(VI) batch sorption results, two simple U(VI) monodentate surface species, SO U O 2 HCO 3 and SO U O 2 OH on ferrihydrite and phyllosillicate in HFS, respectively, can be successfully used to describe U(VI) sorption onto Hanford Site sediment contacting varying geochemical solutions

  19. Kinetic and equilibrium characterization of uranium(VI) adsorption onto carboxylate-functionalized poly(hydroxyethylmethacrylate)-grafted lignocellulosics.

    Science.gov (United States)

    Anirudhan, T S; Divya, L; Suchithra, P S

    2009-01-01

    This study investigated the feasibility of using a new adsorbent prepared from coconut coir pith, CP (a coir industry-based lignocellulosic residue), for the removal of uranium [U(VI)] from aqueous solutions. The adsorbent (PGCP-COOH) having a carboxylate functional group at the chain end was synthesized by grafting poly(hydroxyethylmethacrylate) onto CP using potassium peroxydisulphate-sodium thiosulphite as a redox initiator and in the presence of N,N'-methylenebisacrylamide as a crosslinking agent. IR spectroscopy results confirm the graft copolymer formation and carboxylate functionalization. XRD studies confirm the decrease of crystallinity in PGCP-COOH compared to CP, and it favors the protrusion of the functional group into the aqueous medium. The thermal stability of the samples was studied using thermogravimetry (TG). Surface charge density of the samples as a function of pH was determined using potentiometric titration. The ability of PGCP-COOH to remove U(VI) from aqueous solutions was assessed using a batch adsorption technique. The maximum adsorption capacity was observed at the pH range 4.0-6.0. Maximum removal of 99.2% was observed for an initial concentration of 25mg/L at pH 6.0 and an adsorbent dose of 2g/L. Equilibrium was achieved in approximately 3h. The experimental kinetic data were analyzed using a first-order kinetic model. The temperature dependence indicates an endothermic process. U(VI) adsorption was found to decrease with an increase in ionic strength due to the formation of outer-sphere surface complexes on PGCP-COOH. Equilibrium data were best modeled by the Langmuir isotherm. The thermodynamic parameters such as DeltaG(0), DeltaH(0) and DeltaS(0) were derived to predict the nature of adsorption. Adsorption experiments were also conducted using a commercial cation exchanger, Ceralite IRC-50, with carboxylate functionality for comparison. Utility of the adsorbent was tested by removing U(VI) from simulated nuclear industry wastewater. Adsorbed U(VI) ions were desorbed effectively (about 96.2+/-3.3%) by 0.1M HCl. The adsorbent was suitable for repeated use (more than four cycles) without any noticeable loss of capacity.

  20. Effect of pH, ionic strength and humic acid on the sorption of uranium(VI) to attapulgite

    Energy Technology Data Exchange (ETDEWEB)

    Niu Zhiwei [Radiochemistry Laboratory, Lanzhou University, Lanzhou 730000, Gansu (China); Fan Qiaohui [Radiochemistry Laboratory, Lanzhou University, Lanzhou 730000, Gansu (China)], E-mail: fanqiaohui@gmail.com; Wang Wenhua; Xu Junzheng [Radiochemistry Laboratory, Lanzhou University, Lanzhou 730000, Gansu (China); Chen Lei [School of Chemical Engineering, Shandong University of Technology, 255049 Zibo, Shandong (China); Wu Wangsuo [Radiochemistry Laboratory, Lanzhou University, Lanzhou 730000, Gansu (China)], E-mail: wuws@lzu.edu.cn

    2009-09-15

    Attapulgite was investigated to remove UO{sub 2}{sup 2+} from aqueous solutions because of its strong sorption capacity. Herein, the attapulgite sample was characterized by Fourier transform infrared spectra (FTIR), X-ray diffraction (XRD) and acid-base titration in detail. Sorption of UO{sub 2}{sup 2+} on attapulgite was strongly dependent on pH values and ionic strength. The presence of humic acid enhanced the sorption of UO{sub 2}{sup 2+} on attapulgite obviously because of the strong complexation of humic acid (HA) with UO{sub 2}{sup 2+} on attapulgite surface. Sorption of UO{sub 2}{sup 2+} on attapulgite was mainly dominated by ion-exchange or outer-sphere complexation at low pH values, and by inner-sphere complexation at high pH values. The results indicated that attapulgite was a suitable material for the preconcentration and solidification of UO{sub 2}{sup 2+} from large volume of solutions because of its negative surface charge and large surface areas.

  1. Bis-phosphonate sequestering agents. Synthesis and preliminary evaluation for in vitro and in vivo uranium(VI) chelation

    Energy Technology Data Exchange (ETDEWEB)

    Sawicki, M.; Lecercle, D.; Taran, F. [CEA Saclay, IBiTecS, Serv Chim Bioorgan et Marquage, F-91191 Gif Sur Yvette (France); Grillon, G.; Le Gall, B.; Serandour, A.L.; Poncy, J.L. [CEA, DSV, DRR, Lab Radiotoxicol, F-91680 Bruyeres Le Chatel (France); Bailly, T.; Burgada, R.; Lecouvey, M.; Challeix, V. [CNRS, Lab Chim Struct Biomol, UMR 7033, F-93017 Bobigny (France); Leydier, A.; Pellet-Rostaing, S. [Univ Lyon 1, ICBMS, UMR 5246, Lab Catalyse et Synth Organ, F-69622 Villeurbanne (France); Ansoborlo, E. [CEA, DEN, DRCP, CETAMA, VRH Marcoule, F-30207 Bagnols Sur Ceze (France)

    2008-07-01

    A library of bis-phosphonate-based ligands was prepared using solution-phase parallel synthesis and tested for its uranium-binding properties. With the help of a screening method, based on a chromo-phoric complex displacement procedure, 23 dipodal and tripodal chelates bearing bis-phosphonate chelating functions were found to display very high affinity for the uranyl ion and were selected for evaluation of their in vivo uranyl-removal efficacy. Among them, 11 ligands induced a huge modification of the uranyl biodistribution by deviating the metal from kidney and bones to liver. Among the other ligands, the most potent was the dipodal bis-phosphonate 3C which reduced the retention of uranyl and increased its excretion by around 10% of the injected metal. (authors)

  2. Solubility and sorption characteristics of uranium(VI) associated with rock samples and brines/groundwaters from WIPP and NTS

    International Nuclear Information System (INIS)

    Dosch, R.G.

    1981-01-01

    Solubility measurements for U(VI) in WIPP-related brines/groundwaters were made using initial U(VI) concentrations in the range of 1 to 50 μg/ml. Distribution coefficients (Kd) for U(VI) were determined for Culebra and Magenta dolomites using four different brine/groundwater compositions and for argillaceous shale and hornfels samples from the Eleana and Calico Hills Formation on NTS using a groundwater simulant typical of that area. The Kd's were evaluated as functions of: (1) U(VI) concentration (1.4 x 10 -4 to 1.4 μg/ml); (2) solution volume-to-rock mass ratios used in the measurements (5 to 100 ml/g), and for WIPP material only; (3) water composition (0 to 100% brine in groundwater); and (4) sample location in the Culebra and Magenta dolomite members of the Rustler Formation. The results indicate that if groundwater intrudes into a repository and leaches a waste form, significant concentrations of dissolved or colloidal U(VI) could be maintained in the liquid phase. Should these solutions enter an aquifer system, there are reasonable sets of conditions which could lead to subsequent migration of U(VI) away from the repository site

  3. Separation of uranium(VI) by liquid-solid extraction with tri-n-octylphosphine oxide diluted with naphthalene

    International Nuclear Information System (INIS)

    Shigetomi, Y.; Kojima, T.; Kamba, H.; Yamamoto, Y.

    1980-01-01

    Liquid-liquid distribution with tri-n-octylphosphine oxide (TOPO) and molten naphthalene has been investigated for the extraction of 20 metals from nitric acid and hydrochloric acid solutions. Uranium is quantitatively extracted from 1 M nitric acid or hydrochloric acid by using 100 mg of TOPO and 200 mg of naphthalene and shaking for 5 min at 80 0 C, and separated from transition metals, alkaline earth metals and rare earth metals (except scandium). Addition of naphthalene increases the extraction efficiency. (Auth.)

  4. Solvent-extraction and purification of uranium(VI) and molybdenum(VI) by tertiary amines from acid leach solutions

    International Nuclear Information System (INIS)

    La Gamma, Ana M.G.; Becquart, Elena T.; Chocron, Mauricio

    2008-01-01

    Considering international interest in the yellow-cake price, Argentina is seeking to exploit new uranium ore bodies and processing plants. A study of similar plants would suggest that solvent- extraction with Alamine 336 is considered the best method for the purification and concentration of uranium present in leaching solutions. In order to study the purification of these leach liquors, solvent-extraction tests under different conditions were performed with simulated solutions which containing molybdenum and molybdenum-uranium mixtures. Preliminary extraction tests carried out on mill acid-leaching liquors are also presented. (authors)

  5. A comparative study of the complexation of uranium(VI) with oxydiacetic acid and its amide derivatives

    International Nuclear Information System (INIS)

    Rao, Linfeng; Tian, Guoxin

    2005-01-01

    There has been significant interest in recent years in the studies of alkyl-substituted amides as extractants for actinide separation because the products of radiolytic and hydrolytic degradation of amides are less detrimental to separation processes than those of organophosphorus compounds traditionally used in actinide separations. Stripping of actinides from the amide-containing organic solvents is relatively easy. In addition, the amide ligands are completely incinerable so that the amount of secondary wastes generated in nuclear waste treatment could be significantly reduced. One group of alkyl-substituted oxa-diamides have been shown to be promising in the separation of actinides from nuclear wastes. For example, tetraoctyl-3-oxa-glutaramide and tetraisobutyl-oxa-glutaramide form actinide complexes that can be effectively extracted from nitric acid solutions. To understand the thermodynamic principles governing the complexation of actinides with oxa-diamides, we have studied the complexation of U(VI) with dimethyl-3-oxa-glutaramic acid (DMOGA) and tetramethyl-3-oxa-glutaramide (TMOGA) in aqueous solutions, in comparison with oxydiacetic acid (ODA) (Figure 1). Previous studies have indicated that the complexation of U(VI) with ODA is strong and entropy-driven. Comparing the results for DMOGA and TMOGA with those for ODA could provide insight into the energetics of amide complexation with U(VI) and the relationship between the thermodynamic properties and the ligand structure

  6. Theoretical Study of the Microhydration of Mononuclear and Dinuclear Uranium(VI) Species Derived from Solvolysis of Uranyl Nitrate in Water

    Czech Academy of Sciences Publication Activity Database

    Ončák, Milan; Schröder, Detlef; Slavíček, Petr

    2010-01-01

    Roč. 31, č. 12 (2010), s. 2294-2306 ISSN 0192-8651 R&D Projects: GA ČR GA203/08/1487; GA ČR GA203/09/0422 Institutional research plan: CEZ:AV0Z40400503; CEZ:AV0Z40550506 Keywords : density functional thoery * ion association * metal hydration Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.050, year: 2010

  7. A modelling exercise on the importance of ternary alkaline earth carbonate species of uranium(VI) in the inorganic speciation of natural waters

    International Nuclear Information System (INIS)

    Vercouter, Thomas; Reiller, Pascal E.; Ansoborlo, Eric; Février, Laureline; Gilbin, Rodolphe; Lomenech, Claire; Philippini, Violaine

    2015-01-01

    Highlights: • The U(VI) speciation in natural waters has been modelled through a modelling exercise. • The results evidence the importance of alkaline earth U(VI) carbonate complexes. • Possible solubility-controlling phases were reported and discussed. • The differences were related to the choice and reliability of thermodynamic data. • Databases need to be improved for reliable U(VI) speciation calculations. - Abstract: Predictive modelling of uranium speciation in natural waters can be achieved using equilibrium thermodynamic data and adequate speciation software. The reliability of such calculations is highly dependent on the equilibrium reactions that are considered as entry data, and the values chosen for the equilibrium constants. The working group “Speciation” of the CETAMA (Analytical methods establishment committee of the French Atomic Energy commission, CEA) has organized a modelling exercise, including four participants, in order to compare modellers’ selections of data and test thermodynamic data bases regarding the calculation of U(VI) inorganic speciation. Six different compositions of model waters were chosen so that to check the importance of ternary alkaline earth carbonate species of U(VI) on the aqueous speciation, and the possible uranium solid phases as solubility-limiting phases. The comparison of the results from the participants suggests (i) that it would be highly valuable for end-users to review thermodynamic constants of ternary carbonate species of U(VI) in a consistent way and implement them in available speciation data bases, and (ii) stresses the necessary care when using data bases to avoid biases and possible erroneous calculations

  8. Spectral and structural correlation for Bis (dibenzoyl methanato) dioxo uranium(VI) diphenyl sulfoxide. [UO2(DBM)2. PhSOPh

    International Nuclear Information System (INIS)

    Kannan, S.; Raj, S.S.S.; Fun, Hoong Kun

    2001-01-01

    In the complex [UO 2 (DBM) 2 . PhSOPh]. the sulfoxide ligand is bonded to uranium (VI) ion through sulfoxide oxygen atom and DBM ligands through the oxygen atoms to give a distorted pentagonal bipyramidal geometry. The structural study is in consistence with the spectral studies. (author)

  9. Solvent extraction of uranium(VI), plutonium(VI) and americium(III) with HTTA/HPMBP using mono- and bi-functional neutral donors. Synergism and thermodynamics

    International Nuclear Information System (INIS)

    Pai, S.A.; Lohithakshan, K.V.; Mithapara, P.D.; Aggarwal, S.K.

    2000-01-01

    Synergistic extraction of hexavalent uranium and plutonium as well as trivalent americium was studied in HNO 3 with thenoyl, trifluoro-acetone (HTTA)/1-phenyl, 3-methyl, 4-benzoyl pyrazolone-5 (HPMBP) in combination with neutral donors viz. DPSO, TBP, TOPO (mono-functional) and DBDECMP, DHDECMP, CMPO (bi-functional) with wide basicity range using benzene as diluent. A linear correlation was observed when the equilibrium constant log Ks for the organic phase synergistic reaction of both U(VI) and Pu(VI) with either of the chelating agents HTTA or HPMBP was plotted vs. the basicity (log Kh) of the donor (both mono- and bi-functional) indicating bi-functional donors also behave as mono-functional. This was supported by the thermodynamic data (ΔG 0 , ΔH 0 , ΔS 0 ) obtained for these systems. The organic phase adduct formation reactions were identified for the above systems from the thermodynamic data. In the Am(III) HTTA system log K s values of bi-functional donors were found to be very high and deviate from the linear plot (log K s vs. log K h ) obtained for mono-functional donors, indicating that they function as bi-functional for the Am(III)/HTTA) system studied. This was supported by high +ve ΔS 0 values obtained for this system. (author)

  10. The use of halloysite functionalized with isothiouronium salts as an organic/inorganic hybrid adsorbent for uranium(VI) ions removal.

    Science.gov (United States)

    Gładysz-Płaska, A; Majdan, M; Tarasiuk, B; Sternik, D; Grabias, E

    2018-07-15

    Elimination of U(VI) from nuclear wastes and from the underground water near the uranium mines is the serious problem. Therefore search for new sorbents for U(VI) is still a big challenge for the scientists. This paper investigates of U(VI) ions sorption on halloysite modified with the isothiouronium salts: S-dodecaneisothiouronium bromide (ligand 1), S,S'-dodecane-1,12-diylbis(isothiouronium bromide) (ligand 2), S-hexadecaneisothiouronium chloride (ligand 3), S,S'-naphthalene-1,4-diylbis(methylisothiouronium) dichloride (ligand 4), and S,S'-2,5-dimethylbenzene-1,4-diylbis(methylisothiouronium) dichloride (ligand 5). It was established that halloysite modified by the ligands with four nitrogen atoms in their structure (ligand-5, 2 and 4) was characterized by higher sorption capacity compared with that modified by the ligands with two donor nitrogens (ligand-1 and 3). The maximum sorption capacity of halloysite-5 toward U(VI) was 157 mg U/g and this places the modified mineral among the most effective sorbents for U(VI) removal from wastes. As follows from ATR, XPS and thermal degradation spectra of the sorption products [R-S-C(NH)(NH 2 )] n = 1-2 (UO 2 2+ ) complexes are formed on the external surface of the halloysite whereas oligomeric hydroxy complexes (UO 2 ) 3 (OH) 5 + and (UO 2 ) 4 (OH) 7 + are present in the interior of halloysite structure and interact predominantly with aluminols. Copyright © 2018 Elsevier B.V. All rights reserved.

  11. A Spectroscopic Study of the effect of Ligand Complexation on the Reduction of Uranium(VI) by Anthraquinone-2,6-disulfonate (AH2DS)

    International Nuclear Information System (INIS)

    Wang, Zheming; Wagnon, Ken B.; Ainsworth, Calvin C.; Liu, Chongxuan; Rosso, Kevin M.; Fredrickson, Jim K.

    2008-01-01

    In this project, the reduction rate of uranyl complexes with hydroxide, carbonate, EDTA, and Desferriferrioxamine B (DFB) by anthraquinone-2,6-disulfonate (AH2DS), a potential electron shuttle for microbial reduction of metal ions (Newman and Kolter 2000), is studied by stopped-flow kinetics techniques under anoxic atmosphere. The apparent reaction rates varied with ligand type, solution pH, and U(VI) concentration. For each ligand, a single largest kobs within the studied pH range was observed, suggesting the influence of pH-dependent speciation on the U(VI) reduction rate. The maximum reaction rate found in each case followed the order of OH- > CO32- > EDTA > DFB, consistent with the same trend of the thermodynamic stability of the uranyl complexes and ionic sizes of the ligands. Increasing the stability of uranyl complexes and ligand size decreased the maximum reduction rate. The pH-dependent rates were modeled using a second-order rate expression that was assumed to be dependent on a single U(VI) complex and AH2DS species. By quantitatively comparing the calculated and measured apparent rate constants as a function of pH, species AHDS3- was suggested as the primary reductant in all cases examined. Species UO2CO3(aq) , UO2HEDTA-, and (UO2)2(OH)22+ were suggested as the principal electron acceptors among the U(VI) species mixture in carbonate, EDTA, and hydroxyl systems, respectively

  12. Comparative studies on the interactions of the natural isolate KS5 and one reference strain (DSM 10134) with uranium(VI)

    Energy Technology Data Exchange (ETDEWEB)

    Gerber, Ulrike; Krawczyk-Baersch, Evelyn [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Div. Biogeochemistry; Arnold, Thuro [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Inst. of Resource Ecology

    2016-07-01

    The yeast KS5 (Rhodosporidium toruloides) was isolated by culture dependent method directly from the flooding water in Koenigstein (Germany). To compare the U tolerance and immobilization ability of the isolate a reference culture DSM 10134 (R. toruloides) was applied. Both cultures displayed the ability to tolerate high amounts of U, in contrast the reference KS5 showed a six-fold higher U tolerance in comparison to the reference strain. U immobilization studies displayed that both organisms are able to remove high amounts. The flooding water in Koenigstein has to be cleaned up for many years by an intensive waste water treatment plant. Possibly, with the help of natural occuring microorganisms the flooding water could be cleaned up using in situ bioremediation.

  13. Modeling uranium(VI) adsorption onto montmorillonite under varying carbonate concentrations: A surface complexation model accounting for the spillover effect on surface potential

    Science.gov (United States)

    Tournassat, C.; Tinnacher, R. M.; Grangeon, S.; Davis, J. A.

    2018-01-01

    The prediction of U(VI) adsorption onto montmorillonite clay is confounded by the complexities of: (1) the montmorillonite structure in terms of adsorption sites on basal and edge surfaces, and the complex interactions between the electrical double layers at these surfaces, and (2) U(VI) solution speciation, which can include cationic, anionic and neutral species. Previous U(VI)-montmorillonite adsorption and modeling studies have typically expanded classical surface complexation modeling approaches, initially developed for simple oxides, to include both cation exchange and surface complexation reactions. However, previous models have not taken into account the unique characteristics of electrostatic surface potentials that occur at montmorillonite edge sites, where the electrostatic surface potential of basal plane cation exchange sites influences the surface potential of neighboring edge sites ('spillover' effect). A series of U(VI) - Na-montmorillonite batch adsorption experiments was conducted as a function of pH, with variable U(VI), Ca, and dissolved carbonate concentrations. Based on the experimental data, a new type of surface complexation model (SCM) was developed for montmorillonite, that specifically accounts for the spillover effect using the edge surface speciation model by Tournassat et al. (2016a). The SCM allows for a prediction of U(VI) adsorption under varying chemical conditions with a minimum number of fitting parameters, not only for our own experimental results, but also for a number of published data sets. The model agreed well with many of these datasets without introducing a second site type or including the formation of ternary U(VI)-carbonato surface complexes. The model predictions were greatly impacted by utilizing analytical measurements of dissolved inorganic carbon (DIC) concentrations in individual sample solutions rather than assuming solution equilibration with a specific partial pressure of CO2, even when the gas phase was laboratory air. Because of strong aqueous U(VI)-carbonate solution complexes, the measurement of DIC concentrations was even important for systems set up in the 'absence' of CO2, due to low levels of CO2 contamination during the experiment.

  14. 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

  15. New Data on Joint Extraction of Nitric Acid, Uranium(VI) and Tetravalent Elements by Diluted TBP and New Approach to Modeling of their Distribution

    International Nuclear Information System (INIS)

    Zilberman, B.Ya.; Fedorov, Yu.S.; Puzikov, E.A.; Blazheva, I.V.

    2008-01-01

    HNO 3 and U(IV) extraction by diluted TBP (tributyl phosphate) appeared significantly higher than believed earlier, requiring correction of mathematical model for extraction of all the species. The proposed model of HNO 3 extraction includes its dissolving in the extracted water, as well as its abduction to UO 2 (NO 3 ) 2 (TBP) 2 . Extraction of U(VI) and tetravalent elements is considered as reaction of their hydrated or partially hydrolyzed forms, the latter could be extracted themselves or as neutral forms with water liberation. The equation of element chemical reaction for modeling is determined by the slope of the linear part of the S-shaped curve representing D/S 2 function as a plot of HNO 3 concentration, where D is a distribution coefficient of the micro-component and S is a TBP concentration free of HNO 3 . The description of tetravalent element extraction in U(VI) presence needs the assumption of cation-cation interaction of element hydrolyzed forms with U(VI) in aqueous phase. Zr distribution is affected by micellar effects. (authors)

  16. Analytical application of poly [dibenzo-18-crown-6] for chromatographic separation of thorium(IV) from uranium(VI) and other elements in glycine medium

    International Nuclear Information System (INIS)

    Kadam, R.B.; Mali, G.G.; Mohite, B.S.

    2013-01-01

    A selective and effective chromatographic separation method for thorium(IV) has been developed by using poly [dibenzo-18-crown-6] as stationary phase. The separations are carried out from glycine medium. The sorption of thorium(IV) was quantitative from 1 x 10 -2 to 1 x 10 -4 M glycine. The elution of thorium(IV) was quantitative with 2.0-8.0 M HCl, 4.0-7.0 HBr, 1.0-2.0 M HClO 4 and 5.0 M H 2 SO 4 . The capacity of poly [dibenzo-18-crown-6] for thorium(IV) was found to be 0.215 ± 0.01 mmol/g of crown polymer. The effect of concentration of glycine, metal ion, foreign ion and eluents has been studied. Thorium(IV) was separated from a number of cations in ternary as well as in multicomponent mixtures. The applicability of the proposed method was checked for the determination of thorium(IV) in real as well as geological sample. The method is simple, rapid, and selective with good reproducibility (approximately ±2 %). (author)

  17. A spectroscopic study of the effect of ligand complexation on the reduction of uranium(VI) by anthraquinone-2,6-disulfonate (AH2DS)

    International Nuclear Information System (INIS)

    Wang, Z.; Wagnon, K.B.; Ainsworth, C.C.; Liu, C.; Rosso, K.M.; Fredrickson, J.K.

    2008-01-01

    In this paper, the reduction rate of uranyl complexes with hydroxide, carbonate, EDTA, and desferriferrioxamine B (DFB) by anthraquinone-2,6-disulfonate (AH 2 DS) is studied by stopped-flow kinetic technique under anoxic atmosphere. The apparent reaction rates varied with ligand type, solution pH, and U(VI) concentration. For each ligand, a single largest pseudo-1 st order reaction rate constant, k obs , within the studied pH range was observed, suggesting the influence of pH-dependent speciation on the U(VI) reduction rate. The maximum reaction rate found in each case followed the order of OH - > CO 3 2- > EDTA > DFB, in reverse order of the trend of the thermodynamic stability of the uranyl complexes and ionic sizes of the ligands. The pH-dependent rates were modeled using a second-order rate expression that was assumed to be dependent on a single U(VI) complex and an AH 2 DS species. By quantitatively comparing the calculated and measured apparent rate constants as a function of pH, species AHDS 3- was suggested as the primary reductant in all cases examined. Species UO 2 CO 3 (aq), UO 2 HEDTA - , and (UO 2 ) 2 (OH) 2 2+ were suggested as the principal electron acceptors among the U(VI) species mixture in each of the carbonate, EDTA, and hydroxyl systems, respectively. (orig.)

  18. The Effect of pH and Time on the Extractability and Speciation of Uranium(VI) Sorbed to SiO2

    International Nuclear Information System (INIS)

    Ilton, Eugene S.; Wang, Zheming; Boily, Jean F.; Qafoku, Odeta; Rosso, Kevin M.; Smith, Steven C.

    2012-01-01

    The effect of pH and contact time on uranium extractability from quartz surfaces was investigated using either acidic or carbonate (CARB) extraction solutions, time-delayed spikes of different U isotopes (i.e., 238U and 233U), and liquid helium temperature time-resolved laser-induced fluorescence spectroscopy (LHeT TRLFS). Quartz powders were reacted with 238U(VI) bearing solutions that were equilibrated with atmospheric CO2 at pH 6, 7, and 8. After a 42 day equilibration period with 238U(VI), the suspensions were spiked with 233U(VI) and reacted for an additional 7 days. Sorbed U was then extracted with either dilute nitric acid or CARB. For the CARB extraction there was a systematic decrease in extraction efficiency for both isotopes from pH 6 to 8. This was mimicked by less desorption of 238U, after the 233U spike, from pH 6 to 8. Further, the efficiency of 233U extraction was consistently greater than that of 238U, indicating a strong temporal component to the strength of U association with the surface that was accentuated with increasing pH. LHeT TRLFS revealed a strong correlation between carbonate extraction efficiency and differences in sorbed U speciation as a function of pH. In contrast, the acid extraction was consistently more efficient than the CARB extraction, with a smaller dependence on both pH and aging time. Collectively, the observations show that aging and pH are critical factors in determining the form and strength of uranium-silica interactions.

  19. Complex formation in the system uranium(VI) - alpha-substituted carboxylic acids studied by TRLFS. Pt. III. Alpha-aminoisobutyric acid at pH 4

    International Nuclear Information System (INIS)

    Moll, H.; Geipel, G.; Bernhard, G.; Fanghaenel, Th.; Grenthe, I.

    2002-01-01

    At higher ligand concentrations a 1:2 complex between UO 2 2+ and α-aminoisobutyric acid was observed at pH 4. Fluorescence lifetimes and spectra were obtained for UO 2 [NH 3 C(CH 3 ) 2 COO] 2 2+ . The complex formation constant was found to be log β 1:2 = 2.07±0.25. (orig.)

  20. Laboratory evaluation of the hydrogen sulfide gas treatment approach for remediation of chromate-, uranium(VI)-, and nitrate-contaminated soils

    International Nuclear Information System (INIS)

    Thornton, E.C.; Baechler, M.A.; Beck, M.A.; Amonette, J.E.

    1994-08-01

    Bench-scale soil treatment tests were conducted as part of an effort to develop and implement an in situ chemical treatment approach to the remediation of metal and radionuclide contaminated soils through the use of reactive gases. In general, > 90% immobilization of chromium and > 50% immobilization of uranium was achieved. Leach test results indicate that the treatment process is irreversible for chromium but partially reversible for uranium indicates that immobilization for this contaminant is more readily achieved in organic rich soils. This observation is ascribed to the reducing nature of organic matter. Additional tests were also conducted with soils contaminated to the 5,000 ppm level with nitrate. Nitrate was not found to interfere significantly with treatment of the contaminants. Nitrite was observed in the leachate samples obtained from tests with an organic-rich soil containing clay, however. Leachate chemistries suggested that no other significantly hazardous byproducts were generated by the treatment process and that soil alteration effects were minimal. Test results also suggest that treatment effectiveness is somewhat lower in very dry soils but still able to immobilize chromium and uranium to an acceptable degree. Results of these testing activities indicate that the concentration of hydrogen sulfide in the gas mixture is not a limited factor in treatment as long as a sufficient volume of the mixture is delivered to the soil to achieve a mole ratio of hydrogen sulfide to contaminant of at least 10

  1. Structural studies on 3-acetyl-1,5-diaryl and 3-cyano-1,5-diaryl formazan chelates with cerium(III), thorium(IV) and uranium(VI)

    International Nuclear Information System (INIS)

    Sherif, O.E.; Issa, Y.M.; Hassouna, M.E.M.; Abass, S.M.

    1993-01-01

    Solid complexes of 3-acetyl-1,5-diaryl and 3-cyano-1,5-diaryl formazans were prepared and characterized by elemental analysis, IR, NMR, TGA and DTA analyses. Based on these studies, the suggested general formula for the complexes is M(HL) m (OH - ) n or (NO 3 - or Cl - ) x *(H 2 O) y or (C 2 H 5 OH or DMSO) z , where HL=formazan M=Ce 3+ , Th 4+ , and UO 2 2+ , m=1-2, n=0-3, x=0-3, y=0-4 and z=0-3. The metal ions are expected to have coordination numbers 6-8

  2. [UO{sub 2}Cl{sub 2}(phen){sub 2}], a simple uranium(VI) compound with a significantly bent uranyl unit (phen=1,10-phenanthroline)

    Energy Technology Data Exchange (ETDEWEB)

    Schoene, Sebastian; Radoske, Thomas; Maerz, Juliane; Stumpf, Thorsten; Patzschke, Michael; Ikeda-Ohno, Atsushi [Helmholtz-Zentrum Dresden-Rossendorf (HZDR), Institute of Resource Ecology, Dresden (Germany)

    2017-10-04

    A simple synthesis based on UO{sub 2}Cl{sub 2}.n H{sub 2}O and 1,10-phenanthroline (phen) resulted in the formation of a new uranyl(VI) complex [UO{sub 2}Cl{sub 2}(phen){sub 2}] (1), revealing a unique dodecadeltahedron coordination geometry around the uranium center with significant bending of the robust linear arrangement of the uranyl (O-U-O) unit. Quantum chemical calculations on complex 1 indicated that the weak but distinct interactions between the uranyl oxygens and the adjacent hydrogens of phen molecules play an important role in forming the dodecadeltahedron geometry that fits to the crystal structure of 1, resulting in the bending the uranyl unit. The uranyl oxygens in 1 are anticipated to be activated as compared with those in other linear uranyl(VI) compounds. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  3. Solid-Phase Extraction of Trace Amounts of Uranium(VI in Environmental Water Samples Using an Extractant-Impregnated Resin Followed by Detection with UV-Vis Spectrophotometry

    Directory of Open Access Journals (Sweden)

    Ahmad Hosseini-Bandegharaei

    2013-01-01

    Full Text Available A stable extractant-impregnated resin (EIR containing Chrome Azurol B was prepared using Amberlite XAD-2010 as a porous polymeric support. The new EIR was employed for trace separation and preconcentration of U(VI ion followed by spectrophotometric determination with the arsenazo III procedure. CAB/XAD-2010 exhibited excellent selectivity for U(VI ion over coexisting ions. Experimental parameters including pH, contact time, shaking speed, and ionic strength were investigated by batch extraction methods. Maximum sorption of U(VI ions occurred at pH 4.3–6.9. The capacity of EIR was found to be 0.632 mmol·g−1. Equilibrium was reached in 25 min and the loading half-time, t1/2, was less than 6 min. The equilibrium adsorption isotherm of U(VI was fitted with the Langmuir adsorption model. In addition, a column packed with CAB/XAD-2010 was used for column-mode separation and preconcentration of U(VI ion. For the optimization of the dynamic procedure, effects of sample volume, sample and eluent flow rate, eluent concentration, and its volume were investigated. The preconcentration factors for U(VI were found out to be 160. But, for convenience, a preconcentration factor of 150 was utilized for the column-mode preconcentration. The dynamic procedure gave a detection limit of 5.0×10-10 mol·L−1 (0.12 μg·L−1 for U(VI ion. The proposed dynamic method showed good performance in analyzing environmental water samples.

  4. Removal of uranium(VI) from aqueous solutions by new phosphorus-containing carbon spheres synthesized via one-step hydrothermal carbonization of glucose in the presence of phosphoric acid

    International Nuclear Information System (INIS)

    Zhi-bin Zhang; East China Institute of Technology, Fuzhou; China University of Geosciences, Wuhan; Zhi-wei Zhou; Xiao-hong Cao; Yun-hai Liu; Guo-xuan Xiong; East China Institute of Technology, Fuzhou; Ping Liang; East China Institute of Technology, Fuzhou; China University of Geosciences, Wuhan

    2014-01-01

    The novel phosphorus-rich hydrothermal carbon spheres (HCSs-PO 4 ) have been synthesized via one-step hydrothermal carbonization of glucose in the presence of phosphoric acid. The textural and surface chemistry properties were characterized using Boehm titrations, scanning electron microscopy and Fourier transform infrared spectrometer. The content of oxygen-containing functional groups on the surface of HCSs increased from 0.053 to 1.009 mmol g -1 by phosphate group modification. The adsorption ability of HCSsPO 4 has been explored for the removal of uranium from aqueous solutions. The adsorption kinetic data were best described by the pseudo-second-order equation. Adsorption process could be well defined by the Langmuir isotherm, the adsorption capacity of HCSs increased from 80.00 to 285.70 mg g -1 after phosphate group modification. And thermodynamic parameters indicated the adsorption process was feasible,endothermic and spontaneous. Selective adsorption studies showed that the HCSs-PO 4 could selectively remove U(VI), and the selectivity coefficients had been improved in the presence of co-existing ions, Na(I), Ni(II), Sr(II), Mn(II), Mg(II) and Zn(II). Complete removal (99.9 %) of U(VI) from 1.0 L industry wastewater containing 15.0 mg U(VI) ions was possible with 12.0 g HCSs-PO 4 . (author)

  5. Predictive calculations to assess the long-term effect of cementitious materials on the pH and solubility of uranium(VI) in a shallow land disposal environment

    International Nuclear Information System (INIS)

    Criscenti, L.J.; Serne, R.J.; Krupka, K.M.; Wood, M.I.

    1996-09-01

    One proposed method of low-level radioactive waste (LLW) disposal is to mix the radioactive waste streams with cement, place the mixture in steel barrels, and dispose of the barrels in near-surface unsaturated sediments. Cement or concrete is frequently used in burial grounds, because cement porewaters are buffered at high pH values and lanthanides and actinides; are very insoluble in highly alkaline environments. Therefore, leaching of these contaminants from the combined cement/low-level radioactive waste streams will at least initially be retarded. The calculations performed in this study demonstrate that the pH of cement porewaters will be maintained at a value greater than 10 for 10,000 years under Hanford specific hydrogeochemical conditions. Ten thousand years is the period generally studied in longterm performance assessments per regulatory guidance. The concentrations of dissolved hexavalent uranium [U(VI)], the valence form of dissolved U usually present in oxidizing surface and groundwaters, are also constrained by the high pH and predicted solution compositions over the 10,000-year period, which is favorable from a long-term performance perspective

  6. Synthesis and structural characterization of nickel(II), cobalt(II), Zinc(II), manganese(II), cadmium(II) and uranium(VI) complexes of α-oximinoacetoacet-o/p-anisidide thiosemicarbazone

    International Nuclear Information System (INIS)

    Patel, P.S.; Patel, M.M.; Ray, R.M.

    1993-01-01

    A few metal complexes of α-oximinoacetoacet-o/p-anisidide thiosemicarbazones (OAOATS)/(OAPATS) with Ni(II), Co(II), Zn(II), Mn(II), Hg(II), Cd(II) and UO 2 (II) have been prepared and characterized by elemental analyses, conductivity, differential scanning calorimetry study, thermogravimetric analyses and infrared and electronic spectral measurements in conjunction with magnetic susceptibility measurements at room temperature. They have also been tested for their antimicrobial activities. (author). 24 refs., 2 tabs

  7. Studies on new complexes of dioxo uranium(VI) and thorium(IV) with some schiff bases derived from trimethoprime salicyldehyde and o-vanillin (Paper No. AL-50)

    International Nuclear Information System (INIS)

    Pujar, M.A.; Pirgonde, B.R.

    1990-02-01

    Dioxouranium(VI) and thorium(IV) form 1:1(Metal:Ligands) complexes with some schiff bases. The complexes have been characterized through elemental analyses, electronic and IR spectral, conductance and magnetic susceptibility measurements. They are considered dimeric or polymeric hexa or octa-coordinated arrangement around metal ion moiety. Force constants and U-O bond lengths have been calculated. (author). 1 tab

  8. Complex formation in the system uranium(VI) - alpha-substituted carboxylic acids studied by TRLFS. Pt. I. Glycolic and alpha-hydroxyisobutyric acid at pH 2

    International Nuclear Information System (INIS)

    Moll, H.; Geipel, G.; Bernhard, G.; Fanghaenel, Th.; Grenthe, I.

    2002-01-01

    We observed a very strong quenching of the U(VI) fluorescence in these systems that can be quantitatively described by the Stern-Volmer equation. The following stability constants were determined: a) for the glycolate system log β 1:1 = 2.52±0.20, b) for the α-hydroxyisobutyrate system log β 1:1 = 3.40±0.21. (orig.)

  9. 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

  10. Luminescence properties of uranyl-acetate species

    Energy Technology Data Exchange (ETDEWEB)

    Brinkmann, Hannes; Moll, Henry [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Inst. of Resource Ecology; Stumpf, Thorsten [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Biogeochemistry

    2017-06-01

    Time-resolved laser-induced fluorescence spectroscopy (TRLFS) was applied to characterize uranium(VI)- acetate species based on their luminescence properties. In contrast to previous interpretations, no indications were detected for the existence of the 1: 3 complex.

  11. A surface enhanced Raman scattering spectroscopic study of UO{sub 2}{sup 2+} at trace concentration

    Energy Technology Data Exchange (ETDEWEB)

    Franzen, Carola [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Surface Processes; Carstensen, Lale [Technische Univ. Dresden (Germany); Firkala, T. [Helmholtz Institute Freiberg for Resource Technology, Freiberg (Germany); Steudtner, Robin [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Inst. of Resource Ecology

    2017-06-01

    Techniques for rapid screening of uranium in environmental samples are needed. This study entails the development of Surface-Enhanced Raman scattering (SERS) spectroscopy for analyzing uranium(VI) in aqueous media with improved sensitivity.

  12. Separation of uranium isotopes by accelerated isotope exchange reactions

    International Nuclear Information System (INIS)

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

    1977-01-01

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

  13. Analytical applications of resins containing amide and polyamine functional groups

    International Nuclear Information System (INIS)

    Orf, G.M.

    1977-12-01

    A dibutyl amide resin is used for the separation of uranium(VI), thorium(IV), and zirconium(IV) from each other and several other metal ions. Uranium(VI) and thorium(IV) are determined in the presence of large excesses of foreign metal ions and anions. A practical application of the amide resin is studied by determining uranium in low grade uranium ores. The amide resin is also used for the selective concentration of gold(III) from sea water

  14. Analytical applications of resins containing amide and polyamine functional groups

    Energy Technology Data Exchange (ETDEWEB)

    Orf, Gene Michael [Iowa State Univ., Ames, IA (United States)

    1977-12-01

    A dibutyl amide resin is used for the separation of uranium(VI), thorium(IV), and zirconium(IV) from each other and several other metal ions. Uranium(VI) and thorium(IV) are determined in the presence of large excesses of foreign metal ions and anions. A practical application of the amide resin is studied by determining uranium in low grade uranium ores. The amide resin is also used for the selective concentration of gold(III) from sea water.

  15. Solid phase extraction of uranium from phosphoric acid. Kinetic and thermodynamic study

    Energy Technology Data Exchange (ETDEWEB)

    Abdel-Magied, Ahmed Fawzy [Nuclear Materials Authority, Cairo (Egypt); Stockholm Univ. (Sweden). Dept. of Organic Chemistry

    2017-07-01

    There is a high interest to develop suitable solid phase extractants for uranium separation from aqueous solutions in order to reduce cost and enhance the efficiency. This paper describes solid phase extraction of uranium(VI) from aqueous phosphoric acid solution using MCM-41 based D2HEPA-TOPO organophosphorous extractants. The mixture of D2HEPA (di-2-ethyl-hexylphosphoric acid) and TOPO (tri-n-octylphosphine oxide) was impregnated into the pores of MCM-41 and the synthesized sorbent was fully characterized. The influences of different factors such as synergistic mixture ratio, phosphoric acid concentration, mixing time and temperature were investigated. The results showed that 90% of uranium(VI) extraction can be achieved within 5 min, using D2HEPA-TOPO rate at MCM-41 (mass ratio 2:1 w/w) from 1 M phosphoric acid containing 64 ppm of uranium at room temperature. High adsorption capacity of uranium(VI) have been achieved at the mentioned conditions. The rate constant for the chemical adsorption of uranium(VI) was 0.988 g mg{sup -1} min{sup -1} calculated by the pseudo-second order rate equation. The obtained thermodynamics parameters showed that uranium(VI) adsorption from H{sub 3}PO{sub 4} is an exothermic and spontaneous process.

  16. Investigations on uranium sorption on bentonite and montmorillonite, respectively, and uranium in environmental samples; Untersuchungen zur Uransorption an Bentonit bzw. Montmorillonit sowie von Uran in Umweltproben

    Energy Technology Data Exchange (ETDEWEB)

    Azeroual, Mohamed

    2010-09-22

    The geotechnical barrier is an important component of a geological repository and consists of compacted bentonite surrounding radioactive waste containers. Its most important functions are, to retard the radionuclide migration into the biosphere and to prevent groundwater contact with containers. lt is therefore of central importance to investigate the bentonite material on its capacity to sorb radionuclides under near-natural chemical and physical conditions. The purpose of this work was to study the adsorption of uranium(VI) on bentonit and on montmorillonite-standards at high uranium concentrations. Thereby, a special account was given to the calcium-uranyl-carbonate complexation, which leads to the formation of very stable and mobile uncharged Ca{sub 2}UO{sub 2}(CO{sub 3}){sub 3} complex. Results of batch experiments showed that the dicalcium-uranyl-tricarbonate complexation lowers the uranium(VI) sorption on natural clay (bentonite) by a factor of up to 3. After 21 days of contact time, about 40 % and 20 % of the initial uranium(VI)concentration were sorbed on Na-bentonite and ea-bentonite, respectively, from a solution with Ca{sub 2}UO{sub 2}(CO{sub 3}){sub 3} dominating the uranium(VI) speciation. On the contrary, about 55 % of the initial uranium(VI)-concentration were sorbed on thes clays from the solution, in which (UO{sub 2}){sub 2}CO{sub 3}(OH){sub 3}{sup -} complex dominated the uranium(VI) speciation. Thus uranium(VI) sorption is more strongly influenced by the solution composition than by bentonite type. Na-bentonite should be used instead of ea-bentonite as a geotechnical barrier, since calcium-uranyl-carbonate complexation may be a realistic scenario. Further SEM-EDX and HREM-EDX studies showed that uranium(VI) sorption occurred predominantly on montmorillonite, which is the main component of bentonite. Uranium(VI) sorption on bentonite's accessory Minerals (pyrite, calcite, mica, and feldspar) was not observed. Investigation of uranium(VI

  17. Differential pulse cathodic stripping voltammetric determination of uranium with arsenazo-III at the hanging mercury dropping electrode

    Energy Technology Data Exchange (ETDEWEB)

    Kadi, M.W.; El-Shahawi, M.S. [Chemistry Dept., King Abdulaziz Univ., Jeddah (Saudi Arabia)

    2009-07-01

    An accurate, inexpensive and less laborious controlled adsorptive accumulation of uranium(VI)-arsenazo-III on a hanging mercury drop electrode (HMDE) has been developed for uranium(VI) determination. The method is based upon the collection of uranium(VI)-arsenazo-III complex at pH 5-6 at the HMDE and subsequent direct stripping measurement of the element in the nanomolar concentration level. The cathodic peak current (i{sub p,c}) of the adsorbed complex ions of uranium(VI) was measured at -0.35 V vs. Ag/AgCl reference electrode by differential pulse cathodic stripping voltammetry (DP-CSV), proceeded by an accumulation period of 150s2.5 in Britton-Robinson buffer of pH 5. The plot of the resulting i{sub p,c} vs. uranium(VI) concentration was linear in the range 2.1 x 10{sup -9} to 9.60 x 10{sup -7} mol L{sup -1} uranium(VI) and tended to level off at above 9.6 x 10{sup -7} mol L{sup -1}. The limits of detection and quantification of uranium(VI) were found to be 4.7 x 10{sup -10} and 1.5 x 10{sup -9} mol L{sup -1}, respectively. A relative standard deviation of {+-}2.39% (n = 5) at 8.5 x 10{sup -7} mol L{sup -1} uranium(VI) was obtained. The method was validated by comparing the results with that obtained by ICP-MS method with RSD less than {+-}3.3%. The method was applied successfully for the analysis of uranium in certified reference material (IAEA soil-7), and in phosphate fertilizers. (orig.)

  18. Extraction equilibrium of uranium (VI) from phosphoric solution with HDEHP and TOPO in cyclohexane

    International Nuclear Information System (INIS)

    You Jianzhang; Zhou Zuming; Qin Qizong

    1988-01-01

    The extraction equilibrium of uranium(VI) from phosphoric acid solution with HDEHP and TOPO in cyclohexane has been investigated to examine the effects of extractant concentration, hydrogen ion concentration and temperature on the extraction of uranium(VI). Experimental results suggest that the composition of synergistic complex species is UO 2 (HA 2 ) 2 ·TOPO and the extraction equilibrium constant β 21 is 10 9.52 at 30 deg C. In addition, the thermodynamic functions of the extraction reaction (ΔG,ΔH,ΔS) and the infra-red spectra of synergistic complexes have also been determined

  19. Simple method for preparation of secondary amides of phosphorylacetic acids and their use for actinide extraction and sorption from nitric acid solutions

    International Nuclear Information System (INIS)

    Artyushin, O.I.; Sharova, E.V.; Odinets, I.L.; Lenevich, S.V.; Mastruykova, T.A.; Morgalyuk, V.P.; Tananaev, I.G.; Pribylova, G.V.; Myasoedova, G.V.; Myasoedov, B.F.

    2004-01-01

    An effective method of synthesis of secondary alkylamides of phosphorylacetic acids (APA), based on amidation of ethyl esters of phosphorylacetic acids with primary aliphatic amines, was developed. Extraction of americium(III) complexes with APA solutions in dichloroethane and uranium(VI) sorption by sorbents with non-covalently fixed APA from nitric acid solutions were studied. In the course of americium(III) extraction there is no correlation between Am III distribution factor and APA structure, whereas during uranium(VI) sorption a dependence of U VI extraction degree on the complexing agent structure is observed [ru

  20. Syntheses of polystyrene supported chelating resin containing the Schiff base derived from salicylaldehyde and triethylene tetramine and its copper(II), nickel(II), cobalt(II), iron(III), zinc(II), cadmium(II), molybdenum(VI), zirconium(IV) and uranium(VI) complexes

    International Nuclear Information System (INIS)

    Syamal, A.; Singh, M.M.

    1998-01-01

    A new polymer-anchored chelating ligand has been synthesized by the reaction of chloromethylated polystyrene (containing 0.94 mmol of Cl per gram of resin and 1% cross-linked with divinylbenzene) and the Schiff base derived from salicylaldehyde and triethylenetetramine. A new series of polystyrene supported, Cu(II), Ni(II), Co(II), Fe(III), Zn(II), Cd(II), Zr(IV), dioxomolybdenum (VI) and dioxouranium (VI) complexes of the formulae PS-LCu, PS-LNi, PS-LCo, PS-LFeCl.DMF, PS-LZn, PS-LCd, PS-LZr(OH) 2 . DMF, PS L MoO 2 and PS-LUO 2 (where PS-LH 2 = polymer-anchored Schiff base and DMF dimethyl-formamide) have been synthesized and characterised by elemental analysis, infrared, electronic spectra and magnetic susceptibility measurements. The complexes PS-LCu, PS-LNi and PS-LCo have square planar structure, PS-LFeCl.DMF, PS-LMoO 2 and PS-LUO 2 have octahedral structure, PS L Zn and PS-LCd are tetrahedral and PS-LZr(OH) 2 .DMF is pentagonal bipyramidal. The polymer-anchored Cu(II), Co(II) and Fe(III) complexes are paramagnetic while Ni(II), Zn(II), Cd(II), Zr(IV), dioxomolybdenum(VI) and dioxouranium(VI) complexes are diamagnetic. The negative shift of the v (C=N) (azomethine) and the positive shift of v (C--O)(phenolic) are indicative of ONNO donor behaviour of the polymer-anchored Schiff base. (author)

  1. Environmental qualitative assessment of water resources in Tehran

    Directory of Open Access Journals (Sweden)

    T. Jafarynasab

    2017-01-01

    Full Text Available Increasing water demand and reducing its contaminations are the main concerns and challenges for water resource managers and planner due to its limited sources and high value. This study aims to assess and understand the factors which threaten the quality of groundwater resources and to achieve this, samples were taken from 14 active wells in District 3 of the Municipality of Tehran. After categorizing the parameters to distinct measurable groups containing anions (SO4, Cl, NO2, NO3, HCO3, CO3, cations (Mg, Na, k heavy metals (Ag, Pb, Cd physical parameters (temperature, color and odor chemical parameters (Total Dissolved Solid , Electrical conductivity, Total Suspended Solids and pH, the data  were analyzed  using SPSS (version 16 software. The results revealed that excessive amount of nitrate anion in Paidari and Naji station is related to the slope and sandy texture of the wells and also the surrounding area’s soil. Increased cation concentration was visible in Resalat well, which indicated the use of excessive amount of fertilizers containing sodium and also the clay soil texture. Cadmium was the only heavy metal with the concentrations of more than the standard amount. Domestic sewage and surface runoff and also regional geological structure, the lack of appropriate distance between water wells with sewage wells were among other reasons, causing underground water pollution.

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

    International Nuclear Information System (INIS)

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

    1992-01-01

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

  3. Electrospun chitosan/baker's yeast nanofibre adsorbent: preparation ...

    Indian Academy of Sciences (India)

    poration, complexation, reverse osmosis and membrane pro- cesses [2–4]. ... activities and some human activities such as exploitation of uranium and ... bre adsorbent for U(VI) and Th(IV) removal from aqueous solutions. 2. Experimental ..... Adsorption capacity of uranium(VI) and thorium(IV) in binary systems. where. H.

  4. Identification of Uranyl Surface Complexes an Ferrihydrite: Advanced EXAFS Data Analysis and CD-MUSIC Modeling

    NARCIS (Netherlands)

    Rossberg, A.; Ulrich, K.U.; Weiss, S.; Tsushima, S.; Hiemstra, T.; Scheinost, A.C.

    2009-01-01

    Previous spectroscopic research suggested that uranium(VI) adsorption to iron oxides is dominated by ternary uranyl-carbonato surface complexes across an unexpectedly wide pH range. Formation of such complexes would have a significant impact on the sorption behavior and mobility of uranium in

  5. Br as a Tribromide-Type Catalyst for the Trimethylsilylation ...

    African Journals Online (AJOL)

    NICO

    [II] sensor based on poly aniline,3 encapsulation of alkali metal especially K+,4 ... tion of uranium(VI),6 exchanging cations of micas7 and extrac- tion of copper(II) with ... reagents and lithium alkyls, reduction with hydride, oxidation, oxidative ...

  6. X-ray Absorption Spectroscopy Identifies Calcium-Uranyl-Carbonate Complexes at Environmental Concentrations

    International Nuclear Information System (INIS)

    Kelly, Shelly D.; Kemner, Kenneth M.; Brooks, Scott C.

    2007-01-01

    Current research on bioremediation of uranium-contaminated groundwater focuses on supplying indigenous metal-reducing bacteria with the appropriate metabolic requirements to induce microbiological reduction of soluble uranium(VI) to poorly soluble uranium(IV). Recent studies of uranium(VI) bioreduction in the presence of environmentally relevant levels of calcium revealed limited and slowed uranium(VI) reduction and the formation of a Ca-UO2-CO3 complex. However, the stoichiometry of the complex is poorly defined and may be complicated by the presence of a Na-UO2-CO3 complex. Such a complex might exist even at high calcium concentrations, as some UO2-CO3 complexes will still be present. The number of calcium and/or sodium atoms coordinated to a uranyl carbonate complex will determine the net charge of the complex. Such a change in aqueous speciation of uranium(VI) in calcareous groundwater may affect the fate and transport properties of uranium. In this paper, we present the results from X-ray absorption fine structure (XAFS) measurements of a series of solutions containing 50 lM uranium(VI) and 30 mM sodium bicarbonate, with various calcium concentrations of 0-5 mM. Use of the data series reduces the uncertainty in the number of calcium atoms bound to the UO2-CO3 complex to approximately 0.6 and enables spectroscopic identification of the Na-UO2-CO3 complex. At nearly neutral pH values, the numbers of sodium and calcium atoms bound to the uranyl triscarbonate species are found to depend on the calcium concentration, as predicted by speciation calculations

  7. Extração líquido-líquido de urânio(VI do colofanito de itataia (Santa Quitéria, Ceará por extratantes orgânicos em presença de ácido fosfórico Liquid-liquid extraction of uranium(VI from colofanite of itataia (Santa Quitéria, Ceará by organic extractants in the presence of phosphoric acid

    Directory of Open Access Journals (Sweden)

    Valeria Aparecida Leitão Ribeiro

    2008-01-01

    Full Text Available This work describes the liquid-liquid extraction of uranium after digestion of colofanite (a fluoroapatite from Itataia with sulfuric acid. The experiments were run at room temperature in one stage. Among the solutions tested the highest distribution coefficient (D > 60 was found for 40%vol. DEHPA (di(2-ethyl-hexylphosphoric acid + 20% vol. TOPO (trioctylphosphine oxide in kerosene. Thorium in the raffinate was quantitatively extracted by TOPO (0.1% vol. in cyclohexane. Uranium stripping and separation from iron was possible using 1.5 mol L-1 ammonium or sodium carbonate (room temperature, one stage. However, pH control is essential for a good separation.

  8. Retention and reduction of uranium on pyrite surface

    International Nuclear Information System (INIS)

    Eglizaud, N.

    2006-12-01

    In the hypothesis of a storage of the spent fuel in a deep geological formation, understanding the uranium dispersion in the environment is important. Pyrite is a reducing mineral present in the Callovo-Oxfordian argilites, the geological formation actually studied for such a storage. However, pyrite impact on uranium migration has already been poorly studied. The aim of the study was to understand the mechanisms of uranium(VI) retention and reduction on the pyrite surface (FeS 2 ). Solution chemistry was therefore coupled with solid spectroscopic studies (XPS and Raman spectroscopy). All uranium-pyrite interactions experiments were performed under an anoxic atmosphere, in a glove box. Pyrite dissolution under anoxic conditions releases sulfoxy-anions and iron(II), which can then be adsorbed on the pyrite surface. This adsorption was confirmed by interaction experiments using iron(II) isotopic dilution. Uranium(VI) is retained by an exchange reaction with iron(II) adsorbed on sulphur sites, with a maximal amount of sorbed uranium at pH ≥ 5.5. Cobalt(II) and europium(III) are also adsorbed on the pyrite surface above pH 5.5 confirming then that reduction is not required for species to adsorb on pyrite. When the concentration of uranium retained is lower than 4 x 10 -9 mol g -1 , an oxidation-reduction reaction leads to the formation of a uranium (VI) (IV) mixed oxide and to solid sulphur (d.o. ≥ -I). During this reaction, iron remains mostly at the +II oxidation degree. The reaction products seem to passivate the pyrite surface: at higher amounts of retained uranium, the oxidation-reduction reaction is no longer observed. The surface is saturated by the retention of (3.4 ± 0.8) x 10 -7 mol L -1 of uranium(VI). Modelling of uranium sorption at high surface coverage (≥ 4 x 10 -9 mol g -1 ) by the Langmuir model yields an adsorption constant of 8 x 10 7 L mol -1 . Finally, a great excess of uranium(VI) above the saturation concentration allows the observation of

  9. Synthesis, radiometric determination of functional groups, complexation

    International Nuclear Information System (INIS)

    Pompe, S.; Bubner, M.; Schmeide, K.; Heise, K.H.; Bernhard, G.; Nitsche, H.

    2000-01-01

    The interaction behavior of humic acids with uranium(VI) and the influence of humic substances on the migration behavior of uranium was investigated. A main focus of this work was the synthesis of four different humic acid model substances and their characterization and comparison to the natural humic acid from Aldrich. A radiometric method for the determination of humic acid functional groups was applied in addition to conventional methods for the determination of the functionality of humic acids. The humic acid model substances show functional and structural properties comparable to natural humic acids. Modified humic acids with blocked phenolic OH were synthesized to determine the influence of phenolic OH groups on the complexation behavior of humic acids. A synthesis method for 14 C-labeled humic acids with high specific activity was developed. The complexation behavior of synthetic and natural humic acids with uranium(VI) was investigated by X-ray absorption spectroscopy, laser-induced fluorescence spectroscopy and FTIR spectroscopy. The synthetic model substances show an interaction behavior with uranium(VI) that is comparable to natural humic acids. This points to the fact that the synthetic humic acids simulate the functionality of their natural analogues very well. For the first time the influence of phenolic OH groups on the complexation behavior of humic acids was investigated by applying a modified humic acid with blocked phenolic OH groups. The formation of a uranyl hydroxy humate complex was identified by laserspectroscopic investigations of the complexation of Aldrich humic acid with uranium(VI) at pH 7. The migration behavior of uranium in a sandy aquifer system rich is humic substances was investigated in column experiments. A part of uranium migrates non-retarded through the sediment, bound to humic colloids. The uranium migration behavior is strongly influenced by the kinetically controlled interaction processes of uranium with the humic colloids

  10. Retention and reduction of uranium on pyrite surface; Retention et reduction de l'uranium a la surface de la pyrite

    Energy Technology Data Exchange (ETDEWEB)

    Eglizaud, N

    2006-12-15

    In the hypothesis of a storage of the spent fuel in a deep geological formation, understanding the uranium dispersion in the environment is important. Pyrite is a reducing mineral present in the Callovo-Oxfordian argilites, the geological formation actually studied for such a storage. However, pyrite impact on uranium migration has already been poorly studied. The aim of the study was to understand the mechanisms of uranium(VI) retention and reduction on the pyrite surface (FeS{sub 2}). Solution chemistry was therefore coupled with solid spectroscopic studies (XPS and Raman spectroscopy). All uranium-pyrite interactions experiments were performed under an anoxic atmosphere, in a glove box. Pyrite dissolution under anoxic conditions releases sulfoxy-anions and iron(II), which can then be adsorbed on the pyrite surface. This adsorption was confirmed by interaction experiments using iron(II) isotopic dilution. Uranium(VI) is retained by an exchange reaction with iron(II) adsorbed on sulphur sites, with a maximal amount of sorbed uranium at pH {>=} 5.5. Cobalt(II) and europium(III) are also adsorbed on the pyrite surface above pH 5.5 confirming then that reduction is not required for species to adsorb on pyrite. When the concentration of uranium retained is lower than 4 x 10{sup -9} mol g{sup -1}, an oxidation-reduction reaction leads to the formation of a uranium (VI) (IV) mixed oxide and to solid sulphur (d.o. {>=} -I). During this reaction, iron remains mostly at the +II oxidation degree. The reaction products seem to passivate the pyrite surface: at higher amounts of retained uranium, the oxidation-reduction reaction is no longer observed. The surface is saturated by the retention of (3.4 {+-} 0.8) x 10{sup -7} mol L{sup -1} of uranium(VI). Modelling of uranium sorption at high surface coverage ({>=} 4 x 10{sup -9} mol g{sup -1}) by the Langmuir model yields an adsorption constant of 8 x 10{sup 7} L mol{sup -1}. Finally, a great excess of uranium(VI) above the

  11. Influence of humic acids on the migration behavior of radioactive and non-radioactive substances under conditions close to nature. Synthesis, radiometric determination of functional groups, complexation

    International Nuclear Information System (INIS)

    Pompe, S.; Bubner, M.; Schmeide, K.; Heise, K.H.; Bernhard, G.; Nitsche, H.

    2000-04-01

    The interaction behavior of humic acids with uranium(VI) and the influence of humic substances on the migration behavior of uranium was investigated. A main focus of this work was the synthesis of four different humic acid model substances and their characterization and comparison to the natural humic acid from Aldrich. A radiometric method for the determination of humic acid functional groups was applied in addition to conventional methods for the determination of the functionality of humic acids. The humic acid model substances show functional and structural properties comparable to natural humic acids. Modified humic acids with blocked phenolic OH were synthesized to determine the influence of phenolic OH groups on the complexation behavior of humic acids. A synthesis method for 14 C-labeled humic acids with high specific activity was developed. The complexation behavior of synthetic and natural humic acids with uranium(VI) was investigated by X-ray absorption spectroscopy, laser-induced fluorescence spectroscopy and FTIR spectroscopy. The synthetic model substances show an interaction behavior with uranium(VI) that is comparable to natural humic acids. This points to the fact that the synthetic humic acids simulate the functionality of their natural analogues very well. For the first time the influence of phenolic OH groups on the complexation behavior of humic acids was investigated by applying a modified humic acid with blocked phenolic OH groups. The formation of a uranyl hydroxy humate complex was identified by laserspectroscopic investigations of the complexation of Aldrich humic acid with uranium(VI) at pH7. The migration behavior of uranium in a sandy aquifer system rich in humic substances was investigated in column experiments. A part of uranium migrates non-retarded through the sediment, bound to humic colloids. The uranium migration behavior is strongly influenced by the kinetically controlled interaction processes of uranium with the humic colloids

  12. Extraction kinetics of uranium (VI) with polyurethane foam

    International Nuclear Information System (INIS)

    Huang, Ting-Chia; Chen, Dong-Hwang; Huang, Shius-Dong; Huang, Ching-Tsven; Shieh, Mu-Chang.

    1993-01-01

    The extraction kinetics of uranium(VI) from aqueous nitrate solution with polyether-based polyurethane foam was investigated in a batch reactor with automatic squeezing. The extraction curves of uranium(VI) concentration in solution vs. extraction time exhibited a rather rapid exponential decay within the first few minutes, followed by a slower exponential decay during the remaining period. This phenomenon can be attributed to the presence of two-phase structure, hard segment domains and soft segment matrix in the polyurethane foam. A two-stage rate model expressed by a superposition of two exponential curves was proposed, according to which the experimental data were fitted by an optimization method. The extraction rate of uranium (VI) was also found to increase with increasing temperature, nitrate concentration, and hydration of the cation of nitrate salt. (author)

  13. Liquid-liquid extraction of Th4+ and UO22+ by LIX-26 and its mixtures

    International Nuclear Information System (INIS)

    Singh, S.; Panda, C.R.; Chakravortty, V.; Dash, K.C.

    1988-01-01

    Solvent extractions of thorium(IV) and uranium(VI) by a commercially available chelating extractant LIX-26 (an alkylated 8-hydroxyquinoline) of 8-hydroxyquinoline, benzoic or salicylic acid, dipentyl sulfoxide (DPSO) and their mixtures with butanol as modifier in benzene/methylisobutyl ketone (MIBK) as a diluent were studied. The influence of concentration of various anions on the extraction of Th 4+ by mixtures of LIX-26 and benzoic acid was studied. Studies on extraction of thorium(IV) and uranium(VI) by mixtures of LIX-26 (HQ) and DPSO show that the extracted species are possibly of the type [(ThQ 2 (DPSO) 2 (SCN) 2 )] and [(UO 2 Q 2 (DPSO)]), respectively. (author) 22 refs.; 8 figs

  14. Influence of U(VI) on the metabolism of plant cells studied by microcalorimetry and TRLFS

    Energy Technology Data Exchange (ETDEWEB)

    Sachs, Susanne; Geipel, Gerhard [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Biogeochemistry; Fahmy, Karim; Oertel, Jana [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Biophysics; Bok, Frank [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Surface Processes

    2017-06-01

    Uranium(VI) shows a concentration-dependent influence on the metabolic activity of plant cells. With increasing U(VI) concentration, the predominant U(VI) species in medium R{sub red} changes from UO{sub 2}HPO{sub 4}(s) to (UO{sub 2}){sub 3}(OH){sub 5}{sup +}, which may affect the bioavailability of U(VI).

  15. Significant Association between Sulfate-Reducing Bacteria and Uranium-Reducing Microbial Communities as Revealed by a Combined Massively Parallel Sequencing-Indicator Species Approach▿ †

    OpenAIRE

    Cardenas, Erick; Wu, Wei-Min; Leigh, Mary Beth; Carley, Jack; Carroll, Sue; Gentry, Terry; Luo, Jian; Watson, David; Gu, Baohua; Ginder-Vogel, Matthew; Kitanidis, Peter K.; Jardine, Philip M.; Zhou, Jizhong; Criddle, Craig S.; Marsh, Terence L.

    2010-01-01

    Massively parallel sequencing has provided a more affordable and high-throughput method to study microbial communities, although it has mostly been used in an exploratory fashion. We combined pyrosequencing with a strict indicator species statistical analysis to test if bacteria specifically responded to ethanol injection that successfully promoted dissimilatory uranium(VI) reduction in the subsurface of a uranium contamination plume at the Oak Ridge Field Research Center in Tennessee. Remedi...

  16. Titration of uranium trace amounts in waters environment

    International Nuclear Information System (INIS)

    Larabi-Gruet, N.; Ithurbide, A.; Poulesquen, A.; Beaucaire, C.; Peulon, S.; Chausse, A.

    2007-01-01

    In the framework of studies concerning the uranium migration in soils and rocks, it seems necessary to quantify the uranium(VI) dissolved in solution. In the environmental conditions, the uranium(VI) is present at trace amounts. The most adapted method to this study and easy to carry out is the Adsorptive Stripping Voltammetry. By addition of a compound (ligand) with a reducing and strong complexing power, the uranium(VI) present in solution is reduced into a U(VI)-ligand complex. This specie is then oxidized and adsorbed on the mercury droplet where an electrolytic pre-concentration of the element to determine the quantity of is carried out. At last, a cathodic re-dissolution of the specie adsorbed in the U(IV)-ligand complex is carried out. The chosen analytical method is the differential impulsional voltammetry. With this method, it is possible to quantify low electro-active species quantities (sensitivity ∼25 ppt (10 -10 mol.L -1 ) for the uranium). This titration method in solution has been optimized, at first, in a non complexing medium. Then, the uranium in solution has been titrated in media whose composition has been progressively complexed (additions of CO 3 2- , SO 4 2- , Cl - ..) for being at last representative of the environmental interstitial waters. At last, this study has been carried out too by ICP-MS (Inductively Coupled Plasma-Mass Spectrometry) in order to compare the analysis sensitivity of these two detection methods. (O.M.)

  17. Nuclear energy - Uranium dioxide powder and sintered pellets - Determination of oxygen/uranium atomic ratio by the amperometric method. 2. ed.

    International Nuclear Information System (INIS)

    2007-01-01

    This International Standard specifies an analytical method for the determination of the oxygen/uranium atomic ratio in uranium dioxide powder and sintered pellets. The method is applicable to reactor grade samples of hyper-stoichiometric uranium dioxide powder and pellets. The presence of reducing agents or residual organic additives invalidates the procedure. The test sample is dissolved in orthophosphoric acid, which does not oxidize the uranium(IV) from UO 2 molecules. Thus, the uranium(VI) that is present in the dissolved solution is from UO 3 and/or U 3 O 8 molecules only, and is proportional to the excess oxygen in these molecules. The uranium(VI) content of the solution is determined by titration with a previously standardized solution of ammonium iron(II) sulfate hexahydrate in orthophosphoric acid. The end-point of the titration is determined amperometrically using a pair of polarized platinum electrodes. The oxygen/uranium ratio is calculated from the uranium(VI) content. A portion, weighing about 1 g, of the test sample is dissolved in orthophosphoric acid. The dissolution is performed in an atmosphere of nitrogen or carbon dioxide when sintered material is being analysed. When highly sintered material is being analysed, the dissolution is performed at a higher temperature in purified phosphoric acid from which the water has been partly removed. The cooled solution is titrated with an orthophosphoric acid solution of ammonium iron(II) sulfate, which has previously been standardized against potassium dichromate. The end-point of the titration is detected by the sudden increase of current between a pair of polarized platinum electrodes on the addition of an excess of ammonium iron(II) sulfate solution. The paper provides information about scope, principle, reactions, reagents, apparatus, preparation of test sample, procedure (uranium dioxide powder, sintered pellets of uranium dioxide, highly sintered pellets of uranium dioxide and determination

  18. Study of sorption mechanisms of europium(3) and uranium(6) ions on clays : impact of silicates; Etude des mecanismes de retention des ions U(6) et Eu(3) sur les argiles: influence des silicates

    Energy Technology Data Exchange (ETDEWEB)

    Kowal-Fouchard, A

    2002-11-01

    Bentonite clay has been selected as a potential buffer or backfill material in a number of disposal programmes for high level waste. In order to enhance the thermodynamic database of sorption phenomena at the solid-water interface, we have investigated sorption mechanisms of europium(III) and uranium(VI) ions onto montmorillonite and bentonite. Thermodynamic data were obtained for different ions concentrations, different background electrolytes and different ionic strengths. The structural identification of the surface complexes and sorption sites was carried out using two spectroscopies, XPS and TRLIFS, while sorption edges were performed using batch experiments. However, clays are complex minerals and in order to understand these sorption mechanisms we have studied europium(III) and uranium(VI) retention on a silica and an alumina because these solids are often considered as basic components of clays. The comparison of structural results shows that europium ions are significantly sorbed on permanently charged sites of clay until pH 7. But this ion is also sorbed on {identical_to}SiOH and {identical_to}AlOH sites of montmorillonite at pH higher than 6. Uranyl ions sorption on montmorillonite is mainly explained by retention of three complexes on {identical_to}SiOH sites. Moreover, we have shown that nitrate ions and dissolved silicates affect on uranium(VI) sorption mechanisms onto alumina. Nevertheless, uranyl ions sorption on montmorillonite and bentonite only decreases with increasing carbonate concentration. Finally, all the sorption edges were then modeled using these results and a surface complexation model (2 pK and constant capacitance models). (author)

  19. Uranium chemistry in stack solutions and leachates of phosphogypsum disposed at a coastal area in Cyprus.

    Science.gov (United States)

    Lysandrou, M; Pashalidis, I

    2008-02-01

    The effect of the matrix composition (main constituents) on the concentration and chemical behavior of uranium in phosphogypsum stack solutions and leachates has been investigated. Solid and aqueous samples were taken from three different sub-areas of a phosphogypsum stack at a coastal area in Vasilikos (Cyprus). The sub-areas are characterized whether by their acidity (e.g. "aged" and "non-aged" phosphogypsum) or by their salt content, originating from pulping water during wet stacking or (after deposition) from the adjacent sea. Measurements in stack solutions and leachates showed that phosphogypsum characteristics affect both, the concentration and the chemical behavior of uranium in solution. Uranium concentration in solutions of increased salinity is up to three orders of magnitude higher than in solutions of low salinity and this is attributed to the effect of ionic strength on the solubility of phosphogypsum. Modelling showed that uranium in stack solutions is predominantly present in the form of uranium(VI) phosphate complexes (e.g. UO(2)(H(2)PO(4))(2), UO(2)HPO(4)), whereas in leachates uranium(VI) fluoro complexes (e.g. UO(2)F(2), UO(2)F(3)(-)) are predominant in solution. The latter indicates that elution of uranium from phosphogypsum takes places most probably in the form of fluoro complexes. Both, effective elution by saline water and direct migration of uranium to the sea, where it forms very stable uranium(VI) carbonato complexes, indicate that the adjacent sea will be the final receptor of uranium released from Vasilikos phosphogypsum.

  20. Extraction of sulfuric acid with TOPO

    International Nuclear Information System (INIS)

    Shuyun, Xue; Yonghui, Yang; Yanzhao, Yang; Sixiu, Sun; Borong, Bao

    1998-01-01

    A study on solvent extraction of sulfuric acid by tri-octylphosphine oxide (TOPO) in n-heptane has been made. Extraction coefficients of H 2 SO 4 as a function of H 2 SO 4 concentration in aqueous phase, and extractant concentrations in organic phase have been studied. The composition of extracted species, equilibrium constants of extraction reaction have been evaluated. These results are important for interpreting extraction equilibrium data of uranium(VI) or other metal ions with TOPO in sulfuric acid media. (author)

  1. Studies on extraction of uranium (VI) with petroleum sulfoxides

    International Nuclear Information System (INIS)

    Yang Yanzhao; Sun Sixiu; Bao Borong

    1999-01-01

    The extraction of uranium(VI) with petroleum sulfoxides(PSO) in different diluents is studied. The extraction ability of U(VI) decreases in the following order: benzene, toluene, cyclohexane, heptane, kerosene, carbon tetrachloride and chloroform. The influence of the concentrations of nitric acid, PSO, salting out agent, complexing anion and temperature on the extraction equilibrium is also investigated, and the enthalpy of the extraction reaction is obtained. The relationship between the extraction equilibrium constants K ex and the physical parameters of diluents is derived. The extraction mechanism and equilibrium are examined by measurement of IR spectrophotometry

  2. The effect of various cations and pH on the adsorption of U(VI) on Amberlite IR-118H resin

    International Nuclear Information System (INIS)

    Kilislioglu, Ayben

    2003-01-01

    The effects of various metal cations and pH on the adsorption of uranium(VI) on strongly acidic cation exchanger Amberlite IR-118H (AIR-118H) were studied. The metal cations suppress U(VI) adsorption differently depending on their ionic radii. Adsorption of U(VI) on AIR-118H peaks at pH 3.4, which was attributed to the occurrence of different forms of U(VI) at different pH values. The adsorption data were then processed using the Frumkin-Fowler-Guggenheim equation, and the standard free energy of adsorption was calculated

  3. UO{sub 2}{sup 2+}/protein complexation sites screening

    Energy Technology Data Exchange (ETDEWEB)

    Guilbaud, P.; Pible, O

    2004-07-01

    Uranium(VI) is likely to make strong coordination with some proteins in the plasma and in targeted cells. In the frame of a nuclear toxicology program, a biochemical strategy has been developed to identify these targets in complex biological media. The present work focuses on an approach based on the screening of 3D protein structures in order to identify proteins able to bind UO{sub 2}{sup 2+} and the corresponding complexation sites in these proteins. Our preliminary results show that indeed a few proteins display a high affinity to uranyl salt. The site of interaction may be mapped using molecular modeling, providing coherent results with the biochemical data. (authors)

  4. Design and assembling of a moving bed column to operate with ion exchange resin

    International Nuclear Information System (INIS)

    Franca Junior, J.M.; Abrao, A.

    1976-01-01

    A new moving bed column specially designed to operate with ion exchange resins in such peculiar situations where there is gas evolution is reported. The second part reports the use of the column in the preparation of nuclear grade ammonium uranyl tricarbonate (AUTC), from crude uranyl nitrate solution. Uranium-VI is binded into a strong cationic ion exchanger and then eluted with (NH 4 ) 2 CO 3 . The final product is crystallized from the eluate by simply cooling down the temperature to 5 0 or by addition of ethanol. Loading of resin with uranyl ion, its elution with ammonium carbonate and the crystallization of AUTC is described [pt

  5. Reaction between uranium hexafluoride and trimethylsilylhalides

    Energy Technology Data Exchange (ETDEWEB)

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

    1938-07-01

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

  6. Solar UV-assisted sample preparation of river water for ultra-trace determination of uranium by adsorptive stripping voltammetry

    International Nuclear Information System (INIS)

    Woldemichael, G.; Tulu, T.; Flechsig, G.-U.

    2012-01-01

    The article describes how solar ultraviolet-A radiation can be used to digest samples as needed for voltammetric ultratrace determination of uranium(VI) in river water. We applied adsorptive stripping voltammetry (AdSV) using chloranilic acid as the complexing agent. Samples from the river Warnow in Rostock (Germany) were pretreated with either soft solar UV or wit artificial hard UV from a 30-W source emitting 254-nm light. Samples were irradiated for 12 h, and both methods yielded the same results. We were able to detect around 1 μg.L -1 of uranium(VI) in a sample of river water that also contained dissolved organic carbon at a higher mg.L -1 levels. No AdSV signal was obtained for U(VI) without any UV pre-treatment. Pseudo-polarographic experiments confirmed the dramatic effect of both digestion techniques the the AdSV response. The new method is recommended for use in mobile ultratrace voltammetry of heavy metals for most kinds of natural water samples including tap, spring, ground, sea, and river waters. The direct use of solar radiation for sample pre-treatment represents a sustainable technique for sample preparation that does not consume large quantities of chemicals or energy. (author)

  7. Actinide metals

    Energy Technology Data Exchange (ETDEWEB)

    Brown, Paul L. [Geochem Australia, Kiama, NSW (Australia); Ekberg, Christian [Chalmers Univ. of Technology, Goeteborg (Sweden). Nuclear Chemistry/Industrial Materials Recycling

    2016-07-01

    All isotopes of actinium are radioactive and exist in aqueous solution only in the trivalent state. There have been very few studies on the hydrolytic reactions of actinium(III). The hydrolysis reactions for uranium would only be important in alkaline pH conditions. Thermodynamic parameters for the hydrolysis species of uranium(VI) and its oxide and hydroxide phases can be determined from the stability and solubility constants. The hydrolytic behaviour of neptunium(VI) is quite similar to that of uranium(VI). The solubility constant of NpO{sub 2}OH(am) has been reported a number of times for both zero ionic strength and in fixed ionic strength media. Americium can form four oxidation states in aqueous solution, namely trivalent, tetravalent, pentavalent and hexavalent. Desire, Hussonnois and Guillaumont determined stability constants for the species AmOH{sup 2+} for the actinides, plutonium(III), americium(III), curium(III), berkelium(III) and californium(III) using a solvent extraction technique.

  8. Speciation and bioaccumulation in a model organism of U, Np and Am in the marine environment

    International Nuclear Information System (INIS)

    Maloubier, Melody

    2015-01-01

    The fate of natural and anthropogenic radionuclides in the environment remains a major concern in our modern nuclearized societies. Among the environmental compartments, the hydrosphere is ubiquitous and can transport compounds or elements over very long distances. The recent event of Fukushima demonstrated that the marine environment could be directly affected and this raises both scientific and societal questions. Moreover, some studies have already shown that radionuclides present in seawater can be strongly accumulated by marine organisms although their speciation is most of the time unknown. Yet this knowledge is essential to better understand the transfer mechanisms from the hydrosphere to the biosphere and to evaluate their global impact on humans. In this work, we chose to experimentally determine the speciation of three actinides in doped seawater: uranium(VI), neptunium(V) and americium(III) (and the chemical surrogate europium(III)) by coupling speciation modeling with spectroscopic tools among which Time-Resolved Laser-Induced Fluorescence (TRLIF) and X-ray Absorption Spectroscopy (XAS). Then, we have studied the accumulation process in the sponge A. cavernicola, chosen here because it is considered as a bio-monitor of heavy metal pollution. The accumulation of europium(III), americium(III) and uranium(VI) in A. cavernicola were investigated at trace and ultra-trace levels. Besides, for europium, X-ray and electronic imaging permit to localize the accumulated element in the sponge and to specify its speciation [fr

  9. Actinide metals

    International Nuclear Information System (INIS)

    Brown, Paul L.; Ekberg, Christian

    2016-01-01

    All isotopes of actinium are radioactive and exist in aqueous solution only in the trivalent state. There have been very few studies on the hydrolytic reactions of actinium(III). The hydrolysis reactions for uranium would only be important in alkaline pH conditions. Thermodynamic parameters for the hydrolysis species of uranium(VI) and its oxide and hydroxide phases can be determined from the stability and solubility constants. The hydrolytic behaviour of neptunium(VI) is quite similar to that of uranium(VI). The solubility constant of NpO 2 OH(am) has been reported a number of times for both zero ionic strength and in fixed ionic strength media. Americium can form four oxidation states in aqueous solution, namely trivalent, tetravalent, pentavalent and hexavalent. Desire, Hussonnois and Guillaumont determined stability constants for the species AmOH 2+ for the actinides, plutonium(III), americium(III), curium(III), berkelium(III) and californium(III) using a solvent extraction technique.

  10. Sodium dodecyl sulfate coated alumina modified with a new Schiff's base as a uranyl ion selective adsorbent

    Energy Technology Data Exchange (ETDEWEB)

    Tashkhourian, J., E-mail: tashkhourian@susc.ac.ir [Department of Chemistry, College of Science, Shiraz University, 71454 Shiraz (Iran, Islamic Republic of); Moradi Abdoluosofi, L.; Pakniat, M. [Department of Chemistry, Faculty of Science, Persian Gulf University, Bushehr 75169 (Iran, Islamic Republic of); Montazerozohori, M. [Department of Chemistry, Faculty of Science, Yasouj University, Yasouj (Iran, Islamic Republic of)

    2011-03-15

    A simple and selective method was used for the preconcentration and determination of uranium(VI) by solid-phase extraction (SPE). In this method, a column of alumina modified with sodium dodecyl sulfate (SDS) and a new Schiff's base ligand was prepared for the preconcentration of trace uranyl(VI) from water samples. The uranium(VI) was completely eluted with HCl 2 M and determined by a spectrophotometeric method with Arsenazo(III). The preconcentration steps were studied with regard to experimental parameters such as amount of extractant, type, volume and concentration of eluent, pH, flow rate of sample source and tolerance limit of diverse ions on the recovery of uranyl ion. A preconcentration factor more than 200 was achieved and the average recovery of uranyl(VI) was 99.5%. The relative standard deviation was 1.1% for 10 replicate determinations of uranyl(VI) ion in a solution with a concentration of 5 {mu}g mL{sup -1}. This method was successfully used for the determination of spiked uranium in natural water samples.

  11. Study of the role of magnetite in the immobilisation of U(VI) by reduction to U(IV) under the presence of H{sub 2}(g) in hydrogen carbonate medium

    Energy Technology Data Exchange (ETDEWEB)

    Rovira, Miquel; Pablo, Joan de [Centre Tecnologic de Manresa (Spain); El Aamrani, Souad [Univ. Politecnica de Catalunya, Barcelona (Spain); Duro, Lara; Grive, Mireia; Bruno, Jordi [Enviros Spain SL (Spain)

    2003-01-01

    This report corresponds to the work carried out during the period March 2001-July 2002. The interaction of Uranium(VI) in hydrogen carbonate medium with commercial magnetite as well as with magnetite formed as a corrosion product on the surface of a steel coupon has been studied. The influence of the hydrogen pressure and the mass of magnetite have been two of the factors studied in detail. Results obtained with commercial magnetite indicates that uranium concentration in solution can be explained taking into account the solubility of UO{sub 2}(am) at the experimental conditions employed (pe+pH{approx}6) and at different hydrogen pressures. The uranium(VI) reduction has been clearly demonstrated by using X-Ray Absorption Near Edge Structure (XANES). Experiments performed during 30 days in hydrogen atmosphere showed a reduction of the 80% of U(VI). Results obtained by using X-Ray Photoelectron Spectroscopy also corroborate the U(VI) reduction on the surface of the magnetite. In the case of magnetite obtained on a steel coupon, it seems that the presence of zero-valent iron below the magnetite surface might account for an increase of the electronic density at the surface and, therefore causing a preferential oxidation of the structural iron in front of the experiment conducted with commercial magnetite. Uranium concentration seems also to be controlled by UO{sub 2}(am) solubility.

  12. Study of the role of magnetite in the immobilisation of U(VI) by reduction to U(IV) under the presence of H2(g) in hydrogen carbonate medium

    International Nuclear Information System (INIS)

    Rovira, Miquel; Pablo, Joan de; El Aamrani, Souad; Duro, Lara; Grive, Mireia; Bruno, Jordi

    2003-01-01

    This report corresponds to the work carried out during the period March 2001-July 2002. The interaction of Uranium(VI) in hydrogen carbonate medium with commercial magnetite as well as with magnetite formed as a corrosion product on the surface of a steel coupon has been studied. The influence of the hydrogen pressure and the mass of magnetite have been two of the factors studied in detail. Results obtained with commercial magnetite indicates that uranium concentration in solution can be explained taking into account the solubility of UO 2 (am) at the experimental conditions employed (pe+pH∼6) and at different hydrogen pressures. The uranium(VI) reduction has been clearly demonstrated by using X-Ray Absorption Near Edge Structure (XANES). Experiments performed during 30 days in hydrogen atmosphere showed a reduction of the 80% of U(VI). Results obtained by using X-Ray Photoelectron Spectroscopy also corroborate the U(VI) reduction on the surface of the magnetite. In the case of magnetite obtained on a steel coupon, it seems that the presence of zero-valent iron below the magnetite surface might account for an increase of the electronic density at the surface and, therefore causing a preferential oxidation of the structural iron in front of the experiment conducted with commercial magnetite. Uranium concentration seems also to be controlled by UO 2 (am) solubility

  13. The influence of biofilms on the migration of uranium in acid mine drainage (AMD) waters

    Energy Technology Data Exchange (ETDEWEB)

    Krawczyk-Baersch, E., E-mail: E.Krawczyk-Baersch@hzdr.de [Helmholtz-Zentrum Dresden-Rossendorf, Institute of Radiochemistry, P.O. Box 51 01 19, D-01314 Dresden (Germany); Luensdorf, H. [Helmholtz Centre for Infection Research, Department of Vaccinology and Applied Microbiology, Inhoffenstr. 7, D-38124 Braunschweig (Germany); Arnold, T.; Brendler, V. [Helmholtz-Zentrum Dresden-Rossendorf, Institute of Radiochemistry, P.O. Box 51 01 19, D-01314 Dresden (Germany); Eisbein, E. [TU Bergakademie Freiberg, Institute of Physical Chemistry, Akademiestrasse 6, D-09596 Freiberg (Germany); Jenk, U.; Zimmermann, U. [Wismut GmbH, Jagdschaenkenstr. 29, D-09117 Chemnitz (Germany)

    2011-07-15

    The uranium mine in Koenigstein (Germany) is currently in the process of being flooded. Huge mass of Ferrovum myxofaciens dominated biofilms are growing in the acid mine drainage (AMD) water as macroscopic streamers and as stalactite-like snottites hanging from the ceiling of the galleries. Microsensor measurements were performed in the AMD water as well as in the biofilms from the drainage channel on-site and in the laboratory. The analytical data of the AMD water was used for the thermodynamic calculation of the predominance fields of the aquatic uranium sulfate (UO{sub 2}SO{sub 4}) and UO{sub 2}{sup ++} speciation as well as of the solid uranium species Uranophane [Ca(UO{sub 2}){sub 2}(SiO{sub 3}OH){sub 2}{center_dot}5H{sub 2}O] and Coffinite [U(SiO{sub 4}){sub 1-x}(OH){sub 4x}], which are defined in the stability field of pH > 4.8 and Eh < 960 mV and pH > 0 and Eh < 300 mV, respectively. The plotting of the measured redox potential and pH of the AMD water and the biofilm into the calculated pH-Eh diagram showed that an aqueous uranium(VI) sulfate complex exists under the ambient conditions. According to thermodynamic calculations a retention of uranium from the AMD water by forming solid uranium(VI) or uranium(IV) species will be inhibited until the pH will increase to > 4.8. Even analysis by Energy-filtered Transmission Electron Microscopy (EF-TEM) and electron energy loss spectroscopy (EELS) within the biofilms did not provide any microscopic or spectroscopic evidence for the presence of uranium immobilization. In laboratory experiments the first phase of the flooding process was simulated by increasing the pH of the AMD water. The results of the experiments indicated that the F. myxofaciens dominated biofilms may have a substantial impact on the migration of uranium. The AMD water remained acid although it was permanently neutralized with the consequence that the retention of uranium from the aqueous solution by the formation of solid uranium species will be

  14. Membrane extraction in preconcentration of some uranium fission products

    International Nuclear Information System (INIS)

    Macasek, F.; Rajec, P.; Kopunec, R.; Mikulaj, V.

    1984-01-01

    Theoretical comparison of the equilibria and kinetics of solvent extraction (SX) and emulsion liquid membrane extraction (MX) was performed using the distribution ratios at the outer inner boundaries of liquid membrane. Enhancement factors, pertraction factor (p) and mulitplication factor (N), were proposed to express efficiency of the MX technique. The extraction of cesium, strontium, cobalt(II), uranium(VI), cerium(III) and technetium(VII) was investigated from this point of view. The most perspective systems are those with chelating agents (e.g. di-2-ethylhexyl-phosporic acid and 8-hydroquinoline), especially at low concentrations (substioichiometric amounts), with which high enhancement factors can be achieved. The results with the ion-exchange systems (bis(1,2-dicarbollyl)-cobalt(III) and quaternary ammonium salts) may be interpreted as indicating some surface barriers which prevent the transport of ions. 20 references, 14 figures, 6 tables

  15. Some reactions of uranium chloride pentafluoride

    International Nuclear Information System (INIS)

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

    1986-01-01

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

  16. Indirect determination of uranium by atomic-absorption spectrophotometry using an air-acetylene flame

    International Nuclear Information System (INIS)

    Alder, J.F.; Das, B.C.

    1977-01-01

    An indirect method has been developed for the determination of uranium by atomic-absorption spectrophotometry using an air-acetylene flame. Use is made of the reduction of copper(II) by uranium(IV) followed by complex formation of the copper(I) ions so produced with neocuproine (2,9-dimethyl-1,10-phenanthroline) and finally the determination of copper in this complex by atomic-absorption spectrophotometry. The results show that the method can be recommended, provided that care is taken to ensure the complete reduction of uranium(VI) to uranium(IV). The sensitivity of the method is 4.9 μg of uranium and the upper limit 500 μg without dilution. (author)

  17. Kinetics of the reduction of plutonium(IV) by hydroxyurea, a novel salt-free agent

    International Nuclear Information System (INIS)

    Zhu Zhaowu; He Jianyu; Zhang Zefu; Zhang Yu; Zheng Weifang

    2004-01-01

    The kinetics of the reduction of plutonium(IV) by hydroxyurea (HU), a novel salt free reductant, in nitric acid solutions has been studied. The observed reaction rate can be expressed as: -d[Pu(IV)]/dt=k 0 [Pu(IV)] 2 [HU]/[H + ] 0.9 , where k 0 = 5853 ± 363 (l 1.1 x mol -1.1 x s -1 ) at t = 13 deg C. The activation energy is about 81.2 kJ/mol. It was also shows that uranium(VI) has no appreciable influence on the reaction rate. Compared with other organic reductants our experiments indicate that HU is a very fast reductant for plutonium(IV). (author)

  18. Extractive spectrophotometric determination of thorium

    International Nuclear Information System (INIS)

    Venkatesan, M.; Gopalakrishnan, V.; Ramanujam, A.; Nadkarni, M.N.

    1981-01-01

    An extractive spectrophotometric method has been standardized for the analysis of 0.2 to 1.6 milligrams of thorium present in nitric acid solutions. The method involves the extraction of thorium from nitric acid solutions into 0.5 M thenoyl trifluoro acetone (HTTA) in benzene and its direct estimation from the organic extract by spectrophotometry as Thoron colour complex. In this method, interference due to iron upto 5 milligrams can be suppressed by adding ascorbic acid in the ratio of 1:2 prior to HTTA extraction. Uranium(VI) does not interefere even when present in 2000 times the amount of thorium. Plutonium and cerium do not interfere at one milligram level whereas zirconium interferes in this method. The overall error variation and precision of this method has been determined to be +- 3.5%. (author)

  19. Solvent extraction of uranium (VI) by Amberlite Lsub(A-1)

    International Nuclear Information System (INIS)

    Kim, S.S.

    1977-01-01

    The effects of uranium, amine and sulfuric acid concentrate, and temperature on the extraction of uranium(VI) from acidic sulphate solutions by Amberlite Lsub(A-1) in benzene was studied. The extraction of sulfuric acid by Amberlite Lsub(A-1) in benzene was also examined. It was found that 92 to 98 percent extraction was obtained for a uranyl sulphate solution of 5g/1 concentrate containing of 0.2M to 0.3M sulfuric acid, a Amberlite Lsub(A-1) of 5 to 10 percent (weight) in benzene, at a temperature of less than 20 0 C. The mechanism of uranium extraction was discussed on the basis of the resluts obtained. (author)

  20. ALTERATION OF U(VI)-PHASES UNDER OXIDIZING CONDITIONS

    Energy Technology Data Exchange (ETDEWEB)

    A.P. Deditius; S. Utsunomiya; R.C. Ewing

    2006-02-21

    Uranium-(VI) phases are the primary alteration products of the UO{sub 2} in spent nuclear fuel and the UO{sub 2+x}, in natural uranium deposits. The U(VI)-phases generally form sheet structures of edge-sharing UO{sub 2}{sup 2+} polyhedra. The complexity of these structures offers numerous possibilities for coupled-substitutions of trace metals and radionuclides. The incorporation of radionuclides into U(VI)-structures provides a potential barrier to their release and transport in a geologic repository that experiences oxidizing conditions. In this study, we have used natural samples of UO{sub 2+x}, to study the U(VI)-phases that form during alteration and to determine the fate of the associated trace elements.

  1. ALTERATION OF U(VI)-PHASES UNDER OXIDIZING CONDITIONS

    International Nuclear Information System (INIS)

    A.P. Deditius; S. Utsunomiya; R.C. Ewing

    2006-01-01

    Uranium-(VI) phases are the primary alteration products of the UO 2 in spent nuclear fuel and the UO 2+x , in natural uranium deposits. The U(VI)-phases generally form sheet structures of edge-sharing UO 2 2+ polyhedra. The complexity of these structures offers numerous possibilities for coupled-substitutions of trace metals and radionuclides. The incorporation of radionuclides into U(VI)-structures provides a potential barrier to their release and transport in a geologic repository that experiences oxidizing conditions. In this study, we have used natural samples of UO 2+x , to study the U(VI)-phases that form during alteration and to determine the fate of the associated trace elements

  2. Aqueous suspensions of carbon nanotubes: surface oxidation, colloidal stability and uranium sorption.

    Science.gov (United States)

    Schierz, A; Zänker, H

    2009-04-01

    The objective of this study is to obtain information on the behaviour of carbon nanotubes (CNTs) as potential carriers of pollutants in the case of accidental CNT release to the environment and on the properties of CNTs as a potential adsorbent material in water purification. The effects of acid treatment of CNTs on (i) the surface properties, (ii) the colloidal stability and (iii) heavy metal sorption are investigated, the latter being exemplified by uranium(VI) sorption. There is a pronounced influence of surface treatment on the behaviour of the CNTs in aqueous suspension. Results showed that acid treatment increases the amount of acidic surface groups on the CNTs. Therefore, acid treatment has an increasing effect on the colloidal stability of the CNTs and on their adsorption capacity for U(VI). Another way to stabilise colloids of pristine CNTs in aqueous suspension is the addition of humic acid.

  3. Transport of uranium by supported liquid membrane containing bis(2-ethylhexyl) hydrogenphosphate and 1-octanol

    International Nuclear Information System (INIS)

    Akiba, Kenichi; Kanno, Takuji; Takahashi, Toshihiko.

    1984-01-01

    Carrier-mediated transport of uranium(VI) has been studied by means of liquid membranes impregnated in a microporous polymer. Liquid membranes containing bis(2-ethylhexyl) hydrogenphosphate (DEHPA) alone yielded inadequate stripping of uranium. The addition of 1-octanol to DEHPA solutions resulted in a decrease in extractability, and made it possible to control the distribution ratio of uranium. Uranium in the feed solution was sufficiently transported across the liquid membrane containing this DEHPA-1-octanol mixture into the product solution. The apparent rate constant (ksub(obs)) of transport increased slightly with an increase in carrier concentrations. Variations in acid concentrations of the feed solution (pH 2.5--3.2) and the product solution (0.1--1.0 M H 2 SO 4 ) had little effect on the transport rate. A large excess of uranium, more than the carrier content in the liquid membrane, was finally concentrated in the stripping acid. (author)

  4. Ultrafiltration evaluation with depleted uranium oxide

    International Nuclear Information System (INIS)

    Weisbrod, K.R.; Schake, A.R.; Morgan, A.N.; Purdy, G.M.; Martinez, H.E.; Nelson, T.O.

    1998-03-01

    Scientists at the Los Alamos National Laboratory Plutonium Facility are using electrodissolution in neutral to alkaline solutions to decontaminate oralloy parts that have surface plutonium contamination. Ultrafiltration of the electrolyte stream removes precipitate so that the electrolyte stream to the decontamination fixture is precipitate free. This report describes small-scale laboratory ultrafiltration experiments that the authors performed to determine conditions necessary for full-scale operation of an ultrafiltration module. Performance was similar to what they observed in the ferric hydroxide system. At 12 psi transmembrane pressure, a shear rate of 12,000 sec -1 was sufficient to sustain membrane permeability. Ultrafiltration of uranium(VI) oxide appears to occur as easily as ultrafiltration of ferric hydroxide. Considering the success reported in this study, the authors plan to add ultrafiltration to the next decontamination system for oralloy parts

  5. Determination of uranium in aqueous solutions by HPLC post column UV/VIS detection

    International Nuclear Information System (INIS)

    Abbasi, W.A.; Street, M.

    1995-01-01

    Analysis of uranium in different nitric acid concentration solutions is interest in nuclear industry where it is present in various process and waste streams. A method for the determination of uranium(VI) in nitric acid solution in described using ion chromatography and post-column derivatization with 4-(2-pyridylazo) resorcinol (PAR). The method does not require any sample treatment for acid removal or neutralization and can be used for routine laboratory analysis. The effluent used was ammonium sulphate / sulphuric acid and PAR was present in ammonium hydroxide/acetic acid buffer. The column effluents is reacted with PAR in a reaction coil and U(VI)-PAR complex is detector at 528 nm. The lowest uranium concentration detected was 100 ppb (0.1 mg/sup -1/) and linearity of up to 8 mgl -1 concentration was verified. The standard deviation in reproducibility at uranium concentration of 0.1 mgl/sup -1/ was 0.82%. (author)

  6. Interfacial tension in systems involving TBP in dodecane, nitric acid, uranyl nitrate and water

    International Nuclear Information System (INIS)

    Kolarik, Z.; Pipkin, N.

    1982-08-01

    The interfacial tension was measured at 25 0 C in the systems TBP - n-dodecane/nitric acid - water and TBP - n-dodecane/nitric acid - uranyl nitrate - water. Empirical equations describing the interfacial tension as a function of the concentration of TBP in the starting organic phase and of uranium-(VI) and nitric acid in the equilibrium aqueous phase were suggested. In the absence of uranium (VI), the interfacial tension can also be correlated with the concentration of water in the equilibrium organic phase. Free TBP, hydrated or nonhydrated, and hydrated TBP solvates of nitric acid are interfacially active. Anhydrous TBP solvates of nitric acid and the TBP solvate of uranyl nitrate, which neither is hydrated, do not exhibit any visible interfacial activity. (orig.) [de

  7. Elucidating bonding preferences in tetrakis(imido)uranate(VI) dianions

    Science.gov (United States)

    Anderson, Nickolas H.; Xie, Jing; Ray, Debmalya; Zeller, Matthias; Gagliardi, Laura; Bart, Suzanne C.

    2017-09-01

    Actinyl species, [AnO2]2+, are well-known derivatives of the f-block because of their natural occurrence and essential roles in the nuclear fuel cycle. Along with their nitrogen analogues, [An(NR)2]2+, actinyls are characterized by their two strong trans-An-element multiple bonds, a consequence of the inverse trans influence. We report that these robust bonds can be weakened significantly by increasing the number of multiple bonds to uranium, as demonstrated by a family of uranium(VI) dianions bearing four U-N multiple bonds, [M]2[U(NR)4] (M = Li, Na, K, Rb, Cs). Their geometry is dictated by cation coordination and sterics rather than by electronic factors. Multiple bond weakening by the addition of strong π donors has the potential for applications in the processing of high-valent actinyls, commonly found in environmental pollutants and spent nuclear fuels.

  8. Coordination compounds of titanium, zirconium, tin, thorium and uranium

    International Nuclear Information System (INIS)

    Deshpande, S.G.; Jain, S.C.

    1990-01-01

    Reactions of isatin, furoic acid and picolinic acid have been carried out with titanium tetrachloride, tin tetrachloride, thorium tetrachloride, zirconyl chloride and uranyl nitrate. While 2:3(metal:ligand) type compounds of isatin have been obtained with Ti(IV) and Sn(IV), zirconium(IV), thorium(IV), and uranium(VI) do not react with the ligand under similar experimental conditions. Furoic acid (FAH) and picolinic acid(PicH) form various chloro furoates and picolinates when reacted with TiCl 4 , ZrOCl 2 and ThCl 4 , but do not react with SnCl 4 . The various compounds synthesised have been characterised on the basis of elemental analysis, infrared studies, conductivity and thermogravimetric measurements. (author). 1 tab., 10 refs

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

    OpenAIRE

    Kosog, Boris

    2012-01-01

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

  10. The application of extraction chromatography for analysis of alkali and alkaline earth uranates

    International Nuclear Information System (INIS)

    Tomazic, B.; Cukovic, M.

    1978-01-01

    A method for rapid analysis of alkali and alkaline earth uranates is proposed. The method is based on the use of an HDEHP extraction chromatographic column, which makes possible quantitative separations of alkaline earth ions from macroamounts of uranium(VI). Composition of alkaline earth uranates, based on regression analysis, are presented. The results, which show that under the given experimental conditions alkaline earth triuranates precipitate, are in good agreement with previous data from same laboratory. In addition the HDEHP extraction chromatographic column can be suggested as a tool for separation of representative fission products from irradiated uranium for the purpose of determination of the burn-up factor of nuclear reactor materials. (T.G.)

  11. 13C and 17O NMR binding constant studies of uranyl carbonate complexes in near-neutral aqueous solution. Yucca Mountain Project Milestone Report 3351

    International Nuclear Information System (INIS)

    Clark, D.L.; Newton, T.W.; Palmer, P.D.; Zwick, B.D.

    1995-01-01

    Valuable structural information, much of it unavailable by other methods, can be obtained about complexes in solution through NMR spectroscopy. From chemical shift and intensity measurements of complexed species, NMR can serve as a species-specific structural probe for molecules in solution and can be used to validate thermodynamic constants used in geochemical modeling. Fourier-transform nuclear magnetic resonance (FT-NMR) spectroscopy has been employed to study the speciation of uranium(VI) ions in aqueous carbonate solutions as a function of pH, ionic strength, carbonate concentration, uranium concentration, and temperature. Carbon-13 and oxygen-17 NMR spectroscopy were used to monitor the fractions, and hence thermodynamic binding constants of two different uranyl species U0 2 (CO 3 ) 3 4- and (UO 2 ) 3 (CO 3 ) 6 6- in aqueous solution. Synthetic buffer solutions were prepared under the ionic strength conditions used in the NMR studies in order to obtain an accurate measure of the hydrogen ion concentration, and a discussion of pH = -log(a H + ) versus p[H] = -log[H+] is provided. It is shown that for quantitative studies, the quantity p[H] needs to be used. Fourteen uranium(VI) binding constants recommended by the OECD NEA literature review were corrected to the ionic strengths employed in the NMR study using specific ion interaction theory (SIT), and the predicted species distributions were compared with the actual species observed by multinuclear NMR. Agreement between observed and predicted stability fields is excellent. This establishes the utility of multinuclear NMR as a species-specific tool for the study of the actinide carbonate complexation constants, and serves as a means for validating the recommendations provided by the OECD NEA

  12. On the interaction of uranium with the bioligands citric acid and glucose; Zur Wechselwirkung von Uran mit den Bioliganden Citronensaeure und Glucose

    Energy Technology Data Exchange (ETDEWEB)

    Steudtner, Robin

    2011-10-26

    For a better understanding of the actinide behaviour in human (in term of metabolism, retention, excretion) and in geological and biological systems, it is of prime importance to have a good knowledge of the relevant speciation. In model systems the chemical behaviour of uranium regarding complex formation and redox reaction were investigated. On this basis determinates thermodynamics constants and redox behaviour are used to prognoses a safety assessment for the respective system. The pentavalent uranium(V) is a metastable intermediate in natural redox system between uranium(IV) and uranium(VI). In this study the uranium(V) fluorescence was detected by laser spectroscopic methods ({lambda}{sub ex} = 255 nm) for the first time. The peak maxima ({lambda}{sub ex} = 255 nm) of luminescence spectrum of the photo reduced U(V) in aqueous perchlorate/2-propanol solution was detected at 440 nm and a fluorescence lifetime of 1.1 {+-} 0.02 {mu}s was calculated. The stable aqueous uranyl(V)-tricarbonate complex was characterized by fluorescence spectroscopy ({lambda}{sub ex} = 255 nm and 408 nm). The known quench effects of carbonate could be minimized by coupling the laser fluorescence system with the low temperature technique. The resulting U(V) fluorescence emission bands were detected between 375 nm and 445 nm. The peak maxima were identified at 401.5 nm ({lambda}{sub ex} = 255 nm) and 413.0 nm ({lambda}{sub ex} = 408 nm). The fluorescence lifetime of the uranyl(V)-carbonate species was determined at 153 K as 120 {+-} 0.1 {mu}s ({lambda}{sub ex} = 255 nm). In addition the fluorescence of uranium(V) was verifies by confocal laser scanning microscopy. The oxidation process from uranium(IV) to uranium(VI) was investigated on solid uraninite (UO{sub 2}) and uranium(IV) tetra chloride (UCl{sub 4}) and a 1 x 10{sup -2} M uranium(IV) sulphate (U{sup IV}SO{sub 4}) solution. By continuous oxygen transfer the uranium(IV) was oxidized slowly to uranium(VI). The temporal process was

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

    International Nuclear Information System (INIS)

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

    2017-01-01

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

  14. On the interaction of uranium with the bioligands citric acid and glucose

    International Nuclear Information System (INIS)

    Steudtner, Robin

    2011-01-01

    For a better understanding of the actinide behaviour in human (in term of metabolism, retention, excretion) and in geological and biological systems, it is of prime importance to have a good knowledge of the relevant speciation. In model systems the chemical behaviour of uranium regarding complex formation and redox reaction were investigated. On this basis determinates thermodynamics constants and redox behaviour are used to prognoses a safety assessment for the respective system. The pentavalent uranium(V) is a metastable intermediate in natural redox system between uranium(IV) and uranium(VI). In this study the uranium(V) fluorescence was detected by laser spectroscopic methods (λ ex = 255 nm) for the first time. The peak maxima (λ ex = 255 nm) of luminescence spectrum of the photo reduced U(V) in aqueous perchlorate/2-propanol solution was detected at 440 nm and a fluorescence lifetime of 1.1 ± 0.02 μs was calculated. The stable aqueous uranyl(V)-tricarbonate complex was characterized by fluorescence spectroscopy (λ ex = 255 nm and 408 nm). The known quench effects of carbonate could be minimized by coupling the laser fluorescence system with the low temperature technique. The resulting U(V) fluorescence emission bands were detected between 375 nm and 445 nm. The peak maxima were identified at 401.5 nm (λ ex = 255 nm) and 413.0 nm (λ ex = 408 nm). The fluorescence lifetime of the uranyl(V)-carbonate species was determined at 153 K as 120 ± 0.1 μs (λ ex = 255 nm). In addition the fluorescence of uranium(V) was verifies by confocal laser scanning microscopy. The oxidation process from uranium(IV) to uranium(VI) was investigated on solid uraninite (UO 2 ) and uranium(IV) tetra chloride (UCl 4 ) and a 1 x 10 -2 M uranium(IV) sulphate (U IV SO 4 ) solution. By continuous oxygen transfer the uranium(IV) was oxidized slowly to uranium(VI). The temporal process was studied by the confocal laser scanning microscopy using an excitation wavelength of 408 nm. The

  15. Analytical applications of resins containing amide and polyamine functional groups

    International Nuclear Information System (INIS)

    Orf, G.M.

    1977-01-01

    Resins are prepared by chemically bonding N,N-dialkylamides and polyamine functional groups to Amberlite XAD-4. These resins are applied to the concentration of metal ions from dilute aqueous solution and the rapid separation of metal ions by high-speed liquid chromatography with continuous on-line detection of the eluent stream. A dibutyl amide resin is used for the separation of uranium(VI), thorium(IV), and zirconium(IV) from each other and several other metal ions. Uranium(VI) and thorium(IV) are determined in the presence of large excesses of foreign metal ions and anions. A practical application of the amide resin is studied by determining uranium in low grade uranium ores. The amide resin is also used for the selective concentration of gold(III) from seawater. A triethylenetetramine resin is used for the separation of copper(II) from equal molar amounts and large excesses of nickel(II), cobalt(II), zinc(II), cadmium(II), iron(III) and aluminum(III). Copper(II), nickel(II), zinc(II), cobalt(II) and cadmium(II) are determined in the presence of large excesses of calcium(II) and magnesium(II). The resin was found to be selective for silver(I) and mercury(II) at low pH values and a rapid separation of equal molar amounts of copper(II) and silver(I) was performed. The resin was also found to have an affinity for anionic metal complexes such as iron(III)-tartrate when the resin is in the hydrogen form. A study of the retention of the anions chromium(III)-tartrate and dichromate at various pH values was performed to better understand the anion exchange properties of the resin. Triethylenetetramine resins were also prepared from polystyrene gel to make a resin with higher capacities for copper

  16. Final Report - Phase II - Biogeochemistry of Uranium Under Reducing and Re-oxidizing Conditions: An Integrated Laboratory and Field Study ($20,575 extension)

    International Nuclear Information System (INIS)

    Brent Peyton; Rajesh Sani

    2006-01-01

    Our understanding of subsurface microbiology is hindered by the inaccessibility of this environment, particularly when the hydrogeologic medium is contaminated with toxic substances. Past research in our labs indicated that the composition of the growth medium (e.g., bicarbonate complexation of U(VI)) and the underlying mineral phase (e.g., hematite) significantly affects the rate and extent of U(VI) reduction and immobilization through a variety of effects. Our research was aimed at elucidating those effects to a much greater extent, while exploring the potential for U(IV) reoxidation and subsequent re-mobilization, which also appears to depend on the mineral phases present in the system. The project reported on here was an extension ($20,575) of the prior (much larger) project. This report is focused only on the work completed during the extension period. Further information on the larger impacts of our research, including 28 publications, can be found in the final report for the following projects: (1) Biogeochemistry of Uranium Under Reducing and Re-oxidizing Conditions: An Integrated Laboratory and Field Study Grant DE-FG03-01ER63270, and (2) Acceptable Endpoints for Metals and Radionuclides: Quantifying the Stability of Uranium and Lead Immobilized Under Sulfate Reducing Conditions Grant DE-FG03-98ER62630/A001 In this Phase II project, the toxic effects of uranium(VI) were studied using Desulfovibrio desulfuricans G20 in a medium containing bicarbonate or 1, 4-piperazinediethane sulfonic acid disodium salt monohydrate (PIPES) buffer (each at 30 mM, pH 7). The toxicity of uranium(VI) was dependent on the medium buffer and was observed in terms of longer lag times and in some cases, no measurable growth. The minimum inhibiting concentration (MIC) was 140 (micro)M U(VI) in PIPES buffered medium. This is 36 times lower than previously reported for D. desulfuricans. These results suggest that U(VI) toxicity and the detoxification mechanisms of G20 depend greatly

  17. Final Report - Phase II - Biogeochemistry of Uranium Under Reducing and Re-oxidizing Conditions: An Integrated Laboratory and Field Study

    Energy Technology Data Exchange (ETDEWEB)

    Peyton, Brent; Sani, Rajesh

    2006-09-28

    Our understanding of subsurface microbiology is hindered by the inaccessibility of this environment, particularly when the hydrogeologic medium is contaminated with toxic substances. Past research in our labs indicated that the composition of the growth medium (e.g., bicarbonate complexation of U(VI)) and the underlying mineral phase (e.g., hematite) significantly affects the rate and extent of U(VI) reduction and immobilization through a variety of effects. Our research was aimed at elucidating those effects to a much greater extent, while exploring the potential for U(IV) reoxidation and subsequent re-mobilization, which also appears to depend on the mineral phases present in the system. The project reported on here was an extension ($20,575) of the prior (much larger) project. This report is focused only on the work completed during the extension period. Further information on the larger impacts of our research, including 28 publications, can be found in the final report for the following projects: 1) Biogeochemistry of Uranium Under Reducing and Re-oxidizing Conditions: An Integrated Laboratory and Field Study Grant # DE-FG03-01ER63270, and 2) Acceptable Endpoints for Metals and Radionuclides: Quantifying the Stability of Uranium and Lead Immobilized Under Sulfate Reducing Conditions Grant # DE-FG03-98ER62630/A001 In this Phase II project, the toxic effects of uranium(VI) were studied using Desulfovibrio desulfuricans G20 in a medium containing bicarbonate or 1, 4-piperazinediethane sulfonic acid disodium salt monohydrate (PIPES) buffer (each at 30 mM, pH 7). The toxicity of uranium(VI) was dependent on the medium buffer and was observed in terms of longer lag times and in some cases, no measurable growth. The minimum inhibiting concentration (MIC) was 140 M U(VI) in PIPES buffered medium. This is 36 times lower than previously reported for D. desulfuricans. These results suggest that U(VI) toxicity and the detoxification mechanisms of G20 depend greatly on the

  18. Fast Oxidation Processes in a Naturally Reduced Aquifer Zone Caused by Dissolved Oxygen

    Science.gov (United States)

    Davis, J. A.; Jemison, N. E.; Williams, K. H.; Hobson, C.; Bush, R. P.

    2014-12-01

    The occurrence of naturally reduced zones is quite common in alluvial aquifers in the western U.S.A. due to the burial of woody debris in flood plains. The naturally reduced zones are heterogeneously dispersed in such aquifers and are characterized by high concentrations of organic carbon and reduced phases, including iron sulfides and reduced forms of metals, including uranium(IV). The persistence of high concentrations of dissolved uranium(VI) at uranium-contaminated aquifers on the Colorado Plateau has been attributed to slow oxidation of insoluble uranium(IV) mineral phases that are found in association with these natural reducing zones, although there is little understanding of the relative importance of various potential oxidants. Three field experiments were conducted within an alluvial aquifer adjacent to the Colorado River near Rifle, CO wherein groundwater associated with naturally reduced zones was pumped into a gas-impermeable tank, mixed with a conservative tracer (Br-), bubbled with a gas phase composed of 97% O2 and 3% CO2, and then returned to the subsurface in the same well from which it was withdrawn. Within minutes of re-injection of the oxygenated groundwater, dissolved uranium(VI) concentrations increased from less than 1 μM to greater than 2.5 μM, demonstrating that oxygen can be an important oxidant for uranium in these field systems if supplied to the naturally reduced zones. Small concentrations of nitrate were also observed in the previously nitrate-free groundwater, and Fe(II) decreased to the detection limit. These results contrast with other laboratory and field results in which oxygen was introduced to systems containing high concentrations of mackinawite (FeS) rather than the more crystalline iron sulfides found in aged, naturally reduced zones. The flux of oxygen to the naturally reduced zones in the alluvial aquifers occurs mainly through interactions between groundwater and gas phases at the water table, and seasonal variations

  19. Oxidation of naturally reduced uranium in aquifer sediments by dissolved oxygen and its potential significance to uranium plume persistence

    Science.gov (United States)

    Davis, J. A.; Smith, R. L.; Bohlke, J. K.; Jemison, N.; Xiang, H.; Repert, D. A.; Yuan, X.; Williams, K. H.

    2015-12-01

    The occurrence of naturally reduced zones is common in alluvial aquifers in the western U.S.A. due to the burial of woody debris in flood plains. Such reduced zones are usually heterogeneously dispersed in these aquifers and characterized by high concentrations of organic carbon, reduced mineral phases, and reduced forms of metals, including uranium(IV). The persistence of high concentrations of dissolved uranium(VI) at uranium-contaminated aquifers on the Colorado Plateau has been attributed to slow oxidation of insoluble uranium(IV) mineral phases found in association with these reducing zones, although there is little understanding of the relative importance of various potential oxidants. Four field experiments were conducted within an alluvial aquifer adjacent to the Colorado River near Rifle, CO, wherein groundwater associated with the naturally reduced zones was pumped into a gas-impermeable tank, mixed with a conservative tracer (Br-), bubbled with a gas phase composed of 97% O2 and 3% CO2, and then returned to the subsurface in the same well from which it was withdrawn. Within minutes of re-injection of the oxygenated groundwater, dissolved uranium(VI) concentrations increased from less than 1 μM to greater than 2.5 μM, demonstrating that oxygen can be an important oxidant for uranium in such field systems if supplied to the naturally reduced zones. Dissolved Fe(II) concentrations decreased to the detection limit, but increases in sulfate could not be detected due to high background concentrations. Changes in nitrogen species concentrations were variable. The results contrast with other laboratory and field results in which oxygen was introduced to systems containing high concentrations of mackinawite (FeS), rather than the more crystalline iron sulfides found in aged, naturally reduced zones. The flux of oxygen to the naturally reduced zones in the alluvial aquifers occurs mainly through interactions between groundwater and gas phases at the water table

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-02-24

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

  1. Extraction and separation of U(VI and Th(IV from hydrobromic acid media using Cyanex-923 extractant

    Directory of Open Access Journals (Sweden)

    Ghag Snehal M.

    2010-01-01

    Full Text Available A systematic study of the solvent extraction of uranium(VI and thorium(IV from hydrobromic acid media was performed using the neutral phosphine oxide extractant Cyanex-923 in toluene. These metal ions were found to be quantitatively extracted with Cyanex-923 in toluene in the acidity range 5x10-5-1x10-4 M and 5x10-5-5x10-3 M, respectively, and they are stripped from the organic phase with 7.0 M HClO4 and 2.0- 4.0 M HCl, respectively. The effect of the equilibrium period, diluents, diverse ions and stripping agent on the extraction of U(VI and Th(IV was studied. The stoichiometry of the extracted species of these metal ions was determined based on the slope analysis method. The extraction reactions proceed by solvation and their probable extracted species found in the organic phase were UO2Br2•2Cyanex-923 and ThBr4•2Cyanex-923. Based on these results, a sequential procedure for their separation from each other was developed.

  2. Layered Double Hydroxides as Effective Adsorbents for U(VI and Toxic Heavy Metals Removal from Aqueous Media

    Directory of Open Access Journals (Sweden)

    G. N. Pshinko

    2013-01-01

    Full Text Available Capacities of different synthesized Zn,Al-hydrotalcite-like adsorbents, including the initial carbonate [Zn4Al2(OH12]·CO3·8H2O and its forms intercalated with chelating agents (ethylenediaminetetraacetic acid (EDTA, diethylenetriaminepentaacetic acid (DTPA, and hexamethylenediaminetetraacetic acid (HMDTA and heat-treated form Zn4Al2O7, to adsorb uranium(VI and ions of toxic heavy metals have been compared. Metal sorption capacities of hydrotalcite-like adsorbents have been shown to correlate with the stability of their complexes with the mentioned chelating agents in a solution. The synthesized layered double hydroxides (LDHs containing chelating agents in the interlayer space are rather efficient for sorption purification of aqueous media free from U(VI irrespective of its forms of natural abundance (including water-soluble bi- and tricarbonate forms and from heavy metal ions. [Zn4Al2(OH12]·EDTA·nH2O is recommended for practical application as one of the most efficient and inexpensive synthetic adsorbents designed for recovery of both cationic and particularly important anionic forms of U(VI and other heavy metals from aqueous media. Carbonate forms of LDHs turned out to be most efficient for recovery of Cu(II from aqueous media with pH0≥7 owing to precipitation of Cu(II basic carbonates and Cu(II hydroxides. Chromate ions are efficiently adsorbed from water only by calcinated forms of LDHs.

  3. Acidic aqueous uranium electrodeposition for target fabrication

    International Nuclear Information System (INIS)

    Saliba-Silva, A.M.; Oliveira, E.T.; Garcia, R.H.L.; Durazzo, M.

    2013-01-01

    Direct irradiation of targets inside nuclear research or multiple purpose reactors is a common route to produce 99 Mo- 99m Tc radioisotopes. The electroplating of low enriched uranium over nickel substrate might be a potential alternative to produce targets of 235 U. The electrochemistry of uranium at low temperature might be beneficial for an alternative route to produce 99 Mo irradiation LEU targets. Electrodeposition of uranium can be made using ionic and aqueous solutions producing uranium oxide deposits. The performance of uranium electrodeposition is relatively low because a big competition with H 2 evolution happens inside the window of electrochemical reduction potential. This work explores possibilities of electroplating uranium as UO 2 2+ (Uranium-VI) in order to achieve electroplating uranium in a sufficient amount to be commercially irradiated in the future Brazilian RMB reactor. Electroplated nickel substrate was followed by cathodic current electrodeposition from aqueous UO 2 (NO 3 ) 2 solution. EIS tests and modeling showed that a film formed differently in the three tested cathodic potentials. At the lower level, (-1.8V) there was an indication of a double film formation, one overlaying the other with ionic mass diffusion impaired at the interface with nickel substrate as showed by the relatively lower admittance of Warburg component. (author)

  4. Microbial Communities in Contaminated Sediments, Associated with Bioremediation of Uranium to Submicromolar Levels▿

    Science.gov (United States)

    Cardenas, Erick; Wu, Wei-Min; Leigh, Mary Beth; Carley, Jack; Carroll, Sue; Gentry, Terry; Luo, Jian; Watson, David; Gu, Baohua; Ginder-Vogel, Matthew; Kitanidis, Peter K.; Jardine, Philip M.; Zhou, Jizhong; Criddle, Craig S.; Marsh, Terence L.; Tiedje, James M.

    2008-01-01

    Microbial enumeration, 16S rRNA gene clone libraries, and chemical analysis were used to evaluate the in situ biological reduction and immobilization of uranium(VI) in a long-term experiment (more than 2 years) conducted at a highly uranium-contaminated site (up to 60 mg/liter and 800 mg/kg solids) of the U.S. Department of Energy in Oak Ridge, TN. Bioreduction was achieved by conditioning groundwater above ground and then stimulating growth of denitrifying, Fe(III)-reducing, and sulfate-reducing bacteria in situ through weekly injection of ethanol into the subsurface. After nearly 2 years of intermittent injection of ethanol, aqueous U levels fell below the U.S. Environmental Protection Agency maximum contaminant level for drinking water and groundwater (reducers were detected, including Desulfovibrio, Geobacter, Anaeromyxobacter, Desulfosporosinus, and Acidovorax spp. The predominant sulfate-reducing bacterial species were Desulfovibrio spp., while the iron reducers were represented by Ferribacterium spp. and Geothrix spp. Diversity-based clustering revealed differences between treated and untreated zones and also within samples of the treated area. Spatial differences in community structure within the treatment zone were likely related to the hydraulic pathway and to electron donor metabolism during biostimulation. PMID:18456853

  5. [UO2(NH3)5]Br2·NH3: synthesis, crystal structure, and speciation in liquid ammonia solution by first-principles molecular dynamics simulations.

    Science.gov (United States)

    Woidy, Patrick; Bühl, Michael; Kraus, Florian

    2015-04-28

    Pentaammine dioxido uranium(VI) dibromide ammonia (1/1), [UO2(NH3)5]Br2·NH3, was synthesized in the form of yellow crystals by the reaction of uranyl bromide, UO2Br2, with dry liquid ammonia. The compound crystallizes orthorhombic in space group Cmcm and is isotypic to [UO2(NH3)5]Cl2·NH3 with a = 13.2499(2), b = 10.5536(1), c = 8.9126(1) Å, V = 1246.29(3) Å(3) and Z = 4 at 123 K. The UO2(2+) cation is coordinated by five ammine ligands and the coordination polyhedron can be best described as pentagonal bipyramid. Car-Parrinello molecular dynamics simulations are reported for [UO2(NH3)5](2+) in the gas phase and in liquid NH3 solution (using the BLYP density functional). According to free-energy simulations, solvation by ammonia has only a small effect on the uranyl-NH3 bond strength.

  6. Polyaniline (PANI) modified bentonite by plasma technique for U(VI) removal from aqueous solution

    International Nuclear Information System (INIS)

    Liu, Xinghao; Cheng, Cheng; Xiao, Chengjian; Shao, Dadong; Xu, Zimu; Wang, Jiaquan; Hu, Shuheng; Li, Xiaolong; Wang, Weijuan

    2017-01-01

    Highlights: • PANI/bentonie can be synthesized by simple plasma technique. • PANI/bentonie has an excellent adsorption capacity for trace uranium in solution. • U(VI) adsorption on PANI/bentonite is a spontaneous and endothermic process. - Abstract: Polyaniline (PANI) modified bentonite (PANI/bentonie) was synthesized by plasma induced polymerization of aniline on bentonite surface, and applied to uptake of uranium(VI) ions from aqueous solution. The as-synthesized PANI/bentonie was characterized by scanning electron microscopy (SEM), powder X-ray diffraction (XRD), thermal gravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS). Batch adsorption technique was utilized to investigate the adsorption of U(VI) on bentonite and PANI/bentonite. The adsorption of U(VI) (10 mg/L) on PANI/bentonite surface is fairly depend on solution pH, ionic strength, and temperature in solution. The modified PANI on PANI/bentonite surface significantly enhances its adsorption capability for U(VI). The presence of humic acid (HA) can sound enhance U(VI) adsorption on PANI/bentonite at pH 6.5. According to the thermodynamic parameters, the adsorption of U(VI) on PANI/bentonite surface is a spontaneous and endothermic process. The results highlight the application of PANI/bentonite composites as candidate material for the uptake of trace U(VI) from aqueous solution.

  7. Synthesis and characterization of an N-(2-hydroxyethyl)-ethylenediaminetriacetic acid resin

    International Nuclear Information System (INIS)

    Lai, Y.F.

    1977-10-01

    A chelating ion-exchange resin with N-(2-hydroxyethyl)ethylene-diaminetriacetic acid (HEDTA) used as the ligand chemically bonded to XAD-4 by an ester linkage, HEDTA-4, was synthesized. It is stable under normal experimental conditions with the liquid chromatograph. The structure of the resin was confirmed by an infrared spectrum, and by potentiometric titrations. The capacity of the resin was also obtained by potentiometric titration and by a nitrogen analysis. The resin was used to pack a column of 5 mm internal diameter and 5 cm long. The effect of pH on the retention of different metal ions on the resin was studied. It was found that the resin was most selective for chromium(III), copper(II), lead(II), mercury(II), uranium(VI), zirconium(IV) and zinc(II) at a pH of less than 3. Furthermore, the resin proves to be functioning with a chelating mechanism rather than ion-exchange, and it can concentrate trace metal ions in the presence of a large excess of calcium and magnesium. This makes the resin potentially useful for purifying and analyzing drinking water

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

    Science.gov (United States)

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

    2015-03-28

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

  9. Comparative density functional study of the complexes [UO2(CO3)3]4- and [(UO2)3(CO3)6]6- in aqueous solution.

    Science.gov (United States)

    Schlosser, Florian; Moskaleva, Lyudmila V; Kremleva, Alena; Krüger, Sven; Rösch, Notker

    2010-06-28

    With a relativistic all-electron density functional method, we studied two anionic uranium(VI) carbonate complexes that are important for uranium speciation and transport in aqueous medium, the mononuclear tris(carbonato) complex [UO(2)(CO(3))(3)](4-) and the trinuclear hexa(carbonato) complex [(UO(2))(3)(CO(3))(6)](6-). Focusing on the structures in solution, we applied for the first time a full solvation treatment to these complexes. We approximated short-range effects by explicit aqua ligands and described long-range electrostatic interactions via a polarizable continuum model. Structures and vibrational frequencies of "gas-phase" models with explicit aqua ligands agree best with experiment. This is accidental because the continuum model of the solvent to some extent overestimates the electrostatic interactions of these highly anionic systems with the bulk solvent. The calculated free energy change when three mono-nuclear complexes associate to the trinuclear complex, agrees well with experiment and supports the formation of the latter species upon acidification of a uranyl carbonate solution.

  10. Sorption and desorption reactions of radionuclides with a crushed basalt-bentonite packing material

    International Nuclear Information System (INIS)

    Barney, G.S.; Lane, D.L.; Allen, C.C.; Jones, T.E.

    1985-04-01

    Current design of waste packages for disposal of high-level radioactive wastes in underground basalt formations includes a layer of packing material that surrounds the waste container. One of the functions of this material is to limit the release of radionuclides from a breached container into groundwater by providing a low hydraulic conductivity zone and by sorbing dissolved radionuclides. The objective of this study was to assess the radionuclide sorption capability of a proposed packing material composed of 25% sodium bentonite and 75% crushed basalt (by weight). Sorption and desorption reactions of several important waste radioelements (neptunium, uranium, plutonium, technetium, selenium, and radium) were investigated in the absence of air at 90 0 C. Uranium and neptunium were sorbed by slow reactions that follow first-order kinetics. The reaction rates are probably controlled by reduction of weakly sorbed uranium(VI) and neptunium(V) by ferrous iron in the crushed basalt component. Technetium(VII) was not reduced or sorbed under these conditions. Freundlich sorption and desorption isotherms for a given radionuclide were non-singular and show a strong tendency for sorption hysteresis. Applying the isotherm data to a one-dimensional transport model indicated that hysteretic sorption on the packing material provides an important safety factor in controlling releases of some radionuclides

  11. Isolation and characterization of a uranium(VI)-nitride triple bond

    Science.gov (United States)

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

    2013-06-01

    The nature and extent of covalency in uranium bonding is still unclear compared with that of transition metals, and there is great interest in studying uranium-ligand multiple bonds. Although U=O and U=NR double bonds (where R is an alkyl group) are well-known analogues to transition-metal oxo and imido complexes, the uranium(VI)-nitride triple bond has long remained a synthetic target in actinide chemistry. Here, we report the preparation of a uranium(VI)-nitride triple bond. We highlight the importance of (1) ancillary ligand design, (2) employing mild redox reactions instead of harsh photochemical methods that decompose transiently formed uranium(VI) nitrides, (3) an electrostatically stabilizing sodium ion during nitride installation, (4) selecting the right sodium sequestering reagent, (5) inner versus outer sphere oxidation and (6) stability with respect to the uranium oxidation state. Computational analyses suggest covalent contributions to U≡N triple bonds that are surprisingly comparable to those of their group 6 transition-metal nitride counterparts.

  12. Sorption of uranium on rocks in anaerobic groundwater

    International Nuclear Information System (INIS)

    Hakanen, M.

    1992-12-01

    Spent nuclear fuel contains substantial amounts of long lived isotopes of actinoide elements, the most abundant of which is the oxide from uranium in the fuel matrix. The behaviour of uranium, also present in small concentrations in natural rocks and waters, is redox sensitive. The concentration controlling mechanisms in groundwaters of uranium are not well-known. In this work a series of laboratory experiments was made to study the redox and sorption behaviour of uranium under anaerobic conditions. The experiments indicated that a part of uranium(VI) was reduced to uranium(IV). The sorbed uranium was of mixed oxidation states. The redox potential of water was not an appropriate indicator of the U(IV)/U(VI) ratio. Spiking of the water with the U(IV) was followed by very strong sorption. The derived lower limit (conservative) and the realistic mass distribution ratios (R d ) for U(IV) are 0.7 m 3 /kg and 3.5 m 3 /kg. (orig.)

  13. Polyaniline (PANI) modified bentonite by plasma technique for U(VI) removal from aqueous solution

    Science.gov (United States)

    Liu, Xinghao; Cheng, Cheng; Xiao, Chengjian; Shao, Dadong; Xu, Zimu; Wang, Jiaquan; Hu, Shuheng; Li, Xiaolong; Wang, Weijuan

    2017-07-01

    Polyaniline (PANI) modified bentonite (PANI/bentonie) was synthesized by plasma induced polymerization of aniline on bentonite surface, and applied to uptake of uranium(VI) ions from aqueous solution. The as-synthesized PANI/bentonie was characterized by scanning electron microscopy (SEM), powder X-ray diffraction (XRD), thermal gravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS). Batch adsorption technique was utilized to investigate the adsorption of U(VI) on bentonite and PANI/bentonite. The adsorption of U(VI) (10 mg/L) on PANI/bentonite surface is fairly depend on solution pH, ionic strength, and temperature in solution. The modified PANI on PANI/bentonite surface significantly enhances its adsorption capability for U(VI). The presence of humic acid (HA) can sound enhance U(VI) adsorption on PANI/bentonite at pH 6.5. According to the thermodynamic parameters, the adsorption of U(VI) on PANI/bentonite surface is a spontaneous and endothermic process. The results highlight the application of PANI/bentonite composites as candidate material for the uptake of trace U(VI) from aqueous solution.

  14. LabVIEW-based sequential-injection analysis system for the determination of trace metals by square-wave anodic and adsorptive stripping voltammetry on mercury-film electrodes.

    Science.gov (United States)

    Economou, Anastasios; Voulgaropoulos, Anastasios

    2003-01-01

    The development of a dedicated automated sequential-injection analysis apparatus for anodic stripping voltammetry (ASV) and adsorptive stripping voltammetry (AdSV) is reported. The instrument comprised a peristaltic pump, a multiposition selector valve and a home-made potentiostat and used a mercury-film electrode as the working electrodes in a thin-layer electrochemical detector. Programming of the experimental sequence was performed in LabVIEW 5.1. The sequence of operations included formation of the mercury film, electrolytic or adsorptive accumulation of the analyte on the electrode surface, recording of the voltammetric current-potential response, and cleaning of the electrode. The stripping step was carried out by applying a square-wave (SW) potential-time excitation signal to the working electrode. The instrument allowed unattended operation since multiple-step sequences could be readily implemented through the purpose-built software. The utility of the analyser was tested for the determination of copper(II), cadmium(II), lead(II) and zinc(II) by SWASV and of nickel(II), cobalt(II) and uranium(VI) by SWAdSV.

  15. Annual Report 2010. Institute of Radiochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Bernhard, G. (ed.)

    2011-10-26

    The Institute of Radiochemistry is one of the six research institutes of the Helmholtz center Dresden-Rossendorf. The report covers contributions in two parts. Part 1; long-lived radionuclides in biosystems: Several contributions concern the determination of formation and structures of various uranium, americium, and curium complexes with relevant organic and inorganic ligands. First results about the dependency of uranium(VI) complexation with small organic ligands at elevated temperatures were achieved. New insights in the mechanisms of luminescence quenching of uranyl complexes by density functional theory calculations are reported. Bacteria, algae, and fungi can influence the mobilization or immobilization of heavy metals in water and soils. Part II: long-lived radionuclides at permanent disposal sites. Several contributions report research on the behavior of biofilms in uranium contaminated sites. To describe the aqueous transport of actinides and other long-lived radionuclides the dominating processes on the liquid/solid interfaces must be considered. Interesting results about the sorption and surface complexation of different metals (long-lived radionuclides) during interaction with various mineral surfaces, and colloids were achieved. Substantial progress was made on knowledge about the visualization and quantification of fluid flow in salt rock formations by using positron emission tomography.

  16. Structural determination of individual chemical species in a mixed system by iterative transformation factor analysis-based X-ray absorption spectroscopy combined with UV-visible absorption and quantum chemical calculation.

    Science.gov (United States)

    Ikeda, Atsushi; Hennig, Christoph; Rossberg, André; Tsushima, Satoru; Scheinost, Andreas C; Bernhard, Gert

    2008-02-15

    A multitechnique approach using extended X-ray absorption fine structure (EXAFS) spectroscopy based on iterative transformation factor analysis (ITFA), UV-visible absorption spectroscopy, and density functional theory (DFT) calculations has been performed in order to investigate the speciation of uranium(VI) nitrate species in acetonitrile and to identify the complex structure of individual species in the system. UV-visible spectral titration suggests that there are four different species in the system, that is, pure solvated species, mono-, di-, and trinitrate species. The pure EXAFS spectra of these individual species are extracted by ITFA from the measured spectral mixtures on the basis of the speciation distribution profile calculated from the UV-visible data. Data analysis of the extracted EXAFS spectra, with the help of DFT calculations, reveals the most probable complex structures of the individual species. The pure solvated species corresponds to a uranyl hydrate complex with an equatorial coordination number (CNeq) of 5, [UO2(H2O)5]2+. Nitrate ions tend to coordinate to the uranyl(VI) ion in a bidentate fashion rather than a unidentate one in acetonitrile for all the nitrate species. The mononitrate species forms the complex of [UO2(H2O)3NO3]+ with a CNeq value of 5, while the di- and trinitrate species have a CNeq value of 6, corresponding to [UO2(H2O)2(NO3)2]0 (D2h) and [UO2(NO3)3]- (D3h), respectively.

  17. Microbial reductive transformation of phyllosilicate Fe(III) and U(VI) in fluvial subsurface sediments.

    Science.gov (United States)

    Lee, Ji-Hoon; Fredrickson, James K; Kukkadapu, Ravi K; Boyanov, Maxim I; Kemner, Kenneth M; Lin, Xueju; Kennedy, David W; Bjornstad, Bruce N; Konopka, Allan E; Moore, Dean A; Resch, Charles T; Phillips, Jerry L

    2012-04-03

    The microbial reduction of Fe(III) and U(VI) was investigated in shallow aquifer sediments collected from subsurface flood deposits near the Hanford Reach of the Columbia River in Washington State. Increases in 0.5 N HCl-extractable Fe(II) were observed in incubated sediments and (57)Fe Mössbauer spectroscopy revealed that Fe(III) associated with phyllosilicates and pyroxene was reduced to Fe(II). Aqueous uranium(VI) concentrations decreased in subsurface sediments incubated in sulfate-containing synthetic groundwater with the rate and extent being greater in sediment amended with organic carbon. X-ray absorption spectroscopy of bioreduced sediments indicated that 67-77% of the U signal was U(VI), probably as an adsorbed species associated with a new or modified reactive mineral phase. Phylotypes within the Deltaproteobacteria were more common in Hanford sediments incubated with U(VI) than without, and in U(VI)-free incubations, members of the Clostridiales were dominant with sulfate-reducing phylotypes more common in the sulfate-amended sediments. These results demonstrate the potential for anaerobic reduction of phyllosilicate Fe(III) and sulfate in Hanford unconfined aquifer sediments and biotransformations involving reduction and adsorption leading to decreased aqueous U concentrations.

  18. Synthesis of iminodi(methylphosphonic acid)-type chitosan resin and its adsorption behavior for trace metals

    International Nuclear Information System (INIS)

    Yamakawa, Satoko; Oshita, Koji; Sabarudin, Akhmad; Oshima, Mitsuko; Motomizu, Shoji

    2004-01-01

    A chitosan-based resin possessing the iminodi(methyphosphonic acid) moiety (IDP-type chitrosan resin) was synthesized by using cross-linked chitosan as a base material. The adsorption behavior of trace metal ions on the IDP-type chitosan resin was systematically investigated using a mini-column (1 ml of the resin) packed with the resin. The concentrations of metal ions in the effluents were measured by ICP-MS and ICP-AES. The resin could adsorb four metals, such as In(III), Sn(II), Th(IV), and U(VI), by almost 100% over a wide pH range (1-7). Uranium(VI) and thorium could not be eluted with nitric acid and hydrochloric acid (1-6 M); other metal ions were easily and readily eluted with 1 M nitric acid. The IDP-type chitosan resin synthesized in this work can be applied to the separation of U(VI) and Th(IV) from other metal ions. (author)

  19. Complexation studies of actinides (U, Pu, Am) with linear polyamino-carboxylate ligands and sidero-chelates

    International Nuclear Information System (INIS)

    Nguyen, L.V.

    2010-01-01

    As part of our research endeavour aimed at developing and improving decontamination processes of wastewater containing alpha emitters, physico-chemical complexation studies of actinides (U, Pu, Am) with organic open-chain ligands such as poly-aminocarboxylic acids (H 4 EDTA) and sidero-chelates (di-hydroxamic acids and desferrioxamine B) have been carried out. Gaining a clear understanding of the coordination properties of the targeted actinides is an essential step towards the selection of the most appropriate chelating agents that will exhibit high uptake efficiencies. EXAFS (Extended X-ray Absorption Fine Structure) measurements at the ESRF synchrotron enabled to elucidate the coordination scheme of uranium and plutonium complexes. Solution thermodynamic investigations were intended to provide valuable information about the nature and the stability of the uranium(VI) and americium(III) complexes prevailing at a given pH in solution. The set of stability constants determined from potentiometric and UV-visible spectrophotometric titrations, allowed to predict the speciation of the selected actinides in presence of the aforementioned ligands and to determine the pH range required for achieving 'ultimate' decontamination. (author) [fr

  20. Uranium in drinking water. A simple determination of uranium (VI) according to DIN standard 38406-17

    International Nuclear Information System (INIS)

    Haug, Sandro

    2009-01-01

    The number of reports on uranium loads in tap water and drinking water increases. Already for years, the organization Foodwatch e.V. (Berlin, Federal Republic of Germany) warns about to high concentrations of uranium in tap water. So far, only a limit value for mineral water exists in the Mineral Water Regulation which is suitable for the production of infant diet. This limit value amounts 2 microgram per litre. Temporarily, also in the policy a national limit value for uranium in drinking water is introduced. The Federal Office for Environment Protection (Dessau, FRG) designates a value of ten microgram uranium per litre of drinking water and mineral water as an approximate value. The effective control of water quality presupposes high-performance, simple and economical analysis methods. A particularly well suitable measuring technique for the determination of uranium(VI) in groundwater, raw water and drinking water is the voltammetry. In the last years, a national standard was compiled based on this measuring technique: DIN standard 38406-17

  1. Polyaniline (PANI) modified bentonite by plasma technique for U(VI) removal from aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Xinghao [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900 (China); Intelligent Manufacturing Technology Research Institute, Hefei University of Technology, Hefei 230088 (China); Cheng, Cheng [Institute of Plasma Physics, Chinese Academy of Sciences, Hefei 230031 (China); Xiao, Chengjian, E-mail: xiaocj@caep.cn [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900 (China); Shao, Dadong, E-mail: shaodadong@126.com [Institute of Plasma Physics, Chinese Academy of Sciences, Hefei 230031 (China); Xu, Zimu, E-mail: xzm@mail.ustc.edu.cn [Intelligent Manufacturing Technology Research Institute, Hefei University of Technology, Hefei 230088 (China); Wang, Jiaquan; Hu, Shuheng [Intelligent Manufacturing Technology Research Institute, Hefei University of Technology, Hefei 230088 (China); Li, Xiaolong; Wang, Weijuan [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900 (China)

    2017-07-31

    Highlights: • PANI/bentonie can be synthesized by simple plasma technique. • PANI/bentonie has an excellent adsorption capacity for trace uranium in solution. • U(VI) adsorption on PANI/bentonite is a spontaneous and endothermic process. - Abstract: Polyaniline (PANI) modified bentonite (PANI/bentonie) was synthesized by plasma induced polymerization of aniline on bentonite surface, and applied to uptake of uranium(VI) ions from aqueous solution. The as-synthesized PANI/bentonie was characterized by scanning electron microscopy (SEM), powder X-ray diffraction (XRD), thermal gravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS). Batch adsorption technique was utilized to investigate the adsorption of U(VI) on bentonite and PANI/bentonite. The adsorption of U(VI) (10 mg/L) on PANI/bentonite surface is fairly depend on solution pH, ionic strength, and temperature in solution. The modified PANI on PANI/bentonite surface significantly enhances its adsorption capability for U(VI). The presence of humic acid (HA) can sound enhance U(VI) adsorption on PANI/bentonite at pH < 6.5 because of the strong complexation, and inhibits U(VI) adsorption at pH > 6.5. According to the thermodynamic parameters, the adsorption of U(VI) on PANI/bentonite surface is a spontaneous and endothermic process. The results highlight the application of PANI/bentonite composites as candidate material for the uptake of trace U(VI) from aqueous solution.

  2. In situ spectroscopy and spectroelectrochemistry of uranium in high-temperature alkali chloride molten salts.

    Science.gov (United States)

    Polovov, Ilya B; Volkovich, Vladimir A; Charnock, John M; Kralj, Brett; Lewin, Robert G; Kinoshita, Hajime; May, Iain; Sharrad, Clint A

    2008-09-01

    Soluble uranium chloride species, in the oxidation states of III+, IV+, V+, and VI+, have been chemically generated in high-temperature alkali chloride melts. These reactions were monitored by in situ electronic absorption spectroscopy. In situ X-ray absorption spectroscopy of uranium(VI) in a molten LiCl-KCl eutectic was used to determine the immediate coordination environment about the uranium. The dominant species in the melt was [UO 2Cl 4] (2-). Further analysis of the extended X-ray absorption fine structure data and Raman spectroscopy of the melts quenched back to room temperature indicated the possibility of ordering beyond the first coordination sphere of [UO 2Cl 4] (2-). The electrolytic generation of uranium(III) in a molten LiCl-KCl eutectic was also investigated. Anodic dissolution of uranium metal was found to be more efficient at producing uranium(III) in high-temperature melts than the cathodic reduction of uranium(IV). These high-temperature electrolytic processes were studied by in situ electronic absorption spectroelectrochemistry, and we have also developed in situ X-ray absorption spectroelectrochemistry techniques to probe both the uranium oxidation state and the uranium coordination environment in these melts.

  3. Effects of organic degradation products on the sorption of actinides

    International Nuclear Information System (INIS)

    Baston, G.M.N.; Berry, J.A.; Bond, K.A.; Brownsword, M.; Linklater, C.M.

    1992-01-01

    Previous work has shown that products from the chemical degradation of cellulosic matter can significantly reduce sorption of uranium(VI) and plutonium(IV) on geological materials. Uranium(IV) batch sorption experiments have now been performed to study the effect of organic degradation products in a reducing environment. Thorium(IV) sorption has also been studied since thorium is an important radioelement in its own right and has potential use as a simulant for other tetravalent actinides. Sorption onto London clay, Caithness flagstones and St. Bees sandstone was investigated. Experimental conditions were chosen to simulate both those expected close to cementitious repository (pH ∝ 11) and at the edge of the zone of migration of the alkaline plume (pH ∝ 8). Work was carried out with both authentic degradation products and with gluconate, acting as a well-characterized simulant for cellulosic degradation products. The results show that the presence of organic species can cause a reduction in sorption. This is especially so in the presence of a high concentration of gluconate ions, but the reduction is significantly less with authentic degradation products. (orig.)

  4. Effects of organic degradation products on the sorption of actinides

    Energy Technology Data Exchange (ETDEWEB)

    Baston, G.M.N.; Berry, J.A.; Bond, K.A.; Brownsword, M.; Linklater, C.M. (AEA Decommissioning and Radwaste, Harwell Lab. (United Kingdom))

    1992-01-01

    Previous work has shown that products from the chemical degradation of cellulosic matter can significantly reduce sorption of uranium(VI) and plutonium(IV) on geological materials. Uranium(IV) batch sorption experiments have now been performed to study the effect of organic degradation products in a reducing environment. Thorium(IV) sorption has also been studied since thorium is an important radioelement in its own right and has potential use as a simulant for other tetravalent actinides. Sorption onto London clay, Caithness flagstones and St. Bees sandstone was investigated. Experimental conditions were chosen to simulate both those expected close to cementitious repository (pH [proportional to] 11) and at the edge of the zone of migration of the alkaline plume (pH [proportional to] 8). Work was carried out with both authentic degradation products and with gluconate, acting as a well-characterized simulant for cellulosic degradation products. The results show that the presence of organic species can cause a reduction in sorption. This is especially so in the presence of a high concentration of gluconate ions, but the reduction is significantly less with authentic degradation products. (orig.).

  5. Coordination and solvent extraction behaviour of oxozirconium(IV), thorium(IV) and dioxouranium(VI)

    International Nuclear Information System (INIS)

    Dash, K.C.

    1989-01-01

    The systematic liquid-liquid extraction behaviour of oxozirconium (IV), thorium(IV) and dioxouranium(VI) have been investigated using a number of synthesised and commercial chelating extractants. The synergism or antagonism for these processes in presence of neutral donor ligands have also been identified and the conditions for separation and isolation of pure individual metal ions have been established. The coordination behaviour of oxozirconium(IV), thorium(IV) and dioxouranium(VI) with a large number of mono- and polydentate ligands have been studied. With oxozirconium(IV), invariably always a cyclic, tetranuclear species is obtained, derived from the tetrameric structure of the parent ZrOCl 2 .8H 2 O which is actually (Zr 4 (OH) 8 (H 2 O) 16 )Cl 8 .12H 2 O. No simple, monomeric oxozirconium(IV) complex was obtained. Uranium(VI) and thorium(IV) form a wide variety of complexes of higher coordination numbers and several bi- and trinuclear complexes were also characterised where the two adjacent metal centres are joined to each other by a double hydroxo-bridge. (author). 69 refs., 3 figs., 4 tabs

  6. Plutonium(VI) accumulation and reduction by lichen biomass: correlation with U(VI)

    International Nuclear Information System (INIS)

    Ohnuki, Toshihiko; Aoyagi, Hisao; Kitatsuji, Yoshihiro; Samadfam, Mohammad; Kimura, Yasuhiko; William Purvis, O.

    2004-01-01

    The uptake of plutonium(VI) and uranium(VI) by lichen biomass was studied in the foliose lichen Parmotrema tinctorum to elucidate the migration behavior of Pu and U in the terrestrial environment. Pu and U uptake by P. tinctorum averaged 0.040±0.010 and 0.055±0.015 g g dry -1 , respectively, after 96 h incubation with 4.0x10 -4 mol l -1 Pu solutions of pH 3, 4 and 5. SEM observations showed that the accumulated Pu is evenly distributed on the upper and lower surfaces of P. tinctorum, in contrast to U(VI), which accumulated in both cortical and medullary layers. UV/VIS absorption spectroscopy demonstrates that a fraction of Pu(VI) in the solution is reduced to Pu(V) by the organic substances released from P. tinctorum, and the accumulated Pu on the surface is reduced to Pu(IV), while U(VI) keeps the oxidation state of VI. Since the solubility of Pu(IV) hydroxides is very low, reduced Pu(VI) does not penetrate to the medullary layers, but is probably precipitated as Pu(IV) hydroxides on the cortical lichen surface. It is concluded that the uptake and reduction of Pu(VI) by lichens is important to determine the mobilization and oxidation states of Pu in the terrestrial environment

  7. Development of reliable analytical method for extraction and separation of thorium(IV) by Cyanex 272 in kerosene

    International Nuclear Information System (INIS)

    Madane, N.S.; Mohite, B.S.

    2011-01-01

    A simple and selective spectrophotometric method has been developed for the extraction and separation of thorium(IV) from sodium salicylate media using Cyanex 272 in kerosene. Thorium(IV) was quantitatively extracted by 5 x 10 -4 M Cyanex 272 in kerosene from 1 x 10 -5 M sodium salicylate medium. The extracted thorium(IV) was stripped out quantitatively from the organic phase with 4.0 M hydrochloric acid and determined spectrophotometrically with arsenazo(III) at 620 nm. The effect of concentrations of sodium salicylate, extractant, diluents, metal ion and strippants has been studied. Separation of thorium(IV) from other elements was achieved from binary as well as multicomponent mixtures such as uranium(VI), strontium(II), rubidium(I), cesium(I), potassium(I), Sodium(I), lithium(I), lead(II), barium(II), beryllium(II) etc. Using this method separation and determination of thorium(IV) in geological and real samples has been carried out. The method is simple, rapid and selective with good reproducibility (approximately ±2%). (author)

  8. Mineral solubility and free energy controls on microbial reaction kinetics: Application to contaminant transport in the subsurface

    Energy Technology Data Exchange (ETDEWEB)

    Taillefert, Martial [Georgia Inst. of Technology, Atlanta, GA (United States); Van Cappellen, Philippe [Univ. of Waterloo, ON (Canada)

    2016-11-14

    Recent developments in the theoretical treatment of geomicrobial reaction processes have resulted in the formulation of kinetic models that directly link the rates of microbial respiration and growth to the corresponding thermodynamic driving forces. The overall objective of this project was to verify and calibrate these kinetic models for the microbial reduction of uranium(VI) in geochemical conditions that mimic as much as possible field conditions. The approach combined modeling of bacterial processes using new bioenergetic rate laws, laboratory experiments to determine the bioavailability of uranium during uranium bioreduction, evaluation of microbial growth yield under energy-limited conditions using bioreactor experiments, competition experiments between metabolic processes in environmentally relevant conditions, and model applications at the field scale. The new kinetic descriptions of microbial U(VI) and Fe(III) reduction should replace those currently used in reactive transport models that couple catabolic energy generation and growth of microbial populations to the rates of biogeochemical redox processes. The above work was carried out in collaboration between the groups of Taillefert (batch reactor experiments and reaction modeling) at Georgia Tech and Van Cappellen (retentostat experiments and reactive transport modeling) at University of Waterloo (Canada).

  9. Mass spectrometric studies of the complexing behaviour of actinide ions in solution

    International Nuclear Information System (INIS)

    Steppert, Michael

    2012-01-01

    As the long-term radiotoxicity of spent nuclear fuel is governed by Plutonium and the Minor Actinides, these elements are focussed on for investigations in the framework of safety assessment for nuclear waste repositories. To shed more light on the selectivity of the partitioning ligands BTP and BTBP towards the extraction of trivalent actinides, the complexes these ligands form with lanthanides in octanolic solution were characterized. The differences in the extraction efficiencies among the different lanthanides were traced back to the varying preferential formation of Ln(BTP)3 complexes, depending on the ionic radius of the lanthanides. Additionally it was shown that depending on the sterical demand of BTBP ligands nitrate anions coordinate in the first coordination shell of Eu(BTBP)2-complexes. As the behavior of Plutonium under geochemical conditions is of particular interest for the safety assessment of potential nuclear waste repositories, the second part of the thesis focuses on the hydrolysis and colloid formation behavior of aqueous Plutonium solutions. The solution species of Zirconium(IV) as analogue for Plutonium(IV) as well as of Uranium(VI) and Plutonium(VI) were characterized and quantified by means of electrospray ionization mass spectrometry. Moreover the colloid-induced reduction of Pu(V) to Pu(IV) and the subsequent formation of colloidal species was investigated. [de

  10. Linking Chaotic Advection with Subsurface Biogeochemical Processes

    Science.gov (United States)

    Mays, D. C.; Freedman, V. L.; White, S. K.; Fang, Y.; Neupauer, R.

    2017-12-01

    This work investigates the extent to which groundwater flow kinematics drive subsurface biogeochemical processes. In terms of groundwater flow kinematics, we consider chaotic advection, whose essential ingredient is stretching and folding of plumes. Chaotic advection is appealing within the context of groundwater remediation because it has been shown to optimize plume spreading in the laminar flows characteristic of aquifers. In terms of subsurface biogeochemical processes, we consider an existing model for microbially-mediated reduction of relatively mobile uranium(VI) to relatively immobile uranium(IV) following injection of acetate into a floodplain aquifer beneath a former uranium mill in Rifle, Colorado. This model has been implemented in the reactive transport code eSTOMP, the massively parallel version of STOMP (Subsurface Transport Over Multiple Phases). This presentation will report preliminary numerical simulations in which the hydraulic boundary conditions in the eSTOMP model are manipulated to simulate chaotic advection resulting from engineered injection and extraction of water through a manifold of wells surrounding the plume of injected acetate. This approach provides an avenue to simulate the impact of chaotic advection within the existing framework of the eSTOMP code.

  11. The extraction of trace amounts of tantalum(V) from different mineral acid solutions by 4-(5-nonyl) pyridine oxide and trioctylamine oxide

    International Nuclear Information System (INIS)

    Ejaz, M.; Carswell, D.J.

    1976-01-01

    Data are presented on the distribution of trace amounts of tantalum(V) between different mineral acid solutions and 0.1M solutions of N-oxides of 4-(5-nonyl) pyridine and trioctylamine. The optimal acidity is 0.01-0.5M, depending on the nature of the acid. Common anions have little effect on extraction. Possible mechanism of extraction are suggested making use of slope analysis data. Separation factors for a number of metal ions with respect to tantalum are reported for the 0.1M 4-(5-nonyl)pyridine oxide - 1M sulphuric acid extraction system. Separation from uranium(VI), thorium(IV) and a number of fission products is suggested. The conclusions are unique as follows: Amine oxides are as unique as oxygen-donor extractants in their extraction of tantalum(V) from weakly acid solutions; tantalum is almost completely extracted from weakly nitric, hydrochloric and sulphuric acid solutions by both of the amine oxides; the extraction in low acidity solutions is independent of the nature of the anion of the acids present, indicating the ability of amine oxides to extract the product of hydrolysis of hydrolysable elements. In this respect amine oxides are much better than tributyl phosphate. (T.G.)

  12. Lithium alkyl anions of uranium(IV) and uranium(V)

    International Nuclear Information System (INIS)

    Sigurdson, E.R.; Wilkinson, G.

    1977-01-01

    Organouranium compounds with six or eight uranium-to-carbon sigma-bonds have been synthesized for the first time. The interaction of uranium tetrachloride with lithium alkyls in diethyl ether leads to the isolation of unstable lithium alkyluranate(IV) compounds of stoicheiometry Li 2 UR 6 .8Et 2 0 (R = Me, CH 2 SiMe 3 . Ph, and o-Me 2 NCH 2 C 6 H 4 ). These lithium salts can also be obtained with other donor solvents, such as tetrahydrofuran or NNN'N'-tetramethylethylenediamine. From uranium pentaethoxide similar lithium salts of stoicheiometry Li 3 UR 8 .3 dioxan (R = Me, CH 2 CMe 3 , and CH 2 SiMe 3 ) can be obtained. The interaction of uranium(VI) hexaisopropoxide with lithium, magnesium, or aluminium alkyls does not give compounds containing U-C bonds, but green oils, e.g. U(OPrsup(i)) 6 (MgMe 2 ) 3 , that appear to be adducts in which the oxygen atom of the isopropoxide group bound to uranium is acting as a donor. I.r. and n.m.r. spectroscopy and analytical data for the new compounds are presented. (author)

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

    International Nuclear Information System (INIS)

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

    1987-01-01

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

  14. Enzymatic U(VI) reduction by Desulfosporosinus species

    International Nuclear Information System (INIS)

    Suzuki, Y.; Kelly, S.D.; Kemner, K.M.; Banfield, J.F.

    2004-01-01

    Here we tested U(VI) reduction by a Desulfosporosinus species (sp.) isolate and type strain (DSM 765) in cell suspensions (pH 7) containing 1 mM U(VI) and lactate, under an atmosphere containing N 2 -CO 2 -H 2 (90: 5: 5). Although neither Desulfosporosinus species (spp.) reduced U(VI) in cell suspensions with 0.25% Na-bicarbonate or 0.85% NaCl, U(VI) was reduced in these solutions by a control strain, desulfovibrio desulfuricans (ATCC 642). However, both Desulfosporosinus strains reduced U(VI) in cell suspensions depleted in bicarbonate and NaCl. No U(VI) reduction was observed without lactate and H 2 electron donors or with heat-killed cells, indicating enzymatic U(VI) reduction. Uranium(VI) reduction by both strains was inhibited when 1 mM CuCl 2 was added to the cell suspensions. Because the Desulfosporosinus DSM 765 does not contain cytochrome c 3 used by Desulfovibrio spp. to reduce U(VI), Desulfosporosinus species reduce uranium via a different enzymatic pathway. (orig.)

  15. Highly efficient extraction and selective separation of uranium (VI) from transition metals using new class of undiluted ionic liquids based on H-phosphonate anions.

    Science.gov (United States)

    Zarrougui, Ramzi; Mdimagh, Raouf; Raouafi, Nourreddine

    2018-01-15

    In this paper, we report the development of an environmental friendly process to decontaminate uranium-containing ores and nuclear wastes by using non-fluorinated ionic liquids (ILs). The main advantages of this extraction process are the absence of any organic diluent and extra extraction agents added to the organic phase. Moreover, the process is cost-effective and maybe applied as a sustainable hydrometallurgical method to recover uranium. The distribution ratio (D U ) and the extraction efficiency (%E) of uranium(VI) (UO 2 2+ ) were found to be dependent on the acidity of the aqueous phase, the extraction time, the alkyl chain length in the ILs, the concentration of the aqueous feed and molar quantity of ILs. The D U value is higher than 600 and the %E is equal to 98.6% when [HNO 3 ]=7M. The extraction reactions follows a neutral partition or ionic exchange mechanism depending on nitric acid concentration. The nature of bonding in the extracted complexes was investigated by spectroscopic techniques. The potential use of Mor 1-8 -OP for the separation of UO 2 2+ from a mixture containing transition metal ions M n+ was also examined. The UO 2 2+ ions were separated and extracted efficiently. These ILs are promising candidates for the recovery and separation of uranium. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. Interaction of uranium with in situ anoxically generated magnetite on steel

    International Nuclear Information System (INIS)

    Rovira, Miquel; El Aamrani, Souad; Duro, Lara; Gimenez, Javier; Pablo, Joan de; Bruno, Jordi

    2007-01-01

    In the high level nuclear waste repository concept, spent nuclear fuel is designed to be encapsulated in steel canisters. Thus, it is necessary to study the influence of the steel and/or its corrosion products on the behaviour of the radionuclides released from the fuel. In this sense, the main objective of this work is to contribute to the knowledge of the influence of the steel and/or its corrosion products on the uranium(VI) retention. To this aim, magnetite (Fe 3 O 4 ) has been generated by anaerobic steel corrosion in an autoclave reactor at an overpressure of 8 atm of H 2 (g). After characterisation by X-ray diffraction (XRD), the obtained corroded steel coupons were contacted, at two different H 2 (g) pressures (1 atm and 7.6 atm), with a U(VI) solution. The evolution of the uranium concentration in solution is determined and a study of the composition of the coupons at the end of the experiments is carried out. The main conclusion obtained from this work is that magnetite generated on a steel coupon is able not only to retain uranium via sorption, but also to reduce hexavalent to tetravalent uranium in a higher extent than commercial magnetite, thus, providing an effective retardation path to the migration of uranium (and, potentially, other actinides) out of the repository

  17. Surface complexation models for uranium adsorption in the sub-surface environment

    International Nuclear Information System (INIS)

    Payne, T.E.

    2007-01-01

    Adsorption experiments with soil component minerals under a range of conditions are being used to develop models of uranium(VI) uptake in the sub-surface environment. The results show that adsorption of U on iron oxides and clay minerals is influenced by chemical factors including the pH, partial pressure of CO 2 , and the presence of ligands such as phosphate. Surface complexation models (SCMs) can be used to simulate U adsorption on these minerals. The SCMs are based on plausible mechanistic assumptions and describe the experimental data more adequately than Kd values or sorption isotherms. It is conceptually possible to simulate U sorption data on complex natural samples by combining SCMs for individual component minerals. This approach was used to develop a SCM for U adsorption to mineral assemblages from Koongarra (Australia), and produced a reasonable description of U uptake. In order to assess the applicability of experimental data to the field situation, in-situ measurements of U distributions between solid and liquid phases were undertaken at the Koongarra U deposit. This field partitioning data showed a satisfactory agreement with laboratory sorption data obtained under comparable conditions. (author)

  18. The application of iterative transformation factor analysis to resolve multi-component EXAFS spectra of uranium(6) complexes with acetic acid as a function of pH

    International Nuclear Information System (INIS)

    Robberg, A.; Reich, T.

    2002-01-01

    Synchrotron-based EXAFS spectroscopy is a powerful technique to obtain structural information on radionuclide complexes in solution. Depending on the chemical conditions of the samples several radionuclide species can coexist in the solution as is often the case for environmentally related samples. All radionuclide species, which may have different near-neighbour environments, contribute to the measured EXAFS signal. In order to isolate the EXAFS spectra of the individual species (pure spectral components), it is necessary, in a first step, to measure a series of samples where their composition is changed by variation of one physico-chemical parameter (e.g. pH, concentration, etc.). For the spectral decomposition it is necessary that the EXAFS signal change as a function of the chosen physico-chemical parameter. In a second step, the series of EXAFS spectra is analysed with Eigen analysis and Iterative Transformation Factor Analysis (ITFA). As a result of the ITFA one obtains: a) for each sample the relative concentration of the structural distinguishable species and b) their corresponding pure spectral components. From the information obtained in a), one can construct a speciation diagram. The pure spectral components contain the structural information of the individual species, which can be extracted by conventional EXAFS analysis. To evaluate our ITFA algorithm for EXAFS analysis of mixtures, we prepared a series of eight solution samples of 0.05 M uranium(VI) and 1 M acetate (Ac) in the pH range of 0.1 to 4.5. From thermodynamic constants it is known that under these conditions up to four species can occur: uranyl hydrate, and the 1:1, 1:2 and 1:3 complexes of uranyl acetate. The uranium L III -edge EXAFS spectra were measured at room temperature in transmission mode at the Rossendorf Beamline (ROBL) at the ESRF. The average bond length between uranium and the equatorial oxygen atoms (O eq ) increases from 2.40 to 2.46 angstrom with increasing pH. This increase

  19. Impact of the uranium (VI) speciation in mineralised urines on its extraction by calix[6]arene bearing hydroxamic groups used in chromatography columns.

    Science.gov (United States)

    Baghdadi, S; Bouvier-Capely, C; Ritt, A; Peroux, A; Fevrier, L; Rebiere, F; Agarande, M; Cote, G

    2015-11-01

    Actinides determination in urine samples is part of the analyses performed to monitor internal contamination in case of an accident or a terrorist attack involving nuclear matter. Mineralisation is the first step of any of these analyses. It aims at reducing the sample volume and at destroying all organic compounds present. The mineralisation protocol is usually based on a wet ashing step, followed by actinides co-precipitation and a furnace ashing step, before redissolution and the quantification of the actinides by the appropriate techniques. Amongst the existing methods to perform the actinides co-precipitation, alkali-earth (typically calcium) precipitation is widely used. In the present work, the extraction of uranium(VI), plutonium(IV) and americium(III) from the redissolution solutions (called "mineralised urines") on calix[6]arene columns bearing hydroxamic groups was investigated as such an extraction is a necessary step before their determination by ICP-MS or alpha spectrometry. Difficulties were encountered in the transfer of uranium(VI) from raw to mineralised urines, with yield of transfer ranging between 0% and 85%, compared to about 90% for Pu and Am, depending on the starting raw urines. To understand the origin of such a difficulty, the speciation of uranium (VI) in mineralised urines was investigated by computer simulation using the MEDUSA software and the associated HYDRA database, compiled with recently published data. These calculations showed that the presence of phosphates in the "mineralised urines" leads to the formation of strong uranyl-phosphate complexes (such as UO2HPO4) which compete with the uranium (VI) extraction by the calix[6]arene bearing hydroxamic groups. The extraction constant of uranium (VI) by calix[6]arene bearing hydroxamic groups was determined in a 0.04 mol L(-1) sodium nitrate solution (logK=4.86±0.03) and implemented in an extraction model taking into account the speciation in the aqueous phase. This model allowed to

  20. Solubility and dissolution kinetics study of uranium phosphates and vanadates: implications for the front end of the electronuclear cycle

    International Nuclear Information System (INIS)

    Cretaz, F.

    2013-01-01

    In the current context of restart of the nuclear energy, the needs in uranium are expected to increase significantly. Moreover, in a perspective of sustainable development, the exploitation, the treatment and the purification of uranium ores need to be optimized. It is thus necessary to determine reliable thermodynamic data (and especially solubility constants) for the systems of interest, especially uranium(VI) phosphates and vanadates. In this aim, a multi parametric study of the dissolution of meta-torbernite Cu 0.8 (H 3 O) 0.2 (UO 2 ) 2 (PO 4 ) 2.8 H 2 O, meta-autunite Ca(UO 2 ) 2 (PO 4 ) 2.6 H 2 O, meta-ankoleite K 2 (UO 2 ) 2 (PO 4 ) 2.6 H 2 O and carnotite K 2 (UO 2 ) 2 (VO 4 ) 2.3 H 2 O was undertaken. First, analogues of these four minerals were synthesized, based only on dry chemistry process for carnotite or on wet chemistry methods for the phosphate phases. They were then extensively characterized (in terms of structure, microstructure and chemical composition). It particularly highlighted the similar structures of such compounds. The anionic groups (PO 4 3- or V 2 O 8 6- ) and uranyl form parallel layers between which counter cations (Cu 2+ , Ca 2+ or K + ) and water molecules are inserted. However, the counter cations present in the interlayer space of the three phosphate phases present different lability. The synthetic phases were also compared to their natural analogues, except for meta-ankoleite, which allowed us to point out significant differences in the composition (presence of impurities in natural samples) and the morphology (grain size). The dissolution of these phases was then studied from a kinetic and thermodynamic point of view, through leaching tests in static and dynamic conditions, in various acid media (sulfuric, nitric and hydrochloric) and at different temperatures. In these conditions, the dissolution of meta-autunite was found to be un-congruent due to the precipitation of uranyl phosphate then avoiding the determination of

  1. Gene expression correlates with process rates quantified for sulfate- and Fe(III-reducing bacteria in U(VI-contaminated sediments

    Directory of Open Access Journals (Sweden)

    Denise M Akob

    2012-08-01

    Full Text Available Though iron- and sulfate-reducing bacteria are well known for mediating uranium(VI reduction in contaminated subsurface environments, quantifying the in situ activity of the microbial groups responsible remains a challenge. The objective of this study was to demonstrate the use of quantitative molecular tools that target mRNA transcripts of key genes related to Fe(III and sulfate reduction pathways in order to monitor these processes during in situ U(VI remediation in the subsurface. Expression of the Geobacteraceae-specific citrate synthase gene (gltA and the dissimilatory (bisulfite reductase gene (dsrA, were correlated with the activity of iron- or sulfate-reducing microorganisms, respectively, under stimulated bioremediation conditions in microcosms of sediments sampled from the U.S. Department of Energy’s Oak Ridge Integrated Field Research Challenge (OR-IFRC site at Oak Ridge, Tennessee. In addition, Geobacteraceae-specific gltA and dsrA transcript levels were determined in parallel with the predominant electron acceptors present in moderately and highly contaminated subsurface sediments from the OR-IFRC. Phylogenetic analysis of the cDNA generated from dsrA mRNA, sulfate-reducing bacteria-specific 16S rRNA, and gltA mRNA identified activity of specific microbial groups. Active sulfate reducers were members of the Desulfovibrio, Desulfobacterium, and Desulfotomaculum genera. Members of the subsurface Geobacter clade, closely related to uranium-reducing Geobacter uraniireducens and Geobacter daltonii, were the metabolically-active iron-reducers in biostimulated microcosms and in situ core samples. Direct correlation of transcripts and process rates demonstrated evidence of competition between the functional guilds in subsurface sediments. We further showed that active populations of Fe(III-reducing bacteria and sulfate-reducing bacteria are present in OR-IFRC sediments and are good potential targets for in situ bioremediation.

  2. Significant Association between Sulfate-Reducing Bacteria and Uranium-Reducing Microbial Communities as Revealed by a Combined Massively Parallel Sequencing-Indicator Species Approach▿ †

    Science.gov (United States)

    Cardenas, Erick; Wu, Wei-Min; Leigh, Mary Beth; Carley, Jack; Carroll, Sue; Gentry, Terry; Luo, Jian; Watson, David; Gu, Baohua; Ginder-Vogel, Matthew; Kitanidis, Peter K.; Jardine, Philip M.; Zhou, Jizhong; Criddle, Craig S.; Marsh, Terence L.; Tiedje, James M.

    2010-01-01

    Massively parallel sequencing has provided a more affordable and high-throughput method to study microbial communities, although it has mostly been used in an exploratory fashion. We combined pyrosequencing with a strict indicator species statistical analysis to test if bacteria specifically responded to ethanol injection that successfully promoted dissimilatory uranium(VI) reduction in the subsurface of a uranium contamination plume at the Oak Ridge Field Research Center in Tennessee. Remediation was achieved with a hydraulic flow control consisting of an inner loop, where ethanol was injected, and an outer loop for flow-field protection. This strategy reduced uranium concentrations in groundwater to levels below 0.126 μM and created geochemical gradients in electron donors from the inner-loop injection well toward the outer loop and downgradient flow path. Our analysis with 15 sediment samples from the entire test area found significant indicator species that showed a high degree of adaptation to the three different hydrochemical-created conditions. Castellaniella and Rhodanobacter characterized areas with low pH, heavy metals, and low bioactivity, while sulfate-, Fe(III)-, and U(VI)-reducing bacteria (Desulfovibrio, Anaeromyxobacter, and Desulfosporosinus) were indicators of areas where U(VI) reduction occurred. The abundance of these bacteria, as well as the Fe(III) and U(VI) reducer Geobacter, correlated with the hydraulic connectivity to the substrate injection site, suggesting that the selected populations were a direct response to electron donor addition by the groundwater flow path. A false-discovery-rate approach was implemented to discard false-positive results by chance, given the large amount of data compared. PMID:20729318

  3. Significant association between sulfate-reducing bacteria and uranium-reducing microbial communities as revealed by a combined massively parallel sequencing-indicator species approach.

    Science.gov (United States)

    Cardenas, Erick; Wu, Wei-Min; Leigh, Mary Beth; Carley, Jack; Carroll, Sue; Gentry, Terry; Luo, Jian; Watson, David; Gu, Baohua; Ginder-Vogel, Matthew; Kitanidis, Peter K; Jardine, Philip M; Zhou, Jizhong; Criddle, Craig S; Marsh, Terence L; Tiedje, James M

    2010-10-01

    Massively parallel sequencing has provided a more affordable and high-throughput method to study microbial communities, although it has mostly been used in an exploratory fashion. We combined pyrosequencing with a strict indicator species statistical analysis to test if bacteria specifically responded to ethanol injection that successfully promoted dissimilatory uranium(VI) reduction in the subsurface of a uranium contamination plume at the Oak Ridge Field Research Center in Tennessee. Remediation was achieved with a hydraulic flow control consisting of an inner loop, where ethanol was injected, and an outer loop for flow-field protection. This strategy reduced uranium concentrations in groundwater to levels below 0.126 μM and created geochemical gradients in electron donors from the inner-loop injection well toward the outer loop and downgradient flow path. Our analysis with 15 sediment samples from the entire test area found significant indicator species that showed a high degree of adaptation to the three different hydrochemical-created conditions. Castellaniella and Rhodanobacter characterized areas with low pH, heavy metals, and low bioactivity, while sulfate-, Fe(III)-, and U(VI)-reducing bacteria (Desulfovibrio, Anaeromyxobacter, and Desulfosporosinus) were indicators of areas where U(VI) reduction occurred. The abundance of these bacteria, as well as the Fe(III) and U(VI) reducer Geobacter, correlated with the hydraulic connectivity to the substrate injection site, suggesting that the selected populations were a direct response to electron donor addition by the groundwater flow path. A false-discovery-rate approach was implemented to discard false-positive results by chance, given the large amount of data compared.

  4. c-Type cytochrome-dependent formation of U(IV nanoparticles by Shewanella oneidensis.

    Directory of Open Access Journals (Sweden)

    Matthew J Marshall

    2006-09-01

    Full Text Available Modern approaches for bioremediation of radionuclide contaminated environments are based on the ability of microorganisms to effectively catalyze changes in the oxidation states of metals that in turn influence their solubility. Although microbial metal reduction has been identified as an effective means for immobilizing highly-soluble uranium(VI complexes in situ, the biomolecular mechanisms of U(VI reduction are not well understood. Here, we show that c-type cytochromes of a dissimilatory metal-reducing bacterium, Shewanella oneidensis MR-1, are essential for the reduction of U(VI and formation of extracellular UO(2 nanoparticles. In particular, the outer membrane (OM decaheme cytochrome MtrC (metal reduction, previously implicated in Mn(IV and Fe(III reduction, directly transferred electrons to U(VI. Additionally, deletions of mtrC and/or omcA significantly affected the in vivo U(VI reduction rate relative to wild-type MR-1. Similar to the wild-type, the mutants accumulated UO(2 nanoparticles extracellularly to high densities in association with an extracellular polymeric substance (EPS. In wild-type cells, this UO(2-EPS matrix exhibited glycocalyx-like properties and contained multiple elements of the OM, polysaccharide, and heme-containing proteins. Using a novel combination of methods including synchrotron-based X-ray fluorescence microscopy and high-resolution immune-electron microscopy, we demonstrate a close association of the extracellular UO(2 nanoparticles with MtrC and OmcA (outer membrane cytochrome. This is the first study to our knowledge to directly localize the OM-associated cytochromes with EPS, which contains biogenic UO(2 nanoparticles. In the environment, such association of UO(2 nanoparticles with biopolymers may exert a strong influence on subsequent behavior including susceptibility to oxidation by O(2 or transport in soils and sediments.

  5. Root uptake of uranium by a higher plant model (Phaseolus vulgaris) bioavailability from soil solution

    Energy Technology Data Exchange (ETDEWEB)

    Laroche, L.; Henner, P.; Camilleri, V.; Garnier-Laplace, J. [CEA Cadarache (DEI/SECRE/LRE), Laboratory of Radioecology and Ecotoxicology, Institute for Radioprotection and Nuclear Safety, 13 - Saint-Paul-lez-Durance (France)

    2004-07-01

    Uranium behaviour in soils is controlled by actions and interactions between physicochemical and biological processes that also determine its bioavailability. In soil solution, uranium(+VI) aqueous speciation undergoes tremendous changes mainly depending on pH, carbonates, phosphates and organic matter. In a first approach to identify bioavailable species of U to plants, cultures were performed using hydroponics, to allow an easy control of the composition of the exposure media. The latter, here an artificial soil solution, was designed to control the uranium species in solution. The geochemical speciation code JCHESS using a database compiled from the OECD/NEA thermochemical database project and verified was used to perform the solution speciation calculations. On this theoretical basis, three domains were defined for short-duration well-defined laboratory experiments in simplified conditions: pH 4.9, 5.8 and 7 where predicted dominant species are uranyl ions, hydroxyl complexes and carbonates respectively. For these domains, biokinetics and characterization of transmembrane transport according to a classical Michaelis Menten approach were investigated. The Free Ion Model (or its derived Biotic Ligand Model) was tested to determine if U uptake is governed by the free uranyl species or if other metal complexes can be assimilated. The effect of different variables on root assimilation efficiency and phyto-toxicity was explored: presence of ligands such as phosphates or carbonates and competitive ions such as Ca{sup 2+} at the 3 pH. According to previous experiments, uranium was principally located in roots whatever the pH and no difference in uranium uptake was evidenced between the main growth stages of the plant. Within the 3 studied chemical domains, results from short-term kinetics evidenced a linear correlation between total uranium concentration in bean roots and that in exposure media, suggesting that total uranium in soil solution could be a good predictor

  6. Influence of Bicarbonate, Sulfate, and Electron Donors on Biological reduction of Uranium and Microbial Community Composition

    Energy Technology Data Exchange (ETDEWEB)

    Luo, Wensui [ORNL; Zhou, Jizhong [ORNL; Wu, Weimin [ORNL; Yan, Tingfen [ORNL; Criddle, Craig [ORNL; Jardine, Philip M [ORNL; Gu, Baohua [ORNL

    2007-01-01

    A microcosm study was performed to investigate the effect of ethanol and acetate on uranium(VI) biological reduction and microbial community changes under various geochemical conditions. Each microcosm contained an uranium-contaminated sediment (up to 2.8 g U/kg) suspended in buffer with bicarbonate at concentrations of either 1 mM or 40 mM and sulfate at either 1.1 or 3.2 mM. Ethanol or acetate was used as an electron donor. Results indicate that ethanol yielded in significantly higher U(VI) reduction rates than acetate. A low bicarbonate concentration (1 mM) was favored for U(VI) bioreduction to occur in sediments, but high concentrations of bicarbonate (40 mM) and sulfate (3.2 mM) decreased the reduction rates of U(VI). Microbial communities were dominated by species from the Geothrix genus and Proteobacteria phylum in all microcosms. However, species in the Geobacteraceae family capable of reducing U(VI) were significantly enriched by ethanol and acetate in low bicarbonate buffer. Ethanol increased the population of unclassified Desulfuromonales, while acetate increased the population of Desulfovibrio. Additionally, species in the Geobacteraceae family were not enriched in high bicarbonate buffer, but the Geothrix and the unclassified Betaproteobacteria species were enriched. This study concludes that ethanol could be a better electron donor than acetate for reducing U(VI) under given experimental conditions, and electron donor and geoundwater geochemistry alter microbial communities responsible for U(VI) reduction.

  7. Influence of bicarbonate, sulfate, and electron donors on biological reduction of uranium and microbial community composition

    Energy Technology Data Exchange (ETDEWEB)

    Luo Wensui [Oak Ridge Inst. for Science and Education, TN (United States); Oak Ridge National Lab., TN (United States). Environmental Sciences Div.; Wu Wei-Min; Criddle, C.S. [Stanford Univ., CA (United States). Dept. of Civil and Environmental Engineering; Yan Tingfen [Oak Ridge Inst. for Science and Education, TN (United States); Jardine, P.M.; Gu Baohua [Oak Ridge National Lab., TN (United States). Environmental Sciences Div.; Zhou Jizhong [Oklahoma Univ., Norman, OK (United States). Dept. of Botany and Microbiology

    2007-12-15

    A microcosm study was performed to investigate the effect of ethanol and acetate on uranium(VI) biological reduction and microbial community changes under various geochemical conditions. Each microcosm contained an uranium-contaminated sediment (up to 2.8 g U/kg) suspended in buffer with bicarbonate at concentrations of either 1 or 40 mM and sulfate at either 1.1 or 3.2 mM. Ethanol or acetate was used as an electron donor. Results indicate that ethanol yielded in significantly higher U(VI) reduction rates than acetate. A low bicarbonate concentration (1 mM) was favored for U(VI) bioreduction to occur in sediments, but high concentrations of bicarbonate (40 mM) and sulfate (3.2 mM) decreased the reduction rates of U(VI). Microbial communities were dominated by species from the Geothrix genus and Proteobacteria phylum in all microcosms. However, species in the Geobacteraceae family capable of reducing U(VI) were significantly enriched by ethanol and acetate in low-bicarbonate buffer. Ethanol increased the population of unclassified Desulfuromonales, while acetate increased the population of Desulfovibrio. Additionally, species in the Geobacteraceae family were not enriched in high-bicarbonate buffer, but the Geothrix and the unclassified Betaproteobacteria species were enriched. This study concludes that ethanol could be a better electron donor than acetate for reducing U(VI) under given experimental conditions, and electron donor and groundwater geochemistry alter microbial communities responsible for U(VI) reduction. (orig.)

  8. Equilibrium and kinetics of co-extraction of U(VI) and HNO3 using tri-n-butyl phosphate and tri-iso-amyl phosphate in paraffin

    International Nuclear Information System (INIS)

    Das, Diptendu; Juvekar, V.A.; Biswas, Sujoy; Roy, S.B.; Bhattacharya, R.

    2014-01-01

    Tri-n-butyl phosphate (TBP) is versatile solvent for recovery of actinides as it is cheaper and the extracted actinides can be stripped from the loaded organic phase using plain water. However there are inherent problems associated TBP such as i) formation of the third phase ii) high solubility in aqueous phase iii) radiolytic hydrolysis at high radiation environment and iv) high propensity for extraction of mineral acids. The last mentioned property makes it less suitable for liquid emulsion membrane (LEM) extraction where acid transport to the strip phase drastically reduces extraction efficiency. Therefore there is need to replace TBP with an extractant which has lesser propensity for acid extraction. Many researcher reported Tri-iso-amyl phosphate (TiAP) as an alternative extractant which can sustain high radiation environment without chemical/radiative degradation. However there are no studies available on co-extraction of U(VI) and mineral acids by TiAP. In this research paper equilibrium and kinetics of co-extraction of U(VI) and HNO 3 from nitric acid medium into a hydrocarbon phase (paraffin) using Tri n- butyl phosphate (TBP), Tri-iso-amyl phosphate (TiAP) has been studied. Relative rates of extraction of uranium(VI) and HNO 3 by TiAP and TBP were measured simultaneously using bulk-liquid membrane (BLM) system. Study reveals although TiAP is less efficient in extracting U(IV), than TBP, it transfers lesser quantity of nitric acid to organic phase. Hence TiAP is more suitable as a carrier for LEM extraction than TBP

  9. Determination of free acid by standard addition method in potassium thiocyanate

    International Nuclear Information System (INIS)

    1981-01-01

    An analytical method for determination of free acidity in all SRP process solutions has been developed. Free acidity was successfully determined in solutions of nitric acid and the nitrates of aluminum, chromium(III), iron(III), mercury(II), nickel(II), thorium, and uranium(VI), at metal-to-acid ratios <2.5. Sample requirements, instrumentation, and mode of operation are similar to those currently used in the Laboratories Department free acid procedures. The simple procedure would be suitable for automation and microprocessor control. The method consists of two additions of known increments of acid into a solution containing the sample aliquot (10 μmoles free acid) and 10 mL 1M potassium thiocyanate. The potential is determined in the initial solution and after each addition with a glass electrode and pH meter. The sample concentration is calculated by solution of three simultaneous Nernst equations. Two programs for this iterative computation are available: one written for the PDP-15 computer and another for a Hewlett-Packard 67 (or 97) programmable calculator. The accuracy of the result is verified by a slope that approximates the theoretical Nernst value. The relative standard deviation is <2.5%. This memorandum includes a survey of experiments with thermometric, pH, and Gran plot titrations in a variety of complexants, from which this particular system and technique logically evolved. The appendix includes a literature survey of sixty references, a discussion of the basic measurements, and a complete analytical procedure. The final step for completion of this RTA is training and consultation at the convenience of the Laboratories Department for demonstration of the method with process samples

  10. Electron transfer. 93. Further reactions of transition-metal-center oxidants with vitamin B12s (Cob(I)alamin)

    International Nuclear Information System (INIS)

    Pillai, G.C.; Ghosh, S.K.; Gould, E.S.

    1988-01-01

    Vitamin B 12s (cob(I)alamin) reduces europium(III), titanium(IV) (TiO(C 2 O 4 ) 2 2- ), and uranium(VI) in aqueous solution. These oxidants undergo one-electron changes, leading in each case to the cobalt product cob(II)alamin (B 12r ). The reduction of Eu 3+ , which is inhibited by TES buffer, but not by glycine, is outer sphere. Its limiting specific rate (1 x 10 2 M -1 s -1 ), incorporated in the Marcus treatment, yields a B 12s ,B 12r self-exchange rate of 10 4.8±0.5 M -1 s -1 . Reductions of TiO(C 2 O 4 ) 2 2- are accelerated by H + and by acetic acid. Kinetic patterns suggest three competing reaction paths involving varying degrees of protonation of the Ti(IV) center or its association with acetic acid. The very rapid reduction of U(VI) (k = 4 x 10 6 M -1 s -1 ) yields U(V) in several buffering media, even when B 12s is taken in excess. The much slower conversion of U(V) to U(IV), although thermodynamically favored, appears to be retarded by the extensive reorganization of the coordination sphere of oxo-bound U(V) that must accompany its acceptance of an additional electron. The observed specific rate for the B 12s -U(VI) reaction is in reasonable agreement, in the framework of the Marcus formalism, with reported values of the formal potential and the self-exchange rate for U(V,VI). 37 references, 4 tables

  11. Analytical control of reducing agents on uranium/plutonium partitioning at purex process

    International Nuclear Information System (INIS)

    Araujo, Izilda da Cruz de

    1995-01-01

    Spectrophotometric methods for uranium (IV), hydrazine (N 2 H 4 ) and its decomposition product hydrazoic acid(HN 3 ), and hydroxylamine (NH 2 OH) determinations were developed aiming their applications for the process control of CELESTE I installation at IPEN/CNEN-SP. These compounds are normally present in the U/Pu partitioning phase of the spent nuclear treatment via PUREX process. The direct spectrophotometry was used for uranium (IV) analysis in nitric acid-hydrazine solutions based on the absorption measurement at 648 nm. The azomethine compound formed by reaction of hydrazine and p-dimethylamine benzaldehyde with maximum absorption at 457 nm was the basis for the specific analytical method for hydrazine determination. The hydrazoic acid analysis was performed indirectly by its conversion into ferric azide complex with maximum absorption at 465 nm. The hydroxylamine detection was accomplished based on its selective oxidation to nitrous acid which is easily analyzed by the reaction with Griess reagent. The resulted azocompound gas a maximum absorption at 520 nm. The sensibility of 1,4x10 -6 M for U(IV) with 0,8% of precision, 1,6x10 -6 M for hydrazine with 0,8% of precision, 2,3x10 -6 M hydrazoic acid with 0,9% of precision and 2,5x10 -6 M for hydroxylamine with 0,8% of precision were achieved. The interference studies have shown that each reducing agent can be determined in the presence of each other without any interference. Uranium(VI) and plutonium have also shown no interference in these analysis. The established methods were adapted to run inside glove-boxes by using an optical fiber colorimetry and applied to process control of the CELESTE I installation. The results pointed out that the methods are reliable and safety in order to provide just-in-time information about process conditions. (author)

  12. Study of Thorium Phosphate Diphosphate (TPD) formation in nitric medium for the decontamination of high activity actinides bearing effluents

    International Nuclear Information System (INIS)

    Rousselle, Jerome

    2004-01-01

    Considering several activities in the nuclear industry and research, several low-level liquids wastes (LLLW) containing actinides in nitric medium must be decontaminated before being released in the environment. These liquid wastes mainly contain significant amounts of uranium(VI), neptunium(V) and plutonium(IV). In this work, two chemical ways were studied to decontaminate LLLW then to incorporate simultaneously uranium, neptunium and plutonium in the Thorium Phosphate Diphosphate (TPD). Both ways started from a nitric solution containing thorium and the actinides considered, present at their lower stable oxidation state. The first way consisted in the initial precipitation of actinide and thorium mixed oxalate. After drying the mixture containing the powder and phosphoric acid under dried argon, a poly-phase system was obtained. It was mainly composed by a thorium-actinide oxalate-phosphate. This mixture was transformed into a TPDAn solid solution (An = U, Np and/or Pu) by heating treatment at 1200 deg. C under inert atmosphere. The second way consisted in the precipitation of a precursor of TPD, identified as the Thorium Phosphate Hydrogen Phosphate loaded with the actinides considered. The gel initially formed by mixing concentrated phosphoric acid solution with the nitric actinide solution was heated at 90 - 160 deg. C in a closed PTFE container for several weeks. It led to the TPDAn solid solutions after heating at 1100 deg. C in air or under inert argon. The efficiency of both processes was evaluated through the determination of the decontamination for each actinide considered. Considering the encouraging results obtained for both kinds of processes, some complementary studies are now required before performing the effective decontamination of real Low-Level Liquid Waste using one of the methods proposed. (author) [fr

  13. Root uptake of uranium by a higher plant model (Phaseolus vulgaris) bioavailability from soil solution

    International Nuclear Information System (INIS)

    Laroche, L.; Henner, P.; Camilleri, V.; Garnier-Laplace, J.

    2004-01-01

    Uranium behaviour in soils is controlled by actions and interactions between physicochemical and biological processes that also determine its bioavailability. In soil solution, uranium(+VI) aqueous speciation undergoes tremendous changes mainly depending on pH, carbonates, phosphates and organic matter. In a first approach to identify bioavailable species of U to plants, cultures were performed using hydroponics, to allow an easy control of the composition of the exposure media. The latter, here an artificial soil solution, was designed to control the uranium species in solution. The geochemical speciation code JCHESS using a database compiled from the OECD/NEA thermochemical database project and verified was used to perform the solution speciation calculations. On this theoretical basis, three domains were defined for short-duration well-defined laboratory experiments in simplified conditions: pH 4.9, 5.8 and 7 where predicted dominant species are uranyl ions, hydroxyl complexes and carbonates respectively. For these domains, biokinetics and characterization of transmembrane transport according to a classical Michaelis Menten approach were investigated. The Free Ion Model (or its derived Biotic Ligand Model) was tested to determine if U uptake is governed by the free uranyl species or if other metal complexes can be assimilated. The effect of different variables on root assimilation efficiency and phyto-toxicity was explored: presence of ligands such as phosphates or carbonates and competitive ions such as Ca 2+ at the 3 pH. According to previous experiments, uranium was principally located in roots whatever the pH and no difference in uranium uptake was evidenced between the main growth stages of the plant. Within the 3 studied chemical domains, results from short-term kinetics evidenced a linear correlation between total uranium concentration in bean roots and that in exposure media, suggesting that total uranium in soil solution could be a good predictor for

  14. Selective separation of uranium using alizarin red S (ARS)-modified anion-exchange resin or by flotation of U-ARS chelate

    International Nuclear Information System (INIS)

    Khalifa, M.E.

    1998-01-01

    An alizarin red S (ARS)-modified anion exchange resin was prepared by a simple reaction of ARS with the anion exchange Doulite A101 and used for the efficient sorption of uranium from aqueous media. The effect of various parameters on the sorption of U(VI) (pH effect, sorption kinetics, resin capacity and breakthrough curves) was investigated. The modified resin sorbs U(VI) over a wide range of pH (2.8--5) with a maximum sorption capacity of 0.68 mmol/g at pH 3.2 to 4.0. Iron(III), Zr(IV), Ti(IV), Cu(II), and Th(IV) ions are also sorbed to different extents, but Be(II), Bi(III), Ca(II), Mg(II), Pb(II), Hg(II), Zn(II), Cd(II), Al(III), Mn(II), Co(II) and Ni(II) are not sorbed; thus, conditions for separating U(VI) from these metal ions have been identified. For eluting U(VI) from the resin, 0.2 mol/L HCl was used and the recovery recorded was as high as 99.9%. The use of ARS is extended to float uranium quantitatively and selectively from aqueous media at pH ∼ 4 by using oleic acid as a surfactant. The different parameters affecting the flotation process have also been investigated. Uranium(VI) has been effectively separated from natural water samples and certified uranium ores using both procedures

  15. Preparation and characterization of porous reduced graphene oxide based inverse spinel nickel ferrite nanocomposite for adsorption removal of radionuclides

    Energy Technology Data Exchange (ETDEWEB)

    Lingamdinne, Lakshmi Prasanna; Choi, Yu-Lim [Department of Environmental Engineering, Kwangwoon University, Seoul, 139-701 (Korea, Republic of); Kim, Im-Soon [Graduate School of Environmental Studies, Kwangwoon University, Seoul, 139-701 (Korea, Republic of); Yang, Jae-Kyu [Ingenium College of Liberal Arts, Kwangwoon University, Seoul, 139-701 (Korea, Republic of); Koduru, Janardhan Reddy, E-mail: reddyjchem@gmail.com [Graduate School of Environmental Studies, Kwangwoon University, Seoul, 139-701 (Korea, Republic of); Chang, Yoon-Young, E-mail: yychang@kw.ac.kr [Department of Environmental Engineering, Kwangwoon University, Seoul, 139-701 (Korea, Republic of)

    2017-03-15

    Highlights: • Novel porous Ferromagnetic, GONF and Superparamagnetic, rGONF preparation. • The nanosize particles GONF (41.14 nm) and rGONF (32.16 nm) preparation. • Adsorption mechanism and modeling developments for radionuclides. • Zeta potential and surface site density of nanocomposites for comparison. - Abstract: For the removal of uranium(VI) (U(VI)) and thorium(IV) (Th(IV)), graphene oxide based inverse spinel nickel ferrite (GONF) nanocomposite and reduced graphene oxide based inverse spinel nickel ferrite (rGONF) nanocomposite were prepared by co-precipitation of GO with nickel and iron salts in one pot. The spectral characterization analyses revealed that GONF and rGONF have a porous surface morphology with an average particle size of 41.41 nm and 32.16 nm, respectively. The magnetic property measurement system (MPMS) studies confirmed the formation of ferromagnetic GONF and superparamagnetic rGONF. The adsorption kinetics studies found that the pseudo-second-order kinetics was well tune to the U(VI) and Th(IV) adsorption. The results of adsorption isotherms showed that the adsorption of U(VI) and Th(IV) were due to the monolayer on homogeneous surface of the GONF and rGONF. The adsorptions of both U(VI) and Th(IV) were increased with increasing system temperature from 293 to 333 ± 2 K. The thermodynamic studies reveal that the U(VI) and Th(IV) adsorption onto GONF and rGONF was endothermic. GONF and rGONF, which could be separated by external magnetic field, were recycled and re-used for up to five cycles without any significant loss of adsorption capacity.

  16. Basic chemistry for radioactive waste management

    International Nuclear Information System (INIS)

    Park, Kyong Kyun; Kim, Won Ho; Jee, Kwang Yong; Kim, Jong Goo; Park, Yeong Jae; Yu, Mahn Su; Jee, Choun Suk; Song, Byoung Chul; Choi, Ke Chon; Eom, Tae Yoon

    1991-03-01

    The complex formation between uranium(VI) ion and chloride ion in aqueous solution can be confirmed by UV-Vis absorption spectroscopy and differential pulse polarography. Absorption spectra and differential pulse polarograms of uranyl ion in hypochlorite/chloride media shows for its interaction with hypochlorite ion. Although the spectral changes for its interaction are ambiguous, new half-wave potential due to the interaction of uranium(VI)-hypochlorite ion appears in the differential pulse polarogram. Kinetic studies on the electron transfer reaction between U(IV) ion and Fe(III)(phen)3 complex in the solution containing dipicolinic acid or phosphoric acid show that the reaction rate slows down in low ligands concentration and speeds up in high ligands concentration. This result indicates that free functional group of multidentate ligands coordinated to U(IV) ion interacts at the 2 or 9 position carbon atom of phenanthroline ring in iron(III) complex. The presence of 5-sulfosalicylic acid slows down the electron transfer reaction between U(IV) ion and Fe(III) ion through the complex formation with two reactants. More information about the complex formation between U(IV) ion and 5-sulfosalicylic acid is needed for accurate explanation of the reaction mechanism. Both plutonium and uranium are extracted by TBP/dodecane from the aqueous solution, in which the post-irradiated nuclear fuel pellet is dissolved. They are back-extracted into 2M HCl solution after reducing plutonium(IV) ion to plutonium(III) ion by added U(IV) ion. Removing uranium on the DOWEX A-l anion exchange column, plutonium is eluted later for its purification. Gamma and alpha spectroscopic measurements shows the high decontamination factor and 95% recovery for the initial amounts of plutonium. (Author)

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

    International Nuclear Information System (INIS)

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

    2002-01-01

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

  18. Adsorption of uranium ions by crosslinked polyester resin functionalized with acrylic acid from aqueous solutions

    International Nuclear Information System (INIS)

    Cemal Oezeroglu; Niluefer Metin

    2012-01-01

    In this paper, the crosslinked polyester resin containing acrylic acid functional groups was used for the adsorption of uranium ions from aqueous solutions. For this purpose, the crosslinked polyester resin of unsaturated polyester in styrene monomer (Polipol 353, Poliya) and acrylic acid as weight percentage at 80 and 20%, respectively was synthesized by using methyl ethyl ketone peroxide (MEKp, Butanox M60, Azo Nobel)-cobalt octoate initiator system. The adsorption of uranium ions on the sample (0.05 g copolymer and 5 mL of U(VI) solution were mixed) of the crosslinked polyester resin functionalized with acrylic acid was carried out in a batch reactor. The effects of adsorption parameters of the contact time, temperature, pH of solution and initial uranium(VI) concentration for U(VI) adsorption on the crosslinked polyester resin functionalized with acrylic acid were investigated. The adsorption data obtained from experimental results depending on the initial U(VI) concentration were analyzed by the Freundlich, Langmuir and Dubinin-Radushkevich (D-R) adsorption isotherms. The adsorption capacity and free energy change were determined by using D-R isotherm. The obtained experimental adsorption data depending on temperature were evaluated to calculate the thermodynamic parameters of enthalpy (ΔH o ), entropy (ΔS o ) and free energy change (ΔG o ) for the U(VI) adsorption on the crosslinked polyester resin functionalized with acrylic acid from aqueous solutions. The obtained adsorption data depending on contact time were analyzed by using adsorption models such as the modified Freundlich, Elovich, pseudo-first order and pseudo-second-order kinetic models. (author)

  19. Analytical control of reducing agents on uranium/plutonium partitioning at purex process; Controle analitico dos agentes redutores na particao uranio/plutonio no processo purex

    Energy Technology Data Exchange (ETDEWEB)

    Araujo, Izilda da Cruz de

    1995-07-01

    Spectrophotometric methods for uranium (IV), hydrazine (N{sub 2}H{sub 4}) and its decomposition product hydrazoic acid(HN{sub 3}), and hydroxylamine (NH{sub 2} OH) determinations were developed aiming their applications for the process control of CELESTE I installation at IPEN/CNEN-SP. These compounds are normally present in the U/Pu partitioning phase of the spent nuclear treatment via PUREX process. The direct spectrophotometry was used for uranium (IV) analysis in nitric acid-hydrazine solutions based on the absorption measurement at 648 nm. The azomethine compound formed by reaction of hydrazine and p-dimethylamine benzaldehyde with maximum absorption at 457 nm was the basis for the specific analytical method for hydrazine determination. The hydrazoic acid analysis was performed indirectly by its conversion into ferric azide complex with maximum absorption at 465 nm. The hydroxylamine detection was accomplished based on its selective oxidation to nitrous acid which is easily analyzed by the reaction with Griess reagent. The resulted azocompound gas a maximum absorption at 520 nm. The sensibility of 1,4x10{sup -6}M for U(IV) with 0,8% of precision, 1,6x10{sup -6}M for hydrazine with 0,8% of precision, 2,3x10{sup -6}M hydrazoic acid with 0,9% of precision and 2,5x10{sup -6}M for hydroxylamine with 0,8% of precision were achieved. The interference studies have shown that each reducing agent can be determined in the presence of each other without any interference. Uranium(VI) and plutonium have also shown no interference in these analysis. The established methods were adapted to run inside glove-boxes by using an optical fiber colorimetry and applied to process control of the CELESTE I installation. The results pointed out that the methods are reliable and safety in order to provide just-in-time information about process conditions. (author)

  20. Formation of ternary CaUO2(CO3)3(2-) and Ca2UO2(CO3)3(aq) complexes under neutral to weakly alkaline conditions.

    Science.gov (United States)

    Lee, Jun-Yeop; Yun, Jong-Il

    2013-07-21

    The chemical behavior of ternary Ca-UO2-CO3 complexes was investigated by using time-resolved laser fluorescence spectroscopy (TRLFS) in combination with EDTA complexation at pH 7-9. A novel TRLFS revealed two distinct fluorescence lifetimes of 12.7 ± 0.2 ns and 29.2 ± 0.4 ns for uranyl complexes which were formed increasingly dependent upon the calcium ion concentration, even though nearly indistinguishable fluorescence peak shapes and positions were measured for both Ca-UO2-CO3 complexes. For identifying the stoichiometric number of complexed calcium ions, slope analysis in terms of relative fluorescence intensity versus calcium concentration was employed in a combination with the complexation reaction of CaEDTA(2-) by adding EDTA. The formation of CaUO2(CO3)3(2-) and Ca2UO2(CO3)3(aq) was identified under given conditions and their formation constants were determined at I = 0.1 M Na/HClO4 medium, and extrapolated to infinitely dilute solution using specific ion interaction theory (SIT). As a result, the formation constants for CaUO2(CO3)3(2-) and Ca2UO2(CO3)3(aq) were found to be log β113(0) = 27.27 ± 0.14 and log β213(0) = 29.81 ± 0.19, respectively, providing that the ternary Ca-UO2-CO3 complexes were predominant uranium(vi) species at neutral to weakly alkaline pH in the presence of Ca(2+) and CO3(2-) ions.

  1. New functionalized β-diketiminate ligands and f elements

    International Nuclear Information System (INIS)

    Dulong, Florian

    2013-01-01

    β-diketiminate ligands have received increased interest in coordination chemistry, especially for homogeneous catalysis. Their successful applications arise from an easy and fine tuning of the ligand electronic and geometric properties. However, these modifications are limited to the introduction of neutral donors (ethers or amines), on the nitrogen substituents of the β-diketiminate skeleton. The main focus of this research project is to overcome this limitation by synthesizing new β-diketiminate ligands functionalized by one or two anionic aryl-oxide groups, and to study their coordination chemistry with lanthanide and actinide ions. Access to these species relies on a fine understanding of the mechanism underlying their formation, and the sensitivity of the β-di-iminium skeleton towards nucleophiles (phenols) has been identified as the limiting side reaction in the synthetic route. Addition of reactants in well defined order allowed the formation of two new N-aryl-oxy-β-diketiminate dianions on a multi-gram scale. The two ligands differ by their steric bulk and exhibit different coordination behaviors towards lanthanides and actinide ions, which were rationalized on geometric considerations. The reactivity of three of these new complexes has been investigated. A Ce(III) N-aryl-oxy-β-diketiminate complex exhibits interesting reduction properties, due to the shift of its oxidation potential to negative values by its coordination environment. A Th(IV) complex presents a vacant coordination site, which has been probed with different Lewis bases, emphasizing two spatial arrangements ruled by inter-ligand repulsion. It has been compared to its U(IV) analogue, which can be oxidized to a rare terminal mono-oxo uranium(VI) species. The latter was reversibly reduced to its U(V) and U(IV) derivatives, creating the first series of terminal mono-oxo uranium complexes with three successive oxidation states. These compounds represent an opportunity to better understand

  2. Investigation of uranium binding forms in environmentally relevant waters and bio-fluids

    International Nuclear Information System (INIS)

    Osman, Alfatih Ahmed Alamin

    2014-01-01

    knowledge on uranium(VI) speciation in natural waters and bio-fluids which offers a reliable basis and a better understanding as a basic mechanism of redistribution of uranium after exposure, and thus for more insight research on its biokinetics.

  3. Investigation of uranium binding forms in environmentally relevant waters and bio-fluids

    Energy Technology Data Exchange (ETDEWEB)

    Osman, Alfatih Ahmed Alamin

    2014-06-04

    knowledge on uranium(VI) speciation in natural waters and bio-fluids which offers a reliable basis and a better understanding as a basic mechanism of redistribution of uranium after exposure, and thus for more insight research on its biokinetics.

  4. Geobacter daltonii sp. nov., an Fe(III)- and uranium(VI)-reducing bacterium isolated from a shallow subsurface exposed to mixed heavy metal and hydrocarbon contamination.

    Science.gov (United States)

    Prakash, Om; Gihring, Thomas M; Dalton, Dava D; Chin, Kuk-Jeong; Green, Stefan J; Akob, Denise M; Wanger, Greg; Kostka, Joel E

    2010-03-01

    An Fe(III)- and uranium(VI)-reducing bacterium, designated strain FRC-32(T), was isolated from a contaminated subsurface of the USA Department of Energy Oak Ridge Field Research Center (ORFRC) in Oak Ridge, Tennessee, where the sediments are exposed to mixed waste contamination of radionuclides and hydrocarbons. Analyses of both 16S rRNA gene and the Geobacteraceae-specific citrate synthase (gltA) mRNA gene sequences retrieved from ORFRC sediments indicated that this strain was abundant and active in ORFRC subsurface sediments undergoing uranium(VI) bioremediation. The organism belonged to the subsurface clade of the genus Geobacter and shared 92-98 % 16S rRNA gene and 75-81 % rpoB gene sequence similarities with other recognized species of the genus. In comparison to its closest relative, Geobacter uraniireducens Rf4(T), according to 16S rRNA gene sequence similarity, strain FRC-32(T) showed a DNA-DNA relatedness value of 21 %. Cells of strain FRC-32(T) were Gram-negative, non-spore-forming, curved rods, 1.0-1.5 microm long and 0.3-0.5 microm in diameter; the cells formed pink colonies in a semisolid cultivation medium, a characteristic feature of the genus Geobacter. The isolate was an obligate anaerobe, had temperature and pH optima for growth at 30 degrees C and pH 6.7-7.3, respectively, and could tolerate up to 0.7 % NaCl although growth was better in the absence of NaCl. Similar to other members of the Geobacter group, strain FRC-32(T) conserved energy for growth from the respiration of Fe(III)-oxyhydroxide coupled with the oxidation of acetate. Strain FRC-32(T) was metabolically versatile and, unlike its closest relative, G. uraniireducens, was capable of utilizing formate, butyrate and butanol as electron donors and soluble ferric iron (as ferric citrate) and elemental sulfur as electron acceptors. Growth on aromatic compounds including benzoate and toluene was predicted from preliminary genomic analyses and was confirmed through successive transfer with

  5. Thermodynamic study of uranyl sorption onto lanthanum monophosphate (LaPO4) and magnetite (Fe3O4)

    International Nuclear Information System (INIS)

    Felix, Olivia

    2012-01-01

    The migration of radio-toxic elements in the geosphere is mainly regulated by chemical parameters which control the partitioning of the elements between mineral phases and aqueous solutions. Variation in temperature may affect the retention properties of a mineral surface and requires a careful investigation in order to understand the radionuclides behavior in the geosphere. In this way, the interaction mechanisms between uranium(VI) and two minerals (LaPO 4 and Fe 3 O 4 ) have been studied. In a first step, the monazite (LaPO 4 ) has been chosen as methodological solid in order to clearly define all the different stages needed to completely characterize the influence of temperature on the sorption phenomena. To reach that goal, three media, more or less complexants towards aqueous uranyl and the mineral surface, have been considered. Physico-chemical as well as surface acid-base properties of the solid surface have been studied by considering three electrolytes (NaClO 4 , NaNO 3 and Na 2 SO 4 ) and temperatures ranged from 25 C to 95 C. The point of zero charge has been found to be identical for perchlorate and nitrate media (pH PZC =2.1) but it was found to be one pK unit higher for the sulfate medium indicating a sorption of the background electrolyte ions. The reaction heats associated to the hydration of the solid have been measured by using microcalorimetry and the nature of the reactive surface sites has been determined by carrying out Time-Resolved Laser-Induced Fluorescence Spectroscopy (TRLFS). On the basis of these experimental constraints, the titration curves obtained for the monazite suspensions were fitted by using the Constant Capacitance Model and the 1-pK model was preferred to characterize the surface charge evolution, due to the limited number of adjustable parameters. The surface protonation constants being determined, the behavior of U(VI) towards the monazite surface in the three electrolytes has been investigated. On the basis of both U

  6. Biosorption of U(VI) by the green algae Chlorella vulgaris in dependence of pH value and cell activity

    Energy Technology Data Exchange (ETDEWEB)

    Vogel, M., E-mail: M.Vogel@fzd.de; Guenther, A.; Rossberg, A.; Li, B.; Bernhard, G.; Raff, J.

    2010-12-15

    Biosorption of uranium(VI) by the green alga Chlorella vulgaris was studied at varying uranium concentrations from 5 {mu}M to 1 mM, and in the environmentally relevant pH range of 4.4 to 7.0. Living cells bind in a 0.1 mM uranium solution at pH 4.4 within 5 min 14.3 {+-} 5.5 mg U/g dry biomass and dead cells 28.3 {+-} 0.6 mg U/g dry biomass which corresponds to 45% and 90% of total uranium in solution, respectively. During 96 h of incubation with uranium initially living cells died off and with 26.6 {+-} 2.1 mg U/g dry biomass bound similar amounts of uranium compared to dead cells, binding 27.0 {+-} 0.7 mg U/g dry biomass. In both cases, these amounts correspond to around 85% of the initially applied uranium. Interestingly, at a lower and more environmentally relevant uranium concentration of 5 {mu}M, living cells firstly bind with 1.3 {+-} 0.2 mg U/g dry biomass to 1.4 {+-} 0.1 mg U/g dry biomass almost all uranium within the first 5 min of incubation. But then algal cells again mobilize up to 80% of the bound uranium during ongoing incubation in the time from 48 h to 96 h. The release of metabolism related substances is suggested to cause this mobilization of uranium. As potential leachates for algal-bound uranium oxalate, citrate and ATP were tested and found to be able to mobilize more than 50% of the algal-bound uranium within 24 h. Differences in complexation of uranium by active and inactive algae cells were investigated with a combination of time-resolved laser-induced fluorescence spectroscopy (TRLFS), extended X-ray absorption fine structure (EXAFS) spectroscopy and attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy. Obtained results demonstrated an involvement of carboxylic and organic/inorganic phosphate groups in the uranium complexation with varying contributions dependent on cell status, uranium concentration and pH.

  7. Biosorption of U(VI) by the green algae Chlorella vulgaris in dependence of pH value and cell activity

    International Nuclear Information System (INIS)

    Vogel, M.; Guenther, A.; Rossberg, A.; Li, B.; Bernhard, G.; Raff, J.

    2010-01-01

    Biosorption of uranium(VI) by the green alga Chlorella vulgaris was studied at varying uranium concentrations from 5 μM to 1 mM, and in the environmentally relevant pH range of 4.4 to 7.0. Living cells bind in a 0.1 mM uranium solution at pH 4.4 within 5 min 14.3 ± 5.5 mg U/g dry biomass and dead cells 28.3 ± 0.6 mg U/g dry biomass which corresponds to 45% and 90% of total uranium in solution, respectively. During 96 h of incubation with uranium initially living cells died off and with 26.6 ± 2.1 mg U/g dry biomass bound similar amounts of uranium compared to dead cells, binding 27.0 ± 0.7 mg U/g dry biomass. In both cases, these amounts correspond to around 85% of the initially applied uranium. Interestingly, at a lower and more environmentally relevant uranium concentration of 5 μM, living cells firstly bind with 1.3 ± 0.2 mg U/g dry biomass to 1.4 ± 0.1 mg U/g dry biomass almost all uranium within the first 5 min of incubation. But then algal cells again mobilize up to 80% of the bound uranium during ongoing incubation in the time from 48 h to 96 h. The release of metabolism related substances is suggested to cause this mobilization of uranium. As potential leachates for algal-bound uranium oxalate, citrate and ATP were tested and found to be able to mobilize more than 50% of the algal-bound uranium within 24 h. Differences in complexation of uranium by active and inactive algae cells were investigated with a combination of time-resolved laser-induced fluorescence spectroscopy (TRLFS), extended X-ray absorption fine structure (EXAFS) spectroscopy and attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy. Obtained results demonstrated an involvement of carboxylic and organic/inorganic phosphate groups in the uranium complexation with varying contributions dependent on cell status, uranium concentration and pH.

  8. Potassium and magnesium succinatouranilates – Synthesis and crystal structure

    Energy Technology Data Exchange (ETDEWEB)

    Novikov, S.A., E-mail: serg.alex.novikov@gmail.com [Samara National Research University, 443086 Samara (Russian Federation); Grigoriev, M.S. [Frumkin Institute of Physical Chemistry and Electrochemistry RAS, 119071 Moscow (Russian Federation); Serezhkina, L.B.; Serezhkin, V.N. [Samara National Research University, 443086 Samara (Russian Federation)

    2017-04-15

    Single crystal X-ray diffraction has been applied to determine the structures of two new uranyl coordination polymers: K{sub 2}[(UO{sub 2}){sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}] (1) and [Mg(H{sub 2}O){sub 6}] [(UO{sub 2}){sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}]·2H{sub 2}O (2), where C{sub 4}H{sub 4}O{sub 4}{sup 2-} is succinate anion. Crystals of 1 and 2 contain polymeric complex anions [(UO{sub 2}){sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}]{sup 2-} with the same A{sub 2}Q{sup 02}{sub 3} crystallochemical formula (A=UO{sub 2}{sup 2+}, Q{sup 02}=C{sub 4}O{sub 4}H{sub 4}{sup 2-}), and have layered (1) or chain (2) structure. It has been found, that conformation of succinate ions is one of the factors, which affects the structure of [(UO{sub 2}){sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}]{sup 2-} anions. IR spectra of these new compounds are in good agreement with crystallographic data. Topological analysis of the uranium dicarboxylates with A{sub 2}Q{sup 02}{sub 3} crystallochemical formula has shown the presence of five isomers which differ from each other in coordination sequences and / or dimensionality. - Graphical abstract: Crystal structures of two new uranium(VI) coordination polymers with succinate linkers, namely K{sub 2}[(UO{sub 2}){sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}] (1) and [Mg(H{sub 2}O){sub 6}][(UO{sub 2}){sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}]·2H{sub 2}O (2), were determined by single-crystal XRD. Crystals of studied compounds are based on 2D or 1D structural units with the same composition and crystallochemical formula. Topological isomerism in A{sub 2}Q{sup 02}{sub 3} crystallochemical group and conformations of succinate anions in uranyl complexes are under discussion. - Highlights: • Two new uranium coordination polymers were synthesized. • Their structural units have the same composition and crystallochemical formula. • In spite the same composition and CCF dimensionality of units is different. • Structural features of uranyl CPs

  9. Complexation studies of actinides (U, Pu, Am) with linear polyamino-carboxylate ligands and sidero-chelates; Etudes de la chelation d'actinides (U, Pu, Am) par des ligands polyaminocarboxylate lineaires et des siderochelates d'interet environnemental

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen, L.V.

    2010-11-25

    As part of our research endeavour aimed at developing and improving decontamination processes of wastewater containing alpha emitters, physico-chemical complexation studies of actinides (U, Pu, Am) with organic open-chain ligands such as poly-aminocarboxylic acids (H{sub 4}EDTA) and sidero-chelates (di-hydroxamic acids and desferrioxamine B) have been carried out. Gaining a clear understanding of the coordination properties of the targeted actinides is an essential step towards the selection of the most appropriate chelating agents that will exhibit high uptake efficiencies. EXAFS (Extended X-ray Absorption Fine Structure) measurements at the ESRF synchrotron enabled to elucidate the coordination scheme of uranium and plutonium complexes. Solution thermodynamic investigations were intended to provide valuable information about the nature and the stability of the uranium(VI) and americium(III) complexes prevailing at a given pH in solution. The set of stability constants determined from potentiometric and UV-visible spectrophotometric titrations, allowed to predict the speciation of the selected actinides in presence of the aforementioned ligands and to determine the pH range required for achieving 'ultimate' decontamination. (author) [French] Dans le cadre du developpement et de l'amelioration des procedes de decontamination d'effluents aqueux contamines par des radioelements emetteurs alpha, des etudes physico-chimiques sur la complexation des actinides (U, Pu, Am) avec des ligands organiques tels que des acides polyaminocarboxyliques lineaires (H{sub 4}EDTA) et des siderochelates (acides dihydroxamiques et desferrioxamine B) ont ete effectuees. La comprehension des proprietes de coordination est une etape essentielle pour selectionner les meilleurs agents chelatants qui se montreront efficaces dans le traitement des effluents. Les schemas de coordination des complexes d'uranium et de plutonium avec ces ligands ont ete determines a l

  10. The influence of biofilms on the migration of uranium in acid mine drainage (AMD) waters

    International Nuclear Information System (INIS)

    Krawczyk-Baersch, E.; Luensdorf, H.; Arnold, T.; Brendler, V.; Eisbein, E.; Jenk, U.; Zimmermann, U.

    2011-01-01

    The uranium mine in Koenigstein (Germany) is currently in the process of being flooded. Huge mass of Ferrovum myxofaciens dominated biofilms are growing in the acid mine drainage (AMD) water as macroscopic streamers and as stalactite-like snottites hanging from the ceiling of the galleries. Microsensor measurements were performed in the AMD water as well as in the biofilms from the drainage channel on-site and in the laboratory. The analytical data of the AMD water was used for the thermodynamic calculation of the predominance fields of the aquatic uranium sulfate (UO 2 SO 4 ) and UO 2 ++ speciation as well as of the solid uranium species Uranophane [Ca(UO 2 ) 2 (SiO 3 OH) 2 ·5H 2 O] and Coffinite [U(SiO 4 ) 1-x (OH) 4x ], which are defined in the stability field of pH > 4.8 and Eh 0 and Eh 4.8. Even analysis by Energy-filtered Transmission Electron Microscopy (EF-TEM) and electron energy loss spectroscopy (EELS) within the biofilms did not provide any microscopic or spectroscopic evidence for the presence of uranium immobilization. In laboratory experiments the first phase of the flooding process was simulated by increasing the pH of the AMD water. The results of the experiments indicated that the F. myxofaciens dominated biofilms may have a substantial impact on the migration of uranium. The AMD water remained acid although it was permanently neutralized with the consequence that the retention of uranium from the aqueous solution by the formation of solid uranium species will be inhibited. - Highlights: → Redox potential and pH of the biofilm differ significantly compared to the AMD water. → Formation of an aqueous uranium(VI) sulfate complex in the biofilm and in the AMD water. → Experiments revealed that the F. myxofaciens dominated biofilms have a substantial impact on the migration of uranium. → Due to homeostatic mechanisms the microbes maintain their intracellular pH even when the pH of the water increases.

  11. New Insights into the Functional Behavior of Antibodies as Revealed by Binding Studies on an Anti-Uranium Monoclonal Antibody

    International Nuclear Information System (INIS)

    Blake, Diane A.; Xia Li; Haini Yu; Blake, Robert C.

    2004-01-01

    As part of an ongoing effort to develop immunoassays for chelated uranium(VI) on a hand-held flow fluorimeter, an anti-uranium monoclonal antibody designated as 8A11 was fluorescently labeled using two different strategies. When 8A11 was coupled via reactive lysines to either ALEXATM 488 or Cy5TM, the resulting fluorescent antibody conjugate exhibited positive cooperativity in the presence of its antigen, U(VI) chelated with 2,9-dicarboxy-1,10-phenanthroline (U(VI)-DCP). That is, when one of the two binding sites on the covalently modified 8A11 was occupied with bound antigen, the affinity of the remaining site on the antibody for U(VI)-DCP appeared to increase. Unmodified 8A11 bound U(VI)-DCP with the expected hyperbolic dependence on the concentration of antigen, consistent with independent and equal binding of ligand at both sites. Proteolytic cleavage of the fluorescently conjugated 8A11 to produce the fluorescent monovalent Fab fragment yielded an active preparation that now bound U(VI)-DCP with no evidence of positive cooperativity. Although, in principle, any divalent antibody has the potential to exhibit positive cooperativity in its binding interactions with its antigen, very little literature precedent for this type of behavior exists. Native 8A11 was also noncovalently labeled with highly fluorescent ZENONTM reagents. These reagents are fluorescently-labeled Fab fragments of goat anti-mouse antibodies that bind to the Fc portion of 8A11. These high-affinity, monovalent fluorescent reagents permitted the intact 8A11 mouse antibody to be labeled in situ with no covalent modifications. Incubation of the 8A11 with ZENON 647 produced a fluorescent protein complex that showed an 8-fold higher affinity for U(VI)-DCP than did the free 8A11 alone. Again, very few literature precedents exist for this phenomenon, where agents that bind to the Fc portion of an intact antibody change the affinity of the antibody for the antigen at the structurally distant Fab portion

  12. Characterization of Secondary Mineral Grain Coatings and their Role as Diffusion-controlled Sinks and Sources for Metal Contaminants

    Science.gov (United States)

    Davis, J. A.; Guo, H.; Lai, B.; Kemner, K. M.; Ercius, P.; Fox, P. M.; Singer, D. M.; Minor, A.; Waychunas, G.

    2012-12-01

    Many important geochemical reactions occur at the mineral-water interface, including sorption and desorption reactions of contaminants. Fundamental knowledge of the kinetics of these processes is based primarily on experimental observations of reactions at faces of single crystals or macroscopic data from pure mineral powder suspensions. Sorption reactions at crystal faces are generally very fast, on the order of microseconds or less, with reaction times often limited only by film diffusion at the mineral-water interface. In well-stirred suspensions of aquifer sediments, however, sorptive equilibrium can take many hours or days to achieve steady-state concentrations. We have examined the potential reasons for sorption rate limitation using uranium(VI) sorption by sediments from a sandy aquifer in Savannah River, South Carolina (USA). U(VI) sorption by sand-sized grains from the aquifer is dominated by reaction with secondary mineral coatings on quartz and feldspar grains. The coatings studied were on the order of 15 microns in thickness (i.e., from quartz grain to aqueous solution) and composed primarily of clay minerals and hematite of varying particle size. Microfocused-XRF imaging of elemental concentrations (e.g., U, Fe) of polished cross-sections of the grain/coating contact showed strong spatial correlations of U and Fe within the coatings, regardless of the length of reaction time (30 minutes to 4 weeks). The spatial resolution of the μ-XRF technique is of the order of 2 microns in horizontal directions, but the uncertainty of the observed spatial gradients is high due to grain curvature away from the polished surface and fluorescence contributed from the entire 30 micron thickness of a typical grain/epoxy thin section. TEM characterization of focused-ion-beam (FIB), vertically-extracted samples of the grain-coating contact shows that complex pore networks exist within the coatings of variable dimensions and unknown connectivity. Using scanning TEM (STEM

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

    International Nuclear Information System (INIS)

    Kosog, Boris

    2012-01-01

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

  14. Formation of colloids of the tetravalent uranium under influence of silicate in neutral and low alkaline aqueous systems; Bildung von Kolloiden des tetravalenten Urans unter Einfluss von Silikat in neutralen und schwachalkalischen waessrigen Systemen

    Energy Technology Data Exchange (ETDEWEB)

    Ulbricht, Isabell

    2016-03-30

    silicate to uranium(IV) content ratio and the higher the pH of the solution are, the smaller and more stable (in terms of pH-changes) are the particles. It should be noted that no colloids were formed in absence of uranium(IV). The mechanism of the colloidal stabilization can be regarded as ''sequestration'' by silicate, a phenomenon well known from heavy metal ions of high ion potential such as iron(III) or manganese(III,IV), but never reported for uranium(IV) so far. Extended X-ray absorption fine structure (EXAFS) spectroscopy showed that U-O-Si bonds, which increasingly replace the U-O-U bonds of the amorphous uranium(IV) oxyhydroxide with increasing silicate concentration, make up the internal structure of the colloids. The next-neighbor coordination of uranium(IV) in the uranium(IV)-silica colloids is comparable with that of coffinite, USiO{sub 4}. The assessment of uranium behavior in the aquatic environment should take the possible existence of uranium(IV)-silica colloids into consideration. Their occurrence might influence uranium migration in anoxic waters. The silicate-stabilized colloids have been generated in laboratory experiments under controlled conditions; i.e., it is not known yet whether these phases can occur in natural water. The qualitative composition of the matrix of the experimental solutions (H{sup +}, OH{sup -}, Na{sup +}, HCO{sub 3}{sup -}/CO{sub 3}{sup 2-}, silicate) was chosen similar to the geochemical nature of groundwater. Thereby, it can be assumed that such colloids are present in natural waters. The existence of such particles would provide an ex-planation for the occurrence of uranium(IV) colloids in anoxic pore waters or groundwaters. However, it should be noted that these results were observed by the reduction of uranium(VI) carbonate and dilution in the presence of silicate. Studies on the mobility and stability of these colloids in aquatic systems were not subject of this work and an environmental assessment of