U(VI) speciation and reduction in acid chloride fluids in hydrothermal conditions: from transport to deposition of uranium in unconformity-related deposits

International Nuclear Information System (INIS)

Dargent, Maxime

2014-01-01

Circulations of acidic chloride brines in the earth's crust are associated with several types of uranium deposits, particularly unconformity-related uranium (URU) deposits. The spectacular high grade combined with the large tonnage of these deposits is at the origin of the key questions concerning the geological processes responsible for U transport and precipitation. The aim of this work is to performed experimental studies of U(VI) speciation and its reduction to U(IV) subsequently precipitation to uraninite under hydrothermal condition. About uranium transport, the study of U(VI) speciation in acidic brines at high temperature is performed by Raman and XAS spectroscopy, showing the coexistence of several uranyl chloride complexes UO 2 Cl n 2-n (n = 0 - 5). From this study, complexation constants are proposed. The strong capability of chloride to complex uranyl is at the origin of the transport of U(VI) at high concentration in acidic chloride brines. Concerning uranium precipitation, the reactivity of four potential reductants under conditions relevant for URU deposits genesis is investigated: H 2 , CH 4 , Fe(II) and the C-graphite. The kinetics of reduction reaction is measured as a function of temperature, salinity, pH and concentration of reductant. H 2 , CH 4 , and the C-graphite are very efficient while Fe(II) is not able to reduce U(VI) in same conditions. The duration of the mineralizing event is controlled by (i) the U concentration in the ore-forming fluids and (ii) by the generation of gaseous reductants, and not by the reduction kinetics. These mobile and efficient gaseous reductant could be at the origin of the extremely focus and massive character of ore in URU deposits. Finally, first partition coefficients uraninite/fluid of trace elements are obtained. This last part opens-up new perspectives on (i) REE signatures interpretation for a given type of uranium deposit (ii) and reconstruction of mineralizing fluids composition. (author) [fr

Uranium sorption on tezontle volcanic rock

Energy Technology Data Exchange (ETDEWEB)

Lopez M, B. E.; Duran B, J. M.; Iturbe G, J. L.; Olguin G, M. T., E-mail: beatriz.lopez@inin.gob.m [ININ, Departamento de Quimica, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico)

2009-07-01

It is described a study that demonstrates that hexavalent uranium ions were sorbed by the naturally occurring mineral using a batch technique. This mineral is found in abundant quantities in Mexico. Our study focused on the separation of U Vi from synthetic aqueous systems of both H{sub 2}O-UO{sub 2}(NO{sub 3}){sub 2}.6H{sub 2}O (acid) and H{sub 2}O-Na{sub 4}[UO{sub 2}(CO{sub 3}){sub 3}] (basic). The chemical speciation was performed by using high voltage electrophoresis, and the uranium content was determined by UV-Vis spectroscopy. The quantified U(Vi) sorption by tezontle from acidic and basic systems was 2.72 and 1.68 mumol/g, respectively, and the sorption behavior is discussed considering the surface charge of the tezontle at different ph values based on the point of zero charge characteristic of this material. (Author)

Role of U(VI) adsorption in U(VI) Reduction by Geobacter species

International Nuclear Information System (INIS)

Lovely, Derrick

2008-01-01

Previous work had suggested that Acholeplasma palmae has a higher capacity for uranium sorption than other bacteria studied. Sorption studies were performed with cells in suspension in various solutions containing uranium, and results were used to generate uranium-biosorption isotherms. Results from this study showed that the U(VI) sorption capacity of G. uraniireducens was relatively similar in simple solutions, such as sodium chloride or bicarbonate. However, this ability to sorb uranium significantly decreased in groundwater. This suggested that certain chemicals present in the groundwater were inhibiting the ability of cell components of Geobacter to adsorb uranium. It was hypothesized that uranium removal would also be diminished in the bicarbonate solution. However, this did not seem to be the case, as uranium was as easily removed in the bicarbonate solution as in the sodium chloride solution.

Evidence for Multiple Modes of Uranium Immobilization by an Anaerobic Bacterium

International Nuclear Information System (INIS)

Ray, Allison; Bargar, John R.; Sivaswamy, Vaideeswaran; Dohnalkova, Alice; Fujita, Yoshiko; Peyton, Brent M.; Magnuson, Timothy S.

2011-01-01

Microbial reduction of hexavalent uranium has been studied widely for its potential role in bioremediation and immobilization of soluble U(VI) in contaminated groundwater. More recently, some microorganisms have been examined for their role in immobilization of U(VI) via precipitation of uranyl phosphate minerals mediated by microbial phosphate release, alleviating the requirement for long-term redox control. Here, we investigated the mechanism of U(VI) removal mediated by an environmental isolate, strain UFO1, that is indigenous to the Field Research Center (FRC) in Oak Ridge, TN and has been detected in U(VI)-contaminated sediments. Changes in U(VI) speciation were examined in the presence and absence of the electron-shuttling moiety, anthraquinone-2,6-disulfonate (AQDS). Cell suspensions were capable of nearly complete removal of 100 (micro)M U(VI) from solution within 48 hours; U(VI) removal was not dependent on the presence of an exogenous electron donor or AQDS, although AQDS increased the rate of U(VI) removal. X-ray Absorption Near Edge Structure (XANES) spectroscopic measurements indicated that U(IV) was the predominant oxidation state of uranium in cell suspensions in both the absence and presence of 100 (micro)M AQDS. However, extended X-ray Absorption Fine Structure spectroscopy (EXAFS) measurements indicated that 17% of the cell-associated precipitates in a U(VI)-treated suspension that lacked AQDS had spectral characteristics consistent with a uranyl phosphate solid phase. The potential involvement of phosphate was consistent with observed increases in soluble phosphate concentrations over time in UFO1 cell suspensions, which suggested phosphate liberation from the cells. TEM-EDS confirmed the presence of uranyl phosphate with a U:P ratio consistent with autunite (1:1). EXAFS analyses further showed that U(IV) was present predominantly as a monomeric complex sorbed to carboxylate functional groups on biomass and also suggested that a fraction of the U

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).

Bicarbonate Impact on U(VI) Bioreduction in a Shallow Alluvial Aquifer

Energy Technology Data Exchange (ETDEWEB)

Long, Philip E.; Williams, Kenneth H.; Davis, James A.; Fox, Patricia M.; Wilkins, Michael J.; Yabusaki, Steven B.; Fang, Yilin; Waichler, Scott R.; Berman, Elena S.; Gupta, Manish; Chandler, Darrell P.; Murray, Christopher J.; Peacock, Aaron D.; Giloteaux, L.; Handley, Kim M.; Lovley, Derek R.; Banfield, Jillian F.

2015-02-01

Field-scale biostimulation and desorption tracer experiments conducted in a uranium (U) contaminated, shallow alluvial aquifer have provided insight into the coupling of microbiology, biogeochemistry, and hydrogeology that control U mobility in the subsurface. Initial experiments successfully tested the concept that Fe-reducing bacteria such as Geobacter sp. could enzymatically reduce soluble U(VI) to insoluble U(IV) during in situ electron donor amendment (Anderson et al. 2003, Williams et al. 2011). In parallel, in situ desorption tracer tests using bicarbonate amendment demonstrated rate-limited U(VI) desorption (Fox et al. 2012). These results and prior laboratory studies underscored the importance of enzymatic U(VI)-reduction and suggested the ability to combine desorption and bioreduction of U(VI). Here we report the results of a new field experiment in which bicarbonate-promoted uranium desorption and acetate amendment were combined and compared to an acetate amendment-only experiment in the same experimental plot. Results confirm that bicarbonate amendment to alluvial aquifer desorbs U(VI) and increases the abundance of Ca-uranyl-carbonato complexes. At the same time, that the rate of acetate-promoted enzymatic U(VI) reduction was greater in the presence of added bicarbonate in spite of the increased dominance of Ca-uranyl-carbonato aqueous complexes. A model-simulated peak rate of U(VI) reduction was ~3.8 times higher during acetate-bicarbonate treatment than under acetate-only conditions. Lack of consistent differences in microbial community structure between acetate-bicarbonate and acetate-only treatments suggest that a significantly higher rate of U(VI) reduction the bicarbonate-impacted sediment may be due to a higher intrinsic rate of microbial reduction induced by elevated concentrations of the bicarbonate oxyanion. The findings indicate that bicarbonate amendment may be useful in improving the engineered bioremediation of uranium in aquifers.

Bicarbonate impact on U(VI) bioreduction in a shallow alluvial aquifer

Science.gov (United States)

Long, Philip E.; Williams, Kenneth H.; Davis, James A.; Fox, Patricia M.; Wilkins, Michael J.; Yabusaki, Steven B.; Fang, Yilin; Waichler, Scott R.; Berman, Elena S. F.; Gupta, Manish; Chandler, Darrell P.; Murray, Chris; Peacock, Aaron D.; Giloteaux, Ludovic; Handley, Kim M.; Lovley, Derek R.; Banfield, Jillian F.

2015-02-01

Field-scale biostimulation and desorption tracer experiments conducted in a uranium (U) contaminated, shallow alluvial aquifer have provided insight into the coupling of microbiology, biogeochemistry, and hydrogeology that control U mobility in the subsurface. Initial experiments successfully tested the concept that Fe-reducing bacteria such as Geobacter sp. could enzymatically reduce soluble U(VI) to insoluble U(IV) during in situ electron donor amendment (Anderson et al., 2003; Williams et al., 2011). In parallel, in situ desorption tracer tests using bicarbonate amendment demonstrated rate-limited U(VI) desorption (Fox et al., 2012). These results and prior laboratory studies underscored the importance of enzymatic U(VI)-reduction and suggested the ability to combine desorption and bioreduction of U(VI). Here we report the results of a new field experiment in which bicarbonate-promoted uranium desorption and acetate amendment were combined and compared to an acetate amendment-only experiment in the same experimental plot. Results confirm that bicarbonate amendment to alluvial aquifer sediments desorbs U(VI) and increases the abundance of Ca-uranyl-carbonato complexes. At the same time, the rate of acetate-promoted enzymatic U(VI) reduction was greater in the presence of added bicarbonate in spite of the increased dominance of Ca-uranyl-carbonato aqueous complexes. A model-simulated peak rate of U(VI) reduction was ∼3.8 times higher during acetate-bicarbonate treatment than under acetate-only conditions. Lack of consistent differences in microbial community structure between acetate-bicarbonate and acetate-only treatments suggest that a significantly higher rate of U(VI) reduction in the bicarbonate-impacted sediment may be due to a higher intrinsic rate of microbial reduction induced by elevated concentrations of the bicarbonate oxyanion. The findings indicate that bicarbonate amendment may be useful in improving the engineered bioremediation of uranium in

Valence-associated uranium isotope fractionation of uranium enriched phosphate in a shallow aquifer, Lee County, Florida

International Nuclear Information System (INIS)

Weinberg, J.M.; Levine, B.R.; Cowart, J.B.

1993-01-01

The source of anomalously high concentrations of uranium, characterized by U-234/U-238 activity ratios significantly less than unity, in shallow groundwaters of Lee County, Florida, was investigated. Uranium in cores samples was separated into U(IV) and U(VI) oxidation state fractions, and uranium analyses were conducted by alpha spectrometry. Uranium mobility was also studied in selected leaching experiments. Results indicate that mobilization of unusually soluble uranium, present in uranium enriched phosphate of the Pliocene age Tamiami Formation at determined concentrations of up to 729 ppm, is the source for high uranium concentrations in groundwater. In leaching experiments, approximately one-third of the uranium present in the uranium enriched phosphate was mobilized into the aqueous phase. Results of previous investigations suggest that U-234, produced in rock by U-238 decay, is selectively oxidized to U(VI). The uranium enriched phosphate studied in this investigation is characterized by selective reduction of U-234, with a pattern of increasing isotopic fractionation with core depth. As a consequence, U-234/U-238 activity ratios greater than 1.0 in the U(IV) fraction, and less than 1.0 in the U(VI) fraction have developed in the rock phase. In leaching experiments, the U(VI) fraction from the rock was preferentially mobilized into the aqueous phase, suggesting that U-234/U-238 activity ratios of leaching groundwaters are strongly influenced by the isotopic characteristics of the U(VI) fraction of rock. It is suggested that preferential leaching of U(VI), present in selectivity reduced uranium enriched phosphate, is the source for low activity ratio groundwaters in Lee County

Removal of U(VI) from aqueous solutions using Shewanella sp. RCRI7, isolated from Qurugoel Lake in Iran

Energy Technology Data Exchange (ETDEWEB)

Abdehvand, Adib Zaheri; Keshtkar, Alireza; Fatemi, Faezeh [Nuclear Science and Technology Research Institute, Tehran (Iran, Islamic Republic of). Nuclear Fuel Cycle Research School; Tarhiz, Vahideh; Hejazi, Mohammad Saeid [Tabriz Univ. of Medical Sciences (Iran, Islamic Republic of). Molecular Medicine Research Center

2017-04-01

Isolation, genotypic and phenotypic characterization of an aqueous bacterium, Shewanella sp RCRI7, from Qurugoel Lake in Iran and uranium removal from aqueous solutions using the isolate is described. Based on 16S rRNA gene sequence analysis and phylogenetic tree, strain RCRI7{sup T} falls into genus Shewanella. Closely related type strains include Shewanella xiamenensis S4{sup T} KJ542801, Shewanella profunda DSM15900{sup T} FR733713, Shewanella putrefaciens LMG 26268{sup T} X81623 and Shewanella oneidensis MR-1{sup T} AE014299. Anaerobic incubation of the bacteria in the presence of U(VI) led to uranium removal from the solution and formation of a black precipitate. Analysis of the precipitate using UV-vis confirmed the reduction of U(VI) to U(IV). The effects of pH, temperature, U(VI) concentration and cell density on uranium removal were elucidated. The maximum uranium removal was 97%. As a conclusion, the findings revealed the ability of the local strain RCRI7 for U(VI) bioreduction as an effective bacterium for uranium immobilization.

Removal of U(VI) from aqueous solutions using Shewanella sp. RCRI7, isolated from Qurugoel Lake in Iran

International Nuclear Information System (INIS)

Abdehvand, Adib Zaheri; Keshtkar, Alireza; Fatemi, Faezeh; Tarhiz, Vahideh; Hejazi, Mohammad Saeid

2017-01-01

Isolation, genotypic and phenotypic characterization of an aqueous bacterium, Shewanella sp RCRI7, from Qurugoel Lake in Iran and uranium removal from aqueous solutions using the isolate is described. Based on 16S rRNA gene sequence analysis and phylogenetic tree, strain RCRI7 T falls into genus Shewanella. Closely related type strains include Shewanella xiamenensis S4 T KJ542801, Shewanella profunda DSM15900 T FR733713, Shewanella putrefaciens LMG 26268 T X81623 and Shewanella oneidensis MR-1 T AE014299. Anaerobic incubation of the bacteria in the presence of U(VI) led to uranium removal from the solution and formation of a black precipitate. Analysis of the precipitate using UV-vis confirmed the reduction of U(VI) to U(IV). The effects of pH, temperature, U(VI) concentration and cell density on uranium removal were elucidated. The maximum uranium removal was 97%. As a conclusion, the findings revealed the ability of the local strain RCRI7 for U(VI) bioreduction as an effective bacterium for uranium immobilization.

New Technique for Speciation of Uranium in Sediments Following Acetate-Stimulated Bioremediation

Energy Technology Data Exchange (ETDEWEB)

2011-06-22

Acetate-stimulated bioremediation is a promising new technique for sequestering toxic uranium contamination from groundwater. The speciation of uranium in sediments after such bioremediation attempts remains unknown as a result of low uranium concentration, and is important to analyzing the stability of sequestered uranium. A new technique was developed for investigating the oxidation state and local molecular structure of uranium from field site sediments using X-Ray Absorption Spectroscopy (XAS), and was implemented at the site of a former uranium mill in Rifle, CO. Glass columns filled with bioactive Rifle sediments were deployed in wells in the contaminated Rifle aquifer and amended with a hexavalent uranium (U(VI)) stock solution to increase uranium concentration while maintaining field conditions. This sediment was harvested and XAS was utilized to analyze the oxidation state and local molecular structure of the uranium in sediment samples. Extended X-Ray Absorption Fine Structure (EXAFS) data was collected and compared to known uranium spectra to determine the local molecular structure of the uranium in the sediment. Fitting was used to determine that the field site sediments did not contain uraninite (UO{sub 2}), indicating that models based on bioreduction using pure bacterial cultures are not accurate for bioremediation in the field. Stability tests on the monomeric tetravalent uranium (U(IV)) produced by bioremediation are needed in order to assess the efficacy of acetate-stimulation bioremediation.

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.

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.

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).

Persistent U(IV) and U(VI) following in-situ recovery (ISR) mining of a sandstone uranium deposit, Wyoming, USA

Science.gov (United States)

Gallegos, Tanya J.; Campbell, Kate M.; Zielinski, Robert A.; Reimus, P.W.; J.T. Clay,; N. Janot,; J. J. Bargar,; Benzel, William M.

2015-01-01

Drill-core samples from a sandstone-hosted uranium (U) deposit in Wyoming were characterized to determine the abundance and distribution of uranium following in-situ recovery (ISR) mining with oxygen- and carbon dioxide-enriched water. Concentrations of uranium, collected from ten depth intervals, ranged from 5 to 1920 ppm. A composite sample contained 750 ppm uranium with an average oxidation state of 54% U(VI) and 46% U(IV). Scanning electron microscopy (SEM) indicated rare high uranium (∼1000 ppm U) in spatial association with P/Ca and Si/O attributed to relict uranium minerals, possibly coffinite, uraninite, and autunite, trapped within low permeability layers bypassed during ISR mining. Fission track analysis revealed lower but still elevated concentrations of U in the clay/silica matrix and organic matter (several 10 s ppm) and yet higher concentrations associated with Fe-rich/S-poor sites, likely iron oxides, on altered chlorite or euhedral pyrite surfaces (but not on framboidal pyrite). Organic C (mining, the likely sequestration of uranium within labile iron oxides following mining and sensitivity to changes in redox conditions requires careful attention during groundwater restoration.

Factors influencing U(VI adsorption onto soil from a candidate very low level radioactive waste disposal site in China

Directory of Open Access Journals (Sweden)

Zuo Rui

2016-01-01

Full Text Available The properties of soil at disposal sites are very important for geological disposal of very low level radioactive waste in terms of U(VI. In this study, soil from a candidate very low level radioactive waste disposal site in China was evaluated for its capacity on uranium sorption. Specifically, the equilibrium time, initial concentration, soil particle, pH, temperature, and carbonate were evaluated. The results indicated that after 15-20 days of sorption, the Kd value fluctuated and stabilized at 355-360 mL/g. The adsorptive capacity of uranium was increased as the initial uranium concentration increased, while it decreased as the soil particle size increased. The pH value played an important role in the U(VI sorption onto soil, especially under alkaline conditions, and had a great effect on the sorption capacity of soil for uranium. Moreover, the presence of carbonate decreased the sorption of U(VI onto soil because of the role of the strong complexation of carbonate with U(VI in the groundwater. Overall, this study assessed the behavior of U(VI sorption onto natural soil, which would be an important factor in the geological barrier of the repository, has contribution on mastering the characteristic of the adsorption of uranium in the particular soil media for the process of very low level radioactive waste disposal.

Thermodynamic parameters and sorption of U(VI) on ACSD

International Nuclear Information System (INIS)

Donat, R.; Cilgi, G.K.; Cetisli, H.; Aytas, S.

2009-01-01

This paper discusses the sorption properties for U(VI) by alginate coated CaSO 4 x 2H 2 O sepiolite and calcined diatomite earth (Kieselguhr) (ACSD). The removal of U(VI) from aqueous solution by sorption onto ACSF in a single component system with various contact times, pH, temperatures, and initial concentrations of U(VI) was investigated. The sorption patterns of uranium on the composite adsorbent followed the Langmuir, Freundlich and Dubinin-Radushkhevic (D-R) isotherms. The Freundlich, Langmuir, and D-R models have been applied and the data correlated well with Freundlich model and that the sorption was physical in nature (sorption energy, E a = 17.05 kJ/mol). The thermodynamic parameters such as variation of enthalpy ΔH, variation of entropy ΔS and variation of Gibbs free energy ΔG were calculated from the slope and intercept of lnK 0 vs. 1/T plots. Thermodynamic parameters (ΔH ads = 31.83 kJ/mol, ΔS ads = 167 J/mol x K, ΔGdeg ads (293.15 K) = -17.94 kJ/mol) showed the endothermic heat of sorption and the feasibility of the process. The thermodynamics of U(VI) ion/ACSD system indicates the spontaneous and endothermic nature of the process. It was noted that an increase in temperature resulted in a higher uranium loading per unit weight of the adsorbent. (author)

Uranium extraction history using pressure leaching

International Nuclear Information System (INIS)

Fraser, K.S.; Thomas, K.G.

2010-01-01

Over the past 60 years of uranium process development only a few commercial uranium plants have adopted a pressure leaching process in their flowsheet. The selection of acid versus alkaline pressure leaching is related to the uranium and gangue mineralogy. Tetravalent (U"+"4) uranium has to be oxidized to hexavalent (U"+"6) uranium to be soluble. Refractory tetravalent uranium requires higher temperature and pressure, as practised in pressure leaching, for conversation to soluble hexavalent uranium. This paper chronicles the history of these uranium pressure leaching facilities over the past 60 years, with specific details of each design and operation. (author)

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

Interactions of U(VI), Nd, and Th(IV) at the Calcite-solution interface

International Nuclear Information System (INIS)

Carroll, S.A.; Dran, J.C.

1992-01-01

The interactions of U(VI), Nd, and Th(IV) at the calcite-solution interface at controlled pCO 2 (g) have been investigated by Rutherford backscattering (RBS), scanning electron microscopy (SEM) and energy dispersive (EDS) analyses of reacted calcite. Uranium precipitation at the calcite-solution interface was observed only for those experiments in which the initial [U(VI)] was greater than the solubility of rutherfordine, UO 2 CO 3 (s). At pH 8.0, flat radial uranium and calcium zoned precipitates form at the mineral-solution interface. At pH 4.3, uranium forms an anastomosing precipitate throughout the calcite surface. RBS analyses confirmed the SEM analyses showing that uranium forms a solid phase within the calcite surface, but formation of an uranium-calcium solid solution at depth is limited. In sharp contrast to U(VI), Nd is concentrated in the solid phase as individual neodymium-calcium carbonate crystals. Calcite and pure orthorhombic neodymium carbonate crystals dissolve at the expense of the formation of a more stable neodymium-calcium solid solution. In the presence of calcite, a thorium-calcium solid solution forms by exchanging Th for Ca in the calcite structure. Thorium precipitates in two linear trends which intersect each other at approximately 105deg C and 75deg C, parallel to calcite rhombohedral cleavage faces. (orig.)

Uranium speciation in Fernald soils

International Nuclear Information System (INIS)

Morris, D.E.; Conradson, S.D.; Tait, C.D.; Chisholm-Brause, C.J.; Berg, J.; Musgrave, J.

1992-01-01

This report details progress made from January 1 to May 31, 1992 in this analytical support task to determine the speciation of uranium in contaminated soil samples from the Fernald Environmental Management Project site under the auspices of the Uranium in Soils Integrated Demonstration funded through the US DOE's Office of Technology Development. The authors' efforts have focused on characterization of soil samples collected by S.Y. Lee (Oak Ridge National Laboratory) from five locales at the Fernald site. These were chosen to sample a broad range of uranium source terms. On the basis of x-ray absorption spectroscopy data, they have determined that the majority of uranium (> 80--90%) exists in the hexavalent oxidation state for all samples examined. This is a beneficial finding from the perspective of remediation, because U(VI) species are more soluble in general than uranium species in other oxidation states. Optical luminescence data from many of the samples show the characteristic structured yellow-green emission from the uranyl (UO 2 2+ ) moiety. The luminescence data also suggest that much of the uranium in these soils is present as well-crystallized UO 2 2+ species. Some clear spectroscopic distinctions have been noted for several samples that illustrate significant differences in the speciation (1) from site to site, (2) within different horizons at the same site, and (3) within different size fractions of the soils in the same horizon at the same site. This marked heterogeneity in uranyl speciation suggests that several soil washing strategies may be necessary to reduce the total uranium concentrations within these soils to regulatory limits

Determining uranium speciation in contaminated soils by molecular spectroscopic methods: Examples from the Uranium in Soils Integrated Demonstration

International Nuclear Information System (INIS)

Allen, P.G.; Berg, J.M.; Chisholm-Brause, C.J.; Conradson, S.D.; Donohoe, R.J.; Morris, D.E.; Musgrave, J.A.; Tait, C.D.

1994-01-01

The US Department of Energy's former uranium production facility located at Fernald, OH (18 mi NW of Cincinnati) is the host site for an Integrated Demonstration for remediation of uranium-contaminated soils. A wide variety of source terms for uranium contamination have been identified reflecting the diversity of operations at the facility. Most of the uranium contamination is contained in the top ∼1/2 m of soil, but uranium has been found in perched waters indicating substantial migration. In support of the development of remediation technologies and risk assessment, we are conducting uranium speciation studies on untreated and treated soils using molecular spectroscopies. Untreated soils from five discrete sites have been analyzed. We have found that ∼80--90% of the uranium exists as hexavalent UO 2 2+ species even though many source terms consisted of tetravalent uranium species such as UO 2 . Much of the uranium exists as microcrystalline precipitates (secondary minerals). There is also clear evidence for variations in uranium species from the microscopic to the macroscopic scale. However, similarities in speciation at sites having different source terms suggest that soil and groundwater chemistry may be as important as source term in defining the uranium speciation in these soils. Characterization of treated soils has focused on materials from two sites that have undergone leaching using conventional extractants (e.g., carbonate, citrate) or novel chelators such as Tiron. Redox reagents have also been used to facilitate the leaching process. Three different classes of treated soils have been identified based on the speciation of uranium remaining in the soils. In general, the effective treatments decrease the total uranium while increasing the ratio of U(IV) to U(VI) species

Complexation of Eu(III), Th(IV) and U(VI) by humic substances

International Nuclear Information System (INIS)

Moulin, V.; Reiller, P.; Dautel, C.; Plancque, G.; Laszak, I.; Moulin, C.

1999-01-01

Complexation of actinides by humic substances has been studied by different techniques depending on the actinide and its oxidation state. For trivalent actinide (using a rare earth element, Eu as an analogue of trivalent actinide), Time-Resolved Laser-Induced Fluorescence (TRLIF) has been retained as a method for direction speciation at low level. By varying pH and physicochemical conditions (absence of carbonate ions) and at fixed ionic strength, it is possible together to identify spectrally and temporally, all the hydroxo and carbonato complexes. This approach has also been retained for U(VI) as a model of hexavalent actinide, for which hydroxo complexes have been characterized by TRLIF (the simple carbonato complexes are not fluorescent). In the case of U(VI), titrations hy humic acids of U(VI) solutions at various pH have allowed to characterize organic complexes formed with U(VI): single complexes (UO 2 HA) and mixed complexes (UO 2 (OH) 3 HA). The impact on U(VI) speciation has then been identified. In the case of Th(IV) as a model of tetravalent actinides, a competitive method has been used to obtain data on the Th-HA system by studying the ternary system silica colloid/HA/Th at constant pH (Schubert method). Apparent interaction constants have been calculated depending on Th hydrolysis constants used. A study of the system Th/HA/silica has a function of pH and for different HA concentrations has shown the strong complexing character of humic acids towards Th in the pH range 4-9. (orig.)

Stripping study of U(VI) from loaded TBP/n-paraffin using ammonium nitrate bearing waste as strippant

International Nuclear Information System (INIS)

Shrishma Paik; Biswas, S.; Bhattacharya, S.; Roy, S.B.

2013-01-01

Stripping studies of U(VI) from loaded solvent TBP/n-paraffin was carried out using ammonium nitrate solution as strippant. Effects of various stripping parameters such as concentration of ammonium nitrate solution, U(VI) concentration in organic phase, initial pH of strippant, temperature etc. have been investigated in detail. Kinetics of the stripping process by ammonium nitrate was found to be slower than that of stripping with water. It was observed that with the increase in ammonium nitrate concentration in aqueous solution, stripping of U(VI) decreased. With the increase in U(VI) loading in the organic phase, there was an increase in uranium stripping for ammonium nitrate whereas for distilled water it becomes reverse. With the increase in pH of the aqueous ammonium nitrate solution, stripping increased up to a certain pH of 8.5 and after that precipitation of uranium started. Increase in temperature of the biphasic system shows an enhancing effect of U(VI) stripping. Evaluation of thermodynamic data such as ΔH indicated that the process is endothermic. Based on the optimized conditions, McCabe-Thiele diagram was constructed for U(VI) stripping using ammonium nitrate solution at room temperature. (author)

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

International Nuclear Information System (INIS)

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

1995-11-01

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

Inhibition of bacterial U(VI) reduction by calcium

International Nuclear Information System (INIS)

Brooks, Scott C.; Fredrickson, Jim K.; Carroll, S. L.; Kennedy, David W.; Zachara, John M.; Plymale, Andrew E.; Kelly, S. D.; Kemner, K. M.; Fendorf, S.

2003-01-01

The rapid kinetics of bacterial U(VI) reduction and low solubility of uraninite (UO2,cr) make this process an attractive option for removing uranium from groundwater. Nevertheless, conditions that may promote or inhibit U(VI) reduction are not well-defined. Recent descriptions of Ca-UO2-CO3 complexes indicate that these species may dominate the aqueous speciation of U(VI) in many environments. We monitored the bacterial reduction of U(VI) in bicarbonate-buffered solution in the presence and absence of Ca. XAFS measurements confirmed the presence of a Ca-U(VI)-CO3 complex in the initial solutions containing calcium. Calcium, at millimolar concentrations (0.45-5 mM), caused a significant decrease in the rate and extent of bacterial U(VI) reduction. Both facultative (Shewanella putrefaciens strain CN32) and obligate (Desulfovibrio desulfuricans, Geobacter sulfurreducens) anaerobic bacteria were affected by the presence of calcium. Reduction of U(VI) ceased when the calculated system Eh re ached -0.046+/- 0.001 V, based on the Ca2UO2(CO3)(3) -- > UO2,cr couple. The results are consistent with the hypothesis that U is a less energetically favorable electron acceptor when the Ca-UO2-CO3 complexes are present. The results do not support Ca inhibition caused by direct interactions with the cells or with the electron donor as the reduction of fumarate or Tc(VII)O-4(-) under identical conditions was unaffected by the presence of Ca

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

The Effect of Si and Al Concentration Ratios on the Removal of U(VI) under Hanford Site 200 Area Conditions-12115

Energy Technology Data Exchange (ETDEWEB)

Katsenovich, Yelena; Gonzalez, Nathan; Moreno-Pastor, Carol; Lagos, Leonel [Applied Research Center, Florida International University, 10555 W. Flagler Street, Miami, FL 33174 (United States)

2012-07-01

Injection of reactive gases, such as NH{sub 3}, is an innovative technique to mitigate uranium contamination in soil for a vadose zone (VZ) contaminated with radionuclides. A series of experiments were conducted to examine the effect of the concentration ratio of silicon to aluminum in the presence of various bicarbonate concentrations on the coprecipitation process of U(VI). The concentration of Al in all tests remained unchanged at 2.8 mM. Experiments showed that the removal efficiency of uranium was not significantly affected by the different bicarbonate and U(VI) concentrations tested. For the lower Si:Al molar ratios of 2:1 and 18:1, the removal efficiency of uranium was relatively low (≤ 8%). For the Si:Al molar ratio of 35:1, the removal efficiency of uranium was increased to an average of ∼82% for all bicarbonate concentrations tested. At higher Si:Al molar ratios (53:1 and above), a relatively high removal efficiency of U(VI), approximately 85% and higher, was observed. These results demonstrate that the U(VI) removal efficiency is more affected by the Si:Al molar ratio than by the bicarbonate concentration in solution. The results of this experiment are promising for the potential implementation of NH{sub 3} gas injection for the remediation of U(VI) -contaminated VZ. (authors)

Uranium adsorption by non-treated and chemically modified cactus fibres in aqueous solutions

International Nuclear Information System (INIS)

Melpomeni Prodromou; Ioannis Pashalidis

2013-01-01

The adsorption efficiency of Opuntia ficus indica fibres regarding the removal of hexavalent uranium [U(VI)] from aqueous solutions has been investigated prior and after the chemical treatment (e.g. phosphorylation and MnO 2 -coating) of the biomass. The separation/removal efficiency has been studied as a function of pH, uranium concentration, adsorbent mass, ionic strength, temperature and contact time. Evaluation of the experimental data shows that biosorption is strongly pH-depended and that the MnO 2 -coated product presents the highest adsorption capacity followed by the phosphorylated and non-treated material. Experiments with varying ionic strength/salinity don't show any significant effect on the adsorption efficiency, indicating the formation of inner-sphere surface complexes. The adsorption reactions are in all cases exothermic and relatively fast, particularly regarding the adsorption on the MnO 2 -coated product. The results of the present study indicate that adsorption of uranium from waters is very effective by cactus fibres and particularly the modified treated fibres. The increased adsorption efficiency of the cactus fibres is attributed to their primary and secondary fibrillar structure, which result in a relative relative high specific surface available for sorption. (author)

Energy Transfer between U(VI) and Eu(III) Ions Adsorbed on a Silica Surface

Energy Technology Data Exchange (ETDEWEB)

Park, K. K.; Cha, W.; Cho, H. R.; Im, H. J.; Jung, E. C.; Song, K. [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

2011-05-15

Understanding of chemical behavior of actinide in a groundwater flow is important for assessing the possibility of their migration with water flows in a radioactive waste disposal site. Uranium is ubiquitous in the environment and a major actinide in a nuclear fuel cycle. Americium and curium having isotopes of long half life are minor actinides in a spent fuel. If a minor actinide coexists with uranium in a groundwater flow, some interactions between them could be expected such as minor actinide adsorption onto uranium precipitates and competition with each other for an adsorption to a mineral surface site. Eu(III) ion is frequently used as a chemical analogue of Am(III) and Cm(III) ions in a migration chemistry. The luminescent spectra of U(VI) and Eu(III) ions show a dependency on the coordination symmetry around them, and the changes in intensity or bandwidth of spectra can yield valuable information on their local environment. The luminescent lifetime also strongly depends on the coordination environment, and its measurement is valuable in probe studies on micro-heterogeneous systems. The excited U(VI) ion can be quenched through Stern.Volmer process, hydrolysis of excited species, exciplex formation, electron transfer or energy transfer. In case of U(VI)-Eu(III) system, the interaction between two ions can be studied by measuring the effect of Eu(III) ion on the quenching of U(VI) ion luminescence. There are only a few investigations on the interaction between an excited U(VI) ion and a lanthanide(III) ion. In perchlorate solution, the energy transfer to Eu(III) ion occurred only in solutions of pH>3.87. In this study, the quenching of U(VI) luminescence by Eu(III) on a silica surface was measured. The results will be discussed on the basis of a chemical interaction between them

Sediment studies of the biological factors controlling the reduction of U(VI)

International Nuclear Information System (INIS)

Lovley, Derek R.

2004-01-01

Studies were conducted primarily with sediments, both in laboratory incubations and in a field experiment, with supporting studies with pure cultures. To our knowledge the sediment studies were the first on microbial U(VI) reduction in actual uranium-contaminated subsurface sediments, under conditions that mimic those found in situ. Important findings included: (1) U(VI) reduction is a biotic process in subsurface sediments. (2) U(VI) reduction can be stimulated most effectively with the addition of acetate. Although it had been speculated that microbial U(VI) reduction might be capable of this type of environmental remediation ever since the discovery of microbial U(VI) reduction, this had not been previously demonstrated under environmentally relevant conditions. (3) U(VI) is reduced concurrently with Fe(III) and prior to sulfate reduction. U(VI) and Fe(III) reduction proceeded concurrently, accompanied by a dramatic enrichment in organisms in the Geobacteraceae. Sulfate-reducing microorganisms do not appear to be important components of the microbial community reducing U(VI) in these subsurface sediments. (4) Nitrate has important influences on U(VI) reduction. Nitrate inhibits the reduction of metals until nitrate is depleted. Fe(III)-reducing microorganisms such as Geobacter metallireducens and Desulfitobacterium species can oxidize Fe(II) with the reduction of nitrate which is an important consideration because our previous studies have demonstrated that freshly precipitated Fe(III) oxides can reoxidize U(IV) to U(VI). The discovery that G. metallireducens can ''run backwards'' and oxidize U(IV) when nitrate is present reveals another mechanism preventing precipitation of U(IV) in the presence of nitrate as well as potential novel strategy for removing uranium from the subsurface after a site has been remediated. (5) Importance of understanding Fe(III) forms available for microbial reduction. Fe(III) is orders of magnitude more abundant than U(VI) as an

Spectroscopic Evidence of Uranium Immobilization in Acidic ...

Science.gov (United States)

Biogeochemistry of uranium in wetlands plays important roles in U immobilization in storage ponds of U mining and processing facilities but has not been well understood. The objective of this work was to study molecular mechanisms responsible for high U retention by Savannah River Site (SRS) wetland sediments under varying redox and acidic (pH = 2.6-5.8) conditions using U L3-edge X-ray absorption spectroscopy. Uranium in the SRS wetland sediments existed primarily as U(VI) bonded as a bidentate to carboxylic sites (U-C bond distance at ~2.88 Å), rather than phenolic or other sites of natural organic matter (NOM). In microcosms simulating the SRS wetland process, U immobilization on roots was 2 orders of magnitude higher than on the adjacent brown or more distant white sands in which U was U(VI). Uranium on the roots were both U(IV) and U(VI), which were bonded as a bidentate to carbon, but the U(VI) may also form a U phosphate mineral. After 140 days of air exposure, all U(IV) was reoxidized to U(VI) but remained as a bidentate bonding to carbon. This study demonstrated NOM and plant roots can highly immobilize U(VI) in the SRS acidic sediments, which has significant implication on the long-term stewardship of U-contaminated wetlands. There were several former U processing facilities at the Savannah River Site (SRS), Aiken, SC. As a result of their operations, uranium has entered the surrounding environments. For example, approximately 45,000 kg o

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.

Modeling the effectiveness of U(VI) biomineralization in dual-porosity porous media

Science.gov (United States)

Rotter, B. E.; Barry, D. A.; Gerhard, J. I.; Small, J. S.

2011-05-01

SummaryUranium contamination is a serious environmental concern worldwide. Recent attention has focused on the in situ immobilization of uranium by stimulation of dissimilatory metal-reducing bacteria (DMRB). The objective of this work was to investigate the effectiveness of this approach in heterogeneous and structured porous media, since such media may significantly affect the geochemical and microbial processes taking place in contaminated sites, impacting remediation efficiency during biostimulation. A biogeochemical reactive transport model was developed for uranium remediation by immobile-region-resident DMRB in two-region porous media. Simulations were used to investigate the parameter sensitivities of the system over wide-ranging geochemical, microbial and groundwater transport conditions. The results suggest that optimal biomineralization is generally likely to occur when the regional mass transfer timescale is less than one-thirtieth the value of the volumetric flux timescale, and/or the organic carbon fermentation timescale is less than one-thirtieth the value of the advective timescale, and/or the mobile region porosity ranges between equal to and four times the immobile region porosity. Simulations including U(VI) surface complexation to Fe oxides additionally suggest that, while systems exhibiting U(VI) surface complexation may be successfully remediated, they are likely to display different degrees of remediation efficiency over varying microbial efficiency, mobile-immobile mass transfer, and porosity ratios. Such information may aid experimental and field designs, allowing for optimized remediation in dual-porosity (two-region) biostimulated DMRB U(VI) remediation schemes.

Uranium isotopic effect studies on cation and anion exchange resins

International Nuclear Information System (INIS)

Sarpal, S.K.; Gupta, A.R.

1975-01-01

Uranium isotope effects in exchange reactions involving hexavalent and tetravalent uranium, on ion exchange resins, have been re-examined. The earlier work on uranium isotope effects in electron exchange reactions involving hexavalent and tetravalent uranium, has been critically reviewed. New experimental data on these systems in hydrochloric acid medium, has been obtained, using break-through technique on anion-exchange columns. The isotope effects in these break-through experiments have been reinterpreted in a way which is consistent with the anion exchange behaviour of the various uranium species in these systems. (author)

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)

Recovery of U(Vi) with unexpanded perlite; Recuperacion de U(VI) con perlita no expandida

Energy Technology Data Exchange (ETDEWEB)

Cuevas J, A.K.; Davila R, J. I.; Lopez del R, H.; Mireles G, F., E-mail: cuja2105@hotmail.com [Universidad Autonoma de Zacatecas, Unidad Academica de Estudios Nucleares, Cipres No. 10, Fracc. La Penuela, 98068 Zacatecas, Zac. (Mexico)

2015-09-15

Perlite is a glass volcanic rock that is hydrated by the addition of water during its formation. Is a natural material widely used in the chemical and construction industries, but recently beginning to be studied their adsorptive properties. In this paper the adsorption capacity of unexpanded perlite to remove U(Vi) in aqueous solution depending on the grain size of the material was investigated, as well as the contact time between the liquid and solid phases, ph of solution and initial concentration of uranium. The adsorption was dependent on the surface area of the material, recovering higher uranium percentage to smaller particle size. Meanwhile kinetics showed that the uranium adsorption is rapid, reaching equilibrium in 1 h. Adsorption to slightly acidic conditions was favored but dropped dramatically to ph highly acidic and basic; at a concentration of 1 x 10{sup -3} M UO{sub 2}{sup +2} the maximum uranium recovery was 46% at ph 6. In dilute solutions (1 x 10{sup -5} to 1 x 10{sup -3} M) the adsorption percentage reached values between 34 and 42%, but was reduced to 1% at a concentration of 1 x 10{sup -2} M. (Author)

Speciation of uranium with respect to hydrogeological aspects

International Nuclear Information System (INIS)

Meinrath, G.

1997-01-01

Until 1991, eastern Germany has been third largest uranium producer in the world. After the cease of uranium production, larger areas remained contaminated by uranium mining debris, mill-tailings and mining areas. Since 1991 these areas are in the process of remediation by intervention. In Germany, legal stipulations require the prognosis of the likely mid-term impact of an intervention. The benefit of a planned remediation procedure must be evident against the Zero option (doing nothing) and alternative actions. Thermodynamic data of geochemically relevant reactions for uranium under conditions of natural aqueous solution serve as important input data into geochemical reactive transport codes. Especially hydrolysis and carbonato complexation of hexavalent uranium influence the geochemical behaviour of uranium. The first part of the report report summarizes the fundamental chemical facts on mineralogy, electronic structure, UV-Vis and emission spectroscopy of hexavalent uranium. A second part reports in depth the experimental and numerical procedures to study the hydrolytic and carbonate complexation behaviour of hexavalent uranium. The evaluation of single component spectra of the relevant uranium species is discussed. Spectral curves are quantitatively deconcoluted into single components. In all cases the associated uncertainties are given. Thermodynamic data on hydrolysis and carbonato species derived from these experiments are compared to existing data in the literature. (orig.)

Sorption study of 226Ra(II) et 238U(VI) on to peat organic matter, in mining environment

International Nuclear Information System (INIS)

Bordelet, Gabrielle

2014-01-01

The environmental footprint of former uranium mining sites is a major concern for society. In order to guarantee the protection of ecosystems and thus a minimal radiological impact on the biosphere, it is important to understand and to be able to model the phenomena controlling the migration of uranium and its decay products, specially radium ( 226 Ra) (AREVA's Envir-at-Mines project). In the environment, among solid phases which can retain 238 U(VI) and 226 Ra(II), peat is known to have relevant affinity for U(VI). Because peat is usually composed at 90% dry weight of organic matter, the aim of this study was to qualify and quantify peat organic matter affinity for 238 U(VI) and 226 Ra(II). Peat samples extracted from Les Sagnes (close to a former uranium mining site in Limousin area, France) was characterised and batch adsorption/desorption experiments were conducted. The results indicate that 226 Ra(II) adsorption onto that peat is higher than 97% for pH ≥ 4-6 (depending on the organic/mineral ratio in dry peat) corresponding to K d values about 4500 ± 500 mL/g and 238 U(VI) adsorption is higher than 80% at pH ≥ 3 with K d maximal values reaching 11000 mL/g around pH 4.5. Only a little desorption was measured after one month. An ion exchange modelling for radium adsorption onto one type of organic matter sorption site was enough to fit the experimental adsorption K d for the peat over the whole range of pH. However, uranium sorption on peat can be modelled on that organic sorption site only from pH 1 to 5. From pH 5 to 10, to explain the experimental uranium adsorption K d values (close to 1500 mL/g), uranium sorption onto mineral phases (such as smectite and iron oxide in this study) has to be considered. An operational data set is given for both 238 U(VI) and 226 Ra(II) sorption onto Les Sagnes peat. Unlike usual peat, peat from Les Sagnes contains more than 10% dry weight of mineral matter. That is why it is necessary to model sorption of those two

Simultaneous removal and recovery of uranium from aqueous solution using TiO_2 photoelectrochemical reduction method

International Nuclear Information System (INIS)

Huichao He; Meirong Zong; Faqin Dong; Southwest University of Science and Technology, Sichuan; Pengpan Yang; Gaili Ke; Mingxue Liu; Xiaoqin Nie; Wei Ren; Liang Bian; Southwest University of Science and Technology, Sichuan; Chinese Academy of Sciences, Xinjiang

2017-01-01

U(VI)-containing wastewater has potential radiation hazard to the environment, but contains valuable uranium resource. Based on the reduction of U(VI) and the difference in solubility between U(VI) and U(IV), here we construct a TiO_2-based photoelectrochemical cell to remove U(VI) and recover uranium from aqueous solution. By irradiating TiO_2 photoanode at E = 0.45 V versus SCE, U(VI) can be simultaneously removed from aqueous solution and recovered as solid uranium compounds on a FTO glass cathode. Since ethanol can act as hole scavenger to protect the formed U(IV) and provide CO_2"−"· as reductant, ethanol adding improved the U(VI) reduction efficiency of TiO_2-based photoelectrochemical cell. (author)

Kinetic study of time-dependent fixation of U"V"I on biochar

International Nuclear Information System (INIS)

Ashry, A.; Bailey, E.H.; Chenery, S.R.N.; Young, S.D.

2016-01-01

Biochar, a by-product from the production of biofuel and syngas by gasification, was tested as a material for adsorption and fixation of U"V"I from aqueous solutions. A batch experiment was conducted to study the factors that influence the adsorption and time-dependent fixation on biochar at 20 °C, including pH, initial concentration of U"V"I and contact time. Uranium (U"V"I) adsorption was highly dependent on pH but adsorption on biochar was high over a wide range of pH values, from 4.5 to 9.0, and adsorption strength was time-dependent over several days. The experimental data for pH > 7 were most effectively modelled using a Freundlich adsorption isotherm coupled to a reversible first order kinetic equation to describe the time-dependent fixation of U"V"I within the biochar structure. Desorption experiments showed that U"V"I was only sparingly desorbable from the biochar with time and isotopic dilution with "2"3"3U"V"I confirmed the low, or time-dependent, lability of adsorbed "2"3"8U"V"I. Below pH 7 the adsorption isotherm trend suggested precipitation, rather than true adsorption, may occur. However, across all pH values (4.5-9) measured saturation indices suggested precipitation was possible: autunite below pH 6.5 and either swartzite, liebigite or bayleyite above pH 6.5.

Ex-situ bioremediation of U(VI from contaminated mine water using Acidithiobacillus ferrooxidans strains

Directory of Open Access Journals (Sweden)

Maria eRomero-Gonzalez

2016-05-01

Full Text Available The ex-situ bioremoval of U(VI from contaminated water using Acidithiobacillus ferrooxidans strain 8455 and 13538 was studied under a range of pH and uranium concentrations. The effect of pH on the growth of bacteria was evaluated across the range 1.5 – 4.5 pH units. The respiration rate of At. ferrooxidans at different U(VI concentrations was quantified as a measure of the rate of metabolic activity over time using an oxygen electrode. The biosorption process was quantified using a uranyl nitrate solution, U-spiked growth media and U-contaminated mine water. The results showed that both strains of At. ferrooxidans are able to remove U(VI from solution at pH 2.5 – 4.5, exhibiting a buffering capacity at pH 3.5. The respiration rate of the micro-organism was affected at U(VI concentration of 30 mg L-1. The kinetics of the sorption fitted a pseudo-first order equation, and depended on the concentration of U(VI. The KD obtained from the biosorption experiments indicated that strain 8455 is more efficient for the removal of U(VI. A bioreactor designed to treat a solution of 100 mg U(VI L-1 removed at least 50% of the U(VI in water. The study demonstrated that At. ferrooxidans can be used for the ex-situ bioremediation of U(VI contaminated mine water.

Uranium nanoparticle synthesis from leaching solution

International Nuclear Information System (INIS)

Sadowski, Z.; Sklodowska, A.

2014-01-01

The removal of uranium from leaching and bioleaching solutions is of great significance for an environment protection. In comparison with conventional separation techniques, synthesis of uranium nanoparticles has a number of benefits. It has been demonstrated that the uranium nanoparticles show high catalytic activity. In the present studies a variety of synthesis systems have been used for reduction of uranium from bioleaching solution. Among various catalytical templates the hematite Fe_2O_3 nanoparticles are most interest It was presented the report on development of synthesis method to produce nano structured Fe_2O_3 particles. The efficiency of hematite nanoparticles for adsorption of uranium ions from bioleaching solutions was investigated. Bacterial leaching is alternate technique used to extract uranium from mining wastes. The bioleaching process is environment friendly and gives the extraction yield of over 90%. The bioleaching solutions were obtained from bioleaching experiments using waste materials from different places at Lower Silesia (Kowary, Grzmiaca, Kopaniec, Radoniow). Chemoautotrophic bacteria were used for bioleaching tests. The significant adsorption capacity of U(VI) onto iron oxide and hydroxides (goethite, hematite, and magnetite) was observed. The sorption of U(VI) onto the hematite surface was connected with the chemical reduction of U(VI) to U(IV) by Fe"2"+ ions. The initial reaction system contained excess of Fe"2"+ ions which were used to reduce of U(VI). The reduction of U(VI) occurred at pH at the vicinity of pH=2.4. The colloid particles of hematite with UO_2 nanoparticles were obtained. The results of zeta potential measurements of hematite nanoparticles showed that at the ionic strength equals 10"-"3M NaCl, the average zeta potential was +32.4±3.5 mV at pH = 2.6. The interaction of hematite nanoparticles with the bioleaching solutions led to decrease of positive zeta potential to the value of 6.4± 2.7 mV. (author)

Kinetics of U(VI) reduction by a dissimilatory Fe(III)-reducing bacterium under non-growth conditions

International Nuclear Information System (INIS)

Truex, M.J.; Peyton, B.M.; Valentine, N.B.; Gorby, Y.A.

1997-01-01

Dissimilatory metal-reducing microorganisms may be useful in processes designed for selective removal of uranium from aqueous streams. These bacteria can use U(VI) as an electron acceptor and thereby reduce soluble U(VI) to insoluble U(IV). While significant research has been devoted to demonstrating and describing the mechanism of dissimilatory metal reduction, the reaction kinetics necessary to apply this for remediation processes have not been adequately defined. In this study, pure culture Shewanella alga strain BrY reduced U(VI) under non-growth conditions in the presence of excess lactate as the electron donor. Initial U(VI) concentrations ranged from 13 to 1,680microM. A maximum specific U(VI) reduction rate of 2.37 micromole-U(VI)/(mg-biomass h) and Monod half-saturation coefficient of 132 microM-U(VI) were calculated from measured U(VI) reduction rates. U(VI) reduction activity was sustained at 60% of this rate for at least 80 h. The initial presence of oxygen at a concentration equal to atmospheric saturation at 22 C delays but does not prevent U(VI) reduction. The rate of U(VI) reduction by BrY is comparable or better than rates reported for other metal reducing species. BrY reduces U(VI) at a rate that is 30% of its Fe(III) reduction rate

The reduction of U(VI) on corroded iron under anoxic conditions

International Nuclear Information System (INIS)

Cui, D.; Spahiu, K.

2002-01-01

The corrosion of iron and the interaction between corroded iron and U(VI) in anoxic conditions were investigated. The anoxic conditions were obtained by flushing an 99.97% Ar-0.03% CO 2 gas mixture through the test vessel, in which an oxygen trap and six reaction bottles containing synthetic groundwater (10 mM NaCl and 2 mM HCO 3 - .) were placed. The dark-green coloured corrosion product, formed on iron surface after three months corrosion in synthetic groundwater solutions, was identified by powder X-ray diffraction to be carbonate green rust, Fe 4 II Fe 2 III (OH) 12 CO 3 . The iron foil that reacted in a solution (10 ppm U(VI), 10 mM NaCl and 2 mM HCO 3 - ) for three months was analysed by SEM-EDS. The result shows that: (i) an uneven layer of carbonate green rust (1-5 μm thick) formed on the metallic iron; (ii) a thin (0.3 μm) uranium-rich layer deposited on top of the carbonate green rust layer; and (iii) some UO 2 crystals (3-5 μm sized) on the thin uranium layer. The experimental results proved that the U(VI) removal capacity of metal iron is not hindered by formation of a layer of carbonate green rust on the iron. Tests with cast iron and pure iron indicate that they have similar U(VI) removal capacities. At the end of experiment, U concentrations in solution approached the solubility of UO 2 (s), 10 -8 M. The stability of the carbonate green rust at the experimental conditions, pH, E h , [Fe 2+ ] and [HCO 3 - ], is discussed. (orig.)

Biotransformations Involved in Sustained Reductive Removal of Uranium in Contaminated Aquifers. Final report

International Nuclear Information System (INIS)

Lovley, Derek R.

2008-01-01

The studies completed under this grant significantly advanced the understanding and design of strategies for in situ uranium bioremediation. Novel strategies identified show promise to make in situ uranium bioremediation technically simpler and less expensive. As detailed, important findings included: (1) Development of an electron donor delivery strategy to prolong the in situ activity of Geobacter species and enhance the removal of uranium from the groundwater; (2) Demonstration that reproducible year-to-year field experiments were possible at the ERSP study site in Rifle, CO, making hypothesis-driven field experimentation possible; (3) Elucidation of the geochemical and microbiological heterogeneities with the subsurface during in situ uranium bioremediation, which must be accounted for to accurately model the bioremediation process; (4) The discovery that most of the U(VI) contamination at the Rifle site is sediment-associated rather than mobile in the groundwater, as previously considered; (5) The finding that unlike soluble U(VI), sediment-associated U(VI) is not microbially reducible; (6) The demonstration that electrodes may be an effective alternative to acetate as an electron donor to promote microbial U(VI) reduction in the subsurface with the added benefit that electrode-promoted microbial U(VI) reduction offers the possibility of removing the immobilized uranium from the subsurface; and (7) The finding that, after extended acetate inputs, U(VI) continues to be removed from groundwater long after the introduction of acetate into the subsurface is terminated and that this appears to be due to adsorption onto biomass. This potentially will make in situ uranium bioremediation much less expensive than previously envisioned.

Uranium geochemistry and dating of Pacific island apatite

Energy Technology Data Exchange (ETDEWEB)

Roe, K K; Burnett, W C [Florida State Univ., Tallahassee (USA). Dept. of Oceanography

1985-07-01

Uranium-series disequilibrium dating of island phosphate deposits is evaluated in terms of known associated coral ages, uranium geochemistry, and stratigraphic sequences as well as the concordance between the geochronometers /sup 234/U//sup 238/U, /sup 230/Th//sup 234/U and /sup 226/Ra//sup 238/U. U(VI) is the predominant oxidation state of uranium in island phosphorites and by analogy to the youngest surficial deposits, most of the uranium initially bound is in the form of U(VI) sorbed by surfaces from seawater. Insular deposits contain more organic matter than even very young ocean floor samples and this leads to a greater probability of reduction of available recoil uranium than occurs in marine deposits. As a consequence, R(VI) <= R(T) <= R(VI), where R represents the /sup 234/U//sup 238/U activity ratio. This situation is completely opposite from that observed for marine-origin phosphorites. We determined that a fraction of U(VI) in ancient insular phosphorites is very labile and lost to alkaline carbonate solutions with a uranium activity ratio even more depleted in /sup 234/U than the bulk R(VI). The results are discussed.

Characterization of U(VI) Sorption-Desorption Processes and Model Upscaling

International Nuclear Information System (INIS)

Bai, Jing; Dong, Wenming; Ball, William P.

2006-01-01

The objectives of the overall collaborative EMSP effort (with which this project is associated) were to characterize sorption and desorption processes of U(VI) on pristine and contaminated Hanford sediments over a range of sediment facies and materials properties and to relate such characterization both to fundamental molecular-scale understanding and field-scale models of geochemistry and mass transfer. The research was intended to provide new insights on the mechanisms of U(VI) retardation at Hanford, and to allow the development of approaches by which laboratory-developed geochemical models could be upscaled for defensible field-scale predictions of uranium transport in the environment. Within this broader context, objectives of the JHU-based project were to test hypotheses regarding the coupled roles of adsorption and impermeable-zone diffusion in controlling the fate and transport of U(VI) species under conditions of comparatively short-term exposure. In particular, this work tested the following hypotheses: (1) the primary adsorption processes in the Hanford sediment over the pH range of 7 to 10 are surface complexation reactions of aqueous U(VI) hydroxycarbonate and carbonate complexes with amphoteric edge sites on detrital phyllosilicates in the silt/clay size fraction; (2) macroscopic adsorption intensity (at given aqueous conditions) is a function of mineral composition and aquatic chemistry; and (3) equilibrium sorption and desorption to apply in short-term, laboratory-spiked pristine sediments; and (4) interparticle diffusion can be fully understood in terms of a model that couples molecular diffusion of uranium species in the porewater with equilibrium sorption under the relevant aqueous conditions. The primary focus of the work was on developing and applying both models and experiments to test the applicability of ''local equilibrium'' assumptions in the modeling interpretation of sorption retarded interparticle diffusion, as relevant to processes of

Biotransformation involved in sustained reductive removal of uranium in contaminant aquifers

International Nuclear Information System (INIS)

Lovley, Derek R.

2005-01-01

This report summarizes progress made from August 2004 to July 2005. During this period research focused primarily on obtaining a better understanding of the factors controlling the reduction of U(VI) during in situ uranium bioremediation as well as investigating the potential for using electrodes as an alternative electron donor to promote in situ uranium reduction. Analysis of the 2003 experiment at the field study site in Rifle, CO was completed. The results demonstrated the substantial heterogeneity of the zone undergoing bioremediation, both in terms of geochemistry and microbiology. The lack of U(VI) reduction under sulfate-reducing conditions was clearly documented. The need for more detailed sampling both with time and with depth in the aquifer was demonstrated. For the first time a comparison between the composition of the microbial community in the sediments and the microbes in the corresponding groundwater was attempted. The findings from this study are important not only in further demonstrating the potential for in situ uranium bioremediation, but also for indicating how methods and sampling approaches should be improved in the future. A manuscript summarizing these findings has been accepted for publication in Applied and Environmental Microbiology. In summer of 2004 a new field experiment was conducted at the Rifle site. A novel feature of this study was much more intensive sampling in order to better define the progression of microbial processes during in situ uranium bioremediation. The results demonstrated that stimulation of in situ uranium bioremediation with added acetate was a repeatable phenomenon and that U(VI) reduction was clearly linked to the presence and activity of microorganisms in the family Geobacteraceae. A manuscript summarizing these results is in preparation. A surprising result of the field studies at the Rifle site was that although Geobacter species actively reduced U(VI) in the groundwater, removing it from solution, a high

In situ Microbial Community Control of the Stability of Bio-Reduced Uranium

International Nuclear Information System (INIS)

Long, Phillip E.; McKinley, James P.; White, David C.

2006-01-01

In aerobic aquifers typical of many Department of Energy (DOE) legacy waste sites, uranium is present in the oxidized U(VI) form which is soluble and thus mobile compared to U(IV). Previous work at the Old Rifle Uranium Mill Tailings Remedial Action (UMTRA) site demonstrated that biostimulation by acetate injection promoted growth of Geobacteraceae and stimulated the microbial reduction of U(VI) to less soluble U(IV) (1, 4). Despite the potential for oxidative dissolution of bio-reduced U(IV), field experiments at the Old Rifle site show that although the rate of U(VI) reduction decreases following the on-set of sulfate reduction, U(VI) reduction continues even following the cessation of acetate injection (1, 4). However, U(VI) reduction is reversible and the basis for the observed maintenance of U(VI) reduction post-stimulation is a critical but as yet unresolved issue for the application of biostimulation as a treatment technology. The continued U(VI) reduction and the maintenance of reduced U(IV) may result from many factors including U(VI) reduction by sulfate reducing bacteria (SRB), generation of H2S or FeS0.9 which serves as an oxygen sink, or the preferential sorption of U(VI) by microbial cells or biopolymers. The overall goal of the project is to develop an understanding of the mechanisms for the maintenance of bio-reduced uranium in an aerobic aquifer under field conditions following the cessation of electron donor addition

Geochemical behaviour of uranium in sedimentary formations: insights from a natural analogue study - 16340

International Nuclear Information System (INIS)

Noseck, Ulrich; Brasser, Thomas; Havlova, Vaclava; Cervinka, Radek; Suksi, Juhani

2009-01-01

Groundwater data from the natural analogue site Ruprechtov have been evaluated with special emphasis on the uranium behaviour in the so-called uranium-rich clay/lignite horizon. In this horizon in-situ Eh-values in the range of -160 to -280 mV seem to be determined by the SO 4 2- /HS - couple. Under these conditions U(IV) is expected to be the preferential redox state in solution. However, on-site measurements in groundwater from the clay/lignite horizon show only a fraction of about 20 % occurring in the reduced state U(IV). Thermodynamic calculations reveal that the high CO 2 partial pressure in the clay/lignite horizon can stabilise hexavalent uranium, which explains the occurrence of U(VI). The calculations also indicate that the low uranium concentrations in the range between 0.2 and 2.1 μg/l are controlled by amorphous UO 2 and/or the U(IV) phosphate mineral ningyoite. This confirms the findings from previous work that the uranium (IV) mineral phases are long-term stable under the reducing conditions in the clay/lignite horizon without any signatures for uranium mobilisation. It supports the current knowledge of the geological development of the site and is also another important indication for the long-term stability of the sedimentary system itself, namely of the reducing geochemical conditions in the near-surface (30 m to 60 m deep) clay/lignite horizon. Further work with respect to the impact of changes in redox conditions on the uranium speciation is on the way. (authors)

Application of HDTMA-intercalated bentonites in water waste treatment for U(VI) removal

International Nuclear Information System (INIS)

Krajnak, Adrian; Viglasova, Eva; Galambos, Michal; Krivosudsky, Lukas; Universitat Wien, Vienna

2017-01-01

Bentonite deposits in Slovakia are systematically investigated as potential adsorbents for wastewater and radioactive waste treatment applications. Herein, adsorption properties (isotherms, kinetics and thermodynamics) of raw and organo-modified bentonites towards uranium species in aqueous solutions were investigated. Organo-modified bentonites was prepared by practical and simple chemical modification method with hexadecyltrimethylammonium bromide (denoted as HDTMA-bentonites). The adsorption processes of U(VI) on HDTMA-bentonites were spontaneous and endothermic, and well simulated by pseudo-second-order model. The maximum adsorption capacity of U(VI) was calculated to be 31.45 mg/g at pH 8.5 and T = 298 K. Slovak bentonites Jelsovy potok and Kopernica, their natural and HDTMA-modified forms might be a promising sorbent for the treatment of U(VI) contaminants in aqueous solutions. (author)

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

International Nuclear Information System (INIS)

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

2010-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2010-01-29

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

In Situ Microbial Community Control of the Stability of Bio-reduced Uranium

International Nuclear Information System (INIS)

Baldwin, Brett R.; Peacock, Aaron D.; Resch, Charles T.; Arntzen, Evan; Smithgall, Amanda N.; Pfiffner, Susan; Gan, M.; McKinley, James P.; Long, Philip E.; White, David C.

2008-01-01

In aerobic aquifers typical of many Department of Energy (DOE) legacy waste sites, uranium is present in the oxidized U(VI) form which is more soluble and thus more mobile. Field experiments at the Old Rifle UMTRA site have demonstrated that biostimulation by electron donor addition (acetate) promotes biological U(VI) reduction (2). However, U(VI) reduction is reversible and oxidative dissolution of precipitated U(IV) after the cessation of electron donor addition remains a critical issue for the application of biostimulation as a treatment technology. Despite the potential for oxidative dissolution, field experiments at the Old Rifle site have shown that rapid reoxidation of bio-reduced uranium does not occur and U(VI) concentrations can remain at approximately 20% of background levels for more than one year. The extent of post-amendment U(VI) removal and the maintenance of bioreduced uranium may result from many factors including U(VI) sorption to iron-containing mineral phases, generation of H2S or FeS0.9, or the preferential sorption of U(VI) by microbial cells or biopolymers, but the processes controlling the reduction and in situ reoxidation rates are not known. To investigate the role of microbial community composition in the maintenance of bioreduced uranium, in-well sediment incubators (ISIs) were developed allowing field deployment of amended and native sediments during on-going experiments at the site. Field deployment of the ISIs allows expedient interrogation of microbial community response to field environmental perturbations and varying geochemical conditions.

In Situ Microbial Community Control of the Stability of Bio-reduced Uranium

Energy Technology Data Exchange (ETDEWEB)

Baldwin, Brett, R.; Peacock, Aaron, D.; Resch, Charles, T.; Arntzen, Evan; Smithgall, Amanda, N.; Pfiffner, Susan; Gan, M.; McKinley, James, P.; Long, Philip, E.; White, David, C.

2008-03-28

In aerobic aquifers typical of many Department of Energy (DOE) legacy waste sites, uranium is present in the oxidized U(VI) form which is more soluble and thus more mobile. Field experiments at the Old Rifle UMTRA site have demonstrated that biostimulation by electron donor addition (acetate) promotes biological U(VI) reduction (2). However, U(VI) reduction is reversible and oxidative dissolution of precipitated U(IV) after the cessation of electron donor addition remains a critical issue for the application of biostimulation as a treatment technology. Despite the potential for oxidative dissolution, field experiments at the Old Rifle site have shown that rapid reoxidation of bio-reduced uranium does not occur and U(VI) concentrations can remain at approximately 20% of background levels for more than one year. The extent of post-amendment U(VI) removal and the maintenance of bioreduced uranium may result from many factors including U(VI) sorption to iron-containing mineral phases, generation of H2S or FeS0.9, or the preferential sorption of U(VI) by microbial cells or biopolymers, but the processes controlling the reduction and in situ reoxidation rates are not known. To investigate the role of microbial community composition in the maintenance of bioreduced uranium, in-well sediment incubators (ISIs) were developed allowing field deployment of amended and native sediments during on-going experiments at the site. Field deployment of the ISIs allows expedient interrogation of microbial community response to field environmental perturbations and varying geochemical conditions.

Microbial Community Changes in Response to Ethanol or Methanol Amendments for U(VI) Reduction

International Nuclear Information System (INIS)

Vishnivetskaya, Tatiana A.; Brandt, Craig C.; Madden, Andrew; Drake, Meghan M.; Kostka, Joel; Akob, Denise M.; Kusel, Kirsten; Palumbo, Anthony Vito

2010-01-01

Microbial community responses to ethanol, methanol and methanol + humics amendments in relationship to uranium bioremediation were studied in laboratory microcosm experiments using sediments and ground water from a uranium-contaminated site in Oak Ridge, Tennessee. Ethanol addition always resulted in uranium reduction at rate of 0.8-1.0 mol l -1 d -1 while methanol addition did so occasionally at rate 0.95 mol l -1 d -1 . The type of carbon source added, the duration of incubation, and the sampling site influenced the bacterial community structure upon incubation. Analysis of 16S rRNA gene clone libraries indicated (1) bacterial communities found in ethanol- and methanol-amended samples with U(VI) reduction were similar due to presence of -Proteobacteria, and -Proteobacteria (members of the families Burkholderiaceae, Comamonadaceae, Oxalobacteraceae, and Rhodocyclaceae); (2) methanol-amended samples without U(VI) reduction exhibited the lowest diversity and the bacterial community contained 69.2-92.8% of the family Methylophilaceae; and (3) the addition of humics resulted in an increase of phylogenetic diversity of -Proteobacteria (Rodoferax, Polaromonas, Janthinobacterium, Methylophilales, unclassified) and Firmicutes (Desulfosporosinus, Clostridium).

Extraction and Separation of Uranium (VI) and Thorium (IV) Using Tri-n-dodecylamine Impregnated Resins

International Nuclear Information System (INIS)

Metwally, E.; Saleh, A.Sh.; El-Naggar, H.A.

2005-01-01

Extraction of U(VI) and Th(IV) from chloride and nitrate solutions with tri-n- dodecylamine impregnated on Amberlite XAD4, was investigated. The distribution of U(VI) and Th(IV) was studied at different concentrations of acid, salting-out agent, extractant, aqueous metal ion and other parameters. Absorption spectral studies have been investigated for uranium species in both aqueous HCl solution and the resin phase. From these studies, it is suggested that the tetrachloro complex of U(VI) is formed in the extraction of uranium (VI) from hydrochloric acid solutions by TDA impregnated resin. Stripping of the extracted U(VI) and Th(IV) was assayed with HCl and HNO 3 . Finally, the separation of uranium from thorium and fission products in HCl media was achieved

Ammonium carbonate and/or bicarbonate plus alkaline chlorate oxidant for recovery of uranium values

International Nuclear Information System (INIS)

Stapp, P.R.

1983-01-01

In accordance with the present invention, uranium values are extracted from materials containing uranium in valence states lower than its hexavalent state by contacting the materials containing uranium with an aqueous alkaline leach solution containing an alkaline chlorate in an amount sufficient to oxidize at least a portion of the uranium in valence states lower than its hexavalent state to its hexavalent state. In a further embodiment of the present invention, the alkaline leach solution is an aqueous solution of a carbonate selected from the group consisting of ammonium carbonate, ammonium bicarbonate and mixtures thereof. In yet another embodiment of the present invention, at least one catalytic compound of a metal selected from the group consisting of copper, cobalt, iron, nickel, chromium and mixtures thereof adapted to assure the presence of the ionic species Cu ++ , Co ++ , Fe +++ , Ni ++ , Cr +++ and mixtures thereof, respectively, during the contacting of the material containing uranium with the alkaline leach solution and in an amount sufficient to catalyze the oxidation of at least a portion of the uranium in its lower valence states to its hexavalent state, is present

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

Modeling of geochemical processes related to uranium mobilization in the groundwater of a uranium mine

International Nuclear Information System (INIS)

Gomez, P.; Garralon, A.; Buil, B.; Turrero, Ma.J.; Sanchez, L.; Cruz, B. de la

2006-01-01

This paper describes the processes leading to uranium distribution in the groundwater of five boreholes near a restored uranium mine (dug in granite), and the environmental impact of restoration work in the discharge area. The groundwater uranium content varied from < 1 μg/L in reduced water far from the area of influence of the uranium ore-containing dyke, to 104 μg/L in a borehole hydraulically connected to the mine. These values, however, fail to reflect a chemical equilibrium between the water and the pure mineral phases. A model for the mobilization of uranium in this groundwater is therefore proposed. This involves the percolation of oxidized waters through the fractured granite, leading to the oxidation of pyrite and arsenopyrite and the precipitation of iron oxyhydroxides. This in turn leads to the dissolution of the primary pitchblende and, subsequently, the release of U(VI) species to the groundwater. These U(VI) species are retained by iron hydroxides. Secondary uranium species are eventually formed as reducing conditions are re-established due to water-rock interactions

Multistage bioassociation of uranium onto an extremely halophilic archaeon revealed by a unique combination of spectroscopic and microscopic techniques

Energy Technology Data Exchange (ETDEWEB)

Bader, Miriam; Müller, Katharina; Foerstendorf, Harald; Drobot, Björn [Helmholtz-Zentrum Dresden – Rossendorf, Institute of Resource Ecology, Bautzner Landstraße 400, 01328 Dresden (Germany); Schmidt, Matthias; Musat, Niculina [Helmholtz Centre for Environmental Research–UFZ, Department of Isotope Biogeochemistry, Permoserstraße 15, 04318 Leipzig (Germany); Swanson, Juliet S.; Reed, Donald T. [Los Alamos National Laboratory, Repository Science and Operations, 1400 University Drive, Carlsbad, NM, 88220 (United States); Stumpf, Thorsten [Helmholtz-Zentrum Dresden – Rossendorf, Institute of Resource Ecology, Bautzner Landstraße 400, 01328 Dresden (Germany); Cherkouk, Andrea, E-mail: a.cherkouk@hzdr.de [Helmholtz-Zentrum Dresden – Rossendorf, Institute of Resource Ecology, Bautzner Landstraße 400, 01328 Dresden (Germany)

2017-04-05

Highlights: • First prolonged kinetics study of uranium to halophilic archaea was performed. • An atypical time-dependent bioassociation behavior of uranium was observed. • Unique combination of spectroscopic and microscopic methods was used. • In situ ATR FT-IR showed association of U(VI) to phosphoryl and carboxylate groups. • Time-dependent changes of U(VI) localization could be monitored by SEM/EDX. - Abstract: The interactions of two extremely halophilic archaea with uranium were investigated at high ionic strength as a function of time, pH and uranium concentration. Halobacterium noricense DSM-15987 and Halobacterium sp. putatively noricense, isolated from the Waste Isolation Pilot Plant repository, were used for these investigations. The kinetics of U(VI) bioassociation with both strains showed an atypical multistage behavior, meaning that after an initial phase of U(VI) sorption, an unexpected interim period of U(VI) release was observed, followed by a slow reassociation of uranium with the cells. By applying in situ attenuated total reflection Fourier-transform infrared spectroscopy, the involvement of phosphoryl and carboxylate groups in U(VI) complexation during the first biosorption phase was shown. Differences in cell morphology and uranium localization become visible at different stages of the bioassociation process, as shown with scanning electron microscopy in combination with energy dispersive X-ray spectroscopy. Our results demonstrate for the first time that association of uranium with the extremely halophilic archaeon is a multistage process, beginning with sorption and followed by another process, probably biomineralization.

Multistage bioassociation of uranium onto an extremely halophilic archaeon revealed by a unique combination of spectroscopic and microscopic techniques

International Nuclear Information System (INIS)

Bader, Miriam; Müller, Katharina; Foerstendorf, Harald; Drobot, Björn; Schmidt, Matthias; Musat, Niculina; Swanson, Juliet S.; Reed, Donald T.; Stumpf, Thorsten; Cherkouk, Andrea

2017-01-01

Highlights: • First prolonged kinetics study of uranium to halophilic archaea was performed. • An atypical time-dependent bioassociation behavior of uranium was observed. • Unique combination of spectroscopic and microscopic methods was used. • In situ ATR FT-IR showed association of U(VI) to phosphoryl and carboxylate groups. • Time-dependent changes of U(VI) localization could be monitored by SEM/EDX. - Abstract: The interactions of two extremely halophilic archaea with uranium were investigated at high ionic strength as a function of time, pH and uranium concentration. Halobacterium noricense DSM-15987 and Halobacterium sp. putatively noricense, isolated from the Waste Isolation Pilot Plant repository, were used for these investigations. The kinetics of U(VI) bioassociation with both strains showed an atypical multistage behavior, meaning that after an initial phase of U(VI) sorption, an unexpected interim period of U(VI) release was observed, followed by a slow reassociation of uranium with the cells. By applying in situ attenuated total reflection Fourier-transform infrared spectroscopy, the involvement of phosphoryl and carboxylate groups in U(VI) complexation during the first biosorption phase was shown. Differences in cell morphology and uranium localization become visible at different stages of the bioassociation process, as shown with scanning electron microscopy in combination with energy dispersive X-ray spectroscopy. Our results demonstrate for the first time that association of uranium with the extremely halophilic archaeon is a multistage process, beginning with sorption and followed by another process, probably biomineralization.

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2010-03-15

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

Migration of uranium process wastes from the uranium-233--thorium-232 cycle

International Nuclear Information System (INIS)

Fried, S.; Sabau, C.; Hines, J.; Friedman, A.

1978-03-01

With the advent of fuel loadings of 233 U in the Shippingport Reactor, it has become important to understand the migratory behavior of uranium. The purpose of this study is the determination of the parameters influencing the migration of U(VI), the most likely chemical form of uranium to be mobilized from a repository. Samples of rhyolite tuff were used to measure the absorption coefficients of solutions of U(VI) in ground waters. In addition, columns of tuff were used to measure the elution behavior of U(VI) at various conditions of pH, U(VI) concentration, and flow saturation. These results indicate that there are several elution peaks with values of K/sub d/ between 35 and 120. This behavior is not the same as that of Pu(VI) on tuff; and the experimental results to date have not revealed the reason for this difference. Values of K/sub d/ in this range imply that geological containment would be difficult in strata of this type. It may be possible to find more retentive strata than tuff. Rocks containing reducing components are the most likely candidates and further investigation is urgently needed if the 233 U-Th cycle is to be widely used

Polarography applied to the determination of uranium oxide composition; Application de la polarographie a la determination de la composition d'oxydes d'uranium

Energy Technology Data Exchange (ETDEWEB)

Nens, C; Canton, C; Molina, R [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires, Departement de Chimie, Services d' Etudes Chimiques et d' Analyse, Service d' Etudes Analytiques, Section de Chimie Analytique du Plutonium et d' Electroanalyse

1967-03-01

An analytical method based on conventional polarography has been developed, for the determination of the O/U ratio in uranium oxides. The dissolution of the samples is effected by means of molten ammonium bifluoride. After a transfer to aqueous solution, polarography is used to determine the oxide composition by measurement of both the hexavalent and the total uranium. (author) [French] Une methode d'analyse utilisamt la polarographie conventionnelle a ete mise au point pour la determination du rapport O/U dans les oxydes d'uranium. La mise en solution des echgantillons est realisee en milieu de bifluorure d'ammonium fondu. Apres passage en salution aqueuse, la polarographie permet d'atteindre la composition de l'oxyde par determination de l'uranium hexavalent et de l'uranium total. (auteur)

Recovery of uranium (VI) from low level aqueous radioactive waste

International Nuclear Information System (INIS)

Kulshrestha, Mukul

1996-01-01

Investigation was undertaken to evaluate the uranium (VI) removal and recovery potential of a naturally occurring, nonviable macrofungus, Ganoderma Lucidum from the simulated low level aqueous nuclear waste. These low level waste waters discharged from nuclear mine tailings and nuclear power reactors have a typical U(VI) concentration of 10-100 mg/L. It is possible to recover this uranium economically with the advent of biosorption as a viable technology. Extensive laboratory studies have revealed Ganoderma Lucidum to be a potential biosorbent with a specific uptake of 2.75 mg/g at an equilibrium U(VI) concentration of 10 mg/L at pH 4.5. To recover the sorbed U(VI), the studies indicated 0.2N Na 2 CO 3 to be an effective elutant. The kinetics of U(VI) desorption from loaded Ganoderma Lucidum with 0.2N Na 2 CO 3 as elutant, was found to be rapid with more than 75% recovery occurring in the first five minutes, the specific metal release rate being 0.102 mg/g/min. The equilibrium data fitted to a linearised Freundlich plot and exhibited a near 100% recovery of sorbed U(VI), clearly revealing a cost-effective method of recovery of precious uranium from low level wastewater. (author). 7 refs., 3 figs., 1 tab

Tetra- and hexavalent uranium forms bidentate-mononuclear complexes with particulate organic matter in a naturally uranium-enriched peatland

International Nuclear Information System (INIS)

Mikutta, Christian; Langner, Peggy; Bargar, John R.; Kretzschmar, Ruben

2016-01-01

Peatlands frequently serve as efficient biogeochemical traps for U. Mechanisms of U immobilization in these organic matter-dominated environments may encompass the precipitation of U-bearing mineral(oid)s and the complexation of U by a vast range of (in)organic surfaces. The objective of this work was to investigate the spatial distribution and molecular binding mechanisms of U in soils of an alpine minerotrophic peatland (pH 4.7–6.6, E_h = –127 to 463 mV) using microfocused X-ray fluorescence spectrometry and bulk and microfocused U L_3-edge X-ray absorption spectroscopy. The soils contained 2.3–47.4 wt % organic C, 4.1–58.6 g/kg Fe, and up to 335 mg/kg geogenic U. Uranium was found to be heterogeneously distributed at the micrometer scale and enriched as both U(IV) and U(VI) on fibrous and woody plant debris (48 ± 10% U(IV), x̄ ± σ, n = 22). Bulk U X-ray absorption near edge structure (XANES) spectroscopy revealed that in all samples U(IV) comprised 35–68% of total U (x̄ = 50%, n = 15). Shell-fit analyses of bulk U L_3-edge extended X-ray absorption fine structure (EXAFS) spectra showed that U was coordinated to 1.3 ± 0.2 C atoms at a distance of 2.91 ± 0.01 Å (x̄ ± σ), which implies the formation of bidentate-mononuclear U(IV/VI) complexes with carboxyl groups. We neither found evidence for U shells at ~3.9 Å, indicative of mineral-associated U or multinuclear U(IV) species, nor for a substantial P/Fe coordination of U. As a result, our data indicates that U(IV/VI) complexation by natural organic matter prevents the precipitation of U minerals as well as U complexation by Fe/Mn phases at our field site, and suggests that organically complexed U(IV) is formed via reduction of organic matter-bound U(VI).

Tetra- and Hexavalent Uranium Forms Bidentate-Mononuclear Complexes with Particulate Organic Matter in a Naturally Uranium-Enriched Peatland.

Science.gov (United States)

Mikutta, Christian; Langner, Peggy; Bargar, John R; Kretzschmar, Ruben

2016-10-04

Peatlands frequently serve as efficient biogeochemical traps for U. Mechanisms of U immobilization in these organic matter-dominated environments may encompass the precipitation of U-bearing mineral(oid)s and the complexation of U by a vast range of (in)organic surfaces. The objective of this work was to investigate the spatial distribution and molecular binding mechanisms of U in soils of an alpine minerotrophic peatland (pH 4.7-6.6, E h = -127 to 463 mV) using microfocused X-ray fluorescence spectrometry and bulk and microfocused U L 3 -edge X-ray absorption spectroscopy. The soils contained 2.3-47.4 wt % organic C, 4.1-58.6 g/kg Fe, and up to 335 mg/kg geogenic U. Uranium was found to be heterogeneously distributed at the micrometer scale and enriched as both U(IV) and U(VI) on fibrous and woody plant debris (48 ± 10% U(IV), x̅ ± σ, n = 22). Bulk U X-ray absorption near edge structure (XANES) spectroscopy revealed that in all samples U(IV) comprised 35-68% of total U (x̅ = 50%, n = 15). Shell-fit analyses of bulk U L 3 -edge extended X-ray absorption fine structure (EXAFS) spectra showed that U was coordinated to 1.3 ± 0.2 C atoms at a distance of 2.91 ± 0.01 Å (x̅ ± σ), which implies the formation of bidentate-mononuclear U(IV/VI) complexes with carboxyl groups. We neither found evidence for U shells at ∼3.9 Å, indicative of mineral-associated U or multinuclear U(IV) species, nor for a substantial P/Fe coordination of U. Our data indicates that U(IV/VI) complexation by natural organic matter prevents the precipitation of U minerals as well as U complexation by Fe/Mn phases at our field site, and suggests that organically complexed U(IV) is formed via reduction of organic matter-bound U(VI).

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

International Nuclear Information System (INIS)

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

2002-01-01

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

Recovery of U(Vi) with unexpanded perlite

International Nuclear Information System (INIS)

Cuevas J, A.K.; Davila R, J. I.; Lopez del R, H.; Mireles G, F.

2015-09-01

Perlite is a glass volcanic rock that is hydrated by the addition of water during its formation. Is a natural material widely used in the chemical and construction industries, but recently beginning to be studied their adsorptive properties. In this paper the adsorption capacity of unexpanded perlite to remove U(Vi) in aqueous solution depending on the grain size of the material was investigated, as well as the contact time between the liquid and solid phases, ph of solution and initial concentration of uranium. The adsorption was dependent on the surface area of the material, recovering higher uranium percentage to smaller particle size. Meanwhile kinetics showed that the uranium adsorption is rapid, reaching equilibrium in 1 h. Adsorption to slightly acidic conditions was favored but dropped dramatically to ph highly acidic and basic; at a concentration of 1 x 10 -3 M UO 2 +2 the maximum uranium recovery was 46% at ph 6. In dilute solutions (1 x 10 -5 to 1 x 10 -3 M) the adsorption percentage reached values between 34 and 42%, but was reduced to 1% at a concentration of 1 x 10 -2 M. (Author)

Potentiometric determination of hexavalent uranium in uranium silicide samples

International Nuclear Information System (INIS)

Arlegui, Oscar

1999-01-01

The Chilean Nuclear Energy Commission's Department of Nuclear Materials has among its projects the production of fuels elements for nuclear reactors, and, therefore, the Chemical Analysis Laboratory must have a rapid and reliable method for uranium analysis, to control the uranium concentration during each stage of the production process. For this reason the Chilean Nuclear Energy Commission's Chemical Analysis Laboratory has validated a potentiometric method, which is a modification of the Davies and Gray method proposed by A.R. Eberle. This method uses the Potentiometric Titration Technique and is based on the direct and rapid reduction of uranium (VI) to Uranium (IV), in a concentrated phosphoric acid medium, with excess iron (II) used as a reducing agent. In this medium the excess iron (II) selectively oxidizes to iron (III) with nitric acid, using molybdenum (IV) as a catalyzer, the nitrous acid that is produced is eliminated by adding amidosulfuric acid. The solution is diluted with 1M sulfuric acid and the uranium (IV) obtained is titrated potentiometrically with potassium dichromate in the presence of vanadilic sulfate to obtain a better defined final titration point. The samples were softened with hydrochloric acid and nitric acid and later 50 ml were estimated in a 20% sulfuric acid medium. The analytical method was validated by comparing it with Certified Reference Material (C.R.M.) from the New Brunswick Laboratory (NBL), Metallic Uranium, CRM 112-A. The F Test and the T Test show that the value calculated is less than the tabulated value so the result is traceable to the reference material. The quantification limit, sensitivity, precision and accuracy were quantified for the method

Mechanisms of uranium interactions with hydroxyapatite: Implications for groundwater remediation

Science.gov (United States)

Fuller, C.C.; Bargar, J.R.; Davis, J.A.; Piana, M.J.

2002-01-01

The speciation of U(VI) sorbed to synthetic hydroxyapatite was investigated using a combination of U LIII-edge XAS, synchrotron XRD, batch uptake measurements, and SEM-EDS. The mechanisms of U(VI) removal by apatite were determined in order to evaluate the feasibility of apatitebased in-situ permeable reactive barriers (PRBs). In batch U(VI) uptake experiments with synthetic hydroxyapatite (HA), near complete removal of dissolved uranium (>99.5%) to use in development of PRBs for groundwater U(VI) remediation.

Nuclear waste glasses of SON68 type and their weathering products, optical spectroscopy of uranium and rare earth elements

International Nuclear Information System (INIS)

Ollier, N.

2002-09-01

This study concerns the long-term behaviour of high-level waste glasses and more precisely lanthanides and uranium behaviour with weathering. The leaching was performed on glass powder at 90 deg. C in a pseudo-dynamic mode. Two weathering gels were obtained, with different renewal rate and leaching duration. In glass, we demonstrate that U(IV) and U(VI) species coexist. Time-resolved spectroscopy and XPS measurements show that hexavalent uranium is present under uranyl entities and UO 3 type environment. In weathering gels, U(VI) is still present under uranyl form as well as uranyl hydroxide. It means that U behaviour depends on renewal rate, moreover precipitation of crystallized phases like bauranolte BaU 2 O 7 .xH 2 O and uranyl silicate of uranophane type occur. Concerning lanthanides, Eu 3+ was used as a luminescent local probe. Two sites were found in glass and gels. In glass, the sites were attributed to a silicate and a borate one. In gels, the silicate site is conserved whereas the second one is supposed to correspond to an aluminate one. Photoluminescence and Moessbauer measurements show that the rare earth site symmetry increases in gel. This result confirms that order is higher in gels than in glass. The third part of the thesis concerns irradiation effect in glasses. The main result shows some behaviour differences between a 5 oxides borosilicate glass and a more complex one close to the SON68 glass. Presence of mixed alkali (Na, Li and Cs) seems to notably reduce the Na migration. (author)

U(VI) sorption on kaolinite. Effects of pH, U(VI) concentration and oxyanions

International Nuclear Information System (INIS)

Liang Gao; Ziqian Yang; Keliang Shi; Xuefeng Wang; Zhijun Guo; Wangsuo Wu

2010-01-01

U(VI) sorption on kaolinite was studied as functions of contact time, pH, U(VI) concentration, solid-to-liquid ratio (m/V) by using a batch experimental method. The effects of sulfate and phosphate on U(VI) sorption were also investigated. It was found that the sorption kinetics of U(VI) can be described by a pseudo-second-order model. Potentiometric titrations at variable ionic strengths indicated that the titration curves of kaolinite were not sensitive to ionic strength, and that the pH of the zero net proton charge (pH PZNPC ) was at 6.9. The sorption of U(VI) on kaolinite increased with pH up to 6.5 and reached a plateau at pH >6.5. The presence of phosphate strongly increased U(VI) sorption especially at pH <5.5, which may be due to formation of ternary surface complexes involving phosphate. In contrast, the presence of sulfate did not cause any apparent effect on U(VI) sorption. A double layer model was used to interpret both results of potentiometric titrations and U(VI) sorption on kaolinite. (author)

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

The solubility of uranium in cementitious near-field chemical conditions

Energy Technology Data Exchange (ETDEWEB)

Baston, G.M.N.; Brownsword, M.; Cross, J.E.; Hobley, J.; Moreton, A.D.; Smith-Briggs, J.L.; Thomason, H.P. [AEA Decommissioning and Waste Management, Harwell (United Kingdom)

1993-05-01

Tetravalent and hexavalent uranium solubilities have been measured in cement-equilibriated water for pH values from 4 to 13. Tetravalent uranium solubilities at pH 12 have been measured by three experimental techniques: oversaturation, undersaturation and by the use of an electrochemical cell which controlled the redox conditions. The experimentally obtained data have been simulated using the thermodynamic equilibrium program HARPHRQ in conjunction with three different sets of thermodynamic data for uranium. In each case, differences were found between the predicted and measured uranium behaviour. For hexavalent uranium at high pH values the model suggested the formation of anionic hydrolysis products which led to the prediction of uranium solubilities significantly higher than those observed. Refinement of the thermodynamic data used in the model enabled the derivation of maximum values for the formation constants of these species under cementitious conditions. Similarly, the experimental data have been used to refine a model of tetravalent uranium solubility under cementitious near-field conditions. (author).

The solubility of uranium in cementitious near-field chemical conditions

International Nuclear Information System (INIS)

Baston, G.M.N.; Brownsword, M.; Cross, J.E.; Hobley, J.; Moreton, A.D.; Smith-Briggs, J.L.; Thomason, H.P.

1993-05-01

Tetravalent and hexavalent uranium solubilities have been measured in cement-equilibriated water for pH values from 4 to 13. Tetravalent uranium solubilities at pH 12 have been measured by three experimental techniques: oversaturation, undersaturation and by the use of an electrochemical cell which controlled the redox conditions. The experimentally obtained data have been simulated using the thermodynamic equilibrium program HARPHRQ in conjunction with three different sets of thermodynamic data for uranium. In each case, differences were found between the predicted and measured uranium behaviour. For hexavalent uranium at high pH values the model suggested the formation of anionic hydrolysis products which led to the prediction of uranium solubilities significantly higher than those observed. Refinement of the thermodynamic data used in the model enabled the derivation of maximum values for the formation constants of these species under cementitious conditions. Similarly, the experimental data have been used to refine a model of tetravalent uranium solubility under cementitious near-field conditions. (author)

Carbon Paste Electrode Modified with Carbamoylphosphonic Acid Functionalized Mesoporous Silica: A New Mercury-Free Sensor for Uranium Detection

International Nuclear Information System (INIS)

Yantasee, Wassana; Lin, Yuehe; Fryxell, Glen E.; Wang, Zheming

2004-01-01

This study reports a new approach for developing a uranium (U(VI)) electrochemical sensor that is mercury-free, solid-state, and has less chance for ligand depletion than existing sensors. A carbon-paste electrode modified with carbamoylphosphonic acid self-assembled monolayer on mesoporous silica was developed for uranium detection based on an adsorptive square-wave stripping voltammetry technique. Voltammetric responses for U(VI) detection are reported as a function of pH, preconcentration time, and aqueous phase U(VI) concentration. The uranium detection limit is 25 ppb after 5 minutes preconcentration and improved to 1 ppb after 20 minutes preconcentration. The relative standard deviations are normally less than 5%

In Situ Bioreduction of Uranium (VI) to Submicromolar Levels and Reoxidation by Dissolved Oxygen

International Nuclear Information System (INIS)

Wu, Weimin; Carley, Jack M.; Luo, Jian; Ginder-Vogel, Matthew A.; Cardenas, Erick; Leigh, Mary Beth; Hwang, Chaichi; Kelly, Shelly D.; Ruan, Chuanmin; Wu, Liyou; Van Nostrand, Joy; Gentry, Terry J.; Lowe, Kenneth Alan; Mehlhorn, Tonia L.; Carroll, Sue L.; Luo, Wensui; Fields, Matthew Wayne; Gu, Baohua; Watson, David B.; Kemner, Kenneth M.; Marsh, Terence; Tiedje, James; Zhou, Jizhong; Fendorf, Scott; Kitanidis, Peter K.; Jardine, Philip M.; Criddle, Craig

2007-01-01

Groundwater within Area 3 of the U.S. Department of Energy (DOE) Environmental Remediation Sciences Program (ERSP) Field Research Center at Oak Ridge, TN (ORFRC) contains up to 135 (micro)M uranium as U(VI). Through a series of experiments at a pilot scale test facility, we explored the lower limits of groundwater U(VI) that can be achieved by in-situ biostimulation and the effects of dissolved oxygen on immobilized uranium. Weekly 2 day additions of ethanol over a 2-year period stimulated growth of denitrifying, Fe(III)-reducing, and sulfate-reducing bacteria, and immobilization of uranium as U(IV), with dissolved uranium concentrations decreasing to low levels. Following sulfite addition to remove dissolved oxygen, aqueous U(VI) concentrations fell below the U.S. Environmental Protection Agency maximum contaminant limit (MCL) for drinking water ( -1 or 0.126 (micro)M). Under anaerobic conditions, these low concentrations were stable, even in the absence of added ethanol. However, when sulfite additions stopped, and dissolved oxygen (4.0-5.5 mg L -1 ) entered the injection well, spatially variable changes in aqueous U(VI) occurred over a 60 day period, with concentrations increasing rapidly from <0.13 to 2.0 (micro)M at a multilevel sampling (MLS) well located close to the injection well, but changing little at an MLS well located further away. Resumption of ethanol addition restored reduction of Fe(III), sulfate, and U(VI) within 36 h. After 2 years of ethanol addition, X-ray absorption near-edge structure spectroscopy (XANES) analyses indicated that U(IV) comprised 60-80% of the total uranium in sediment samples. At the completion of the project (day 1260), U concentrations in MLS wells were less than 0.1 (micro)M. The microbial community at MLS wells with low U(VI) contained bacteria that are known to reduce uranium, including Desulfovibrio spp. and Geobacter spp., in both sediment and groundwater. The dominant Fe(III)-reducing species were Geothrix spp

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...

Retention of U(VI) onto silica in presence of model organic molecules

International Nuclear Information System (INIS)

Pham, T.T.H.; Mercier-Bion, F.; Drot, R.; Lagarde, G.; Simoni, E.; Lambert, J.

2008-01-01

It is well-known that the organic matter influences the retention of ions onto mineral surfaces. However, the major part of concerned studies implies humic substances and complex solids. Another approach for identifying the sorption mechanisms is possible by studying simpler solids than those present in natural medium. So, silica is chosen as mineral surface because of its abundance in soils and of the presence of Si-O groups in clayey minerals. Uranium (VI) is selected as cation. Simple organic molecules like acetic (one carboxylic group) and oxalic (two carboxylic functions) acids are considered as models of the natural organic matter for understanding their role in the retention of U(VI) onto powders and slides of silica. Binary (organics/silica, U(VI)/silica) and ternary systems (organics/silica/U(VI)) are studied by complementary approaches. Sorption edges as function of pH are obtained by liquid scintillation methods and capillary electrophoresis. Different spectroscopic techniques are used to deduce the interactions between the organic matter and U(VI) sorbed onto the silica whose: Time-Resolved Laser induced Fluorescence Spectroscopy (TRLFS), X-ray Photoelectron Spectroscopy (XPS), Nuclear Microprobe Analysis (NMA). The results of the effect of these model organic molecules onto the U(VI) retention showed a good agreement between the different techniques. Concerning the acetic acid, there are not differences in the sorption percentages of uranyl (see the figure). All these results indicate that the uranyl-acetate complexes stay in the aqueous solution rather than sorbing onto the silica. On the contrary, oxalic acid influences the sorption of U(VI) onto the silica surface. The sorption percentage of U(VI) in the ternary system (oxalic acid/silica/U(VI)) is lower than the binary system (U(VI)/silica) (see the figure). So, the presence of oxalic acid decreases the sorption of U(VI) onto the silica surface. (authors)

Understanding Uranium Behavior in a Reduced Aquifer

Science.gov (United States)

Janot, N.; Lezama-Pacheco, J. S.; Williams, K. H.; Bernier-Latmani, R.; Long, P. E.; Davis, J. A.; Fox, P. M.; Yang, L.; Giammar, D.; Cerrato, J. M.; Bargar, J.

2012-12-01

Uranium contamination of groundwater is a concern at several US Department of Energy sites, such Old Rifle, CO. Uranium transport in the environment is mainly controlled by its oxidation state, since oxidized U(VI) is relatively mobile, whereas U(IV) is relatively insoluble. Bio-remediation of contaminated aquifers aims at immobilizing uranium in a reduced form. Previous laboratory and field studies have shown that adding electron donor (lactate, acetate, ethanol) to groundwater stimulates the activity of metal- and sulfate-reducing bacteria, which promotes U(VI) reduction in contaminated aquifers. However, obtaining information on chemical and physical forms of U, Fe and S species for sediments biostimulated in the field, as well as kinetic parameters such as U(VI) reduction rate, is challenging due to the low concentration of uranium in the aquifers (typically bio-remediation experiment at the Old Rifle site, CO, from early iron-reducing conditions to the transition to sulfate-reducing conditions. Several in-well chromatographic columns packed with sediment were deployed and were sampled at different days after the start of bio-reduction. X-ray absorption spectroscopy and X-ray microscopy were used to obtain information on Fe, S and U speciation and distribution. Chemical extractions of the reduced sediments have also been performed, to determine the rate of Fe(II) and U(IV) accumulation.

Incorporation of Uranium into Hematite during Crystallization from Ferrihydrite

Science.gov (United States)

2014-01-01

Ferrihydrite was exposed to U(VI)-containing cement leachate (pH 10.5) and aged to induce crystallization of hematite. A combination of chemical extractions, TEM, and XAS techniques provided the first evidence that adsorbed U(VI) (≈3000 ppm) was incorporated into hematite during ferrihydrite aggregation and the early stages of crystallization, with continued uptake occurring during hematite ripening. Analysis of EXAFS and XANES data indicated that the U(VI) was incorporated into a distorted, octahedrally coordinated site replacing Fe(III). Fitting of the EXAFS showed the uranyl bonds lengthened from 1.81 to 1.87 Å, in contrast to previous studies that have suggested that the uranyl bond is lost altogether upon incorporation into hematite. The results of this study both provide a new mechanistic understanding of uranium incorporation into hematite and define the nature of the bonding environment of uranium within the mineral structure. Immobilization of U(VI) by incorporation into hematite has clear and important implications for limiting uranium migration in natural and engineered environments. PMID:24580024

Uranium Biominerals Precipitated by an Environmental Isolate of Serratia under Anaerobic Conditions

Science.gov (United States)

Newsome, Laura; Morris, Katherine; Lloyd, Jonathan. R.

2015-01-01

Stimulating the microbially-mediated precipitation of uranium biominerals may be used to treat groundwater contamination at nuclear sites. The majority of studies to date have focussed on the reductive precipitation of uranium as U(IV) by U(VI)- and Fe(III)-reducing bacteria such as Geobacter and Shewanella species, although other mechanisms of uranium removal from solution can occur, including the precipitation of uranyl phosphates via bacterial phosphatase activity. Here we present the results of uranium biomineralisation experiments using an isolate of Serratia obtained from a sediment sample representative of the Sellafield nuclear site, UK. When supplied with glycerol phosphate, this Serratia strain was able to precipitate 1 mM of soluble U(VI) as uranyl phosphate minerals from the autunite group, under anaerobic and fermentative conditions. Under phosphate-limited anaerobic conditions and with glycerol as the electron donor, non-growing Serratia cells could precipitate 0.5 mM of uranium supplied as soluble U(VI), via reduction to nano-crystalline U(IV) uraninite. Some evidence for the reduction of solid phase uranyl(VI) phosphate was also observed. This study highlights the potential for Serratia and related species to play a role in the bioremediation of uranium contamination, via a range of different metabolic pathways, dependent on culturing or in situ conditions. PMID:26132209

Determination of U(VI) using novel reagent by extractive spectrophotometry

International Nuclear Information System (INIS)

Suvardhan, K.; Subrahmanyam, P.; Dilip Kumar, J.; Chiranjeevi, P.

2007-01-01

A simple and spectrophotometric method for the determination of U(VI) using a 5-(4-pyridyl azo)-8-quinolinol (PAQ) is developed the reagent was synthesized and used for extraction of uranium. At pH 7.0 ±0.2 uranium forms a yellowish orange colored complex with PAQ, which was then quantitatively extracted from chloroform showing maximum absorbance at wavelength of 485 nm. The proposed method obeys Beer's law in the range of 0.2-10.0 μg ml -1 . Molar absorptivity and Sandelson's sensitivity of extracted species was calculated to be 1.325x10 4 lmol -1 cm -1 and 0.421 x10 -4 μg cm -2 respectively. The method was applied for the determination of uranium in food and plant samples. It was found that the newly developed method is competent to those of standard methods. (author)

Sorption of Cs, Eu and U(VI) onto rock samples from Nizhnekansky massive

Energy Technology Data Exchange (ETDEWEB)

Petrov, V.; Vlasova, I.; Kalmykov, S. [Lomonosov Moscow State University (Russian Federation); Kuzmenkova, N. [Vernadsky Institute of Geochemistry and Analytical Chemistry, Russian Academy of Science (Russian Federation); Petrov, V.; Poluektov, V. [Institute of Geology of Ore Deposits, Petrography, Mineralogy and Geochemistry, Russian Academy of Sciences - IGEM RAS (Russian Federation)

2014-07-01

The accepted in Russia concept for high level wastes (HLW) and spent nuclear fuel (SNF) disposal is based on their isolation into the deep underground crystalline rock formations. The 'Eniseysky' area (Nizhnekansky massive) is supposed as the most perspective location for the future HLW and SNF repository. Core materials from different areas of Nizhnekasnsky massive have been studied in terms of petrographic and mineralogical characterization; definition of filtration, elastic, petro-physical and strength properties; estimation of hydrothermal-metasomatic transformation of rocks. We used both undisturbed sliced cores and crushed material for the sorption experiments. Preliminary results of uranium sorption show some significant differences between used rock samples from different depth in sorption rate and pH-dependence. In all cases maximum sorption (more than 90%) is reached in 2-3 weeks. The pH-dependence of sorbed uranium fraction has typical hump-shape: increase of sorption percentage with increasing pH values to 6, plateau (90-98 % of uranium sorbed), decrease of sorption percentage with increasing pH values from 8 due to U(VI) hydrolysis. In the case of cesium the sorption maximum is reached within 10-12 days and in the case of europium - about 5 days. All radionuclides sorbed preferentially onto dark minerals. Local distribution and preferential sorption of cesium, europium and uranium (VI) onto different minerals within the sample were studied by radiography, SEM-EDX, etc. These data accompanying with rock sample composition will allow the development of quantitative model for Cs, Eu and U(VI) sorption onto investigated rocks. Document available in abstract form only. (authors)

Anaerobic bacterial systems result in the removal of soluble uranium

International Nuclear Information System (INIS)

Thomson, B.M.; Barton, L.L.; Steenhoudt, K.; Tucker, M.D.

1994-01-01

Sulfate-reducing bacteria, nitrate-reducing bacteria and bacteria present in sewage sludge were examined for their ability to reduce the level of soluble U(VI) in enriched media. Cultures of Desulfovibrio desulfuricans, D. gigas, and D. vulgaris were grown in sulfate-containing media while Pseudomonas putida and P. denitrificans were cultivated in nitrate media. The amount of U(VI) removed from solution was dependent on metabolism because greater levels of uranium were removed when U(VI) was added to a growing culture than when added to a culture in stationary phase. The presence of vanadate, arsenate, selenate or molybdate at 0.1 and 0.01 M levels in sulfate-reducing cultures, nitrate-respiring cultures or in sludge cultures did not have an effect on the amount of uranium removed. In all cultures the amount of uranium in solution was markedly reduced after 10 to 20 days and reduced uranium, as U(IV), was detected in several cultures. Present in the cultures of D. desulfuricans were crystals of uranium. Examination of these cultures by electron microscopy indicates that the uranium (IV) is deposited outside of the cell and these needle-like crystals are associated with cellular material. X-ray probe analysis with the electron microscope gave an image that was in close agreement with U(IV). With D. desulfuricans in a continuous stirred tank reactor, kinetic parameters have been calculated for uranium reduction. Over a period of 20 to 60 hours, the amount of soluble uranium removed from the bioreactor was proportional to residence time over a period of 20 to 60 hours

Surface complexation modeling of U(VI) adsorption by aquifer sediments from a former mill tailings site at Rifle, Colorado

Science.gov (United States)

Hyun, S.P.; Fox, P.M.; Davis, J.A.; Campbell, K.M.; Hayes, K.F.; Long, P.E.

2009-01-01

A study of U(VI) adsorption by aquifer sediment samples from a former uranium mill tailings site at Rifle, Colorado, was conducted under oxic conditions as a function of pH, U(VI), Ca, and dissolved carbonate concentration. Batch adsorption experiments were performed using tailings site at Naturita, Colorado, indicated that possible calcite nonequilibrium of dissolved calcium concentration should be evaluated. The modeling results also illustrate the importance of the range of data used in deriving the best fit model parameters. ?? 2009 American Chemical Society.

Multistage bioassociation of uranium onto an extremely halophilic archaeon revealed by a unique combination of spectroscopic and microscopic techniques.

Science.gov (United States)

Bader, Miriam; Müller, Katharina; Foerstendorf, Harald; Drobot, Björn; Schmidt, Matthias; Musat, Niculina; Swanson, Juliet S; Reed, Donald T; Stumpf, Thorsten; Cherkouk, Andrea

2017-04-05

The interactions of two extremely halophilic archaea with uranium were investigated at high ionic strength as a function of time, pH and uranium concentration. Halobacterium noricense DSM-15987 and Halobacterium sp. putatively noricense, isolated from the Waste Isolation Pilot Plant repository, were used for these investigations. The kinetics of U(VI) bioassociation with both strains showed an atypical multistage behavior, meaning that after an initial phase of U(VI) sorption, an unexpected interim period of U(VI) release was observed, followed by a slow reassociation of uranium with the cells. By applying in situ attenuated total reflection Fourier-transform infrared spectroscopy, the involvement of phosphoryl and carboxylate groups in U(VI) complexation during the first biosorption phase was shown. Differences in cell morphology and uranium localization become visible at different stages of the bioassociation process, as shown with scanning electron microscopy in combination with energy dispersive X-ray spectroscopy. Our results demonstrate for the first time that association of uranium with the extremely halophilic archaeon is a multistage process, beginning with sorption and followed by another process, probably biomineralization. Copyright © 2016. Published by Elsevier B.V.

Efficient removal of uranium from aqueous solution by zero-valent iron nanoparticle and its graphene composite

International Nuclear Information System (INIS)

Li, Zi-Jie; Wang, Lin; Yuan, Li-Yong; Xiao, Cheng-Liang; Mei, Lei; Zheng, Li-Rong; Zhang, Jing; Yang, Ju-Hua; Zhao, Yu-Liang; Zhu, Zhen-Tai; Chai, Zhi-Fang; Shi, Wei-Qun

2015-01-01

Highlights: • Uranium removal by ZVI-nps: independent of pH, the presence of CO 3 2− , humic acid, or mimic groundwater constituents. • Rapid removal kinetics and sorption capacity of ZVI-nps is 8173 mg U/g. • Two reaction mechanisms: sufficient Fe 0 → reductive precipitation as U 3 O 7 ; insufficient Fe 0 → hydrolysis precipitation of U(VI). • Fe/graphene composites: improved kinetics and higher U(VI) reduction ratio. - Abstract: Zero-valent iron nanoparticle (ZVI-np) and its graphene composites were prepared and applied in the removal of uranium under anoxic conditions. It was found that solutions containing 24 ppm U(VI) could be completely cleaned up by ZVI-nps, regardless of the presence of NaHCO 3 , humic acid, mimic groundwater constituents or the change of solution pH from 5 to 9, manifesting the promising potential of this reactive material in permeable reactive barrier (PRB) to remediate uranium-contaminated groundwater. In the measurement of maximum sorption capacity, removal efficiency of uranium kept at 100% until C 0 (U) = 643 ppm, and the saturation sorption of 8173 mg U/g ZVI-nps was achieved at C 0 (U) = 714 ppm. In addition, reaction mechanisms were clarified based on the results of SEM, XRD, XANES, and chemical leaching in (NH 4 ) 2 CO 3 solution. Partially reductive precipitation of U(VI) as U 3 O 7 was prevalent when sufficient iron was available; nevertheless, hydrolysis precipitation of U(VI) on surface would be predominant as iron got insufficient, characterized by releases of Fe 2+ ions. The dissolution of Fe 0 cores was assigned to be the driving force of continuous formation of U(VI) (hydr)oxide. The incorporation of graphene supporting matrix was found to facilitate faster removal rate and higher U(VI) reduction ratio, thus benefitting the long-term immobilization of uranium in geochemical environment

Uranium sorption onto activated carbon prepared from rice straw: Competition with humic acids

International Nuclear Information System (INIS)

Yakout, S.M.; Metwally, S.S.; El-Zakla, T.

2013-01-01

Adsorptive competition between uranium (VI) and humic acids (HA) was investigated using Rice Straw activated carbon modified with KOH (RSK carbon). The investigations were conducted for individual components adsorption along with simultaneous and sequential adsorption of both components. The experimental results showed that the equilibrium data fit well Langmuir equation. It was found that, for single component system, RSK carbon can achieve adsorption of U(VI) ion at 100 mg/g, and HA at 21.1 mg/g, respectively. Adsorption isotherms for multi-component systems were studied. U(VI) showed a decreased adsorbability when it coexisted with HA from the start (41.5 mg/g in simultaneous) compared with the case when U(VI) was added after equilibrium adsorption of HA on activated carbon (11.9 mg/g in sequential). The interactions between uranium ions and HA caused the formation of U–HA complexes that changed the surface interactions of both uranium ions and HA with carbon surface. The underlying mechanism of the difference in the uranium sorption was discussed in the view of absence and presences (sequential and Simultaneous) of HA. It could be concluded that, humic substance is strong inhibitor of uranium binding and should be removed before from waste water treatment for uranium.

Feasibility studies on electrochemical recovery of uranium from solid wastes contaminated with uranium using 1-butyl-3-methylimidazorium chloride as an electrolyte

Energy Technology Data Exchange (ETDEWEB)

Ohashi, Yusuke, E-mail: ohhashi.yusuke@jaea.go.jp [Ningyo-toge Environmental Engineering center, Japan Atomic Energy Agency, 1550 Kamisaibara, Kagamino-cho, Tomata-gun, Okayama 708-0698 (Japan); Harada, Masayuki [Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology, 2-12-1-N1-34 Ookayama, Meguro-ku, Tokyo 152-8550 (Japan); Asanuma, Noriko [Department of Nuclear Engineering, School of Engineering, Tokai University, 4-1-1 Kitakaname, Hiratsuka-shi, Kanagawa 259-1292 (Japan); Ikeda, Yasuhisa [Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology, 2-12-1-N1-34 Ookayama, Meguro-ku, Tokyo 152-8550 (Japan)

2015-09-15

Highlights: • The uranium component of steel wastes and spent NaF adsorbent are easily dissolved into BMICl. • The uranyl(VI) species in BMICl are reduced to U(V) irreversibly around −0.8 to −1.3 V. • The dissolved uranium species in BMICl are recovered as black deposits electrolytically. • The deposit is the mixtures of U(IV) and U(VI) compounds containing O, F, Cl, and N elements. - Abstract: In order to examine feasibility of the electrochemical deposition method for recovering uranium from the solid wastes contaminated with uranium using ionic liquid as electrolyte, we have studied the electrochemical behavior of each solution prepared by soaking the spent NaF adsorbents and the steel waste contaminated with uranium in BMICl (1-butyl-3-methyl- imidazolium chloride). The uranyl(VI) species in BMICl solutions were found to be reduced to U(V) irreversibly around −0.8 to −1.3 V vs. Ag/AgCl. The resulting U(V) species is followed by disproportionation to U(VI) and U(IV). Based on the electrochemical data, we have performed potential controlled electrolysis of each solution prepared by soaking the spent NaF adsorbents and steel wastes in BMICl at −1.5 V vs. Ag/AgCl. Black deposit was obtained, and their composition analyses suggest that the deposit is the mixtures of U(IV) and U(VI) compounds containing O, F, Cl, and N elements. From the present study, it is expected that the solid wastes contaminated with uranium can be decontaminated by treating them in BMICl and the dissolved uranium species are recovered electrolytically.

Current status and future prospects of uranium resources

International Nuclear Information System (INIS)

Kuronuma, Chosuke

1997-01-01

Uranium is contained in various things in natural world, for example, 3 ppm in granite and 3x10 -3 ppm in seawater. Uranium exists in the state of tetra, penta and hexa-valence in nature, and in oxidizing environment, it exists as uranyl radical of hexa-valence, forms soluble complexes, and easily moves with water. In reducing environment, it becomes insoluble state of tetra-valence and precipitates. This property of uranium is deeply related to the way of forming the deposit, and it is explained. The uranium resources of the recovery cost being 80 dollars per kg U or less are 2,120,000 t, and 60% of the total exists in Australia, Kazakstan and Canada. The cumulative production of uranium in the world from 1945 to 1995 was 1,810,000 t. Of the total production, 875,000 t was used for civil purpose, and 750,000 t was used for military purpose. The uranium deposits in Canada are very high quality, and produce 1/3 of the world uranium production. There are the inventories of 150,000-200,000 t U. The diversion of military high enriched uranium to civil purpose is reported. The state of uranium market, the prospect of demand and supply of uranium, and the exploration and development of uranium resources are described. (K.I.)

Fundamental study on decontamination of wastes contaminated by uranium fluorides by using ionic liquids - dissolution and electrochemistry of uranium in 1-butyl-3-methylimidazolium chloride

International Nuclear Information System (INIS)

Noriko Asanuma; Yusuke Ohhashi; Yukio Wada; Masayuki Harada; Yasuhisa Ikeda

2008-01-01

Treatment method for wastes contaminated uranium fluorides by using ionic liquids as media of pyrochemical process instead of alkali metal chloride molten salts was proposed. In this method, uranium fluorides such as UF 4 or NaF adsorbing UF 6 are dissolved in 1-butyl-3-methylimidazolium chloride (BMICl) and dissolved uranium species are recovered as deposits by electrochemical reduction. Under the atmospheric condition, UF 4 was completely dissolved in BMICl at 100 deg. C. UV-vis absorption spectra of the sample solution indicated that main species of uranium are U(VI) and a part of uranium exists as U(IV). Chemical form of uranium in the NaF adsorbents is Na 3 UO 2 F 5 . Therefore, it was immediately dissolved to BMICl. However, complete dissolution was not achieved. Cyclic voltammetry of the solutions prepared by dissolution experiments was performed. Redox properties of uranium species in each sample were irreversible. It was assigned to reduction of U(VI) to U(IV). As a result of preliminary bulk electrolysis, it was expected that reduction products are deposited on the carbon cathode. (authors)

Bio-precipitation of uranium by two bacterial isolates recovered from extreme environments as estimated by potentiometric titration, TEM and X-ray absorption spectroscopic analyses

Energy Technology Data Exchange (ETDEWEB)

Merroun, Mohamed L., E-mail: merroun@ugr.es [Institute of Radiochemistry, Helmholtz Centre Dresden-Rossendorf, Dresden (Germany); Departamento de Microbiologia, Universidad de Granada, Campus Fuentenueva s/n 18071, Granada (Spain); Nedelkova, Marta [Institute of Radiochemistry, Helmholtz Centre Dresden-Rossendorf, Dresden (Germany); Ojeda, Jesus J. [Cell-Mineral Interface Research Programme, Kroto Research Institute, University of Sheffield, Broad Lane, Sheffield S3 7HQ (United Kingdom); Experimental Techniques Centre, Brunel University, Uxbridge, Middlesex UB8 3PH (United Kingdom); Reitz, Thomas [Institute of Radiochemistry, Helmholtz Centre Dresden-Rossendorf, Dresden (Germany); Fernandez, Margarita Lopez; Arias, Jose M. [Departamento de Microbiologia, Universidad de Granada, Campus Fuentenueva s/n 18071, Granada (Spain); Romero-Gonzalez, Maria [Cell-Mineral Interface Research Programme, Kroto Research Institute, University of Sheffield, Broad Lane, Sheffield S3 7HQ (United Kingdom); Selenska-Pobell, Sonja [Institute of Radiochemistry, Helmholtz Centre Dresden-Rossendorf, Dresden (Germany)

2011-12-15

Highlights: Black-Right-Pointing-Pointer Precipitation of uranium as U phosphates by natural bacterial isolates. Black-Right-Pointing-Pointer The uranium biomineralization involves the activity of acidic phosphatase. Black-Right-Pointing-Pointer Uranium bioremediation could be achieved via the biomineralization of U(VI) in phosphate minerals. - Abstract: This work describes the mechanisms of uranium biomineralization at acidic conditions by Bacillus sphaericus JG-7B and Sphingomonas sp. S15-S1 both recovered from extreme environments. The U-bacterial interaction experiments were performed at low pH values (2.0-4.5) where the uranium aqueous speciation is dominated by highly mobile uranyl ions. X-ray absorption spectroscopy (XAS) showed that the cells of the studied strains precipitated uranium at pH 3.0 and 4.5 as a uranium phosphate mineral phase belonging to the meta-autunite group. Transmission electron microscopic (TEM) analyses showed strain-specific localization of the uranium precipitates. In the case of B. sphaericus JG-7B, the U(VI) precipitate was bound to the cell wall. Whereas for Sphingomonas sp. S15-S1, the U(VI) precipitates were observed both on the cell surface and intracellularly. The observed U(VI) biomineralization was associated with the activity of indigenous acid phosphatase detected at these pH values in the absence of an organic phosphate substrate. The biomineralization of uranium was not observed at pH 2.0, and U(VI) formed complexes with organophosphate ligands from the cells. This study increases the number of bacterial strains that have been demonstrated to precipitate uranium phosphates at acidic conditions via the activity of acid phosphatase.

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

Synergetic treatment of uranium-bearing waste water with sulfate reducing bacteria and zero-valent iron

International Nuclear Information System (INIS)

Zhou Quanyu; Tan Kaixuan; Zeng Sheng; Liu Dong

2009-01-01

The treatment of uranium-bearing wastewater from uranium mine and using microorganism to treat wastewater were paid much attention to environmental researchers. Based on column experiments, we investigated the potential using sulfate reducing bacteria (SRB) and zero-valent iron (ZVI) to synergetic treat contamination in wastewater such as sulfate, uranium, etc. SRB+ZVI can effectively remove contamination U(VI) and SO 4 2- in wastewater. The removal rate is 99.4% and 86.2% for U(VI) and SO 4 2- , respectively. The pH of wastewater can be basified to neutral. U(VI) and SO 4 2- as electron acceptor of sulfate reducing bacteria are removed by biological reduction. The corrosion of ZVI is benefit to enhance the pH of wastewater, forms anaerobic reducing environment, strengthens survival and metabolism reaction of SRB, and plays a synergetic enhancement. (authors)

Influence of Reactive Transport on the Reduction of U(VI) in the Presence of Fe(III) and Nitrate: Implications for U(VI) Immobilization by Bioremediation/Biobarriers - Final Report

International Nuclear Information System (INIS)

B.D. Wood

2007-01-01

Subsurface contamination by metals and radionuclides represent some of the most challenging remediation problems confronting the Department of Energy (DOE) complex. In situ remediation of these contaminants by dissimilatory metal reducing bacteria (DMRB) has been proposed as a potential cost effective remediation strategy. The primary focus of this research is to determine the mechanisms by which the fluxes of electron acceptors, electron donors, and other species can be controlled to maximize the transfer of reductive equivalents to the aqueous and solid phases. The proposed research is unique in the NABIR portfolio in that it focuses on (i) the role of flow and transport in the initiation of biostimulation and the successful sequestration of metals and radionuclides [specifically U(VI)], (ii) the subsequent reductive capacity and stability of the reduced sediments produced by the biostimulation process, and (iii) the potential for altering the growth of biomass in the subsurface by the addition of specific metabolic uncoupling compounds. A scientifically-based understanding of these phenomena are critical to the ability to design successful bioremediation schemes. The laboratory research will employ Shewanella putrefaciens (CN32), a facultative DMRB that can use Fe(III) oxides as a terminal electron acceptor. Sediment-packed columns will be inoculated with this organism, and the reduction of U(VI) by the DMRB will be stimulated by the addition of a carbon and energy source in the presence of Fe(III). Separate column experiments will be conducted to independently examine: (1) the importance of the abiotic reduction of U(VI) by biogenic Fe(II); (2) the influence of the transport process on Fe(III) reduction and U(VI) immobilization, with emphasis on methods for controlling the fluxes of aqueous species to maximize uranium reduction; (3) the reductive capacity of biologically-reduced sediments (with respect to re-oxidation by convective fluxes of O2 and NO3-) and

Adsorption of uranium from aqueous solution by PAMAM dendron functionalized styrene divinylbenzene

Energy Technology Data Exchange (ETDEWEB)

Ilaiyaraja, P., E-mail: chemila07@gmail.com [Radiological Safety Division, Radiological Safety and Environmental Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102, Tamilnadu (India); Singha Deb, Ashish Kumar; Sivasubramanian, K. [Radiological Safety Division, Radiological Safety and Environmental Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102, Tamilnadu (India); Ponraju, D. [Safety Engineering Division, Reactor Design Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102, Tamilnadu (India); Venkatraman, B. [Radiological Safety Division, Radiological Safety and Environmental Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102, Tamilnadu (India)

2013-04-15

Highlights: ► A new chelating resin PAMAMG{sub 3} -SDB has been synthesized for uranium adsorption. ► The maximum adsorption capacity was determined to be 130.25 mg g{sup −1} at pH 5.5. ► Adsorption capacity increases linearly with increasing dendron generation. ► The adsorbed uranium shall be easily desorbed by simply adjusting the pH < 3. ► Quantitative adsorption of uranium was observed even at high ionic strength. -- Abstract: A new polymeric chelating resin was prepared by growing third generation poly(amido)amine (PAMAMG{sub 3}) dendron on the surface of styrene divinylbenzene (SDB) and characterized by FTIR, TGA and SEM. The ideal branching of dendron in the chelating resin was determined from potentiometric titration. Adsorption of uranium (VI) from aqueous solution using PAMAMG{sub 3}-SDB chelating resin was studied in a series of batch experiments. Effect of contact time, pH, ionic strength, adsorbent dose, initial U(VI) concentration, dendron generation and temperature on adsorption of U(VI) were investigated. Kinetic experiments showed that U(VI) adsorption on PAMAMG{sub 3}-SDB followed pseudo-second-order kinetics model appropriately and equilibrium data agreed well with the Langmuir isotherm model. Thermodynamic parameters (ΔH°, ΔS°, ΔG°) were evaluated from temperature dependent adsorption data and the uranium adsorption on PAMAMG{sub 3}-SDB was found to be endothermic and spontaneous in nature. The sticking probability value (5.303 × 10{sup −9}), kinetic and isotherm data reveal the chemisorption of uranium on PAMAMG{sub 3}-SDB and adsorption capacity of the chelating resin was estimated to be 130.25 mg g{sup −1} at 298 K. About 99% of adsorbed U(VI) can be desorbed from PAMAMG{sub 3}-SDB by a simple acid treatment suggesting that the chelating resin is reusable.

Studies on the sorption behaviours of Th(IV) and U(VI) from aqueous sulphate solutions using impregnated resin

International Nuclear Information System (INIS)

Khatab, A.F.; Sheta, M.E.; Mahfouz, M.G.; Tolba, A.A.

2007-01-01

The sorption behaviours of thorium (IV) and uranium (VI) from aqueous sulphate solutions have been studied using n-dodecylamine and tri-n-octylamine (TOA) dissolved in benzene and impregnated onto amberlite XAD-4 (styrene-divinyl benzene copolymer). The sorption behaviours were evaluated as a function of free acidity, salting out effect, ph value, equilibrium time, V/m ratio, initial metal ion concentration, loaded amine concentration and sorption temperature. The equilibrium time for Th(IV) and U(VI) sorption from aqueous sulphate solution was found to be 90 and 60 minutes, respectively. The sorption of Th(IV) was quantitatively at ph range 3.7-4.3 and at 4.3-5.2 for U(VI). The sorption capacity of the impregnated resin was determined by batch method and it was found to be 0.031 and 0.033 mmol/g for Th(IV) and U(VI), respectively. Elution of Th(IV) from thorium-loaded impregnated resin was quantitatively achieved by using 2 mol/l HNO 3 and by using 0.1 mol/l HCl for U(VI)

Aqueous Complexation Reactions Governing the Rate and Extent of Biogeochemical U(VI) Reduction

International Nuclear Information System (INIS)

Scott C. Brooks; Wenming Dong; Sue Carroll; James K. Fredrickson; Kenneth M. Kemner; Shelly D. Kelly

2006-01-01

The proposed research will elucidate the principal biogeochemical reactions that govern the concentration, chemical speciation, and reactivity of the redox-sensitive contaminant uranium. The results will provide an improved understanding and predictive capability of the mechanisms that govern the biogeochemical reduction of uranium in subsurface environments. In addition, the work plan is designed to: (1) Generate fundamental scientific understanding on the relationship between U(VI) chemical speciation and its susceptibility to biogeochemical reduction reactions. (2) Elucidate the controls on the rate and extent of contaminant reactivity. (3) Provide new insights into the aqueous and solid speciation of U(VI)/U(IV) under representative groundwater conditions

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)

Uranium Phases in Contaminated Sediments Below Hanford's U Tank Farm

International Nuclear Information System (INIS)

Um, Wooyong; Wang, Zheming; Serne, R. Jeffrey; Williams, Benjamin D.; Brown, Christopher F.; Dodge, Cleveland J.; Francis, Arokiasamy J.

2009-01-01

Macroscopic and spectroscopic investigations (XAFS, XRF and TRLIF) on Hanford contaminated vadose zone sediments from the U-tank farm showed that U(VI) exists as different surface phases as a function of depth below ground surface (bgs). Dominant U(VI) silicate precipitates (boltwoodite and uranophane) were present in shallow-depth sediments (15-16 m bgs). In the intermediate depth sediments (20-25 m bgs), adsorbed U(VI) phases dominated but small amounts of surface precipitates consisting of polynuclear U(VI) surface complex were also identified. The deep depth sediments (> 28 m bgs) showed no signs of contact with tank wastes containing Hanford-derived U(VI), but natural uranium solid phases were observed. Most of the U(VI) was preferentially associated with the silt and clay size fractions and showed strong correlation with Ca, especially for the precipitated U(VI) silicate phase in the shallow depth sediments. Because U(VI) silicate precipitates dominate the U(VI) phases in the shallow depth sediments, macroscopic (bi)carbonate leaching should result in U(VI) releases from both desorption and dissolution processes. Having several different U(VI) surface phases in the Hanford contaminated sediments indicates that the U(VI) release mechanism could be complicated and that detailed characterization of the sediments would be needed to estimate U(VI) fate and transport in vadose zone

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.

Bioleaching of UO22+ ions from a Romanian poor uranium ore

International Nuclear Information System (INIS)

Cecal, Al.; Popa, K.; Moraru, R.T.; Patachia, S.

2002-01-01

An experimental study on the bioleaching of a poor uranium ore by means of hydrophytic plants Lemna minor and Riccia fluitans, under various operating conditions is discussed. The maximum degree of bioleaching (42%) of the reduced uranium species to U(VI) has been attained for the ore-Lemna minor-alkaline carbonate solution system. The UO 2 2+ ions amount accumulated in the plants is negligible as compared to the dissolved quantity, owing to the ionic competition between uranyl ions and the cations necessary to the mineral nutrition. The X-ray diffraction patterns prove that the uranium species in pyrochlore mineral are completely oxidized to U(VI), while thucolite is only partially turned into UO 2 2+ ions, in the presence of living plants. (author)

Laser based analytical spectroscopy of uranium

International Nuclear Information System (INIS)

Argekar, A.A.; Kulkarni, M.J.; Godbole, S.V.; Page, A.G.; Samuel, J.K.; Paranjape, D.B.; Singh Mudher, K.D.

1992-01-01

Analytical spectroscopy of uranium has been studied using a XeCl excimer laser, using the fluorescence emission of U(VI) ions doped in a solid solution of sodium fluoride (NaF) and sodium chloride (NaCl) in 3:2 proportion. An electronic circuitry involving time-gating of the photomultiplier tube and facility to integrate the analytical signal over ten laser pulses has been developed to enable laser operation and signal detection with high S/N ratio. The matrix enhanced U(VI) fluorescence emission is free from chemical and spectral interferences due to the concomitant presence of ten metallic elements generally associated with uranium. The digital signal output is highly precise and does not saturate upto 5 ppm uranium concentration. X-ray diffraction patterns obtained for uranium doped compounds at 2.5% and 10% dopant concentrations are broadly similar to that of Na 2 U 2 O 7 . The detailed studies have, however, revealed fine structure for individual peaks, thereby, revealing the formation of sodium fluoro-uranate complex which is responsible for the enhanced intensity of fluorescence emission. (author). 10 refs., 6 figs., 2 tabs

Sorption of U(VI) species on hydroxyapatite

International Nuclear Information System (INIS)

Thakur, P.; Moore, R.C.; Choppin, G.R.

2005-01-01

The sorption of uranyl (UO 2 2+ ) cations to hydroxyapatite was studied as a function of the amount of sorbent, ionic strength, U(VI) concentration, pH and temperature. The rate of uranyl sorption on hydroxyapatite decreased with increased uranyl concentrations. The amount sorbed decreased with increased ionic strength and increased with pH to a maximum at 7-8. The sorption data for UO 2 2+ were fitted well by the Freundlich and Dubinin-Radushkevich (D-R) isotherms. The anions Cl - , NO 3 - , SO 4 2- and CH 3 COO - decreased the sorption of uranium on hydroxyapatite while S 2 O 3 2- slightly increased it. The sorbed uranium was desorbed by 0.10 M and 1.00 M solutions of HCl and HNO 3 . The thermodynamic parameters for the sorption of UO 2 2+ were measured at temperatures of 298, 313, 323 and 333 K. The temperature dependence confirmed an endothermic heat of sorption. The activation energy for the sorption process was calculated to be +2.75±0.02 kJ/mol. (orig.)

Fate of Uranium in Wetlands: Impact of Drought Followed by Re-flooding

Science.gov (United States)

Gilson, E.; Huang, S.; Koster van Groos, P. G.; Scheckel, K.; Peacock, A. D.; Kaplan, D. I.; Jaffe, P. R.

2014-12-01

Uranium contamination in groundwater can be mitigated in anoxic zones by iron-reducing bacteria that reduce soluble U(VI) to insoluble U(IV) and by uranium immobilization through complexation and sorption. Wetlands often link ground and surface-waters, making them strategic systems for potentially limiting migration of uranium contamination. Little is known about how drought periods that result in the drying of wetland soils, and consequent redox changes, affect uranium fate and transport in wetlands. In order to better understand the fate and stability of immobilized uranium in wetland soils, and how dry periods affect the uranium stability, we dosed saturated wetland mesocosms planted with Scirpus acutus with low levels of uranyl-acetate for 5 months before imposing a 9-day drying period followed by a 13-day rewetting period. Concentrations of uranium in mesocosm effluent increased after rewetting, but the cumulative amount of uranium released in the 13 days following the drying constituted less than 1% of the uranium immobilized in the soil during the 5 months prior to the drought. This low level of remobilization suggests that the uranium immobilized in these soils was not primarily bioreduced U(IV), which could have been oxidized to soluble U(VI) during the drought and released in the effluent during the subsequent flood. XANES analyses confirm that most of the uranium immobilized in the mesocosms was U(VI) sorbed to iron oxides. Compared to mesocosms that did not experience drying or rewetting, mesocosms that were sacrificed immediately after drying and after 13 days of rewetting had less uranium in soil near roots and more uranium on root surfaces. Metal-reducing bacteria only dominated the bacterial community after 13 days of rewetting and not immediately after drying, indicating that these bacteria are not responsible for this redistribution of uranium after the drying and rewetting. Results show that short periods of drought conditions in a wetland may

Fundamental study on decontamination of wastes contaminated by uranium fluorides by using ionic liquids - dissolution and electrochemistry of uranium in 1-butyl-3-methylimidazolium chloride

Energy Technology Data Exchange (ETDEWEB)

Noriko Asanuma [Department of Energy Science and Engineering, School of Engineering, Tokai University 1117 Kitakaname, Hiratsuka-shi, Kanagawa 259-1292 (Japan); Yusuke Ohhashi; Yukio Wada [Ningyo-toge Environmental Engineering Center, Japan Atomic Energy Agency Kagamino-cho, Tomata-gun, Okayama 708-0698 (Japan); Masayuki Harada; Yasuhisa Ikeda [Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology 2-12-1-N1-34 Ookayama, Meguro-ku, Tokyo 152-8550 (Japan)

2008-07-01

Treatment method for wastes contaminated uranium fluorides by using ionic liquids as media of pyrochemical process instead of alkali metal chloride molten salts was proposed. In this method, uranium fluorides such as UF{sub 4} or NaF adsorbing UF{sub 6} are dissolved in 1-butyl-3-methylimidazolium chloride (BMICl) and dissolved uranium species are recovered as deposits by electrochemical reduction. Under the atmospheric condition, UF{sub 4} was completely dissolved in BMICl at 100 deg. C. UV-vis absorption spectra of the sample solution indicated that main species of uranium are U(VI) and a part of uranium exists as U(IV). Chemical form of uranium in the NaF adsorbents is Na{sub 3}UO{sub 2}F{sub 5}. Therefore, it was immediately dissolved to BMICl. However, complete dissolution was not achieved. Cyclic voltammetry of the solutions prepared by dissolution experiments was performed. Redox properties of uranium species in each sample were irreversible. It was assigned to reduction of U(VI) to U(IV). As a result of preliminary bulk electrolysis, it was expected that reduction products are deposited on the carbon cathode. (authors)

Phosphoryl functionalized mesoporous silica for uranium adsorption

International Nuclear Information System (INIS)

Xue, Guo; Yurun, Feng; Li, Ma; Dezhi, Gao; Jie, Jing; Jincheng, Yu; Haibin, Sun; Hongyu, Gong; Yujun, Zhang

2017-01-01

Highlights: • Phosphoryl functionalized mesoporous silica (TBP-SBA-15) is synthesized. • The amino and phosphoryl groups are successfully grafted on SBA-15. • TBP-SBA-15 has high and rapid uranium adsorption capacity in broad pH range. • The U(VI) adsorption of TBP-SBA-15 is spontaneous and belongs to chemical adsorption. - Abstract: Phosphoryl functionalized mesoporous silica (TBP-SBA-15) was synthesized by modified mesoporous silica with γ-amino propyl triethoxy silane and tributyl phosphate. The obtained samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), small angle X-ray diffraction (SAXRD), thermo-gravimetric/differential thermalanalyzer (TG/DTA), N_2 adsorption–desorption (BET) and Fourier transform infrared spectroscopy (FT-IR) techniques. Results showed that TBP-SBA-15 had large surface areas with ordered channel structure. Moreover, the effects of adsorption time, sorbent dose, solution pH, initial uranium concentration and temperature on the uranium adsorption behaviors were investigated. TBP-SBA-15 showed a high uranium adsorption capacity in a broad range of pH values. The U(VI) adsorption rate of TBP-SBA-15 was fast and nearly achieved completion in 10 min with the sorbent dose of 1 g/L. The U(VI) adsorption of TBP-SBA-15 followed the pseudo-second-order kinetic model and Freundlich isotherm model, indicating that the process was belonged to chemical adsorption. Furthermore, the thermodynamic parameters (ΔG"0, ΔH"0 and ΔS"0) confirmed that the adsorption process was endothermic and spontaneous.

Phosphoryl functionalized mesoporous silica for uranium adsorption

Energy Technology Data Exchange (ETDEWEB)

Xue, Guo; Yurun, Feng; Li, Ma; Dezhi, Gao; Jie, Jing; Jincheng, Yu; Haibin, Sun [Key Laboratory for Liquid-Solid Structural Evolution & Processing of Materials of Ministry of Education, Shandong University, Jinan 250061 (China); Key Laboratory of Special Functional Aggregated Materials, Ministry of Education, Shandong University, Jinan 250061 (China); Hongyu, Gong, E-mail: gong_hongyu@163.com [Key Laboratory for Liquid-Solid Structural Evolution & Processing of Materials of Ministry of Education, Shandong University, Jinan 250061 (China); Key Laboratory of Special Functional Aggregated Materials, Ministry of Education, Shandong University, Jinan 250061 (China); Yujun, Zhang, E-mail: yujunzhangcn@163.com [Key Laboratory for Liquid-Solid Structural Evolution & Processing of Materials of Ministry of Education, Shandong University, Jinan 250061 (China); Key Laboratory of Special Functional Aggregated Materials, Ministry of Education, Shandong University, Jinan 250061 (China)

2017-04-30

Highlights: • Phosphoryl functionalized mesoporous silica (TBP-SBA-15) is synthesized. • The amino and phosphoryl groups are successfully grafted on SBA-15. • TBP-SBA-15 has high and rapid uranium adsorption capacity in broad pH range. • The U(VI) adsorption of TBP-SBA-15 is spontaneous and belongs to chemical adsorption. - Abstract: Phosphoryl functionalized mesoporous silica (TBP-SBA-15) was synthesized by modified mesoporous silica with γ-amino propyl triethoxy silane and tributyl phosphate. The obtained samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), small angle X-ray diffraction (SAXRD), thermo-gravimetric/differential thermalanalyzer (TG/DTA), N{sub 2} adsorption–desorption (BET) and Fourier transform infrared spectroscopy (FT-IR) techniques. Results showed that TBP-SBA-15 had large surface areas with ordered channel structure. Moreover, the effects of adsorption time, sorbent dose, solution pH, initial uranium concentration and temperature on the uranium adsorption behaviors were investigated. TBP-SBA-15 showed a high uranium adsorption capacity in a broad range of pH values. The U(VI) adsorption rate of TBP-SBA-15 was fast and nearly achieved completion in 10 min with the sorbent dose of 1 g/L. The U(VI) adsorption of TBP-SBA-15 followed the pseudo-second-order kinetic model and Freundlich isotherm model, indicating that the process was belonged to chemical adsorption. Furthermore, the thermodynamic parameters (ΔG{sup 0}, ΔH{sup 0} and ΔS{sup 0}) confirmed that the adsorption process was endothermic and spontaneous.

The blue complexes of U in aqueous solutions

International Nuclear Information System (INIS)

Musikas, C.

1976-01-01

Mixed-valence uranium complexes were synthesized. Hydrolysis of hexavalent U leads to anionic species soluble in aqueous solutions when the UO 2 ++ ions are neutralized by tetraalkylammonium hydroxides. These complexes are polynuclear and the size and interatomic distances found for the polyanions are those of macromolecules. By hydrazine of these complexes, solutions were obtained and their absorption spectra studied. The spectra of U(VI) and U(V) ions are observed, together with new bands attributable to a charge transfer. It may be concluded that the blue complexes of uranium are type II composite-valence complexes for which the delocalization coefficient α can be calculated [fr

Uranium speciation in plants

International Nuclear Information System (INIS)

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

2003-01-01

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

Controlling Hexavalent Americium – A Centerpiece to a Compact Nuclear Fuel Cycle

Energy Technology Data Exchange (ETDEWEB)

Shafer/Braley, Jenifer; Nash, Kenneth L; Lumetta, Gregg; McCann, Kevin; Sinkov, Sergey I

2014-10-01

Closing the nuclear fuel cycle could be simplified by recovering the actinides U through Am as a group. This could be achieved by converting U, Np, Pu and Am to the hexavalent state. Uranium, Np and Pu are readily oxidized to the hexavalent state. Generation of hexavalent Am in acidic solutions is more difficult, as the standard reduction potential of the Am(VI) /Am(III) couple (+1.68 V in 1 M HClO4) is well outside of the electrochemical stability window of water. While the oxidation and separation of Am has been demonstrated under laboratory conditions, several issues could plague scale up and implementation of this separation with used fuel. Two primary concerns are considered. The first issue concerns the stability of the oxidized Am. The second involves the undesirable co-extraction of tetravalent f-elements with the hexavalent actinides. To address the first concern regarding Am redox instability, Am reduction will be monitored under a variety of different conditions to establish the means of improving the stability of Am(VI) in the organic phase. Identifying the components contributing most significantly to its reduction will allow thoughtful modification of the process. To address the second concern, we propose to apply branched chain extractants to separate hexavalent actinides from tetravalent f-elements. Both branched monoamide and organophosphorus extractants have demonstrated significant selectivity for UO22+ versus Th4+, with separation factors generally on the order of 100. The efforts of this two-pronged research program should represent a significant step forward in the development of aqueous separations approaches designed to recover the U-Am actinides based on the availability of the hexavalent oxidation state. For the purposes of this proposal, separations based on this approach will be called SAn(VI) separations, indicating the Separation of An(VI).

Influence of radiolytic products on the chemistry of uranium VI in brines

International Nuclear Information System (INIS)

Lucchini, J-F.; Reed, D.T.; Borkowski, M.; Rafalski, A.; Conca, J.

2004-01-01

In the near field of a salt repository of nuclear waste, ionizing radiations can strongly affect the chemistry of concentrated saline solutions. Radiolysis can locally modify the redox conditions, speciation, solubility and mobility of the actinide compounds. In the case of uranium VI, radiolytic products can not only reduce U(VI), but also react with uranium species. The net effect on the speciation of uranyl depends on the relative kinetics of the reactions and the buildup of molecular products in brine solutions. The most important molecular products in brines are expected to be hypochlorite ion, hypochlorous acid and hydrogen peroxide. Although U(VI) is expected not to be significantly affected by radiolysis, the combined effects of the major molecular radiolytic products on the chemistry of U(VI) in brines have not been experimentally established previously. (authors)

Bio-precipitation of uranium by two bacterial isolates recovered from extreme environments as estimated by potentiometric titration, TEM and X-ray absorption spectroscopic analyses.

Science.gov (United States)

Merroun, Mohamed L; Nedelkova, Marta; Ojeda, Jesus J; Reitz, Thomas; Fernández, Margarita López; Arias, José M; Romero-González, María; Selenska-Pobell, Sonja

2011-12-15

This work describes the mechanisms of uranium biomineralization at acidic conditions by Bacillus sphaericus JG-7B and Sphingomonas sp. S15-S1 both recovered from extreme environments. The U-bacterial interaction experiments were performed at low pH values (2.0-4.5) where the uranium aqueous speciation is dominated by highly mobile uranyl ions. X-ray absorption spectroscopy (XAS) showed that the cells of the studied strains precipitated uranium at pH 3.0 and 4.5 as a uranium phosphate mineral phase belonging to the meta-autunite group. Transmission electron microscopic (TEM) analyses showed strain-specific localization of the uranium precipitates. In the case of B. sphaericus JG-7B, the U(VI) precipitate was bound to the cell wall. Whereas for Sphingomonas sp. S15-S1, the U(VI) precipitates were observed both on the cell surface and intracellularly. The observed U(VI) biomineralization was associated with the activity of indigenous acid phosphatase detected at these pH values in the absence of an organic phosphate substrate. The biomineralization of uranium was not observed at pH 2.0, and U(VI) formed complexes with organophosphate ligands from the cells. This study increases the number of bacterial strains that have been demonstrated to precipitate uranium phosphates at acidic conditions via the activity of acid phosphatase. Copyright © 2011 Elsevier B.V. All rights reserved.

Simultaneous adsorption and reduction of U(VI) on reduced graphene oxide-supported nanoscale zerovalent iron

Energy Technology Data Exchange (ETDEWEB)

Sun, Yubing [School of Environment and Chemical Engineering, North China Electric Power University, Beijing 102206 (China); Institute of Plasma Physics, Chinese Academy of Science, P.O. Box 1126, Hefei, 230031 (China); Ding, Congcong; Cheng, Wencai [Institute of Plasma Physics, Chinese Academy of Science, P.O. Box 1126, Hefei, 230031 (China); Wang, Xiangke, E-mail: xkwang@ipp.ac.cn [School of Environment and Chemical Engineering, North China Electric Power University, Beijing 102206 (China); Faculty of Engineering, King Abdulaziz University, Jeddah 21589 (Saudi Arabia)

2014-09-15

Graphical abstract: - Highlights: • Sorption and in-situ reduction of U(VI) is observed. • The composites are more effective for U(VI) removal and solidification. • The inner-sphere surface complexes are observed. - Abstract: The reduced graphene oxide-supported nanoscale zero-valent iron (nZVI/rGO) composites were synthesized by chemical deposition method and were characterized by SEM, high resolution TEM, Raman and potentiometric acid-base titrations. The characteristic results showed that the nZVI nanoparticles can be uniformly dispersed on the surface of rGO. The removal of U(VI) on nZVI/rGO composites as a function of contact time, pH and U(VI) initial concentration was investigated by batch technique. The removal kinetics of U(VI) on nZVI and nZVI/rGO were well simulated by a pseudo-first-order kinetic model and pseudo-second-order kinetic model, respectively. The presence of rGO on nZVI nanoparticles increased the reaction rate and removal capacity of U(VI) significantly, which was attributed to the chemisorbed OH{sup −} groups of rGO and the massive enrichment of Fe{sup 2+} on rGO surface by XPS analysis. The XRD analysis revealed that the presence of rGO retarded the transformation of iron corrosion products from magnetite/maghemite to lepidocrocite. According to the fitting of EXAFS spectra, the U-C (at ∼2.9 Å) and U-Fe (at ∼3.2 Å) shells were observed, indicating the formation of inner-sphere surface complexes on nZVI/rGO composites. Therefore, the nZVI/rGO composites can be suitable as efficient materials for the in-situ remediation of uranium-contaminated groundwater in the environmental pollution management.

Uranium speciation and stability after reductive immobilization in sediments.

OpenAIRE

Sharp J.O

2011-01-01

It has generally been assumed that the bioreduction of hexavalent uranium in groundwater systems will result in the precipitation of immobile uraninite (UO2). In order to explore the form and stability of uranium immobilized under these conditions we introduced lactate (15 mM for 3 months) into flow through columns containing sediments derived from a former uranium processing site at Old Rifle CO. This resulted in metal reducing conditions as evidenced by concurrent uranium uptake and iron re...

Uranium speciation and stability after reductive immobilization in sediments

OpenAIRE

Sharp, Jonathan O.; Schofield, Eleanor J.; Lezama-Pacheco, Juan S.; Webb, Sam; Ulrich, Kai-Uwe; Blue, Lisa; Chinni, Satyavani; Veeramani, Harish; Junier, Pilar; Margot-Roquier, Camille; Suvorova Buffat, Elena; Tebo, Bradley M.; Giammar, Daniel E.; Bargar, John R.; Bernier-Latmani, Rizlan

2011-01-01

It has generally been assumed that the bioreduction of hexavalent uranium in groundwater systems will result in the precipitation of immobile uraninite (UO2). In order to explore the form and stability of uranium immobilized under these conditions, we introduced lactate (15 mM for 3 months) into flow-through columns containing sediments derived from a former uranium-processing site at Old Rifle, CO. This resulted in metal-reducing conditions as evidenced by concurrent uranium uptake and iron ...

Effect of pH and Fe/U ratio on the U(VI) removal rate by the synergistic effect of Fe(II) and O2

Science.gov (United States)

Fu, Yukui; Luo, Yingfeng; Fang, Qi; Xie, Yanpei; Wang, Zhihong; Zhu, Xiangyu

2018-02-01

As for the decommissioned uranium deposits of acid in-situ leaching, both of the concentrations of U(VI) and Fe(II) are relatively high in groundwater. In the presence of O2, the oxidation of Fe(II) into Fe(III) that forms Fe-hydroxides could effectively remove U(VI) in the forms of sorption or co-precipitation. In this process, pH condition and Fe content will have a significant effect on the U(VI) removal rate by the synergistic effect of Fe(II) and O2. In the present work, a series of batch experiments were carried out to investigate the effect of pH values and Fe/U mass ratio on the U(VI) removal rate by the synergistic effect of Fe(II) and O2. Experiment results show that the removal rate of U(VI) is mainly controlled by pH and secondly by Fe/U mass ratio. In the neutral conditions with pH at 7 and 8, the removal rate of U(VI) reaches up to 90% for all solutions with different initial Fe(II) concentrations. The optimal pH for the removal rate of U(VI) is above 7. In the acidic conditions with pH below 6, the effect of Fe/U mass ratio on the removal rate of U(VI) becomes more obvious and the optimal Fe/U mass ratio for U(VI) removal is 1:2.

Adsorptive property of rice husk for uranium

International Nuclear Information System (INIS)

Feng Yuan; Yi Facheng

2011-01-01

The adsorption experiments were researched by using the rice husk powder as the adsorbent to remove the U(VI) from aqueous solution. The affecting factors on the U(VI) removal rate such as rice husk particle size, pH, initial concentration, adsorption time, temperature and dosage of adsorbent were evaluated, kinetics and adsorption isotherm law were analyzed, and mechanisms for U(VI) removal were discussed by SEM, FT-IR and energy spectrum analysis. The results show that U(VI) removal rate increases with the decrease of the size of adsorbent, and with the increase of adsorbent dosage and temperature. The process of adsorption can be described by an equation of pseudo 2nd-order mode, and the relation coefficient is 1. The process of adsorption also fits to Freundlich isotherm (R 2 =0.995 4). The adsorption of uranium on rice husk changes the surface form of rice husk. Hydroxyl, carboxylic, P-O and Si-O are the main functional groups in the reaction with U(VI). The adsorption mechanism is mixture adsorption, including the physical and chemical adsorption. (authors)

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.

Selective removal of U(VI) from low concentration wastewater by functionalized HKUST-1@H3PW12O40

International Nuclear Information System (INIS)

Hui Zhang; Jinhua Xue; Nan Hu; Jing Sun; Dexin Ding; Yongdong Wang; Le Li

2016-01-01

The adsorption of U(VI) from low concentration solution by HKUST-1@H 3 PW 12 O 40 was studied as a function of various experimental parameters including pH, interfering ions, contact time, initial uranium concentration and temperature by batch experiments. Equilibrium data were found to fit with Langmuir isotherm model better than Freundlich isotherm model. The kinetic adsorption was fitted by the pseudo-second-order model well. Thermodynamic data from the adsorption experiments indicate that adsorption process is spontaneous and endothermic. HKUST-1@H 3 PW 12 O 40 can selectively adsorb U(VI) from multi-metal ion solutions and the adsorption capacity of HKUST-1@H 3 PW 12 O 40 don't decrease significantly after three cycles of desorption-reuse. The results show that HKUST-1@H 3 PW 12 O 40 is suitable for removal of U(VI) from low concentration solutions. (author)

Effect of natural uranium on the UMR-106 osteoblastic cell line: impairment of the autophagic process as an underlying mechanism of uranium toxicity.

Science.gov (United States)

Pierrefite-Carle, Valérie; Santucci-Darmanin, Sabine; Breuil, Véronique; Gritsaenko, Tatiana; Vidaud, Claude; Creff, Gaelle; Solari, Pier Lorenzo; Pagnotta, Sophie; Al-Sahlanee, Rasha; Auwer, Christophe Den; Carle, Georges F

2017-04-01

Natural uranium (U), which is present in our environment, exerts a chemical toxicity, particularly in bone where it accumulates. Generally, U is found at oxidation state +VI in its oxocationic form [Formula: see text] in aqueous media. Although U(VI) has been reported to induce cell death in osteoblasts, the cells in charge of bone formation, the molecular mechanism for U(VI) effects in these cells remains poorly understood. The objective of our study was to explore U(VI) effect at doses ranging from 5 to 600 µM, on mineralization and autophagy induction in the UMR-106 model osteoblastic cell line and to determine U(VI) speciation after cellular uptake. Our results indicate that U(VI) affects mineralization function, even at subtoxic concentrations (metal exposure. We observed that U(VI) was able to rapidly activate autophagy but an inhibition of the autophagic flux was observed after 24 h. Thus, our results indicate that U(VI) perturbs osteoblastic functions by reducing mineralization capacity. Our study identifies for the first time U(VI) in the form of meta-autunite in mammalian cells. In addition, U(VI)-mediated inhibition of the autophagic flux may be one of the underlying mechanisms leading to the decreased mineralization and the toxicity observed in osteoblasts.

Behavior of Colorado Plateau uranium minerals during oxidation

Science.gov (United States)

Garrels, Robert Minard; Christ, C.L.

1956-01-01

Uranium occurs as U(VI) and U(IV) in minerals of the Colorado Plateau ores. The number of species containing U(VI) is large, but only two U(IV) minerals are known from the Plateau: uraninite, and oxide, and coffinite, a hydroxy-silicate. These oxidize to yield U(VI) before reacting significantly with other mineral constituents. Crystal-structure analysis has shown that U(VI) invariable occurs as uranyl ion, UO2+2. Uranyl ion may form complex carbonate or sulfate ions with resulting soluble compounds, but only in the absence of quinquevalent vanadium, arsenic, or phosphorous. In the presence of these elements in the +5 valence state, the uranyl ion is fixed in insoluble layer compounds formed by union of uranyl ion with orthovanadate, orthophosphate, or orthoarsenate. Under favorable conditions UO2+2 may react to form the relatively insoluble rutherfordine, UO2CO3, or hydrated uranyl hydroxides. These are rarely found on the Colorado Plateau as opposed to their excellent development in other uraniferous areas, a condition which is apparently related to the semiarid climate and low water table of the Plateau. Uranium may also be fixed as uranyl silicate, but little is known about minerals of this kind. In the present study emphasis has been placed on a detailing of the chemical and crystal structural changes which occur in the oxidation paragenetic sequence.

Inherently safe in situ uranium recovery

Science.gov (United States)

Krumhansl, James L; Brady, Patrick V

2014-04-29

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

Removing uranium (VI) from aqueous solution with insoluble humic acid derived from leonardite.

Science.gov (United States)

Meng, Fande; Yuan, Guodong; Larson, Steven L; Ballard, John H; Waggoner, Charles A; Arslan, Zikri; Han, Fengxiang X

2017-12-01

The occurrence of uranium (U) and depleted uranium (DU)-contaminated wastes from anthropogenic activities is an important environmental problem. Insoluble humic acid derived from leonardite (L-HA) was investigated as a potential adsorbent for immobilizing U in the environment. The effect of initial pH, contact time, U concentration, and temperature on U(VI) adsorption onto L-HA was assessed. The U(VI) adsorption was pH-dependent and achieved equilibrium in 2 h. It could be well described with pseudo-second-order model, indicating that U(VI) adsorption onto L-HA involved chemisorption. The U(VI) adsorption mass increased with increasing temperature with maximum adsorption capacities of 91, 112 and 120 mg g -1 at 298, 308 and 318 K, respectively. The adsorption reaction was spontaneous and endothermic. We explored the processes of U(VI) desorption from the L-HA-U complex through batch desorption experiments in 1 mM NaNO 3 and in artificial seawater. The desorption process could be well described by pseudo-first-order model and reached equilibrium in 3 h. L-HA possessed a high propensity to adsorb U(VI). Once adsorbed, the release of U(VI) from L-HA-U complex was minimal in both 1 mM NaNO 3 and artificial seawater (0.06% and 0.40%, respectively). Being abundant, inexpensive, and safe, L-HA has good potential for use as a U adsorbent from aqueous solution or immobilizing U in soils. Copyright © 2017 Elsevier Ltd. All rights reserved.

Hexavalent Chromium Minimization Strategy

Science.gov (United States)

2011-05-01

Logistics 4 Initiative - DoD Hexavalent Chromium Minimization Non- Chrome Primer IIEXAVAJ ENT CHRO:M I~UMI CHROMIUM (VII Oil CrfVli.J CANCEfl HAnRD CD...Management Office of the Secretary of Defense Hexavalent Chromium Minimization Strategy Report Documentation Page Form ApprovedOMB No. 0704-0188...00-2011 4. TITLE AND SUBTITLE Hexavalent Chromium Minimization Strategy 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6

Reactivity of Uranium and Ferrous Iron with Natural Iron Oxyhydroxides.

Science.gov (United States)

Stewart, Brandy D; Cismasu, A Cristina; Williams, Kenneth H; Peyton, Brent M; Nico, Peter S

2015-09-01

Determining key reaction pathways involving uranium and iron oxyhydroxides under oxic and anoxic conditions is essential for understanding uranium mobility as well as other iron oxyhydroxide mediated processes, particularly near redox boundaries where redox conditions change rapidly in time and space. Here we examine the reactivity of a ferrihydrite-rich sediment from a surface seep adjacent to a redox boundary at the Rifle, Colorado field site. Iron(II)-sediment incubation experiments indicate that the natural ferrihydrite fraction of the sediment is not susceptible to reductive transformation under conditions that trigger significant mineralogical transformations of synthetic ferrihydrite. No measurable Fe(II)-promoted transformation was observed when the Rifle sediment was exposed to 30 mM Fe(II) for up to 2 weeks. Incubation of the Rifle sediment with 3 mM Fe(II) and 0.2 mM U(VI) for 15 days shows no measurable incorporation of U(VI) into the mineral structure or reduction of U(VI) to U(IV). Results indicate a significantly decreased reactivity of naturally occurring Fe oxyhydroxides as compared to synthetic minerals, likely due to the association of impurities (e.g., Si, organic matter), with implications for the mobility and bioavailability of uranium and other associated species in field environments.

Real-Time Speciation of Uranium During Active Bioremediation and U(IV) Reoxidation

International Nuclear Information System (INIS)

Komlos, J.; Mishra, B.; Lanzirotti, A.; Myneni, S.; Jaffe, P.

2008-01-01

The biological reduction of uranium from soluble U(VI) to insoluble U(IV) has shown potential to prevent uranium migration in groundwater. To gain insight into the extent of uranium reduction that can occur during biostimulation and to what degree U(IV) reoxidation will occur under field relevant conditions after biostimulation is terminated, X-ray absorption near edge structure (XANES) spectroscopy was used to monitor: (1) uranium speciation in situ in a flowing column while active reduction was occurring; and (2) in situ postbiostimulation uranium stability and speciation when exposed to incoming oxic water. Results show that after 70 days of bioreduction in a high (30 mM) bicarbonate solution, the majority (>90%) of the uranium in the column was immobilized as U(IV). After acetate addition was terminated and oxic water entered the column, in situ real-time XANES analysis showed that U(IV) reoxidation to U(VI) (and subsequent remobilization) occurred rapidly (on the order of minutes) within the reach of the oxygen front and the spatial and temporal XANES spectra captured during reoxidation allowed for real-time uranium reoxidation rates to be calculated.

Functionalized Sugarcane Bagasse for U(VI) Adsorption from Acid and Alkaline Conditions.

Science.gov (United States)

Su, Shouzheng; Liu, Qi; Liu, Jingyuan; Zhang, Hongsen; Li, Rumin; Jing, Xiaoyan; Wang, Jun

2018-01-15

The highly efficient removal of uranium from mine tailings effluent, radioactive wastewater and enrichment from seawater is of great significance for the development of nuclear industry. In this work, we prepared an efficient U(VI) adsorbent by EDTA modified sugarcane bagasse (MESB) with a simple process. The prepared adsorbent preserves high adsorptive capacity for UO 2 2+ (pH 3.0) and uranyl complexes, such as UO 2 (OH) + , (UO 2 ) 2 (OH) 2 2+ and (UO 2 ) 3 (OH) 5 + (pH 4.0 and pH 5.0) and good repeatability in acidic environment. The maximum adsorption capacity for U(VI) at pH 3.0, 4.0 and 5.0 is 578.0, 925.9 and 1394.1 mg/g and the adsorption capacity loss is only 7% after five cycles. With the pH from 3.0 to 5.0, the inhibitive effects of Na + and K + decreased but increased of Mg 2+ and Ca 2+ . MESB also exhibits good adsorption for [UO 2 (CO 3 ) 3 ] 4- at pH 8.3 from 10 mg/L to 3.3 μg/L. Moreover, MESB could effectively extract U(VI) from simulated seawater in the presence of other metals ions. This work provided a general and efficient uranyl enriched material for nuclear industry.

Biosorption of uranium by Pseudomonas aeruginosa strain CSU: Characterization and comparison studies

International Nuclear Information System (INIS)

Hu, M.Z.C.; Norman, J.M.; Faison, B.D.; Reeves, M.E.

1996-01-01

Pseudomonas aeruginosa strain CSU, a nongenetically engineered bacterial strain known to bind dissolved hexavalent uranium (as UO 2 2+ and/or its cationic hydroxo complexes) was characterized with respect to its sorptive activity. The uranium biosorption equilibrium could be described by the Langmuir isotherm. The rate of uranium adsorption increased following permeabilization of the outer and/or cytoplasmic membrane by organic solvents such as acetone. P. aeruginosa CSU biomass was significantly more sorptive toward uranium than certain novel, patented biosorbents derived from algal or fungal biomass sources. P. aeruginosa CSU biomass was also competitive with commercial cation-exchange resins, particularly in the presence of dissolved transition metals. Uranium binding by P. aeruginosa CSU was clearly pH dependent. Uranium loading capacity increased with increasing pH under acidic conditions, presumably as a function of uranium speciation and due to the H + competition at some binding sites. Nevertheless, preliminary evidence suggests that this microorganism is also capable of binding anionic hexavalent uranium complexes. Ferric iron was a strong inhibitor of uranium binding to P. aeruginosa CSU biomass, and the presence of uranium also decreased the Fe 3+ loading when the biomass was not saturated with Fe 3+ . Thus, a two-state process in which iron and uranium are removed in consecutive steps was proposed for efficient use of the biomass as a biosorbent in uranium removal from mine wastewater, especially acidic leachates

Titrimetric determination of uranium in tributyl phosphate

International Nuclear Information System (INIS)

Sobkowska, A.

1978-01-01

The titrimetric method involving the reduction of U(VI) to uranium(IV) by iron(II) in phosphoric acid, selective oxidation of the excess of iron(II) and potentiometric titration with dichromate was directly used for the determination of uranium in tributyl phosphate mixtures. The procedure was applied to solutions containing more than 2 mg of uranium in the sample but the highest precision and accuracy were obtained in the range from 20 to 200 mg of uranium. Dibutyl phosphate and monobutyl phosphate as well as the other radiolysis products of TBP had no influence on the results of determinations. (author)

WFC3 UVIS Detector Performance

Science.gov (United States)

Gunning, Heather C.; Baggett, Sylvia M.; Gosmeyer, Catherine; Bourque, Matthew; MacKenty, John W.; Anderson, Jay; WFC3 Team

2015-01-01

The Wide Field Camera 3 (WFC3) is a fourth-generation imaging instrument installed on the Hubble Space Telescope (HST) during Servicing Mission 4 (SM4) in May 2000. WFC3 has two observational channels, UV/visible (UVIS) and infrared (IR); both have been performing well on-orbit. Since installation, the WFC3 team has been diligent in monitoring the performance of both detectors. The UVIS channel consists of two e2v, backside illuminated, 2Kx4K CCDs arranged in a 2x1 mosaic. We present results from some of the monitoring programs used to check various aspects of the UVIS detector. We discuss the growth trend of hot pixels and the efficacy of regular anneals in controlling the hot pixel population. We detail a pixel population with lowered-sensitivity that evolves during the time between anneals, and is largely reset by each anneal procedure. We discuss the stability of the post-flash LED lamp, used and recommended for CTE mitigation in observations with less than 12 e-/pixel backgrounds. Finally, we summarize long-term photometric trends of the UVIS detector, as well as the absolute gain measurement, used as a proxy for the on-orbit evolution of the UVIS channel.

Potential Aquifer Vulnerability in Regions Down-Gradient from Uranium In Situ Recovery (ISR) Sites

Science.gov (United States)

Sandstone-hosted roll-front uranium ore deposits originate when U(VI) dissolved in groundwater is reduced and precipitated as insoluble U(IV) minerals. Groundwater redox geochemistry, aqueous complexation, and solute migration are instrumental in leaching uranium from source rock...

Reduction of uranium in disposal conditions of spent nuclear fuel

International Nuclear Information System (INIS)

Myllykylae, E.

2008-02-01

This literature study is a summary of publications, in which the reduction of uranium by iron has been investigated in anaerobic groundwater conditions or in aqueous solution in general. The basics of the reduction phenomena and the oxidation states, complexes and solubilities of uranium and iron in groundwaters are discussed as an introduction to the subject, as well as, the Finnish disposal concept of spent nuclear fuel. The spent fuel itself mainly (∼96 %) consists of a sparingly soluble uranium(IV) dioxide, UO 2 (s), which is stable phase in the anticipated reducing disposal conditions. If spent fuel gets in contact with groundwater, oxidizing conditions might be induced by the radiolysis of water, or by the intrusion of oxidizing glacial melting water. Under these conditions, the oxidation and dissolution of uranium dioxide to more soluble U(VI) species could occur. This could lead to the mobilization of uranium and other components of spent fuel matrix including fission products and transuranium elements. The reduction of uranium back to oxidation state U(IV) can be considered as a favourable immobilization mechanism in a long-term, leading to precipitation due to the low solubility of U(IV) species. The cast iron insert of the disposal canister and its anaerobic corrosion products are the most important reductants under disposal conditions, but dissolved ferrous iron may also function as reductant. Other iron sources in the buffer or near-field rock, are also considered as possible reductants. The reduction of uranium is a very challenging phenomenon to investigate. The experimental studies need e.g. well-controlled anoxic conditions and measurements of oxidation states. Reduction and other simultaneous phenomena are difficult to distinghuish. The groundwater conditions (pH, Eh and ions) influence on the prevailing complexes of U and Fe and on forming corrosion products of iron and, thus they determine also the redox chemistry. The partial reduction of

Technical Basis for Assessing Uranium Bioremediation Performance

International Nuclear Information System (INIS)

PE Long; SB Yabusaki; PD Meyer; CJ Murray; AL N'Guessan

2008-01-01

In situ bioremediation of uranium holds significant promise for effective stabilization of U(VI) from groundwater at reduced cost compared to conventional pump and treat. This promise is unlikely to be realized unless researchers and practitioners successfully predict and demonstrate the long-term effectiveness of uranium bioremediation protocols. Field research to date has focused on both proof of principle and a mechanistic level of understanding. Current practice typically involves an engineering approach using proprietary amendments that focuses mainly on monitoring U(VI) concentration for a limited time period. Given the complexity of uranium biogeochemistry and uranium secondary minerals, and the lack of documented case studies, a systematic monitoring approach using multiple performance indicators is needed. This document provides an overview of uranium bioremediation, summarizes design considerations, and identifies and prioritizes field performance indicators for the application of uranium bioremediation. The performance indicators provided as part of this document are based on current biogeochemical understanding of uranium and will enable practitioners to monitor the performance of their system and make a strong case to clients, regulators, and the public that the future performance of the system can be assured and changes in performance addressed as needed. The performance indicators established by this document and the information gained by using these indicators do add to the cost of uranium bioremediation. However, they are vital to the long-term success of the application of uranium bioremediation and provide a significant assurance that regulatory goals will be met. The document also emphasizes the need for systematic development of key information from bench scale tests and pilot scales tests prior to full-scale implementation

Technical Basis for Assessing Uranium Bioremediation Performance

Energy Technology Data Exchange (ETDEWEB)

PE Long; SB Yabusaki; PD Meyer; CJ Murray; AL N’Guessan

2008-04-01

In situ bioremediation of uranium holds significant promise for effective stabilization of U(VI) from groundwater at reduced cost compared to conventional pump and treat. This promise is unlikely to be realized unless researchers and practitioners successfully predict and demonstrate the long-term effectiveness of uranium bioremediation protocols. Field research to date has focused on both proof of principle and a mechanistic level of understanding. Current practice typically involves an engineering approach using proprietary amendments that focuses mainly on monitoring U(VI) concentration for a limited time period. Given the complexity of uranium biogeochemistry and uranium secondary minerals, and the lack of documented case studies, a systematic monitoring approach using multiple performance indicators is needed. This document provides an overview of uranium bioremediation, summarizes design considerations, and identifies and prioritizes field performance indicators for the application of uranium bioremediation. The performance indicators provided as part of this document are based on current biogeochemical understanding of uranium and will enable practitioners to monitor the performance of their system and make a strong case to clients, regulators, and the public that the future performance of the system can be assured and changes in performance addressed as needed. The performance indicators established by this document and the information gained by using these indicators do add to the cost of uranium bioremediation. However, they are vital to the long-term success of the application of uranium bioremediation and provide a significant assurance that regulatory goals will be met. The document also emphasizes the need for systematic development of key information from bench scale tests and pilot scales tests prior to full-scale implementation.

Potential for Methanosarcina to contribute to uranium reduction during acetate-promoted groundwater bioremediation

DEFF Research Database (Denmark)

Holmes, Dawn E; Orellana, Roberto; Giloteaux, Ludovic

2018-01-01

Previous studies of acetate-promoted bioremediation of uranium-contaminated aquifers focused on Geobacter because no other microorganisms that can couple the oxidation of acetate with U(VI) reduction had been detected in situ. Monitoring the levels of methyl CoM reductase subunit A (mcrA) transcr......Previous studies of acetate-promoted bioremediation of uranium-contaminated aquifers focused on Geobacter because no other microorganisms that can couple the oxidation of acetate with U(VI) reduction had been detected in situ. Monitoring the levels of methyl CoM reductase subunit A (mcr......(VI) reduction was observed in inactive controls. These results demonstrate that Methanosarcina species could play an important role in the long-term bioremediation of uranium-contaminated aquifers after depletion of Fe(III) oxides limits the growth of Geobacter species. The results also suggest...

Determination of kinetic coefficients for the simultaneous reduction of sulfate and uranium by Desulfovibrio desulfuricans bacteria

International Nuclear Information System (INIS)

Tucker, M.D.

1995-05-01

Uranium contamination of groundwaters and surface waters near abandoned mill tailings piles is a serious concern in many areas of the western United States. Uranium usually exists in either the U(IV) or the U(VI) oxidation state. U(VI) is soluble in water and, as a result, is very mobile in the environment. U(IV), however, is generally insoluble in water and, therefore, is not subject to aqueous transport. In recent years, researchers have discovered that certain anaerobic microorganisms, such as the sulfate-reducing bacteria Desulfovibrio desulfuricans, can mediate the reduction of U(VI) to U(IV). Although the ability of this microorganism to reduce U(VI) has been studied in some detail by previous researchers, the kinetics of the reactions have not been characterized. The purpose of this research was to perform kinetic studies on Desulfovibrio desulficans bacteria during simultaneous reduction of sulfate and uranium and to determine the phase in which uranium exists after it has been reduced and precipitated from solution. The studies were conducted in a laboratory-scale chemostat under substrate-limited growth conditions with pyruvate as the substrate. Kinetic coefficients for substrate utilization and cell growth were calculated using the Monod equation. The maximum rate of substrate utilization (k) was determined to be 4.70 days -1 while the half-velocity constant (K s ) was 140 mg/l COD. The yield coefficient (Y) was determined to be 0.17 mg cells/mg COD while the endogenous decay coefficient (k d ) was calculated as 0.072 days -1 . After reduction, U(IV) Precipitated from solution in the uraninite (UO 2 ) phase. Uranium removal efficiency as high as 90% was achieved in the chemostat

Uranium redox transition pathways in acetate-amended sediments

Science.gov (United States)

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

2013-01-01

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

Promoting Uranium Immobilization by the Activities of Microbial Phosphatases

Energy Technology Data Exchange (ETDEWEB)

Martinez, Robert J.; Beazley, Melanie J.; Wilson, Jarad J.; Taillefert, Martial; Sobecky, Patricia A.

2005-04-05

The overall goal of this project is to examine the role of nonspecific phosphohydrolases present in naturally occurring subsurface microorganisms for the purpose of promoting the immobilization of radionuclides through the production of uranium [U(VI)] phosphate precipitates. Specifically, we hypothesize that the precipitation of U(VI) phosphate minerals may be promoted through the microbial release and/or accumulation of PO{sub 4}{sup 3-}. During this phase of the project we have been conducting assays to determine the effects of pH, inorganic anions and organic ligands on U(VI) mineral formation and precipitation when FRC bacterial isolates were grown in simulated groundwater medium. The molecular characterization of FRC isolates has also been undertaken during this phase of the project. Analysis of a subset of gram-positive FRC isolates cultured from FRC soils (Areas 1, 2 and 3) and background sediments have indicated a higher percentage of isolates exhibiting phosphatase phenotypes (i.e., in particular those surmised to be PO{sub 4}{sup 3-}-irrepressible) relative to isolates from the reference site. A high percentage of strains that exhibited such putatively PO{sub 4}{sup 3-}-irrepressible phosphatase phenotypes were also resistant to the heavy metals lead and cadmium. Previous work on FRC strains, including Arthrobacter, Bacillus and Rahnella spp., has demonstrated differences in tolerance to U(VI) toxicity (200 {micro}M) in the absence of organophosphate substrates. For example, Arthrobacter spp. exhibited the greatest tolerance to U(VI) while the Rahnella spp. have been shown to facilitate the precipitation of U(VI) from solution and the Bacillus spp. demonstrate the greatest sensitivity to acidic conditions and high concentrations of U(VI). PCR-based detection of FRC strains are being conducted to determine if non-specific acid phosphatases of the known molecular classes [i.e., classes A, B and C] are present in these FRC isolates. Additionally, these

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

Uranium Biomineralization By Natural Microbial Phosphatase Activities in the Subsurface

Energy Technology Data Exchange (ETDEWEB)

Taillefert, Martial [Georgia Tech Research Corporation, Atlanta, GA (United States)

2015-04-01

This project investigated the geochemical and microbial processes associated with the biomineralization of radionuclides in subsurface soils. During this study, it was determined that microbial communities from the Oak Ridge Field Research subsurface are able to express phosphatase activities that hydrolyze exogenous organophosphate compounds and result in the non-reductive bioimmobilization of U(VI) phosphate minerals in both aerobic and anaerobic conditions. The changes of the microbial community structure associated with the biomineralization of U(VI) was determined to identify the main organisms involved in the biomineralization process, and the complete genome of two isolates was sequenced. In addition, it was determined that both phytate, the main source of natural organophosphate compounds in natural environments, and polyphosphate accumulated in cells could also be hydrolyzed by native microbial population to liberate enough orthophosphate and precipitate uranium phosphate minerals. Finally, the minerals produced during this process are stable in low pH conditions or environments where the production of dissolved inorganic carbon is moderate. These findings suggest that the biomineralization of U(VI) phosphate minerals is an attractive bioremediation strategy to uranium bioreduction in low pH uranium-contaminated environments. These efforts support the goals of the SBR long-term performance measure by providing key information on "biological processes influencing the form and mobility of DOE contaminants in the subsurface".

Characterization of uranium redox state in organic-rich Eocene sediments.

Science.gov (United States)

Cumberland, Susan A; Etschmann, Barbara; Brugger, Joël; Douglas, Grant; Evans, Katy; Fisher, Louise; Kappen, Peter; Moreau, John W

2018-03-01

The presence of organic matter (OM) has a profound impact on uranium (U) redox cycling, either limiting or promoting the mobility of U via binding, reduction, or complexation. To understand the interactions between OM and U, we characterised U oxidation state and speciation in nine OM-rich sediment cores (18 samples), plus a lignite sample from the Mulga Rock polymetallic deposit in Western Australia. Uranium was unevenly dispersed within the analysed samples with 84% of the total U occurring in samples containing >21 wt % OM. Analyses of U speciation, including x-ray absorption spectroscopy and bicarbonate extractions, revealed that U existed predominately (∼71%) as U(VI), despite the low pH (4.5) and nominally reducing conditions within the sediments. Furthermore, low extractability by water, but high extractability by a bi-carbonate solution, indicated a strong association of U with particulate OM. The unexpectedly high proportion of U(VI) relative to U(IV) within the OM-rich sediments implies that OM itself does not readily reduce U, and the reduction of U is not a requirement for immobilizing uranium in OM-rich deposits. The fact that OM can play a significant role in limiting the mobility and reduction of U(VI) in sediments is important for both U-mining and remediation. Copyright © 2017 Elsevier Ltd. All rights reserved.

In Situ Community Control of the Stability of Bioreduced Uranium

International Nuclear Information System (INIS)

White, David C.

2006-01-01

The overall objective of this research is to understand the mechanisms for maintenance of bio-reduced uranium in an aerobic to microaerophylic aquifer under actual field conditions after electron donor addition for biostimulation has ended. Primary Objectives: (1) Determine the relative importance of microbial communities and/or chemical and physical environments mediating uranium reduction/oxidation after cessation of donor addition in an aerobic aquifer. (2) Determine, after cessation of donor addition, the linkages between microbial functions and abiotic processes mediating. Initial Hypotheses: (1) The typical bio-reduced subsurface environments that maintain U(VI) reduction rates after biostimulation contain limited amounts of oxidized iron on mineral surfaces. Therefore, the non sulfate-reducing dissimilatory iron reducing bacteria will move to more conducive areas or be out-competed by more versatile microbes. (2) Microbes capable of sulfate reduction play an important role in the post-treatment maintenance of bio-reduced uranium because these bacteria either directly reduce U(VI) or generate H2S, and/or FeS0.9 which act as oxygen sinks maintaining U(IV) in a reduced state. (3) The presence of bioprecipitated amorphous FeS0.9 in sediments will maintain low U(IV) reoxidation rates under conditions of low biomass, but FeS0.9 by itself is not sufficient to remove U(VI) from groundwater by abiotic reduction. FIELD SCALE EXPERIMENTS: Field-scale electron donor amendment experiments were conducted in 2002, 2003, and 2004 at the Old Rifle Uranium Mill Tailings Remedial Action (UMTRA) site in Rifle, Colorado

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.

U(VI) sorption on granite: prediction and experiments

International Nuclear Information System (INIS)

Nebelung, C.; Brendler, V.

2010-01-01

One widely accepted approach - component additivity (CA) - to describe the sorption of contaminants onto complex materials such as rocks or soils is based on the assumption that the surface of a complex mineral assemblage is composed of a mixture of mineral constituents whose surface properties are known from independent studies. An internally consistent SCM (surface complexation model) database can be developed that describes the adsorption reactions of solutes to each phase. Here, the capability of such a methodology was tested, using the code MINTEQA2 including thermodynamic data of the NEA-TDB, and literature data for SCM, namely the DDL model. The sorption characteristics of U(VI) on granite (from Eibenstock, Saxony, Germany, with the main components quartz, albite, orthoclase, and muscovite) was predicted and then compared to batch experiments. Granite plays an important role in the remediation of former uranium ore mining and milling sites, but is also one of the host rocks considered for final disposal of nuclear materials. Safety assessment requires a detailed understanding of this system and its retention potential with regard to hazardous components. Namely the sorption of uranium in this complex rock is not fully understood yet. The experiments thus also provided a better understanding of the far-field behaviour in granitic geological nuclear repositories. The robustness of the prediction was tested by variation of the granite composition and the variation of the specific surface area (SSA) - first all components were predicted with a uniform granite SSA, second with a distinct SSA for each granite component (determined on pure minerals for the same grain size fractions). Changes in compositions yielded only marginal differences in the prediction. Different approaches to SSA showed somewhat larger deviations. In conclusion, the CA methodology is a valid and robust approach to U(VI) sorption onto complex substrates such as granite, provided sufficient

Adsorption of uranium from aqueous solution using biochar produced by hydrothermal carbonization

International Nuclear Information System (INIS)

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

2013-01-01

The ability of biochar produced by hydrothermal carbonization (HTC) has been explored for the removal and recovery of uranium from aqueous solutions. The micro-morphology and structure of HTC were characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The influences of different experimental parameters such as solution pH, initial concentration, contact time, ionic strength and temperature on adsorption were investigated. The HTC showed the highest uranium sorption capacity at initial pH of 6.0 and contact time of 50 min. Adsorption kinetics was better described by the pseudo-second-order model and adsorption process could be well defined by the Langmuir isotherm. The thermodynamic parameters, ΔGdeg(298 K), ΔHdeg and ΔSdeg were determined to be -14.4, 36.1 kJ mol -1 and 169.7 J mol -1 K -1 , respectively, which demonstrated the sorption process of HTC towards U(VI) was feasible, spontaneous and endothermic in nature. The adsorbed HTC could be effectively regenerated by 0.05 mol/L HCl solution for the removal and recovery of U(VI). Complete removal (99.9 %) of U(VI) from 1.0 L industry wastewater containing 15.0 mg U(VI) ions was possible with 2.0 g HTC. (author)

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.

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.

In situ mobility of uranium in the presence of nitrate following sulfate-reducing conditions.

Science.gov (United States)

Paradis, Charles J; Jagadamma, Sindhu; Watson, David B; McKay, Larry D; Hazen, Terry C; Park, Melora; Istok, Jonathan D

2016-04-01

Reoxidation and mobilization of previously reduced and immobilized uranium by dissolved-phase oxidants poses a significant challenge for remediating uranium-contaminated groundwater. Preferential oxidation of reduced sulfur-bearing species, as opposed to reduced uranium-bearing species, has been demonstrated to limit the mobility of uranium at the laboratory scale yet field-scale investigations are lacking. In this study, the mobility of uranium in the presence of nitrate oxidant was investigated in a shallow groundwater system after establishing conditions conducive to uranium reduction and the formation of reduced sulfur-bearing species. A series of three injections of groundwater (200 L) containing U(VI) (5 μM) and amended with ethanol (40 mM) and sulfate (20 mM) were conducted in ten test wells in order to stimulate microbial-mediated reduction of uranium and the formation of reduced sulfur-bearing species. Simultaneous push-pull tests were then conducted in triplicate well clusters to investigate the mobility of U(VI) under three conditions: 1) high nitrate (120 mM), 2) high nitrate (120 mM) with ethanol (30 mM), and 3) low nitrate (2 mM) with ethanol (30 mM). Dilution-adjusted breakthrough curves of ethanol, nitrate, nitrite, sulfate, and U(VI) suggested that nitrate reduction was predominantly coupled to the oxidation of reduced-sulfur bearing species, as opposed to the reoxidation of U(IV), under all three conditions for the duration of the 36-day tests. The amount of sulfate, but not U(VI), recovered during the push-pull tests was substantially more than injected, relative to bromide tracer, under all three conditions and further suggested that reduced sulfur-bearing species were preferentially oxidized under nitrate-reducing conditions. However, some reoxidation of U(IV) was observed under nitrate-reducing conditions and in the absence of detectable nitrate and/or nitrite. This suggested that reduced sulfur-bearing species may not be fully effective at

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)

Sorption of environmentally relevant radionuclides (U(VI), Np(V)) and lanthanides (Nd(III)) on feldspar and mica

Energy Technology Data Exchange (ETDEWEB)

Richter, Constanze

2015-11-05

A safe storage of radioactive waste in repositories is an important task to protect humans and the environment from radio- and chemotoxicity. Long-term safety assessments predict the behavior of potential environmental contaminants like the actinides plutonium, uranium, or neptunium, in the near and far field of repositories. For such safety assessments, it is necessary to know the migration behavior of the contaminants in the environment, which is mainly dependent on the aquatic speciation, the solubility product of relevant solid phases, and the retardation due to sorption on surrounding minerals. Thus, an investigation of sorption processes of contaminants onto different minerals as well as the derivation of mineral specific surface complexation model (SCM) parameters is of great importance. Feldspar and mica are widely distributed in nature. They occur as components of granite, which is considered as a potential host rock for a repository in Germany, and in numerous other rocks, and thus also in the far field of nearly all repositories. However, their sorption behavior with actinides has only been scarcely investigated until now. In order to better characterize these systems and subsequently to integrate these minerals into the long-term safety assessments, this work focuses on the investigation of the sorption behavior of U(VI), Np(V), and Nd(III) as analogue for An(III) onto the minerals orthoclase and muscovite, representing feldspars and mica, respectively. All investigations were performed under conditions relevant to the far field of a repository. In addition to the extensive characterization of the minerals, batch sorption experiments, spectroscopic investigations, and surface complexation modeling were performed to elucidate the uptake and speciation of actinides on the mineral surfaces. In addition, the influence of microorganisms naturally occurring on the mineral surfaces and the effect of Ca{sup 2+} on U(VI) uptake on the minerals was studied. The

Sorption of environmentally relevant radionuclides (U(VI), Np(V)) and lanthanides (Nd(III)) on feldspar and mica

International Nuclear Information System (INIS)

Richter, Constanze

2015-01-01

A safe storage of radioactive waste in repositories is an important task to protect humans and the environment from radio- and chemotoxicity. Long-term safety assessments predict the behavior of potential environmental contaminants like the actinides plutonium, uranium, or neptunium, in the near and far field of repositories. For such safety assessments, it is necessary to know the migration behavior of the contaminants in the environment, which is mainly dependent on the aquatic speciation, the solubility product of relevant solid phases, and the retardation due to sorption on surrounding minerals. Thus, an investigation of sorption processes of contaminants onto different minerals as well as the derivation of mineral specific surface complexation model (SCM) parameters is of great importance. Feldspar and mica are widely distributed in nature. They occur as components of granite, which is considered as a potential host rock for a repository in Germany, and in numerous other rocks, and thus also in the far field of nearly all repositories. However, their sorption behavior with actinides has only been scarcely investigated until now. In order to better characterize these systems and subsequently to integrate these minerals into the long-term safety assessments, this work focuses on the investigation of the sorption behavior of U(VI), Np(V), and Nd(III) as analogue for An(III) onto the minerals orthoclase and muscovite, representing feldspars and mica, respectively. All investigations were performed under conditions relevant to the far field of a repository. In addition to the extensive characterization of the minerals, batch sorption experiments, spectroscopic investigations, and surface complexation modeling were performed to elucidate the uptake and speciation of actinides on the mineral surfaces. In addition, the influence of microorganisms naturally occurring on the mineral surfaces and the effect of Ca 2+ on U(VI) uptake on the minerals was studied. The

Laser fluorimetric analysis of uranium in water from Vishakhapatnam and estimation of health risk

International Nuclear Information System (INIS)

Bhangare, R.C.; Tiwari, M.; Ajmal, P.Y.; Sahu, S.K.; Pandit, G.G.

2014-01-01

Uranium is a naturally occurring radioactive element that is both radiologically and chemically toxic. The presence of uranium in the aquatic environment is due to the leaching from natural deposits, release in mill tailings, the combustion of coal and other fuels, and the use of phosphate fertilizers that contain uranium up to a concentration of 150g g -1 and contribute to ground water pollution. The most prevalent states of uranium are the hexavalent and tetravalent. The hexavalent state of uranium is particularly important in water because of the insolubility of almost all tetravalent compounds. Uranium enters into human tissues mainly through drinking water, food, air and other occupational and accidental exposures. Intake of uranium through air and water is normally low, but in circumstances in which uranium is present in a drinking water source the majority of intake can be through drinking water. Seeing potential health hazards from natural radionuclides in consuming water, many countries worldwide adopted the guideline activity concentration for drinking water quality recommended by the WHO (2011). For uranium WHO has set limit for drinking water to 30μgL -1 . The main purpose of this study was to measure the level of uranium in drinking water samples from the health hazard point of view and to observe the trend in the variation of uranium content in drinking water from upcoming BARC site at Vishakhapatnam area

Uranium extraction in phosphoric acid

International Nuclear Information System (INIS)

Araujo Figueiredo, C. de

1984-01-01

Uranium is recovered from the phosphoric liquor produced from the concentrate obtained from phosphorus-uraniferous mineral from Itataia mines (CE, Brazil). The proposed process consists of two extraction cycles. In the first one, uranium is reduced to its tetravalent state and then extracted by dioctylpyrophosphoric acid, diluted in Kerosene. Re-extraction is carried out with concentrated phosphoric acid containing an oxidising agent to convert uranium to its hexavalent state. This extract (from the first cycle) is submitted to the second cycle where uranium is extracted with DEPA-TOPO (di-2-hexylphosphoric acid/tri-n-octyl phosphine oxide) in Kerosene. The extract is then washed and uranium is backextracted and precipitated as commercial concentrate. The organic phase is recovered. Results from discontinuous tests were satisfactory, enabling to establish operational conditions for the performance of a continuous test in a micro-pilot plant. (Author) [pt

Interaction between U(VI) and Fe(II) in aqueous solution under anaerobic conditions. Closed system experiments

International Nuclear Information System (INIS)

Myllykylae, E.; Ollila, K.

2011-01-01

The aim of these experiments is to investigate the potential reduction of U(VI) carbonate and hydroxide complexes by aqueous Fe(II). This reduction phenomenon could be important under the disposal conditions of spent fuel. If groundwater enters the copper/iron canister, alpha radiolysis of the water may locally induce oxidizing conditions on the surface of UO 2 fuel, leading to the dissolution of UO 2 as more soluble U(VI) species. A potential reducing agent in the intruding water is Fe(II)(aq) from anaerobic corrosion of the copper/iron canister. The reduction of U(VI) to U(IV) would substantially decrease the solubility of U as well as co-precipitate other actinides and radionuclides. The interaction experiments were conducted in 0.01 M NaCl and 0.002 M NaHCO 3 solutions using an initial uranium concentration of either 8.4 x 10 -8 or 4.2 x 10 -7 mol/L with an initial Fe(II) concentration of 1.8 x 10 -6 in the NaCl solutions and 1.3 x 10 -6 mol/L in the NaHCO 3 solutions. Only after an equilibration period for U(VI) complexation was Fe(II) added to the solutions. The reaction times varied from 1 week to 5 months. For extra protection against O 2 , even inside a glove-box (N 2 atmosphere), the plastic reaction vessels were closed in metallic containers. The concentrations of U, Fe TOT and Fe(II) were analysed as a function of time for unfiltered, micro- and ultrafiltered samples. In addition, the precipitate on the ultrafilters was analysed with ESEM-EDS. The evolution of pH and Eh values was measured. The oxidation state of U in solution was preliminarily analysed for chosen periods. The results of the tests in 0.01 M NaCl showed an initial rapid decrease in U concentration after the addition of Fe(II) to the solution. The U found on test vessel walls at the end of the reaction periods, as well as the ESEM-EDS analyses of the filtered precipitates from the test solutions, showed that precipitation of U had occurred. The oxidation state analyses showed the presence

Hexavalent Chromium Free Coatings Projects for Aerospace Applications

Science.gov (United States)

2012-08-01

laboratory qualification of a total hexavalent chrome free coating systems for use on magnesium transmission housings. This project will leverage... hexavalent chrome free coating system by utilizing a hexavalent chrome free topcoat, primer, and pretreatment for magnesium parts used on Army...of the hexavalent chrome free conversion coatings. Hexavalent Chromium Free Coating System for Magnesium Housings on Aviation Systems Desert

Uranium Immobilization in Wetland Soils

Science.gov (United States)

Jaffe, Peter R.; Koster van Groos, Paul G.; Li, Dien; Chang, Hyun-Shik; Seaman, John C.; Kaplan, Daniel I.; Peacock, Aaron D.; Scheckel, Kirk

2014-05-01

In wetlands, which are a major feature at the groundwater-surface water interface, plants deliver oxygen to the subsurface to keep root tissue aerobic. Some of this oxygen leaches into the rhizosphere where it will oxidize iron that typically precipitates on or near roots. Furthermore, plans provide carbon via root exudates and turnover, which in the presence of the iron oxides drives the activity of heterotrophic iron reducers in wetland soils. Oxidized iron is an important electron acceptor for many microbially-driven transformations, which can affect the fate and transport of several pollutants. It has been shown that heterotrophic iron reducing organisms, such as Geobacter sp., can reduce water soluble U(VI) to insoluble U(IV). The goal of this study was to determine if and how iron cycling in the wetland rhizosphere affects uranium dynamics. For this purpose, we operated a series of small-scale wetland mesocosms in a greenhouse to simulate the discharge of uranium-contaminated groundwater to surface waters. The mesocosms were operated with two different Fe(II) loading rates, two plant types, and unplanted controls. The mesocosms contained zones of root exclusion to differentiate between the direct presence and absence of roots in the planted mesocosms. The mesocosms were operated for several month to get fully established, after which a U(VI) solution was fed for 80 days. The mesocosms were then sacrificed and analyzed for solid-associated chemical species, microbiological characterization, micro-X-ray florescence (µ-XRF) mapping of Fe and U on the root surface, and U speciation via X-ray Absorption Near Edge Structure (XANES). Results showed that bacterial numbers including Geobacter sp., Fe(III), as well as total uranium, were highest on roots, followed by sediments near roots, and lowest in zones without much root influence. Results from the µ-XRF mapping on root surfaces indicated a strong spatial correlation between Fe and U. This correlation was

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.

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.)

Reduction of hexavalent chromium collected on PVC filters.

Science.gov (United States)

Shin, Y C; Paik, N W

2000-01-01

Chromium exists at various valences, including elemental, trivalent, and hexavalent chromium, and undergoes reduction-oxidation reactions in the environment. Since hexavalent chromium is known as a human carcinogen, it is most important to evaluate the oxidation-reduction characteristics of the hexavalent chromium species. Although hexavalent chromium can be reduced to trivalent state, the detailed information on this in workplace environments is limited. The purpose of this study was to investigate hexavalent chromium reduction in time in various conditions. A pilot chrome plating operation was prepared and operated in a laboratory for this study. There was evidence that the hexavalent chromium was reduced by time after mist generation. The percentage ratio (with 95% confidence intervals in parentheses) of hexavalent chromium to total chromium was almost 100% (99.1 approximately 102.3) immediately after mist generation, and was reduced to 87.4% (84.8 approximately 89.9) at 1 hour and 81.0% (78.3 approximately 83.5) at 2 hours, respectively. Another test indicated that hexavalent chromium collected on PVC filters was also reduced by time after sampling. Hexavalent chromium was reduced to 90.8% (88.2 approximately 93.3) at 2 hours after sampling. It also was found that hexavalent chromium was reduced during storage in air. It is recommended that air samples of hexavalent chromium be protected against reduction during storage.

Changes in Uranium Speciation through a Depth Sequence of Contaminated Hanford Sediments

International Nuclear Information System (INIS)

Catalano, Jeffrey G.; McKinley, James P.; Zachara, John M.; Heald, Steve M.; Smith, Steven C.; Brown, Gordon E.

2006-01-01

The disposal of basic sodium-aluminate and acidic U(VI)-Cu(II) wastes into the now-dry North and South 300 A Process Ponds at the Hanford site resulted in U(VI) groundwater plume. To gain insight into the geochemical processes that occurred during waste disposal and that will affect the future fate and transport of this uranium plume, the solid-phase speciation of uranium in a depth sequence from the base of the North Process Pond through the vadose zone to the water table was investigated using electron microprobe measurements and x-ray absorption fine structure spectroscopy. Uranium in sediments from the base of the pond was predominantly coprecipitated with calcite. From ∼2 m below the pond base to the water table uranium occurred dominantly in a sorbed form, likely on the surface aluminosilicate clay minerals. The presence of a U(VI)-phosphate phase was also observed in this region, but it only occurred as a major uranium species at one depth. The initial sequestration of U(VI) in these sediments likely occurred through coprecipitation with calcite as conditions did not favor adsorption. As the calcite-bearing pond sediments have been removed as part of a remediation effort, future uranium fate and transport will likely be controlled primarily by adsorption/desorption phenomena

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

International Nuclear Information System (INIS)

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

1994-01-01

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

The potential impact of microbial Fe(III) reduction on subsurface U(VI) mobility at a low level radioactive waste storage site

International Nuclear Information System (INIS)

Wilkins, M.J.; Livens, F.R.; Vaughan, D.J.; Lloyd, J.R.; Beadle, I.; Small, J.S.

2005-01-01

Full text of publication follows: Fe(III) oxy-hydroxides have the potential to be utilised as terminal electron acceptors by indigenous microbial communities in the British Nuclear Fuels (BNFL) low level radioactive waste storage site at Drigg (Cumbria, UK) and these organisms may have a critical control on the biogeochemical cycling of several environmentally important radionuclides. In terms of radiological impact at Drigg, uranium is the most significant contributor to radiological impact and it is strongly influenced by biogeochemical processes. In terms of mass (moles) it is also the most abundant radionuclide in the Drigg inventory. Thus, the potential biotic and abiotic effects of Fe(III) reduction on U(VI) mobility in the Drigg subsurface are of interest. Culture-dependent and molecular techniques showed that the sediments in and around the Drigg site contained a diversity of Fe(III)-reducing bacteria. A series of microcosm experiments were utilised to create environmentally relevant experimental conditions. Microcosms set up using Drigg sediment and synthetic ground water were spiked with 100 μM U(VI) and acetate as an electron donor. U(VI) concentrations in groundwater were measured using a chemical assay while total U levels were determined using ICP-MS. Fe(II) levels were determined using the ferrozine method. Sediment surface areas were measured using BET analysis. The low surface area of the sediments resulted in only a small proportion of the 100 μM U(VI) spike sorbing onto mineral surfaces. The addition of ferri-hydrite to some microcosms resulted in an immediate lowering of soluble U(VI) concentrations, suggesting that the formation of soluble U(VI) complexes were not responsible for the minimal adsorption. The presence of biogenic Fe(II) in the microcosms did not affect the soluble U(VI) concentration. Similarly, soluble U(VI) levels remained unchanged when sediments were spiked with U(VI) post-microbial Fe(III) reduction. However, a lowering in

Genes for Uranium Bioremediation in the Anaerobic Sulfate-Reducing Bacteria

Energy Technology Data Exchange (ETDEWEB)

Wall, Judy D.

2003-06-01

Surprising results were obtained following an attempt to induce or derepress the machinery for U(VI) reduction by growing Desulfovibrio desulfuricans G20 in the presence of 1 mM uranyl acetate. G20 cells grown on lactate-sulfate medium amended with U(VI) reduced uranium at a slower rate than cells grown in the absence of this metal. When periplasmic extracts of these cells were prepared, Western analysis of the proteins revealed that the cytochrome c3 was absent. This observation has been further investigated.

REMOVAL OF U(VI) IN MULTI-COMPONENT SYSTEMS BY ADSORPTION USING ACTIVATED CARBON DERIVED FROM RICE STRAW

International Nuclear Information System (INIS)

YAKOUT, S.M.; RIZK, M.A.

2008-01-01

The use of low cost activated carbon derived from rice straw has been investigated as a replacement for the current expensive methods for radionuclides removal from wastewater. The adsorption studies were carried out in multi-component systems. The effects of common cations and anions on uranium uptake were investigated. Different cations under investigation showed marginal effect on the adsorption of uranium, except in case of iron ion where the adsorption was significantly depressed by the addition of Fe ion (R % was 20%). Coexistence of iron ions at high levels may compete strongly for the adsorption sites with uranium ions resulting in a substantial reduction of uranium removal. The prepared activated carbon showed good selectivity in uranium extraction even in the presence of large concentrations (100 ppm) of anionic complexing agents and common electrolyte species.The simultaneous presence of both U(VI) / Th(IV) reduced sorption through competition for sorption sites on carbon surface. It is concluded that multi-species adsorption can be significantly affected by adsorbate interactions. Understanding these interactions needs great attention in adsorption study in the future

Development and demonstration of biosorbents for clean-up of uranium in water. CRADA final report

International Nuclear Information System (INIS)

Faison, B.D.; Hu, M.Z.C.; Norman, J.M.; Reeves, M.E.; Williams, L.; Schmidt-Kuster, W.; Darnell, K.

1997-08-01

Pseudomonas aeruginosa strain CSU, a nongenetically engineered bacterial strain known to bind dissolved hexavalent uranium, shows particular promise as the basis of an immobilized-cell process for removal of dissolved uranium from contaminated wastewaters. It was characterized with respect to its sorptive active. Living, heat-killed, permeabilized, and unreconstituted lyophilized cells were all capable of binding uranium. The uranium biosorption equilibrium could be described by the Langmuir isotherm. The rate of uranium adsorption increased following permeabilization of the outer and/or cytoplasmic membrane by organic solvents such as acetone. P. aeruginosa CSU biomass was significantly more sorptive toward uranium than certain novel, patented biosorbents derived from algal or fungal biomass sources. P. aeruginosa CSU biomass was also competitive with commercial cation-exchange resins, particularly in the presence of dissolved transition metals. Uranium binding by P. aeruginosa was clearly pH dependent. Uranium loading capacity increased with increasing pH under acidic conditions, presumably as a function of uranium speciation and due to the H + competition at some binding sites. Nevertheless, preliminary evidence suggests that this microorganism is also capable of binding anionic hexavalent uranium complexes. Ferric iron was a strong inhibitor of uranium binding to P. aeruginosa CSU biomass, and the presence of uranium also decreased the Fe 3+ loading when the biomass was not saturated with Fe 3+ , suggesting that Fe 3+ and uranium may share the same binding sites on biomass

Development and demonstration of biosorbents for clean-up of uranium in water. CRADA final report

Energy Technology Data Exchange (ETDEWEB)

Faison, B.D.; Hu, M.Z.C.; Norman, J.M.; Reeves, M.E.; Williams, L.; Schmidt-Kuster, W.; Darnell, K. [Oak Ridge National Lab., TN (United States)]|[Ogden Environmental Service, Oak Ridge, TN (United States)

1997-08-01

Pseudomonas aeruginosa strain CSU, a nongenetically engineered bacterial strain known to bind dissolved hexavalent uranium, shows particular promise as the basis of an immobilized-cell process for removal of dissolved uranium from contaminated wastewaters. It was characterized with respect to its sorptive active. Living, heat-killed, permeabilized, and unreconstituted lyophilized cells were all capable of binding uranium. The uranium biosorption equilibrium could be described by the Langmuir isotherm. The rate of uranium adsorption increased following permeabilization of the outer and/or cytoplasmic membrane by organic solvents such as acetone. P. aeruginosa CSU biomass was significantly more sorptive toward uranium than certain novel, patented biosorbents derived from algal or fungal biomass sources. P. aeruginosa CSU biomass was also competitive with commercial cation-exchange resins, particularly in the presence of dissolved transition metals. Uranium binding by P. aeruginosa was clearly pH dependent. Uranium loading capacity increased with increasing pH under acidic conditions, presumably as a function of uranium speciation and due to the H{sup +} competition at some binding sites. Nevertheless, preliminary evidence suggests that this microorganism is also capable of binding anionic hexavalent uranium complexes. Ferric iron was a strong inhibitor of uranium binding to P. aeruginosa CSU biomass, and the presence of uranium also decreased the Fe{sup 3+} loading when the biomass was not saturated with Fe{sup 3+}, suggesting that Fe{sup 3+} and uranium may share the same binding sites on biomass.

An experimental and modeling study of grain-scale uranium desorption from field-contaminated sediments and the potential influence of microporosity on mass-transfer

Science.gov (United States)

Stoliker, D.; Liu, C.; Kent, D. B.; Zachara, J. M.

2012-12-01

The aquifer below the 300-Area of the Hanford site (Richland, WA, USA) is plagued by a persistent plume of dissolved uranium (U(VI)) in excess of the Environmental Protection Agency drinking water maximum contamination level even after the removal of highly contaminated sediments. The aquifer sediments in the seasonally saturated lower vadose zone act as both a source and sink for uranium during stage changes in the nearby Columbia River. Diffusion limitation of uranium mass-transfer within these sediments has been cited as a potential cause of the plume's persistence. Equilibrium U(VI) sorption is a strong function of variable chemical conditions, especially carbonate, hydrogen, and uranyl ion activities. Field-contaminated sediments from the site require up to 1,000 hours to reach equilibrium in static batch reactors. Increases in U(VI) concentrations over longer time-scales result from changes in chemical conditions, which drive reactions with sediments that favor U(VI) desorption. Grain-scale U(VI) sorption/desorption rates are slow, likely owing to diffusion of U(VI) and other solutes through intra-granular pore domains. In order to improve understanding of the impact of intra-granular diffusion and chemical reactions controlling grain-scale U(VI) release, experiments were conducted on individual particle size fractions of a single set of constant chemical conditions with multiple stop-flow events, were similar for all size fractions displacement from equilibrium and multiple diffusion domains were described with a two-parameter lognormal distribution of mass-transfer rate coefficients. Parameters describing mass transfer were the same for all size fractions reaction models calibrated with individual size fractions predicted U(VI) and chemical composition as a function of time for the bulk sediment sample. Volumes of pores less than 2.4 nm, quantified using nitrogen adsorption-desorption isotherms, were the same for all size fractions < 2 mm, nearly double

Efficacy of a novel chelator BPCBG for removing uranium and protecting against uranium-induced renal cell damage in rats and HK-2 cells

Energy Technology Data Exchange (ETDEWEB)

Bao, Yizhong; Wang, Dan [Institute of Radiation Medicine, Fudan University, Shanghai 200032 (China); Li, Zhiming [Department of Chemistry, Fudan University, Shanghai 200433 (China); Hu, Yuxing; Xu, Aihong [Institute of Radiation Medicine, Fudan University, Shanghai 200032 (China); Wang, Quanrui [Department of Chemistry, Fudan University, Shanghai 200433 (China); Shao, Chunlin [Institute of Radiation Medicine, Fudan University, Shanghai 200032 (China); Chen, Honghong, E-mail: hhchen@shmu.edu.cn [Institute of Radiation Medicine, Fudan University, Shanghai 200032 (China)

2013-05-15

Chelation therapy is a known effective method to increase the excretion of U(VI) from the body. Until now, no any uranium chelator has been approved for emergency medical use worldwide. The present study aimed to evaluate the efficacy of new ligand BPCBG containing two catechol groups and two aminocarboxylic acid groups in decorporation of U(VI) and protection against acute U(VI) nephrotoxicity in rats, and further explored the detoxification mechanism of BPCBG for U(VI)-induced nephrotoxicity in HK-2 cells with comparison to DTPA-CaNa{sub 3}. Chelating agents were administered at various times before or after injections of U(VI) in rats. The U(VI) levels in urine, kidneys and femurs were measured 24 h after U(VI) injections. Histopathological changes in the kidney and serum urea and creatinine and urine protein were examined. After treatment of U(VI)-exposed HK-2 cells with chelating agent, the intracellular U(VI) contents, formation of micronuclei, lactate dehydrogenase (LDH) activity and production of reactive oxygen species (ROS) were assessed. It was found that prompt, advanced or delayed injections of BPCBG effectively increased 24 h-urinary U(VI) excretion and decreased the levels of U(VI) in kidney and bone. Meanwhile, BPCBG injection obviously reduced the severity of the U(VI)-induced histological alterations in the kidney, which was in parallel with the amelioration noted in serum indicators, urea and creatinine, and urine protein of U(VI) nephrotoxicity. In U(VI)-exposed HK-2 cells, immediate and delayed treatment with BPCBG significantly decreased the formation of micronuclei and LDH release by inhibiting the cellular U(VI) intake, promoting the intracellular U(VI) release and inhibiting the production of intracellular ROS. Our data suggest that BPCBG is a novel bi-functional U(VI) decorporation agent with a better efficacy than DTPA-CaNa{sub 3}. - Highlights: ► BPCBG accelerated the urine U(VI) excretion and reduced the tissues U(VI) in rats. �

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

Evaluation of adsorption of uranium from aqueous solution using biochar materials

Energy Technology Data Exchange (ETDEWEB)

Correa, Wagner Clayton; Guilhen, Sabine Neusatz; Ortiz, Nilce; Fungaro, Denise Alves, E-mail: wcorrea@ipen.br, E-mail: snguilhen@ipen.br, E-mail: notriz@ipen.br, E-mail: dfungaro@ipen.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

2015-07-01

Uranium is present in the environment as a result of leaching from natural deposits and activities associated with nuclear fuel, copper mining, uranium mining, milling industry, etc. For the purpose of protecting ecosystem stability and public health, it is crucial to eliminate uranium from aqueous solutions before they are discharged into the environment. Various technologies have been used for removing U(VI) ions from aqueous systems. Among these methods, adsorption has been applied in wastewater because of simple operation procedure and high removal efficiency. Brazil is the largest producer of charcoal in the world, with nearly half of the woody biomass harvested for energy in Brazil being transformed into charcoal. Biochar exhibits a great potential as an adsorbent because of favorable physical/chemical surface characteristics. The objective of this work was to evaluate the adsorption potential of biochar materials prepared from pyrolysis of Bamboo (CBM), Eucalyptus (CEM) and Macauba (CMA) nuts for the removal of uranium from solutions. Adsorption experiments were carried out by a batch technique. Equilibrium adsorption experiments were performed by shaking a known amount of biochar material with 100 mL of U(VI) solution in Erlenmeyer flasks in a shaker at 120 rpm and room temperature (25 deg C) for 24 h. The adsorbent was separated by centrifugation from the solution. The U(VI) concentration remaining in the supernatant solution was determined using inductively coupled plasma optical emission spectrometry (ICP-OES). The influences of different experimental parameters such as solution pH and bioadsorbent dose on adsorption were investigated. The highest uranium adsorption capacity were obtained at pH 3.0 and 16 g/L biomass dosage for CMA, pH 3.0 and 12 g/L biomass dosage for CBM and pH 2.0 and 10 g/L biomass dosage for CEM. The results demonstrated that the biomass derived char can be used as a low-cost adsorbent for removal of uranium from wastewater. (author)

Evaluation of adsorption of uranium from aqueous solution using biochar materials

International Nuclear Information System (INIS)

Correa, Wagner Clayton; Guilhen, Sabine Neusatz; Ortiz, Nilce; Fungaro, Denise Alves

2015-01-01

Uranium is present in the environment as a result of leaching from natural deposits and activities associated with nuclear fuel, copper mining, uranium mining, milling industry, etc. For the purpose of protecting ecosystem stability and public health, it is crucial to eliminate uranium from aqueous solutions before they are discharged into the environment. Various technologies have been used for removing U(VI) ions from aqueous systems. Among these methods, adsorption has been applied in wastewater because of simple operation procedure and high removal efficiency. Brazil is the largest producer of charcoal in the world, with nearly half of the woody biomass harvested for energy in Brazil being transformed into charcoal. Biochar exhibits a great potential as an adsorbent because of favorable physical/chemical surface characteristics. The objective of this work was to evaluate the adsorption potential of biochar materials prepared from pyrolysis of Bamboo (CBM), Eucalyptus (CEM) and Macauba (CMA) nuts for the removal of uranium from solutions. Adsorption experiments were carried out by a batch technique. Equilibrium adsorption experiments were performed by shaking a known amount of biochar material with 100 mL of U(VI) solution in Erlenmeyer flasks in a shaker at 120 rpm and room temperature (25 deg C) for 24 h. The adsorbent was separated by centrifugation from the solution. The U(VI) concentration remaining in the supernatant solution was determined using inductively coupled plasma optical emission spectrometry (ICP-OES). The influences of different experimental parameters such as solution pH and bioadsorbent dose on adsorption were investigated. The highest uranium adsorption capacity were obtained at pH 3.0 and 16 g/L biomass dosage for CMA, pH 3.0 and 12 g/L biomass dosage for CBM and pH 2.0 and 10 g/L biomass dosage for CEM. The results demonstrated that the biomass derived char can be used as a low-cost adsorbent for removal of uranium from wastewater. (author)

Selective Adsorption of Uranium (VI) on NaHCO 3 Leached ...

African Journals Online (AJOL)

Ion imprinted nano-magnetic composite polymers for selective removal of hexavalent uranium were prepared by a precipitation polymerization technique in the presence of γ-methacryloxypropyltrimethoxysilane (γ-MPS) coated magnetite and other pre-polymerization reagents. The synthesized magnetic polymers were then ...

Mesoporous polymer-coated PAN beads for environmental applications. Fabrication, characterisation and uranium adsorption studies

International Nuclear Information System (INIS)

Aly, Z.; Scales, N.; Davis, J.; Lumpkin, G.

2017-01-01

Adsorption of U(VI) and other heavy metals on millimetre sized polymer-coated polyacrylinitrile (PAN) beads was investigated. PAN was used as scaffolds for the polymer layer thus producing porous material of high surface area, improved mechanical strength and improved adsorption capabilities. Extensive U(VI) adsorption studies were undertaken and results modelled using different kinetic and equilibrium models. Parameters including thermodynamic parameters were evaluated. Sorbent capacities were assessed as 124, 16, and 33 mg g"-"1 for PCP, SPP and Dowex at 60 deg C respectively. U(VI) adsorption mechanism for these adsorbents was postulated. Recovered uranium may be used for production of cheap electricity. (author)

Influence of attrition scrubbing, ultrasonic treatment, and oxidant additions on uranium removal from contaminated soils

International Nuclear Information System (INIS)

Timpson, M.E.; Elless, M.P.; Francis, C.W.

1994-01-01

As part of the Uranium in Soils Integrated Demonstration Project being conducted by the US Department of Energy, bench-scale investigations of selective leaching of uranium from soils at the Fernald Environmental Management Project site in Ohio were conducted at Oak Ridge National Laboratory. Two soils (storage pad soil and incinerator soil), representing the major contaminant sources at the site, were extracted using carbonate- and citric acid-based lixiviants. Physical and chemical processes were used in combination with the two extractants to increase the rate of uranium release from these soils. Attrition scrubbing and ultrasonic dispersion were the two physical processes utilized. Potassium permanganate was used as an oxidizing agent to transform tetravalent uranium to the hexavalent state. Hexavalent uranium is easily complexed in solution by the carbonate radical. Attrition scrubbing increased the rate of uranium release from both soils when compared with rotary shaking. At equivalent extraction times and solids loadings, however, attrition scrubbing proved effective only on the incinerator soil. Ultrasonic treatments on the incinerator soil removed 71% of the uranium contamination in a single extraction. Multiple extractions of the same sample removed up to 90% of the uranium. Additions of potassium permanganate to the carbonate extractant resulted in significant changes in the extractability of uranium from the incinerator soil but had no effect on the storage pad soil

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)

Aqueous U(VI) interaction with magnetite nanoparticles in a mixed flow reactor system: HR-XANES study

International Nuclear Information System (INIS)

Pidchenko, I; Heberling, F; Finck, N; Schild, D; Bohnert, E; Schäfer, T; Rothe, J; Geckeis, H; Vitova, T; Kvashnina, KO

2016-01-01

The redox variations and changes in local atomic environment of uranium (U) interacted with the magnetite nanoparticles were studied in a proof of principle experiment by the U L 3 and M 4 edges high energy resolution X-ray absorption near edge structure (HR-XANES) technique. We designed and applied a mixed flow reactor (MFR) set-up to maintain dynamic flow conditions during U-magnetite interactions. Formation of hydrolyzed, bi- and poly-nuclear U species were excluded by slow continuous injection of U(VI) (10 -6 M) and pH control integrated in the MFR set-up. The applied U HR-XANES technique is more sensitive to minor changes in the U redox states and bonding compared to the conventional XANES method. Major U(VI) contribution in uranyl type of bonding is found in the magnetite nanoparticles after three days operation time of the MFR. Indications for shortening of the U-O axial bond length for the magnetite compared to the maghemite system are present too. (paper)

Rapid removal of uranium from aqueous solutions using magnetic Fe3O4@SiO2 composite particles.

Science.gov (United States)

Fan, Fang-Li; Qin, Zhi; Bai, Jing; Rong, Wei-Dong; Fan, Fu-You; Tian, Wei; Wu, Xiao-Lei; Wang, Yang; Zhao, Liang

2012-04-01

Rapid removal of U(VI) from aqueous solutions was investigated using magnetic Fe(3)O(4)@SiO(2) composite particles as the novel adsorbent. Batch experiments were conducted to study the effects of initial pH, amount of adsorbent, shaking time and initial U(VI) concentrations on uranium sorption efficiency as well as the desorbing of U(VI). The sorption of uranium on Fe(3)O(4)@SiO(2) composite particles was pH-dependent, and the optimal pH was 6.0. In kinetics studies, the sorption equilibrium can be reached within 180 min, and the experimental data were well fitted by the pseudo-second-order model, and the equilibrium sorption capacities calculated by the model were almost the same as those determined by experiments. The Langmuir sorption isotherm model correlates well with the uranium sorption equilibrium data for the concentration range of 20-200 mg/L. The maximum uranium sorption capacity onto magnetic Fe(3)O(4)@SiO(2) composite particles was estimated to be about 52 mg/g at 25 °C. The highest values of uranium desorption (98%) was achieved using 0.01 M HCl as the desorbing agent. Fe(3)O(4)@SiO(2) composite particles showed a good selectivity for uranium from aqueous solution with other interfering cation ions. Present study suggested that magnetic Fe(3)O(4)@SiO(2) composite particles can be used as a potential adsorbent for sorption uranium and also provided a simple, fast separation method for removal of heavy metal ion from aqueous solution. Copyright © 2011 Elsevier Ltd. All rights reserved.

Performance Indicators for Uranium Bioremediation in the Subsurface: Basis and Assessment

Energy Technology Data Exchange (ETDEWEB)

Long, Philip E. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Yabusaki, Steven B. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

2006-12-29

The purpose of this letter report is to identify performance indicators for in situ engineered bioremediation of subsurface uranium (U) contamination. This report focuses on in situ treatment of groundwater by biostimulation of extant in situ microbial populations (see http://128.3.7.51/NABIR/generalinfo/primers_guides/03_NABIR_primer.pdf for background information on bioremediation of metals and radionuclides). The treatment process involves amendment of the subsurface with an electron donor such as acetate, lactate, ethanol or other organic compound such that in situ microorganisms mediate the reduction of U(VI) to U(IV). U(VI) precipitates as uraninite or other insoluble U phase. Uranium is thus immobilized in place by such processes and is subject to reoxidation that may remobilize the reduced uranium. Related processes include augmenting the extant subsurface microbial populations, addition of electron acceptors, and introduction of chemically reducing materials such as zero-valent Fe. While metrics for such processes may be similar to those for in situ biostimulation, these related processes are not directly in the scope of this letter report.

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)

Irradiation defects in clayey minerals in association with discordance-type uranium deposit; Les Defauts d'Irradiation dans les Mineraux argileux associes aux gisements d'Uranium de type Discordance

Energy Technology Data Exchange (ETDEWEB)

Morichon, E.; Beaufort, D. [Universite de Poitiers, Laboratoire HydrASA, CNRS-FRE 3114, 86 - Poitiers (France); Morichon, E.; Allard, Th. [IMPMC, UMR 7590, 75 - Paris (France)

2009-07-01

Radioactivity generates defects in minerals and these defects are the witnesses of the presence of radio-elements, and therefore represent an interesting potential for uranium prospecting. Investigations made in the Athabasca basin in Canada reveal irradiation defects in very old clays (kaolinite, illite and sudoite) in the alteration halo of discordance-type uranium deposits. The authors comment the defect concentration variation among the different drillings. These differences show that hexavalent uranium circulated in the whole geological system

Determination of the oxygen-metal-ratio of uranium-americium mixed oxides

International Nuclear Information System (INIS)

Bartscher, W.

1982-01-01

During the dissolution of uranium-americium mixed oxides in phosphoric acid under nitrogen tetravalent uranium is oxidized by tetravalent americium. The obtained hexavalent uranium is determined by constant potential coulometry. The coulombs measured are equivalent to the oxygen in excess of the minimum composition of UO 2 x AmO 1 . 5 . The total uranium content of the sample is determined in a subsequent coulometric titration. The oxygen-metal ratio of the sample can be calculated for a given uranium-americium ratio. An excess of uranium dioxide is necessary in order to suppress the oxidation of water by tetravalent americium. The standard deviation of the method is 0.0017 O/M units. (orig.) [de

Uranium band types in carbonaceous sediments with different diagenesis levels

International Nuclear Information System (INIS)

Borstel, D. von.

1984-01-01

Uraniferous peats, lignites and coals were studied by chemical and geological methods in order to determine the influence of carbonaceous substances with different diagenesis levels on uranium enrichment in sediments. It was found that the main factor of deposit genesis is not the chemical bending of uranium to the organic substance but rather the reduction from mobile U(VI) to immobile U(IV) in the course of diagenesis to epigenesis. (orig./PW) [de

Evaluation of an automatic uranium titration system

International Nuclear Information System (INIS)

Lewis, K.

1980-01-01

The titration system utilizes the constant current coulometric titration of Goldbeck and Lerner. U(VI) is reduced to U(IV) by Fe(II). V(V) is generated to titrate the U(IV), and the titration is followed potentiometrically. The evaluation shows that the recovery of uranium is 100% at the 40-mg level. The accuracy is generally +-0.10% or better. The smallest sample weight at which reliable results were obtained was 40 mg of uranium. Time for one analysis is 15 minutes. Advantages and disadvantages of the automated titrator are listed

Uranium preconcentration from seawater using adsorptive membranes

International Nuclear Information System (INIS)

Das, Sadananda; Pandey, A.K.; Manchanda, V.K.; Athawale, A.A.

2009-01-01

Uranium recovery from bio-aggressive but lean feed like seawater is a challenging problem as it requires in situ preconcentration of uranium in presence of huge excess of competing ions with fast sorption kinetics. In our laboratory, widely used amidoxime membrane (AO-membrane) was evaluated for uranium sorption under seawater conditions. This study indicated that AO-membrane was inherently slow because of the complexation chemistry involved in transfer of U(VI) from (UO 2 (CO 3 ) 3 ) 4 - to AO sites in membrane. In order to search better options, several chemical compositions of membrane were scanned for their efficacy for uranium preconcentration from seawater, and concluded that EGMP-membrane offers several advantages over AO-membrane. In this paper, the comparison of EGMP-membrane with AO-membrane for uranium sorption under seawater conditions has been reviewed. (author)

Adsorption property of Br-PADAP-impregnated multiwall carbon nanotubes towards uranium and its performance in the selective separation and determination of uranium in different environmental samples.

Science.gov (United States)

Khamirchi, Ramzanali; Hosseini-Bandegharaei, Ahmad; Alahabadi, Ahmad; Sivamani, Selvaraju; Rahmani-Sani, Abolfazl; Shahryari, Taher; Anastopoulos, Ioannis; Miri, Mohammad; Tran, Hai Nguyen

2018-04-15

A newer efficient U(VI) ion adsorbent was synthesized by impregnating Br-PADAP [2-(5-Bromo-2-pyridylazo)-5-(diethylamino)phenol] onto multiwall carbon nanotubes (MWCNTs). The effects of various operation conditions on uranium adsorption (i.e., pH contact time, temperature, and initial uranium concentration) were systematically evaluated using batch experiments. The results indicated that the uranium adsorption on modified MWNCTs (5.571 × 10 -3 g/mg × min) reached faster equilibrium than that on pristine MWNCTs (4.832 × 10 -3 g/mg × min), reflecting the involvement of appropriate functional groups of Br-PADAP on the chelating ion-exchange mechanism of U(VI) adsorption. Modified MWNCTs (83.4mg/g) exhibited significantly higher maximum Langmuir adsorption capacity than pristine MWNCTs (15.1mg/g). Approximately 99% of uranium adsorbed onto modified MWNCTs can be desorbed by 2.5mL of 1M HNO 3 solution. Therefore, Br-PADAP-modified MWNCTs can server as a promising adsorbent for efficient uranium adsorption applications in water treatment. Subsequently, the proposed solid-phase extraction (using a mini-column packed with Br-PADAP/MWCNT) was successfully utilized for analysing trace uranium levels by the ICP-AES method in different environmental samples with a pre-concentration factor of 300-fold. The coexistence of other ions demonstrated an insignificant interference on the separative pre-concentration of uranium. the detection limit was recognized as 0.14μg/L, and the relative standard deviation was approximately 3.3% (n = 7). Copyright © 2017 Elsevier Inc. All rights reserved.

Biosolubilization of uranyl ions in uranium ores by hydrophyte plants

International Nuclear Information System (INIS)

Cecal, Alexandru; Calmoi, Rodica; Melniciuc-Puica, Nicoleta

2006-01-01

This paper investigated the bioleaching of uranyl ions from uranium ores, in aqueous medium by hydrophyte plants: Lemna minor, Azolla caroliniana and Elodea canadensis under different experimental conditions. The oxidation of U(IV) to U(VI) species was done by the atomic oxygen generated in the photosynthesis process by the aquatic plants in the solution above uranium ores. Under identical experimental conditions, the capacity of bioleaching of uranium ores decreases according to the following series: Lemna minor > Elodea canadensis > Azolla caroliniana. The results of IR spectra suggest the possible use of Lemna minor and Elodea canadensis as a biological decontaminant of uranium containing wastewaters. (author)

A process for uranium recovery in phosphoric acid

International Nuclear Information System (INIS)

Duarte Neto, J.

1984-01-01

Results are presented about studies carried out envisaging the development of a process for uranium recovery from phosphoric acid, produced from the concentrate obtained from phosphorus-uraniferous mineral from Itataia mines (CE, Brazil). This process uses a mixture of DEPA-TOPO as extractant and the extraction cycle involves the following stages: acid pre-treatment; adjustment of the oxidation potential so to ensure that all uranium is hexavalent; extraction of uranium from the acid; screening of the solvent to remove undesirable impurities; uranium re-extraction and precipitation; solvent recovery. A micro-pilot plant for continuous processing was built up. Data collected showed that uranium can be recovered with an yield greater than 99%, thus proving the feasibility of the process and encouraging the construction of a bigger scale plant. (Author) [pt

Speciation and spectrophotometric determination of uranium in seawater

Directory of Open Access Journals (Sweden)

M. KONSTANTINOU

2004-06-01

Full Text Available A series of ion-exchange and extraction procedures for the separation of uranium from seawater samples and subsequent spectrophotometric determination of uranium in seawater by means of arsenazo(III is described. According to the measurements performed by means of traced samples at every stage of separation, the yield of the pre-analytical procedures is generally over 90% and the separation of uranium very selective. The mean uranium concentration in seawater samples collected from five different coastal areas in Cyprus was found to be 3.2 ± 0.2 & micro; g L-1. Uranium in seawater is stable in its hexavalent oxidation state and UO2 (CO334- is the predominant species under normal coastal conditions (pH ≥ 8, EH ≥ 0.35 mV, 1 atm and 0.03% CO2.

Sphaerotilus natans, a neutrophilic iron-related filamentous bacterium : mechanisms of uranium scavenging

International Nuclear Information System (INIS)

Seder-Colomina, Marina

2014-01-01

Heavy metals and radionuclides are present in some ecosystems worldwide due to natural contaminations or anthropogenic activities. The use of microorganisms to restore those polluted ecosystems, a process known as bioremediation, is of increasing interest, especially under near-neutral pH conditions. Iron minerals encrusting neutrophilic iron-related bacteria, especially Bacterio-genic Iron Oxides (BIOS), have a poorly crystalline structure, which in addition to their large surface area and reactivity make them excellent scavengers for inorganic pollutants. In this PhD work we studied the different mechanisms of uranium scavenging by the neutrophilic bacterium Sphaerotilus natans, chosen as a model bacterium for iron-related sheath-forming filamentous microorganisms. S. natans can grow as single cells and filaments. The latter were used to investigate U(VI) bio-sorption and U(VI) sorption onto BIOS. In addition, uranium sorption onto the abiotic analogues of such iron minerals was assessed. In order to use S. natans filaments for U(VI) scavenging, it was necessary to identify factors inducing S. natans filamentation. The influence of oxygen was ascertained by using molecular biology techniques and our results revealed that while saturated oxygen conditions resulted in single cell growth, a moderate oxygen depletion to ∼ 3 mg O 2 .L -1 led to the desired filamentous growth of S. natans. BIOS attached to S. natans filaments as well as the abiotic analogues were analysed by XAS at Fe K-edge. Both materials were identified as amorphous iron(III) phosphates with a small component of Fe(II), with a high reactivity towards scavenging of inorganic pollutants. In addition, EXAFS at the U LIII-edge revealed a common structure for the O shells, while those for P, Fe and C were different for each sorbent. An integrated approach combining experimental techniques and speciation calculations made it possible to describe U(VI) adsorption isotherms by using a surface complexation

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.

SEPARATION OF URANIUM, PLUTONIUM, AND FISSION PRODUCTS

Science.gov (United States)

Spence, R.; Lister, M.W.

1958-12-16

Uranium and plutonium can be separated from neutron-lrradiated uranium by a process consisting of dissolvlng the lrradiated material in nitric acid, saturating the solution with a nitrate salt such as ammonium nitrate, rendering the solution substantially neutral with a base such as ammonia, adding a reducing agent such as hydroxylamine to change plutonium to the trivalent state, treating the solution with a substantially water immiscible organic solvent such as dibutoxy diethylether to selectively extract the uranium, maklng the residual aqueous solutlon acid with nitric acid, adding an oxidizing agent such as ammonlum bromate to oxidize the plutonium to the hexavalent state, and selectlvely extracting the plutonium by means of an immlscible solvent, such as dibutoxy dlethyletber.

Comparative analysis of uranium bioassociation with halophilic bacteria and archaea

Science.gov (United States)

Bader, Miriam; Müller, Katharina; Foerstendorf, Harald; Schmidt, Matthias; Simmons, Karen; Swanson, Juliet S.; Reed, Donald T.; Stumpf, Thorsten

2018-01-01

Rock salt represents a potential host rock formation for the final disposal of radioactive waste. The interactions between indigenous microorganisms and radionuclides, e.g. uranium, need to be investigated to better predict the influence of microorganisms on the safety assessment of the repository. Hence, the association process of uranium with two microorganisms isolated from rock salt was comparatively studied. Brachybacterium sp. G1, which was isolated from the German salt dome Gorleben, and Halobacterium noricense DSM15987T, were selected as examples of a moderately halophilic bacterium and an extremely halophilic archaeon, respectively. The microorganisms exhibited completely different association behaviors with uranium. While a pure biosorption process took place with Brachybacterium sp. G1 cells, a multistage association process occurred with the archaeon. In addition to batch experiments, in situ attenuated total reflection Fourier-transform infrared spectroscopy was applied to characterize the U(VI) interaction process. Biosorption was identified as the dominating process for Brachybacterium sp. G1 with this method. Carboxylic functionalities are the dominant interacting groups for the bacterium, whereas phosphoryl groups are also involved in U(VI) association by the archaeon H. noricense. PMID:29329319

A gravimetric method for the determination of oxygen in uranium oxides and ternary uranium oxides by addition of alkaline earth compounds

International Nuclear Information System (INIS)

Fujino, Takeo; Tagawa, Hiroaki; Adachi, Takeo; Hashitani, Hiroshi

1978-01-01

A simple gravimetric determination of oxygen in uranium oxides and ternary uranium oxides is described. In alkaline earth uranates which are formed by heating in air at 800-1100 0 C, uranium is in the hexavalent state over certain continuous ranges of alkaline earth-to-uranium ratios. Thus, if an alkaline earth uranate or a compound containing an alkaline earth element, e.g. MgO, is mixed with the oxide sample and heated in air under suitable conditions, oxygen can be determined from the weight change before and after the reaction. The standard deviation of the O:U ratio for a UOsub(2+x) test sample is +-0.0008-0.001, if a correction is applied for atmospheric moisture absorbed during mixing. (Auth.)

Application of supported liquid membranes for removal of uranium from groundwater

International Nuclear Information System (INIS)

Chiarizia, R.; Horwitz, E.P.; Rickert, P.G.; Hodgson, K.M.

1989-01-01

The separation of uranium from Hanford site groundwater as studied by hollow-fiber supported liquid membranes, SLM. The carrier bis(2,4,4-trimethylpentyl)phosphinic acid, H[DTMPep], contained in the commercial extractant Cyanex trademark 272 was used as a membrane carrier, because of its selectivity for U over calcium and magnesium. The water soluble complexing agent, 1-hydroxyethane-1,1-diphosphonic acid, HEDPA, was used as stripping agent. Polypropylene hollow-fibers and n-dodecane were used as polymeric support and diluent, respectively. Laboratory scale hollow-fiber modules were employed in a recycling mode, using as feed synthetic groundwater at pH 2, to confirm the capability of the proposed SLM system to separate and concentrate U(VI) in the strip solution. Information was obtained on the U(VI) concentration factor and on the long-term performance of the SLMs. Encouraging results were obtained both with a conventional module and with a module containing a carrier solution reservoir. Industrial scale modules were used at Hanford to test the SLM separation of U(VI) from real contaminated groundwater. The uranium concentration was reduced from approximately 3500 ppB to about 1 ppB in a few hours. 9 refs., 8 figs., 4 tabs

Determination of kinetic coefficients for the reduction and removal of uranium from water by the Desulfovibrio desulfuricans bacteria

International Nuclear Information System (INIS)

Tucker, M.D.; Barton, L.L.; Thomson, B.M.

1996-01-01

Uranium contamination of groundwater and surface water from abandoned uranium mill tailings piles is a serious concern in many areas of the western United States. U(VI) is soluble in water and, as a result, is relatively mobile in the environment. U(IV), however, is generally insoluble in water and, therefore, is not subject to aqueous transport. In recent years, researchers have discovered that certain microorganisms, such as the sulfate-reducing bacteria Desuffiovibrio desulfricans, can mediate the reduction of U(VI) to U(IV) by anaerobic respiration. Although the ability of this microorganism to reduce U(VI) has been studied in some detail by previous researchers, the kinetics of the reaction have not been characterized. The purpose of this research was to perform kinetic studies on Desuffiovibrio desulfricans during simultaneous reduction of sulfate and uranium and to determine the mineral phase of uranium after it has been reduced. The studies were conducted in a laboratory-scale chemostat under substrate-limited growth conditions with pyruvate as the substrate. The maximum rate of substrate utilization (k) was determined to be 4.70 days -1 while the half-velocity constant (Ks) was 140 mg CODA. The yield coefficient (Y) was determined to be 0. 17 mg cells/mg COD while the endogenous decay coefficient (kd) was found to be 0.072 days -1 . After reduction, U(IV) precipitated from solution in the uraninite (UO 2 ) phase as predicted by thermodynamics. Uranium removal efficiency as high as 90% was achieved in the chemostat

Uranium Bio-accumulation and Cycling as revealed by Uranium Isotopes in Naturally Reduced Sediments from the Upper Colorado River Basin

Science.gov (United States)

Lefebvre, Pierre; Noël, Vincent; Jemison, Noah; Weaver, Karrie; Bargar, John; Maher, Kate

2016-04-01

Uranium (U) groundwater contamination following oxidized U(VI) releases from weathering of mine tailings is a major concern at numerous sites across the Upper Colorado River Basin (CRB), USA. Uranium(IV)-bearing solids accumulated within naturally reduced zones (NRZs) characterized by elevated organic carbon and iron sulfide compounds. Subsequent re-oxidation of U(IV)solid to U(VI)aqueous then controls the release to groundwater and surface water, resulting in plume persistence and raising public health concerns. Thus, understanding the extent of uranium oxidation and reduction within NRZs is critical for assessing the persistence of the groundwater contamination. In this study, we measured solid-phase uranium isotope fractionation (δ238/235U) of sedimentary core samples from four study sites (Shiprock, NM, Grand Junction, Rifle and Naturita, CO) using a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS). We observe a strong correlation between U accumulation and the extent of isotopic fractionation, with Δ238U up to +1.8 ‰ between uranium-enriched and low concentration zones. The enrichment in the heavy isotopes within the NRZs appears to be especially important in the vadose zone, which is subject to variations in water table depth. According to previous studies, this isotopic signature is consistent with biotic reduction processes associated with metal-reducing bacteria. Positive correlations between the amount of iron sulfides and the accumulation of reduced uranium underline the importance of sulfate-reducing conditions for U(IV) retention. Furthermore, the positive fractionation associated with U reduction observed across all sites despite some variations in magnitude due to site characteristics, shows a regional trend across the Colorado River Basin. The maximum extent of 238U enrichment observed in the NRZ proximal to the water table further suggests that the redox cycling of uranium, with net release of U(VI) to the groundwater by

Influence of Uranium on Bacterial Communities: A Comparison of Natural Uranium-Rich Soils with Controls

Science.gov (United States)

Mondani, Laure; Benzerara, Karim; Carrière, Marie; Christen, Richard; Mamindy-Pajany, Yannick; Février, Laureline; Marmier, Nicolas; Achouak, Wafa; Nardoux, Pascal; Berthomieu, Catherine; Chapon, Virginie

2011-01-01

This study investigated the influence of uranium on the indigenous bacterial community structure in natural soils with high uranium content. Radioactive soil samples exhibiting 0.26% - 25.5% U in mass were analyzed and compared with nearby control soils containing trace uranium. EXAFS and XRD analyses of soils revealed the presence of U(VI) and uranium-phosphate mineral phases, identified as sabugalite and meta-autunite. A comparative analysis of bacterial community fingerprints using denaturing gradient gel electrophoresis (DGGE) revealed the presence of a complex population in both control and uranium-rich samples. However, bacterial communities inhabiting uraniferous soils exhibited specific fingerprints that were remarkably stable over time, in contrast to populations from nearby control samples. Representatives of Acidobacteria, Proteobacteria, and seven others phyla were detected in DGGE bands specific to uraniferous samples. In particular, sequences related to iron-reducing bacteria such as Geobacter and Geothrix were identified concomitantly with iron-oxidizing species such as Gallionella and Sideroxydans. All together, our results demonstrate that uranium exerts a permanent high pressure on soil bacterial communities and suggest the existence of a uranium redox cycle mediated by bacteria in the soil. PMID:21998695

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

Evaluating chemical extraction techniques for the determination of uranium oxidation state in reduced aquifer sediments

Science.gov (United States)

Stoliker, Deborah L.; Campbell, Kate M.; Fox, Patricia M.; Singer, David M.; Kaviani, Nazila; Carey, Minna; Peck, Nicole E.; Barger, John R.; Kent, Douglas B.; Davis, James A.

2013-01-01

Extraction techniques utilizing high pH and (bi)carbonate concentrations were evaluated for their efficacy in determining the oxidation state of uranium (U) in reduced sediments collected from Rifle, CO. Differences in dissolved concentrations between oxic and anoxic extractions have been proposed as a means to quantify the U(VI) and U(IV) content of sediments. An additional step was added to anoxic extractions using a strong anion exchange resin to separate dissolved U(IV) and U(VI). X-ray spectroscopy showed that U(IV) in the sediments was present as polymerized precipitates similar to uraninite and/or less ordered U(IV), referred to as non-uraninite U(IV) species associated with biomass (NUSAB). Extractions of sediment containing both uraninite and NUSAB displayed higher dissolved uranium concentrations under oxic than anoxic conditions while extractions of sediment dominated by NUSAB resulted in identical dissolved U concentrations. Dissolved U(IV) was rapidly oxidized under anoxic conditions in all experiments. Uraninite reacted minimally under anoxic conditions but thermodynamic calculations show that its propensity to oxidize is sensitive to solution chemistry and sediment mineralogy. A universal method for quantification of U(IV) and U(VI) in sediments has not yet been developed but the chemical extractions, when combined with solid-phase characterization, have a narrow range of applicability for sediments without U(VI).

Electrochemistry of uranium in sodium chloroaluminate melts

International Nuclear Information System (INIS)

D'olieslager, W.; Meuris, F.; Heerman, L.

1990-01-01

The electrochemical behaviour of uranium was studied in basic, NaCl-saturated NaAlCl 4 melts at 175 deg C. Solutions of UO 3 exhibit two oxidation/reduction waves (cyclic voltammetry). Analysis of the peak currents (cyclic voltammetry), the limiting currents (pulse polarography) and the non-linear log i-t curves (anodic controlled potential coulometry) leads to the conclusion that uranium(IV) in the basic chloroaluminate melt exists as two different species in slow equilibrium with one another, of which only one species can be oxidized to U(VI). (author) 16 refs.; 7 figs.; 3 tabs

Persistence of uranium groundwater plumes: Contrasting mechanisms at two DOE sites in the groundwater-river interaction zone

Science.gov (United States)

Zachara, John M.; Long, Philip E.; Bargar, John; Davis, James A.; Fox, Patricia; Fredrickson, Jim K.; Freshley, Mark D.; Konopka, Allan E.; Liu, Chongxuan; McKinley, James P.; Rockhold, Mark L.; Williams, Kenneth H.; Yabusaki, Steve B.

2013-04-01

We examine subsurface uranium (U) plumes at two U.S. Department of Energy sites that are located near large river systems and are influenced by groundwater-river hydrologic interaction. Following surface excavation of contaminated materials, both sites were projected to naturally flush remnant uranium contamination to levels below regulatory limits (e.g., 30 μg/L or 0.126 μmol/L; U.S. EPA drinking water standard), with 10 years projected for the Hanford 300 Area (Columbia River) and 12 years for the Rifle site (Colorado River). The rate of observed uranium decrease was much lower than expected at both sites. While uncertainty remains, a comparison of current understanding suggests that the two sites have common, but also different mechanisms controlling plume persistence. At the Hanford 300 A, the persistent source is adsorbed U(VI) in the vadose zone that is released to the aquifer during spring water table excursions. The release of U(VI) from the vadose zone and its transport within the oxic, coarse-textured aquifer sediments is dominated by kinetically-limited surface complexation. Modeling implies that annual plume discharge volumes to the Columbia River are small (oxidation of naturally reduced, contaminant U(IV) in the saturated zone and a continuous influx of U(VI) from natural, up-gradient sources influence plume persistence. Rate-limited mass transfer and surface complexation also control U(VI) migration velocity in the sub-oxic Rifle groundwater. Flux of U(VI) from the vadose zone at the Rifle site may be locally important, but it is not the dominant process that sustains the plume. A wide range in microbiologic functional diversity exists at both sites. Strains of Geobacter and other metal reducing bacteria are present at low natural abundance that are capable of enzymatic U(VI) reduction in localized zones of accumulated detrital organic carbon or after organic carbon amendment. Major differences between the sites include the geochemical nature of

Fracture-filling minerals as uranium sinks and sources, a natural analogue study at Palmottu, Finland

International Nuclear Information System (INIS)

Cui, D.; Eriksen, T.

2000-01-01

The nucleation of a mineral crystal and its growth in groundwater carrying fractures 300 m above the Palmottu uranium deposit provide an impressive example of geochemical selectivity of uranium. Fracture-filling material was collected from a 3 mm thick fracture at depth 74.8-75 m (drillcore R348). SEM and EDS analyses on a thin section of the original fracture-filling show that the fracture filling is heterogeneous, composing mineral crystal particles and very porous clay-rich aggregates. The results of INAA on millimetre-sized single mineral crystals and aggregates selected from grinded fracture-filling show that porous aggregates (composed of clays and micrometer sized mineral particles) contain up to 1000 ppm U, which is higher than the average of the whole fracture-filling (400 ppm) and host rock related millimetre sized mineral particles (18-100 ppm). 233 U/ 238 U isotope exchange proves that a large fraction of the uranium in the fracture-filling is not easily exchanged with uranium in the solution. The amount of 238 U released in the isotope exchange experiment is too high to be explained by reversible U(VI) sorption. Oxidation state analyses show that 30% of the uranium exists as U(IV). Laboratory batch experiment at anoxic conditions proved that pyrite can immobilise U(VI). (orig.)

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.

Uranium extremophily is an adaptive, rather than intrinsic, feature for extremely thermoacidophilic Metallosphaera species

Science.gov (United States)

Mukherjee, Arpan; Wheaton, Garrett H.; Blum, Paul H.; Kelly, Robert M.

2012-01-01

Thermoacidophilic archaea are found in heavy metal-rich environments, and, in some cases, these microorganisms are causative agents of metal mobilization through cellular processes related to their bioenergetics. Given the nature of their habitats, these microorganisms must deal with the potentially toxic effect of heavy metals. Here, we show that two thermoacidophilic Metallosphaera species with nearly identical (99.99%) genomes differed significantly in their sensitivity and reactivity to uranium (U). Metallosphaera prunae, isolated from a smoldering heap on a uranium mine in Thüringen, Germany, could be viewed as a “spontaneous mutant” of Metallosphaera sedula, an isolate from Pisciarelli Solfatara near Naples. Metallosphaera prunae tolerated triuranium octaoxide (U3O8) and soluble uranium [U(VI)] to a much greater extent than M. sedula. Within 15 min following exposure to “U(VI) shock,” M. sedula, and not M. prunae, exhibited transcriptomic features associated with severe stress response. Furthermore, within 15 min post-U(VI) shock, M. prunae, and not M. sedula, showed evidence of substantial degradation of cellular RNA, suggesting that transcriptional and translational processes were aborted as a dynamic mechanism for resisting U toxicity; by 60 min post-U(VI) shock, RNA integrity in M. prunae recovered, and known modes for heavy metal resistance were activated. In addition, M. sedula rapidly oxidized solid U3O8 to soluble U(VI) for bioenergetic purposes, a chemolithoautotrophic feature not previously reported. M. prunae, however, did not solubilize solid U3O8 to any significant extent, thereby not exacerbating U(VI) toxicity. These results point to uranium extremophily as an adaptive, rather than intrinsic, feature for Metallosphaera species, driven by environmental factors. PMID:23010932

Hexavalent Chromium Substitution Projects

Science.gov (United States)

2011-05-12

Hexavalent Chromium Substitution Projects Date (12 May 2011) Gene McKinley ASC/WNV (937) 255-3596 Gene.McKinley@wpafb.af.mil Aeronautical Systems...valid OMB control number. 1. REPORT DATE 12 MAY 2011 2. REPORT TYPE 3. DATES COVERED 00-00-2011 to 00-00-2011 4. TITLE AND SUBTITLE Hexavalent ...A-10) – AETC (T-6, T-38 and T1A) • Both Cr Primers & Non-Cr primers as well as Cr Surface Treatment – F-22 8 Non- Chrome Tie-coat & touch-up

Acid Dissolution of Depleted Uranium from Catalyst using Microwave

Energy Technology Data Exchange (ETDEWEB)

Sung, Jin Hyun; Jeong, Seong Gi; Park, Kwang Heon [Kyunghee University, Yongin (Korea, Republic of)

2011-05-15

The separation process of uranium is one of the most important fields in nuclear industry because uranium is used primary in nuclear power plants. Uranium ores are treated by either acid or alkaline reagents. Uranium can be dissolved by acid or alkaline solutions. There are two oxidation states in which the hexavalent form, the oxide of which is UO{sub 3}, and the tetravalent form, the oxide of which is UO{sub 2}. However, depleted uranium(DU) has also been used as a catalyst in specialized chemical reaction such as ammoxidation. The preferred catalyst for propylene oxidation with ammonia was a uranium oxide-antimony oxide composition. The active phase of catalyst was known as USbO{sub 5} and USb{sub 3}O{sub 10}. There is pentavalent form. Waste catalyst containing DU was generated and stored in chemical industry. In this work, we removed DU from catalyst by acid dissolution

Using proteomic data to assess a genome-scale "in silico" model of metal reducing bacteria in the simulation of field-scale uranium bioremediation

Science.gov (United States)

Yabusaki, S.; Fang, Y.; Wilkins, M. J.; Long, P.; Rifle IFRC Science Team

2011-12-01

A series of field experiments in a shallow alluvial aquifer at a former uranium mill tailings site have demonstrated that indigenous bacteria can be stimulated with acetate to catalyze the conversion of hexavalent uranium in a groundwater plume to immobile solid-associated uranium in the +4 oxidation state. While this bioreduction of uranium has been shown to lower groundwater concentrations below actionable standards, a viable remediation methodology will need a mechanistic, predictive and quantitative understanding of the microbially-mediated reactions that catalyze the reduction of uranium in the context of site-specific processes, properties, and conditions. At the Rifle IFRC site, we are investigating the impacts on uranium behavior of pulsed acetate amendment, acetate-oxidizing iron and sulfate reducing bacteria, seasonal water table variation, spatially-variable physical (hydraulic conductivity, porosity) and geochemical (reactive surface area) material properties. The simulation of three-dimensional, variably saturated flow and biogeochemical reactive transport during a uranium bioremediation field experiment includes a genome-scale in silico model of Geobacter sp. to represent the Fe(III) terminal electron accepting process (TEAP). The Geobacter in silico model of cell-scale physiological metabolic pathways is comprised of hundreds of intra-cellular and environmental exchange reactions. One advantage of this approach is that the TEAP reaction stoichiometry and rate are now functions of the metabolic status of the microorganism. The linkage of in silico model reactions to specific Geobacter proteins has enabled the use of groundwater proteomic analyses to assess the accuracy of the model under evolving hydrologic and biogeochemical conditions. In this case, the largest predicted fluxes through in silico model reactions generally correspond to high abundances of proteins linked to those reactions (e.g. the condensation reaction catalyzed by the protein

Potential for Methanosarcina to contribute to uranium reduction during acetate-promoted groundwater bioremediation

DEFF Research Database (Denmark)

Holmes, Dawn E; Orellana, Roberto; Giloteaux, Ludovic

2017-01-01

Previous studies of in situ bioremediation of uranium-contaminated groundwater with acetate injections have focused on the role of Geobacter species in U(VI) reduction because of a lack of other abundant known U(VI)-reducing microorganisms. Monitoring the levels of methyl CoM reductase subunit...... an important role in the long-term bioremediation of uranium-contaminated aquifers after depletion of Fe(III) oxides limits the growth of Geobacter species. The results also suggest that Methanosarcina have the potential to influence uranium geochemistry in a diversity of anaerobic sedimentary environments....

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

Science.gov (United States)

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

2014-10-01

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

Impact of water quality parameters on the sorption of U(VI) onto hematite

International Nuclear Information System (INIS)

Zhao Donglin; Wang Xianbiao; Yang Shitong; Guo Zhiqiang; Sheng Guodong

2012-01-01

In this study, the sorption of U(VI) from aqueous solution on hematite was studied as a function of various water quality parameters such as contact time, pH, ionic strength, soil humic acid (HA) or fulvic acid (FA), solid content and temperature by using a batch technique. The results demonstrated that the sorption of U(VI) was strongly dependent on ionic strength at pH 6.0 and the sorption was mainly dominated by inner-sphere surface complexation. The presence of HA/FA increases U(VI) sorption at low pH, whereas decreases U(VI) sorption at high pH. The thermodynamic parameters (ΔH 0 , ΔS 0 , and ΔG 0 ) were calculated from the temperature dependent sorption isotherms, and the results suggested that U(VI) sorption was a spontaneous and endothermic process. The results might be important for the application of hematite in U(VI) pollution management. Highlights: ► The sorption of U(VI) was strongly dependent on ionic strength at pH 6.0. ► A positive effect of HA/FA on U(VI) sorption was found at low pH, whereas a negative effect was observed at high pH. ► U(VI) sorption was a spontaneous and endothermic process. ► The results are quite important for the application of hematite in U(VI) pollution management.

Potentiometric determination of uranium with cobalt (3) acetate as oxidimetric titrant

International Nuclear Information System (INIS)

Muhammad, H.; Ishrat, P.; Zyka, J.

1972-01-01

A potentiometric method for the determination of uranium through the reduction of hexavalent to tetravalent state and its potentiometric oxidation in 8 N sulphuric acid with standard cobalt (3)-acetate has been worked out. The method is quite accurate with the error not exceeding 1% for mg amounts. Moreover an apparatus for preservation of reduced solution of uranium and its delivery for titrations has been designed. The same apparatus can be used for reducing and preserving solutions of strong reducing titrants. (author)

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

Kinetic studies on uranium stripping in D2EHPA+TBP/phosphoric acid system

International Nuclear Information System (INIS)

Yadav, K.K.; Singh, D.K.; Kotekar, M.K.; Anitha, M.; Vijayalakshmi, R.; Singh, H.

2010-01-01

Full text: A novel process based on synergistic mixture of 1.5 M D2EHPA (di 2 ethyl hexyl phosphoric acid) + 0.2 M TBP (tri-n-butyl phosphate) to recover uranium from wet process phosphoric acid (WPA) has been developed. Though the equilibrium study for the above process has been investigated in detail its kinetic behavior has not been reported so far. The work presented in the paper is an attempt to study the kinetics of U(VI) stripping from extractant phase to aqueous phase in a constant interfacial area cell (Lewis cell). Kinetic study of the solvent extraction process helps in designing of equipment and optimizing process condition for the better utilization of solvent inventory. Mass transfer kinetics of stripping of U(VI) from loaded 1.5M D2EHPA+ 0.2M TBP with phosphoric acid (AR) has been studied over a wide range of experimental conditions such as stirring speed, interfacial contact area, phosphoric acid concentration, uranium concentration, extractant concentration in organic phase and temperature. Investigation on effect of stirring speed (100-500 rpm) on stripping of U(VI) showed that the rate constant (k) values increases linearly with increase in stirring speeds from 100 to 300 rpm (0.03 to 0.075 cm/min), while the k values were almost constant (0.0819 cm/min) in 300 to 400 rpm range, beyond 450 rpm the k values again increased due to increased turbulence at the interface. The rate constant value (∼0.0814 cm/min) was found to be independent of interfacial contact area (24.6 to 67.02 cm 2 ) available for mass transfer. The rate constants were found to increase with increase in phosphoric acid concentration (6-10M) and temperature (30-60 deg C), the values being in the range of 0.01 to 0.082 cm/min. The slopes of ln-ln plot showed that the stripping of U(VI) has a second order dependence on phosphoric acid concentration (slope∼2) at temperatures ranging from 30 to 60 deg C. The activation energy value for uranium stripping was found to be in the

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

Solvent impregnated resin for isolation of U(VI) from industrial wastes

International Nuclear Information System (INIS)

Karve, M.; Rajgor, R.V.

2008-01-01

A solid-phase extraction method based upon impregnation of Cyanex 302 (bis(2,4,4- trimethylpentyl)mono-thio-phosphinic acid) on Amberlite XAD-2 resin is proposed for isolation of U(VI) from uranmicrolite ore tailing samples and industrial effluent samples. U(VI) was sorbed from nitric acid media on the solvent-impregnated resin (SIR) and was recovered completely with 1.0 M HCl. Based upon sorption behavior of U(VI) with Cyanex 302, it was quantitatively sorbed on the SIR in a dynamic method, while the other metal ions were not sorbed by the modified resin. The preparation of impregnated resin is simple, based upon physical interaction of the extractant and solid support, has good sorption capacity for U(VI), and is also reliable for detection of traces of U(VI). (authors)

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

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

Solvent extraction as a method of promoting uranium enrichment by chemical exchange

International Nuclear Information System (INIS)

Fathurrachman.

1995-01-01

This thesis examines a chemical exchange process for uranium enrichment using solvent extraction. The system selected is the isotope exchange for uranium species in the form of uranous and uranyl chloride complexes. Solvent extraction has been studied before by French workers for this application but little was published on this. Much of this present work is therefore novel. The equilibrium data for the extraction of U(IV) as U 4+ and U(VI) as UO 2 2+ from hydrochloric media into an organic phase containing tri-n-octylamine (TOA) in benzene is given. Benzene is used to prevent third phase formation. In 4 M HCl U(VI) was found to be very soluble in the organic phase but U(IV) was virtually insoluble. Most of the equilibrium data has been correlated by the Langmuir isotherm. This thesis also outlines the methodology that has to be used to design a plant based on this process. (author)

Bacillus lichenformis γ-glutamyl exopolymer: Physicochemical characterization and U(VI) interaction

International Nuclear Information System (INIS)

He, L.M.; Neu, M.P.; Vanderberg, L.A.

2000-01-01

Complexation by microbially produced exopolymers may significantly impact the environmental mobility and toxicity of metals. This study focused on the conformational structure of the bacterial exopolymer, γ-D-poly(glutamic acid) and its interactions with U(VI) examined using ATR-FTIR spectroscopy. Solution pH, polymer concentration, and ionic strength affected the conformation of the exopolymer, and U(VI) binding was monitored. At low pH, low concentration, or low ionic strength, this exopolymer exists in an α-helical conformation, while at high pH, concentration, or ionic strength the exopolymer exhibits a β-sheet structure. The change in exopolymer conformation is likely to influence the number and nature of exposed surface functional groups, sites most responsible for metal complexation. The authors found the polyglutamate capsule binds U(VI) in a binuclear, bidentate fashion; in contrast the glutamate monomer forms a mononuclear, bidentate complex with U(VI). The apparent polynuclear binding of U(VI) may induce β-sheet structure formation provided the U(VI) Concentration is sufficiently high

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)

Subcellular distribution of uranium in the roots of Spirodela punctata and surface interactions

Energy Technology Data Exchange (ETDEWEB)

Nie, Xiaoqin, E-mail: xiaoqin_nie@163.com [Fundamental Science on Nuclear Wastes and Environmental Safety Laboratory, Mianyang 621010 (China); Key Laboratory of Radiation Physics and Technology (Sichuan University), Ministry of Education, Institute of Nuclear Science and Technology, Sichuan University, Chengdu 610064 (China); Dong, Faqin, E-mail: fqdong2004@163.com [Fundamental Science on Nuclear Wastes and Environmental Safety Laboratory, Mianyang 621010 (China); Liu, Ning [Key Laboratory of Radiation Physics and Technology (Sichuan University), Ministry of Education, Institute of Nuclear Science and Technology, Sichuan University, Chengdu 610064 (China); Liu, Mingxue [Fundamental Science on Nuclear Wastes and Environmental Safety Laboratory, Mianyang 621010 (China); Zhang, Dong; Kang, Wu [Institute of Nuclear Physics and Chemistry,China Academy of Engineering Physics, Mianyang 621900 (China); Sun, Shiyong; Zhang, Wei; Yang, Jie [Fundamental Science on Nuclear Wastes and Environmental Safety Laboratory, Mianyang 621010 (China)

2015-08-30

Graphical abstract: - Highlights: • The proportion of uranium concentration approximate as 8:2:1 in the cell wall organelle and cytosol fractions of roots of S. punctata. • The particles including 35% Fe (wt%) released from the cells after 100 mg/L U treatment 48 h. • Most of the uranium bound onto the root surface and contacted with phosphorus ligands and formed as nano-scales U-P lamellar crystal. • FTIR and XPS analyses result indicates the uranium changed the band position and shapes of phosphate group, and the region of characteristic peak belongs to U(VI) and U(IV) were also observed. - Abstract: The subcellular distribution of uranium in roots of Spirodela punctata (duckweed) and the process of surface interaction were studied upon exposure to U (0, 5–200 mg/L) at pH 5. The concentration of uranium in each subcelluar fraction increased significantly with increasing solution U level, after 200 mg/L uranium solution treatment 120 h, the proportion of uranium concentration approximate as 8:2:1 in the cell wall organelle and cytosol fractions of roots of S. punctata. OM SEM and EDS showed after 5–200 mg/L U treatment 4–24 h, some intracellular fluid released from the root cells, after 100 mg/L U treatment 48 h, the particles including 35% Fe (wt%) and other organic matters such as EPS released from the cells, most of the uranium bound onto the root surface and contacted with phosphorus ligands and formed as nano-scales U-P lamellar crystal, similar crystal has been found in the cell wall and organelle fractions after 50 mg/L U treatment 120 h. FTIR and XPS analyses result indicates the uranium changed the band position and shapes of phosphate group, and the region of characteristic peak belongs to U(VI) and U(IV) were also observed.

Contribution of extracellular polymeric substances from Shewanella sp. HRCR-1 biofilms to U(VI) immobilization.

Science.gov (United States)

Cao, Bin; Ahmed, Bulbul; Kennedy, David W; Wang, Zheming; Shi, Liang; Marshall, Matthew J; Fredrickson, Jim K; Isern, Nancy G; Majors, Paul D; Beyenal, Haluk

2011-07-01

The goal of this study was to quantify the contribution of extracellular polymeric substances (EPS) to U(VI) immobilization by Shewanella sp. HRCR-1. Through comparison of U(VI) immobilization using cells with bound EPS (bEPS) and cells with minimal EPS, we show that (i) bEPS from Shewanella sp. HRCR-1 biofilms contribute significantly to U(VI) immobilization, especially at low initial U(VI) concentrations, through both sorption and reduction; (ii) bEPS can be considered a functional extension of the cells for U(VI) immobilization and they likely play more important roles at lower initial U(VI) concentrations; and (iii) the U(VI) reduction efficiency is dependent upon the initial U(VI) concentration and decreases at lower concentrations. To quantify the relative contributions of sorption and reduction to U(VI) immobilization by EPS fractions, we isolated loosely associated EPS (laEPS) and bEPS from Shewanella sp. HRCR-1 biofilms grown in a hollow fiber membrane biofilm reactor and tested their reactivity with U(VI). We found that, when reduced, the isolated cell-free EPS fractions could reduce U(VI). Polysaccharides in the EPS likely contributed to U(VI) sorption and dominated the reactivity of laEPS, while redox active components (e.g., outer membrane c-type cytochromes), especially in bEPS, possibly facilitated U(VI) reduction.

Fate of Uranium During Transport Across the Groundwater-Surface Water Interface

Energy Technology Data Exchange (ETDEWEB)

Jaffe, Peter R. [Princeton Univ., NJ (United States); Kaplan, Daniel I. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

2017-06-30

Discharge of contaminated groundwater to surface waters is of concern at many DOE facilities. For example, at F-Area and TNX-Area on the Savannah River Site, contaminated groundwater, including uranium, is already discharging into natural wetlands. It is at this interface where contaminants come into contact with the biosphere. These this research addressed a critical knowledge gap focusing on the geochemistry of uranium (or for that matter, any redox-active contaminant) in wetland systems. Understanding the interactions between hydrological, microbial, and chemical processes will make it possible to provide a more accurate conceptual and quantitative understanding of radionuclide fate and transport under these unique conditions. Understanding these processes will permit better long-term management and the necessary technical justification for invoking Monitored Natural Attenuation of contaminated wetland areas. Specifically, this research did provide new insights on how plant-induced alterations to the sediment biogeochemical processes affect the key uranium reducing microorganisms, the uranium reduction, its spatial distribution, the speciation of the immobilized uranium, and its long-term stability. This was achieved by conducting laboratory mesocosm wetland experiments as well as field measurements at the SRNL. Results have shown that uranium can be immobilized in wetland systems. To a degree some of the soluble U(VI) was reduced to insoluble U(IV), but the majority of the immobilized U was incorporated into iron oxyhydroxides that precipitated onto the root surfaces of wetland plants. This U was immobilized mostly as U(VI). Because it was immobilized in its oxidized form, results showed that dry spells, resulting in the lowering of the water table and the exposure of the U to oxic conditions, did not result in U remobilization.

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

Studies on the determination of uranium by potentiometry

International Nuclear Information System (INIS)

Venkataramana, P.; John, Mary; Nair, P.R.; Kasar, U.M.; Natarajan, P.R.

1981-01-01

A potentiometric method for the determination of uranium standardised earlier has been in use for the chemical quality control of plutonium fuels. The method involves the reduction of U(VI) in phosphoric acid medium and titration of U(IV) against Cr(VI). An extension of the range of the quantity of uranium determined by the same method is reported here. The precisions have been evaluated at 13 concentration levels. 20 titrations were carried out at each concentration. the precision at 20 μg level was found to be 3.8% while it was better than 0.03% at concentrations ranging from 20 mg upto 200 mg. At 100 mg and 200 mg of uranium the total volume of the reagent solutions was 50 ml while in other cases it was 25 ml. The effects of a few impurities on the uranium determination were also studied for the 2-5 mg range of uranium. (author)

Biosorption of heavy metals and uranium by starfish and Pseudomonas putida

International Nuclear Information System (INIS)

Choi, Jaeyoung; Lee, Ju Young; Yang, Jung-Seok

2009-01-01

Biosorption of heavy metals and uranium from contaminated wastewaters may represent an innovative purification process. This study investigates the removal ability of unit mass of Pseudomonas putida and starfish for lead, cadmium, and uranium by quantifying the adsorption capacity. The adsorption of heavy metals and uranium by the samples was influenced by pH, and increased with increasing Pb, Cd, and U concentrations. Dead cells adsorbed the largest quantity of all heavy metals than live cells and starfish. The adsorption capacity followed the order: U(VI) > Pb > Cd. The results also suggest that bacterial membrane cells can be used successfully in the treatment of high strength metal-contaminated wastewaters

Uranium Sequestration During Biostimulated Reduction and In Response to the Return of Oxic Conditions In Shallow Aquifers

Science.gov (United States)

Fuller, Christopher C.; Johnson, Kelly J.; Akstin, Katherine; Singer, David M.; Yabusaki, Steven B.; Fang, Yilin; Fuhrmann, M.

2015-01-01

A proposed approach for groundwater remediation of uranium contamination is to generate reducing conditions by stimulating the growth of microbial populations through injection of electron donor compounds into the subsurface. Sufficiently reducing conditions will result in reduction of soluble hexavalent uranium, U(VI), and precipitation of the less soluble +4 oxidation state uranium, U(IV). This process is termed biostimulated reduction. A key issue in the remediation of uranium (U) contamination in aquifers by biostimulated reduction is the long term stability of the sequestered uranium. Three flow-through column experiments using aquifer sediment were used to evaluate the remobilization of bioreduced U sequestered under conditions in which biostimulation extended well into sulfate reduction to enhance precipitation of reduced sulfur phases such as iron sulfides. One column received added ferrous iron, Fe(II), increasing production of iron sulfides, to test their effect on remobilization of the sequestered uranium, either by serving as a redox buffer by competing for dissolved oxygen, or by armoring the reduced uranium. During biostimulation of the ambient microbial population with acetate, dissolved uranium was lowered by a factor of 2.5 or more with continued removal for over 110 days of biostimulation, well after the onset of sulfate reduction at ~30 days. Sequestered uranium was essentially all U(IV) resulting from the formation of nano-particulate uraninite that coated sediment grains to a thickness of a few 10’s of microns, sometimes in association with S and Fe. A multicomponent biogeochemical reactive transport model simulation of column effluents during biostimulation was generally able to describe the acetate oxidation, iron, sulfate, and uranium reduction for all three columns using parameters derived from simulations of field scale biostimulation experiments. Columns were eluted with artificial groundwater at equilibrium with atmospheric oxygen to

Kinetic analysis and modeling of oleate and ethanol stimulated uranium (VI) bio-reduction in contaminated sediments under sulfate reduction conditions

Energy Technology Data Exchange (ETDEWEB)

Zhang Fan, E-mail: zhangfan@itpcas.ac.cn [Key Laboratory of Tibetan Environment Changes and Land Surface Processes, Institute of Tibetan Plateau Research, Chinese Academy of Sciences, P.O. Box 2871, Beijing 100085 (China); Wu Weimin [Department of Civil and Environmental Engineering, Stanford University, Stanford, CA 94305 (United States); Parker, Jack C. [Department of Civil and Environmental Engineering, University of Tennessee, Knoxville, TN 37996 (United States); Mehlhorn, Tonia [Environmental Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Kelly, Shelly D.; Kemner, Kenneth M. [Biosciences Division, Argonne National Laboratory, Argonne, IL 60439 (United States); Zhang, Gengxin [Key Laboratory of Tibetan Environment Changes and Land Surface Processes, Institute of Tibetan Plateau Research, Chinese Academy of Sciences, P.O. Box 2871, Beijing 100085 (China); Schadt, Christopher; Brooks, Scott C. [Environmental Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Criddle, Craig S. [Department of Civil and Environmental Engineering, Stanford University, Stanford, CA 94305 (United States); Watson, David B. [Environmental Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Jardine, Philip M. [Biosystems Engineering and Soil Science Department, University of Tennessee, Knoxville, TN 37996 (United States)

2010-11-15

Microcosm tests with uranium contaminated sediments were performed to explore the feasibility of using oleate as a slow-release electron donor for U(VI) reduction in comparison to ethanol. Oleate degradation proceeded more slowly than ethanol with acetate produced as an intermediate for both electron donors under a range of initial sulfate concentrations. A kinetic microbial reduction model was developed and implemented to describe and compare the reduction of sulfate and U(VI) with oleate or ethanol. The reaction path model considers detailed oleate/ethanol degradation and the production and consumption of intermediates, acetate and hydrogen. Although significant assumptions are made, the model tracked the major trend of sulfate and U(VI) reduction and describes the successive production and consumption of acetate, concurrent with microbial reduction of aqueous sulfate and U(VI) species. The model results imply that the overall rate of U(VI) bioreduction is influenced by both the degradation rate of organic substrates and consumption rate of intermediate products.

Kinetic analysis and modeling of oleate and ethanol stimulated uranium (VI) bio-reduction in contaminated sediments under sulfate reduction conditions

International Nuclear Information System (INIS)

Zhang Fan; Wu Weimin; Parker, Jack C.; Mehlhorn, Tonia; Kelly, Shelly D.; Kemner, Kenneth M.; Zhang, Gengxin; Schadt, Christopher; Brooks, Scott C.; Criddle, Craig S.; Watson, David B.; Jardine, Philip M.

2010-01-01

Microcosm tests with uranium contaminated sediments were performed to explore the feasibility of using oleate as a slow-release electron donor for U(VI) reduction in comparison to ethanol. Oleate degradation proceeded more slowly than ethanol with acetate produced as an intermediate for both electron donors under a range of initial sulfate concentrations. A kinetic microbial reduction model was developed and implemented to describe and compare the reduction of sulfate and U(VI) with oleate or ethanol. The reaction path model considers detailed oleate/ethanol degradation and the production and consumption of intermediates, acetate and hydrogen. Although significant assumptions are made, the model tracked the major trend of sulfate and U(VI) reduction and describes the successive production and consumption of acetate, concurrent with microbial reduction of aqueous sulfate and U(VI) species. The model results imply that the overall rate of U(VI) bioreduction is influenced by both the degradation rate of organic substrates and consumption rate of intermediate products.

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)

Uranium

International Nuclear Information System (INIS)

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

2010-01-01

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

Extractants for uranium recovery from wet phosphoric acid

International Nuclear Information System (INIS)

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

1981-08-01

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

Primary uranium mineralization in paleochannels of the Um Bogma formation at Allouga Southwestern Sinai

International Nuclear Information System (INIS)

Bisher, A. H.

2012-12-01

The Um Bogama formation in the Allouga area is within a major Graben trending NNW-SSE. The formation is composed mainly of sandy dolostone. Lactomicin marl, siltstone and carbonaceous shale with a high content of organic matter. The black carbonaceous shale represents the redox-front (reduced facies) at which hexavalent uranium can reduce to the presence state, resulting in the redeposition of uranium mineral. The presence of uranium minerals are increased with an increasing amount of carbonaceous matter in the paleochannels of the Allouga area. Small-scale fault planes also show an increase in the uranium content. The present study reveals the presence of the primary uranium contents, uranium, pitch blends and coffinite, which are recorded for the first time in the area. (Author)

Comparison of U(VI) adsorption onto nanoscale zero-valent iron and red soil in the presence of U(VI)–CO_3/Ca–U(VI)–CO_3 complexes

International Nuclear Information System (INIS)

Zhang, Zhibin; Liu, Jun; Cao, Xiaohong; Luo, Xuanping; Hua, Rong; Liu, Yan; Yu, Xiaofeng; He, Likai

2015-01-01

Highlights: • NZVI can be used for adsorbing U(VI)–CO_3 complexes. • Use of NZVI is feasible for remediation of uranium-contaminated soils. • The mechanism of U(VI)–CO_3 complexes adsorbing onto NZVI has been explained. - Abstract: The influence of U(VI)–CO_3 and Ca–U(VI)–CO_3 complexes on U(VI) adsorption onto red soil and nanoscale zero-valent iron (NZVI) was investigated using batch adsorption and fixed-bed column experiments to simulate the feasibility of NZVI as the reactive medium in permeable- reactive barriers (PRB) for in situ remediation of uranium-contaminated red soils. The adsorption capacity (q_e) and distribution constant (K_d) of NZVI and red soil decreased with increasing pH, dissolved carbonate and calcium concentrations, but the q_e and K_d values of NZVI were 5–10 times higher than those of red soil. The breakthrough pore volume (PV) values increased with the decrease of pH, dissolved carbonate and calcium concentration; however, the breakthrough PV values of the PRB column filled with 5% NZVI were 2.0–3.5 times higher than the 100% red soil column. The U(VI)–CO_3 complexes adsorbed onto the surface of red soil/NZVI (≡SOH) to form SO–UO_2CO_3"− or SO–UO_2 (CO_3)_2"3"−. XPS and XRD analysis further confirmed the reduction of U(VI) to U(IV) and the formation of FeOOH on NZVI surfaces. The findings of this study are significant to the remediation of uranium-contaminated red soils and the consideration of practical U(VI) species in the natural environment.

Contribution of Extracellular Polymeric Substances from Shewanella sp. HRCR-1 Biofilms to U(VI) Immobilization

Energy Technology Data Exchange (ETDEWEB)

Cao, Bin; Ahmed, B.; Kennedy, David W.; Wang, Zheming; Shi, Liang; Marshall, Matthew J.; Fredrickson, Jim K.; Isern, Nancy G.; Majors, Paul D.; Beyenal, Haluk

2011-06-05

The goal of this study was to quantify the contribution of extracellular polymeric substances (EPS) in U(VI) immobilization by Shewanella sp. HRCR-1. Through comparison of U(VI) immobilization using cells with bound EPS (bEPS) and cells without EPS, we showed that i) bEPS from Shewanella sp. HRCR-1 biofilms contributed significantly to U(VI) immobilization, especially at low initial U(VI) concentrations, through both sorption and reduction; ii) bEPS could be considered as a functional extension of the cells for U(VI) immobilization and they likely play more important roles at initial U(VI) concentrations; and iii) U(VI) reduction efficiency was found to be dependent upon initial U(VI) concentration and the efficiency decreased at lower concentrations. To quantify relative contribution of sorption and reduction in U(VI) immobilization by EPS fractions, we isolated loosely associated EPS (laEPS) and bEPS from Shewanella sp. HRCR-1 biofilms grown in a hollow fiber membrane biofilm reactor and tested their reactivity with U(V). We found that, when in reduced form, the isolated cell-free EPS fractions could reduce U(VI). Polysaccharides in the EPS likely contributed to U(VI) sorption and dominated reactivity of laEPS while redox active components (e.g., outer membrane c-type cytochromes), especially in bEPS, might facilitate U(VI) reduction.

The effect of dispersed materials on baro-membrane treatment of uranium-containing waters

International Nuclear Information System (INIS)

Kryvoruchko, Antonina P.; Atamanenkoa, Irina D.

2007-01-01

The paper investigated a treatment process of uranium-containing waters in a membrane reactor while using natural mineral kizelgur and synthetic sorbent SKN-1K with subsequent ultra- and nano-filtration separation of the mixture. The retention coefficient of U(VI) by membrane UPM-20 under conditions of quasi-stationary equilibrium reached the levels of 0.87-0.89 and 0.89-0.91, respectively, while using natural mineral kizelgur and synthetic sorbent SKN-1K. In the case of membrane OPMN-P and natural mineral kizelgur the retention coefficient of U(VI) was 0.990-0.991 and 0.993-0.996, respectively, while using natural mineral kizelgur and synthetic sorbent SKN-1K. Data regarding the state of water in membranes formed from natural mineral or synthetic sorbent on the surface of substrate membranes UPM-20 and OPMN-P made it possible to conclude that dispersed materials of different chemical nature affect the process of baro-membrane treatment of uranium-containing waters. (authors)

A combined wet chemistry and EXAFS study of U(VI) uptake by cementitious materials

International Nuclear Information System (INIS)

Wieland, E.; Harfouche, M.; Tits, J.; Kunz, D.; Daehn, R.; Fujita, T.; Tsukamoto, M.

2006-01-01

The sorption behaviour and speciation of U(VI) in cementitious systems was investigated by a combination of wet chemistry experiments and synchrotron-based X-ray absorption spectroscopy (XAS) measurements. Radiotracer studies using 233 U were carried out on hardened cement paste (HCP) and calcium silicate hydrates (C-S-H), which are the major constituents of HCP, to determine the uptake kinetics and sorption isotherms. C-S-H phases were synthesized using different methods for solid phase preparation, which enabled us to study the U(VI) uptake by different types of C-S-H phases and a wide range of Ca/Si compositions, and to distinguish U(VI) sorption on the surface of C-S-H from U(VI) incorporation into the structure. XAS measurements were performed using U(VI) loaded HCP and C-S-H materials (sorption and co-precipitation samples) to gain structural information on the U(VI) speciation in these systems, i.e., the type and number of neighbouring atoms, and bond distances. Examples of studies that have utilized XAS to characterize U(VI) speciation in cementitious systems are still rare, and to the best of our knowledge, detailed XAS investigations of the U(VI)/C-S-H system are lacking. The results obtained from the combined use of wet chemical and spectroscopic techniques allow mechanistic models of the immobilization process to be proposed for cementitious waste forms containing low and high U(VI) inventories. In the latter case U(VI) immobilization is controlled by a solubility-limiting process with the U(VI) mineral predominantly formed under the conditions prevailing in cementitious systems. At low U(VI) concentrations, however, U(VI) appears to be predominantly bound onto C-S-H phases. The coordination environment of U(VI) taken up by C-S-H was found to resemble that of U(VI) in uranophane. A mechanistic understanding of the U(VI) binding by cementitious materials will allow more detailed and scientifically well founded predictions of the retention of

Persistence of uranium groundwater plumes: contrasting mechanisms at two DOE sites in the groundwater-river interaction zone.

Science.gov (United States)

Zachara, John M; Long, Philip E; Bargar, John; Davis, James A; Fox, Patricia; Fredrickson, Jim K; Freshley, Mark D; Konopka, Allan E; Liu, Chongxuan; McKinley, James P; Rockhold, Mark L; Williams, Kenneth H; Yabusaki, Steve B

2013-04-01

We examine subsurface uranium (U) plumes at two U.S. Department of Energy sites that are located near large river systems and are influenced by groundwater-river hydrologic interaction. Following surface excavation of contaminated materials, both sites were projected to naturally flush remnant uranium contamination to levels below regulatory limits (e.g., 30 μg/L or 0.126 μmol/L; U.S. EPA drinking water standard), with 10 years projected for the Hanford 300 Area (Columbia River) and 12 years for the Rifle site (Colorado River). The rate of observed uranium decrease was much lower than expected at both sites. While uncertainty remains, a comparison of current understanding suggests that the two sites have common, but also different mechanisms controlling plume persistence. At the Hanford 300 A, the persistent source is adsorbed U(VI) in the vadose zone that is released to the aquifer during spring water table excursions. The release of U(VI) from the vadose zone and its transport within the oxic, coarse-textured aquifer sediments is dominated by kinetically-limited surface complexation. Modeling implies that annual plume discharge volumes to the Columbia River are small (oxidation of naturally reduced, contaminant U(IV) in the saturated zone and a continuous influx of U(VI) from natural, up-gradient sources influence plume persistence. Rate-limited mass transfer and surface complexation also control U(VI) migration velocity in the sub-oxic Rifle groundwater. Flux of U(VI) from the vadose zone at the Rifle site may be locally important, but it is not the dominant process that sustains the plume. A wide range in microbiologic functional diversity exists at both sites. Strains of Geobacter and other metal reducing bacteria are present at low natural abundance that are capable of enzymatic U(VI) reduction in localized zones of accumulated detrital organic carbon or after organic carbon amendment. Major differences between the sites include the geochemical nature of

Stripping of Uranium (IV) from D2EHPA + TBP system with ammonium oxalate and its recovery as uranium peroxide

International Nuclear Information System (INIS)

Singh, D.K.; Singh, H.

2014-01-01

Uranium is an important fissile material for the generation of electricity by nuclear reactors. To obtain uranium as a final product meeting the stringent nuclear specifications, many process steps are involved starting from ore processing to the precipitation of yellow cake. Solvent extraction is one of the process industrially adopted worldwide to achieve such purity of uranium from leach liquor and usually uses amine or organophosphorus types of extractant depending upon the composition of feed material. In solvent extraction technique, stripping is a prominent hydrometallurgical operation which brings the metal values of interest in aqueous solution for further treatment. In the case of uranium, stripping is dependent on its oxidation state. For hexavalent state generally carbonate solutions are used, where as in the case of tetravalent form salt solution such as ammonium oxalate is effective. Use of ammonium oxalate as stripping agent for tetravalent uranium from pyrophosphoric acid has been reported in patent however the details are not disclosed. In the present investigation an effort has been made to investigate the stripping behaviour of uranium from a synthetically loaded synergistic solvent mixture of uranium in tetravalent state

Adsorption of uranium on halloysite

International Nuclear Information System (INIS)

Kilislioglu, A.; Bilgin, B.

2002-01-01

Adsorption of uranium (U(VI)) from aqueous solutions on halloysite type clay was studied as a function of amount of adsorbent, initial concentration and pH. The values of adsorption data were fitted to Freundlich, Langmuir and Dubinin-Radushkevich (D-R) adsorption isotherms. The mean energy of adsorption was calculated as 5.91 kJ/mol from D-R adsorption isotherm. Lagergren and Bangham equation has been used for dynamic modelling of process and the rate constants of adsorption of uranium on halloysite type clay were calculated at 293, 313 and 333 K. In order to explain the mechanism of adsorption reaction, the rate constants were calculated at high and low uranium concentrations. Adsorption reaction was studied at 293, 303, 313, 323 and 333 K for halloysite type clay and also thermodynamic constants have been calculated. The results show that the adsorption reaction was endothermic and more spontaneous at high temperature. (orig.)

Adsorption of uranium on halloysite

Energy Technology Data Exchange (ETDEWEB)

Kilislioglu, A.; Bilgin, B. [Istanbul Univ. (Turkey). Faculty of Engineering

2002-07-01

Adsorption of uranium (U(VI)) from aqueous solutions on halloysite type clay was studied as a function of amount of adsorbent, initial concentration and pH. The values of adsorption data were fitted to Freundlich, Langmuir and Dubinin-Radushkevich (D-R) adsorption isotherms. The mean energy of adsorption was calculated as 5.91 kJ/mol from D-R adsorption isotherm. Lagergren and Bangham equation has been used for dynamic modelling of process and the rate constants of adsorption of uranium on halloysite type clay were calculated at 293, 313 and 333 K. In order to explain the mechanism of adsorption reaction, the rate constants were calculated at high and low uranium concentrations. Adsorption reaction was studied at 293, 303, 313, 323 and 333 K for halloysite type clay and also thermodynamic constants have been calculated. The results show that the adsorption reaction was endothermic and more spontaneous at high temperature. (orig.)

Extractive behavior of U(VI) in the paraffin soluble ionic liquid

International Nuclear Information System (INIS)

Rama, R.; Kumaresan, R.; Venkatesan, K.A.; Antony, M.P.; Vasudeva Rao, P.R.

2013-01-01

An Aliquat-336 based ionic liquid namely, tri-n-octylmethylammonium bis(2-ethylhexyl)phosphate ((A3636) + (DEHP) - ) was prepared and studied for the extraction of U(VI) from nitric acid medium. Since the ionic liquid, (A336) + (DEHP) - , was miscible in n-dodecane (n-DD), the extraction of U(VI) in the solution of tri-n-butylphosphate (TBP) in n-DD, was investigated in the presence of small concentrations of ionic liquid. The distribution ratio of U(VI) in 0.3 M (A336) + (DEHP) - /n-DD decreased with increase in the concentration of nitric acid. The effect of concentration of TBP, ionic liquid nitric acid and nitrate ion on the extraction of U(VI) in ionic liquid medium was studied. The mechanistic aspect of extraction was investigated by the slope analysis of the extraction data. The studies indicated the feasibility of modifying the extractive properties of U(VI) in TBP/n-DD using ionic liquid. (author)

Biomineralization of Uranium by PhoY Phosphatase Activity Aids Cell Survival in Caulobacter crescentus

Energy Technology Data Exchange (ETDEWEB)

Yung, M C [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Jiao, Y [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

2014-07-22

Caulobacter crescentus is known to tolerate high levels of uranium [U(VI)], but its detoxification mechanism is poorly understood. Here we show that C. crescentus is able to facilitate U(VI) biomineralization through the formation of U-P_i precipitates via its native alkaline phosphatase activity. The U-P_i precipitates, deposited on the cell surface in the form of meta-autunite structures, have a lower U/P_i ratio than do chemically produced precipitates. The enzyme that is responsible for the phosphatase activity and thus the biomineralization process is identified as PhoY, a periplasmic alkaline phosphatase with broad substrate specificity. Furthermore, PhoY is shown to confer a survival advantage on C. crescentus toward U(VI) under both growth and nongrowth conditions. Results obtained in this study thus highlight U(VI) biomineralization as a resistance mechanism in microbes, which not only improves our understanding of bacterium-mineral interactions but also aids in defining potential ecological niches for metal-resistant bacteria.

Geochemical control on the reduction of U(VI) to mononuclear U(IV) species in lacustrine sediments

Science.gov (United States)

Stetten, L.; Mangeret, A.; Brest, J.; Seder-Colomina, M.; Le Pape, P.; Ikogou, M.; Zeyen, N.; Thouvenot, A.; Julien, A.; Alcalde, G.; Reyss, J. L.; Bombled, B.; Rabouille, C.; Olivi, L.; Proux, O.; Cazala, C.; Morin, G.

2018-02-01

Contaminated systems in which uranium (U) concentrations slightly exceed the geochemical background are of particular interest to identify natural processes governing U trapping and accumulation in Earth's surface environments. For this purpose, we examined the role of early diagenesis on the evolution of U speciation and mobility in sediments from an artificial lake located downstream from a former mining site. Sediment and pore water chemistry together with U and Fe solid state speciation were analyzed in sediment cores sampled down to 50 cm depth at four locations in the lake. These organic-rich sediments (∼12% organic C) exhibited U concentrations in the 40-80 mg kg-1 range. The sediment columns were anoxic 2-3 mm below the sediment-water interface and pore waters pH was circumneutral. Pore water chemistry profiles showed that organic carbon mineralization was associated with Fe and Mn reduction and was correlated with a decrease in dissolved U concentration with depth. Immobilization of U in the sediment was correlated with the reduction of U(VI) to U(IV) at depth, as shown by U LIII-edge XANES spectroscopic analysis. XANES and EXAFS spectroscopy at the Fe K-edge showed the reduction of structural Fe(III) to Fe(II) in phyllosilicate minerals with depth, coincident with U(VI) to U(IV) reduction. Thermodynamic modeling suggests that Fe(II) could act as a major reducing agent for U(VI) during early diagenesis of these sediments, leading to complete U reduction below ∼30 cm depth. Shell-by-shell and Cauchy-Wavelet analysis of U LIII-EXAFS spectra indicates that U(VI) and U(IV) are mainly present as mononuclear species bound to C, P or Si ligands. Chemical extractions confirmed that ∼60-80% of U was present as non-crystalline species, which emphasizes that such species should be considered when evaluating the fate of U in lacustrine environments and the efficiency of sediment remediation strategies.

Use of combined microscopic and spectroscopic techniques to reveal interactions between uranium and Microbacterium sp. A9, a strain isolated from the Chernobyl exclusion zone

Energy Technology Data Exchange (ETDEWEB)

Theodorakopoulos, Nicolas [CEA, DSV, IBEB, SBVME, LIPM, F-13108 Saint-Paul-lez-Durance (France); CNRS, UMR 7265, F-13108 Saint-Paul-lez-Durance (France); Université d' Aix-Marseille, F-13108 Saint-Paul-lez-Durance (France); IRSN/PRP-ENV/SERIS/L2BT, bat 183, B.P. 3, F-13115 Saint Paul-lez-Durance (France); Chapon, Virginie [CEA, DSV, IBEB, SBVME, LIPM, F-13108 Saint-Paul-lez-Durance (France); CNRS, UMR 7265, F-13108 Saint-Paul-lez-Durance (France); Université d' Aix-Marseille, F-13108 Saint-Paul-lez-Durance (France); Coppin, Fréderic; Floriani, Magali [IRSN/PRP-ENV/SERIS/L2BT, bat 183, B.P. 3, F-13115 Saint Paul-lez-Durance (France); Vercouter, Thomas [CEA, DEN, DANS, DPC SEARS, LANIE, F-91191 Gif-Sur-Yvette Cedex (France); Sergeant, Claire [Univ Bordeaux, CENBG, UMR5797, F-33170 Gradignan (France); CNRS, IN2P3, CENBG, UMR5797, F-33170 Gradignan (France); Camilleri, Virginie [IRSN/PRP-ENV/SERIS/L2BT, bat 183, B.P. 3, F-13115 Saint Paul-lez-Durance (France); Berthomieu, Catherine [CEA, DSV, IBEB, SBVME, LIPM, F-13108 Saint-Paul-lez-Durance (France); CNRS, UMR 7265, F-13108 Saint-Paul-lez-Durance (France); Université d' Aix-Marseille, F-13108 Saint-Paul-lez-Durance (France); Février, Laureline, E-mail: laureline.fevrier@irsn.fr [IRSN/PRP-ENV/SERIS/L2BT, bat 183, B.P. 3, F-13115 Saint Paul-lez-Durance (France)

2015-03-21

Highlights: • Microbacterium sp. A9 develops various detoxification mechanisms. • Microbacterium sp. A9 promotes metal efflux from the cells. • Microbacterium sp. A9 releases phosphate to prevent uranium entrance in the cells. • Microbacterium sp. A9 stores U intracellularly as autunite. - Abstract: Although uranium (U) is naturally found in the environment, soil remediation programs will become increasingly important in light of certain human activities. This work aimed to identify U(VI) detoxification mechanisms employed by a bacteria strain isolated from a Chernobyl soil sample, and to distinguish its active from passive mechanisms of interaction. The ability of the Microbacterium sp. A9 strain to remove U(VI) from aqueous solutions at 4 °C and 25 °C was evaluated, as well as its survival capacity upon U(VI) exposure. The subcellular localisation of U was determined by TEM/EDX microscopy, while functional groups involved in the interaction with U were further evaluated by FTIR; finally, the speciation of U was analysed by TRLFS. We have revealed, for the first time, an active mechanism promoting metal efflux from the cells, during the early steps following U(VI) exposure at 25 °C. The Microbacterium sp. A9 strain also stores U intracellularly, as needle-like structures that have been identified as an autunite group mineral. Taken together, our results demonstrate that this strain exhibits a high U(VI) tolerance based on multiple detoxification mechanisms. These findings support the potential role of the genus Microbacterium in the remediation of aqueous environments contaminated with U(VI) under aerobic conditions.

A Site Wide Perspective on Uranium Geochemistry at the Hanford Site

Energy Technology Data Exchange (ETDEWEB)

Zachara, John M.; Brown, Christopher F.; Christensen, J. N.; Davis, Jim A.; Dresel, P. Evan; Liu, Chongxuan; Kelly, S. D.; McKinley, James P.; Serne, R. Jeffrey; Um, Wooyong

2007-10-26

Uranium (U) is an important risk-driving contaminant at the Hanford Site. Over 200,000 kg have been released to the vadose zone over the course of site operations, and a number of vadose zone and groundwater plumes containing the uranyl cation [UO22+, U(VI)] have been identified. U is recognized to be of moderate-to-high mobility, conditions dependent. The site is currently making decisions on several of these plumes with long-lasting implications, and others are soon to come. Uranium is one of nature’s most intriguing and chemically complex elements. The fate and transport of U(VI) has been studied over the long lifetime of the Hanford Site by various contractors, along with the Pacific Northwest National Laboratory (PNNL) and its collaborators. Significant research has more recently been contributed by the national scientific community with support from the U.S. Department of Energy’s (DOE) Office of Science through its Environmental Remediation Sciences Division (ERSD). This report represents a first attempt to integrate these findings into a cohesive view of the subsurface geochemistry of U at the Hanford Site. The objective is to inform all interested Hanford parties about the in-ground inventory of U and its geochemical behavior. This report also comments on the prospects for the development of a robust generic model to more accurately forecast future U(VI) migration at different Hanford waste sites, along with further research necessary to reach this goal.

Bioremediation of ground water contaminants at a uranium mill tailings site

International Nuclear Information System (INIS)

Barton, L.L.; Nuttall, H.E.; Thomson, B.M.; Lutze, W.

1995-01-01

Ground water contaminated with uranium from milling operations must be remediated to reduce the migration of soluble toxic compounds. At the mill tailings site near Tuba City, Arizona (USA) the approach is to employ bioremediation for in situ immobilization of uranium by bacterial reduction of uranyl, U(VI), compounds to uraninite, U(IV). In this initial phase of remediation, details are provided to indicate the magnitude of the contamination problem and to present preliminary evidence supporting the proposition that bacterial immobilization of uranium is possible. Additionally, consideration is given to contaminating cations and anions that may be at toxic levels in ground water at this uranium mill tailing site and detoxification strategies using bacteria are addressed. A model concept is employed so that results obtained at the Tuba City site could contribute to bioremediation of ground water at other uranium mill tailings sites

Local structure and speciation of uranium in strontium orthosilicate: TRFS and EXAFS studies

International Nuclear Information System (INIS)

Gupta, Santosh K.; Thulasidas, S.K.; Natarajan, V.; Yadav, A.K.; Bhattacharya, D.

2015-01-01

TRFS is used to investigate the valence state and coordination behavior of uranium in strontium orthosilicate. From TRFS measurement it was observed that uranium exists as U(VI) in the form of UO 2 2+ in Sr 2 SiO 4 . Based on life time measurement and EXAFS studies it was inferred that uranyl is stabilized on both 9- and 10- coordinated strontium polyhedra. Majority of uranyl ion occupy relatively asymmetric site in strontium silicate most probably 9-coordinated Sr sites. (author)

Study of uranium oxidation states in geological material.

Science.gov (United States)

Pidchenko, I; Salminen-Paatero, S; Rothe, J; Suksi, J

2013-10-01

A wet chemical method to determine uranium (U) oxidation states in geological material has been developed and tested. The problem faced in oxidation state determinations with wet chemical methods is that U redox state may change when extracted from the sample material, thereby leading to erroneous results. In order to quantify and monitor U redox behavior during the acidic extraction in the procedure, an analysis of added isotopic redox tracers, (236)U(VI) and (232)U(IV), and of variations in natural uranium isotope ratio ((234)U/(238)U) of indigenous U(IV) and U(VI) fractions was performed. Two sample materials with varying redox activity, U bearing rock and U-rich clayey lignite sediment, were used for the tests. The Fe(II)/Fe(III) redox-pair of the mineral phases was postulated as a potentially disturbing redox agent. The impact of Fe(III) on U was studied by reducing Fe(III) with ascorbic acid, which was added to the extraction solution. We observed that ascorbic acid protected most of the U from oxidation. The measured (234)U/(238)U ratio in U(IV) and U(VI) fractions in the sediment samples provided a unique tool to quantify U oxidation caused by Fe(III). Annealing (sample heating) to temperatures above 500 °C was supposed to heal ionizing radiation induced defects in the material that can disturb U redox state during extraction. Good agreement between two independent methods was obtained for DL-1a material: an average 38% of U(IV) determined by redox tracer corrected wet chemistry and 45% for XANES. Copyright © 2013 Elsevier Ltd. All rights reserved.

Effect of Salicylic and Picolinic Acids on the Adsorption of U(VI) onto Oxides

International Nuclear Information System (INIS)

Park, Kyoung Kyun; Jung, Euo Chang; Cho, Hye Ryun; Song, Kyu Seok

2009-01-01

The effect of organic acids on the adsorption of U(VI) onto oxide surfaces (TiO 2 (anatase), SiO 2 (amorphous) and Al 2 O-3(amorphous)) has been investigated. Two different organic acids, salicylic and picolinic acids, were used. Changes of adsorption ratio of U(VI), which depend on the existence of organic acids in a sample, were measured as a function of pH. Quantities of adsorbed organic acids, which depend on the existence of U(VI) in a sample, were also measured as a function of pH. It is confirmed that the soluble complex formation of U(VI) with organic acids can deteriorate the adsorption of U(VI) onto TiO 2 surface. It is noteworthy that salicylic acid does not affect the adsorption of U(VI) onto SiO 2 surface, however, picolinic acid enhances the adsorption of U(VI) onto SiO 2 surface. The latter effect can be understood by considering the formation of a ternary surface complex on SiO 2 surface, which was confirmed by the co-adsorption of picolinic acid with U(VI) and the change in a fluorescence spectra of U(VI) on surface, In the case of Al 2 O-3, organic acids themselves were largely adsorbed onto a surface without deteriorating the adsorption of U(VI). This would support the possibility of a ternary surface complex formation on the Al 2 O-3 surface, and an additional spectroscopic study is required.

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

Preconcentration of trace uranium from seawater with solid phase extraction followed by differential pulse polarographic determination in chloroform eluate

International Nuclear Information System (INIS)

Dojozan, Dj.; Pournaghi-Azar, M.H.; Toutounchi-Asr, J.

1998-01-01

In the present study, an effective method is presented for the separation and preconcentration of uranium (VI) by solid phase extraction (SPE). For this purpose, U(VI) oxinate is formed by the reaction of U(VI) with 8-hydroxyquinoline and adsorbed onto the octylsilane (C-8) SPE cartridge. The analyte is completely eluted with chloroform and determined by differential pulse polarography. The SPE conditions were optimized by evaluating the effective factors such as pH, oxine concentration, type and concentration of buffer and masking agent. By the proposed method a preconcentration factor of more than 100 was achieved. The average recovery of uranium (VI) oxinate (0.1 mg l -1 ) was 99.8%. The relative standard deviation was 1.6% for seven replicate determinations of uranyl ion in the solution with a concentration 20 μg l -1 . Some concomitant ions such as Ca +2 , Mg +2 and Fe +3 which interfere in extraction or determination process of uranium were masked with EDTA in aqueous phase during the extraction process. The proposed method was successfully used for the determination of uranium in Caspian Sea and Persian Gulf water samples

Comparison of U(VI) adsorption onto nanoscale zero-valent iron and red soil in the presence of U(VI)–CO{sub 3}/Ca–U(VI)–CO{sub 3} complexes

Energy Technology Data Exchange (ETDEWEB)

Zhang, Zhibin [Key Laboratory of Radioactive Geology and Exploration Technology Fundamental Science for National Defense, East China Institute of Technology, Nanchang 330013 (China); State Key Laboratory Breeding Base of Nuclear Resources and Environment (East China Institute of Technology), Ministry of Education, Nanchang 330013 (China); Chemistry, Biological and Materials Sciences Department, East China Institute of Technology, Nanchang 330013 (China); Liu, Jun [State Key Laboratory Breeding Base of Nuclear Resources and Environment (East China Institute of Technology), Ministry of Education, Nanchang 330013 (China); Cao, Xiaohong, E-mail: xhcao@ecit.cn [Key Laboratory of Radioactive Geology and Exploration Technology Fundamental Science for National Defense, East China Institute of Technology, Nanchang 330013 (China); State Key Laboratory Breeding Base of Nuclear Resources and Environment (East China Institute of Technology), Ministry of Education, Nanchang 330013 (China); Chemistry, Biological and Materials Sciences Department, East China Institute of Technology, Nanchang 330013 (China); Luo, Xuanping [Chemistry, Biological and Materials Sciences Department, East China Institute of Technology, Nanchang 330013 (China); Hua, Rong; Liu, Yan [Key Laboratory of Radioactive Geology and Exploration Technology Fundamental Science for National Defense, East China Institute of Technology, Nanchang 330013 (China); State Key Laboratory Breeding Base of Nuclear Resources and Environment (East China Institute of Technology), Ministry of Education, Nanchang 330013 (China); Chemistry, Biological and Materials Sciences Department, East China Institute of Technology, Nanchang 330013 (China); Yu, Xiaofeng; He, Likai [Chemistry, Biological and Materials Sciences Department, East China Institute of Technology, Nanchang 330013 (China); and others

2015-12-30

Highlights: • NZVI can be used for adsorbing U(VI)–CO{sub 3} complexes. • Use of NZVI is feasible for remediation of uranium-contaminated soils. • The mechanism of U(VI)–CO{sub 3} complexes adsorbing onto NZVI has been explained. - Abstract: The influence of U(VI)–CO{sub 3} and Ca–U(VI)–CO{sub 3} complexes on U(VI) adsorption onto red soil and nanoscale zero-valent iron (NZVI) was investigated using batch adsorption and fixed-bed column experiments to simulate the feasibility of NZVI as the reactive medium in permeable- reactive barriers (PRB) for in situ remediation of uranium-contaminated red soils. The adsorption capacity (q{sub e}) and distribution constant (K{sub d}) of NZVI and red soil decreased with increasing pH, dissolved carbonate and calcium concentrations, but the q{sub e} and K{sub d} values of NZVI were 5–10 times higher than those of red soil. The breakthrough pore volume (PV) values increased with the decrease of pH, dissolved carbonate and calcium concentration; however, the breakthrough PV values of the PRB column filled with 5% NZVI were 2.0–3.5 times higher than the 100% red soil column. The U(VI)–CO{sub 3} complexes adsorbed onto the surface of red soil/NZVI (≡SOH) to form SO–UO{sub 2}CO{sub 3}{sup −} or SO–UO{sub 2} (CO{sub 3}){sub 2}{sup 3−}. XPS and XRD analysis further confirmed the reduction of U(VI) to U(IV) and the formation of FeOOH on NZVI surfaces. The findings of this study are significant to the remediation of uranium-contaminated red soils and the consideration of practical U(VI) species in the natural environment.

Integrative analysis of Geobacter spp. and sulfate-reducing bacteria during uranium bioremediation

Directory of Open Access Journals (Sweden)

D. Lovley

2012-03-01

Full Text Available Enhancing microbial U(VI reduction with the addition of organic electron donors is a promising strategy for immobilizing uranium in contaminated groundwaters, but has yet to be optimized because of a poor understanding of the factors controlling the growth of various microbial communities during bioremediation. In previous field trials in which acetate was added to the subsurface, there were two distinct phases: an initial phase in which acetate-oxidizing, U(VI-reducing Geobacter predominated and U(VI was effectively reduced and a second phase in which acetate-oxidizing sulfate reducing bacteria (SRB predominated and U(VI reduction was poor. The interaction of Geobacter and SRB was investigated both in sediment incubations that mimicked in situ bioremediation and with in silico metabolic modeling. In sediment incubations, Geobacter grew quickly but then declined in numbers as the microbially reducible Fe(III was depleted whereas the SRB grow more slowly and reached dominance after 30–40 days. Modeling predicted a similar outcome. Additional modeling in which the relative initial percentages of the Geobacter and SRB were varied indicated that there was little to no competitive interaction between Geobacter and SRB when acetate was abundant. Further simulations suggested that the addition of Fe(III would revive the Geobacter, but have little to no effect on the SRB. This result was confirmed experimentally. The results demonstrate that it is possible to predict the impact of amendments on important components of the subsurface microbial community during groundwater bioremediation. The finding that Fe(III availability, rather than competition with SRB, is the key factor limiting the activity of Geobacter during in situ uranium bioremediation will aid in the design of improved uranium bioremediation strategies.

Sequential potentiometric determination of uranium and plutonium in a single aliquot

International Nuclear Information System (INIS)

Rao, V.K.; Charyulu, M.M.; Natarajan, P.R.

1983-01-01

A method is reported for sequential potentiometric determination of uranium and plutonium present is an aliquot. Plutonium is first determined by oxidizing it to the hexavalent state with perchloric acid followed by iron(II) reduction and titration of excess ferrous iron with chromium(VI). Uranium is subsequently determined by reduction to the quadrivalent state using titanium(III) and titration with vanadium(V). The interference of plutonium and iron(II) is eliminated by the addition of a mixture containing sulfamic acid, nitric acid, and molybdenum(VI). The results of the analysis of mixture containing 3-5 mg quantities of uranium and plutonium are reliable with errors less than 0.3% and 0.2%, respectively. The application of the method for the analysis of mixtures containing various amounts of uranium and plutonium has been examined. (author)

Investigation on Microbial Dissolution of Uranium (VI) from Autunite Mineral - 13421

International Nuclear Information System (INIS)

Sepulveda, Paola; Katsenovich, Yelena; Lagos, Leonel

2013-01-01

Precipitating autunite minerals by polyphosphate injection was identified as a feasible remediation strategy for sequestering uranium in contaminated groundwater and soil in situ at the Hanford Site. Autunite stability under vadose and saturated zone environmental conditions can help to determine the long-term effectiveness of this remediation strategy. The Arthrobacter bacteria are one of the most common groups in soils and are found in large numbers in Hanford soil as well as other subsurface environments contaminated with radionuclides. Ubiquitous in subsurface microbial communities, these bacteria can play a significant role in the dissolution of minerals and the formation of secondary minerals. The main objective of this investigation was to study the bacterial interactions under oxidizing conditions with uranium (VI); study the potential role of bicarbonate, which is an integral complexing ligand for U(VI) and a major ion in groundwater compositions; and present data from autunite dissolution experiments using Arthrobacter strain G968, a less U(VI)-tolerant strain. Sterile 100 mL glass mixed reactors served as the major bioreactor for initial experimentation. These autunite-containing bioreactors were injected with bacterial cells after the autunite equilibrated with the media solution amended with 0 mM, 3 mM 5 mM and 10 mM concentrations of bicarbonate. G968 Arthrobacter cells in the amount of 10 6 cells/mL were injected into the reactors after 27 days, giving time for the autunite to reach steady state. Abiotic non-carbonate controls were kept without bacterial inoculation to provide a control for the biotic samples. Samples of the solution were analyzed for dissolved U(VI) by means of kinetic phosphorescence analyzer KPA-11 (Chemcheck Instruments, Richland, WA). Analysis showed that as [HCO 3 - ] increases, a diminishing trend on the effect of bacteria on autunite leaching is observed. Viability of cells was conducted after 24 hours of cell incubation with

Investigation on Microbial Dissolution of Uranium (VI) from Autunite Mineral - 13421

Energy Technology Data Exchange (ETDEWEB)

Sepulveda, Paola; Katsenovich, Yelena; Lagos, Leonel [Applied Research Center, Florida International University. 10555 West Flagler St. Suite 2100, Miami Fl 33175 (United States)

2013-07-01

Precipitating autunite minerals by polyphosphate injection was identified as a feasible remediation strategy for sequestering uranium in contaminated groundwater and soil in situ at the Hanford Site. Autunite stability under vadose and saturated zone environmental conditions can help to determine the long-term effectiveness of this remediation strategy. The Arthrobacter bacteria are one of the most common groups in soils and are found in large numbers in Hanford soil as well as other subsurface environments contaminated with radionuclides. Ubiquitous in subsurface microbial communities, these bacteria can play a significant role in the dissolution of minerals and the formation of secondary minerals. The main objective of this investigation was to study the bacterial interactions under oxidizing conditions with uranium (VI); study the potential role of bicarbonate, which is an integral complexing ligand for U(VI) and a major ion in groundwater compositions; and present data from autunite dissolution experiments using Arthrobacter strain G968, a less U(VI)-tolerant strain. Sterile 100 mL glass mixed reactors served as the major bioreactor for initial experimentation. These autunite-containing bioreactors were injected with bacterial cells after the autunite equilibrated with the media solution amended with 0 mM, 3 mM 5 mM and 10 mM concentrations of bicarbonate. G968 Arthrobacter cells in the amount of 10{sup 6} cells/mL were injected into the reactors after 27 days, giving time for the autunite to reach steady state. Abiotic non-carbonate controls were kept without bacterial inoculation to provide a control for the biotic samples. Samples of the solution were analyzed for dissolved U(VI) by means of kinetic phosphorescence analyzer KPA-11 (Chemcheck Instruments, Richland, WA). Analysis showed that as [HCO{sub 3}{sup -}] increases, a diminishing trend on the effect of bacteria on autunite leaching is observed. Viability of cells was conducted after 24 hours of cell

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

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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

Hexavalent Chromium Compounds

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Learn about chromium, exposure to which can increase your risk of lung cancer and cancer of the paranasal sinuses and nasal cavity. Hexavalent chromium compounds have been used as corrosion inhibitors in a wide variety of products and processes.

Carbonate effects and pH-dependence of uranium sorption onto bacteriogenic iron oxides: Kinetic and equilibrium studies

International Nuclear Information System (INIS)

Katsoyiannis, Ioannis A.

2007-01-01

The removal of U(VI) from groundwaters by adsorption onto bacteriogenic iron oxides (BIOS) has been investigated under batch mode. The adsorbent dosage, the uranium concentration, the concentration of carbonate and the use of a real groundwater spiked with uranium comprised the examined parameters. In addition, the effect of pH was examined in two different water matrixes, i.e., in distilled water and in real groundwater. Equilibrium studies were carried out to determine the maximum adsorption capacity of BIOS and the data correlated well with the Langmuir and Freundlich models. The presence of carbonate affected adversely the adsorption of U(VI) onto BIOS. The maximum adsorption capacity of BIOS was 9.25 mg g -1 at 0.1 mM carbonate concentration and decreased to 6.93 mg g -1 at 0.5 mM carbonate concentration, whereas at carbonate concentration of 2 mM practically no adsorption occurred. The data were further analyzed using the pseudo-second order kinetic equation, which fitted best the experimental results. The initial adsorption rate (h) was found to increase with decreasing the concentration of carbonate in all cases. When experiments were accomplished in the absence of carbonate, the pH values did not have an effect on the adsorption of U(VI). However, the extent of U(VI) adsorption was strongly pH-dependent when the experiments were carried out in the real groundwater. The maximum adsorption capacity increased sharply as the pH decreased and optimum removal was obtained in the pH range 3.2-4.0, thus bacteriogenic iron oxides can found application in the removal of U(VI) by adsorption from low pH or low carbonate waters

The unexpected teratogenicity of RXR antagonist UVI3003 via activation of PPARγ in Xenopus tropicalis

International Nuclear Information System (INIS)

Zhu, Jingmin; Janesick, Amanda; Wu, Lijiao; Hu, Lingling; Tang, Weiyi; Blumberg, Bruce; Shi, Huahong

2017-01-01

The RXR agonist (triphenyltin, TPT) and the RXR antagonist (UVI3003) both show teratogenicity and, unexpectedly, induce similar malformations in Xenopus tropicalis embryos. In the present study, we exposed X. tropicalis embryos to UVI3003 in seven specific developmental windows and identified changes in gene expression. We further measured the ability of UVI3003 to activate Xenopus RXRα (xRXRα) and PPARγ (xPPARγ) in vitro and in vivo. We found that UVI3003 activated xPPARγ either in Cos7 cells (in vitro) or Xenopus embryos (in vivo). UVI3003 did not significantly activate human or mouse PPARγ in vitro; therefore, the activation of Xenopus PPARγ by UVI3003 is novel. The ability of UVI3003 to activate xPPARγ explains why UVI3003 and TPT yield similar phenotypes in Xenopus embryos. Our results indicate that activating PPARγ leads to teratogenic effects in Xenopus embryos. More generally, we infer that chemicals known to specifically modulate mammalian nuclear hormone receptors cannot be assumed to have the same activity in non-mammalian species, such as Xenopus. Rather they must be tested for activity and specificity on receptors of the species in question to avoid making inappropriate conclusions. - Highlights: • UVI3003 is a RXRs antagonist and shows teratogenicity to Xenopus embryos. • UVI3003 activated xPPARγ either in Cos7 cells or Xenopus embryos. • UVI3003 did not activate human or mouse PPARγ in Cos7 cells. • Activating PPARγ leads to teratogenic effects in Xenopus embryos.

Uranium 234U and 238U isotopes in the southern Baltic environment

International Nuclear Information System (INIS)

Borylo, A.; Skwarzec, B.

2002-01-01

The concentration and distribution of uranium in water and sediment of selected basins of the southern Baltic Sea have been analysed. It was observed that the concentration of uranium in sediments increases with core depth. This is probably connected to diffusion processes from sediments to water through interstitial water where uranium concentration is much higher than in bottom water. The measurements of 234 U/ 238 U activity ratios indicate that sedimentation of terrigenic material and transport through Vistula river are the major sources of uranium in sediments of the southern Baltic Sea. Estimation of the 234 U/ 238 U ratios in reduction areas of the Baltic Deep and the Bornholm Deep suggest that the processes of reduction of U(VI) to U(IV) and of removal of authogenic uranium from seawater to sediments do not play major roles in the Gdansk Deep. (author)

An experimental study on the sorption of U(VI) onto granite

International Nuclear Information System (INIS)

Baik, Min Hoon; Hahn, Pil Soo

2002-01-01

The sorption of U(VI) on a domestic granite is studied as a function of experimental conditions such as contact time, solution-solid ratio, ionic strength, and pH using a batch procedure. The distribution coefficients, K d 's, of U(VI) are about 1-100mL/g depending on the experimental conditions. The sorption of U(VI) onto granite particles is greatly dependent upon the contact time, solution-solid ratio, and pH, but very little is dependent on the ionic strength. It is noticed that an U(VI)-carbonato ternary surface complex can be formed in the neutral range of pH. In the alkaline range of pH above 7, U(VI) sorption onto granite particles is greatly decreased due to the formation of anionic U(VI)-carbonato aqueous complexes

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.

Uranium-series disequilibria as a means to study recent migration of uranium in a sandstone-hosted uranium deposit, NW China

International Nuclear Information System (INIS)

Min Maozhong; Peng Xinjian; Wang Jinping; Osmond, J.K.

2005-01-01

Uranium concentration and alpha specific activities of uranium decay series nuclides 234 U, 238 U, 230 Th, 232 Th and 226 Ra were measured for 16 oxidized host sandstone samples, 36 oxic-anoxic (mineralized) sandstone samples and three unaltered primary sandstone samples collected from the Shihongtan deposit. The results show that most of the ores and host sandstones have close to secular equilibrium alpha activity ratios for 234 U/ 238 U, 230 Th/ 238 U, 230 Th/ 234 U and 226 Ra/ 230 Th, indicating that intensive groundwater-rock/ore interaction and uranium migration have not taken place in the deposit during the last 1.0 Ma. However, some of the old uranium ore bodies have locally undergone leaching in the oxidizing environment during the past 300 ka to 1.0 Ma or to the present, and a number of new U ore bodies have grown in the oxic-anoxic transition (mineralized) subzone during the past 1.0 Ma. Locally, uranium leaching has taken place during the past 300 ka to 1.0 Ma, and perhaps is still going on now in some sandstones of the oxidizing subzone. However, uranium accumulation has locally occurred in some sandstones of the oxidizing environment during the past 1 ka to 1.0 Ma, which may be attributed to adsorption of U(VI) by clays contained in oxidized sandstones. A recent accumulation of uranium has locally taken place within the unaltered sandstones of the primary subzone close to the oxic-anoxic transition environment during the past 300 ka to 1.0 Ma. Results from the present study also indicate that uranium-series disequilibrium is an important tool to trace recent migration of uranium occurring in sandstone-hosted U deposits during the past 1.0 Ma and to distinguish the oxidation-reduction boundary

Effect of selected ligands on the U(VI) immobilization by zerovalent iron

International Nuclear Information System (INIS)

Noubactep, C.

2006-01-01

The effect of Cl - , CO 3 2- , EDTA, NO 2 - , NO 3 - , PO 4 3- , SO 4 2- , and humic substances (HS) on the U(VI) co-precipitation from aqueous solutions by zerovalent iron (ZVI) was investigated in the neutral pH range.Batch experiments without shaking were conducted for 14 days mostly with five different ZVI materials (15 g/l), selected ligands (10mM) and an U(VI) solution (20 mg/l, 0.084mM). Apart from Cl - , all tested ligands induced a decrease of U(VI) coprecipitation. This decrease is attributed to the surface adsorption and complexation of the ligands at the reactive sites on the surface of ZVI and their corrosion products. The decrease of U(VI) removal was not uniform with the five ZVI materials. Generally, groundwater with elevated EDTA concentration could not be remediated with the ZVI barrier technology. The response of the system on the pre-treating by two ZVI materials in 250mM HCl indicated that in situ generated corrosion products favor an irreversible U(VI) uptake. Thus for the long term performance of ZVI barrier, the iron dissolution should continue in such a way that fresh iron oxide be always available for U(VI) coprecipitation. (author)

Spectroscopic characterization of uranium in evaporation basin sediments

Science.gov (United States)

Duff, M. C.; Morris, D. E.; Hunter, D. B.; Bertsch, P. M.

2000-05-01

Evaporation ponds in the San Joaquin Valley (SJV), CA, used for the containment of irrigation drainage waters contain elevated levels of uranium (U) resulting from the extensive leaching by carbonate-rich irrigation waters of the local agricultural soils that contain low levels of naturally-occurring U. The SJV ponds are subjected to changes in redox chemistry with cycles of drying and flooding. Our past studies have shown that U in the SJV Pond 14 surface sediments is present as mostly the oxidized and soluble form, U(VI). However, we were uncertain whether the U in the soil was only present as a U oxide of mixed stoichiometry, such as U 3O 8(s) (pitchblende) or other species. Here we present characterization information, which includes wet chemical and in situ spectroscopic techniques (X-ray absorption near-edge structure (XANES) and low temperature time-resolved luminescence spectroscopies) for samples from two SJV Pond sediments. Surface sediments from SJV Pond 16 were characterized for average oxidation state of U with XANES spectroscopy. The fraction of U(VI) to U(IV) in the Pond 16 sediments decreased with depth with U(IV) being the dominant oxidation state in the 5 cm to 15 cm depth. Two luminescent U(VI) species were identified in the surface sediments from Pond 14; a U(VI)-tricarbonate phase and another phase likely comprised of U(VI)-hydroxide or hydroxycarbonate. The luminescent U(VI) population in the Pond 16 sediments is dominated by species with comparable spectral characteristics to the U(VI)-hydroxide or hydroxycarbonate species found in the Pond 14 sediments. The luminescence spectroscopic results were complemented by wet chemical U leaching methods, which involved the use of carbonate and sulfuric acid solutions and oxidizing solutions of peroxide, hypochlorite and Mn(IV). Leaching was shown to decrease the total U concentration in the sediments in all cases. However, results from luminescence studies of the residual fraction in the leached

Application of NKF-6 zeolite for the removal of U(VI) from aqueous solution

International Nuclear Information System (INIS)

Pengfei Zong; Hai Wang; Hui Pan; Yaolin Zhao; Chaohui He

2013-01-01

To better understand the application of NKF-6 zeolite as an adsorbent for the removal of U(VI) from radionuclides and heavy metal ions polluted water, herein, NKF-6 zeolite was employed to remove U(VI) at different experimental conditions. The influence of solid/liquid ratio, contact time, pH, ionic strength, humic substances and temperature on sorption of U(VI) to NKF-6 zeolite was investigated using batch technique under ambient conditions. The experimental results demonstrated that the sorption of U(VI) on NKF-6 zeolite was strongly dependent on pH. The sorption property of U(VI) was influenced by ionic strength at pH 7.0. The presence of fulvic acid or humic acid promoted the sorption of U(VI) on NKF-6 zeolite at low pH values while restrained the sorption at high pH values. The thermodynamic parameters (i.e., ΔS 0 , ΔH 0 , and ΔG 0 ) calculated from the temperature-dependent sorption isotherms demonstrated that the sorption process of U(VI) on NKF-6 zeolite was endothermic and spontaneous. At low pH values, the sorption of U(VI) was dominated by outer-sphere surface complexation and ion exchange with Na + /H + on NKF-6 zeolite surfaces, while inner-sphere surface complexation was the main sorption mechanism at high pH values. From the experimental results, one can conclude that NKF-6 zeolite can be used as a potential adsorbent for the preconcentration and solidification of U(VI) from large volumes of aqueous solutions. (author)

Comparison of heavy metals and uranium removal using adsorbent in soil

Science.gov (United States)

Choi, Jaeyoung; Yun, Hunsik

2017-04-01

This study investigates heavy metals (As, Ni, Zn, Cd, and Pb) and uranium removal onto geomaterials (limestone, black shale, and concrete) and biosorbents (Pseudomonas putida and starfish) from waste in soil. Geomaterials or biosorbents with a high capacity for heavy metals and uranium can be obtained and employed of with little cost. For investigating the neutralization capacity, the change in pH, Eh, and EC as a function of time was quantified. The adsorption of heavy metals and uranium by the samples was influenced by pH, and increased with increasing heavy metals and uranium concentrations. Dead cells adsorbed the largest quantity of all heavy metals than lother sorbents. The adsorption capacity followed the order: U(VI) > Pb > Cd > Ni. The results also suggest that bacterial membrane cells can be used successfully in the treatment of high strength metal-contaminated soil.

Uranium in bone: metabolic and autoradiographic studies in the rat

International Nuclear Information System (INIS)

Priest, N.D.; Haines, J.W.; Howells, G.R.; Green, D.

1982-01-01

The distribution and retention of intravenously injected hexavalent uranium-233 in the skeleton of the female rat has been investigated using a variety of autoradiographic and radiochemical techniques. These showed that approximately one third of the injected uranium is deposited in the skeleton where it is retained with an initial biological half-time of approximately 40 days. The studies also showed that: 1) Uranium is initially deposited on to all types of bone surface, but preferentially on to those that are accreting. 2) Uranium is deposited in the calcifying zones of skeletal cartilage. 3) Bone accretion results in the burial of surface deposits of uranium. 4) Bone resorption causes the removal of uranium from surfaces. 5) Resorbed uranium is not retained by osteoclasts and macrophages in the bone marrow. 6) Uranium removed from bone surfaces enters the bloodstream where most is either redeposited in bone or excreted via the kidneys. 7) The recycling of resorbed uranium within the skeleton tends to produce a uniform level of uranium contamination throughout mineralized bone. These results are taken to indicate that uranium deposition in bone shares characteristics in common with both the 'volume-seeking radionuclides' typified by the alkaline earth elements and with the 'bone surface-seeking radionuclides' typified by plutonium. (author)

Uranium in bone: metabolic and autoradiographic studies in the rat.

Science.gov (United States)

Priest, N D; Howells, G R; Green, D; Haines, J W

1982-03-01

The distribution and retention of intravenously injected hexavalent uranium-233 in the skeleton of the female rat has been investigated using a variety of autoradiographic and radiochemical techniques. These showed that approximately one third of the injected uranium is deposited in the skeleton where it is retained with an initial biological half-time of approximately 40 days. The studies also showed that: 1 Uranium is initially deposited onto all types of bone surface, but preferentially onto those that are accreting. 2 Uranium is deposited in the calcifying zones of skeletal cartilage. 3 Bone accretion results in the burial of surface deposits of uranium. 4 Bone resorption causes the removal of uranium from surfaces. 5 Resorbed uranium is not retained by osteoclasts and macrophages in the bone marrow. 6 Uranium removed from bone surfaces enters the bloodstream where most is either redeposited in bone or excreted via the kidneys. 7 The recycling of resorbed uranium within the skeleton tends to produce a uniform level of uranium contamination throughout mineralized bone. These results are taken to indicate that uranium deposition in bone shares characteristics in common with both the 'volume-seeking radionuclides' typified by the alkaline earth elements and with the 'bone surface-seeking radionuclides' typified by plutonium.

Pre-concentration and quantification of uranium from lean feed by stir adsorptive membranes

International Nuclear Information System (INIS)

Das, Sadananda; Pandey, A.K.; Manchanda, V.K.; Athawale, A.A.

2010-01-01

Uranium recovery from bio-aggressive but lean feed like seawater is a challenging problem as it requires in situ preconcentration of uranium in presence of huge excess of competing ions with fast sorption kinetics. In our laboratory, widely used amidoxime membrane (AO-membrane) was evaluated for uranium sorption under seawater conditions. This study indicated that AO-membrane was inherently slow because of the complexation chemistry involved in transfer of U(VI) from (UO 2 (CO 3 ) 3 ) 4- to AO sites in membrane. In order to search better options, several chemical compositions of membrane were scanned for their efficacy for uranium preconcentration from seawater, and concluded that EGMP-membrane offers several advantages over AO-membrane. In this paper, the comparison of EGMP-membrane with AO-membrane for uranium sorption under seawater conditions has been reviewed. (author)

Separation and concentration of uranium by extraction chromatography : U(VI) - H3PO4 system

International Nuclear Information System (INIS)

Nobre, J.S.M.

1981-01-01

The feasibility of using the extraction chromatographic technique as a way to recover uranium from phosphatic rocks evaluated. The behaviour of uranium from raw phsophoric acid solutions in chromatographic systems using the mixture di(2-ethylhexyl) orthophosphoric acid (D2EHPA) - tributyl phosphate (TBP) as the stationary phase was studied. Materials as alumina, activated carbon and the macroporous resins XAD-4 and XAD-7 were used as supports for organic stationary phase. The best results were obtained with poliacrilic polymer XAD-7, due to its excellent chromatographic properties and efficient organic phase retention. Uranium was quantitatively retained by D2EHPA-TBP-XAD-7 columns from synthetic phosphoric acid solutions with typical composition of phosphatic acid liquors. The elution of uranium from this system was also studied, and the best results were obtained with phosphoric acid solutions. This chromatographic column presented a high stability, not changing their properties even after more than twenty cycles, including the conditioning, sorption, wasking and elution steps. Uranium determinations were perfpormed by indirect titration with potassium dichromate and by molecular absorption spectrophotometry with hydrogen peroxide- carbonate. A new and more sensitive method for uranium determination in phosphoric medium, which might be applied to acid liquors of phosphatic ores, was developed. An extraction-photometric method was used, with Arsenazo III (1,8-dihydroxynaphtalene-3,6-disulphonic acid-2,7-bis(azo-2)-phenylarsonic acid) as the reagent for uranium. (Author) [pt

Hexavalent Chromium IV-Free Primer Development

Science.gov (United States)

Alldredge, Michael J.; Buck, Amy L.

2015-01-01

Primer materials provide corrosion protection for metal parts as well as an increased adhesion between metallic substrates and thermal protection systems (TPSs). Current primers for use in cryogenic applications contain hexavalent chromium. This hexavalent chromium provides excellent corrosion protection even in a cryogenic environment, but it is a carcinogen that requires special equipment and waste control procedures to use. The hazardous nature of hexavalent chromium makes it an obsolescence risk in the future. This study included two phases of evaluation. Thirteen primers were initially identified as candidates and twelve of those primers were tested in phase 1. Four of the best performing candidates from phase 1 continued into phase 2 testing. Phase 1 testing consisted mostly of liquid constituent and physical property testing. Cryoflex and salt fog testing were included in phase 1 because of their importance to the overall success of a candidate material. Phase 2 consisted of physical, thermal, and mechanical properties for nominally processed and fabricated specimens.

Study of polyethyleneimine- and amidoxime-functionalized hybrid biomass of Spirulina (Arthrospira) platensis for adsorption of uranium (VI) ion.

Science.gov (United States)

Bayramoglu, Gulay; Akbulut, Aydin; Arica, M Yakup

2015-11-01

This study investigates the potential application of the polyethyleneimine- (PEI) and amidoxime-modified Spirulina (Arthrospira) platensis biomasses for the removal of uranium ion in batch mode using the native biomass as a control system. The uranium ion adsorption was also characterized by attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectra, zeta potential analysis, and surface area measurement studies. The effects of pH, biomass amount, contact time, initial uranium ion concentration, and ionic strength were evaluated by using native and modified algal biomass preparations. The uranium ion removal was rapid, with more than 70% of total adsorption taking place in 40 min, and equilibrium was established within 60 min. From the experimental data, it was found that the amount of adsorption uranium ion on the algal preparations decreased in the following series: amidoxime-modified algal biomass > PEI-modified algal biomass > native algal biomass. Maximum adsorption capacities of amidoxime- and PEI-modified, and native algal biomasses were found to be 366.8, 279.5, and 194.6 mg/g, respectively, in batchwise studies. The adsorption rate of U(VI) ion by amidoxime-modified algal biomass was higher than those of the native and PEI-modified counterparts. The adsorption processes on all the algal biomass preparations followed by the Dubinin-Radushkevitch (D-R) and Temkin isotherms and pseudo-second-order kinetic models. The thermodynamic parameters were determined at four different temperatures (i.e., 15, 25, 35, and 45 °C) using the thermodynamics constant of the Temkin isotherm model. The ΔH° and ΔG° values of U(VI) ion adsorption on algal preparations show endothermic heat of adsorption; higher temperatures favor the process. The native and modified algal biomass preparations were regenerated using 10 mM HNO3. These results show that amidoxime-modified algal biomass can be a potential candidate for effective removal of U(VI) ion from

Hexavalent and trivalent chromium in leather: What should be done?

Science.gov (United States)

Moretto, Angelo

2015-11-01

Trivalent chromium compounds are used for leather tanning, and chromium may be released during use of leather goods. In certain instances, small amounts of hexavalent chromium can be formed and released. Both trivalent and hexavalent chromium can elicit allergic skin reaction in chromium sensitised subjects, the latter being significantly more potent. Induction of sensitisation only occurs after exposure to hexavalent chromium. A minority of subjects are sensitised to chromium, and in a fraction of these subjects allergic skin reaction have been described after wearing leather shoes or, less frequently, other leather goods. The evidence that in all these cases the reaction is related to hexavalent chromium is not always strong. The content of hexavalent chromium in leather is regulated in European Union, but rate of release rather than content is relevant for allergic skin reaction. The role of trivalent chromium appear much less relevant if at all. Modern tanning procedure do not pose significant risk due to either hexavalent or trivalent chromium. Dismissing bad quality and worn-off leather goods is relevant in reducing or eliminating the skin reaction. It should also be pointed out that shoe components or substances other than chromium in leather may cause allergic/irritative skin reactions. Copyright © 2015 Elsevier Inc. All rights reserved.

Polarographic determination of uranium dioxide stoichiometry; La determination polarographique de la stoechiometrie du dioxyde d'uranium

Energy Technology Data Exchange (ETDEWEB)

Viguie, J.; Uny, G. [Commissariat a l' Energie Atomique, Centre d' Etudes Nucleaires de Grenoble, 38 (France)

1966-10-01

The method described allows the determination of small deviations from stoichiometry for uranium dioxide. It was applied to the study of surface oxidation of bulk samples. The sample is dissolved in phosphoric acid under an argon atmosphere; U(VI) is determined by polarography in PO{sub 4}H{sub 3} 4.5 N - H{sub 2}SO{sub 4} 4 N. U(IV) is determined by potentiometry. The detection limit is UO{sub 2,0002}. The accuracy for a single determination at the 95% confidence level is {+-}20 per cent for samples with composition included between UO{sub 2,001} and UO{sub 2,01}. (authors) [French] La methode decrite permet de determiner les faibles ecarts a la stoechiometrie du dioxyde d'uranium. Elle a ete appliquee a l'etude de l'oxydation superficielle des echantillons. La mise en solution s'effectue dans l'acide phosphorique concentre sous atmosphere d'argon; U(VI) est dose par polarographie dans le milieu PO{sub 4}H{sub 3} 4,5 N et H{sub 2}SO{sub 4} 4 N; U(IV) est dose par potentiometrie. La limite de detection est UO{sub 2,0002}. La precision obtenue pour une determination au taux de certitude 0,95 est de l'ordre de 20 pour cent pour des echantillons dont la teneur est comprise entre UO{sub 2,001} et UO{sub 2,01}. (auteurs)

76 FR 71926 - Defense Federal Acquisition Regulation Supplement: Applicability of Hexavalent Chromium Policy to...

Science.gov (United States)

2011-11-21

... 0750-AH39 Defense Federal Acquisition Regulation Supplement: Applicability of Hexavalent Chromium... the use of materials containing hexavalent chromium. DATES: Comment Date: Comments on the proposed... human health and environmental risks related to the use of hexavalent chromium. Hexavalent chromium is a...

Thermodynamics of U(VI) and Eu(III) complexation by unsaturated carboxylates

Energy Technology Data Exchange (ETDEWEB)

Rawat, Neetika; Bhattacharyya, A. [Radiochemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Tomar, B.S., E-mail: bstomar@barc.gov.in [Radiochemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Ghanty, T.K. [Theoretical Chemistry Section, Bhabha Atomic Research Centre, Mumbai 400085 (India); Manchanda, V.K. [Radiochemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India)

2011-05-10

Highlights: {yields} {Delta}H and log K determined for U(VI) and Eu(III) complexes with maleate and fumarate. {yields} log K and coordination environment of Eu(III) complexes has been studied by TRFS. {yields} Higher log K of U(VI) complexes than Eu(III) complexes is due to higher entropy. {yields} Plot of log K vs log K{sub P} suggest charge polarization in fumarate complexes. {yields} Ab initio calculations support charge polarization in fumarate complexes. - Abstract: The thermodynamic parameters ({Delta}G, {Delta}H and {Delta}S) of complexation of U(VI) and Eu(III) by unsaturated dicarboxylic acids, namely, maleic and fumaric acid, has been determined by potentiometric and microcalorimetric titrations at fixed ionic strength (I = 1.0 M) and temperature (298 K). The results show formation of 1:1 complexes by both the ligands with Eu(III). In the case of U(VI), maleate forms both 1:1 and 1:2 complexes, while only 1:1 complex was formed with fumarate. The fluorescence emission spectra of Eu(III)-dicarboxylate solutions at varying ligand to metal ratio were also used to obtain their stability constants. In addition, the fluorescence lifetimes reveal higher dehydration of Eu(III)-maleate compared to Eu(III)-fumarate which corroborates the {Delta}S values. The thermodynamic quantities suggest charge polarization effects in the case of U(VI) and Eu(III) complexes of fumarate, which is further corroborated by theoretical calculations. For the same ligand, U(VI) complexes were found to be more stable which was mainly due to higher entropy term.

Tetra- and hexavalent uranium forms bidentate-mononuclear complexes with particulate organic matter in a naturally uranium-enriched peatland

DEFF Research Database (Denmark)

Mikutta, Christian; Langner, Peggy; Bargar, John R.

2016-01-01

Peatlands frequently serve as efficient biogeochemical traps for U. Mechanisms of U immobilization in these organic matter-dominated environments may encompass the precipitation of U-bearing mineral(oid)s and the complexation of U by a vast range of (in)organic surfaces. The objective of this work...... of bidentate-mononuclear U(IV/VI) complexes with carboxyl groups. We neither found evidence for U shells at ∼3.9 Å, indicative of mineral-associated U or multinuclear U(IV) species, nor for a substantial P/Fe coordination of U. Our data indicates that U(IV/VI) complexation by natural organic matter prevents...... the precipitation of U minerals as well as U complexation by Fe/Mn phases at our field site, and suggests that organically complexed U(IV) is formed via reduction of organic matter-bound U(VI)....

Effect of anthropogenic organic complexants on the solubility of Ni, Th, U(IV) and U(VI)

Energy Technology Data Exchange (ETDEWEB)

Felipe-Sotelo, M., E-mail: m.felipe-sotelo@lboro.ac.uk [Department of Chemistry, Loughborough University, LE11 3TU Loughborough, Leicestershire (United Kingdom); Edgar, M. [Department of Chemistry, Loughborough University, LE11 3TU Loughborough, Leicestershire (United Kingdom); Beattie, T. [MCM Consulting. Täfernstrasse 11, CH 5405 Baden-Dättwil (Switzerland); Warwick, P. [Enviras Ltd., LE11 3TU Loughborough, Leicestershire (United Kingdom); Evans, N.D.M.; Read, D. [Department of Chemistry, Loughborough University, LE11 3TU Loughborough, Leicestershire (United Kingdom)

2015-12-30

Highlights: • Citrate increases the solubility of Ni, Th and U between 3 and 4 orders of magnitude. • Theophrastite is the solubility controlling phase of Ni in 95%-saturated Ca(OH){sub 2}. • U(VI) and Ni may form Metal-citrate-OH complexes stabilised by the presence of Ca{sup 2+}. - Abstract: The influence of anthropogenic organic complexants (citrate, EDTA and DTPA from 0.005 to 0.1 M) on the solubility of nickel(II), thorium(IV) and uranium (U(IV) and U(VI)) has been studied. Experiments were carried out in 95%-saturated Ca(OH){sub 2} solutions, representing the high pH conditions anticipated in the near field of a cementitious intermediate level radioactive waste repository. Results showed that Ni(II) solubility increased by 2–4 orders of magnitude in the presence of EDTA and DTPA and from 3 to 4 orders of magnitude in the case of citrate. Citrate had the greatest effect on the solubility of Th(IV) and U(IV)/(VI). XRD and SEM analyses indicate that the precipitates are largely amorphous; only in the case of Ni(II), is there some evidence of incipient crystallinity, in the form of Ni(OH){sub 2} (theophrastite). A study of the effect of calcium suggests that U(VI) and Ni(II) may form metal-citrate-OH complexes stabilised by Ca{sup 2+}. Thermodynamic modelling underestimates the concentrations in solution in the presence of the ligands for all the elements considered here. Further investigation of the behaviour of organic ligands under hyperalkaline conditions is important because of the use of the thermodynamic constants in preparing the safety case for the geological disposal of radioactive wastes.

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)

Synthesis of Goethite-Coated Sand and Analysis of its Interactions with Uranium

International Nuclear Information System (INIS)

Vijay A. Loganathan; Sushil R. Kanel; Mark O. Barnett; T. Prabhakar Clement

2007-01-01

Iron(III) oxide coating on soils/sediments is reported to be the most important factor for controlling the sorption of radioactive metals in groundwater systems. Various forms of Fe(III) oxides occur in nature; they exist in both crystalline and amorphous forms. Our review indicated that goethite (α-FeOOH) is one of the most common iron oxides present in subsurface sediments. Therefore, it is important to understand the reactive chemistry of U(VI) with goethite-coated sand (GCS). Our overall objective is to develop scalable reaction models to predict uranium fate and transport in subsurface environment. In this paper, we focus on U(VI) interactions with well-characterized, synthetic goethite-coated sand. The objectives of the present work are to: (1) To identify a standard protocol to synthesize pure goethite-coated sand; (2) To characterize the goethite-coated sand synthesized using various methods; (3) To analyze the interaction of U(VI) with the goethite-coated sand; and (4) To predict the adsorption characteristics using surface complexation models

[Occupational exposure to hexavalent chromium during aircraft painting].

Science.gov (United States)

Gherardi, M; Gatto, M P; Gordiani, A; Paci, E; Proietto, A

2007-01-01

Hygienists are interested in hexavalent chromium due to its genotoxic and carcinogenic effect on humans. The use of products containing hexavalent chromium is decreasing in many industrial fields because of the substitution with less-toxic compounds. In the aeronautical industry, however, the chromate are added to primer paint as a corrosion inhibitor of aircrafts surfaces: so hexavalent chromium compounds are available in many primers with a composition ranging from 10% to 13%. The application of these primers by using electrostatic guns potentially exposes painting and coating workers at high concentrations of aerosols containing Cr(VI). The aim of the present study is the evaluation of professional exposure to hexavalent chromium during aircraft painting, by adopting both environmental personal sampling and biological monitoring. To valuate workers exposure levels the personal measurements results have been compared with the exposure limit values (TLV-TWA) and the urinary chromium contents with the biological exposure indices (IBE). Moreover the strategy of coupling environmental sampling with biological monitoring seems to be a useful instrument to measure the validity of the individual protection devices.

Uranium isotope evidence for an expansion of marine anoxia during the end-Triassic extinction

Science.gov (United States)

Jost, Adam B.; Bachan, Aviv; van de Schootbrugge, Bas; Lau, Kimberly V.; Weaver, Karrie L.; Maher, Kate; Payne, Jonathan L.

2017-08-01

The end-Triassic extinction coincided with an increase in marine black shale deposition and biomarkers for photic zone euxinia, suggesting that anoxia played a role in suppressing marine biodiversity. However, global changes in ocean anoxia are difficult to quantify using proxies for local anoxia. Uranium isotopes (δ238U) in CaCO3 sediments deposited under locally well-oxygenated bottom waters can passively track seawater δ238U, which is sensitive to the global areal extent of seafloor anoxia due to preferential reduction of 238U(VI) relative to 235U(VI) in anoxic marine sediments. We measured δ238U in shallow-marine limestones from two stratigraphic sections in the Lombardy Basin, northern Italy, spanning over 400 m. We observe a ˜0.7‰ negative excursion in δ238U beginning in the lowermost Jurassic, coeval with the onset of the initial negative δ13C excursion and persisting for the duration of subsequent high δ13C values in the lower-middle Hettangian stage. The δ238U excursion cannot be realistically explained by local mixing of uranium in primary marine carbonate and reduced authigenic uranium. Based on output from a forward model of the uranium cycle, the excursion is consistent with a 40-100-fold increase in the extent of anoxic deposition occurring worldwide. Additionally, relatively constant uranium concentrations point toward increased uranium delivery to the oceans from continental weathering, which is consistent with weathering-induced eutrophication following the rapid increase in pCO2 during emplacement of the Central Atlantic Magmatic Province. The relative timing and duration of the excursion in δ238U implies that anoxia could have delayed biotic recovery well into the Hettangian stage.

Elucidating Bioreductive Transformations within Physically Complex Media: Impact on the Fate and Transport of Uranium and Chromium

International Nuclear Information System (INIS)

Fendorf, Scott; Francis, Chris; Jardine, Phil; Benner, Shawn

2009-01-01

In situ stabilization (inclusive of natural attenuation) of toxic metals and radionuclides is an attractive approach for remediating many contaminated DOE sites. By immobilizing toxic metals and radionuclides in place, the removal of contaminated water to the surface for treatment as well as the associated disposal costs are avoided. To enhance in situ remediaton, microbiological reductive stabilization of contaminant metals has been, and continues to be, actively explored. It is likely that surface and subsurface microbial activity can alter the redox state of toxic metals and radionuclides, either directly or indirectly, so they are rendered immobile. Furthermore, anaerobic bacterial metabolic products will help to buffer pulses of oxidation, typically from fluxes of nitrate or molecular oxygen, and thus may stabilize reduced contaminants from oxidative mobilization. Uranium and chromium are two elements of particular concern within the DOE complex that, owing to their abundance and toxicity, appear well suited for biologically mediated reductive stabilization. Subsurface microbial activity can alter the redox state of toxic metals and radionuclides, rending them immobile. Imparting an important criterion on the probability that contaminants will undergo reductive stabilization, however, is the chemical and physical heterogeneity of the media. Our research first examined microbially induced transformation of iron (hydr)oxide minerals and their impact on contaminant attenuation. We revealed that in intricate cascade of geochemical reactions is induced by microbially produced Fe(II), and that during transformation contaminants such as U(VI) can be incorporated into the structure, and a set of Fe(II) bearing solids capable of reducing Cr(VI) and stabilizing resulting Cr(III). We also note, however, that common subsurface constituents such as phosphate can modify iron oxide transformation pathways and thus impact contaminant sequestration - affecting both Cr and U

Transient groundwater chemistry near a river: Effects on U(VI) transport in laboratory column experiments

Science.gov (United States)

Yin, Jun; Haggerty, Roy; Stoliker, Deborah L.; Kent, Douglas B.; Istok, Jonathan D.; Greskowiak, Janek; Zachara, John M.

2011-01-01

In the 300 Area of a U(VI)-contaminated aquifer at Hanford, Washington, USA, inorganic carbon and major cations, which have large impacts on U(VI) transport, change on an hourly and seasonal basis near the Columbia River. Batch and column experiments were conducted to investigate the factors controlling U(VI) adsorption/desorption by changing chemical conditions over time. Low alkalinity and low Ca concentrations (Columbia River water) enhanced adsorption and reduced aqueous concentrations. Conversely, high alkalinity and high Ca concentrations (Hanford groundwater) reduced adsorption and increased aqueous concentrations of U(VI). An equilibrium surface complexation model calibrated using laboratory batch experiments accounted for the decrease in U(VI) adsorption observed with increasing (bi)carbonate concentrations and other aqueous chemical conditions. In the column experiment, alternating pulses of river and groundwater caused swings in aqueous U(VI) concentration. A multispecies multirate surface complexation reactive transport model simulated most of the major U(VI) changes in two column experiments. The modeling results also indicated that U(VI) transport in the studied sediment could be simulated by using a single kinetic rate without loss of accuracy in the simulations. Moreover, the capability of the model to predict U(VI) transport in Hanford groundwater under transient chemical conditions depends significantly on the knowledge of real-time change of local groundwater chemistry.

Uranium sorption to natural substrates-insights provided by isotope exchange, selective extraction and surface complexation modelling approaches

International Nuclear Information System (INIS)

Waite, T.D.; Payne T.E.; Davis, J.A.

1993-01-01

An extensive experimental program has been conducted over the last three years into the interaction of U(VI) with both single oxides and clays and complex natural substrates from the weathered zone in the vicinity of a uranium ore body in northern Australia. While iron oxides have frequently been considered to account for much of the uptake on such natural substrates, the results of laboratory open-quotes pH edgeclose quotes studies and of isotope exchange and selective extraction studies suggest that other phases must also play a significant role in controlling the partitioning of U(VI) between solid and solution phases. Supporting studies on kaolinite, the dominant clay in this system, provide insight into the most appropriate method of modelling the interaction of U(VI) with these natural substrates. The problems still remaining in adequately describing sorption of radionuclides and trace elements to complex natural substrates are discussed

Acetate availability and its influence on sustainable bioremediation of uranium-contaminated groundwater

International Nuclear Information System (INIS)

Williams, Kenneth H.; Long, Philip E.; Davis, James A.; Wilkins, Michael J.; N'Guessan, A. Lucie; Steefel, Carl I.; Yang, Li; Newcomer, Darrell R.; Spane, Frank A.; Kerkhof, L.; McGuinness, L.; Dayvault, Richard; Lovley, Derek

2011-01-01

Field biostimulation experiments at the U.S. Department of Energy's Integrated Field Research Challenge (IFRC) site in Rifle, Colorado, have demonstrated that uranium concentrations in groundwater can be decreased to levels below the U.S. Environmental Protection Agency's (EPA) drinking water standard (0.126 (micro)M). During successive summer experiments - referred to as 'Winchester' (2007) and 'Big Rusty' (2008) - acetate was added to the aquifer to stimulate the activity of indigenous dissimilatory metal-reducing bacteria capable of reductively immobilizing uranium. The two experiments differed in the length of injection (31 vs. 110 days), the maximum concentration of acetate (5 vs. 30 mM), and the extent to which iron reduction ('Winchester') or sulfate reduction ('Big Rusty') was the predominant metabolic process. In both cases, rapid removal of U(VI) from groundwater occurred at calcium concentrations (6 mM) and carbonate alkalinities (8 meq/L) where Ca-UO2-CO3 ternary complexes constitute >90% of uranyl species in groundwater. Complete consumption of acetate and increased alkalinity (>30 meq/L) accompanying the onset of sulfate reduction corresponded to temporary increases in U(VI); however, by increasing acetate concentrations in excess of available sulfate (10 mM), low U(VI) concentrations (0.1-0.05 (micro)M) were achieved for extended periods of time (>140 days). Uniform delivery of acetate during 'Big Rusty' was impeded due to decreases in injection well permeability, likely resulting from biomass accumulation and carbonate and sulfide mineral precipitation. Such decreases were not observed during the short-duration 'Winchester' experiment. Terminal restriction fragment length polymorphism (TRFLP) analysis of 16S rRNA genes demonstrated that Geobacter sp. and Geobacter-like strains dominated the groundwater community profile during iron reduction, with 13C stable isotope probing (SIP) results confirming these strains were actively utilizing acetate to

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)

Hexavalent Chrome Free Coatings for Electronics: Electromagnetic Interference (EMI) Shielding Effectiveness (SE)

Science.gov (United States)

Kessel, Kurt R.

2016-01-01

Determine the suitability of trivalent chromium conversion coatings that meet the requirements of MIL-DTL-5541, Type II, for use in applications where high-frequency electrical performance is important. Evaluate the ability of hexavalent chrome free pretreated aluminum to form adequate EMI seals, and maintain that seal while being subjected to harsh environmental conditions. Assess the performance of trivalent chromium pretreatments against a known control hexavalent chrome pretreatment before and after they have been exposed to a set of environmental conditions. It is known that environmental testing causes a decrease in shielding effectiveness when hexavalent chrome pretreatments are used (Alodine 1200s). Need to determine how shielding effectiveness will be affected with the use of hexavalent chrome free pretreatments. Performance will be assessed by evaluating shielding effectiveness (SE) test data from a variety of test samples comprised of different aluminum types and/or conversion coatings. The formation of corrosion will be evaluated between the mating surfaces and gasket to assess the corrosion resistant properties of the pretreatments, comparing the hexavalent control to the hexavalent chrome free pretreatments.

Enhanced Uranium Immobilization and Reduction by Geobacter sulfurreducens Biofilms

Science.gov (United States)

Cologgi, Dena L.; Speers, Allison M.; Bullard, Blair A.; Kelly, Shelly D.

2014-01-01

Biofilms formed by dissimilatory metal reducers are of interest to develop permeable biobarriers for the immobilization of soluble contaminants such as uranium. Here we show that biofilms of the model uranium-reducing bacterium Geobacter sulfurreducens immobilized substantially more U(VI) than planktonic cells and did so for longer periods of time, reductively precipitating it to a mononuclear U(IV) phase involving carbon ligands. The biofilms also tolerated high and otherwise toxic concentrations (up to 5 mM) of uranium, consistent with a respiratory strategy that also protected the cells from uranium toxicity. The enhanced ability of the biofilms to immobilize uranium correlated only partially with the biofilm biomass and thickness and depended greatly on the area of the biofilm exposed to the soluble contaminant. In contrast, uranium reduction depended on the expression of Geobacter conductive pili and, to a lesser extent, on the presence of the c cytochrome OmcZ in the biofilm matrix. The results support a model in which the electroactive biofilm matrix immobilizes and reduces the uranium in the top stratum. This mechanism prevents the permeation and mineralization of uranium in the cell envelope, thereby preserving essential cellular functions and enhancing the catalytic capacity of Geobacter cells to reduce uranium. Hence, the biofilms provide cells with a physically and chemically protected environment for the sustained immobilization and reduction of uranium that is of interest for the development of improved strategies for the in situ bioremediation of environments impacted by uranium contamination. PMID:25128347

Electrodeposited tungsten-nickel-boron: A replacement for hexavalent chromium

International Nuclear Information System (INIS)

Steffani, C.; Meltzer, M.

1995-04-01

Chromium, deposited from acidic solutions of its hexavalent ion, has been the rule for wear resistant, corrosion resistant coatings for many years. Although chromium coatings are durable, the plating process generates air emissions, effluent rinse waters, and process solutions that are toxic, suspected carcinogens, and a risk to human health and the environment. Tungsten-nickel-boron (W-Ni-B) alloy deposition is a potential substitute for hexavalent chrome. It has excellent wear, corrosion, and mechanical properties and also may be less of an environmental risk. This study examines the electroplating process and deposit properties of W-Ni-B and compares them with those of hexavalent chrome

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)

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

International Nuclear Information System (INIS)

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

1975-01-01

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

Chemistry of Uranium in brines related to the spent fuel disposal in a salt repository. Part I

International Nuclear Information System (INIS)

Diaz Arocas, P.; Grambow, B.

1993-01-01

This report describes the work performed from september 1991 to december 1992. Our work is focused on the chemistry of uranium in highly saline solution. Experiments were performed to study the formation process and the stability of solid phases of U(VI) in NaCl solution at different ionic strength. The characterization of solid phases and of uranium concentration in solution are reported as a function of time. Experiments in NaClO 4 at low concentration have been performed for comparison. A method is proposed for uranium analyses in highly concentrated salt solution. The work has been carried out in KfK (INE), Germany. (Author) 10 figs

Removal of U(VI) from aqueous solution using TiO{sub 2} modified β-zeolite

Energy Technology Data Exchange (ETDEWEB)

Liu, Peng; Yuan, Ni; Xiong, Wei; Wu, Hanyu; Pan, Duoqiang; Wu, Wangsuo [Lanzhou Univ. (China). Radiochemistry and Nuclear Environment Laboratory; Ministry of Education, Lanzhou (China). Key Laboratory of Special Function Materials and Structure Design

2017-07-01

β-Zeolite was synthesized and modified with TiO{sub 2}. The synthesized materials were characterized and used for removal of U(VI) from aqueous solutions. The influences of pH, contact time and temperature on U(VI) adsorption onto modified β-zeolite by TiO{sub 2} were studied by batch technique, and XPS was employed to analysed the experimental data. The dynamic process showed that the adsorption of U(VI) onto TiO{sub 2}/β-zeolite matched the pseudo-second-order kinetics model, and the adsorption of U(VI) were significantly dependent on pH values. Through simulating the adsorption isotherms by Langmuir, Freundlich and Dubini-Radushkevich (D-R) models, it could be seen, respectively that the adsorption patterns of U(VI) onto TiO{sub 2}/β-zeolite were mainly controlled by surface complexation, and the adsorption processes were endothermic and spontaneous. The modification of β-zeolite by TiO{sub 2} it shows a novel material for the removing of U(VI) from water environment for industrialized application.

Kinetics of U(VI) reduction control kinetics of U(IV) reoxidation

International Nuclear Information System (INIS)

Senko, J.M.; Minyard, M.L.; Dempsey, B.A.; Roden, E.E.; Yeh, G.-T.; Burgos, W.D.

2006-01-01

For the in situ reductive immobilization of U to be an acceptable strategy for the removal of that element from groundwater, the long-term stability of U(IV) must be determined. Rates of biotransformation of Fe species influence the mineralogy of the resulting products (Fredrickson et al., 2003; Senko et al., 2005), and we hypothesize that the rate of U(VI) reduction influences the mineralogy of resultant U(IV) precipitates. We hypothesize that slower rates of U(VI) reduction will yield U(IV) phases that are more resistant to reoxidation, and will therefore be more stable upon cessation of electron donor addition. U(IV) phases formed by relatively slow reduction may be more crystalline or larger in comparison to their relatively rapidly-formed counterparts (Figure 1), thus limiting the reactivity of slowly-formed U(IV) phases toward various oxidants. The physical location of U(IV) precipitates relative to bacterial cells may also limit the reactivity of biogenic U(IV) phases. In this situation, we expect that precipitation of U(IV) within the bacterial cell may protect U(IV) from reoxidation by limiting physical contact between U(IV) and oxidants (Figure 1). We assessed the effect of U(VI) reduction rate on the subsequent reoxidation of biogenic U(IV) and are currently conducting column scale studies to determine whether U(VI) reduction rate can be manipulated by varying the electron donor concentration used to stimulate U(VI) reduction

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

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.

Photo-oxidation. Of the system chrome hexavalent-4-chlorophenol

International Nuclear Information System (INIS)

Gil Pavas, Edison; Cabrera Limpias, Marianela; Jaramillo Jimenez, Sergio Alejandro

2003-01-01

As a proposal to eliminate highly toxic chemical components derived from industrial waste, the researchers study the behavior of the compound hexavalent chromium / 4-chlorophenol system when subjected to photo degradation in a photo-reactor compound parabolic cylinder (CPC) to scale pilot. The effect is analyzed in order to determine the operation conditions to reach the highest degradation levels possible. The analyzed variables were pH, concentration of catalyst (TiO 2 ), time of recirculation and the relation of initial concentrations among polluting agents. The factor that most influences the levels of removal reached is the pH, which has a different effect for each of the pollutants. This implies that, theoretically, you cannot adopt a unique group of operation parameters to favor the degradation of both however, in the practice; high levels of degradation of both pollutants are obtained in the optimal point of operation of the chrome. It is also observed that the catalyst concentration does not influence the degradation of the polluting agents significantly, at least for the initial concentrations studied. The recirculation time is closely related to the kinetics of degradation of each polluting agent. Elevated degradation levels are reached in a short time for 4-chlorophenol, while more prolonged recirculation times are required for hexavalent chromium. The relation of initial concentrations of the polluting agents also exerts an opposite effect on the degradation levels reached for each polluting agent; the hexavalent chromium reduction is favored with high initial concentrations of 4-chlorophenol, whereas the oxidation of 4-chlorophenol is favored with high initial hexavalent chromium concentrations, which suggests some synergy between the oxidation-reduction reactions of 4-chlorophenol and hexavalent chromium. Finally, a 97% hexavalent chromium reduction and a 94.9% oxidation of 4-chlorophenol were obtained

Polarographic determination of uranium dioxide stoichiometry

International Nuclear Information System (INIS)

Viguie, J.; Uny, G.

1966-10-01

The method described allows the determination of small deviations from stoichiometry for uranium dioxide. It was applied to the study of surface oxidation of bulk samples. The sample is dissolved in phosphoric acid under an argon atmosphere; U(VI) is determined by polarography in PO 4 H 3 4.5 N - H 2 SO 4 4 N. U(IV) is determined by potentiometry. The detection limit is UO 2,0002 . The accuracy for a single determination at the 95% confidence level is ±20 per cent for samples with composition included between UO 2,001 and UO 2,01 . (authors) [fr

A biamperometric method for the determination of O/U ratio in uranium oxide

International Nuclear Information System (INIS)

Xavier, Mary; Nair, P.R.; Aggarwal, S.K.

2007-01-01

The methodology based on the dissolution of the uranium dioxide samples in H 2 SO 4 + HF mixture and the indirect determination of U(VI) by biamperometric redox titration is a simple method for determining ratio in hyperstoichiometric UO 2 powders.Analytical methods for % measurements in hyperstoichiometric. The present paper describes a simple method based on the determination of U(IV) and total U by biamperometric titration

Final Report - Elucidating Bioreductive Transformations within Physically Complex Media: Impact on the Fate and Transport of Uranium and Chromium

International Nuclear Information System (INIS)

Benner, Shawn G.; Fendorf, Scott

2009-01-01

In situ stabilization (inclusive of natural attenuation) of toxic metals and radionuclides is an attractive approach for remediating many contaminated DOE sites. By immobilizing toxic metals and radionuclides in place, the removal of contaminated water to the surface for treatment as well as the associated disposal costs are avoided. To enhance in situ remediaton, microbiological reductive stabilization of contaminant metals has been, and continues to be, actively explored. It is likely that surface and subsurface microbial activity can alter the redox state of toxic metals and radionuclides, either directly or indirectly, so they are rendered immobile. Furthermore, anaerobic bacterial metabolic products will help to buffer pulses of oxidation, typically from fluxes of nitrate or molecular oxygen, and thus may stabilize reduced contaminants from oxidative mobilization. Uranium and chromium are two elements of particular concern within the DOE complex that, owing to their abundance and toxicity, appear well suited for biologically mediated reductive stabilization. Subsurface microbial activity can alter the redox state of toxic metals and radionuclides, rending them immobile. Imparting an important criterion on the probability that contaminants will undergo reductive stabilization, however, is the chemical and physical heterogeneity of the media. Our research first examined microbially induced transformation of iron (hydr)oxide minerals and their impact on contaminant attenuation. We revealed that in intricate cascade of geochemical reactions is induced by microbially produced Fe(II), and that during transformation contaminants such as U(VI) can be incorporated into the structure, and a set of Fe(II) bearing solids capable of reducing Cr(VI) and stabilizing resulting Cr(III). We also note, however, that common subsurface constituents such as phosphate can modify iron oxide transformation pathways and thus impact contaminant sequestration - 'affecting both Cr and U

Zero-valent iron for the removal of soluble uranium in simulated DOE site groundwater

International Nuclear Information System (INIS)

Bostick, W.D.; Jarabek, R.J.; Fiedor, J.N.

1997-01-01

Groundwater at the Bear Creek Valley Characterization Area, located at the Oak Ridge Y-12 Plant, is contaminated with regulated metals and volatile organic compounds (VOCs) due to former site activities and disposal practices. The contaminant of principle concern, from the perspective of protecting human health, is soluble uranium, which is present in some waters at concentrations up to a few parts-per-million. We present product speciation and relative reaction kinetics; for removal of soluble uranium under oxic and anoxic conditions with use of zero-valent iron. Under oxic conditions, U(VI) is rapidly and strongly sorbed to hydrous ferric oxide particulate (open-quotes rustclose quotes), whereas uranium is slowly and incompletely reduced to U(IV) under anoxic conditions

Uranium recovery from phosphate fertilizer in the form of a high purity compound

International Nuclear Information System (INIS)

Bunus, F.; Coroianu, T.; Filip, G.; Filip, D.

2001-01-01

Uranium recovery from phosphate fertilizer industry is based on a one cycle extraction-stripping process. The process was experimented on both sulfuric and nitric acid attack of phosphate rock when uranium is dissolved in phosphoric acid (WPA) or phosphonitric (PN) solution respectively. The WPA and PN solution must be clarified. In the first alternative by ageing and settling and in the second by settling in the presence of flocculant. The organic components must be removed on active carbon for WPA only since in the case of nitric attack calcined phosphates are used. In both alternatives uranium is extracted from aqueous acidic solutions in the same time with the rare earths (REE), by di(2-ethylhexyl) phosphate (DEPA) as basic extractants, eventually in the presence of octylphosphine oxide (TOPO) as synergic agent. The stripping process is carried out in two stages: in the first stage REE are stripped and precipitated by HF or NH 4 F + H 2 S0 4 and in the second stage uranium as U(VI) is stripped by the same reagents but in the presence of Fe(II) as reductant for U(VI) to U(IV) inextractible species. Tetravalent uranium is also precipitated as green cake either UF 4 xH 2 0 or (NH 4 ) 7 U 6 F 31 as dependent on reagents HF or NH 4 F + H 2 S0 4 . Uranium stripping is possible for PN solution only if HNO 3 partially extracted is previously washed out by a urea solution. The green cake washed and filtered is dissolved in nitric acid in presence of Al(OH)3 as complexant for F. The filtered nitric solution is adjusted to 3-5 mol/L HNO 3 and extracted by 20% TBP when uranium is transferred to the organic phase which after scrubbing is stripped in the classic way with acidulated (HN0 3 ) demineralized water. Uranium is precipitated as diuranate of high purity. Rare earths left in the aqueous raffinate are extracted by pure TBP from 8-10 mol/L HNO 3 medium. The stripping process takes place with acidulated water. Rare earths are precipitated as hydroxides. (author)

Separation of Th(IV) and U(VI) by extraction chromatography

International Nuclear Information System (INIS)

Nadkarni, M.N.; Mayankutty, P.C.; Pillai, N.S.

1984-01-01

Application of extraction chromatography to the analytical separation of Th(IV) and U(VI) has been investigated. The stationary phase was a macroporous resin Amberlite XE-270 impregnated with undiluted tri-n-butylphosphate (TBP) and the mobile phase was either 5.0M HNO 3 or 6M HCl. Separation of traces of Th(IV) from large quantities of U(VI) was achieved on a laboratory column by elution of the absorbed Th(IV) with 6M HCl. (author)

75 FR 18041 - Defense Federal Acquisition Regulation Supplement; Minimizing Use of Hexavalent Chromium (DFARS...

Science.gov (United States)

2010-04-08

...-AG35 Defense Federal Acquisition Regulation Supplement; Minimizing Use of Hexavalent Chromium (DFARS... Regulation Supplement (DFARS) to address requirements for minimizing the use of hexavalent chromium in... of items containing hexavalent chromium under DoD contracts unless an exception applies. DATES...

Sorption mechanism of U(VI) on to natural soil system: a study using intra-particle diffusion model

International Nuclear Information System (INIS)

Rout, S.; Kumar, A.; Ravi, P.M.; Tripathi, R.M.

2015-01-01

The rate of U(VI) adsorption onto natural soils from different parent materials has been studied experimentally using the batch adsorption method at five different initial U(VI) concentrations. The utility of Weber and Morris Interparticle diffusion model for describing the mechanism and kinetics of sorption is discussed. The study reveals that the mechanism of U(VI) sorption involves three steps such as: external surface adsorption, gradual adsorption stage which is the rate determining step and the last portion refers to the final equilibrium stage. The steps involved in sorption of U(VI) on to soil is same irrespective of soil types and initial U(VI) concentration. (author)

Screen-printed electro grafted electrode for trace uranium analysis

Energy Technology Data Exchange (ETDEWEB)

Betelu, St.; Vautrin-Ui, Ch.; Chausse, A. [Univ Evry Val Essonne, LAMBE, CNRS CEA, UMR 8587, F-91025 Evry, (France); Ly, J. [CEA, L3MR, Ctr Etud Saclay, DEN DANS DPC SECR, F-91191 Gif Sur Yvette, (France)

2009-07-01

This paper reports the interest of the novel 4-carboxyphenyl-grafted screen-printed electrodes (4-CP-SPEs) for sub-nano-molar analysis of uranium in water samples. Electrodes were easily prepared via electrochemically reduction of the corresponding diazonium salt. The stability of the grafted layer has been clearly demonstrated. Uranium detection was then achieved by immersing the grafted electrode into the sample solution, followed by the electrochemical measurement of adsorbed U(VI) by square wave voltammetry. Adsorption time was investigated so as to find the best compromise between analysis time, repeatability and reproducibility. Limit of detection and quantitation reached 7 * 10{sup -10} and 2 * 10{sup -9} mol L{sup -1} respectively. Moreover, interference study was conducted with Zn(II), Cd(II), Pb(II) and Cu(II); no major interference was established. 4-CP-SPEs were finally applied for uranium determination in estuarine water demonstrating the convenience of these electrodes for environmental analysis. (authors)

Using 238U/235U ratios to understand the formation and oxidation of reduced uranium solids in naturally reduced zones

Science.gov (United States)

Jemison, N.; Johnson, T. M.; Druhan, J. L.; Davis, J. A.

2016-12-01

Uranium occurs in groundwater primarily as soluble and mobile U(VI), which can be reduced to immobile U(IV), often observed in sediments as uraninite. Numerous U(VI)-contaminated sites, such as the DOE field site in Rifle, CO, contain naturally reduced zones (NRZ's) that have relatively high concentrations of organic matter. Reduction of heavy metals occurs within NRZ's, producing elevated concentrations of iron sulfides and U(IV). Slow, natural oxidation of U(IV) from NRZ's may prolong U(VI) contamination of groundwater. The reduction of U(VI) produces U(IV) with a higher 238U/235U ratio. Samples from two NRZ sediment cores recovered from the Rifle site revealed that the outer fringes of the NRZ contain U(IV) with a high 238U/235U ratio, while lower values are observed in the center . We suggest that as aqueous U(VI) was reduced in the NRZ, it was driven to lower 238U/235U values, such that U(IV) formed in the core of the NRZ reflects a lower 238U/235U. Two oxidation experiments were conducted by injecting groundwater containing between 14.9 and 21.2 mg/L dissolved O2 as an oxidant into the NRZ. The oxidation of U(IV) from this NRZ increased aqueous U(VI) concentrations and caused a shift to higher 238U/235U in groundwater as U(IV) was oxidized primarily on the outer fringes of the NRZ. In total these observations suggest that the stability of solid phase uranium is governed by coupled reaction and transport processes. To better understand various reactive transport scenarios we developed a model for the formation and oxidation of NRZ's utilizing the reactive transport software CrunchTope. These simulations suggest that the development of isotopically heterogeneous U(IV) within NRZ's is largely controlled by permeability of the NRZ and the U(VI) reduction rate. Oxidation of U(IV) from the NRZ's is constrained by the oxidation rate of U(IV) as well as iron sulfides, which can prevent oxidation of U(IV) by scavenging dissolved oxygen.

Cassini UVIS Observations of Saturn during the Grand Finale Orbits

Science.gov (United States)

Pryor, W. R.; Esposito, L. W.; West, R. A.; Jouchoux, A.; Radioti, A.; Grodent, D. C.; Gerard, J. C. M. C.; Gustin, J.; Lamy, L.; Badman, S. V.

2017-12-01

In 2016 and 2017, the Cassini Saturn orbiter executed a final series of high inclination, low-periapsis orbits ideal for studies of Saturn's polar regions. The Cassini Ultraviolet Imaging Spectrograph (UVIS) obtained an extensive set of auroral images, some at the highest spatial resolution obtained during Cassini's long orbital mission (2004-2017). In some cases, two or three spacecraft slews at right angles to the long slit of the spectrograph were required to cover the entire auroral region to form auroral images. We will present selected images from this set showing narrow arcs of emission, more diffuse auroral emissions, multiple auroral arcs in a single image, discrete spots of emission, small scale vortices, large-scale spiral forms, and parallel linear features that appear to cross in places like twisted wires. Some shorter features are transverse to the main auroral arcs, like barbs on a wire. UVIS observations were in some cases simultaneous with auroral observations from the Hubble Space Telescope Space Telescope Imaging Spectrograph (STIS) that will also be presented. UVIS polar images also contain spectral information suitable for studies of the auroral electron energy distribution. The long wavelength part of the UVIS polar images contains a signal from reflected sunlight containing absorption signatures of acetylene and other Saturn hydrocarbons. The hydrocarbon spatial distribution will also be examined.

Reductive immobilization of U(VI) in Fe(III) oxide-reducing subsurface sediments: Analysis of coupled microbial-geochemical processes in experimental reactive transport systems. Final Scientific/Technical Report-EMSP 73914

International Nuclear Information System (INIS)

Eric E. Roden Matilde M. Urrutia Mark O. Barnett Clifford R. Lange

2005-01-01

The purpose of this research was to provide information to DOE on microbiological and geochemical processes underlying the potential use of dissimilatory metal-reducing bacteria (DMRB) to create subsurface redox barriers for immobilization of uranium and other redox-sensitive metal/radionuclide contaminants that were released to the environment in large quantities during Cold War nuclear weapons manufacturing operations. Several fundamental scientific questions were addressed in order to understand and predict how such treatment procedures would function under in situ conditions in the subsurface. These questions revolved the coupled microbial-geochemical phenomena which are likely to occur within a redox barrier treatment zone, and on the dynamic interactions between hydrologic flux and biogeochemical process rates. First, we assembled a robust conceptual understanding and numerical framework for modeling the kinetics of microbial Fe(III) oxide reduction and associated DMRB growth in sediments. Development of this framework is a critical prerequisite for predicting the potential effectiveness of DMRB-promoted subsurface bioremediation, since Fe(III) oxides are expected to be the primary source of electron-accepting capacity for growth and maintenance of DMRB in subsurface environments. We also defined in detail the kinetics of microbial (enzymatic) versus abiotic, ferrous iron-promoted reduction of U(VI) in the presence and absence of synthetic and natural Fe(III) oxide materials. The results of these studies suggest that (i) the efficiency of dissolved U(VI) scavenging may be influenced by the kinetics of enzymatic U(VI) reduction in systems with relative short fluid residence times; (2) association of U(VI) with diverse surface sites in natural soils and sediments has the potential to limit the rate and extent of microbial U(VI) reduction, and in turn modulate the effectiveness of in situ U(VI) bioremediation; and (3) abiotic, ferrous iron (Fe(II)) drive n U(VI

The development of a material for uranium sorption in NH_3/N environment

International Nuclear Information System (INIS)

Chen Xiaotong; He Linfeng; Liu Bing; Tang Yaping

2014-01-01

An efficient hybrid silica (TD-silica) bifunctionalized with trimethyl ammonium (TMAP) and phosphonate (DPTS) for Uranium (VI) extraction in NH_3/N media has been developed in this study. The hybrid silica was prepared by a post grafting of N-trimethoxysilylpropyl-N,N,N-trimethylammonium at large-pore silica. The resulting TD-modified silica were observed to possess a good stability and high efficiency for uranium (VI) sorption from solution in coexist with NH_3/N. The adsorbed uranium (VI) can be easily desorbed by using 0.05 mol/L HNO_3 and reused for at least 4 times. It is suggested that TD-silica could be a promising solid phase sorbent for highly-efficient removal of U(VI) from solution in coexist with NH_3/N. (author)

Secondary Uranium-Phase Paragenesis and Incorporation of Radionuclides into Secondary Phase

Energy Technology Data Exchange (ETDEWEB)

R. Finch

2001-06-05

The purpose of this analysis/model report (AMR) is to assess the potential for uranium (U) (VI) compounds, formed during the oxidative corrosion of spent uranium-oxide (UO{sub 2}) fuels, to sequester certain radionuclides and, thereby, limit their release. The ''unsaturated drip tests'' being conducted at Argonne National Laboratory (ANL) provide the basis of this AMR (Table 1). The ANL drip tests on spent fuel are the only experiments on fuel corrosion from which solids have been analyzed for trace levels of radionuclides. Brief summaries are provided of the results from other selected corrosion and dissolution experiments on spent UO{sub 2} fuels, specifically those conducted under nominally oxidizing conditions. Discussions of the current understanding of thermodynamic and kinetic properties of U(VI) compounds is provided in order to outline the scientific basis for modeling precipitation and dissolution of potential radionuclide-bearing phases under repository-relevant conditions. Attachment I provides additional information on corrosion mechanisms and behaviors of radionuclides in the tests at ANL. Attachment II reviews occurrence, formation, and alteration (collectively known as paragenesis) of naturally occurring U(VI) minerals because natural mineral occurrences can be used to assess the possible long-term behaviors of U(VI) compounds formed in short-term laboratory experiments and to extrapolate experimental results to repository-relevant time scales. This AMR develops a model for calculating dissolved concentrations of radionuclides that are incorporated into U(VI) compounds, which is an alternative to models currently used in TSPA to calculate dissolved concentration limits for certain radionuclides. In particular, the model developed in this AMR applies to Np (neptunium) concentrations being controlled by solid uranyl oxyhydroxides that are known to contain trace levels of Np. The results of this AMR and the conceptual model

Secondary Uranium-Phase Paragenesis and Incorporation of Radionuclides into Secondary Phases

International Nuclear Information System (INIS)

Finch, R.

2001-01-01

The purpose of this analysis/model report (AMR) is to assess the potential for uranium (U) (VI) compounds, formed during the oxidative corrosion of spent uranium-oxide (UO 2 ) fuels, to sequester certain radionuclides and, thereby, limit their release. The ''unsaturated drip tests'' being conducted at Argonne National Laboratory (ANL) provide the basis of this AMR (Table 1). The ANL drip tests on spent fuel are the only experiments on fuel corrosion from which solids have been analyzed for trace levels of radionuclides. Brief summaries are provided of the results from other selected corrosion and dissolution experiments on spent UO 2 fuels, specifically those conducted under nominally oxidizing conditions. Discussions of the current understanding of thermodynamic and kinetic properties of U(VI) compounds is provided in order to outline the scientific basis for modeling precipitation and dissolution of potential radionuclide-bearing phases under repository-relevant conditions. Attachment I provides additional information on corrosion mechanisms and behaviors of radionuclides in the tests at ANL. Attachment II reviews occurrence, formation, and alteration (collectively known as paragenesis) of naturally occurring U(VI) minerals because natural mineral occurrences can be used to assess the possible long-term behaviors of U(VI) compounds formed in short-term laboratory experiments and to extrapolate experimental results to repository-relevant time scales. This AMR develops a model for calculating dissolved concentrations of radionuclides that are incorporated into U(VI) compounds, which is an alternative to models currently used in TSPA to calculate dissolved concentration limits for certain radionuclides. In particular, the model developed in this AMR applies to Np (neptunium) concentrations being controlled by solid uranyl oxyhydroxides that are known to contain trace levels of Np. The results of this AMR and the conceptual model developed from it and presented in

Field-scale model for the natural attenuation of uranium at the Hanford 300 area using high performance computing

Energy Technology Data Exchange (ETDEWEB)

Lichtner, Peter C [Los Alamos National Laboratory; Hammond, Glenn E [PNNL

2009-01-01

Three-dimensional reactive flow and transport simulations are carried out to better understand the persistence of uranium [U(VI)] at the Hanford 300 Area bordering the Columbia River. The massively parallel code PFLOTRAN developed under a DOE SciDAC-2 project is employed in the simulations. The calculations were carried out on 4096 processor cores on ORNL's Jaguar XT4 & 5 Cray supercomputers with run times on the order of 6 hours, equivalent to several years if performed on a single processor with sufficient memory. A new conceptual model is presented for understanding present-day and future attenuation rates of U(VI) at the 300 Area site. Unique to the conceptual model is the recognition of three distinct phases in the evolution of the site corresponding to: (I) initial emplacement of waste; (II) present-day conditions of slow leaching of U(VI) from the Hanford sediments; and (III) the complete removal of non-labile U(VI) from the source region. This work focuses on Phase II. Both labile and non-labile forms of U(VI) are included in the model as sorbed and mineralized forms of U(VI), respectively. The non-labile form plays an important role in providing a long-term source of U(VI) as it slowly leaches out of the Hanford sediment. Rapid fluctuations in the Columbia River stage on hourly, weekly and seasonal time scales are found to' playa major role in determining the migration behavior of U(VI). The calculations demonstrate that U(VI) is released into the Columbia River at a highly fluctuating rate in a ratchet-like behavior with nonzero U(VI) flux occurring only during flow from contaminated sediment into the river. The cumulative flux, however, is found to increase approximately linearly with time. The flow rate and U(VI) flux into the Columbia River predicted by the model is highly sensitive to the value used in the conductance boundary condition at the river-sediment interface. By fitting the conductance to the measured piezometric head at well 399

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-12-02

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

WFC3 TV2 Testing: UVIS Channel Glint

Science.gov (United States)

Brown, Thomas M.

2007-10-01

The UVIS spare detector (UVIS build 2) was housed in WFC3 during the most recent epoch of thermal vaccum ground testing. We scanned the chip gap with a HeNe laser, to look for scattering from any material in the CCD chip gap or the edges of the CCD chips themselves. Although we found no such scattering issues, we did find a significant glint problem involving reflection from the surface of the CCD to the CCD housing and back down to the CCD. The glint appears as a large streak, ~10,000 pixels in area, containing anywhere from 1% to 30% of the energy within the source itself, depending upon the wavelength and position of the source. Approximately 10% of the detector area leads to glint when a source is placed in that area. Although any one glint comprises a tiny fraction of the detector area, the glint sweeps over a large area as the source is moved, implying that approximately 15% of the detector could be significantly illuminated by glint when observing a crowded field. As a result, the UVIS detectors currently not installed in the instrument have been modified to mask the surfaces responsible for the glint, to avoid this issue on orbit.

Electrochemically induced chemical sensor properties in graphite screen-printed electrodes: The case of a chemical sensor for uranium

International Nuclear Information System (INIS)

Kostaki, Vasiliki T.; Florou, Ageliki B.; Prodromidis, Mamas I.

2011-01-01

Highlights: → Electrochemical treatment endows analytical characteristics to SPEs. → A sensitive chemical sensor for uranium is described. → Performance is due to a synergy between electrochemical treatment and ink's solvents. → The amount of the solvent controls the achievable sensitivity. - Abstract: We report for the first time on the possibility to develop chemical sensors based on electrochemically treated, non-modified, graphite screen-printed electrodes (SPEs). The applied galvanostatic treatment (5 μA for 6 min in 0.1 M H 2 SO 4 ) is demonstrated to be effective for the development of chemical sensors for the determination of uranium in aqueous solutions. A detailed study of the effect of various parameters related to the fabrication of SPEs on the performance of the resulting sensors along with some diagnostic experiments on conventional graphite electrodes showed that the inducible analytical characteristics are due to a synergy between electrochemical treatment and ink's solvents. Indeed, the amount of the latter onto the printed working layer controls the achievable sensitivity. The preconcentration of the analyte was performed in an electroless mode in an aqueous solutions of U(VI), pH 4.6, and then, the accumulated species was reduced by means of a differential pulse voltammetry scan in 0.1 M H 3 BO 3 , pH 3. Under selected experimental conditions, a linear calibration curve over the range 5 x 10 -9 to 10 -7 M U(VI) was constructed. The 3σ limit of detection at a preconcentration time of 30 min, and the relative standard deviation of the method were 4.5 x 10 -9 M U(VI) and >12% (n = 5, 5 x 10 -8 M U(VI)), respectively. The effect of potential interferences was also examined.

Methylbutylmalonamide as an extractant for U(VI), Pu(IV), and Am(III)

International Nuclear Information System (INIS)

Nair, G.M.; Prabhu, D.R.; Mahajan, G.R.

1994-01-01

The unsymmetrical diamide methylbutylmalonamide has been synthesized and used in the extraction of U(VI), Pu(IV), and Am(III) in benzene medium. The distribution ratio for three cations was found to increase with increasing aqueous nitric acid concentration. U(VI) and Pu(IV) were found to be extracted as disolvates while Am(III) as a trisolvate. The thermodynamic parameters determined by the temperature variation method showed the extraction reactions to be mainly enthalphy-controlled. Am(III) was found to be back-extracted with dilute nitric acid, while Pu(IV) by dilute nitric acid - hydrofluoric acid mixture and U(VI) by dilute sodium carbonate solution. (author) 6 refs.; 3 figs.; 2 tabs

Removal U(VI) from artificial seawater using facilely and covalently grafted polyacrylonitrile fibers with lysine

Energy Technology Data Exchange (ETDEWEB)

Li, Wenting; Liu, Qi; Liu, Jingyuan; Zhang, Hongsen; Li, Rumin; Li, Zhanshuang; Jing, Xiaoyan [Key Laboratory of Superlight Material and Surface Technology, Ministry of Education, Harbin Engineering University, Harbin 150001 (China); Wang, Jun, E-mail: zhqw1888@sohu.com [Key Laboratory of Superlight Material and Surface Technology, Ministry of Education, Harbin Engineering University, Harbin 150001 (China); Institute of Advanced Marine Materials, Harbin Engineering University, 150001 (China)

2017-05-01

Highlights: • Novel lysine modified fibrous adsorbents were prepared using a facile and green method. • PAN-Lys exhibited high adsorption activity and fast adsorption rate. • PAN-Lys significantly remove U(VI) from simulated seawater. - Abstract: Polyacrylonitrile fibers (PANF) covalently modified with lysine (PAN-Lys) was facilely synthesized and carefully characterized. The critical factors affecting U(VI) adsorption from aqueous solution were exploited, such as initial pH, contact time, concentration and temperature. The adsorption process is strongly dependent on solution pH. With excellent adsorption capacity and high affinity toward U(VI), the process for U(VI) is extremely rapid and the equilibrium can be reached within 20 min. The thermodynamics and kinetics were strictly evaluated. In addition, the hypothetical adsorption mechanisms were proposed. Moreover, the adsorption behavior at low concentrations (3–30 μg L{sup −1}) in simulated seawater was also investigated. Therefore, PAN-Lys can be potentially utilized for the efficient removal of U(VI) from seawater.

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)

Application of Taguchi method for separation of uranium from acetate bearing wastewater using hydroxamic acid based sorbent

International Nuclear Information System (INIS)

Satpati, S.K.; Hareendran, K.; Roy, S.B.; Vaidya, A.; Bankar, V.; Dasgupta, K.; Pal, S.

2016-01-01

Separation and recovery of uranium from effluent of nuclear facility has drawn immense attention in separation science research. The acetic acid based uranium solution effluent generated in uranium metal powder production facility was targeted for the study. Solid state separation technique has been employed using hydroxamic acid based chelating sorbent because of several advantages. In the study, the sorbent performances have been evaluated for its important parameters like isotherm, efficiency and kinetics. The equilibrium adsorption capacity (q e ) and distribution coefficient (K d ) of U(VI) have been evaluated as 3.24 mg/g sorbent and 805 ml/g sorbent respectively. Uranium has been recovered using HCl solution. Uranium removal from the feed was found to be more than 95% and the recovery of uranium was more than 99% from the adsorbed phase. Elution process is faster than sorption process. Taguchi optimization method has been applied for designing experimental study and also to identify the optimum operational conditions for uranium separation process.The developed process is useful for separation and recovery of uranium from acetate bearing wastewater generated in uranium processing facilities

Upscaling of U(VI) Desorption and Transport Using Decimeter-Scale Tanks

Energy Technology Data Exchange (ETDEWEB)

Rodriguez, Derrick [Colorado School of Mines, Golden, CO (United States)

2014-12-22

Experimental work was used to validate modeling studies and develop multicontinuum models of U(VI) transport in a contaminated aquifer. At the bench scale, it has been shown that U(VI) desorption is rate-limited and that rates are dependent on the bicarbonate concentration. Two decimeter-scale experiments were conducted in order to help establish rigorous upscaling approaches that could be tested at the tracer test and plume scales.

Interactions of quercetin-uranium complexes with biomembranes and DNA

Energy Technology Data Exchange (ETDEWEB)

Attia, Enas Mohammed Hassan

2014-07-21

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

Interactions of quercetin-uranium complexes with biomembranes and DNA

International Nuclear Information System (INIS)

Attia, Enas Mohammed Hassan

2014-01-01

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

Separation and concentration of uranium by extraction chromatography : U(VI) - H/sub 3/PO/sub 4/ system

Energy Technology Data Exchange (ETDEWEB)

Nobre, J S.M.

1981-01-01

The feasibility of using the extraction chromatographic technique as a way to recover uranium from phosphatic rocks is evaluated. The behaviour of uranium from raw phsophoric acid solutions in chromatographic systems using the mixture di(2-ethylhexyl) orthophosphoric acid (D2EHPA) - tributyl phosphate (TBP) as the stationary phase was studied. Materials as alumina, activated carbon and the macroporous resins XAD-4 and XAD-7 were used as supports for organic stationary phase. The best results were obtained with poliacrilic polymer XAD-7, due to its excellent chromatographic properties and efficient organic phase retention. Uranium was quantitatively retained by D2EHPA-TBP-XAD-7 columns from synthetic phosphoric acid solutions with typical composition of phosphatic acid liquors. The elution of uranium from this system was also studied, and the best results were obtained with phosphoric acid solutions. This chromatographic column presented a high stability, not changing their properties even after more than twenty cycles, including the conditioning, sorption, washing and elution steps. Uranium determinations were perfpormed by indirect titration with potassium dichromate and by molecular absorption spectrophotometry with hydrogen peroxide- carbonate. A new and more sensitive method for uranium determination in phosphoric medium, which might be applied to acid liquors of phosphatic ores, was developed. An extraction-photometric method was used, with Arsenazo III (1,8-dihydroxynaphtalene-3,6-disulphonic acid-2,7-bis(azo-2)-phenylarsonic acid) as the reagent for uranium.

Uranium solubility and speciation in ground water

International Nuclear Information System (INIS)

Ollila, K.

1985-04-01

The purpose of this study has been to assess the solubility and possible species of uranium in groundwater at the disposal conditions of spent fuel. The effects of radiolysis and bentonite are considered. The assessment is based on the theoretical calculations found in the literature. The Finnish experimental results are included. The conservative estimate for uranium solubility under the oxidizing conditions caused by alpha radiolysis is based on the oxidation of uranium to the U(VI) state and formation of carbonate complex. For the groundwater with the typical carbonate content of 275 mg/l and the high carbonate content of 485 mg/l due to bentonite, the solubility values of 360 mg u/l and 950 mg U/l, are obtained, respectively. The experimental results predict considerably lower values, 0.5-20 mg U/l. The solubility of uranium under the undisturbed reducing conditions may be calculated based on the hydrolysis, carbonate complexation and redox reactions. The results vary considerably depending on the thermodynamic data used. The wide ranges of the most important groundwater parameters are seen in the solubility values. The experimental results show the same trends. As a conservative value for the solubility in reducing groundwater 50-500 μg U/l is estimated. (author)

Development of flow injection analysis technique for uranium estimation

International Nuclear Information System (INIS)

Paranjape, A.H.; Pandit, S.S.; Shinde, S.S.; Ramanujam, A.; Dhumwad, R.K.

1991-01-01

Flow injection analysis is increasingly used as a process control analytical technique in many industries. It involves injection of the sample at a constant rate into a steady flowing stream of reagent and passing this mixture through a suitable detector. This paper describes the development of such a system for the analysis of uranium (VI) and (IV) and its gross gamma activity. It is amenable for on-line or automated off-line monitoring of uranium and its activity in process streams. The sample injection port is suitable for automated injection of radioactive samples. The performance of the system has been tested for the colorimetric response of U(VI) samples at 410 nm in the range of 35 to 360mg/ml in nitric acid medium using Metrohm 662 Photometer and a recorder as detector assembly. The precision of the method is found to be better than +/- 0.5%. This technique with certain modifications is used for the analysis of U(VI) in the range 0.1-3mg/ailq. by alcoholic thiocynate procedure within +/- 1.5% precision. Similarly the precision for the determination of U(IV) in the range 15-120 mg at 650 nm is found to be better than 5%. With NaI well-type detector in the flow line, the gross gamma counting of the solution under flow is found to be within a precision of +/- 5%. (author). 4 refs., 2 figs., 1 tab

Study of the oxidation state of arsenic and uranium in individual particles from uranium mine tailings, Hungary

International Nuclear Information System (INIS)

Alsecz, A.; Osan, J.; Palfalvi, J.; Torok, Sz.; Sajo, I.; Mathe, Z.; Simon, R.; Falkenberg, G.

2007-01-01

Uranium ore mining and milling have been terminated in the Mecsek Mountains (southwest Hungary) in 1997. Mine tailings ponds are located between two important water bases, which are resources of the drinking water of the city of Pecs and the neighbouring villages. The average U concentration of the tailings material is 71.73 μg/g, but it is inhomogeneous. Some microscopic particles contain orders of magnitude more U than the rest of the tailings material. Other potentially toxic elements are As and Pb of which chemical state is important to estimate mobility, because in mobile form they can risk the water basis and the public health. Individual U-rich particles were selected with solid state nuclear track detector (SSNTD) and after localisation the particles were investigated by synchrotron radiation based microanalytical techniques. The distribution of elements over the particles was studied by micro beam X-ray fluorescence (μ-XRF) and the oxidation state of uranium and arsenic was determined by micro X-ray absorption near edge structure (μ-XANES) spectroscopy. Some of the measured U-rich particles were chosen for studying the heterogeneity with μ-XRF tomography. Arsenic was present mainly in As(V) and uranium in U(VI) form in the original uranium ore particles, but in the mine tailings samples uranium was present mainly in the less mobile U(IV) form. Correlation was found between the oxidation state of As and U in the same analyzed particles. These results suggest that dissolution of uranium is not expected in short term period. (authors)

Review article. Adverse hematological effects of hexavalent chromium: an overview

Directory of Open Access Journals (Sweden)

Ray Rina Rani

2016-06-01

Full Text Available Workers of tanneries, welding industries, factories manufacturing chromate containing paints are exposed to hexavalent chromium that increas¬es the risk of developing serious adverse health effects. This review elucidates the mode of action of hexavalent chromium on blood and its adverse effects. Both leukocyte and erythrocyte counts of blood sharply decreased in Swiss mice after two weeks of intraperitoneal treatment with Cr (VI, with the erythrocytes transforming into echinocytes. The hexavalent chromium in the blood is readily reduced to trivalent form and the reductive capacity of erythrocytes is much greater than that of plasma. Excess Cr (VI, not reduced in plasma, may enter erythrocytes and lymphocytes and in rodents it induces microcytic anemia. The toxic effects of chromium (VI include mitochondrial injury and DNA damage of blood cells that leads to carcinogenicity. Excess Cr (VI increases cytosolic Ca2+ activity and ATP depletion thereby inducing eryptosis. Se, vitamin C, and quercetin are assumed to have some protective effect against hexavalent chromium induced hematological disorders.

Electrochemical investigations on cation-cation interaction between Np(V) and U(VI) in nitric acid medium

International Nuclear Information System (INIS)

Verma, P.K.; Murali, M.S.; Pathak, P.N.; Mohapatra, P.K.

2014-01-01

Ever since the first report on cation-cation interactions (CCIs) in 1961 by Sullivan et al., many researchers have worked on this using different techniques like optical spectroscopy and potentiometry. However, there is almost no report, in recent times, on this interesting subject using an electrochemical technique. In the present work, we set out to use simple cyclic voltammetry (CV) as a probe to study this phenomenon in the case of Np(V)-U(VI) in nitric acid medium. Accordingly, cyclic voltammograms were recorded individually for Np(V) , U(VI) in 4M HNO 3 and for solutions resulting from a titration of Np(V) with incremental additions of U(VI) in the same medium. These experiments were carried out using AutoLab 30 with three solid electrode system. Ag/AgCl was the reference electrode while Pt wires were used as working and counter electrode. The paper gives the part of CVs for successive additions of only U(VI) (1.4M) at fixed scan rate and room temperature. It can be seen that that the reduction peak shifts only slightly towards left with increased aliquots of U(VI). In contrast, the paper also gives the part of CVs for only U(VI) and for a titration mixture of fixed concentration of Np(V) and successive volume aliquot-additions of U(VI). It can be seen that there was no appreciable shift in the cathodic peak (∼ -0.15V) for additions of 1225μL of only U(VI) and 3225 μL of U(VI) in presence of Np. This showed that no change occurred till this composition. But with the addition of next aliquot of 4225μL of U(VI), there was an appreciable shift in the peak. This signified the formation of a new complex which can be attributed to the cation-cation interaction envisaged for Np(V)-U(VI). With further addition of an aliquot of 4725 μL of U(VI), it can be seen that again there was no appreciable shift in the cathodic peak position which probably underlined that the formation of the complex was complete

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

Hexavalent Chrome Free Coatings for Electronics Applications: Joint Test Report

Science.gov (United States)

Rothgeb, Matt; Kessel, Kurt

2013-01-01

The overall objective of the Hexavalent Chrome Free Coatings for Electronics Applications project is to evaluate and test pretreatments not containing hexavalent chrome in avionics and electronics housing applications. This objective will be accomplished by testing strong performing coating systems from prior NASA and DoD testing or new coating systems as determined by the stakeholders.

Mineral transformations during the dissolution of uranium ore minerals by dissimilatory metal-reducing bacteria

Science.gov (United States)

Glasauer, S.; Weidler, P.; Fakra, S.; Tyliszczak, T.; Shuh, D.

2011-12-01

Carnotite minerals [X2(UO2)2(VO4)2]; X = K, Ca, Ba, Mn, Na, Cu or Pb] form the major ore of uranium in the Colorado Plateau. These deposits are highly oxidized and contain U(VI) and V(IV). The biotransformation of U(VI) bound in carnotite by bacteria during dissimilatory metal reduction presents a complex puzzle in mineral chemistry. Both U(VI) and V(V) can be respired by metal reducing bacteria, and the mineral structure can change depending on the associated counterion. We incubated anaerobic cultures of S. putrefaciens CN32 with natural carnotite minerals from southeastern Utah in a nutrient-limited defined medium. Strain CN32 is a gram negative bacterium and a terrestrial isolate from New Mexico. The mineral and metal transformations were compared to a system that contained similar concentrations of soluble U(VI) and V(V). Electron (SEM, TEM) microscopies and x-ray spectromicroscopy (STXM) were used in conjunction with XRD to track mineral changes, and bacterial survival was monitored throughout the incubations. Slow rates of metal reduction over 10 months for the treatment with carnotite minerals revealed distinct biotic and abiotic processes, providing insight on mineral transformation and bacteria-metal interactions. The bacteria existed as small flocs or individual cells attached to the mineral phase, but did not adsorb soluble U or V, and accumulated very little of the biominerals. Reduction of mineral V(V) necessarily led to a dismantling of the carnotite structure. Bioreduction of V(V) by CN32 contributed small but profound changes to the mineral system, resulting in new minerals. Abiotic cation exchange within the carnotite group minerals induced the rearrangement of the mineral structures, leading to further mineral transformation. In contrast, bacteria survival was poor for treatments with soluble U(VI) and V(V), although both metals were reduced completely and formed solid UO2 and VO2; we also detected V(III). For these treatments, the bacteria

Uranium removal from drinking water by adsorption onto granular ferric hydroxide (GEH)

International Nuclear Information System (INIS)

Bahr, Carsten

2012-01-01

Uranium contamination of groundwater is encountered in many regions worldwide. Effective and simple removal technologies are required by waterworks faced with this problem, particularly in Germany which set a specification for maximum permissible uranium content in drinking water in November 2011. The present thesis examines the suitability of Granular Ferric Hydroxide (GEH) as a water treatment adsorbent for uranium removal. Adsorption isotherms generated in the studies showed that GEH is capable of adsorbing uranium, in fact achieving highest loading levels as compared to other oxide-based absorbents. Experimental data for uranium adsorption as a function of pH for the model systems U(VI) / H 2 O and U(VI) / H 2 O / CO 2 successfully fits the Surface Complexation Model using the adjusted parameter set for ferrihydrite. Test findings showed that adsorption capacity varies substantially depending on the water matrix processed and is significantly reduced when real ground water or drinking water is processed. The main parameters influencing adsorption capacity were found to be pH and the associated carbonate concentration, as well as the concentrations of calcium and phosphate and to a lesser extent of sulfate and humic substances. The reduced capacity is caused by adsorption competition and changes in chemical speciation of uranium brought about by the water matrix at hand. Both the kinetics and the dynamics of adsorption can be successfully described by the Homogeneous Surface Diffusion Model (HSDM). The characteristic transport coefficients for film diffusion and particle diffusion were determined using empirical correlations and lab testing. The comparatively slow kinetics of adsorption are caused by the rate-determining particle diffusion and lead to a relatively flat breakthrough curve. Experiments on small adsorber columns (RSSCT method) were used to simulate uranium breakthrough in GEH fixed-bed filters on a laboratory scale, permitting accurate prediction

High performance of phosphate-functionalized graphene oxide for the selective adsorption of U(VI) from acidic solution

Energy Technology Data Exchange (ETDEWEB)

Liu, Xia [Institute of Plasma Physics, Chinese Academy of Sciences, P.O. Box 1126, Hefei, 230031 (China); University of Science and Technology of China, Hefei, 230026 (China); Li, Jiaxing, E-mail: lijx@ipp.ac.cn [Institute of Plasma Physics, Chinese Academy of Sciences, P.O. Box 1126, Hefei, 230031 (China); Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions (China); School for Radiological and Interdisciplinary Sciences (RAD-X), Soochow University, 215123, Suzhou (China); Wang, Xiangxue; Chen, Changlun [Institute of Plasma Physics, Chinese Academy of Sciences, P.O. Box 1126, Hefei, 230031 (China); Wang, Xiangke [Institute of Plasma Physics, Chinese Academy of Sciences, P.O. Box 1126, Hefei, 230031 (China); Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions (China); School for Radiological and Interdisciplinary Sciences (RAD-X), Soochow University, 215123, Suzhou (China); Faculty of Engineering, King Abdulaziz University, Jeddah 21589 (Saudi Arabia)

2015-11-15

In this study, phosphate-functionalized graphene oxide (PGO) was prepared by grafting triethyl phosphite onto the surface of GO using Arbuzov reaction. The as-prepared PGO was characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, Fourier transformed infrared spectroscopy and Zeta potential. The application of the PGO to remove U(VI) from aqueous solution was investigated with a maximum adsorption capacity of 251.7 mg/g at pH = 4.0 ± 0.1 and T = 303 K. The adsorption mechanism was also investigated by X-ray photoelectron spectroscopy analysis, indicating a chemical adsorption of U(VI) on PGO surface. Moreover, experimental results gave a better removal efficiency toward U(VI) on PGO surface than other heavy metal ions at acidic solution, indicating the selective extraction of U(VI) from environmental pollutants. - Highlights: • The successful grafting phosphonate to graphene oxide by the Arbuzov reaction. • Selective adsorption of U(VI) on PGO surface over other heavy metal ions from acidic solution. • Electrostatic interactions of U(VI) with phosphonate and oxygen-containing functional groups on PGO surface. • Higher sorption capacity on PGO surface than GO surface for the U(VI) removal.

Synthesis and evaluation of N,N-di-alkyl-2-methoxyacetamides for the separation of U(VI) and Pu(IV) from nitric acid medium

Energy Technology Data Exchange (ETDEWEB)

Kumaresan, R.; Prathibha, T.; Selvan, B. Robert; Venkatesan, K.A.; Antony, M.P. [Indira Gandhi Centre for Atomic Research, Kalpakkam (India). Fuel Chemistry Div.

2017-07-01

The homologs of N,N-di-alkyl-2-methoxyacetamides (DAMeOA) having three different alkyl chains varying from hexyl to decyl (C{sub 6}, C{sub 8} and C{sub 10}) were synthesized and characterized by NMR and IR spectral analyses. Extraction behavior of U(VI) and Pu(IV) from nitric acid medium in a solution of 0.5 M of DAMeOA in n-dodecane (n-DD) was studied and the results were compared with those obtained using N,N-di-hexyloctanamide (DHOA) in n-dodecane. The effect of various parameters on the distribution ratio of U(VI) and Pu(IV) in DAMeOA was studied. The extraction of nitric acid increased with decrease in chain length of alkyl group attached to amidic nitrogen atom of DAMeOA and the conditional nitric acid extraction constant was determined. The extraction of nitric acid in DAMeOA/n-DD resulted in the formation of third phase in organic phase and the third phase occurred early with DAMeOA having smaller alkyl chain length. In contrast to this, the distribution ratio (D) of U(VI) and Pu(IV) in DAMeOA/n-DD increased with increase in the concentration of nitric acid and with increase in the chain length of alkyl group attached to amidic nitrogen atom of DAMeOA. The stoichiometry of the metal - solvate was determined from the slope of extraction data. Quantitative recovery of uranium and plutonium from the loaded organic phase was achieved using dilute nitric acid.

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

Retention and chemical speciation of uranium in an oxidized wetland sediment from the Savannah River Site

Energy Technology Data Exchange (ETDEWEB)

Li, Dien; Seaman, John C.; Chang, Hyun-Shik; Jaffe, Peter R.; Koster van Groos, Paul; Jiang, De-Tong; Chen, Ning; Lin, Jinru; Arthur, Zachary; Pan, Yuanming; Scheckel, Kirk G.; Newville, Matthew; Lanzirotti, Antonio; Kaplan, Daniel I.

2014-05-01

Uranium speciation and retention mechanism onto Savannah River Site (SRS) wetland sediments was studied using batch (ad)sorption experiments, sequential extraction desorption tests and U L{sub 3}-edge X-ray absorption near-edge structure (XANES) spectroscopy of contaminated wetland sediments. U was highly retained by the SRS wetland sediments. In contrast to other similar but much lower natural organic matter (NOM) sediments, significant sorption of U onto the SRS sediments was observed at pH <4 and pH >8. Sequential extraction tests indicated that the U(VI) species were primarily associated with the acid soluble fraction (weak acetic acid extractable) and NOM fraction (Na-pyrophosphate extractable). Uranium L3- edge XANES spectra of the U-retained sediments were nearly identical to that of uranyl acetate. The primary oxidation state of U in these sediments was as U(VI), and there was little evidence that the high sorptive capacity of the sediments could be ascribed to abiotic or biotic reduction to the less soluble U(IV) species. The molecular mechanism responsible for the high U retention in the SRS wetland sediments is likely related to the chemical bonding of U to organic carbon.

Facile synthesis of magnetic Fe3O4/graphene composites for enhanced U(VI) sorption

Science.gov (United States)

Zhao, Donglin; Zhu, Hongyu; Wu, Changnian; Feng, Shaojie; Alsaedi, Ahmed; Hayat, Tasawar; Chen, Changlun

2018-06-01

A novel magnetic Fe3O4/graphene composite (FGC) was fabricated by a facile one-step reaction route and shown to be effective for sorbing U(VI) from aqueous solution. The structure, properties and application of the prepared FGC composite were well evaluated. The high saturation magnetization (45.6 emu/g) made FGC easier to be separated from the media within several seconds under an external magnetic. Effects of different ambient conditions (i.e., pH and ionic strength, contact time, temperatures) on sorption behaviors of U(VI) on FGC were carried out by batch experiments. According to the calculation of Langmuir model, the maximum sorption capacity of U(VI) on the FGC at pH 5.5 and 298 K was 176.47 mg/g. The sorption was correlated with the effects of pH, contact time, and temperature. X-ray photoelectron spectroscopy analysis revealed that U(VI) was sorbed on FGC via oxygen-containing functional groups. This work demonstrated that FGC could be recycled and used as an effective recyclable sorbent for sorption of U(VI).

RDT&E Progress and Plansfor Hexavalent Chromium (Cr6+)

Science.gov (United States)

2011-05-12

RDT&E Progress and Plans for Hexavalent Chromium (Cr6+) Bruce Sartwell Weapons Systems and Platforms Program Manager E2S2 Conference May 12, 2011...2011 2. REPORT TYPE 3. DATES COVERED 00-00-2011 to 00-00-2011 4. TITLE AND SUBTITLE RDT&E Progress and Plansfor Hexavalent Chromium (Cr6+) 5a...Development of Accelerated Corrosion Test Protocols Alternatives to Hex Chrome and Cadmium Plating Alternatives to Hex Chrome Pretreatments

Modeling uranium transport in acidic contaminated groundwater with base addition

Energy Technology Data Exchange (ETDEWEB)

Zhang, Fan [Institute of Tibetan Plateau Research, Chinese Academy of Sciences; Luo, Wensui [ORNL; Parker, Jack C. [University of Tennessee, Knoxville (UTK); Brooks, Scott C [ORNL; Watson, David B [ORNL; Jardine, Philip [University of Tennessee, Knoxville (UTK); Gu, Baohua [ORNL

2011-01-01

This study investigates reactive transport modeling in a column of uranium(VI)-contaminated sediments with base additions in the circulating influent. The groundwater and sediment exhibit oxic conditions with low pH, high concentrations of NO{sub 3}{sup -}, SO{sub 4}{sup 2-}, U and various metal cations. Preliminary batch experiments indicate that additions of strong base induce rapid immobilization of U for this material. In the column experiment that is the focus of the present study, effluent groundwater was titrated with NaOH solution in an inflow reservoir before reinjection to gradually increase the solution pH in the column. An equilibrium hydrolysis, precipitation and ion exchange reaction model developed through simulation of the preliminary batch titration experiments predicted faster reduction of aqueous Al than observed in the column experiment. The model was therefore modified to consider reaction kinetics for the precipitation and dissolution processes which are the major mechanism for Al immobilization. The combined kinetic and equilibrium reaction model adequately described variations in pH, aqueous concentrations of metal cations (Al, Ca, Mg, Sr, Mn, Ni, Co), sulfate and U(VI). The experimental and modeling results indicate that U(VI) can be effectively sequestered with controlled base addition due to sorption by slowly precipitated Al with pH-dependent surface charge. The model may prove useful to predict field-scale U(VI) sequestration and remediation effectiveness.

Modeling uranium transport in acidic contaminated groundwater with base addition

International Nuclear Information System (INIS)

Zhang Fan; Luo Wensui; Parker, Jack C.; Brooks, Scott C.; Watson, David B.; Jardine, Philip M.; Gu Baohua

2011-01-01

This study investigates reactive transport modeling in a column of uranium(VI)-contaminated sediments with base additions in the circulating influent. The groundwater and sediment exhibit oxic conditions with low pH, high concentrations of NO 3 - , SO 4 2- , U and various metal cations. Preliminary batch experiments indicate that additions of strong base induce rapid immobilization of U for this material. In the column experiment that is the focus of the present study, effluent groundwater was titrated with NaOH solution in an inflow reservoir before reinjection to gradually increase the solution pH in the column. An equilibrium hydrolysis, precipitation and ion exchange reaction model developed through simulation of the preliminary batch titration experiments predicted faster reduction of aqueous Al than observed in the column experiment. The model was therefore modified to consider reaction kinetics for the precipitation and dissolution processes which are the major mechanism for Al immobilization. The combined kinetic and equilibrium reaction model adequately described variations in pH, aqueous concentrations of metal cations (Al, Ca, Mg, Sr, Mn, Ni, Co), sulfate and U(VI). The experimental and modeling results indicate that U(VI) can be effectively sequestered with controlled base addition due to sorption by slowly precipitated Al with pH-dependent surface charge. The model may prove useful to predict field-scale U(VI) sequestration and remediation effectiveness.

Modeling uranium transport in acidic contaminated groundwater with base addition

Energy Technology Data Exchange (ETDEWEB)

Zhang Fan, E-mail: zhangfan@itpcas.ac.cn [Key Laboratory of Tibetan Environment Changes and Land Surface Processes, Institute of Tibetan Plateau Research, Chinese Academy of Sciences, P.O. Box 2871, Beijing, 100085 (China); Luo Wensui [Institute of Urban Environment, Chinese Academy of Sciences, Xiamen, 361021 (China); Parker, Jack C. [Institute for a Secure and Sustainable Environment, Department of Civil and Environmental Engineering, University of Tennessee, Knoxville, TN 37996 (United States); Brooks, Scott C.; Watson, David B. [Environmental Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Jardine, Philip M. [Biosystems Engineering and Soil Science Department, University of Tennessee, Knoxville, TN 37996 (United States); Gu Baohua [Environmental Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States)

2011-06-15

This study investigates reactive transport modeling in a column of uranium(VI)-contaminated sediments with base additions in the circulating influent. The groundwater and sediment exhibit oxic conditions with low pH, high concentrations of NO{sub 3}{sup -}, SO{sub 4}{sup 2-}, U and various metal cations. Preliminary batch experiments indicate that additions of strong base induce rapid immobilization of U for this material. In the column experiment that is the focus of the present study, effluent groundwater was titrated with NaOH solution in an inflow reservoir before reinjection to gradually increase the solution pH in the column. An equilibrium hydrolysis, precipitation and ion exchange reaction model developed through simulation of the preliminary batch titration experiments predicted faster reduction of aqueous Al than observed in the column experiment. The model was therefore modified to consider reaction kinetics for the precipitation and dissolution processes which are the major mechanism for Al immobilization. The combined kinetic and equilibrium reaction model adequately described variations in pH, aqueous concentrations of metal cations (Al, Ca, Mg, Sr, Mn, Ni, Co), sulfate and U(VI). The experimental and modeling results indicate that U(VI) can be effectively sequestered with controlled base addition due to sorption by slowly precipitated Al with pH-dependent surface charge. The model may prove useful to predict field-scale U(VI) sequestration and remediation effectiveness.

Preparation of hexavalent plutonium and its determination in the presence of tetravalent plutonium; Preparation de plutonium hexavalent et dosage en presence de plutonium tetravalent

Energy Technology Data Exchange (ETDEWEB)

Corpel, J [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires; Corpel, J [Institut du Radium, 75 - Paris (France)

1958-07-01

In order to study the eventual reduction of plutonium from the VI-valent state to the IV-valent state, in sulphuric medium, under the influence of its own {alpha} radiation or of the {gamma}-rays from a cobalt-60 source, we have developed a method for preparing pure hexavalent plutonium and two methods for determining solutions containing tetravalent and hexavalent plutonium simultaneously. Hexavalent plutonium was prepared by anodic oxidation at a platinum electrode. Study of the oxidation yield as a function of various factors has made it possible to define experimental conditions giving complete oxidation. For concentrations in total plutonium greater than 1.5 x 10{sup -3} M, determination of the two valencies IV and VI was carried out by spectrophotometry at two wavelengths. For lower concentrations, the determination was done by counting, after separation of the tetravalent plutonium in the form of fluoride in the presence of a carrier. (author) [French] Afin d'etudier l'eventuelle reduction du plutonium de l'etat de valence VI a l'etat de valence IV, en milieu sulfurique sous l'influence de son propre rayonnement {alpha} ou des rayons {gamma} d'une source de cobalt-60, nous avons mis au point une methode de preparation de plutonium hexavalent pur et deux methodes de dosage des solutions contenant simultanement du plutonium tetravalent et du plutonium hexavalent. Nous avons prepare le plutonium hexavalent par oxydation anodique au contact d'une electrode de platine. L'etude de rendement de l'oxydation en fonction des divers facteurs nous a permis de definir des conditions experimentales donnant une oxydation complete. Pour des concentrations en plutonium total superieures a 1,5.10{sup -3} M, le dosage des deux valences IV et VI a ete realise par spectrophotometrie a deux longueurs d'onde. Pour des concentrations inferieures, le dosage a ete effectue par comptage apres separation du plutonium tetravalent sous la forme du fluorure en presence d'un entraineur

Metabolic fate and evaluation of injury in rats and dogs following exposure to the hydrolysis products of uranium hexafluoride: implications for a bioassay program related to potential releases of uranium hexafluoride, July 1979-October 1981

International Nuclear Information System (INIS)

Morrow, P.E.; Leach, L.J.; Smith, F.A.

1982-12-01

This final report summarizes the experimental studies undertaken in rats and dogs in order to help provide adequate biological bases for quantifying and evaluating uranium hexafluoride (UF 6 ) exposures. Animals were administered the hydrolysis products of UF 6 by inhalation exposures, intratracheal instillations and intravenous injections. Attention was given to dose-effect relationships appropriate to the kidney, the unique site of subacute toxicity; to the rates of uranium excretion; and to uranium retention in renal tissue. These criteria were examined in both naive and multiply-exposed animals. The findings of these studies partly substantiate the ICRP excretion model for hexavalent uranium; generally provide a lower renal injury threshold concentration than implicit in the MPC for natural uranium; indicate distinctions in response (for example, uranium excretion) are based on exposure history; compare and evaluate various biochemical indices of renal injury; raise uncertainties about prevailing views of reversible renal injury, renal tolerance and possible hydrogen fluoride synergism with uranium effects; and reveal species differences in several areas, for example, renal retention of uranium. While these studies present some complicating features to extant bioassay practice, they nevertheless supply data supportive of the bioassay concept

Field-scale evaluation of biological uranium reduction and reoxidation in the near-source zone at the NABIR Field Research Center in Oak Ridge, TN

International Nuclear Information System (INIS)

Craig S. Criddle; Peter Kitanidis; Scott Fendorf; Weimin Wu; Philip M. Jardine; Jizhong Zhou; Baohua Gu

2006-01-01

The primary objective of the project is to advance the understanding and predictive capability of coupled hydrological, geochemical, and microbiological processes that control the in situ transport and bioremediation radionuclides and co-contaminants at multiple scales. Specific objectives include: (1) Investigate the feasibility of in situ bioremediation of uranium in a highly contaminated region within the subsurface of Area 3 of the DoE ERSP FRC (2) Using a variety of tracer strategies, develop and model a system that establishes hydraulic control of the target region for biostimulation (3) Perform long term in situ biostimulation studies that create a microbial communities capable of reducing residual nitrate to N2 and mobile U(VI) to sparingly soluble U(IV) (4) Use a variety of solid and solution phase interrogation techniques to quantify the extent of in situ reduction and immobilization of U(VI). (5) Investigate a variety of geochemical factors that influence the stability and possible reoxidation of reduced uranium

Acetate availability and its influence on sustainable bioremediation of Uranium-contaminated groundwater

Science.gov (United States)

Williams, K.H.; Long, P.E.; Davis, J.A.; Wilkins, M.J.; N'Guessan, A. L.; Steefel, Carl; Yang, L.; Newcomer, D.; Spane, F.A.; Kerkhof, L.J.; Mcguinness, L.; Dayvault, R.; Lovley, D.R.

2011-01-01

Field biostimulation experiments at the U.S. Department of Energy's Integrated Field Research Challenge (IFRC) site in Rifle, Colorado, have demonstrated that uranium concentrations in groundwater can be decreased to levels below the U.S. Environmental Protection Agency's (EPA) drinking water standard (0.126??M).During successive summer experiments - referred to as "Winchester" (2007) and "Big Rusty" (2008) - acetate was added to the aquifer to stimulate the activity of indigenous dissimilatory metal reducing bacteria capable of reductively immobilizing uranium. The two experiments differed in the length of injection (31 vs. 110 days), the maximum concentration of acetate (5 vs. 30 mM),and the extent to which iron reduction ("Winchester") or sulfate reduction("Big Rusty") was the predominant metabolic process. In both cases, rapid removal of U(VI) from groundwater occurred at calcium concentrations (6 mM) and carbonate alkalinities (8 meq/L) where Ca-UO2-CO3 ternary complexes constitute >90% of uranyl species in groundwater. Complete consumption of acetate and increased alkalinity (>30 meq/L) accompanying the onset of sulfate reduction corresponded to temporary increases in U(VI);however, by increasing acetate concentrations in excess of available sulfate (10 mM), low U(VI) concentrations (0.1-0.05 ??M) were achieved for extended periods of time (>140 days). Uniform delivery of acetate during "Big Rusty" was impeded due to decreases in injection well permeability, likely resulting from biomass accumulation and carbonate and sulfide mineral precipitation. Such decreases were not observed during the short-duration "Winchester" experiment. Terminal restriction fragment length polymorphism (TRFLP) analysis of 16S rRNA genes demonstrated that Geobacter sp. and Geobacter-like strains dominated the groundwater community profile during iron reduction, with 13C stable isotope probing (SIP) results confirming these strains were actively utilizing acetate to replicate their

The state-of-the-art and prospects of the oxidation titration method for the determination of uranium in geological samples

International Nuclear Information System (INIS)

Sun Jiayan

1986-01-01

The state-of-the-art of the oxidation titration method for the determination of uranium in geological samples is reviewed in some respects such as the prereduction of U(VI), oxidation of U(IV) and the detection of the end-point. Comments are also made on the prospects of further improvements of this method

Spectrophotometric determination of trace amount of uranium (VI) in different aqueous and organic streams of nuclear fuel processing using 2-(5-bromo-2-pyridylazo-5-diethylaminophenol)

International Nuclear Information System (INIS)

Das, S.K.; Kedari, C.S.; Tripathi, S.C.

2010-01-01

Present investigation describes the development of a spectrophotometric method for trace level determination of U(VI) encountered during the process of nuclear fuel fabrication and reprocessing industries. A chromogenic reagent, 2-(5-bromo-2-pyridylazo-5-diethylaminophenol) (Br-PADAP) is used to complex with U(VI) under optimized solution conditions. The absorption maxima of the uranyl Br-PADAP complex at 578 nm is computed to be 73540 ± 1438 for U-Br-PADAP solution containing 20% ethanol (in aqueous sample media) and 58216 ± 1208 for U-Br-PADAP solution containing 80% ethanol (for organic sample media). Employing suitable sample treatment methods, the scope of analytical method has been widened to permit accurate determination of U(VI) in the samples with variation in the relative compositions of Th(IV), Pu(IV) and Fe(III). The method is applicable to samples matrices with, acidic, alkaline highly salted media. Effect of commonly associated ionic species on the optical density of U-Br-PADAP is determined. Depending on the extent of the interfering impurities present, the method permits estimation of U(VI) either direct or after its selective extraction into tri-octyl phosphine oxide dissolved in cyclohexane. The method is precise with <5% standard error and can be used for the estimation of uranium in organic as well as in aqueous samples. The method has been validated for quantitative determination of uranium extracted in the organic phase comprising of heavy metal extractants like TBP, HDEHP, PC-88A and Aliquot 336. (author)

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.

Behaviour study of trace radioelements in the cycles of uranium conversion

International Nuclear Information System (INIS)

Bertaux, M.

1998-01-01

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

Novel Insights Into Microbial Uranium Reduction and Immobilization

Science.gov (United States)

Loeffler, F. E.; Fletcher, K.; Thomas, S.; Kemner, K. M.; Boyanov, M.; Sanford, R.

2010-12-01

Many ferric iron- and manganese oxide-reducing bacteria affect the oxidation state and complexation of toxic radionuclides in subsurface environments. Relevant to uranium (U) speciation are bacteria that reduce predominantly water-soluble and mobile U(VI) to U(IV), which has reduced solubility and typically forms the uraninite (UO2) mineral. Gram-negative model organisms including Shewanella spp., Geobacter spp., and more recently Anaeromyxobacter spp. use U(VI) as growth-supporting electron acceptor; however, the biomass yields are lower than predicted based on the theoretical free energy changes associated with U(VI)-to-U(IV) reduction. Recent findings demonstrated that U(VI) reduction is not limited to Gram-negative bacteria, and members of the genus Desulfitobacterium, which are commonly found in soil and subsurface environments, share the ability to reduce U(VI). Interestingly, extended X-ray absorption fine structure (EXAFS) analysis demonstrated that the U(IV) produced in cultures of five Desulfitobacterium spp. was not UO2 but rather a phase or mineral composed of mononuclear U(IV) atoms. Since the properties of the reduced product influence U(IV) fate, knowledge of the diversity of U reduction mechanisms and the stability of the end products is desirable for controlling and predicting U fate. For example, UO2 is susceptible to reoxidation by oxidants, and oxic/anoxic interface processes are controlling the stability of the precipitated material. In other words, metal reducers that thrive at the oxic/anoxic interface are likely key players affecting long-term U fate. Anaeromyxobacter spp. are facultative microaerophiles and grow with oxygen as electron acceptor at partial pressures equal to or below 0.18 atm. Thus, Anaeromyxobacter are uniquely adapted to life at the oxic-anoxic interface where they consume oxygen and take advantage of oxidized metal species including U(VI) as electron acceptors. The application of 16S rRNA gene-targeted qPCR approaches

Chemical Interaction between U(VI) and Eu(III) ions on a Silica Surface

International Nuclear Information System (INIS)

Park, K. K.; Cha, W. S.; Cho, H. R.; Im, H. J.; Jung, E. C.

2010-01-01

Understanding the chemical behavior of actinide in groundwater flow is important for assessing the possibility of its migration with water flow in the radioactive waste disposal site. Precipitation/ dissolution in groundwater and adsorption/desorption onto a geological solid surface would determine its migration. The sorption in a geochemical system was expected to be a reaction on a naturally equilibrated surface. However, the construction of a waste disposal facility could disturb this equilibrium state, induce a new reaction environment and affect a nanoscopic surface reaction of actinide. Uranium is ubiquitous in the natural environment and a representative element in a nuclear fuel cycle and in a high level radioactive waste. In oxic environments, it is typically present as uranyl oxocation (UO 2 2+ ), which is easily adsorbed and thereby removed from a solution in the near neutral pH range. This adsorption would form a new surface condition to give an unexpected adsorption behavior for other actinide ions. Eu(III) frequently is used as a chemical analogue of Am(III) and Cm(III) in migration chemistry. The adsorption phenomena has been interpreted with the help of a SCM(surface complexation model). Some spectroscopic techniques such as EPR (Electron Paramagnetic Resonance), IR (InfraRed), EXAFS (Extended X-ray Absorption Fine Structure) and TRLFS (Time Resolved Laser Fluorescence Spectroscopy) have been used for the identification of a modeled adsorbing species. In the case of fluorescence elements, TRLFS has advantages over other techniques for its high sensitivity being proportional to laser source intensity and good selectivity depending on specific transition and lifetime. This technique can be applied to a species on a solid surface not absorbing light such as silica. U(VI) and Eu(III) have fluorescente properties reflecting their coordination structure. In this study, the interaction between U(VI) and Eu(III) on a silica surface was studied by a

Development of supported noble metal catalyst for U(VI) to U(IV) reduction

International Nuclear Information System (INIS)

Tyagi, Deepak; Varma, Salil; Bhattacharyya, K.; Tripathi, A.K.; Bharadwaj, S.R.; Jain, V.K.; Sahu, Avinash; Vincent, Tessy; Jagatap, B.N.; Wattal, P.K.

2015-01-01

Uranium-plutonium separation is an essential step in the PUREX process employed in spent nuclear fuel reprocessing. This partitioning in the PUREX process is achieved by selective reduction of Pu(IV) to Pu(III) using uranous nitrate as reductant and hydrazine as stabilizer. Currently in our Indian reprocessing plants, the requirement of uranous nitrate is met by electrolytic reduction of uranyl nitrate. This process, however, suffers from a major drawback of incomplete reduction with a maximum conversion of ~ 60%. Catalytic reduction of U(VI) to U(IV) is being considered as one of the promising alternatives to the electro-reduction process due to fast kinetics and near total conversion. Various catalysts involving noble metals like platinum (Adams catalyst, Pt/Al 2 O 3 , Pt/SiO 2 etc.) have been reported for the reduction. Sustained activity and stability of the catalyst under harsh reaction conditions are still the issues that need to be resolved. We present here the results on zirconia supported noble metal catalyst that is developed in BARC for reduction of uranyl nitrate to uranous nitrate. Supported noble metal catalysts with varying metal loadings (0.5 - 2 wt%) were prepared via support precipitation and noble metal impregnation. The green catalysts were reduced either by chemical reduction using hydrazine hydrate or by heating in hydrogen flow or combination of both the steps. These catalysts were characterized by various techniques such as, XRD, SEM, TEM, N 2 adsorption and H 2 chemisorption. Performance of these catalysts was evaluated for U(VI) to U(IV) reduction with uranyl nitrate feed using hydrazine as reductant. The results with the most active catalyst are named as 'BARC-CAT', which was developed in our lab. (author)

Uranium fate in wetland mesocosms: Effects of plants at two ...

Science.gov (United States)

Small-scale continuous flow wetland mesocosms (~0.8 L) were used to evaluate how plant roots under different iron loadings affect uranium (U) mobility. When significant concentrations of ferrous iron (Fe) were present at circumneutral pH values, U concentrations in root exposed sediments were an order of magnitude greater than concentrations in root excluded sediments. Micro X-ray absorption near-edge structure (µ-XANES) spectroscopy indicated that U was associated with the plant roots primarily as U(VI) or U(V), with limited evidence of U(IV). Micro X-ray fluorescence (µ-XRF) of plant roots suggested that for high iron loading at circumneutral pH, U was co-located with Fe, perhaps co-precipitated with root Fe plaques, while for low iron loading at a pH of ~4 the correlation between U and Fe was not significant, consistent with previous observations of U associated with organic matter. Quantitative PCR analyses indicated that the root exposed sediments also contained elevated numbers of Geobacter spp., which are likely associated with enhanced iron cycling, but may also reduce mobile U(VI) to less mobile U(IV) species. There are significant uncertainties regarding the environmental fate of uranium (U) and efforts to minimize U exposures require understanding of its mobility in environmental systems. Much research has focused on sequestering U as solids within groundwater aquifers, where localized risks can be controlled.1 Subsurface sequestration limits t

Adsorption of U(VI) onto kaolin studied by batch method

International Nuclear Information System (INIS)

Hongxia Zhang; Zhi Liu; Peizhuo Hu; Tonghuan Liu; Wangsuo Wu

2013-01-01

Adsorption of U(VI) on purified kaolin was studied by batch methods under ambient conditions, including contact time, pH, fulvic acid, etc. Three kinetic models were used to model the kinetic adsorption which was very well described by the pseudo-second-order rate equation, and the activation energy of adsorption was 52.20 kJ/mol. The Freundlich and Dubinin-Radushkevich models fitted the experimental data better than the Langmuir model for the adsorption and desorption isotherms. The thermodynamic parameters indicated that the adsorption of U(VI) on kaolin was an endothermic and spontaneous process. (author)

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.

Regeneration of pilot-scale ion exchange columns for hexavalent chromium removal.

Science.gov (United States)

Korak, Julie A; Huggins, Richard; Arias-Paic, Miguel

2017-07-01

Due to stricter regulations, some drinking water utilities must implement additional treatment processes to meet potable water standards for hexavalent chromium (Cr(VI)), such as the California limit of 10 μg/L. Strong base anion exchange is effective for Cr(VI) removal, but efficient resin regeneration and waste minimization are important for operational, economic and environmental considerations. This study compared multiple regeneration methods on pilot-scale columns on the basis of regeneration efficiency, waste production and salt usage. A conventional 1-Stage regeneration using 2 N sodium chloride (NaCl) was compared to 1) a 2-Stage process with 0.2 N NaCl followed by 2 N NaCl and 2) a mixed regenerant solution with 2 N NaCl and 0.2 N sodium bicarbonate. All methods eluted similar cumulative amounts of chromium with 2 N NaCl. The 2-Stage process eluted an additional 20-30% of chromium in the 0.2 N fraction, but total resin capacity is unaffected if this fraction is recycled to the ion exchange headworks. The 2-Stage approach selectively eluted bicarbonate and sulfate with 0.2 N NaCl before regeneration using 2 N NaCl. Regeneration approach impacted the elution efficiency of both uranium and vanadium. Regeneration without co-eluting sulfate and bicarbonate led to incomplete uranium elution and potential formation of insoluble uranium hydroxides that could lead to long-term resin fouling, decreased capacity and render the resin a low-level radioactive solid waste. Partial vanadium elution occurred during regeneration due to co-eluting sulfate suppressing vanadium release. Waste production and salt usage were comparable for the 1- and 2-Stage regeneration processes with similar operational setpoints with respect to chromium or nitrate elution. Published by Elsevier Ltd.

Uranium Biomineralization by Natural Microbial Phosphatase Activities in the Subsurface

Energy Technology Data Exchange (ETDEWEB)

Sobecky, Patricia A. [Univ. of Alabama, Tuscaloosa, AL (United States)

2015-04-06

In this project, inter-disciplinary research activities were conducted in collaboration among investigators at The University of Alabama (UA), Georgia Institute of Technology (GT), Lawrence Berkeley National Laboratory (LBNL), Brookhaven National Laboratory (BNL), the DOE Joint Genome Institute (JGI), and the Stanford Synchrotron Radiation Light source (SSRL) to: (i) confirm that phosphatase activities of subsurface bacteria in Area 2 and 3 from the Oak Ridge Field Research Center result in solid U-phosphate precipitation in aerobic and anaerobic conditions; (ii) investigate the eventual competition between uranium biomineralization via U-phosphate precipitation and uranium bioreduction; (iii) determine subsurface microbial community structure changes of Area 2 soils following organophosphate amendments; (iv) obtain the complete genome sequences of the Rahnella sp. Y9-602 and the type-strain Rahnella aquatilis ATCC 33071 isolated from these soils; (v) determine if polyphosphate accumulation and phytate hydrolysis can be used to promote U(VI) biomineralization in subsurface sediments; (vi) characterize the effect of uranium on phytate hydrolysis by a new microorganism isolated from uranium-contaminated sediments; (vii) utilize positron-emission tomography to label and track metabolically-active bacteria in soil columns, and (viii) study the stability of the uranium phosphate mineral product. Microarray analyses and mineral precipitation characterizations were conducted in collaboration with DOE SBR-funded investigators at LBNL. Thus, microbial phosphorus metabolism has been shown to have a contributing role to uranium immobilization in the subsurface.

Uranium Biomineralization by Natural Microbial Phosphatase Activities in the Subsurface

International Nuclear Information System (INIS)

Sobecky, Patricia A.

2015-01-01

In this project, inter-disciplinary research activities were conducted in collaboration among investigators at The University of Alabama (UA), Georgia Institute of Technology (GT), Lawrence Berkeley National Laboratory (LBNL), Brookhaven National Laboratory (BNL), the DOE Joint Genome Institute (JGI), and the Stanford Synchrotron Radiation Light source (SSRL) to: (i) confirm that phosphatase activities of subsurface bacteria in Area 2 and 3 from the Oak Ridge Field Research Center result in solid U-phosphate precipitation in aerobic and anaerobic conditions; (ii) investigate the eventual competition between uranium biomineralization via U-phosphate precipitation and uranium bioreduction; (iii) determine subsurface microbial community structure changes of Area 2 soils following organophosphate amendments; (iv) obtain the complete genome sequences of the Rahnella sp. Y9-602 and the type-strain Rahnella aquatilis ATCC 33071 isolated from these soils; (v) determine if polyphosphate accumulation and phytate hydrolysis can be used to promote U(VI) biomineralization in subsurface sediments; (vi) characterize the effect of uranium on phytate hydrolysis by a new microorganism isolated from uranium-contaminated sediments; (vii) utilize positron-emission tomography to label and track metabolically-active bacteria in soil columns, and (viii) study the stability of the uranium phosphate mineral product. Microarray analyses and mineral precipitation characterizations were conducted in collaboration with DOE SBR-funded investigators at LBNL. Thus, microbial phosphorus metabolism has been shown to have a contributing role to uranium immobilization in the subsurface.

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

Energy Technology Data Exchange (ETDEWEB)

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

2015-06-01

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

Laser ablation microprobe inductively coupled plasma mass spectrometry study on diffusion of uranium into cement materials

International Nuclear Information System (INIS)

Sugiyama, D.; Chida, T.; Cowper, M.

2008-01-01

The diffusion of uranium (U(VI)) in solid cement monoliths of ordinary portland cement (OPC) and low-heat portland cement containing 30 wt.% fly ash (FAC) was measured by an in-diffusion technique. Detailed sharp depth profiles of uranium in the solid cement matrices were successively and quantitatively measured using laser ablation microprobe inductively coupled plasma mass spectrometry (LAMP-ICP-MS), and the apparent (D a ) and effective (D e ) diffusion coefficient of uranium in cement matrix were calculated as: D a =∝ 4 x 10 -16 m 2 s -1 and D e =∝ 3 x 10 -11 m 2 s -1 for OPC, and D a =∝ 2 x 10 -17 m 2 s -1 and D e =∝ 6 x 10 -13 m 2 s -1 for FAC. (orig.)

Uranium speciation and stability after reductive immobilization in aquifer sediments

Science.gov (United States)

Sharp, Jonathan O.; Lezama-Pacheco, Juan S.; Schofield, Eleanor J.; Junier, Pilar; Ulrich, Kai-Uwe; Chinni, Satya; Veeramani, Harish; Margot-Roquier, Camille; Webb, Samuel M.; Tebo, Bradley M.; Giammar, Daniel E.; Bargar, John R.; Bernier-Latmani, Rizlan

2011-11-01

It has generally been assumed that the bioreduction of hexavalent uranium in groundwater systems will result in the precipitation of immobile uraninite (UO 2). In order to explore the form and stability of uranium immobilized under these conditions, we introduced lactate (15 mM for 3 months) into flow-through columns containing sediments derived from a former uranium-processing site at Old Rifle, CO. This resulted in metal-reducing conditions as evidenced by concurrent uranium uptake and iron release. Despite initial augmentation with Shewanella oneidensis, bacteria belonging to the phylum Firmicutes dominated the biostimulated columns. The immobilization of uranium (˜1 mmol U per kg sediment) enabled analysis by X-ray absorption spectroscopy (XAS). Tetravalent uranium associated with these sediments did not have spectroscopic signatures representative of U-U shells or crystalline UO 2. Analysis by microfocused XAS revealed concentrated micrometer regions of solid U(IV) that had spectroscopic signatures consistent with bulk analyses and a poor proximal correlation (μm scale resolution) between U and Fe. A plausible explanation, supported by biogeochemical conditions and spectral interpretations, is uranium association with phosphoryl moieties found in biomass; hence implicating direct enzymatic uranium reduction. After the immobilization phase, two months of in situ exposure to oxic influent did not result in substantial uranium remobilization. Ex situ flow-through experiments demonstrated more rapid uranium mobilization than observed in column oxidation studies and indicated that sediment-associated U(IV) is more mobile than biogenic UO 2. This work suggests that in situ uranium bioimmobilization studies and subsurface modeling parameters should be expanded to account for non-uraninite U(IV) species associated with biomass.

Linking specific heterotrophic bacterial populations to bioreduction of uranium and nitrate using stable isotope probing in contaminated subsurface sediments

International Nuclear Information System (INIS)

Akob, Denise M.; Kerkhof, Lee; Kusel, Kirsten; Watson, David B.; Palumbo, Anthony Vito; Kostka, Joel

2011-01-01

Shifts in terminal electron-accepting processes during biostimulation of uranium-contaminated sediments were linked to the composition of stimulated microbial populations using DNA-based stable isotope probing. Nitrate reduction preceded U(VI) and Fe(III) reduction in [ 13 C]ethanol-amended microcosms. The predominant, active denitrifying microbial groups were identified as members of the Betaproteobacteria, whereas Actinobacteria dominated under metal-reducing conditions.

Surface modification to improve the sorption property of U(VI) on mesoporous silica

International Nuclear Information System (INIS)

Lijuan Song; Yulong Wang; Lu Zhu; Bolong Guo; Suwen Chen; Wangsuo Wu

2014-01-01

Polyoxometalates K 7 [α-PW 11 O 39 ]·14H 2 O (PW11) modified mesoporous silica (MCM-48) with cubic structure, was prepared by impregnation and calcination methods. The modified mesoporous silica sorbent (PW11/MCM-48) was studied as a potential adsorbent for U(VI) from aqueous solutions. MCM-48 and PW11/MCM-48 were confirmed by X-ray diffraction and nitrogen physisorption techniques. The results indicate the original keggin structure of PW11 and mesoporous structure of MCM-48 are maintained after supporting PW11 on mesoporous silica MCM-48. The effects of contact time, solid-to-liquid ratio (m/V), solution pH and ionic strength on U(VI) sorption behaviors of the pure and modified mesoporous silicas were also studied. Typical sorption isotherms such as Langmuir and Freundlich isotherms were determined for sorption process. The results suggest that the sorption of U(VI) on MCM-48 or PW11/MCM-48 are strongly dependent on pH values but independent of ionic strength. The sorption capacity of PW11/MCM-48 for U(VI) is about ten times more than that of MCM-48. (author)

An electrochemical study of U(VI) and Cr(VI) in molten borates

International Nuclear Information System (INIS)

Brigaudeau, M.; Gregori de Pinochet, I. de

1977-01-01

The electrochemical reduction of U(VI) and Cr(VI), in molten Na 2 B 4 O 7 at 800 deg C was studied by means of linear sweep voltammetry, and chronopotentiometry. The reduction of U(VI) to U(V) proceeded reversibly at a platinum electrode. The diffusion coefficient for the U(VI) species at 800 deg C was 4.10 -7 cm 2 .s -1 . The activation energy of diffusion was (34,8 +- 0,8) kcal. mole -1 . Electrochemical studies of Cr(VI) at 800 0 C reveal a two-step reduction process at a platinum electrode. Only the voltammogram for the first step charge transfer process was studied. Analysis indicated that Cr(VI) is reversibly reduced to Cr(III) at a platinum electrode. The diffusion coefficient for Cr(VI) at 800 0 C is 1,9.10 -7 cm 2 .s -1 [fr

Ship-in-a-bottle CMPO in MIL-101(Cr) for selective uranium recovery from aqueous streams through adsorption

Energy Technology Data Exchange (ETDEWEB)

De Decker, Jeroen [Department of Inorganic and Physical Chemistry, Center for Ordered Materials, Organometallics, and Catalysis (COMOC), Ghent University, Krijgslaan 281-S3, 9000 Ghent (Belgium); Folens, Karel [Laboratory of Analytical Chemistry and Applied Ecochemistry, Ghent University, Coupure Links 653, 9000 Ghent (Belgium); De Clercq, Jeriffa [Department of Materials, Textiles, and Chemical Engineering, Industrial Catalysis and Adsorption Technology (INCAT), Ghent University, Valentin, Vaerwyckweg 1, 9000 Ghent (Belgium); Meledina, Maria; Van Tendeloo, Gustaaf [EMAT, University of Antwerp, Groenenborgerlaan 171, 2020 Antwerp (Belgium); Du Laing, Gijs [Laboratory of Analytical Chemistry and Applied Ecochemistry, Ghent University, Coupure Links 653, 9000 Ghent (Belgium); Van Der Voort, Pascal, E-mail: pascal.vandervoort@ugent.be [Department of Inorganic and Physical Chemistry, Center for Ordered Materials, Organometallics, and Catalysis (COMOC), Ghent University, Krijgslaan 281-S3, 9000 Ghent (Belgium)

2017-08-05

Highlights: • Highly stable metal-organic framework, MIL-101(Cr), for uses in aqueous, acidic adsorption. • Uranium recovery from low concentration acidic solutions. • One-step ship-around-the-bottle synthetic approach to incorporate CMPO in MIL-101(Cr). • Highly selective U(VI) adsorbent in competition with a high variety of metals, incl. rare earths and transition metals. • Regenerable and reusable adsorbent via 0.1 M nitric acid stripping. - Abstract: Mesoporous MIL-101(Cr) is used as host for a ship-in-a-bottle type adsorbent for selective U(VI) recovery from aqueous environments. The acid-resistant cage-type MOF is built in-situ around N,N-Diisobutyl-2-(octylphenylphosphoryl)acetamide (CMPO), a sterically demanding ligand with high U(VI) affinity. This one-step procedure yields an adsorbent which is an ideal compromise between homogeneous and heterogeneous systems, where the ligand can act freely within the pores of MIL-101, without leaching, while the adsorbent is easy separable and reusable. The adsorbent was characterized by XRD, FTIR spectroscopy, nitrogen adsorption, XRF, ADF-STEM and EDX, to confirm and quantify the successful encapsulation of the CMPO in MIL-101, and the preservation of the host. Adsorption experiments with a central focus on U(VI) recovery were performed. Very high selectivity for U(VI) was observed, while competitive metal adsorption (rare earths, transition metals...) was almost negligible. The adsorption capacity was calculated at 5.32 mg U/g (pH 3) and 27.99 mg U/g (pH 4), by fitting equilibrium data to the Langmuir model. Adsorption kinetics correlated to the pseudo-second-order model, where more than 95% of maximum uptake is achieved within 375 min. The adsorbed U(VI) is easily recovered by desorption in 0.1 M HNO{sub 3}. Three adsorption/desorption cycles were performed.

Ship-in-a-bottle CMPO in MIL-101(Cr) for selective uranium recovery from aqueous streams through adsorption

International Nuclear Information System (INIS)

De Decker, Jeroen; Folens, Karel; De Clercq, Jeriffa; Meledina, Maria; Van Tendeloo, Gustaaf; Du Laing, Gijs; Van Der Voort, Pascal

2017-01-01

Highlights: • Highly stable metal-organic framework, MIL-101(Cr), for uses in aqueous, acidic adsorption. • Uranium recovery from low concentration acidic solutions. • One-step ship-around-the-bottle synthetic approach to incorporate CMPO in MIL-101(Cr). • Highly selective U(VI) adsorbent in competition with a high variety of metals, incl. rare earths and transition metals. • Regenerable and reusable adsorbent via 0.1 M nitric acid stripping. - Abstract: Mesoporous MIL-101(Cr) is used as host for a ship-in-a-bottle type adsorbent for selective U(VI) recovery from aqueous environments. The acid-resistant cage-type MOF is built in-situ around N,N-Diisobutyl-2-(octylphenylphosphoryl)acetamide (CMPO), a sterically demanding ligand with high U(VI) affinity. This one-step procedure yields an adsorbent which is an ideal compromise between homogeneous and heterogeneous systems, where the ligand can act freely within the pores of MIL-101, without leaching, while the adsorbent is easy separable and reusable. The adsorbent was characterized by XRD, FTIR spectroscopy, nitrogen adsorption, XRF, ADF-STEM and EDX, to confirm and quantify the successful encapsulation of the CMPO in MIL-101, and the preservation of the host. Adsorption experiments with a central focus on U(VI) recovery were performed. Very high selectivity for U(VI) was observed, while competitive metal adsorption (rare earths, transition metals...) was almost negligible. The adsorption capacity was calculated at 5.32 mg U/g (pH 3) and 27.99 mg U/g (pH 4), by fitting equilibrium data to the Langmuir model. Adsorption kinetics correlated to the pseudo-second-order model, where more than 95% of maximum uptake is achieved within 375 min. The adsorbed U(VI) is easily recovered by desorption in 0.1 M HNO 3 . Three adsorption/desorption cycles were performed.

REMOVAL OF HEXAVALENT CHROMIUM FROM AQUEOUS ...

African Journals Online (AJOL)

a

be used again to adsorb heavy metal ions. ... Among these heavy metals are chromium, copper and ... poisoning can result from high exposure to hexavalent chromium [2]. Most of the ..... At low pH, the sorbent is positively charged because of.

Kinetic, equilibrium and thermodynamic studies on sorption of uranium and thorium from aqueous solutions by a selective impregnated resin containing carminic acid

International Nuclear Information System (INIS)

Rahmani-Sani, Abolfazl; Hosseini-Bandegharaei, Ahmad; Hosseini, Seyyed-Hossein; Kharghani, Keivan; Zarei, Hossein; Rastegar, Ayoob

2015-01-01

Highlights: • The objective of the study is to investigate the potential application of a selective EIR for sorption of U(VI) and Th(IV) ions. • The effects of several physiochemical parameters were investigated. • The sorption kinetics and sorption isotherms were used to explain the sorption mechanism. • The thermodynamic studies showed the feasibility of sorption process. • The EIR beads showed a great potential for effective removal of U(VI) and Th(IV) ions. - Abstract: In this work, the removal of uranium and thorium ions from aqueous solutions was studied by solid–liquid extraction using an advantageous extractant-impregnated resin (EIR) prepared by loading carminic acid (CA) onto Amberlite XAD-16 resin beads. Batch sorption experiments using CA/XAD-16 beads for the removal of U(VI) and Th(IV) ions were carried out as a function of several parameters, like equilibration time, metal ion concentration, etc. The equilibrium data obtained from the sorption experiments were adjusted to the Langmuir isotherm model and the calculated maximum sorption capacities in terms of monolayer sorption were in agreement with those obtained from the experiments. The experimental data on the sorption behavior of both metal ions onto the EIR beads fitted well in both Bangham and intra-particle diffusion kinetic models, indicating that the intra-particle diffusion is the rate-controlling step. The thermodynamic studies at different temperatures revealed the feasibility and the spontaneous nature of the sorption process for both uranium and thorium ions

Application of insoluble tannin to recovery of uranium, TRU and heavy metals elements form radioactive liquid waste

International Nuclear Information System (INIS)

Hamaguchi, Kazuhiko; Shirato, Wataru; Nakamura, Yasuo; Matsumura, Tatsuro; Takeshita, Kenji; Nakano, Yoshio

1999-01-01

Mitsubishi Nuclear Fuel Co., Ltd. (MNF) has developed a new adsorbent, TANNIX (tread mark), for the recovery of uranium, TRU and heavy metal elements in the liquid waste, in which TANNIX derived from a natural tannin polymer. TANNIX has same advantages that handling is easier than that of standard IX-resin, and that the volume of secondary waste is reduced by burning the used TANNIX. We have replaced its radioactive liquid waste treatment system from the conventional co-precipitation process to adsorption process by using TANNIX. TANNIX was founded to be more effective for the recovery of Pu, TRU, and hexavalent chromium Cr-(VI) as well as Uranium. (author)

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)

NASA and ESA Collaboration on Hexavalent Chrome Free Coatings

Science.gov (United States)

Greene, Brian

2017-01-01

Presentation on the NASA and ESA Collaboration on Hexavalent Chrome Free Coatings project. Project is in response to a Memorandum of Understanding between NASA and ESA Concerning Cooperation in the Field of Space Transportation - signed September 11, 2009. The National Aeronautics and Space Administration (NASA) and the European Space Agency (ESA) have expressed mutual interest in pursuing cooperation in the areas of evaluating hexavalent chrome-free coatings, environmentally-preferable coatings for maintenance of launch facilities and ground support equipment, citric acid as an alternative to nitric acid for passivation of stainless steel alloys.

GSDO Program Hexavalent Chrome Alternatives: Final Pretreatments Test Report

Science.gov (United States)

Kessel, Kurt

2013-01-01

Hexavalent chrome free pretreatments should be considered for use on Ground Support Equipment (OSE) and Electrical Ground Support Equipment (EOSE). Both of the hexavalent chrome free pretreatments (Metalast TCP HF and SurTec 650C) evaluated by this project met, and in some instances exceeded, the requirements ofMIL-DTL-5541 "Chemical Conversion Coatings on Aluminum and Aluminum Alloys". For DC resistance measurements, both Metalast TCP HF and SurTec (!50C met initial requirements following assembly and in many cases continued to maintain passing readings for the duration of testing.

Origin of hexavalent chromium in groundwater

DEFF Research Database (Denmark)

Kazakis, N.; Kantiranis, N.; Kalaitzidou, K.

2017-01-01

Hexavalent chromium constitutes a serious deterioration factor for the groundwater quality of several regions around the world. High concentrations of this contaminant have been also reported in the groundwater of the Sarigkiol hydrological basin (near Kozani city, NW Greece). Specific interest w...

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

International Nuclear Information System (INIS)

Eliet, Veronique

1996-01-01

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

Uranium Sequestration by Aluminum Phosphate Minerals in Unsaturated Soils

International Nuclear Information System (INIS)

Jerden, James L. Jr.

2007-01-01

A mineralogical and geochemical study of soils developed from the unmined Coles Hill uranium deposit (Virginia) was undertaken to determine how phosphorous influences the speciation of uranium in an oxidizing soil/saprolite system typical of the eastern United States. This paper presents mineralogical and geochemical results that identify and quantify the processes by which uranium has been sequestered in these soils. It was found that uranium is not leached from the saturated soil zone (saprolites) overlying the deposit due to the formation of a sparingly soluble uranyl phosphate mineral of the meta-autunite group. The concentration of uranium in the saprolites is approximately 1000 mg uranium per kg of saprolite. It was also found that a significant amount of uranium was retained in the unsaturated soil zone overlying uranium-rich saprolites. The uranium concentration in the unsaturated soils is approximately 200 mg uranium per kg of soil (20 times higher than uranium concentrations in similar soils adjacent to the deposit). Mineralogical evidence indicates that uranium in this zone is sequestered by a barium-strontium-calcium aluminum phosphate mineral of the crandallite group (gorceixite). This mineral is intimately inter-grown with iron and manganese oxides that also contain uranium. The amount of uranium associated with both the aluminum phosphates (as much as 1.4 weight percent) has been measured by electron microprobe micro-analyses and the geochemical conditions under which these minerals formed has been studied using thermodynamic reaction path modeling. The geochemical data and modeling results suggest the meta-autunite group minerals present in the saprolites overlying the deposit are unstable in the unsaturated zone soils overlying the deposit due to a decrease in soil pH (down to a pH of 4.5) at depths less than 5 meters below the surface. Mineralogical observations suggest that, once exposed to the unsaturated environment, the meta-autunite group

Effective bioreduction of hexavalent chromium–contaminated water ...

African Journals Online (AJOL)

AFRICAN JOURNALS ONLINE (AJOL) · Journals · Advanced Search · USING ... Evaluation after reactor termination with SEM-EDX and XRD confirmed the ... Keywords: Bioreduction, fixed-film reactor, hexavalent chromium, microbial diversity ...

Variably Saturated Flow and Multicomponent Biogeochemical Reactive Transport Modeling of a Uranium Bioremediation Field Experiment

International Nuclear Information System (INIS)

Yabusaki, Steven B.; Fang, Yilin; Williams, Kenneth H.; Murray, Christopher J.; Ward, Anderson L.; Dayvault, Richard; Waichler, Scott R.; Newcomer, Darrell R.; Spane, Frank A.; Long, Philip E.

2011-01-01

Field experiments at a former uranium mill tailings site have identified the potential for stimulating indigenous bacteria to catalyze the conversion of aqueous uranium in the +6 oxidation state to immobile solid-associated uranium in the +4 oxidation state. This effectively removes uranium from solution resulting in groundwater concentrations below actionable standards. Three-dimensional, coupled variably-saturated flow and biogeochemical reactive transport modeling of a 2008 in situ uranium bioremediation field experiment is used to better understand the interplay of transport rates and biogeochemical reaction rates that determine the location and magnitude of key reaction products. A comprehensive reaction network, developed largely through previous 1-D modeling studies, was used to simulate the impacts on uranium behavior of pulsed acetate amendment, seasonal water table variation, spatially-variable physical (hydraulic conductivity, porosity) and geochemical (reactive surface area) material properties. A principal challenge is the mechanistic representation of biologically-mediated terminal electron acceptor process (TEAP) reactions whose products significantly alter geochemical controls on uranium mobility through increases in pH, alkalinity, exchangeable cations, and highly reactive reduction products. In general, these simulations of the 2008 Big Rusty acetate biostimulation field experiment in Rifle, Colorado confirmed previously identified behaviors including (1) initial dominance by iron reducing bacteria that concomitantly reduce aqueous U(VI), (2) sulfate reducing bacteria that become dominant after ∼30 days and outcompete iron reducers for the acetate electron donor, (3) continuing iron-reducer activity and U(VI) bioreduction during dominantly sulfate reducing conditions, and (4) lower apparent U(VI) removal from groundwater during dominantly sulfate reducing conditions. New knowledge on simultaneously active metal and sulfate reducers has been

Understanding the solid phase chemical fractionation of uranium in soil and effect of ageing

Energy Technology Data Exchange (ETDEWEB)

Rout, Sabyasachi, E-mail: srout.barc@gmail.com [Health Physics Division, Bhabha Atomic Research Centre, Mumbai (India); Kumar, Ajay [Health Physics Division, Bhabha Atomic Research Centre, Mumbai (India); Ravi, P.M.; Tripathi, R.M. [Homi Bhabha National Institute Anushaktinagar, Mumbai (India)

2016-11-05

Highlights: • Apart of U(VI) converted to U(IV) during adsorption to soil. • Ageing leads to rearrangement of chemical fractionation of U in soil. • Organic matter and carbonate minerals responsible for Surface enrichment of U. • There occurs Occlusion of U-Fe-Oxides (Hydroxide) in to silica. - Abstract: The aim of the present work is to understand the solid phase chemical fractionation of Uranium (U) in soil and the mechanism involved. This study integrated batch experiments of U(VI) adsorption to soil, study of U in different soil fractions, ageing impact on fractionation of U and spectroscopic investigation of adsorbed U(VI) using X-ray Photoelectron Spectroscopy (XPS). For the study three soils, pedogenically different (S1: Igneous, S2: Sedimentary and S3: Metamorphic) were amended with U(VI) and chemical fractionation of U was studied by sequential extraction after an interval of one month and 12 months. It was found that there occurs a significant rearrangement of U in different fractions with ageing and no correlation was observed between the U content in different fractions and the adsorbents of respective fractions such as soil organic matter (SOM), Fe/Mn oxides (hydroxides) carbonates, soil cation exchange capacity (CEC). XPS study revealed that surface enrichment of U mainly governed by the carbonate minerals and SOM, whereas bulk concentration was controlled by the oxides (hydroxides) of Si and Al. Occlusion of U-Fe-oxides (hydroxides) on silica was identified as an important mechanism for bulk enrichment (Increase in residual fraction) and depletion of U concentration in reducible fraction.

Understanding the solid phase chemical fractionation of uranium in soil and effect of ageing

International Nuclear Information System (INIS)

Rout, Sabyasachi; Kumar, Ajay; Ravi, P.M.; Tripathi, R.M.

2016-01-01

Highlights: • Apart of U(VI) converted to U(IV) during adsorption to soil. • Ageing leads to rearrangement of chemical fractionation of U in soil. • Organic matter and carbonate minerals responsible for Surface enrichment of U. • There occurs Occlusion of U-Fe-Oxides (Hydroxide) in to silica. - Abstract: The aim of the present work is to understand the solid phase chemical fractionation of Uranium (U) in soil and the mechanism involved. This study integrated batch experiments of U(VI) adsorption to soil, study of U in different soil fractions, ageing impact on fractionation of U and spectroscopic investigation of adsorbed U(VI) using X-ray Photoelectron Spectroscopy (XPS). For the study three soils, pedogenically different (S1: Igneous, S2: Sedimentary and S3: Metamorphic) were amended with U(VI) and chemical fractionation of U was studied by sequential extraction after an interval of one month and 12 months. It was found that there occurs a significant rearrangement of U in different fractions with ageing and no correlation was observed between the U content in different fractions and the adsorbents of respective fractions such as soil organic matter (SOM), Fe/Mn oxides (hydroxides) carbonates, soil cation exchange capacity (CEC). XPS study revealed that surface enrichment of U mainly governed by the carbonate minerals and SOM, whereas bulk concentration was controlled by the oxides (hydroxides) of Si and Al. Occlusion of U-Fe-oxides (hydroxides) on silica was identified as an important mechanism for bulk enrichment (Increase in residual fraction) and depletion of U concentration in reducible fraction.

The Nopal 1 Uranium Deposit: an Overview

Science.gov (United States)

Calas, G.; Allard, T.; Galoisy, L.

2007-05-01

The Nopal 1 natural analogue is located in the Pena Blanca uranium district, about 50 kms north of Chihuahua City, Mexico. The deposit is hosted in tertiary ignimbritic ash-flow tuffs, dated at 44 Ma (Nopal and Colorados formations), and overlying the Pozos conglomerate formation and a sequence of Cretaceous carbonate rocks. The deposit is exposed at the ground surface and consists of a near vertical zone extending over about 100 m with a diameter of 40 m. An interesting characteristic is that the primary mineralization has been exposed above the water table, as a result of the uplift of the Sierra Pena Blanca, and subsequently oxidized with a remobilization of hexavalent uranium. The primary mineralization has been explained by various genetic models. It is associated to an extensive hydrothermal alteration of the volcanic tuffs, locally associated to pyrite and preserved by an intense silicification. Several kaolinite parageneses occur in fissure fillings and feldspar pseudomorphs, within the mineralized breccia pipe and the barren surrounding rhyolitic tuffs. Smectites are mainly developed in the underlying weakly welded tuffs. Several radiation-induced defect centers have been found in these kaolinites providing a unique picture of the dynamics of uranium mobilization (see Allard et al., this session). Another evidence of this mobilization is given by the spectroscopy of uranium-bearing opals, which show characteristic fluorescence spectra of uranyl groups sorbed at the surface of silica. By comparison with the other uranium deposits of the Sierra Pena Blanca and the nearby Sierra de Gomez, the Nopal 1 deposit is original, as it is one of the few deposits hving retained a reduced uranium mineralization.

Fleet Readiness Center - Southeast Technology Development Program (Cadmium & Hexavalent Chromium Reduction)

Science.gov (United States)

2014-11-01

Fleet Readiness Center - Southeast TECHNOLOGY DEVELOPMENT PROGRAM (Cadmium & Hexavalent Chromium Reduction) Jack Benfer Senior Materials...Development Program (Cadmium & Hexavalent Chromium Reduction) 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) 5d. PROJECT...Rinse Black Oxide Rinse CRES Passivation Chrome Plating Cadmium Plating Cadmium Brush Plating Class N (TRL 9) Class N (TRL 7) Class N (TRL 6

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.

Investigation of alternative phosphating treatments for nickel and hexavalent chromium elimination

International Nuclear Information System (INIS)

Jazbinsek, Luiz Antonio Rossi

2014-01-01

The phosphating processes are widely used in industry as surface treatments for metals, especially for low thickness plates, improving the adhesion between the metallic surface and the paint coating, and increasing the durability of paint systems against corrosion attacks. The tricationic phosphates containing zinc, nickel and manganese are commonly applied on steel. There is much discussion about the replacement of nickel by another element in order to have an environmentally friendly phosphating process. Niobium as a replacement for nickel has been evaluated. The most significant environmental impacts of phosphating processes are related to the presence of nickel and hexavalent chromium used in the process, this last as a passivation treatment. Nickel and hexavalent chromium are harmful to human and environment leading to contamination of water and soil. In the present study phosphate layers containing zinc, manganese and niobium have been evaluated and characterized on galvanized steel, and the results were compared with phosphates containing zinc, manganese and nickel, or a bicationic phosphate layer with zinc and manganese. Although the use of hexavalent chromium is not recommended worldwide, it is still used in processes for sealing the porosity of phosphate layers. This element is carcinogenic and has been associated with various diseases. Due to the passivation characteristics of niobium, this study also evaluated the tricationic bath containing niobium ammonium oxalate as a passivation treatment. The results showed that it could act as a replacement for the hexavalent chromium. The results of the present study showed that formulations containing niobium are potential replacements for hexavalent chromium and similar corrosion protection was obtained for the phosphate containing nickel or that with niobium. The morphology observed by scanning electron microscopy, gravimetric tests, porosity and adhesion evaluation results indicated that the phosphate

Absorption spectra and cyclic voltammograms of uranium species in molten lithium molybdate-sodium molybdate eutectic at 550 C

International Nuclear Information System (INIS)

Nagai, T.; Fukushima, M.; Myochin, M.; Uehara, A.; Fujii, T.; Yamana, H.; Sato, N.

2011-01-01

Absorption spectra of uranium species dissolved in molten lithium molybdate.sodium molybdate eutectic of 0.51Li 2 MoO 4 -0.49Na 2 MoO 4 mixture at 550 C were measured by UV/Vis/NIR spectrophotometry, and their redox reactions were investigated by cyclic voltammetry. We found that the major ions of uranium species dissolved in the melt were uranyl penta-valent. After purging dry oxygen gas into the melt, pentavalent species were oxidized to the uranyl hexa-valent. In the cyclic voltammetry of the melt without uranium species, it was confirmed that the lithium-sodium molybdenum oxide compounds were deposited on the working electrode at the negative potential and the lithium molybdenum oxide compounds were deposited on the counter electrode at positive potential. When UO 2 was dissolved into the melt, the reductive reaction of the uranium species was observed at the reductive potential of the pure melt. This suggests that the uranium species dissolved in the melts could be recovered as mixed uranium-molybdenum oxides by electrolysis. (orig.)

WFC3/UVIS image skew

Science.gov (United States)

Petro, Larry

2009-07-01

This proposal will provide an independent check of the skew in the ACS astrometric catalog of Omega Cen stars, using exposures taken in a 45-deg range of telescope roll. The roll sequence will also provide a test for orbital variation of skew and field angle dependent PSF variations. The astrometric catalog of Omega Cen, improved for a skew, will be used to derive the geometric distorion to all UVIS filters, which has preliminarily been determined from F606W images and an astrometric catalog of 47 Tuc.

A new method in estimation of total hexavalent chromium in Portland pozzolan cement

International Nuclear Information System (INIS)

Sharma, R.; Sharma, D.

2017-01-01

Variamine blue was used first time for the detection of hexavalent chromium from cement samples. In present method, cement was treated sequentially with water, sulphate and carbonate buffer to extract soluble, sparingly soluble and insoluble hexavalent chromium respectively. Extracted Cr (VI) was determined using variamine blue as chromogenic reagent. The determination is based on the reaction of hexavalent chromium with potassium iodide in an acid medium to liberate iodine. This oxidizes variamine blue to form a violet coloured species having an absorption to maximum at 556 nm. Energy-dispersive X-ray spectroscopy (EDX) and Infrared Spectroscopy (IR) confirmed the complete extraction of hexavalent chromium by sequential extraction process. SRM 2701 (Reference material from NIST, USA) was used for revalidating the results. The percentage of recovery for proposed and reference method (diphelycarbazide method) varied from 98.5 to 101 and 97.5 to 100.5. Whereas, their relative error percentage varied from -1.5 to 0.33 and -2.5 to 0.5. [es

The biogeochemical behaviour of U(VI) in the simulated near-field of a low-level radioactive waste repository

International Nuclear Information System (INIS)

Fox, James R.; Mortimer, Robert J.G.; Lear, Gavin; Lloyd, Jonathan R.; Beadle, Ian; Morris, Katherine

2006-01-01

Microbial processes have the potential to affect the mobility of radionuclides, including U in radioactive wastes. A range of geochemical, molecular biological and mineralogical techniques were applied to investigate stable element biogeochemistry and U solubility in the simulated 'near-field' (or local environment) of a low-level radioactive waste (LLW) repository. The experiments used a microbial inoculum from the trench disposal area of the UK LLW repository at Drigg, Cumbria, England, in combination with a synthetic trench leachate representing the local environment at the Drigg site. In batch culture experiments in the absence of U, a classic redox progression of terminal electron accepting processes (TEAPs) occurred in the order NO 3 - , Fe(III) and SO 4 2- reduction. When 126μM U was added to the system as U(VI) aq , up to 80% was reduced to U(IV) by the indigenous microbial consortium. The U(IV) was retained in solution in these experiments, most likely by complexation with citrate present in the experimental medium. No U(VI) aq was reduced in sterile cultures, confirming that U(VI) aq reduction was microbially mediated. Interestingly, when U(VI) aq was present, the progression of TEAPs was altered. The rate of Fe(III) reduction slowed compared to experiments without U(VI) aq , and SO 4 reduction occurred at the same time as U(VI) reduction. Finally, an experiment where SO 4 2- -reducing microorgansisms were inhibited by Na molybdate showed no ingrowth of sulfide minerals, but U(VI) reduction continued in this experiment. This suggested that sulfide minerals did not play a significant role in abiotically reducing U(VI) in these systems, and that metal-reducing microorganisms were dominant in mediating U(VI) reduction. Bacteria closely related to microorganisms found in engineered and U-contaminated environments dominated in the experiments. Denaturing gradient gel electrophoresis (DGGE) on 16SrRNA products amplified from broad specificity primers showed

Enhanced accumulation of U(VI) by Aspergillus oryzae mutant generated by dielectric barrier discharge air plasma

International Nuclear Information System (INIS)

Wencheng Song; North China Electric Power University, Beijing; Xiangxue Wang; Soochow University, Suzhou; Wen Tao; Hongqing Wang; Tasawar Hayat; Quaid-I-Azam University, Islamabad; Xiangke Wang; Soochow University, Suzhou; King Abdulaziz University, Jeddah

2016-01-01

Aspergillus oryzae was isolated from radionuclides' contaminated soils, and dielectric barrier discharge plasma was used to mutate A. oryzae to improve bioremediation capability of U(VI) pollution. The maximum accumulation capacities of U(VI) on mutated A.oryzae was 627.4 mg/g at T = 298 K and pH = 5.5, which was approximately twice than that of raw A.oryzae. XPS analysis indicated that U(VI) accumulation on mutated A. oryzae was largely attributable to nitrogen- and oxygen-containing functional groups on fungal mycelia. The mutated A. oryzae can be harnessed as bioremediation agents for radionuclides pollution. (author)

Extraction of plutonium and uranium from oxalate bearing solutions using phosphonic acid

International Nuclear Information System (INIS)

Godbole, A.G.; Mapara, P.M.; Swarup, Rajendra

1995-01-01

A feasibility study on the solvent extraction of plutonium and uranium from solutions containing oxalic and nitric acids using a phosphonic acid extractant (PC88A) was made to explore the possibility of recovering Pu from these solutions. Batch experiments on the extraction of Pu(IV) and U(VI) under different parameters were carried out using PC88A in dodecane. The results indicated that Pu could be extracted quantitatively by PC88A from these solutions. A good separation of Pu from U could be achieved at higher temperatures. (author). 6 refs., 3 tabs

Mechanisms for the reduction of actinide ions by Geobacter sulfurreducens

International Nuclear Information System (INIS)

Renshaw, J.C.; Livens, F.R.; May, I.; Lloyd, J.R.

2005-01-01

Full text of publication follows: Three of the most problematic radioactive contaminants are the actinide elements uranium, neptunium and plutonium. All three pose considerable long-term environmental risks. The most stable environmental oxidation states of uranium and neptunium are VI and V, respectively, as the di-oxo cations [UO 2 ] 2+ and [NpO 2 ] + ; both are highly soluble and so are relatively mobile and biologically available in the environment. In similar conditions, plutonium mainly exists as Pu(IV), which forms a highly insoluble hydrous oxide, although is also environmentally stable in the more soluble III, V and VI oxidation states. The bio-reduction of U(VI) by anaerobic subsurface microorganisms has been the focus of much recent interest. Both Fe(III)- and sulfate-reducing bacteria have been shown to reduce soluble [U VI O 2 ] 2+ to insoluble U IV O 2 , with c-type cytochromes involved in electron transfer to the actinide. Such transformations offer a strategy for the bio-remediation of uranium contaminated groundwater and a potential mechanism for the bio-deposition of uranium ores. The mechanism of U(VI). reduction has important implications for the potential microbial reduction of transuranic elements with environmentally stable lower oxidation states. Reduction of mobile 237 Np(V) to Np(IV) and subsequent precipitation may be advantageous whilst remobilization of immobile Pu(IV) as more soluble Pu(III) species could have important environmental implications. Conversely, selective reduction might allow targeting of particular radionuclide species. The model anaerobic bacterium Geobacter sulfurreducens is typical of those found in contaminated subsurface environments and has been shown to reduce soluble [U VI O 2 ] 2+ to insoluble U IV O 2 . In the course of this study we use X-ray absorption spectroscopy (XAS) to show that G. sulfurreducens reduces U(VI) by a one-electron reduction, forming an unstable [UO 2 ] + species which subsequently