Alternative alkaline conditioning of amidoxime based adsorbent for uranium extraction from seawater

DOE PAGES

Das, Sadananda; Liao, Wei -Po; Byers, Maggie Flicker; ...

2015-10-18

Alkaline conditioning of the amidoxime based adsorbents is a significant step in the preparation of the adsorbent for uranium uptake from seawater. The effects of various alkaline conditioning parameters such as the type of alkaline reagent, reaction temperature, and reaction time were investigated with respect to uranium adsorption capacity from simulated seawater (spiked with 8 ppm uranium) and natural seawater (from Sequim Bay, WA). An adsorbent (AF1) was prepared at the Oak Ridge National Laboratory by radiation-induced graft polymerization (RIGP) with acrylonitrile and itaconic acid onto high-surface-area polyethylene fibers. For the AF1 adsorbent, sodium hydroxide emerged as a better reagentmore » for alkaline conditioning over potassium hydroxide, which has typically been used in previous studies, because of higher uranium uptake capacity and lower cost over the other candidate alkaline reagents investigated in this study. Furthermore, the use of sodium hydroxide in place of potassium hydroxide is shown to result in a 21–30% decrease in the cost of uranium recovery.« less

Alternative Alkaline Conditioning of Amidoxime Based Adsorbent for Uranium Extraction from Seawater

DOE Office of Scientific and Technical Information (OSTI.GOV)

Das, S.; Liao, W. -P.; Flicker Byers, M.

2016-04-20

Alkaline conditioning of the amidoxime based adsorbents is a significant step in the preparation of the adsorbent for uranium uptake from seawater. The effects of various alkaline conditioning parameters such as the type of alkaline reagent, reaction temperature, and reaction time were investigated with respect to uranium adsorption capacity from simulated seawater (spiked with 8 ppm uranium) and natural seawater (from Sequim Bay, WA). An adsorbent (AF1) was prepared at the Oak Ridge National Laboratory by radiation-induced graft polymerization (RIGP) with acrylonitrile and itaconic acid onto high-surface-area polyethylene fibers. For the AF1 adsorbent, sodium hydroxide emerged as a better reagentmore » for alkaline conditioning over potassium hydroxide, which has typically been used in previous studies, because of higher uranium uptake capacity and lower cost over the other candidate alkaline reagents investigated in this study. Use of sodium hydroxide in place of potassium hydroxide is shown to result in a 21-30% decrease in the cost of uranium recovery.« less

Alternative alkaline conditioning of amidoxime based adsorbent for uranium extraction from seawater

DOE Office of Scientific and Technical Information (OSTI.GOV)

Das, Sadananda; Liao, Wei -Po; Byers, Maggie Flicker

Alkaline conditioning of the amidoxime based adsorbents is a significant step in the preparation of the adsorbent for uranium uptake from seawater. The effects of various alkaline conditioning parameters such as the type of alkaline reagent, reaction temperature, and reaction time were investigated with respect to uranium adsorption capacity from simulated seawater (spiked with 8 ppm uranium) and natural seawater (from Sequim Bay, WA). An adsorbent (AF1) was prepared at the Oak Ridge National Laboratory by radiation-induced graft polymerization (RIGP) with acrylonitrile and itaconic acid onto high-surface-area polyethylene fibers. For the AF1 adsorbent, sodium hydroxide emerged as a better reagentmore » for alkaline conditioning over potassium hydroxide, which has typically been used in previous studies, because of higher uranium uptake capacity and lower cost over the other candidate alkaline reagents investigated in this study. Furthermore, the use of sodium hydroxide in place of potassium hydroxide is shown to result in a 21–30% decrease in the cost of uranium recovery.« less

METHOD FOR DISSOLVING ZIRCONIUM-URANIUM COMPOSITIONS

DOEpatents

Gens, T.A.

1961-07-18

A method is descrioed for treating a zirconium-- uranium composition to form a stable solution from which uranium and other values may be extracted by contacting the composition with at least a 4 molar aqueous solution of ammonium fluoride at a temperature of about 100 deg C, adding a peroxide, in incremental amounts, to the heated solution throughout the period of dissolution until all of the uranium is converted to soluble uranyl salt, adding nitric acid to the resultant solution to form a solvent extraction feed solution to convert the uranyl salt to a solvent extractable state, and thereafter recovering the uranium and other desired values from the feed solution by solvent extraction.

SOLVENT EXTRACTION OF URANIUM VALUES

DOEpatents

Feder, H.M.; Ader, M.; Ross, L.E.

1959-02-01

A process is presented for extracting uranium salt from aqueous acidic solutions by organic solvent extraction. It consists in contacting the uranium bearing solution with a water immiscible dialkylacetamide having at least 8 carbon atoms in the molecule. Mentioned as a preferred extractant is dibutylacetamide. The organic solvent is usually used with a diluent such as kerosene or CCl/sub 4/.

Efficient Functionalization of Polyethylene Fibers for the Uranium Extraction from Seawater through Atom Transfer Radical Polymerization

DOE PAGES

Neti, Venkata S.; Das, Sadananda; Brown, Suree; ...

2017-08-29

Brush-on-brush structures are proposed as one method to overcome support effects in grafted polymers. Utilizing glycidyl methacrylate (GMA) grafted on polyethylene (PE) fibers using radiation-induced graft polymerization (RIGP) provides a hydrophilic surface on the hydrophobic PE. When integrated with atom transfer radical polymerization (ATRP), the grafting of acrylonitrile (AN) and hydroxyethyl acrylate (HEA) can be controlled and manipulated more easily than with RIGP. Poly(acrylonitrile)-co-poly(hydroxyethyl acrylate) chains were grown via ATRP on PE-GMA fibers to generate an adsorbent for the extraction of uranium from seawater. The prepared adsorbents in this study demonstrated promise (159.9 g-U/kg of adsorbent) in laboratory screening testsmore » using a high uranium concentration brine and 1.24 g-U/Kg of adsorbent in the filtered natural seawater in 21-days. Here, the modest capacity in 21-days exceeds previous efforts to generate brush-on-brush adsorbents by ATRP while manipulating the apparent surface hydrophilicity of the trunk material (PE).« less

Efficient Functionalization of Polyethylene Fibers for the Uranium Extraction from Seawater through Atom Transfer Radical Polymerization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Neti, Venkata S.; Das, Sadananda; Brown, Suree

Brush-on-brush structures are proposed as one method to overcome support effects in grafted polymers. Utilizing glycidyl methacrylate (GMA) grafted on polyethylene (PE) fibers using radiation-induced graft polymerization (RIGP) provides a hydrophilic surface on the hydrophobic PE. When integrated with atom transfer radical polymerization (ATRP), the grafting of acrylonitrile (AN) and hydroxyethyl acrylate (HEA) can be controlled and manipulated more easily than with RIGP. Poly(acrylonitrile)-co-poly(hydroxyethyl acrylate) chains were grown via ATRP on PE-GMA fibers to generate an adsorbent for the extraction of uranium from seawater. The prepared adsorbents in this study demonstrated promise (159.9 g-U/kg of adsorbent) in laboratory screening testsmore » using a high uranium concentration brine and 1.24 g-U/Kg of adsorbent in the filtered natural seawater in 21-days. Here, the modest capacity in 21-days exceeds previous efforts to generate brush-on-brush adsorbents by ATRP while manipulating the apparent surface hydrophilicity of the trunk material (PE).« less

Efficient Functionalization of Polyethylene Fibers for the Uranium Extraction from Seawater through Atom Transfer Radical Polymerization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Neti, Venkata S.; Das, Sadananda; Brown, Suree

Brush-on-brush structures are proposed as one method to overcome support effects in grafted polymers. Utilizing glycidyl methacrylate (GMA) grafted on polyethylene (PE) fibers using radiation-induced graft polymerization (RIGP) provides a hydrophilic surface on the hydrophobic PE. When integrated with atom transfer radical polymerization (ATRP), the grafting of acrylonitrile (AN) and hydroxyethyl acrylate (HEA) can be controlled and manipulated more easily than with RIGP. Poly(acrylonitrile)-co-poly(hydroxyethyl acrylate) chains were grown via ATRP on PE-GMA fibers to generate an adsorbent for the extraction of uranium from seawater. The prepared adsorbents in this study demonstrated promise (159.9 g- U/kg of adsorbent) in laboratory screeningmore » tests using a high uranium concentration brine and 1.24 g-U/Kg of adsorbent in the filtered natural seawater in 21-days. The modest capacity in 21- days exceeds previous efforts to generate brush-on-brush adsorbents by ATRP while manipulating the apparent surface hydrophilicity of the trunk material (PE).« less

Development of Novel Porous Sorbents for Extraction of Uranium from Seawater

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Wenbin

Climate disruption is one of the greatest crises the global community faces in the 21st century. Alarming increases in CO 2, NO, SO 2 and particulate matter levels will have catastrophic consequences on the environment, food supplies, and human health if no action is taken to lessen their worldwide prevalence. Nuclear energy remains the only mature technology capable of continuous base-load power generation with ultralow carbon dioxide, nitric oxide, and sulfur dioxide emissions. Over the lifetime of the technology, nuclear energy outputs less than 1.5% the carbon dioxide emissions per gigawatt hour relative to coal—about as much as onshore windmore » power.1 However, in order for nuclear energy to be considered a viable option in the future, a stable supply of uranium must be secured. Current estimates suggest there is less than 100 years’ worth of uranium left in terrestrial ores (6.3 million tons) if current consumption levels remain unchanged.2 It is likely, however, that demand for nuclear fuel will rise as a direct consequence of the ratification of global climate accords. The oceans, containing approximately 4.5 billion tons of uranium (U) at a uniform concentration of ~3 ppb, represent a virtually limitless supply of this resource.3 Development of technologies to recover uranium from seawater would greatly improve the U resource availability, providing a U price ceiling for the current generation and sustaining the nuclear fuel supply for future generations. Several methods have been previously evaluated for uranium sequestration including solvent extraction, ion exchange, flotation, biomass collection, and adsorption; however, none have been found to be suitable for reasons including cost effectiveness, long term stability, and selectivity.4,5 While polymer beads and fibers have been functionalized with amidoxime functional groups to afford U adsorption capacities as high as 1.5 g U/kg,6 further discoveries are needed to make uranium extraction from seawater economically feasible.« less

SEPARATION OF THORIUM FROM URANIUM BY EXTRACTION

DOEpatents

Bohlmann, E.G.

1959-07-28

A method is presented for the recovery and separation of uranium and thorium values contained in an aqueous nitric acid solution which is more than 3 M in nitric acid. The uranium and thorium containing solution preferable about 7 M in nitric acid is contacted with tributyl phosphatekerosene mixture. Both U and Th are extracted by the immiscible organic. After phase separation the Th is selectively back extracted by contacting with an aqueous nitric acid solution preferably between 0.1 to 1.5 M in nitric acid. The uranium which is still in the organic extractant phase may be recovered by contacting with water.

Quantitative determination of environmental levels of uranium, thorium and plutonium in bone by solvent extraction and alpha spectrometry

NASA Astrophysics Data System (ADS)

Singh, Narayani P.; Zimmerman, Carol J.; Lewis, Laura L.; Wrenn, McDonald E.

1984-06-01

Solvent extraction and alpha-spectrometry have been emplyed in the quantitative simultaneous determination of uranium. thorium and plutonium. The bone specimens, spiked with 232U, 229Th and 242Pu tracers, are wet ashed with HNO 3 followed by alternate additions of a new drops of HNO 3 and H 2O 2. Uranium is reduced to the tetravalent state with 200 mg SnCl 2 and 25 ml HI. Uranium, thorium and plutonium are then coprecipitated with calcium as oxalate, heated to 550°C, dissolved in 50 ml HCl, and the acidity adjusted to 10 M. Uranium and plutonium are extracted into a 20% tri-lauryl amine (TLA) solution in xylene, leaving thorium in the aqueous phase. Plutonium is first back-extracted from the TLA phase by shaking with a 1:1.5 volume of 0.05 M NH 4I in 8 M HCl, which reduces Pu(IV) to Pu(III). Uranium is then back-extracted with an equal volume of 0.1 M HCl. Thorium, which was left in the aqueous phase, is evaporated to dryness, dissolved in 4 M HNO 3, and the acidity adjusted to 4 M. Thorium is then extracted into 20% TLA solution in xylene pre-equilibrated with 4 M HNO 3, and back-extracted with 10 M HCl. Uranium, thorium, and plutonium are then electrodeposited separately onto platinum discs and counted by an alpha-spectrometer with a multi-channel analyzer and surface barrier silicon diodes. The mean recoveries of uranium, thorium, and plutonium in bovine, dog, and human bones were over 70%.

Uranium extraction by complexation with siderophores

NASA Astrophysics Data System (ADS)

Bahamonde Castro, Cristina

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

URANIUM RECOVERY PROCESS

DOEpatents

Yeager, J.H.

1958-08-12

In the prior art processing of uranium ores, the ore is flrst digested with nitric acid and filtered, and the uranium values are then extracted tom the filtrate by contacting with an organic solvent. The insoluble residue has been processed separately in order to recover any uranium which it might contain. The improvement consists in contacting a slurry, composed of both solution and residue, with the organic solvent prior to filtration. Tbe result is that uranium values contained in the residue are extracted along with the uranium values contained th the solution in one step.

URANIUM DECONTAMINATION WITH RESPECT TO ZIRCONIUM

DOEpatents

Vogler, S.; Beederman, M.

1961-05-01

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

Recovery of Uranium from Wet Phosphoric Acid by Solvent Extraction Processes

DOE PAGES

Beltrami, Denis; Cote, Gérard; Mokhtari, Hamid; ...

2014-11-17

Between 1951 and 1991, we developed about 17 processes to recover uranium from wet phosphoric acid (WPA), but the viability of these processes was subject to the variation of the uranium price market. Nowadays, uranium from WPA appears to be attractive due to the increase of the global uranium demand resulting from the emergence of developing countries. Moreover, the increasing demand provides impetus for a new look at the applicable technology with a view to improvements as well as altogether new approaches. This paper gives an overview on extraction processes developed in the past to recover uranium from wet phosphoricmore » acid (WPA) as well as the physicochemistry involved in these processes. Recent advances concerning the development of new extraction systems are also reported and discussed.« less

Hydrologic and Temporal Influences of Evaporite Minerals on the Vertical Distribution, Storage, and Mobility of Uranium

NASA Astrophysics Data System (ADS)

Roycroft, S. J.; Noel, V.; Boye, K.; Besancon, C.; Weaver, K. L.; Johnson, R. H.; Dam, W. L.; Fendorf, S. E.; Bargar, J.

2016-12-01

Uranium contaminated groundwater in Riverton, Wyoming persists despite anticipated natural attenuation outside of a former uranium ore processing facility. The inability of natural flushing to dilute the uranium below the regulatory threshold indicates that sediments act as secondary sources likely (re)supplying uranium to groundwater. Throughout the contaminated floodplain, uranium rich-evaporites are readily abundant in the upper 2 m of sediments and are spatially coincident with the location of the plume, which suggests a likely link between evaporites and increased uranium levels. Knowledge of where and how uranium is stored within evaporite-associated sediments is required to understand processes controlling the mobility of uranium. We expect that flooding and seasonal changes in hydrologic conditions will affect U phase partitioning, and thus largely control U mobility. The primary questions we are addressing in this project are: What is the relative abundance of uranium incorporated in various mineral complexes throughout the evaporite sediments? How do the factors of depth, location, and seasonality influence the relative incorporation, mobility and speciation of uranium?We have systematically sampled from two soil columns over three dates in Riverton. The sampling dates span before and after a significant flooding event, providing insight into the flood's impact on local uranium mobility. Sequential chemical extractions are used to decipher the reactivity of uranium and approximate U operationally defined within reactants targeting carbonate, silicate, organic, and metal oxide bound or water and exchangeable phases. Extractions throughout the entirety of the sediment cores provide a high-resolution vertical profile of the distribution of uranium in various extracted phases. Throughout the profile, the majority (50-60%) of uranium is bound within carbonate-targeted extracts, a direct effect of the carbonate-rich evaporite sediments. The sum of our analyses provide a dynamic model of uranium incorporation within evaporite sediments holding implications for the fate of uranium throughout contaminated sites across the Colorado River Basin.

SOLVENT EXTRACTION PROCESS FOR SEPARATING URANIUM AND PLUTONIUM FROM AQUEOUS ACIDIC SOLUTIONS OF NEUTRON IRRADIATED URANIUM

DOEpatents

Bruce, F.R.

1962-07-24

A solvent extraction process was developed for separating actinide elements including plutonium and uranium from fission products. By this method the ion content of the acidic aqueous solution is adjusted so that it contains more equivalents of total metal ions than equivalents of nitrate ions. Under these conditions the extractability of fission products is greatly decreased. (AEC)

Extractive separation of uranium and zirconium sulfates by amines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schroetterova, D.; Nekovar, P.; Mrnka, M.

1992-04-01

This paper describes an amine extraction process for zirconium and uranium separation. The behaviour of an extraction system containing uranium (VI) sulfate, zirconium (IV) sulfate, 0.2 and 0.5 M sulfuric acid (as the original aqueous phase), tertiary amine tri-n-lauryl- amine or primary amine Primene JMT in benzene (as the original organic phase) is discussed on the basis of equilibrium data. The measured dependences show that the degree of extraction of zirconium at the sulfuric acid concentration of 0.5 M and above is only slightly affected by a presence of uranium in solution. From this surprising behaviour it follows that zirconiummore » may be employed for the displacement of uranium from the organic phase. This effect is more pronounced with the primary amine Primene JMT than with TLA. 29 refs., 4 figs., 1 tab.« less

Uranium extraction: Fuel from seawater

DOE PAGES

Tsouris, Costas; Oak Ridge National Lab.

2017-02-17

Over four billion tonnes of uranium are currently in the oceans that could be harvested for nuclear fuel, but current capture methods have limited performance and reusability. Now, an electrochemical method using modified carbon electrodes is shown to be promising for the extraction of uranium from seawater.

URANIUM SEPARATION PROCESS

DOEpatents

Hyde, E.K.; Katzin, L.I.; Wolf, M.J.

1959-07-14

The separation of uranium from a mixture of uranium and thorium by organic solvent extraction from an aqueous solution is described. The uranium is separrted from an aqueous mixture of uranium and thorium nitrates 3 N in nitric acid and containing salting out agents such as ammonium nitrate, so as to bring ihe total nitrate ion concentration to a maximum of about 8 N by contacting the mixture with an immiscible aliphatic oxygen containing organic solvent such as diethyl carbinol, hexone, n-amyl acetate and the like. The uranium values may be recovered from the organic phase by back extraction with water.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Singh, D.K.; Yadav, K.K.; Varshney, L.

The present study deals with the preparation and evaluation of the poly-ethersulfone (PES) based composite beads encapsulating synergistic mixture of D2EHPA and Cyanex 923 (at 4:1 mole ratio) for the separation of uranium from phosphoric acid medium. SEM was used for the characterization of the composite materials. Addition of 1% PVA (polyvinyl alcohol) improved the internal morphology and porosity of the beads. Additionally, microscopic examination of the composite bead confirmed central coconut type cavity surrounded by porous polymer layer of the beads through which exchange of metal ions take place. Effect of various experimental variables including aqueous acidity, metal ionmore » concentration in aqueous feed, concentration of organic extractant inside the beads, extractant to polymer ratio, liquid to solid (L/S) ratio and temperature on the extraction of uranium was studied. Increase in acidity (1-6 M), L/S ratio (1- 10), metal ion concentration (0.2-3 g/L U{sub 3}O{sub 8}) and polymer to extractant ratio (1:4 -1:10) led to decrease in extraction of uranium. At 5.5 M (comparable to wet process phosphoric acid concentration) the extraction of uranium was about 85% at L/S ratio 5. Increase in extractant concentration inside the bead resulted in enhanced extraction of metal ion. Increase in temperature in the range of 30 to 50 Celsius degrees increased the extraction, whereas further increase to 70 C degrees led to the decrease in extraction of uranium. Amongst various reagents tested, stripping of uranium was quantitative by 12% Na{sub 2}CO{sub 3} solution. Polymeric beads were found to be stable and reusable up-to 10 cycles of extraction/stripping. (authors)« less

Evaluating bis(2-ethylhexyl) methanediphosphonic acid (H 2DEH[MDP]) based polymer ligand film (PLF) for plutonium and uranium extraction

DOE PAGES

Rim, Jung H.; Armenta, Claudine E.; Gonzales, Edward R.; ...

2015-09-12

This paper describes a new analyte extraction medium called polymer ligand film (PLF) that was developed to rapidly extract radionuclides. PLF is a polymer medium with ligands incorporated in its matrix that selectively and quickly extracts analytes. The main focus of the new technique is to shorten and simplify the procedure for chemically isolating radionuclides for determination through alpha spectroscopy. The PLF system was effective for plutonium and uranium extraction. The PLF was capable of co-extracting or selectively extracting plutonium over uranium depending on the PLF composition. As a result, the PLF and electrodeposited samples had similar alpha spectra resolutions.

Extraction of reduced alteration information based on Aster data: a case study of the Bashibulake uranium ore district

NASA Astrophysics Data System (ADS)

Ye, Fa-wang; Liu, De-chang

2008-12-01

Practices of sandstone-type uranium exploration in recent years in China indicate that the uranium mineralization alteration information is of great importance for selecting a new uranium target or prospecting in outer area of the known uranium ore district. Taking a case study of BASHIBULAKE uranium ore district, this paper mainly presents the technical minds and methods of extracting the reduced alteration information by oil and gas in BASHIBULAKE ore district using ASTER data. First, the regional geological setting and study status in BASHIBULAKE uranium ore district are introduced in brief. Then, the spectral characteristics of altered sandstone and un-altered sandstone in BASHIBULAKE ore district are analyzed deeply. Based on the spectral analysis, two technical minds to extract the remote sensing reduced alteration information are proposed, and the un-mixing method is introduced to process ASTER data to extract the reduced alteration information in BASHIBULAKE ore district. From the enhanced images, three remote sensing anomaly zones are discovered, and their geological and prospecting significances are further made sure by taking the advantages of multi-bands in SWIR of ASTER data. Finally, the distribution and intensity of the reduced alteration information in Cretaceous system and its relationship with the genesis of uranium deposit are discussed, the specific suggestions for uranium prospecting orientation in outer of BASHIBULAKE ore district are also proposed.

Enhancement of Extraction of Uranium from Seawater

DOE Office of Scientific and Technical Information (OSTI.GOV)

Al-Sheikhly, Mohamad; Dietz, Travis; Tsinas, Zois

2016-04-01

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

Enhancement of Extraction of Uranium from Seawater – Final Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dietz, Travis Cameron; Tsinas, Zois; Tomaszewski, Claire

2016-05-16

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

Diffusive gradient in thin FILMS (DGT) compared with soil solution and labile uranium fraction for predicting uranium bioavailability to ryegrass.

PubMed

Duquène, L; Vandenhove, H; Tack, F; Van Hees, M; Wannijn, J

2010-02-01

The usefulness of uranium concentration in soil solution or recovered by selective extraction as unequivocal bioavailability indices for uranium uptake by plants is still unclear. The aim of the present study was to test if the uranium concentration measured by the diffusive gradient in thin films (DGT) technique is a relevant substitute for plant uranium availability in comparison to uranium concentration in the soil solution or uranium recovered by ammonium acetate. Ryegrass (Lolium perenne L. var. Melvina) is grown in greenhouse on a range of uranium spiked soils. The DGT-recovered uranium concentration (C(DGT)) was correlated with uranium concentration in the soil solution or with uranium recovered by ammonium acetate extraction. Plant uptake was better predicted by the summed soil solution concentrations of UO(2)(2+), uranyl carbonate complexes and UO(2)PO(4)(-). The DGT technique did not provide significant advantages over conventional methods to predict uranium uptake by plants. Copyright 2009 Elsevier Ltd. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Denton, J. S.; Goldstein, S. J.; Paviet, P.

Studies of uranium-series (U-series) disequilibria within and around ore deposits provide valuable information on the extent and timing of actinide mobility, via mineral-fluid interaction, over a range of spatial and temporal scales. Such information is useful in studies of analogs of high-level nuclear-waste repositories, as well as for mining and mineral extraction sites, locations of previous nuclear weapons testing, and legacy nuclear waste contamination. In this study we present isotope dilution mass spectrometry U-series measurements for fracture-fill materials (hematite, goethite, kaolinite, calcite, dolomite and quartz) from one such analog; the Nopal I uranium ore deposit situated at Peña Blanca inmore » the Chihuahua region of northern Mexico. The ore deposit is located in fractured, unsaturated volcanic tuff and fracture-fill materials from surface fractures as well as fractures in a vertical drill core have been analyzed. High uranium concentrations in the fracture-fill materials (between 12 and 7700 ppm) indicate uranium mobility and transport from the deposit. Furthermore, uranium concentrations generally decrease with horizontal distance away from the deposit but in this deposit there is no trend with depth below the surface.« less

A record of uranium-series transport at Nopal I, Sierra Pena Blanca, Mexico: Implications for natural uranium deposits and radioactive waste repositories

DOE PAGES

Denton, J. S.; Goldstein, S. J.; Paviet, P.; ...

2016-04-10

Studies of uranium-series (U-series) disequilibria within and around ore deposits provide valuable information on the extent and timing of actinide mobility, via mineral-fluid interaction, over a range of spatial and temporal scales. Such information is useful in studies of analogs of high-level nuclear-waste repositories, as well as for mining and mineral extraction sites, locations of previous nuclear weapons testing, and legacy nuclear waste contamination. In this study we present isotope dilution mass spectrometry U-series measurements for fracture-fill materials (hematite, goethite, kaolinite, calcite, dolomite and quartz) from one such analog; the Nopal I uranium ore deposit situated at Peña Blanca inmore » the Chihuahua region of northern Mexico. The ore deposit is located in fractured, unsaturated volcanic tuff and fracture-fill materials from surface fractures as well as fractures in a vertical drill core have been analyzed. High uranium concentrations in the fracture-fill materials (between 12 and 7700 ppm) indicate uranium mobility and transport from the deposit. Furthermore, uranium concentrations generally decrease with horizontal distance away from the deposit but in this deposit there is no trend with depth below the surface.« less

Molten salt extraction of transuranic and reactive fission products from used uranium oxide fuel

DOEpatents

Herrmann, Steven Douglas

2014-05-27

Used uranium oxide fuel is detoxified by extracting transuranic and reactive fission products into molten salt. By contacting declad and crushed used uranium oxide fuel with a molten halide salt containing a minor fraction of the respective uranium trihalide, transuranic and reactive fission products partition from the fuel to the molten salt phase, while uranium oxide and non-reactive, or noble metal, fission products remain in an insoluble solid phase. The salt is then separated from the fuel via draining and distillation. By this method, the bulk of the decay heat, fission poisoning capacity, and radiotoxicity are removed from the used fuel. The remaining radioactivity from the noble metal fission products in the detoxified fuel is primarily limited to soft beta emitters. The extracted transuranic and reactive fission products are amenable to existing technologies for group uranium/transuranic product recovery and fission product immobilization in engineered waste forms.

Extraction of uranium from tailings by sulfuric acid leaching with oxidants

NASA Astrophysics Data System (ADS)

Huang, Jing; Li, Mi; Zhang, Xiaowen; Huang, Chunmei; Wu, Xiaoyan

2017-06-01

Recovery of uranium have been performed by leaching uranium-containing tailings in sulfuric acid system with the assistance of HF, HClO4, H2O2 and MnO2. The effect of reagent dosage, sulfuric acid concentration, Liquid/solid ratio, reaction temperature and particle size on the leaching of uranium were investigated. The results show that addiction of HF, HClO4, H2O2 and MnO2 significantly increased the extraction of uranium under 1M sulphuric acid condition and under the optimum reaction conditions a dissolution fraction of 85% by HClO4, 90% by HF, 95% by H2O2 can be reached respectively. The variation of technological mineralogy properites of tailings during leaching process show that the assistants can break gangue effectively. These observations suggest that optimum oxidants could potentially influence the extraction of uranium from tailings even under dilute acid condition.

Incorporation of Uranium into Hematite during Crystallization from Ferrihydrite

PubMed Central

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

Decontamination of uranium-contaminated waste oil using supercritical fluid and nitric acid.

PubMed

Sung, Jinhyun; Kim, Jungsoo; Lee, Youngbae; Seol, Jeunggun; Ryu, Jaebong; Park, Kwangheon

2011-07-01

The waste oil used in nuclear fuel processing is contaminated with uranium because of its contact with materials or environments containing uranium. Under current law, waste oil that has been contaminated with uranium is very difficult to dispose of at a radioactive waste disposal site. To dispose of the uranium-contaminated waste oil, the uranium was separated from the contaminated waste oil. Supercritical R-22 is an excellent solvent for extracting clean oil from uranium-contaminated waste oil. The critical temperature of R-22 is 96.15 °C and the critical pressure is 49.9 bar. In this study, a process to remove uranium from the uranium-contaminated waste oil using supercritical R-22 was developed. The waste oil has a small amount of additives containing N, S or P, such as amines, dithiocarbamates and dialkyldithiophosphates. It seems that these organic additives form uranium-combined compounds. For this reason, dissolution of uranium from the uranium-combined compounds using nitric acid was needed. The efficiency of the removal of uranium from the uranium-contaminated waste oil using supercritical R-22 extraction and nitric acid treatment was determined.

A novel benzimidazole-functionalized 2-D COF material: synthesis and application as a selective solid-phase extractant for separation of uranium.

PubMed

Li, Juan; Yang, Xiaodan; Bai, Chiyao; Tian, Yin; Li, Bo; Zhang, Shuang; Yang, Xiaoyu; Ding, Songdong; Xia, Chuanqin; Tan, Xinyu; Ma, Lijian; Li, Shoujian

2015-01-01

A novel COF-based material (COF-COOH) containing large amounts of carboxylic groups was prepared for the first time by using a simple and effective one-step synthetic method, in which the cheap and commercially available raw materials, trimesoyl chloride and p-phenylenediamine, were used. The as-synthesized COF-COOH was modified with previously synthesized 2-(2,4-dihydroxyphenyl)-benzimidazole (HBI) by "grafting to" method, and a new solid-phase extractant (COF-HBI) with highly efficient sorption performance for uranium(VI) was consequently obtained. A series of characterizations demonstrated that COF-COOH and COF-HBI exhibited great thermostabilities and irradiation stabilities. Sorption behavior of the COF-based materials toward U(VI) was compared in simulated nuclear industrial effluent containing UO2(2+) and 11 undesired ions, and the UO2(2+) sorption amount of COF-HBI was 81 mg g(-1), accounting for approximately 58% of the total sorption amount, which was much higher than the sorption selectivity of COF-COOH to UO2(2+) (39%). Batch sorption experiment results indicated that the uranium(VI) sorption on COF-HBI was a pH dependent, rapid (sorption equilibrium was reached in 30 min), endothermic and spontaneous process. In the most favorable conditions, the equilibrium sorption capacity of the adsorbent for uranium could reach 211 mg g(-1). Copyright © 2014 Elsevier Inc. All rights reserved.

Solubility testing of actinides on breathing-zone and area air samples

NASA Astrophysics Data System (ADS)

Metzger, Robert Lawrence

The solubility of inhaled radionuclides in the human lung is an important characteristic of the compounds needed to perform internal dosimetry assessments for exposed workers. A solubility testing method for uranium and several common actinides has been developed with sufficient sensitivity to allow profiles to be determined from routine breathing zone and area air samples in the workplace. Air samples are covered with a clean filter to form a filter-sample-filter sandwich which is immersed in an extracellular lung serum simulant solution. The sample is moved to a fresh beaker of the lung fluid simulant each day for one week, and then weekly until the end of the 28 day test period. The soak solutions are wet ashed with nitric acid and hydrogen peroxide to destroy the organic components of the lung simulant solution prior to extraction of the nuclides of interest directly into an extractive scintillator for subsequent counting on a Photon-Electron Rejecting Alpha Liquid Scintillation (PERALSsp°ler ) spectrometer. Solvent extraction methods utilizing the extractive scintillators have been developed for the isotopes of uranium, plutonium, and curium. The procedures normally produce an isotopic recovery greater than 95% and have been used to develop solubility profiles from air samples with 40 pCi or less of Usb3Osb8. This makes it possible to characterize solubility profiles in every section of operating facilities where airborne nuclides are found using common breathing zone air samples. The new method was evaluated by analyzing uranium compounds from two uranium mills whose product had been previously analyzed by in vitro solubility testing in the laboratory and in vivo solubility testing in rodents. The new technique compared well with the in vivo rodent solubility profiles. The method was then used to evaluate the solubility profiles in all process sections of an operating in situ uranium plant using breathing zone and area air samples collected during routine plant operations. The solubility profiles developed from this work showed excellent agreement with the results of the worker urine bioassay program at the plant and identified a significant error in existing internal dose assessments at this facility.

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

PubMed

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

2015-11-01

Actinides determination in urine samples is part of the analyses performed to monitor internal contamination in case of an accident or a terrorist attack involving nuclear matter. Mineralisation is the first step of any of these analyses. It aims at reducing the sample volume and at destroying all organic compounds present. The mineralisation protocol is usually based on a wet ashing step, followed by actinides co-precipitation and a furnace ashing step, before redissolution and the quantification of the actinides by the appropriate techniques. Amongst the existing methods to perform the actinides co-precipitation, alkali-earth (typically calcium) precipitation is widely used. In the present work, the extraction of uranium(VI), plutonium(IV) and americium(III) from the redissolution solutions (called "mineralised urines") on calix[6]arene columns bearing hydroxamic groups was investigated as such an extraction is a necessary step before their determination by ICP-MS or alpha spectrometry. Difficulties were encountered in the transfer of uranium(VI) from raw to mineralised urines, with yield of transfer ranging between 0% and 85%, compared to about 90% for Pu and Am, depending on the starting raw urines. To understand the origin of such a difficulty, the speciation of uranium (VI) in mineralised urines was investigated by computer simulation using the MEDUSA software and the associated HYDRA database, compiled with recently published data. These calculations showed that the presence of phosphates in the "mineralised urines" leads to the formation of strong uranyl-phosphate complexes (such as UO2HPO4) which compete with the uranium (VI) extraction by the calix[6]arene bearing hydroxamic groups. The extraction constant of uranium (VI) by calix[6]arene bearing hydroxamic groups was determined in a 0.04 mol L(-1) sodium nitrate solution (logK=4.86±0.03) and implemented in an extraction model taking into account the speciation in the aqueous phase. This model allowed to simulate satisfactorily the experimental uranium extraction data and to support the preliminary conclusions about the role of the phosphates present in mineralised urines. These calculations also showed that the phosphate/calcium ratio is a key parameter as far as the efficiency of the uranium (VI) extraction by the calix[6]arene columns is concerned. It predicted that the addition of CaCl2 in mineralised urines would release uranium (VI) from phosphates by forming calcium (II)-phosphate complexes and thus facilitate the uranium (VI) extraction on calix[6]arene columns. These predictions were confirmed experimentally as the addition of 0.1 mol L(-1) CaCl2 to a mineralised urine containing naturally a high concentration of phosphate (typically 0.04 mol L(-1)) significantly increased the percentage of uranium (VI) extraction on the calix[6]arene columns. Copyright © 2015 Elsevier B.V. All rights reserved.

THE ANALYSIS OF URANIUM-ZIRCONIUM ALLOYS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Milner, G.W.C.; Skewies, A.F.

1953-03-01

A satisfactory procedure is described for the analysis of uranium-zirconium alloys containing up to 25% zirconium. It is based on the separation of the zirconium from the uranium by dissolving the cupferron complex of the former element into chloroform. After the evaporation of the solvent from the combined organic extracts, the residue is ignited to zirconium oxide. The latter is then re-dissolved and zirconium is separated from other elements co-extracted in the solvent extraction procedure by precipitation with mandelic acid. The zirconium mandelate is finally ignited to oxide at 960 deg C. The uranium is separated from the aqueous solutionmore » remaining from the cupferron extraction by precipitating with tannin at a pH of 8; the precipitate being removed by filtration and then ignited a t 800 deg C. The residue is dissolved in nitric acid and the uranium is finally determined by precipitating as ammonium diuranate and then igniting to U{sub 3}O{sub 8}. (auth)« less

Potential uranium supply from phosphoric acid: A U.S. analysis comparing solvent extraction and Ion exchange recovery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Haeyeon; G. Eggert, Roderick; W. Carlsen, Brett

Phosphate rock contains significant amounts of uranium, although in low concentrations. Recovery of uranium as a by-product from phosphoric acid, an intermediate product produced during the recovery of phosphorus from phosphate rock, is not unprecedented. Phosphoric acid plants ceased to produce uranium as a by-product in the early 1990s with the fall of uranium prices. In the last decade, this topic has regained attention due to higher uranium prices and expected increase in demand for uranium. Our study revisits the topic and estimates how much uranium might be recoverable from current phosphoric acid production in the United States and whatmore » the associated costs might be considering two different recovery processes: solvent extraction and ion exchange. Based on U.S. phosphoric acid production in 2014, 5.5 million pounds of U 3O 8 could have been recovered, more than domestic U.S. mine production of uranium in the same year. Annualized costs for a hypothetical uranium recovery plant are US$48-66 per pound U 3O 8 for solvent extraction, the process used historically in the United States to recover uranium from phosphoric acid. For ion exchange, not yet proven at a commercial scale for uranium recovery, the estimated costs are US$33-54 per pound U 3O 8. Our results suggest that it is technically possible for the United States to recover significant quantities of uranium from current phosphoric acid production. And for this type of uranium production to be economically attractive on a large scale, either recovery costs must fall or uranium prices rise.« less

Potential uranium supply from phosphoric acid: A U.S. analysis comparing solvent extraction and Ion exchange recovery

DOE PAGES

Kim, Haeyeon; G. Eggert, Roderick; W. Carlsen, Brett; ...

2016-06-16

Phosphate rock contains significant amounts of uranium, although in low concentrations. Recovery of uranium as a by-product from phosphoric acid, an intermediate product produced during the recovery of phosphorus from phosphate rock, is not unprecedented. Phosphoric acid plants ceased to produce uranium as a by-product in the early 1990s with the fall of uranium prices. In the last decade, this topic has regained attention due to higher uranium prices and expected increase in demand for uranium. Our study revisits the topic and estimates how much uranium might be recoverable from current phosphoric acid production in the United States and whatmore » the associated costs might be considering two different recovery processes: solvent extraction and ion exchange. Based on U.S. phosphoric acid production in 2014, 5.5 million pounds of U 3O 8 could have been recovered, more than domestic U.S. mine production of uranium in the same year. Annualized costs for a hypothetical uranium recovery plant are US$48-66 per pound U 3O 8 for solvent extraction, the process used historically in the United States to recover uranium from phosphoric acid. For ion exchange, not yet proven at a commercial scale for uranium recovery, the estimated costs are US$33-54 per pound U 3O 8. Our results suggest that it is technically possible for the United States to recover significant quantities of uranium from current phosphoric acid production. And for this type of uranium production to be economically attractive on a large scale, either recovery costs must fall or uranium prices rise.« less

ALKYL PYROPHOSPHATE METAL SOLVENT EXTRACTANTS AND PROCESS

DOEpatents

Long, R.L.

1958-09-30

A process is presented for the recovery of uranium from aqueous mineral acidic solutions by solvent extraction. The extractant is a synmmetrical dialkyl pyrophosphate in which the alkyl substituents have a chain length of from 4 to 17 carbon atoms. Mentioned as a preferred extractant is dioctyl pyrophosphate. The uranium is precipitated irom the organic extractant phase with an agent such as HF, fluoride salts. alcohol, or ammonia.

Recovery of uranium values

DOEpatents

Brown, K. B.; Crouse, Jr., D. J.; Moore, J. G.

1959-03-10

A liquid-liquid extraction method is presented for recovering uranium values from an aqueous acidic solution by means of certain high molecular weight amine fn the amine classes of primary, secondary, heterocyclic secondary, tertiary, or heterocyclic tertiary. The uranium bearing aqueous acidic solution is contacted with the selected anine dissolved in a nonpolar waterimmiscible organfc solvent such as kerosene. The uranium which is substantially completely extracted by the organic phase may be stripped therefrom by water, and recovered from the aqueous phase by treatment into ammonia to precipitate ammonium diuranate.

PROCESS FOR REMOVING NOBLE METALS FROM URANIUM

DOEpatents

Knighton, J.B.

1961-01-31

A pyrometallurgical method is given for purifying uranium containing ruthenium and palladium. The uranium is disintegrated and oxidized by exposure to air and then the ruthenium and palladium are extracted from the uranium with molten zinc.

Applied technology for mine waste water decontamination in the uranium ores extraction from Romania

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bejenaru, C.; Filip, G.; Vacariu, V.T.

1996-12-31

The exploitation of uranium ores in Romania is carried out in underground mines. In all exploited uranium deposits, mine waste waters results and will still result after the closure of uranium ore extraction activity. The mine waters are radioactively contaminated with uranium and its decay products being a hazard both for underground waters as for the environment. This paper present the results of research work carried out by authors for uranium elimination from waste waters as the problems involved during the exploitation process of the existent equipment as its maintenance in good experimental conditions. The main waste water characteristics aremore » discussed: solids as suspension, uranium, radium, mineral salts, pH, etc. The moist suitable way to eliminate uranium from mine waste waters is the ion exchange process based on ion exchangers in fluidized bed. A flowsheet is given with main advantages resulted.« less

Rapid extraction and assay of uranium from environmental surface samples

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barrett, Christopher A.; Chouyyok, Wilaiwan; Speakman, Robert J.

Extraction methods enabling faster removal and concentration of uranium compounds for improved trace and low-level assay are demonstrated for standard surface sampling material in support of nuclear safeguards efforts, health monitoring, and other nuclear analysis applications. A key problem with the existing surface sampling swipes is the requirement for complete digestion of sample and sampling matrix. This is a time-consuming and labour-intensive process that limits laboratory throughput, elevates costs, and increases background levels. Various extraction methods are explored for their potential to quickly and efficiently remove different chemical forms of uranium from standard surface sampling material. A combination of carbonatemore » and peroxide solutions is shown to give the most rapid and complete form of uranyl compound extraction and dissolution. This rapid extraction process is demonstrated to be compatible with standard inductive coupled plasma mass spectrometry methods for uranium isotopic assay as well as screening techniques such as x-ray fluorescence. The general approach described has application beyond uranium to other analytes of nuclear forensic interest (e.g., rare earth elements and plutonium) as well as heavy metals for environmental and industrial hygiene monitoring.« less

New Fiber Materials with Sorption Capacity at 5.0 g-U/kg Adsorbent under Marine Testing Conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saito, Tomonori; Brown, S.; Das, Sadananda

The Fuel Resources program of the Fuel Cycle Research and Development program of the Office of Nuclear Energy (NE) has focused on assuring that nuclear fuel resources are available in the United States for a long term. An immense source of uranium is seawater, which contains an estimated amount of 4.5 billion tonnes of dissolved uranium. Extraction of the uranium resource in seawater can provide a price cap and ensure centuries of uranium supply for future nuclear energy production. NE initiated a multidisciplinary program with participants from national laboratories, universities, and research institutes to enable technical breakthroughs related to uraniummore » recovery from seawater. The goal is to develop advanced adsorbents to make the seawater uranium recovery technology a cost competitive, viable technology. Under this program, Oak Ridge National Laboratory (ORNL) has developed several novel adsorbents, which enhanced the uranium capacity 4-5 times from the state-of-the art Japanese adsorbents. Uranium exists uniformly at a concentration of ~3.3 ppb in seawater. Because of the vast volume of the oceans, the total estimated amount of uranium in seawater is approximately 1000 times larger than its amount in terrestrial resources. However, due to the low concentration, a significant challenge remains for making the extraction of uranium from seawater a commercially viable alternative technology. The biggest challenge for this technology to overcome to efficiently reduce the extraction cost is to develop adsorbents with increased uranium adsorption capacity. Two major approaches were investigated for synthesizing novel adsorbents with enhanced uranium adsorption capacity. One method utilized conventional radiation induced graft polymerization (RIGP) to synthesize adsorbents on high-surface area trunk fibers and the other method utilized a chemical grafting technique, atom-transfer radical polymerization (ATRP). Both approaches have shown promising uranium extraction capacities: RIGP adsorbent achieved 5.00 ± 0.15 g U/kg-ads., while ATRP adsorbent achieved 6.56 ± 0.33 g U/kg-ads., after 56 days of seawater exposure. These achieved values are the highest adsorption capacities ever reported for uranium extraction from seawater. The study successfully demonstrated new fiber materials with sorption capacity at 5.0 g-U/kg adsorbent under marine testing conditions. Further optimization, investigation of other new materials as well as deepening our understanding will develop adsorbents that have even higher uranium adsorption capacity, increased selectivity, and faster kinetics.« less

Tetravalent uranium extraction by HDEHP in kerosene from phosphate medium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Daoud, J.A.; Zeid, M.M.; Aly, H.F.

1997-03-01

The extraction of U(IV) by di-2-ethylhexyl phosphoric acid (HDEHP) in kerosene from phosphoric acid was measured spectrophotometrically. The effect of extractant, phosphoric acid, uranium, Fe(II) and Fe(III) concentrations on the extraction process were separately investigated. The effect of different reagents and temperature on the stripping of U(IV) were also tested. The results obtained showed that the extraction increases with the increase in HDEHP and Fe(III) concentrations while it decreases with the increase in phosphoric acid, uranium and Fe(II) concentration. The use of high phosphoric acid concentration as strip solutions at low temperature was found to give good stripping results. 11more » refs., 8 figs., 2 tabs.« less

SEPARATION OF URANIUM FROM THORIUM AND PROTACTINIUM

DOEpatents

Musgrave, W.K.R.

1959-06-30

This patent relates to the separation of uranium from thorium and protactinium; such mixtures of elements usually being obtained by neutron irradiation of thorium. The method of separating the constituents has been first to dissolve the mixture of elements in concertrated nitric acid and then to remove the protactinium by absorption on manganese dioxide and the uranium by solvent extraction with ether. Prior to now, comparatively large amounts of thorium were extracted with the uranium. According to the invention this is completely prevented by adding sodium diethyldithiocarbamate to the mixture of soluble nitrate salts. The organic salt has the effect of reacting only with the uranyl nitrate to form the corresponding uranyl salt which can then be selectively extracted from the mixture with amyl acetate.

Comparison of solvent extraction and extraction chromatography resin techniques for uranium isotopic characterization in high-level radioactive waste and barrier materials.

PubMed

Hurtado-Bermúdez, Santiago; Villa-Alfageme, María; Mas, José Luis; Alba, María Dolores

2018-07-01

The development of Deep Geological Repositories (DGP) to the storage of high-level radioactive waste (HLRW) is mainly focused in systems of multiple barriers based on the use of clays, and particularly bentonites, as natural and engineered barriers in nuclear waste isolation due to their remarkable properties. Due to the fact that uranium is the major component of HLRW, it is required to go in depth in the analysis of the chemistry of the reaction of this element within bentonites. The determination of uranium under the conditions of HLRW, including the analysis of silicate matrices before and after the uranium-bentonite reaction, was investigated. The performances of a state-of-the-art and widespread radiochemical method based on chromatographic UTEVA resins, and a well-known and traditional method based on solvent extraction with tri-n-butyl phosphate (TBP), for the analysis of uranium and thorium isotopes in solid matrices with high concentrations of uranium were analysed in detail. In the development of this comparison, both radiochemical approaches have an overall excellent performance in order to analyse uranium concentration in HLRW samples. However, due to the high uranium concentration in the samples, the chromatographic resin is not able to avoid completely the uranium contamination in the thorium fraction. Copyright © 2018 Elsevier Ltd. All rights reserved.

URANIUM EXTRACTION PROCESS

DOEpatents

Baldwin, W.H.; Higgins, C.E.

1958-12-16

A process is described for recovering uranium values from acidic aqueous solutions containing hexavalent uranium by contacting the solution with an organic solution comprised of a substantially water-immiscible organlc diluent and an organic phosphate to extract the uranlum values into the organic phase. Carbon tetrachloride and a petroleum hydrocarbon fraction, such as kerosene, are sultable diluents to be used in combination with organlc phosphates such as dibutyl butylphosphonate, trlbutyl phosphine oxide, and tributyl phosphate.

Evaluation of N,N-dialkylamides as promising process extractants

NASA Astrophysics Data System (ADS)

Pathak, P. N.; Prabhu, D. R.; Kanekar, A. S.; Manchanda, V. K.

2010-03-01

Studies carried out at BARC, India on the development of new extractants for reprocessing of spent fuel suggested that while straight chain N,N-dihexyloctanamide (DHOA) is promising alternative to TBP for the reprocessing of irradiated uranium based fuels, branched chain N,N-di(2-ethylhexyl)isobutyramide (D2EHIBA) is suitable for the selective recovery of 233U from irradiated Th. In advanced fuel cycle scenarios, the coprocessing of U/Pu stream appears attractive particularly with respect to development of proliferation resistant technologies. DHOA extracted Pu(IV) more efficiently than TBP, both at trace-level concentration as well as under uranium/plutonium loading conditions. Uranium extraction behavior of DHOA was however, similar to that of TBP during the extraction cycle. Stripping behavior of U and Pu (without any reductant) was better for DHOA than that of TBP. It was observed during batch studies that whereas 99% Pu is stripped in four stages in case of DHOA, only 89% Pu is stripped in case of TBP under identical experimental conditions. DHOA offered better fission product decontamination than that of TBP. GANEX (Group ActiNide EXtraction) and ARTIST (Amide-based Radio-resources Treatment with Interim Storage of Transuranics) processes proposed for actinide partitioning use branched chain amides for the selective extraction of uranium from spent fuel feed solutions. The branched-alkyl monoamide (BAMA) proposed to be used in ARTIST process is N,N-di-(2-ethylhexyl)butyramide (D2EHBA). In this context, the extraction behavior of U(VI) and Pu(IV) were compared using D2EHIBA, TBP, and D2EHBA under similar concentration of nitric acid (0.5 — 6M) and of uranium (0-50g/L). These studies suggested that D2EHIBA is a promising extractant for selective extraction of uranium over plutonium in process streams. Similarly, D2EHIBA offered distinctly better decontamination of 233U over Th and fission products under THOREX feed conditions. The possibility of simultaneous stripping and precipitation of thorium (as oxalate) from loaded organic phase was explored using 0.05M oxalic acid. Ammonium diuranate (ADU) precipitation was performed on the oxalate supernatant for the recovery of uranium. Quantitative recovery (>99.9%) of Th as well as of U was achieved. Radiolytic studies suggested that irradiated DHOA and D2EHIBA behaved better with respect to fission product decontamination as compared to that of TBP.

URANIUM EXTRACTION PROCESS USING SYNERGISTIC REAGENTS

DOEpatents

Schmitt, J.M.; Blake, C.A. Jr.; Brown, K.B.; Coleman, C.F.

1958-11-01

Improved methods are presented for recovering uranium values from aqueous solutions by organic solvent extraction. The improvement lies in the use, in combination, of two classes of organic compounds so that their extracting properties are enhanced synergistically. The two classes of organic compounds are dialkylphosphoric acid and certain neutral organophosphorus compounds such as trialkylphosphates, trialkylphosphonates, trlalkylphosphinates and trialkylphosphine oxides.

Ultrasound enhanced process for extracting metal species in supercritical fluids

DOEpatents

Wai, Chien M.; Enokida, Youichi

2006-10-31

Improved methods for the extraction or dissolution of metals, metalloids or their oxides, especially lanthanides, actinides, uranium or their oxides, into supercritical solvents containing an extractant are disclosed. The disclosed embodiments specifically include enhancing the extraction or dissolution efficiency with ultrasound. The present methods allow the direct, efficient dissolution of UO₂ or other uranium oxides without generating any waste stream or by-products.

Evaluating ligands for use in polymer ligand film (PLF) for plutonium and uranium extraction

DOE PAGES

Rim, Jung H.; Peterson, Dominic S.; Armenta, Claudine E.; ...

2015-05-08

We describe a new analyte extraction technique using Polymer Ligand Film (PLF). PLFs were synthesized to perform direct sorption of analytes onto its surface for direct counting using alpha spectroscopy. The main focus of the new technique is to shorten and simplify the procedure for chemically isolating radionuclides for determination through a radiometric technique. 4'(5')-di-t-butylcyclohexano 18-crown-6 (DtBuCH 18C 6) and 2-ethylhexylphosphonic acid (HEH[EHP]) were examined for plutonium extraction. Di(2-ethyl hexyl) phosphoric acid (HDEHP) were examined for plutonium and uranium extraction. DtBuCH 18C 6 and HEH[EHP] were not effective in plutonium extraction. HDEHP PLFs were effective for plutonium but not formore » uranium.« less

PREPARATION OF HIGH PURITY UF$sub 4$

DOEpatents

Magner, J.E.; Long, R.S.; Ellis, D.A.; Grinstead, R.R.

1962-04-17

S>A process for preparing very highly pure uranous tetrafluoride from impure uranium laden solvent extraction strip solutions, ion exchange process and resin-inpulp process eluate solutions which are at least 8M in hydrochloric acid is described. The process first comprises treating any of the above-mentioned solutions with a reducing agent to reduce the uranium to the + 4 oxidation state, and then contacting the reduced solution with an extractant phase comprising about 10 to 70% of tri-butyl phosphate in an organic solvent-diluent selected from benzene, ethyl-benzene, chlorobenzene, xylene, kerosene, or the like. The uranium is extracted into the extractant phase and is subsequently precipitated by treating the extractant with an aqueous fluoride solution. The highly pure uranous tetrafluoride precipitate is separated from the phases and recovered for subsequent utilization. (AEC)

UTEX LEACHING, THICKENING AND FILTRATION TESTS. Topical Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stanley, A.; George, D.R.; Thomas, P.N.

1954-03-15

A series of leaching, thickening, and filtration tests was undertaken to determine minimum conditions for high uranium extractions and obtain thickening and filtration data. The ore represented by the sample responded to cold and hot leaching with the minimum condition for uranium extraction being 500 pounds of H/ sub 2/SO/sub 4/ per ton and five pounds NaClO/sub 3/ per ton leached at room temperature for l6 hours with uranium extraction of over 95%. Thickening and filtration were economical if a reagent such as S-3000 or Guar gum was used. (auth)

Uranium release from different size fractions of sediments in Hanford 300 area, Washington, USA.

PubMed

Du, Jiangkun; Bao, Jianguo; Hu, Qinhong; Ewing, Robert P

2012-05-01

Stirred-flow cell tests were carried out to investigate uranium (U) release from different size fractions of sediments from the U.S. Department of Energy's Hanford 300 Area in Washington, USA. Results show that the measured concentration of U release varies with different size fractions, with the fine-grained mass fractions (<75 μm, 75-500 μm, and 500-2000 μm) being the main U carriers. However, because the sediment is mainly composed of gravel (2000-8000 μm) materials, the gravel fraction is a non-negligible U pool. Our elution experiments give a value of 8.7% of the total U being in the gravel fraction, significantly reducing the current uncertainty in evaluating U inventory. A log-log plot of released U concentration vs. elution volume (i.e., elution time) shows a power-law relationship for all size fractions, with identical exponents for the three fine size fractions (-0.875). For the <2000 μm mass fraction, comparing our eluted U values with reported total U concentrations, we estimate that a lower bound value 8.6% of the total uranium is labile. This compares well with the previously published value of 11.8% labile U after extraction with a dilute extractant for three weeks. Copyright © 2012 Elsevier Ltd. All rights reserved.

Uranium from Seawater Program Review; Fuel Resources Uranium from Seawater Program DOE Office of Nuclear Energy

DOE Office of Scientific and Technical Information (OSTI.GOV)

None

2013-07-01

For nuclear energy to remain sustainable in the United States, economically viable sources of uranium beyond terrestrial ores must be developed. The goal of this program is to develop advanced adsorbents that can extract uranium from seawater at twice the capacity of the best adsorbent developed by researchers at the Japan Atomic Energy Agency (JAEA), 1.5 mg U/g adsorbent. A multidisciplinary team from Oak Ridge National Laboratory, Lawrence Berkeley National Laboratory, Pacific Northwest National Laboratory, and the University of Texas at Austin was assembled to address this challenging problem. Polymeric adsorbents, based on the radiation grafting of acrylonitrile and methacrylicmore » acid onto high surface-area polyethylene fibers followed by conversion of the nitriles to amidoximes, have been developed. These poly(acrylamidoxime-co-methacrylic acid) fibers showed uranium adsorption capacities for the extraction of uranium from seawater that exceed 3 mg U/g adsorbent in testing at the Pacific Northwest National Laboratory Marine Sciences Laboratory. The essence of this novel technology lies in the unique high surface-area trunk material that considerably increases the grafting yield of functional groups without compromising its mechanical properties. This technology received an R&D100 Award in 2012. In addition, high surface area nanomaterial adsorbents are under development with the goal of increasing uranium adsorption capacity by taking advantage of the high surface areas and tunable porosity of carbon-based nanomaterials. Simultaneously, de novo structure-based computational design methods are being used to design more selective and stable ligands and the most promising candidates are being synthesized, tested and evaluated for incorporation onto a support matrix. Fundamental thermodynamic and kinetic studies are being carried out to improve the adsorption efficiency, the selectivity of uranium over other metals, and the stability of the adsorbents. Understanding the rate-limiting step of uranium uptake from seawater is also essential in designing an effective uranium recovery system. Finally, economic analyses have been used to guide these studies and highlight what parameters, such as capacity, recyclability, and stability, have the largest impact on the cost of extraction of uranium from seawater. Initially, the cost estimates by the JAEA for extraction of uranium from seawater with braided polymeric fibers functionalized with amidoxime ligands were evaluated and updated. The economic analyses were subsequently updated to reflect the results of this project while providing insight for cost reductions in the adsorbent development through “cradle-to-grave” case studies for the extraction process. This report highlights the progress made over the last three years on the design, synthesis, and testing of new materials to extract uranium for seawater. This report is organized into sections that highlight the major research activities in this project: (1) Chelate Design and Modeling, (2) Thermodynamics, Kinetics and Structure, (3) Advanced Polymeric Adsorbents by Radiation Induced Grafting, (4) Advanced Nanomaterial Adsorbents, (5) Adsorbent Screening and Modeling, (6) Marine Testing, and (7) Cost and Energy Assessment. At the end of each section, future research directions are briefly discussed to highlight the challenges that still remain to reduce the cost of extractions of uranium for seawater. Finally, contributions from the Nuclear Energy University Programs (NEUP), which complement this research program, are included at the end of this report.« less

PROCESSING OF NEUTRON-IRRADIATED URANIUM

DOEpatents

Hopkins, H.H. Jr.

1960-09-01

An improved "Purex" process for separating uranium, plutonium, and fission products from nitric acid solutions of neutron-irradiated uranium is offered. Uranium is first extracted into tributyl phosphate (TBP) away from plutonium and fission products after adjustment of the acidity from 0.3 to 0.5 M and heating from 60 to 70 deg C. Coextracted plutonium, ruthenium, and fission products are fractionally removed from the TBP by three scrubbing steps with a 0.5 M nitric acid solution of ferrous sulfamate (FSA), from 3.5 to 5 M nitric acid, and water, respectively, and the purified uranium is finally recovered from the TBP by precipitation with an aqueous solution of oxalic acid. The plutonium in the 0.3 to 0.5 M acid solution is oxidized to the tetravalent state with sodium nitrite and extracted into TBP containing a small amount of dibutyl phosphate (DBP). Plutonium is then back-extracted from the TBP-DBP mixture with a nitric acid solution of FSA, reoxidized with sodium nitrite in the aqueous strip solution obtained, and once more extracted with TBP alone. Finally the plutonium is stripped from the TBP with dilute acid, and a portion of the strip solution thus obtained is recycled into the TBPDBP for further purification.

Remediation of soils contaminated with particulate depleted uranium by multi stage chemical extraction.

PubMed

Crean, Daniel E; Livens, Francis R; Sajih, Mustafa; Stennett, Martin C; Grolimund, Daniel; Borca, Camelia N; Hyatt, Neil C

2013-12-15

Contamination of soils with depleted uranium (DU) from munitions firing occurs in conflict zones and at test firing sites. This study reports the development of a chemical extraction methodology for remediation of soils contaminated with particulate DU. Uranium phases in soils from two sites at a UK firing range, MOD Eskmeals, were characterised by electron microscopy and sequential extraction. Uranium rich particles with characteristic spherical morphologies were observed in soils, consistent with other instances of DU munitions contamination. Batch extraction efficiencies for aqueous ammonium bicarbonate (42-50% total DU extracted), citric acid (30-42% total DU) and sulphuric acid (13-19% total DU) were evaluated. Characterisation of residues from bicarbonate-treated soils by synchrotron microfocus X-ray diffraction and X-ray absorption spectroscopy revealed partially leached U(IV)-oxide particles and some secondary uranyl-carbonate phases. Based on these data, a multi-stage extraction scheme was developed utilising leaching in ammonium bicarbonate followed by citric acid to dissolve secondary carbonate species. Site specific U extraction was improved to 68-87% total U by the application of this methodology, potentially providing a route to efficient DU decontamination using low cost, environmentally compatible reagents. Copyright © 2013 The Authors. Published by Elsevier B.V. All rights reserved.

77 FR 53236 - Proposed International Isotopes Fluorine Extraction Process and Depleted Uranium Deconversion...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-08-31

... NUCLEAR REGULATORY COMMISSION [NRC-2010-0143] Proposed International Isotopes Fluorine Extraction Process and Depleted Uranium Deconversion Plant in Lea County, New Mexico AGENCY: Nuclear Regulatory... U.S. Nuclear Regulatory Commission (NRC or the Commission) has published the Final Environmental...

METHOD FOR SEPARATION OF PLUTONIUM FROM URANIUM AND FISSION PRODUCTS BY SOLVENT EXTRACTION

DOEpatents

Seaborg, G.T.; Blaedel, W.J.; Walling, M.T. Jr.

1960-08-23

A process is given for separating from each other uranium, plutonium, and fission products in an aqueous nitric acid solution by the so-called Redox process. The plutonium is first oxidized to the hexavalent state, e.g., with a water-soluble dichromate or sodium bismuthate, preferably together with a holding oxidant such as potassium bromate. potassium permanganate, or an excess of the oxidizing agent. The solution is then contacted with a water-immiscible organic solvent, preferably hexone. whereby uranium and plutonium are extracted while the fission products remain in the aqueous solution. The separated organic phase is then contacted with an aqueous solution of a reducing agent, with or without a holding reductant (e.g., with a ferrous salt plus hydrazine or with ferrous sulfamate), whereby plutonium is reduced to the trivalent state and back- extracted into the aqueous solution. The uranium may finally be back-extracted from the organic solvent (e.g., with a 0.1 N nitric acid).

PROCESS FOR THE RECOVERY OF URANIUM FROM PHOSPHATIC ORE

DOEpatents

Long, R.L.

1959-04-14

A proccss is described for the recovery of uranium from phosphatic products derived from phosphatic ores. It has been discovered that certain alkyl phosphatic, derivatives can be employed in a direct solvent extraction operation to recover uranium from solid products, such as superphosphates, without first dissolving such solids. The organic extractants found suitable include alkyl derivatives of phosphoric, pyrophosphoric, phosof the derivative contains from 4 to 7 carbon atoms. A diluent such as kerosene is also used.

CONTINUOUS CHELATION-EXTRACTION PROCESS FOR THE SEPARATION AND PURIFICATION OF METALS

DOEpatents

Thomas, J.R.; Hicks, T.E.; Rubin, B.; Crandall, H.W.

1959-12-01

A continuous process is presented for separating metal values and groups of metal values from each other. A complex mixture. e.g., neutron-irradiated uranium, can be resolved into component parts. In the present process the values are dissolved in an acidic solution and adjusted to the proper oxidation state. Thenceforth the solution is contacted with an extractant phase comprising a fluorinated beta -diketone in an organic solvent under centain pH conditions whereupon plutonium and zirconium are extracted. Plutonium is extracted from the foregoing extract with reducing aqueous solutions or under specified acidic conditions and can be recovered from the aqueous solution. Zirconium is then removed with an oxalic acid aqueous phase. The uranium is recovered from the residual original solution using hexone and hexone-diketone extractants leaving residual fission products in the original solution. The uranium is extracted from the hexone solution with dilute nitric acid. Improved separations and purifications are achieved using recycled scrub solutions and the "self-salting" effect of uranyl ions.

PROCESS OF SEPARATING URANIUM FROM AQUEOUS SOLUTION BY SOLVENT EXTRACTION

DOEpatents

Warf, J.C.

1958-08-19

A process is described for separating uranium values from aqueous uranyl nitrate solutions. The process consists in contacting the uramium bearing solution with an organic solvent, tributyl phosphate, preferably diluted with a less viscous organic liquida whereby the uranyl nitrate is extracted into the organic solvent phase. The uranvl nitrate may be recovered from the solvent phase bv back extracting with an aqueous mediuin.

Nuclear Weapons. National Nuclear Security Administration’s Plans for Its Uranium Processing Facility Should Better Reflect Funding Estimates and Technology Readiness

DTIC Science & Technology

2010-11-01

metal. Recovery extraction centrifugal contactors A process that uses solvent to extract uranium for purposes of purification. Agile machining A...extraction centrifugal contactors 5 6 Yes 6 No Agile machining 5 5 No 6 No Chip management 5 6 Yes 6 No Special casting 3 6 Yes 6 No Source: GAO

Protein Hydrogel Microbeads for Selective Uranium Mining from Seawater.

PubMed

Kou, Songzi; Yang, Zhongguang; Sun, Fei

2017-01-25

Practical methods for oceanic uranium extraction have yet to be developed in order to tap into the vast uranium reserve in the ocean as an alternative energy. Here we present a protein hydrogel system containing a network of recently engineered super uranyl binding proteins (SUPs) that is assembled through thiol-maleimide click chemistry under mild conditions. Monodisperse SUP hydrogel microbeads fabricated by a microfluidic device further enable uranyl (UO 2 2+ ) enrichment from natural seawater with great efficiency (enrichment index, K = 2.5 × 10 3 ) and selectivity. Our results demonstrate the feasibility of using protein hydrogels to extract uranium from the ocean.

METAL EXTRACTION PROCESS

DOEpatents

Lewis, G.W. Jr.; Rhodes, D.E.

1957-11-01

An improved method for extracting uranium from aqueous solutions by solvent extraction is presented. A difficulty encountered in solvent extraction operations using an organic extractant (e.g., tributyl phosphate dissolved in kerosene or carbon tetrachloride) is that emulsions sometimes form, and phase separation is difficult or impossible. This difficulty is overcome by dissolving the organic extractant in a molten wax which is a solid at operating temperatures. After cooling, the wax which now contains the extractant, is broken into small particles (preferably flakes) and this wax complex'' is used to contact the uranium bearing solutions and extract the metal therefrom. Microcrystalline petroleum wax and certain ethylene polymers have been found suitable for this purpose.

Dissolved radon and uranium in groundwater in a potential coal seam gas development region (Richmond River Catchment, Australia).

PubMed

Atkins, Marnie L; Santos, Isaac R; Perkins, Anita; Maher, Damien T

2016-04-01

The extraction of unconventional gas resources such as shale and coal seam gas (CSG) is rapidly expanding globally and often prevents the opportunity for comprehensive baseline groundwater investigations prior to drilling. Unconventional gas extraction often targets geological layers with high naturally occurring radioactive materials (NORM) and extraction practices may possibly mobilise radionuclides into regional and local drinking water resources. Here, we establish baseline groundwater radon and uranium levels in shallow aquifers overlying a potential CSG target formation in the Richmond River Catchment, Australia. A total of 91 groundwater samples from six different geological units showed highly variable radon activities (0.14-20.33 Bq/L) and uranium levels (0.001-2.77 μg/L) which were well below the Australian Drinking Water Guideline values (radon; 100 Bq/L and uranium; 17 μg/L). Therefore, from a radon and uranium perspective, the regional groundwater does not pose health risks to consumers. Uranium could not explain the distribution of radon in groundwater. Relatively high radon activities (7.88 ± 0.83 Bq/L) in the fractured Lismore Basalt aquifer coincided with very low uranium concentrations (0.04 ± 0.02 μg/L). In the Quaternary Sediments aquifers, a positive correlation between U and HCO3(-) (r(2) = 0.49, p < 0.01) implied the uranium was present as uranyl-carbonate complexes. Since NORM are often enriched in target geological formations containing unconventional gas, establishing radon and uranium concentrations in overlying aquifers comprises an important component of baseline groundwater investigations. Copyright © 2016 Elsevier Ltd. All rights reserved.

75 FR 17170 - Notice of Opportunity To Request a Hearing for the License Application From International...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-04-05

... Fluoride Extraction and Uranium Deconversion Facility in Lea County NM and Order Imposing Procedures for... application from International Isotopes Fluorine Products, Inc. (IIFP), for a proposed fluoride extraction and... applicant to process depleted uranium hexafluoride (DUF 6 ) into commercially resalable fluoride products...

Deep liquid-chromatographic purification of uranium extract from technetium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Volk, V.; Dvoeglazov, K; Podrezova, L.

The recycling of uranium in the nuclear fuel cycle requires the removal of a number of radioactive and stable impurities like {sup 99}Tc from spent fuels. In order to improve the grade of uranium extract purification from technetium the method of liquid chromatography and the apparatus for its performance have been developed. Process of technetium extraction and concentrating in aqueous solution containing reducing agent has been studied on simulated solutions (U-Tc-HNO{sub 3}-30% TBP-isoparM). The dynamic tests of the method have been carried out on the laboratory unit. Solution of diformyl-hydrazine in nitric acid was used as a stationary phase. Silicamore » gel with specific surface of 186 m{sup 2}/g was used as a carrier of the stationary phase. It is shown that the volume of purified extract increases as the solution temperature increases, concentration of reducing agent increases and extract flow rate decreases. It is established that the technetium content in uranium by this method could achieve a value below 0.3 ppm. Some variants of overload and composition of the stationary phase containing the extracted technetium have been offered and tested. It is defined that the method provides reduction of processing medium-active wastes by more than 10 times during finish refining process. (authors)« less

Validation of the SEPHIS Program for the Modeling of the HM Process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kyser, E.A.

The SEPHIS computer program is currently being used to evaluate the effect of all process variables on the criticality safety of the HM 1st Uranium Cycle process in H Canyon. The objective of its use has three main purposes. (1) To provide a better technical basis for those process variables that do not have any realistic effect on the criticality safety of the process. (2) To qualitatively study those conditions that have been previously recognized to affect the nuclear safety of the process or additional conditions that modeling has indicated may pose a criticality safety issue. (3) To judge themore » adequacy of existing or future neutron monitors locations in the detection of the initial stages of reflux for specific scenarios.Although SEPHIS generally over-predicts the distribution of uranium to the organic phase, it is a capable simulation tool as long as the user recognizes its biases and takes special care when using the program for scenarios where the prediction bias is non-conservative. The temperature coefficient used by SEPHIS is poor at predicting effect of temperature on uranium extraction for the 7.5 percent TBP used in the HM process. Therefore, SEPHIS should not be used to study temperature related scenarios. However, within normal operating temperatures when other process variables are being studied, it may be used. Care must be is given to understanding the prediction bias and its effect on any conclusion for the particular scenario that is under consideration. Uranium extraction with aluminum nitrate is over-predicted worse than for nitric acid systems. However, the extraction section of the 1A bank has sufficient excess capability that these errors, while relatively large, still allow SEPHIS to be used to develop reasonable qualitative assessments for reflux scenarios. However, high losses to the 1AW stream cannot be modeled by SEPHIS.« less

PROCESS OF PURIFYING URANIUM

DOEpatents

Seaborg, G.T.; Orlemann, E.F.; Jensen, L.H.

1958-12-23

A method of obtaining substantially pure uranium from a uranium composition contaminated with light element impurities such as sodium, magnesium, beryllium, and the like is described. An acidic aqueous solution containing tetravalent uranium is treated with a soluble molybdate to form insoluble uranous molybdate which is removed. This material after washing is dissolved in concentrated nitric acid to obtaln a uranyl nitrate solution from which highly purified uranium is obtained by extraction with ether.

Method of precipitating uranium from an aqueous solution and/or sediment

DOEpatents

Tokunaga, Tetsu K; Kim, Yongman; Wan, Jiamin

2013-08-20

A method for precipitating uranium from an aqueous solution and/or sediment comprising uranium and/or vanadium is presented. The method includes precipitating uranium as a uranyl vanadate through mixing an aqueous solution and/or sediment comprising uranium and/or vanadium and a solution comprising a monovalent or divalent cation to form the corresponding cation uranyl vanadate precipitate. The method also provides a pathway for extraction of uranium and vanadium from an aqueous solution and/or sediment.

SEPARATION OF URANIUM, PLUTONIUM, AND FISSION PRODUCTS

DOEpatents

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.

Preparation of High Purity, High Molecular-Weight Chitin from Ionic Liquids for Use as an Adsorbate for the Extraction of Uranium from Seawater

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rogers, Robin

Ensuring a domestic supply of uranium is a key issue facing the wider implementation of nuclear power. Uranium is mostly mined in Kazakhstan, Australia, and Canada, and there are few high-grade uranium reserves left worldwide. Therefore, one of the most appealing potential sources of uranium is the vast quantity dissolved in the oceans (estimated to be 4.4 billion tons worldwide). There have been research efforts centered on finding a means to extract uranium from seawater for decades, but so far none have resulted in an economically viable product, due in part to the fact that the materials that have beenmore » successfully demonstrated to date are too costly (in terms of money and energy) to produce on the necessary scale. Ionic Liquids (salts which melt below 100{degrees}C) can completely dissolve raw crustacean shells, leading to recovery of a high purity, high molecular weight chitin powder and to fibers and films which can be spun directly from the extract solution suggesting that continuous processing might be feasible. The work proposed here will utilize the unprecedented control this makes possible over the chitin fiber a) to prepare electrospun nanofibers of very high surface area and in specific architectures, b) to modify the fiber surfaces chemically with selective extractant capacity, and c) to demonstrate their utility in the direct extraction and recovery of uranium from seawater. This approach will 1) provide direct extraction of chitin from shellfish waste thus saving energy over the current industrial process for obtaining chitin; 2) allow continuous processing of nanofibers for very high surface area fibers in an economical operation; 3) provide a unique high molecular weight chitin not available from the current industrial process, leading to stronger, more durable fibers; and 4) allow easy chemical modification of the large surface areas of the fibers for appending uranyl selective functionality providing selectivity and ease of stripping. The resulting sorbent should prove economically feasible, as well as providing an overall net energy gain.« less

Vanadium-uranium extraction from Wyoming vanadiferoud silicates. Report of investigations/1983

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hayashi, M.; Nichols, I.L.; Huiatt, J.L.

1983-11-01

The Bureau of Mines conducted laboratory studies on low-grade vanadiferous silicates from the Pumpkin Buttes and Nine Mile Lake deposits of Wyoming to examine techniques for extracting vanadium and uranium. Recovery from low-grade sources such as these could contribute to future vanadium production and reduce reliance on vanadium imports.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Blay, J.A.

The problem of the determination of micro-amounts of uranium in aqueous and organic phases in liquid-liquid extraction processes, original ones, and extraction residues was solved by a chromatographic separation of the uranium by means of columns of activated cellulose and further spectrophotometric evaluation using the thiocyanate complex in aqueous medium. The usable range is 5 to 200 mu g.

DECONTAMINATION OF URANIUM

DOEpatents

Spedding, F.H.; Butler, T.A.

1962-05-15

A process is given for separating fission products from uranium by extracting the former into molten aluminum. Phase isolation can be accomplished by selectively hydriding the uranium at between 200 and 300 deg C and separating the hydride powder from coarse particles of fissionproduct-containing aluminum. (AEC)

Calixarene-entrapped nanoemulsion for uranium extraction from contaminated solutions.

PubMed

Spagnul, Aurélie; Bouvier-Capely, Céline; Phan, Guillaume; Rebière, François; Fattal, Elias

2010-03-01

Accidental cutaneous contamination by actinides such as uranium occurring to nuclear power plant workers can lead to their dissemination in other tissues and induce severe damages. Until now, no specific emergency treatment for such contamination has been developed. The aim of the present work was to formulate a tricarboxylic calix[6]arene molecule, known to exhibit good affinity and selectivity for complexing uranium, within a topical delivery system for the treatment of skin contamination. Since calixarene was shown to reduce oil/water interfacial tension, we have designed an oil-in-water nanoemulsion, taking advantage of the small droplet size offering a high contact surface with the contaminated aqueous medium. Characterization of the calixarene nanoemulsion was performed by determination of the oily droplet size, zeta potential and pH, measured as a function of the calixarene concentration. The obtained results have confirmed the surface localization of calixarene molecules being potentially available to extract uranyl ions from an aqueous contaminated solution. In a preliminary experiments, the calixarene nanoemulsion was used for the removal of free uranium from an aqueous contaminated solution. Results showed that the calixarene nanoemulsion extracted up to 80 +/- 5% of uranium, which demonstrates the potential interest of this delivery system for uranium skin decontamination. 2009 Wiley-Liss, Inc. and the American Pharmacists Association

Supercritical Fluid Extraction of Toxic Heavy Metals and Uranium from Acidic Solutions with Sulfur-Containing Organophosphorus Reagents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Yuehe; Liu, Chongxuan; Wu, Hong

2003-03-02

The feasibility of using sulfur-containing organophosphorus reagents for the chelation-supercritical fluid extraction (SFE) of toxic heavy metals and uranium from acidic media was investigated. The SFE experiments were conducted in a specially-designed flow-through liquid extractor. Effective extraction of the metal ions from various acidic media was demonstrated. The effect of ligand concentration in supercritical CO{sub 2} on the kinetics of metal extraction was studied. A simplified model is used to describe the extraction kinetics and the good agreement of experimental data with the equilibrium-based model is achieved.

Potential impact of seawater uranium extraction on marine life

DOE Office of Scientific and Technical Information (OSTI.GOV)

Park, Jiyeon; Jeters, Robert T.; Kuo, Li-Jung

A variety of adsorbent materials have been developed to extract uranium from seawater as an alternative traditional terrestrial mining. A large-scale deployment of these adsorbents would be necessary to recover useful quantities of uranium and this raises a number of concerns regarding potential impacts on the surrounding marine environment. Two concerns are whether or not the adsorbent materials are toxic and any potentially harmful effects that may result from depleting uranium or vanadium (also highly concentrated by the adsorbents) from the local environment. To test the potential toxicity of the adsorbent with or without bound metals, Microtox assays were usedmore » to test both direct contact toxicity and the toxicity of any leachate in the seawater. The Microtox assay was chosen because it the detection of non-specific mechanisms of toxicity. Toxicity was not observed with leachates from any of 68 adsorbent materials that were tested, but direct contact with some adsorbents at very high adsorbent con-centrations exhibited toxicity. These concentrations are, however, very unlikely to be seen in the actual marine deployment. Adsor-bents that accumulated uranium and trace metals were also tested for toxicity, and no toxic effect was observed. Biofouling on the adsorbents and in columns or flumes containing the adsorbents also indicates that the adsorbents are not toxic and that there may not be an obvious deleterious effect resulting from removing uranium and vanadium from seawater. An extensive literature search was also performed to examine the potential impact of uranium and vanadium extraction from seawater on marine life using the Pacific Northwest National Laboratory’s (PNNL’s) document analysis tool, IN-SPIRE™. Although other potential environmental effects must also be considered, results from both the Microtox assay and the literature search provide preliminary evidence that uranium extraction from seawater could be performed with minimal impact on marine fauna.« less

Macroporous monoliths for trace metal extraction from seawater

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yue, Yanfeng; Mayes, Richard; Gill, Gary A.

2015-05-29

The viability of seawater-based uranium recovery depends on the uranium adsorption rate and capacity, since the concentration of uranium in the oceans is relatively low (3.3 μgL⁻¹). An important consideration for a fast adsorption is to maximize the adsorption properties of adsorbents such as surface areas and pore structures, which can greatly improve the kinetics of uranium extraction and the adsorption capacity simultaneously. Following this consideration, macroporous monolith adsorbents were prepared from the copolymerization of acrylonitrile (AN) and N, N’-methylenebis(acrylamide) (MBAAm) based on a cryogel method using both hydrophobic and hydrophilic monomers. The monolithic sorbents were tested with simulated seawatermore » containing a high uranyl concentration (–6 ppm) and the uranium adsorption results showed that the adsorption capacities are strongly influenced by the ratio of monomer to the crosslinker, i.e., the density of the amidoxime groups. The preliminary seawater testing indicates the high salinity content of seawater does not hinder the adsorption of uranium.« less

Macroporous monoliths for trace metal extraction from seawater

DOE PAGES

Yue, Yanfeng; Mayes, Richard T.; Gill, Gary; ...

2015-05-29

The viability of seawater-based uranium recovery depends on the uranium adsorption rate and capacity, since the concentration of uranium in the oceans is relatively low (3.3 gL -1). An important consideration for a fast adsorption is to maximize the adsorption properties of adsorbents such as surface areas and pore structures, which can greatly improve the kinetics of uranium extraction and the adsorption capacity simultaneously. Following this consideration, macroporous monolith adsorbents were prepared from the copolymerization of acrylonitrile (AN) and N,N -methylenebis(acrylamide) (MBAAm) based on a cryogel method using both hydrophobic and hydrophilic monomers. The monolithic sorbents were tested with simulatedmore » seawater containing a high uranyl concentration (–6 ppm) and the uranium adsorption results showed that the adsorption capacities are strongly influenced by the ratio of monomer to the crosslinker, i.e., the density of the amidoxime groups. Furthermore, the preliminary seawater testing indicates the high salinity content of seawater does not hinder the adsorption of uranium.« less

PROCESS FOR DECONTAMINATING THORIUM AND URANIUM WITH RESPECT TO RUTHENIUM

DOEpatents

Meservey, A.A.; Rainey, R.H.

1959-10-20

The control of ruthenium extraction in solvent-extraction processing of neutron-irradiated thorium is presented. Ruthenium is rendered organic-insoluble by the provision of sulfite or bisulfite ions in the aqueous feed solution. As a result the ruthenium remains in the aqueous phase along with other fission product and protactinium values, thorium and uranium values being extracted into the organic phase. This process is particularly applicable to the use of a nitrate-ion-deficient aqueous feed solution and to the use of tributyl phosphate as the organic extractant.

Surface Functionalized Nanostructured Ceramic Sorbents for the Effective Collection and Recovery of Uranium from Seawater

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chouyyok, Wilaiwan; Pittman, Jonathan W.; Warner, Marvin G.

2016-05-02

The ability to collect uranium from seawater offers the potential for a nearly limitless fuel supply for nuclear energy. We evaluated the use of functionalized nanostructured sorbents for the collection and recovery of uranium from seawater. Extraction of trace minerals from seawater and brines is challenging due to the high ionic strength of seawater, low mineral concentrations, and fouling of surfaces over time. We demonstrate that rationally assembled sorbent materials that integrate high affinity surface chemistry and high surface area nanostructures into an application relevant micro/macro structure enables collection performance that far exceeds typical sorbent materials. High surface area nanostructuredmore » silica with surface chemistries composed of phosphonic acid, phosphonates, 3,4 hydroxypyridinone, and EDTA showed superior performance for uranium collection. A few phosphorous-based commercial resins, specifically Diphonix and Ln Resin, also performed well. We demonstrate an effective and environmentally benign method of stripping the uranium from the high affinity sorbents using inexpensive nontoxic carbonate solutions. The cyclic use of preferred sorbents and acidic reconditioning of materials was shown to improve performance. Composite thin films composed of the nanostructured sorbents and a porous polymer binder are shown to have excellent kinetics and good capacity while providing an effective processing configuration for trace mineral recovery from solutions. Initial work using the composite thin films shows significant improvements in processing capacity over the previously reported sorbent materials.« less

Development of an extractive spectrophotometric method for estimation of uranium in ore leach solutions using 2-ethylhexyl phosphonic acid-mono-2-ethylhexyl ester (PC88A) and tri-n-octyl phosphine oxide (TOPO) mixture as extractant and 2-(5-bromo-2-pyridylozo)-5-diethyl aminophenol (Br-PADAP) as chromophore

NASA Astrophysics Data System (ADS)

Biswas, Sujoy; Pathak, P. N.; Roy, S. B.

2012-06-01

An extractive spectrophotometric analytical method has been developed for the determination of uranium in ore leach solution. This technique is based on the selective extraction of uranium from multielement system using a synergistic mixture of 2-ethylhexyl phosphonic acid-mono-2-ethylhexyl ester (PC88A) and tri-n-octyl phosphine oxide (TOPO) in cyclohexane and color development from the organic phase aliquot using 2-(5-Bromo-2-pyridylazo)-5-diethyl aminophenol (Br-PADAP) as chromogenic reagent. The absorption maximum (λmax) for UO22+-Br-PADAP complex in organic phase samples, in 64% (v/v) ethanol containing buffer solution (pH 7.8) and 1,2-cyclohexylenedinitrilotetraacetic acid (CyDTA) complexing agent, has been found to be at 576 nm (molar extinction coefficient, ɛ: 36,750 ± 240 L mol-1 cm-1). Effects of various parameters like stability of complex, ethanol volume, ore matrix, interfering ions etc. on the determination of uranium have also been evaluated. Absorbance measurements as a function of time showed that colored complex is stable up to >24 h. Presence of increased amount of ethanol in colored solution suppresses the absorption of a standard UO22+-Br-PADAP solution. Analyses of synthetic standard as well as ore leach a solution show that for 10 determination relative standard deviation (RSD) is <2%. The accuracy of the developed method has been checked by determining uranium using standard addition method and was found to be accurate with a 98-105% recovery rate. The developed method has been applied for the analysis of a number of uranium samples generated from uranium ore leach solutions and results were compared with standard methods like inductively coupled plasma emission spectrometry (ICPAES). The determined values of uranium concentrations by these methods are within ±2%. This method can be used to determine 2.5-250 μg mL-1 uranium in ore leach solutions with high accuracy and precision.

PROCESS OF EXTRACTING URANIUM AND RADIUM FROM ORES

DOEpatents

Sawyer, C.W.; Handley, R.W.

1959-07-14

A process is presented for extracting uranium and radium values from a uranium ore which comprises leaching the ore with a ferric chloride solution at an elevated temperature of above 50 deg C and at a pH less than 4; separating the ore residue from the leaching solution by filtration; precipitating the excess ferric iron present at a pH of less than 5 by adding CaCO/sub 3/ to the filtrate; separating the precipitate by filtration; precipitating the uranium present in the filtrate at a Ph less than 6 by adding BaCO/sub 3/ to the filtrate; separating the precipitate by filtration; and precipitating the radium present in the filtrate by adding H/sub 2/SO/sub 4/ to the filtrate.

PROCESSING OF MONAZITE SAND

DOEpatents

Calkins, G.D.; Bohlmann, E.G.

1957-12-01

A process for the recovery of thorium, uranium, and rare earths from monazite sands is presented. The sands are first digested and dissolved in concentrated NaOH, and the solution is then diluted causing precipitation of uranium, thorium and rare earth hydroxides. The precipitate is collected and dissolved in HCl, and the pH of this solution is adjusted to about 6, precipitating the hydroxides of thorium and uranium but leaving the rare earths in solution. The rare earths are then separated from the solution by precipitation at a still higher pH. The thorium and uranium containing precipitate is redissolved in HNO/sub 3/ and the two elements are separated by extraction into tributyl phosphate and back extraction with a weakly acidic solution to remove the thorium.

FY-15 Progress Report on Cleanup of irradiated SHINE Target Solutions Containing 140g-U/L Uranyl Sulfate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bennett, Megan E.; Bowers, Delbert L.; Vandegrift, George F.

2015-09-01

During FY 2012 and 2013, a process was developed to convert the SHINE Target Solution (STS) of irradiated uranyl sulfate (140 g U/L) to uranyl nitrate. This process is necessary so that the uranium solution can be processed by the UREX (Uranium Extraction) separation process, which will remove impurities from the uranium so that it can be recycled. The uranyl sulfate solution must contain <0.02 M SO 4 2- so that the uranium will be extractable into the UREXsolvent. In addition, it is desired that the barium content be below 0.0007 M, as this is the limit in the Resourcemore » Conservation and Recovery Act (RCRA).« less

Supercritical Fluid Extraction and Separation of Uranium from Other Actinides

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

2014-06-01

This paper investigates the feasibility of separating uranium from other actinides by using supercritical fluid carbon dioxide (sc-CO2) as a solvent modified with tri-n-butylphosphate (TBP) for the development of an extraction and counter current stripping technique, which would be a more efficient and environmentally benign technology for used nuclear fuel reprocessing compared to traditional solvent extraction. Several actinides (U(VI), Np(VI), Pu(IV), and Am(III)) were extracted in sc-CO2 modified with TBP over a range of nitric acid concentrations and then the actinides were exposed to reducing and complexing agents to suppress their extractability. According to this study, the separation of uraniummore » from plutonium in sc-CO2 modified with TBP was successful at nitric acid concentrations of less than 3 M in the presence of acetohydroxamic acid or oxalic acid, and the separation of uranium from neptunium was successful at nitric acid concentrations of less than 1 M in the presence of acetohydroxamic acid, oxalic acid, or sodium nitrite.« less

PYROMETALLURGICAL METHOD

DOEpatents

Nelson, P.A.

1961-07-18

The liquid--liquid extraction of plutonium by magnesium from uranium or uranium--chromium alloy is described. Calcium is added to magnesium in about eutectic proportions, which results in a purer plutonium.

Field Testing of Downgradient Uranium Mobility at an In-Situ Recovery Uranium Mine

NASA Astrophysics Data System (ADS)

Reimus, P. W.; Clay, J. T.; Rearick, M.; Perkins, G.; Brown, S. T.; Basu, A.; Chamberlain, K.

2015-12-01

In-situ recovery (ISR) mining of uranium involves the injection of O2 and CO2 (or NaHCO3) into saturated roll-front deposits to oxidize and solubilize the uranium, which is then removed by ion exchange at the surface and processed into U3O8. While ISR is economical and environmentally-friendly relative to conventional mining, one of the challenges of extracting uranium by this process is that it leaves behind a geochemically-altered aquifer that is exceedingly difficult to restore to pre-mining geochemical conditions, a regulatory objective. In this research, we evaluated the ability of the aquifer downgradient of an ISR mining area to attenuate the transport of uranium and other problem constituents that are mobilized by the mining process. Such an evaluation can help inform both regulators and the mining industry as to how much restoration of the mined ore zone is necessary to achieve regulatory compliance at various distances downgradient of the mining zone even if complete restoration of the ore zone proves to be difficult or impossible. Three single-well push-pull tests and one cross-well test were conducted in which water from an unrestored, previously-mined ore zone was injected into an unmined ore zone that served as a geochemical proxy for the downgradient aquifer. In all tests, non-reactive tracers were injected with the previously-mined ore zone water to allow the transport of uranium and other constituents to be compared to that of the nonreactive species. In the single-well tests, it was shown that the recovery of uranium relative to the nonreactive tracers ranged from 12-25%, suggesting significant attenuation capacity of the aquifer. In the cross-well test, selenate, molybdate and metavanadate were injected with the unrestored water to provide information on the transport of these potentially-problematic anionic constituents. In addition to the species-specific transport information, this test provided valuable constraints on redox conditions within the system, as redox couples involving these species collectively bracket the predicted transition redox potential for the U(VI)/U(IV) couple. Reduction should provide much longer-lasting immobilization of constituents than adsorption, especially given the inherent reducing characteristics of roll-front systems.

URANIUM PURIFICATION PROCESS

DOEpatents

Ruhoff, J.R.; Winters, C.E.

1957-11-12

A process is described for the purification of uranyl nitrate by an extraction process. A solution is formed consisting of uranyl nitrate, together with the associated impurities arising from the HNO/sub 3/ leaching of the ore, in an organic solvent such as ether. If this were back extracted with water to remove the impurities, large quantities of uranyl nitrate will also be extracted and lost. To prevent this, the impure organic solution is extracted with small amounts of saturated aqueous solutions of uranyl nitrate thereby effectively accomplishing the removal of impurities while not allowing any further extraction of the uranyl nitrate from the organic solvent. After the impurities have been removed, the uranium values are extracted with large quantities of water.

Reductive stripping process for uranium recovery from organic extracts

DOEpatents

Hurst, F.J. Jr.

1983-06-16

In the reductive stripping of uranium from an organic extractant in a uranium recovery process, the use of phosphoric acid having a molarity in the range of 8 to 10 increases the efficiency of the reductive stripping and allows the strip step to operate with lower aqueous to organic recycle ratios and shorter retention time in the mixer stages. Under these operating conditions, less solvent is required in the process, and smaller, less expensive process equipment can be utilized. The high strength H/sub 3/PO/sub 4/ is available from the evaporator stage of the process.

Reductive stripping process for uranium recovery from organic extracts

DOEpatents

Hurst, Jr., Fred J.

1985-01-01

In the reductive stripping of uranium from an organic extractant in a uranium recovery process, the use of phosphoric acid having a molarity in the range of 8 to 10 increases the efficiency of the reductive stripping and allows the strip step to operate with lower aqueous to organic recycle ratios and shorter retention time in the mixer stages. Under these operating conditions, less solvent is required in the process, and smaller, less expensive process equipment can be utilized. The high strength H.sub.3 PO.sub.4 is available from the evaporator stage of the process.

SEPARATION OF URANIUM FROM ZIRCONIUM AND NIOBIUM BY SOLVENT EXTRACTION

DOEpatents

Voiland, E.E.

1958-05-01

A process for separation of the uranium from zirconium and/or niobium values contained in 3 to 7M aqueous nitric acid solutions is described. This is accomplished by adding phosphoric acid anions to the nitric acid solution containing the uranium, zirconium, and/or niobium in an amount sufficient to make the solution 0.05 to 0.2M in phosphate ion and contacting the solution with an organic water-immiscible solvent such as MEK, whereby the uranyl values are taken up by the extract phase while the zirconium and niobium preferentially remain in the aqueous raffinate.

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

PubMed

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

2010-04-15

A new solid phase extractant selective for uranium(VI) based on benzoylthiourea anchored to activated carbon was developed via hydroxylation, amidation and reaction with benzoyl isothiocyanate in sequence. Fourier transform infrared spectroscopy and total element analysis proved that benzoylthiourea had been successfully grafted to the surface of the activated carbon, with a loading capacity of 1.2 mmol benzoylthiourea per gram of activated carbon. The parameters that affect the uranium(VI) sorption, such as contact time, solution pH, initial uranium(VI) concentration, adsorbent dose and temperature, have been investigated. Results have been analyzed by Langmuir and Freundlich isotherm; the former was more suitable to describe the sorption process. The maximum sorption capacity (82 mg/g) for uranium(VI) was obtained at experimental conditions. The rate constant for the uranium sorption by the as-synthesized extractant was 0.441 min(-1) from the first order rate equation. Thermodynamic parameters (DeltaH(0)=-46.2 kJ/mol; DeltaS(0)=-98.0 J/mol K; DeltaG(0)=-17.5 kJ/mol) showed the adsorption of an exothermic process and spontaneous nature, respectively. Additional studies indicated that the benzoylthiourea-anchored activated carbon (BT-AC) selectively sorbed uranyl ions in the presence of competing ions, Na(+), Co(2+), Sr(2+), Cs(+) and La(3+). 2009 Elsevier B.V. All rights reserved.

Processing of irradiated, enriched uranium fuels at the Savannah River Plant

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hyder, M L; Perkins, W C; Thompson, M C

Uranium fuels containing /sup 235/U at enrichments from 1.1% to 94% are processed and recovered, along with neptunium and plutonium byproducts. The fuels to be processed are dissolved in nitric acid. Aluminum-clad fuels are disssolved using a mercury catalyst to give a solution rich in aluminum. Fuels clad in more resistant materials are dissolved in an electrolytic dissolver. The resulting solutions are subjected to head-end treatment, including clarification and adjustment of acid and uranium concentration before being fed to solvent extraction. Uranium, neptunium, and plutonium are separated from fission products and from one another by multistage countercurrent solvent extraction withmore » dilute tri-n-butyl phosphate in kerosene. Nitric acid is used as the salting agent in addition to aluminum or other metal nitrates present in the feed solution. Nuclear safety is maintained through conservative process design and the use of monitoring devices as secondary controls. The enriched uranium is recovered as a dilute solution and shipped off-site for further processing. Neptunium is concentrated and sent to HB-Line for recovery from solution. The relatively small quantities of plutonium present are normally discarded in aqueous waste, unless the content of /sup 238/Pu is high enough to make its recovery desirable. Most of the /sup 238/Pu can be recovered by batch extraction of the waste solution, purified by counter-current solvent extraction, and converted to oxide in HB-Line. By modifying the flowsheet, /sup 239/Pu can be recovered from low-enriched uranium in the extraction cycle; neptunium is then not recovered. The solvent is subjected to an alkaline wash before reuse to remove degraded solvent and fission products. The aqueous waste is concentrated and partially deacidified by evaporation before being neutralized and sent to the waste tanks; nitric acid from the overheads is recovered for reuse.« less

URANIUM SEPARATION PROCESS

DOEpatents

McVey, W.H.; Reas, W.H.

1959-03-10

The separation of uranium from an aqueous solution containing a water soluble uranyl salt is described. The process involves adding an alkali thiocyanate to the aqueous solution, contacting the resulting solution with methyl isobutyl ketons and separating the resulting aqueous and organic phase. The uranium is extracted in the organic phase as UO/sub 2/(SCN)/sub/.

Electrochemical separation of uranium in the molten system LiF-NaF-KF-UF4

NASA Astrophysics Data System (ADS)

Korenko, M.; Straka, M.; Szatmáry, L.; Ambrová, M.; Uhlíř, J.

2013-09-01

This article is focused on the electrochemical investigation (cyclic voltammetry and related studies) of possible reduction of U4+ ions to metal uranium in the molten system LiF-NaF-KF(eut.)-UF4 that can provide basis for the electrochemical extraction of uranium from molten salts. Two-step reduction mechanism for U4+ ions involving one electron exchange in soluble/soluble U4+/U3+ system and three electrons exchange in the second step were found on the nickel working electrode. Both steps were found to be reversible and diffusion controlled. Based on cyclic voltammetry, the diffusion coefficients of uranium ions at 530 °C were found to be D(U4+) = 1.64 × 10-5 cm2 s-1 and D(U3+) 1.76 × 10-5 cm2 s-1. Usage of the nickel spiral electrode for electrorefining of uranium showed fairly good feasibility of its extraction. However some oxidant present during the process of electrorefining caused that the solid deposits contained different uranium species such as UF3, UO2 and K3UO2F5.

Separation of uranium from technetium in recovery of spent nuclear fuel

DOEpatents

Pruett, D.J.; McTaggart, D.R.

1983-08-31

Uranium and technetium in the product stream of the Purex process for recovery of uranium in spent nuclear fuel are separated by (1) contacting the aqueous Purex product stream with hydrazine to reduce Tc/sup +7/ therein to a reduced species, and (2) contacting said aqueous stream with an organic phase containing tributyl phosphate and an organic diluent to extract uranium from said aqueous stream into said organic phase.

REMOVAL OF URANIUM FROM ORGANIC LIQUIDS

DOEpatents

Vavalides, S.P.

1959-08-25

A process is described for recovering small quantities of uranium from organic liquids such as hydrocarbon oils. halogen-substituted hydrocarbons, and alcohols. The organic liquid is contacted with a comminuted alkaline earth hydroxide, calcium hydroxide particularly, and the resulting uranium-bearing solid is separated from the liquid by filtration. Uranium may then be recovered from the solid by means of dissolution in nitric acid and conventional extraction with an organic solvent such as tributyl phosphate.

Separation of uranium from technetium in recovery of spent nuclear fuel

DOEpatents

Pruett, David J.; McTaggart, Donald R.

1984-01-01

Uranium and technetium in the product stream of the Purex process for recovery of uranium in spent nuclear fuel are separated by (1) contacting the aqueous Purex product stream with hydrazine to reduce Tc.sup.+7 therein to a reduced species, and (2) contacting said aqueous stream with an organic phase containing tributyl phosphate and an organic diluent to extract uranium from said aqueous stream into said organic phase.

Uranium contents in plants and mushrooms grown on a uranium-contaminated site near Ronneburg in Eastern Thuringia/Germany.

PubMed

Baumann, Nils; Arnold, Thuro; Haferburg, Götz

2014-01-01

Uranium concentrations in cultivated (sunflower, sunchoke, potato) and native plants, plant compartment specimens, and mushrooms, grown on a test site within a uranium-contaminated area in Eastern Thuringia, were analyzed and compared. This test site belongs to the Friedrich-Schiller University Jena and is situated on the ground of a former but now removed uranium mine waste leaching heap. For determination of the U concentrations in the biomaterials, the saps of the samples were squeezed out by using an ultracentrifuge, after that, the uranium concentrations in the saps and the remaining residue were measured, using ICP-MS. The study further showed that uranium concentrations observed in plant compartment and mushroom fruiting bodies sap samples were always higher than their associated solid residue sample. Also, it was found that the detected uranium concentration in the root samples were always higher than were observed in their associated above ground biomass, e.g., in shoots, leaves, blossoms etc. The highest uranium concentration was measured with almost 40 ppb U in a fruiting body of a mushroom and in roots of butterbur. However, the detected uranium concentrations in plants and mushrooms collected in this study were always lower than in the associated surface and soil water of the test site, indicating that under the encountered natural conditions, none of the studied plant and mushroom species turned out to be a hyperaccumulator for uranium, which could have extracted uranium in sufficient amounts out of the uranium-contaminated soil. In addition, it was found that the detected uranium concentrations in the sap samples, despite being above the sensitivity limit, proved to be too low-in combination with the presence of fluorescence quenching substances, e.g., iron and manganese ions, and/or organic quenchers-to extract a useful fluorescence signal, which could have helped to identify the uranium speciation in plants.

SEPARATION OF URANIUM, PLUTONIUM AND FISSION PRODUCTS

DOEpatents

Nicholls, C.M.; Wells, I.; Spence, R.

1959-10-13

The separation of uranium and plutonium from neutronirradiated uranium is described. The neutron-irradiated uranium is dissolved in nitric acid to provide an aqueous solution 3N in nitric acid. The fission products of the solution are extruded by treating the solution with dibutyl carbitol substantially 1.8N in nitric acid. The organic solvent phase is separated and neutralized with ammonium hydroxide and the plutonium reduced with hydroxylamine base to the trivalent state. Treatment of the mixture with saturated ammonium nitrate extracts the reduced plutonium and leaves the uranium in the organic solvent.

Reductive stripping process for the recovery of uranium from wet-process phosphoric acid

DOEpatents

Hurst, Fred J.; Crouse, David J.

1984-01-01

A reductive stripping flow sheet for recovery of uranium from wet-process phosphoric acid is described. Uranium is stripped from a uranium-loaded organic phase by a redox reaction converting the uranyl to uranous ion. The uranous ion is reoxidized to the uranyl oxidation state to form an aqueous feed solution highly concentrated in uranium. Processing of this feed through a second solvent extraction cycle requires far less stripping reagent as compared to a flow sheet which does not include the reductive stripping reaction.

A multi-instrumental geochemical study of anomalous uranium enrichment in coal.

PubMed

Havelcová, Martina; Machovič, Vladimír; Mizera, Jiří; Sýkorová, Ivana; Borecká, Lenka; Kopecký, Lubomír

2014-11-01

Contents of uranium in coals from Odeř in the northernmost part of the Sokolov Basin, Czech Republic, in the vicinity of the well known St. Joachimsthal uranium ore deposits, reach extremely high values. In the present work, coal samples with contents of uranium ranging from 0.02 to 6 wt.% were studied. The study employing a whole complex of analytical techniques has been aimed at identification of changes in the structure of coal organic matter, which are associated with the high contents of uranium in coal. The study includes proximate and ultimate analyses, multielement analysis by instrumental neutron and photon activation analyses, micropetrographic analysis by optical microscopy, ESEM/EDX analysis of mineral matter, infrared and Raman spectroscopies, solvent extraction followed by gas chromatography with mass spectroscopy (GC/MS), and analytical pyrolysis (Py-GC/MS). The study has confirmed previously proposed explanation of uraniferous mineralization in sedimentary carboniferous substances by the mechanism of reduction and fixation of soluble U(VI) (uranyl, UO2(2+)) species (e.g., humic, carbonate/hydroxo/phosphate complexes) by sedimentary organic matter under diagenetic or hydrothermal conditions, and formation of insoluble U(IV) species as phosphate minerals and uraninite. The process is accompanied with alteration and destruction of the coal organic matter. The changes in the structure of coal organic matter involve dehydrogenation and oxidation mainly in the aliphatic, aromatic and hydroxyl structures, and an increase in aromaticity, content of ether bonds, and the degree of coalification. Copyright © 2014 Elsevier Ltd. All rights reserved.

PROCESS OF RECOVERING URANIUM FROM ITS ORES

DOEpatents

Galvanek, P. Jr.

1959-02-24

A process is presented for recovering uranium from its ores. The crushed ore is mixed with 5 to 10% of sulfuric acid and added water to about 5 to 30% of the weight of the ore. This pugged material is cured for 2 to 3 hours at 100 to 110 deg C and then cooled. The cooled mass is nitrate-conditioned by mixing with a solution equivalent to 35 pounds of ammunium nitrate and 300 pounds of water per ton of ore. The resulting pulp containing 70% or more solids is treated by upflow percolation with a 5% solution of tributyl phosphate in kerosene at a rate equivalent to a residence time of about one hour to extract the solubilized uranium. The uranium is recovered from the pregnant organic liquid by counter-current washing with water. The organic extractant may be recycled. The uranium is removed from the water solution by treating with ammonia to precipitate ammonium diuranate. The filtrate from the last step may be recycled for the nitrate-conditioning treatment.

Development of an extractive spectrophotometric method for estimation of uranium in ore leach solutions using 2-ethylhexyl phosphonic acid-mono-2-ethylhexyl ester (PC88A) and tri-n-octyl phosphine oxide (TOPO) mixture as extractant and 2-(5-bromo-2-pyridylozo)-5-diethyl aminophenol (Br-PADAP) as chromophore.

PubMed

Biswas, Sujoy; Pathak, P N; Roy, S B

2012-06-01

An extractive spectrophotometric analytical method has been developed for the determination of uranium in ore leach solution. This technique is based on the selective extraction of uranium from multielement system using a synergistic mixture of 2-ethylhexyl phosphonic acid-mono-2-ethylhexyl ester (PC88A) and tri-n-octyl phosphine oxide (TOPO) in cyclohexane and color development from the organic phase aliquot using 2-(5-Bromo-2-pyridylazo)-5-diethyl aminophenol (Br-PADAP) as chromogenic reagent. The absorption maximum (λ(max)) for UO(2)(2+)-Br-PADAP complex in organic phase samples, in 64% (v/v) ethanol containing buffer solution (pH 7.8) and 1,2-cyclohexylenedinitrilotetraacetic acid (CyDTA) complexing agent, has been found to be at 576 nm (molar extinction coefficient, ɛ: 36,750 ± 240 L mol(-1)cm(-1)). Effects of various parameters like stability of complex, ethanol volume, ore matrix, interfering ions etc. on the determination of uranium have also been evaluated. Absorbance measurements as a function of time showed that colored complex is stable up to > 24h. Presence of increased amount of ethanol in colored solution suppresses the absorption of a standard UO(2)(2+)-Br-PADAP solution. Analyses of synthetic standard as well as ore leach a solution show that for 10 determination relative standard deviation (RSD) is < 2%. The accuracy of the developed method has been checked by determining uranium using standard addition method and was found to be accurate with a 98-105% recovery rate. The developed method has been applied for the analysis of a number of uranium samples generated from uranium ore leach solutions and results were compared with standard methods like inductively coupled plasma emission spectrometry (ICPAES). The determined values of uranium concentrations by these methods are within ± 2%. This method can be used to determine 2.5-250 μg mL(-1) uranium in ore leach solutions with high accuracy and precision. Copyright © 2012 Elsevier B.V. All rights reserved.

Understanding Uranium Behavior in a Reduced Aquifer

NASA Astrophysics Data System (ADS)

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 < 10 ppm) and the expense of collecting large number of cores. An in-situ technique has been developed for studying uranium, iron and sulfur reduction dynamics during such bioremediation episodes. This technique uses in-well columns to obtain direct access to chemical and physical forms of U(IV) produced in the aquifer, evolving microbial communities, and trace and major ion groundwater constituents. While several studies have explored bioreduction of uranium under sulfate-reducing conditions, less attention has been paid to the initial iron-reducing phase, noted as being of particular importance to uranium removal. The aim of this work was to assess the formation of U(IV) during the early stages of a 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.

Method of separating and recovering uranium and related cations from spent Purex-type systems

DOEpatents

Mailen, J.C.; Tallent, O.K.

1987-02-25

A process for separating uranium and related cations from a spent Purex-type solvent extraction system which contains degradation complexes of tributylphosphate wherein the system is subjected to an ion-exchange process prior to a sodium carbonate scrubbing step. A further embodiment comprises recovery of the separated uranium and related cations. 5 figs.

Volumetric determination of uranium using titanous sulfate as reductant before oxidimetric titration

USGS Publications Warehouse

Wahlberg, James S.; Skinner, Dwight L.; Rader, Lewis F.

1956-01-01

A new method for determining uranium in samples containing 0.05 percent or more U3O8, using titanous sulfate as reducing agent, is much shorter, faster, and has fewer interferences than conventional methods using reductor columns. The sample is dissolved with sulfuric, nitric, perchloric, and hydrofluoric acids. Elements that would otherwise form insoluble fluorides are kept in solution by complexing the fluoride ion with boric acid. A precipitation is made with cupferron to remove interfering elements. The solution is filtered to remove the precipitated cupferrates instead of extracting them with chloroform as is usually done. Filtration is preferred to extraction because any niobium that may be in solution forms an insoluble cupferrate that may be removed by filtering but is very difficult to extract with chloroform. Excess cupferron is destroyed by oxidizing with nitric and perchloric acids, and evaporating to dense fumes of sulfuric acid. The uranium is reduced to U(IV) by the addition of titanous sulfate, with cupric sulfate used as an indicator of the completeness of the reduction. Metallic copper is formed when all the uranium is reduced. The reduced copper is then reoxidized by the addition of mercuric perchlorate, an excess of ferric sulfate added, and the solution titrated immediately with standard ceric sulfate with ferroin as an indicator. Precision of the method compared favorable with methods in common use, both for uranium ores and for most types of uranium-rich materials.

IMPROVEMENT OF THE EXTRACTION SEPARATION OF URANIUM AND ZIRCONIUM USING ZIRCONIUM-MASKING REAGENTS (in German)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kyrs, M.; Caletka, R.; Selucky, P.

1963-12-01

The masking capacities of a series of reagents were studied in the zirconium extraction with tributyl phosphate solution in the presence of nitric acid. It was established that with many reagents an improvement of the separation of uranium from zirconium could be obtained. The efficiency of the reagents increases in the series tannin, oxalic acid, tiron, pyrogallol, and Arsenazo I. (tr-auth)

PYROCHEMICAL DECONTAMINATION METHOD FOR REACTOR FUEL

DOEpatents

Buyers, A.G.

1959-06-30

A pyro-chemical method is presented for decontaminating neutron irradiated uranium and separating plutonium therefrom by contact in the molten state with a metal chloride salt. Uranium trichloride and uranium tetrachloride either alone or in admixture with alkaline metal and alkaline eanth metal fluorides under specified temperature and specified phase ratio conditions extract substantially all of the uranium from the irradiated uranium fuel together with certain fission products. The phases are then separated leaving purified uranium metal. The uranium and plutonium in the salt phase can be reduced to forin a highly decontaminated uraniumplutonium alloy. The present method possesses advantages for economically decontaminating irradiated nuclear fuel elements since irradiated fuel may be proccessed immediately after withdrawal from the reactor and the uranium need not be dissolved and later reduced to the metallic form. Accordingly, the uranium may be economically refabricated and reinserted into the reactor.

PRODUCTION OF URANIUM AND THORIUM COMPOUNDS

DOEpatents

Arden, T.V.; Burstall, F.H.; Linstead, R.P.; Wells, R.A.

1955-12-27

Compounds of Th and U are extracted with an organic solvent in the presence of an adsorbent substance which has greater retentivity for impurities present than for the uranium and/or thorium. The preferred adsorbent material is noted as being cellulose. The uranium and thoriumcontaining substances treated are preferably in the form of dissolved nitrates, and the preferred organic solvent is diethyl ether.

SEPARATION OF URANIUM FROM OTHER METALS

DOEpatents

Hyman, H.H.

1959-07-01

The separation of uranium from other elements, such as ruthenium, zirconium, niobium, cerium, and other rare earth metals is described. According to the invention, this is accomplished by adding hydrazine to an acid aqueous solution containing salts of uranium, preferably hexavalent uranium, and then treating the mixture with a substantially water immiscible ketone, such as hexone. A reaction takes place between the ketone and the hydrazine whereby a complex, a ketazine, is formed; this complex has a greater power of extraction for uranium than the ketone by itself. When contaminating elements are present, they substantially remain in ihe aqueous solution.

URANIUM RECOVERY PROCESS

DOEpatents

Kaufman, D.

1958-04-15

A process of recovering uranium from very low-grade ore residues is described. These low-grade uraniumcontaining hydroxide precipitates, which also contain hydrated silica and iron and aluminum hydroxides, are subjected to multiple leachings with aqueous solutions of sodium carbonate at a pH of at least 9. This leaching serves to selectively extract the uranium from the precipitate, but to leave the greater part of the silica, iron, and aluminum with the residue. The uranium is then separated from the leach liquor by the addition of an acid in sufficient amount to destroy the carbonate followed by the addition of ammonia to precipitate uranium as ammonium diuranate.

Separation of uranium from technetium in recovery of spent nuclear fuel

NASA Astrophysics Data System (ADS)

Friedman, H. A.

1984-06-01

A method for decontaminating uranium product from the Purex 5 process is described. Hydrazine is added to the product uranyl nitrate stream from the Purex process, which contains hexavalent (UO2(2+)) uranium and heptavalent technetius (TcO4-). Technetium in the product stream is reduced and then complexed by the addition of oxalic acid (H2O2O4), and the Tc-oxalate complex is readily separated from the 10 uranium by solvent extraction with 30 vol % tributyl phosphate in n-dodecane.

RECOVERY OF URANIUM VALUES

DOEpatents

Brown, K.B.; Crouse, D.J. Jr.; Moore, J.G.

1959-03-10

A liquid-liquid extraction method is presented for recovering uranium values from an aqueous acidic solution by means of certain high molecular weight amine in the amine classes of primary, secondary, heterocyclic secondary, tertiary, or heterocyclic tertiary. The uranium bearing aqueous acidic solution is contacted with the selected amine dissolved in a nonpolar water-immiscible organic solvent such as kerosene. The uranium which is substantially completely exiracted by the organic phase may be stripped therefrom by waters and recovered from the aqueous phase by treatment into ammonia to precipitate ammonium diuranate.

Determination of uranium in zircon

USGS Publications Warehouse

Cuttitta, F.; Daniels, G.J.

1959-01-01

A routine fluorimetric procedure is described for the determination of trace amounts of uranium in zircon. It employs the direct extraction of uranyl nitrate with ethyl acetate using phosphate as a retainer for zirconium. Submicrogram amounts or uranium are separated in the presence of 100,000 times the amount of zirconium. The modified procedure has been worked out using synthetic mixtures of known composition and zircon. Results of analyses have an accuracy of 97-98% of the contained uranium and a standard deviation of less than 2.5%. ?? 1959.

Combination of solid phase extraction and dispersive liquid-liquid microextraction for separation/preconcentration of ultra trace amounts of uranium prior to its fiber optic-linear array spectrophotometry determination.

PubMed

Dadfarnia, Shayessteh; Shabani, Ali Mohammad Haji; Shakerian, Farid; Shiralian Esfahani, Golnaz

2013-12-15

A simple and sensitive method for the separation and preconcentration of the ultra trace amounts of uranium and its determination by spectrophotometry was developed. The method is based on the combination of solid phase extraction and dispersive liquid-liquid microextraction. Thus, by passing the sample through the basic alumina column, the uranyl ion and some cations are separated from the sample matrix. The retained uranyl ion along with the cations are eluted with 5 mL of nitric acid (2 mol L(-1)) and after neutralization of the eluent, the extracted uranyl ion is converted to its anionic benzoate complex and is separated from other cations by extraction of its ion pair with malachite green into small volume of chloroform using dispersive liquid-liquid microextraction. The amount of uranium is then determined by the absorption measurement of the extracted ion pair at 621 nm using flow injection spectrophotometry. Under the optimum conditions, with 500 mL of the sample, a preconcentration factor of 1980, a detection limit of 40 ng L(-1), and a relative standard deviation of 4.1% (n=6) at 400 ng L(-1) were obtained. The method was successfully applied to the determination of uranium in mineral water, river water, well water, spring water and sea water samples. Copyright © 2013 Elsevier B.V. All rights reserved.

PREVENTION OF SCALE FORMATION IN URANIUM SOLVENT EXTRACTOR

DOEpatents

Delaplaine, J.W.

1957-11-01

A method for preventing the formation of scale in uranium solvent extraction apparatus is presented. The scale, consisting chiefly of precipitated silica and the sulfates uf calcium and lead, may be prevented by a combination of measures, chiefly by prior heating and agitation to crystallize and remove silica, and by a maintenance of uranyl nitrate concentration in the feed and extractant above certain levels to increase the solubility of the calcium and lead sulfates.

40 CFR 440.30 - Applicability; description of the uranium, radium and vanadium ores subcategory.

Code of Federal Regulations, 2014 CFR

2014-07-01

... vanadium ores are produced; and (b) mills using the acid leach, alkaline leach, or combined acid and alkaline leach process for the extraction of uranium, radium and vanadium. Only vanadium byproduct...

40 CFR 440.30 - Applicability; description of the uranium, radium and vanadium ores subcategory.

Code of Federal Regulations, 2012 CFR

2012-07-01

... vanadium ores are produced; and (b) mills using the acid leach, alkaline leach, or combined acid and alkaline leach process for the extraction of uranium, radium and vanadium. Only vanadium byproduct...

40 CFR 440.30 - Applicability; description of the uranium, radium and vanadium ores subcategory.

Code of Federal Regulations, 2013 CFR

2013-07-01

... vanadium ores are produced; and (b) mills using the acid leach, alkaline leach, or combined acid and alkaline leach process for the extraction of uranium, radium and vanadium. Only vanadium byproduct...

Dissolution of uranium oxides from simulated environmental swipes using ammonium bifluoride

DOE PAGES

Meyers, Lisa A.; Yoshida, Thomas M.; Chamberlin, Rebecca M.; ...

2016-11-01

We developed an analytical chemistry method to quantitatively recover microgram quanties of solid uranium oxides from swipe media using ammonium bifluoride (ABF, NH 4HF 2) solution. Recovery of uranium from surrogate swipe media (filter paper) was demonstrated at initial uranium loading levels between 3 and 20 µg filter -1. Moreover, the optimal conditions for extracting U 3O 8 and UO 2 are using 1 % ABF solution and incubating at 80 °C for one hour. The average uranium recoveries are 100 % for U 3O 8, and 90 % for UO 2. Finally, with this method, uranium concentration as lowmore » as 3 µg filter -1 can be recovered for analysis.« less

Pilot Study to Evaluate Hydrogen Injection for Stimulating Reduction and Immobilization of Uranium in Groundwater at an ISR Mining Site

NASA Astrophysics Data System (ADS)

Clapp, L. W.; Cabezas, J.; Gamboa, Y.; Fernandez, W.

2011-12-01

State and federal regulations require that groundwater at in-situ recovery (ISR) uranium mining operations be restored to pre-mining conditions. Reverse osmosis (RO) filtration of several pore volumes of the post-leached groundwater and reinjection of the clean permeate is the most common technology currently used for restoring groundwater at uranium ISR sites. However, this approach does not revert the formation back to its initial reducing conditions, which can potentially impede timely groundwater restoration. In-situ biostimulation of indigenous iron- and sulfate reducing bacteria by injection of organic electron donors (e.g., ethanol, acetate, and lactate) to promote soluble uranium reduction and immobilization has been the subject of previous studies. However, injection of organic substrates has been observed to cause aquifer clogging near the injection point. In addition, U(VI) solubility may be enhanced through complexation with carbonate generated by organic carbon oxidation. An alternative approach that may overcome these problems involves the use of hydrogen as a reductant to promote microbial reduction and immobilization of U(VI) in situ. To test this approach, approximately 100,000 scf of compressed hydrogen gas was injected into a leached unconsolidated sand zone over two months at an ISR mining site. During this time groundwater was recirculated between injection and extraction wells (separated by 130 ft) at a rate of about 40 gpm and bromide was coinjected as a conservative tracer. A well monitoring program has been executed since June 2009 to evaluate the performance of the hydrogen injection. Current results show that U(VI) has been reduced from 4.2 to 0.05 ppm in the area surrounding the injection well and to 2.0 ± 0.3 ppm in the area surrounding the extraction well and two intermediate monitoring wells. Other water quality changes near the injection well include significant decreases in concentrations of Mo, sulfate, Fe, Mn, bicarbonate, Ca, and Eh, and increases in pH, methane, and sulfide. No significant rebound of soluble uranium concentrations was observed, but significant rebounds in molybdenum and sulfate have been observed. Ongoing studies are evaluating the effective zone of influence of the hydrogen injection.

Effects of organic carbon supply rates on uranium mobility in a previously bioreduced contaminated sediment.

PubMed

Wan, Jiamin; Tokunaga, Tetsu K; Kim, Yongman; Brodie, Eoin; Daly, Rebecca; Hazen, Terry C; Firestone, Mary K

2008-10-15

Bioreduction-based strategies for remediating uranium (U)-contaminated sediments face the challenge of maintaining the reduced status of U for long times. Because groundwater influxes continuously bring in oxidizing terminal electron acceptors (O2, NO3(-)), it is necessary to continue supplying organic carbon (OC) to maintain the reducing environment after U bioreduction is achieved. We tested the influence of OC supply rates on mobility of previously microbial reduced uranium U(IV) in contaminated sediments. We found that high degrees of U mobilization occurred when OC supply rates were high, and when the sediment still contained abundant Fe(III). Although 900 days with low levels of OC supply minimized U mobilization, the sediment redox potential increased with time as did extractable U(VI) fractions. Molecular analyses of total microbial activity demonstrated a positive correlation with OC supply and analyses of Geobacteraceae activity (RT-qPCR of 16S rRNA) indicated continued activity even when the effluent Fe(II) became undetectable. These data support our hypothesis on the mechanisms responsible for remobilization of U under reducing conditions; that microbial respiration caused increased (bi)carbonate concentration and formation of stable uranyl carbonate complexes, thereby shifted U(IV)/U(VI) equilibrium to more reducing potentials. The data also suggested that low OC concentrations could not sustain the reducing condition of the sediment for much longer time. Bioreduced U(IV) is not sustainable in an oxidizing environment for a very long time.

Determination of trace uranium by resonance fluorescence method coupled with photo-catalytic technology and dual cloud point extraction

NASA Astrophysics Data System (ADS)

Li, Jiekang; Li, Guirong; Han, Qian

2016-12-01

In this paper, two kinds of salophens (Sal) with different solubilities, Sal1 and Sal2, have been respectively synthesized, and they all can combine with uranyl to form stable complexes: [UO22 +-Sal1] and [UO22 +-Sal2]. Among them, [UO22 +-Sal1] was used as ligand to extract uranium in complex samples by dual cloud point extraction (dCPE), and [UO22 +-Sal2] was used as catalyst for the determination of uranium by photocatalytic resonance fluorescence (RF) method. The photocatalytic characteristic of [UO22 +-Sal2] on the oxidized pyronine Y (PRY) by potassium bromate which leads to the decrease of RF intensity of PRY were studied. The reduced value of RF intensity of reaction system (ΔF) is in proportional to the concentration of uranium (c), and a novel photo-catalytic RF method was developed for the determination of trace uranium (VI) after dCPE. The combination of photo-catalytic RF techniques and dCPE procedure endows the presented methods with enhanced sensitivity and selectivity. Under optimal conditions, the linear calibration curves range for 0.067 to 6.57 ng mL- 1, the linear regression equation was ΔF = 438.0 c (ng mL- 1) + 175.6 with the correlation coefficient r = 0.9981. The limit of detection was 0.066 ng mL- 1. The proposed method was successfully applied for the separation and determination of uranium in real samples with the recoveries of 95.0-103.5%. The mechanisms of the indicator reaction and dCPE are discussed.

Transport of U(VI) through sediments amended with phosphate to induce in situ uranium immobilization.

PubMed

Mehta, Vrajesh S; Maillot, Fabien; Wang, Zheming; Catalano, Jeffrey G; Giammar, Daniel E

2015-02-01

Phosphate amendments can be added to U(VI)-contaminated subsurface environments to promote in situ remediation. The primary objective of this study was to evaluate the impacts of phosphate addition on the transport of U(VI) through contaminated sediments. In batch experiments using sediments (<2 mm size fraction) from a site in Rifle, Colorado, U(VI) only weakly adsorbed due to the dominance of the aqueous speciation by Ca-U(VI)-carbonate complexes. Column experiments with these sediments were performed with flow rates that correspond to a groundwater velocity of 1.1 m/day. In the absence of phosphate, the sediments took up 1.68-1.98 μg U/g of sediments when the synthetic groundwater influent contained 4 μM U(VI). When U(VI)-free influents were then introduced with and without phosphate, substantially more uranium was retained within the column when phosphate was present in the influent. Sequential extractions of sediments from the columns revealed that uranium was uniformly distributed along the length of the columns and was primarily in forms that could be extracted by ion exchange and contact with a weak acid. Laser induced fluorescence spectroscopy (LIFS) analysis along with sequential extraction results suggest adsorption as the dominant uranium uptake mechanism. The response of dissolved uranium concentrations to stopped-flow events and the comparison of experimental data with simulations from a simple reactive transport model indicated that uranium adsorption to and desorption from the sediments was not always at local equilibrium. Copyright © 2014 Elsevier Ltd. All rights reserved.

Preliminary Interpretation of a Radionuclide and Colloid Tracer Test in a Granodiorite Shear Zone at the Grimsel Test Site, Switzerland

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reimus, Paul W.

2012-08-30

In February and March 2012, a tracer test involving the injection of a radionuclide-colloid cocktail was conducted in the MI shear zone at the Grimsel Test Site, Switzerland, as part of the Colloids Formation and Migration (CFM) project. The colloids were derived from FEBEX bentonite, which is mined in Spain and is being considered as a potential waste package backfill in a Spanish nuclear waste repository. The tracer test, designated test 12-02 (second test in 2012), involved the injection of the tracer cocktail into borehole CFM 06.002i2 and extraction from the Pinkel surface packer at the main access tunnel wallmore » approximately 6.1 m from the injection interval. The test configuration is depicted in Figure 1. This configuration has been used in several conservative tracer tests and two colloid-homologue tracer tests since 2007, and it is will be employed in an upcoming test involving the emplacement of a radionuclide-doped bentonite plug into CFM 06.002i2 to evaluate the swelling and erosion of the bentonite and the transport of bentonite colloids and radionuclides from the source to the extraction point at the tunnel wall. Interpretive analyses of several of the previous tracer tests, from 09-01 through 12-02 were provided in two previous Used Fuel Disposition Program milestone reports (Arnold et al., 2011; Kersting et al., 2012). However, only the data for the conservative tracer Amino-G Acid was previously analyzed from test 12-02 because the other tracer data from this test were not available at the time. This report documents the first attempt to quantitatively analyze the radionuclide and colloid breakthrough curves from CFM test 12-02. This report was originally intended to also include an experimental assessment of colloid-facilitated transport of uranium by bentonite colloids in the Grimsel system, but this assessment was not conducted because it was reported by German collaborators at the Karlsruhe Institute of Technology (KIT) that neither uranium nor neptunium adsorbed appreciably to FEBEX bentonite colloids in Grimsel groundwater (Huber et al., 2011). The Grimsel groundwater has a relatively high pH of {approx}9, so the lack of uranium and neptunium adsorption to clay is not surprising given the tendency for these actinides to form very stable negative or neutrally-charged uranyl- or calcium-uranyl-carbonate complexes at these pH, particularly in a water that is effectively saturated with respect to calcite. It was also observed in testing conducted at LANL earlier in 2012 that uranium did not adsorb measurably to Grimsel granodiorite in a synthetic Grimsel groundwater at pH {approx}8.5 (Kersting et al., 2012). Thus, the planned experimental work was not pursued because all the available information clearly pointed to an expected result that uranium transport would not be facilitated by clay colloids in the Grimsel system.« less

SEPARATION OF PLUTONIUM FROM URANIUM

DOEpatents

Feder, H.M.; Nuttall, R.L.

1959-12-15

A process is described for extracting plutonium from powdered neutron- irradiated urarium metal by contacting the latter, while maintaining it in the solid form, with molten magnesium which takes up the plutonium and separating the molten magnesium from the solid uranium.

RECOVERY OF URANIUM BY SECONDARY XANTHATE COMPLEXING

DOEpatents

Neville, O.K.

1959-09-01

A method is described for separating and recovering uranium values contained in an acidic aqueous solution together with thorium or protactinium values. In accordance with the invention, the acidic solution containing uranium in the uranyl form is contacted with an organic xanthate. The xanthate forms a urano-xanthate complex but is substantially non-reactive with thorium and protactinium. The urano-xanthate complex is recovered by organic solvent extraction.

A poly(acrylonitrile)-functionalized porous aromatic framework synthesized by atom-transfer radical polymerization for the extraction of uranium from seawater

DOE PAGES

Yue, Yanfeng; Zhang, Chenxi; Tang, Qing; ...

2015-10-30

In order to ensure a sustainable reserve of fuel for nuclear power generation, tremendous research efforts have been devoted to developing advanced sorbent materials for extracting uranium from seawater. In this work, a porous aromatic framework (PAF) was surface-functionalized with poly(acrylonitrile) through atom-transfer radical polymerization (ATRP). Batches of this adsorbent were conditioned with potassium hydroxide (KOH) at room temperature or 80 °C prior to contact with a uranium-spiked seawater simulant, with minimal differences in uptake observed as a function of conditioning temperature. A maximum capacity of 4.81 g-U/kg-ads was obtained following 42 days contact with uranium-spiked filtered environmental seawater, whichmore » demonstrates a comparable adsorption rate. A kinetic investigation revealed extremely rapid uranyl uptake, with more than 80% saturation reached within 14 days. Furthermore, relying on the semiordered structure of the PAF adsorbent, density functional theory (DFT) calculations reveal cooperative interactions between multiple adsorbent groups yield a strong driving force for uranium binding.« less

Aqueous biphasic extraction of uranium and thorium from contaminated soils. Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chaiko, D.J.; Gartelmann, J.; Henriksen, J.L.

1995-07-01

The aqueous biphasic extraction (ABE) process for soil decontamination involves the selective partitioning of solutes and fine particulates between two immiscible aqueous phases. The biphase system is generated by the appropriate combination of a water-soluble polymer (e.g., polyethlene glycol) with an inorganic salt (e.g., sodium carbonate). Selective partitioning results in 99 to 99.5% of the soil being recovered in the cleaned-soil fraction, while only 0.5 to 1% is recovered in the contaminant concentrate. The ABE process is best suited to the recovery of ultrafine, refractory material from the silt and clay fractions of soils. During continuous countercurrent extraction tests withmore » soil samples from the Fernald Environmental Management Project site (Fernald, OH), particulate thorium was extracted and concentrated between 6- and 16-fold, while the uranium concentration was reduced from about 500 mg/kg to about 77 mg/kg. Carbonate leaching alone was able to reduce the uranium concentration only to 146 mg/kg. Preliminary estimates for treatment costs are approximately $160 per ton of dry soil. A detailed flowsheet of the ABE process is provided.« less

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

PubMed

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

2013-08-20

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).

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

USGS Publications Warehouse

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).

Colorimetric detection of uranium in water

DOEpatents

DeVol, Timothy A [Clemson, SC; Hixon, Amy E [Piedmont, SC; DiPrete, David P [Evans, GA

2012-03-13

Disclosed are methods, materials and systems that can be used to determine qualitatively or quantitatively the level of uranium contamination in water samples. Beneficially, disclosed systems are relatively simple and cost-effective. For example, disclosed systems can be utilized by consumers having little or no training in chemical analysis techniques. Methods generally include a concentration step and a complexation step. Uranium concentration can be carried out according to an extraction chromatographic process and complexation can chemically bind uranium with a detectable substance such that the formed substance is visually detectable. Methods can detect uranium contamination down to levels even below the MCL as established by the EPA.

Molecular marker and stable carbon isotope analyses of carbonaceous Ambassador uranium ores of Mulga Rock in Western Australia

NASA Astrophysics Data System (ADS)

Jaraula, C.; Schwark, L.; Moreau, X.; Grice, K.; Bagas, L.

2013-12-01

Mulga Rock is a multi-element deposit containing uranium hosted by Eocene peats and lignites deposited in inset valleys incised into Permian rocks of the Gunbarrel Basin and Precambrian rocks of the Yilgarn Craton and Albany-Fraser Orogen. Uranium readily adsorbs onto minerals or phytoclasts to form organo-uranyl complexes. This is important in pre-concentrating uranium in this relatively young ore deposit with rare uraninite [UO2] and coffinite [U(SiO4)1-x(OH)4x], more commonly amorphous and sub-micron uranium-bearing particulates. Organic geochemical and compound-specific stable carbon isotope analyses were conducted to identify possible associations of molecular markers with uranium accumulation and to recognize effect(s) of ionizing radiation on molecular markers. Samples were collected from the Ambassador deposit containing low (<200 ppm) to high (>2000 ppm) uranium concentrations. The bulk rock C/N ratios of 82 to 153, Rock-Eval pyrolysis yields of 316 to 577 mg hydrocarbon/g TOC (Hydrogen Index, HI) and 70 to 102 mg CO2/g TOC (Oxygen Index, OI) are consistent with a terrigenous and predominantly vascular plant OM source deposited in a complex shallow water system, ranging from lacustrine to deltaic, swampy wetland and even shallow lake settings as proposed by previous workers. Organic solvent extracts were separated into saturated hydrocarbon, aromatic hydrocarbon, ketone, and a combined free fatty acid and alcohol fraction. The molecular profiles appear to vary with uranium concentration. In samples with relatively low uranium concentrations, long-chain n-alkanes, alcohols and fatty acids derived from epicuticular plant waxes dominate. The n-alkane distributions (C27 to C31) reveal an odd/even preference (Carbon Preference Index, CPI=1.5) indicative of extant lipids. Average δ13C of -27 to -29 ‰ for long-chain n-alkanes is consistent with a predominant C3 plant source. Samples with relatively higher uranium concentrations contain mostly intermediate-length n-alkanes, ketones, alcohols, and fatty acids (C20 to C24) with no preferential distribution (CPI~1). Intermediate length n-alkanes have modest carbon isotope enrichment compared to long-chain n-alkanes. These shorter-chain hydrocarbons are interpreted to represent alteration products. The diversity and relative abundance of ketones in highly mineralised Mulga Rock peats and lignites are not consistent with aerobic and diagenetic degradation of terrigenous OM in oxic environments. Moreover, molecular changes cannot be associated with thermal breakdown due to the low maturity of the deposits. It is possible that the association of high uranium concentrations and potential radiolysis resulted in the oxidation of alcohol functional groups into aldehydes and ketones and breakdown of highly aliphatic macromolecules (i.e. spores, pollen, cuticles, and algal cysts). These phytoclasts are usually considered to be recalcitrant as they evolved to withstand chemical and physical degradation. Previous petrographic analyses show that spores, pollen and wood fragments are preferentially enriched in uranium. Their molecular compositions are feasible sources of short- to intermediate-length n-alkanes that dominate the mineralised peats and lignites.

Method for converting uranium oxides to uranium metal

DOEpatents

Duerksen, Walter K.

1988-01-01

A process is described for converting scrap and waste uranium oxide to uranium metal. The uranium oxide is sequentially reduced with a suitable reducing agent to a mixture of uranium metal and oxide products. The uranium metal is then converted to uranium hydride and the uranium hydride-containing mixture is then cooled to a temperature less than -100.degree. C. in an inert liquid which renders the uranium hydride ferromagnetic. The uranium hydride is then magnetically separated from the cooled mixture. The separated uranium hydride is readily converted to uranium metal by heating in an inert atmosphere. This process is environmentally acceptable and eliminates the use of hydrogen fluoride as well as the explosive conditions encountered in the previously employed bomb-reduction processes utilized for converting uranium oxides to uranium metal.

Separation of uranium from technetium in recovery of spent nuclear fuel

DOEpatents

Friedman, H.A.

1984-06-13

A method for decontaminating uranium product from the Purex 5 process comprises addition of hydrazine to the product uranyl nitrate stream from the Purex process, which contains hexavalent (UO/sub 2//sup 2 +/) uranium and heptavalent technetium (TcO/sub 4/-). Technetium in the product stream is reduced and then complexed by the addition of oxalic acid (H/sub 2/C/sub 2/O/sub 4/), and the Tc-oxalate complex is readily separated from the 10 uranium by solvent extraction with 30 vol % tributyl phosphate in n-dodecane.

Separation of uranium from technetium in recovery of spent nuclear fuel

DOEpatents

Friedman, Horace A.

1985-01-01

A method for decontaminating uranium product from the Purex process comprises addition of hydrazine to the product uranyl nitrate stream from the Purex process, which contains hexavalent (UO.sub.2.sup.2+) uranium and heptavalent technetium (TcO.sub.4 -). Technetium in the product stream is reduced and then complexed by the addition of oxalic acid (H.sub.2 C.sub.2 O.sub.4), and the Tc-oxalate complex is readily separated from the uranium by solvent extraction with 30 vol. % tributyl phosphate in n-dodecane.

Energy dispersive X-ray fluorescence determination of cadmium in uranium matrix using Cd Kα line excited by continuum

NASA Astrophysics Data System (ADS)

Dhara, Sangita; Misra, N. L.; Aggarwal, S. K.; Venugopal, V.

2010-06-01

An energy dispersive X-ray fluorescence method for determination of cadmium (Cd) in uranium (U) matrix using continuum source of excitation was developed. Calibration and sample solutions of cadmium, with and without uranium were prepared by mixing different volumes of standard solutions of cadmium and uranyl nitrate, both prepared in suprapure nitric acid. The concentration of Cd in calibration solutions and samples was in the range of 6 to 90 µg/mL whereas the concentration of Cd with respect to U ranged from 90 to 700 µg/g of U. From the calibration solutions and samples containing uranium, the major matrix uranium was selectively extracted using 30% tri-n-butyl phosphate in dodecane. Fixed volumes (1.5 mL) of aqueous phases thus obtained were taken directly in specially designed in-house fabricated leak proof Perspex sample cells for the energy dispersive X-ray fluorescence measurements and calibration plots were made by plotting Cd Kα intensity against respective Cd concentration. For the calibration solutions not having uranium, the energy dispersive X-ray fluorescence spectra were measured without any extraction and Cd calibration plots were made accordingly. The results obtained showed a precision of 2% (1 σ) and the results deviated from the expected values by < 4% on average.

Project C-018H, 242-A Evaporator/PUREX Plant Process Condensate Treatment Facility, functional design criteria. Revision 3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sullivan, N.

1995-05-02

This document provides the Functional Design Criteria (FDC) for Project C-018H, the 242-A Evaporator and Plutonium-Uranium Extraction (PUREX) Plant Condensate Treatment Facility (Also referred to as the 200 Area Effluent Treatment Facility [ETF]). The project will provide the facilities to treat and dispose of the 242-A Evaporator process condensate (PC), the Plutonium-Uranium Extraction (PUREX) Plant process condensate (PDD), and the PUREX Plant ammonia scrubber distillate (ASD).

URANIUM DECONTAMINATION

DOEpatents

Buckingham, J.S.; Carroll, J.L.

1959-12-22

A process is described for reducing the extractability of ruthenium, zirconium, and niobium values into hexone contained in an aqueous nitric acid uranium-containing solution. The solution is made acid-deficient, heated to between 55 and 70 deg C, and at that temperature a water-soluble inorganic thiosulfate is added. By this, a precipitate is formed which carries the bulk of the ruthenium, and the remainder of the ruthenium as well as the zirconium and niobium are converted to a hexone-nonextractable form. The rutheniumcontaining precipitate can either be removed from the solu tion or it can be dissolved as a hexone-non-extractable compound by the addition of sodium dichromate prior to hexone extraction.

Application of bimodal distribution to the detection of changes in uranium concentration in drinking water collected by random daytime sampling method from a large water supply zone.

PubMed

Garboś, Sławomir; Święcicka, Dorota

2015-11-01

The random daytime (RDT) sampling method was used for the first time in the assessment of average weekly exposure to uranium through drinking water in a large water supply zone. Data set of uranium concentrations determined in 106 RDT samples collected in three runs from the water supply zone in Wroclaw (Poland), cannot be simply described by normal or log-normal distributions. Therefore, a numerical method designed for the detection and calculation of bimodal distribution was applied. The extracted two distributions containing data from the summer season of 2011 and the winter season of 2012 (nI=72) and from the summer season of 2013 (nII=34) allowed to estimate means of U concentrations in drinking water: 0.947 μg/L and 1.23 μg/L, respectively. As the removal efficiency of uranium during applied treatment process is negligible, the effect of increase in uranium concentration can be explained by higher U concentration in the surface-infiltration water used for the production of drinking water. During the summer season of 2013, heavy rains were observed in Lower Silesia region, causing floods over the territory of the entire region. Fluctuations in uranium concentrations in surface-infiltration water can be attributed to releases of uranium from specific sources - migration from phosphate fertilizers and leaching from mineral deposits. Thus, exposure to uranium through drinking water may increase during extreme rainfall events. The average chronic weekly intakes of uranium through drinking water, estimated on the basis of central values of the extracted normal distributions, accounted for 3.2% and 4.1% of tolerable weekly intake. Copyright © 2015 Elsevier Ltd. All rights reserved.

Determination of trace uranium by resonance fluorescence method coupled with photo-catalytic technology and dual cloud point extraction.

PubMed

Li, Jiekang; Li, Guirong; Han, Qian

2016-12-05

In this paper, two kinds of salophens (Sal) with different solubilities, Sal1 and Sal2, have been respectively synthesized, and they all can combine with uranyl to form stable complexes: [UO2(2+)-Sal1] and [UO2(2+)-Sal2]. Among them, [UO2(2+)-Sal1] was used as ligand to extract uranium in complex samples by dual cloud point extraction (dCPE), and [UO2(2+)-Sal2] was used as catalyst for the determination of uranium by photocatalytic resonance fluorescence (RF) method. The photocatalytic characteristic of [UO2(2+)-Sal2] on the oxidized pyronine Y (PRY) by potassium bromate which leads to the decrease of RF intensity of PRY were studied. The reduced value of RF intensity of reaction system (ΔF) is in proportional to the concentration of uranium (c), and a novel photo-catalytic RF method was developed for the determination of trace uranium (VI) after dCPE. The combination of photo-catalytic RF techniques and dCPE procedure endows the presented methods with enhanced sensitivity and selectivity. Under optimal conditions, the linear calibration curves range for 0.067 to 6.57ngmL(-1), the linear regression equation was ΔF=438.0 c (ngmL(-1))+175.6 with the correlation coefficient r=0.9981. The limit of detection was 0.066ngmL(-1). The proposed method was successfully applied for the separation and determination of uranium in real samples with the recoveries of 95.0-103.5%. The mechanisms of the indicator reaction and dCPE are discussed. Copyright © 2016 Elsevier B.V. All rights reserved.

SOLVENT EXTRACTION PROCESS

DOEpatents

Jonke, A.A.

1957-10-01

In improved solvent extraction process is described for the extraction of metal values from highly dilute aqueous solutions. The process comprises contacting an aqueous solution with an organic substantially water-immiscible solvent, whereby metal values are taken up by a solvent extract phase; scrubbing the solvent extract phase with an aqueous scrubbing solution; separating an aqueous solution from the scrubbed solvent extract phase; and contacting the scrubbed solvent phase with an aqueous medium whereby the extracted metal values are removed from the solvent phase and taken up by said medium to form a strip solution containing said metal values, the aqueous scrubbing solution being a mixture of strip solution and an aqueous solution which contains mineral acids anions and is free of the metal values. The process is particularly effective for purifying uranium, where one starts with impure aqueous uranyl nitrate, extracts with tributyl phosphate dissolved in carbon tetrachloride, scrubs with aqueous nitric acid and employs water to strip the uranium from the scrubbed organic phase.

Can we predict uranium bioavailability based on soil parameters? Part 2: soil solution uranium concentration is not a good bioavailability index.

PubMed

Vandenhove, H; Van Hees, M; Wannijn, J; Wouters, K; Wang, L

2007-01-01

The present study aimed to quantify the influence of soil parameters on uranium uptake by ryegrass. Ryegrass was established on eighteen distinct soils, spiked with (238)U. Uranium soil-to-plant transfer factors (TF) ranged from 0.0003 to 0.0340kgkg(-1). There was no significant relation between the U soil-to-plant transfer (or total U uptake or flux) and the uranium concentration in the soil solution or any other soil factor measured, nor with the U recovered following selective soil extractions. Multiple linear regression analysis resulted in a significant though complex model explaining up to 99% of variation in TF. The influence of uranium speciation on uranium uptake observed was featured: UO(2)(+2), uranyl carbonate complexes and UO(2)PO(4)(-) seem the U species being preferentially taken up by the roots and transferred to the shoots. Improved correlations were obtained when relating the uranium TF with the summed soil solution concentrations of mentioned uranium species.

Investigations into the Reusability of Amidoxime-Based Polymeric Adsorbents for Seawater Uranium Extraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuo, Li-Jung; Pan, Horng-Bin; Wai, Chien M.

The ability to re-use amidoxime-based polymeric adsorbents is a critical component in reducing the overall cost of the technology to extract uranium from seawater. This report describes an evaluation of adsorbent reusability in multiple re-use (adsorption/stripping) cycles in real seawater exposures with potassium bicarbonate (KHCO3) elution using several amidoxime-based polymeric adsorbents. The KHCO3 elution technique achieved ~100% recovery of uranium adsorption capacity in the first re-use. Subsequent re-uses showed significant drops in adsorption capacity. After the 4th re-use with the ORNL AI8 adsorbent, the 56-day adsorption capacity dropped to 28% of its original capacity. FTIR spectra revealed that there wasmore » a conversion of the amidoxime ligands to carboxylate groups during extended seawater exposure, becoming more significant with longer the exposure time. Ca and Mg adsorption capacities also increased with each re-use cycle supporting the hypothesis that long term exposure resulted in converting amidoxime to carboxylate, enhancing the adsorption of Ca and Mg. Shorter seawater exposure (adsorption/stripping) cycles (28 vs. 42 days) had higher adsorption capacities after re-use, but the shorter exposure cycle time did not produce an overall better performance in terms of cumulative exposure time. Recovery of uranium capacity in re-uses may also vary across different adsorbent formulations. Through multiple re-use the adsorbent AI8 can harvest 10 g uranium/kg adsorbent in ~140 days, using a 28-day adsorption/stripping cycle, a performance much better than would be achieved with a single use of the adsorbent through very long-term exposure (saturation capacity = 7.4 g U/kg adsorbent). A time dependent seawater exposure model to evaluate the cost associated with reusing amidoxime-based adsorbents in real seawater exposures was developed. The cost to extract uranium from seawater ranged from $610-830/kg U was predicted. Model simulation suggests that a short seawater exposure cycle (< 15 days) is the optimal deployment period for lower uranium production cost in seawater uranium mining.« less

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

PubMed

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 mechanisms onto Savannah River Site (SRS) wetland sediments was studied using batch (ad)sorption experiments, sequential extraction, U L3-edge X-ray absorption near-edge structure (XANES) spectroscopy, fluorescence mapping and μ-XANES. Under oxidized conditions, 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 indicated that the U species were primarily associated with the acid soluble fraction (weak acetic acid extractable) and organic fraction (Na-pyrophosphate extractable). Uranium L3-edge XANES spectra of the U-bound sediments were nearly identical to that of uranyl acetate. Based on fluorescence mapping, U and Fe distributions in the sediment were poorly correlated, U was distributed throughout the sample and did not appear as isolated U mineral phases. The primary oxidation state of U in these oxidized sediments was 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 or to secondary mineral formation. Collectively, this study suggests that U may be strongly bound to wetland sediments, not only under reducing conditions by reductive precipitation, but also under oxidizing conditions through NOM-uranium bonding. Published by Elsevier Ltd.

Distribution and mode of occurrence of uranium in bottom ash derived from high-germanium coals.

PubMed

Sun, Yinglong; Qi, Guangxia; Lei, Xuefei; Xu, Hui; Li, Lei; Yuan, Chao; Wang, Yi

2016-05-01

The radioactivity of uranium in radioactive coal bottom ash (CBA) may be a potential danger to the ambient environment and human health. Concerning the limited research on the distribution and mode of occurrence of uranium in CBA, we herein report our investigations into this topic using a number of techniques including a five-step Tessier sequential extraction, hydrogen fluoride (HF) leaching, Siroquant (Rietveld) quantification, magnetic separation, and electron probe microanalysis (EPMA). The Tessier sequential extraction showed that the uranium in the residual and Fe-Mn oxide fractions was dominant (59.1% and 34.9%, respectively). The former was mainly incorporated into aluminosilicates, retained with glass and cristobalite, whereas the latter was especially enriched in the magnetic fraction, of which about 50% was present with magnetite (Fe3O4) and the rest in other iron oxides. In addition, the uranium in the magnetic fraction was 2.6 times that in the non-magnetic fraction. The experimental findings in this work may be important for establishing an effective strategy to reduce radioactivity from CBA for the protection of our local environment. Copyright © 2015. Published by Elsevier B.V.

Simultaneous extraction and preconcentration of uranium and thorium in aqueous samples by new modified mesoporous silica prior to inductively coupled plasma optical emission spectrometry determination.

PubMed

Yousefi, Seyed Reza; Ahmadi, Seyed Javad; Shemirani, Farzaneh; Jamali, Mohammad Reza; Salavati-Niasari, Masoud

2009-11-15

A new synthesized modified mesoporous silica (MCM-41) using 5-nitro-2-furaldehyde (fural) was applied as an effective sorbent for the solid phase extraction of uranium(VI) and thorium(IV) ions from aqueous solution for the measurement by inductively coupled plasma optical emission spectrometry (ICP OES). The influences of some analytical parameters on the quantitative recoveries of the analyte ions were investigated in batch method. Under optimal conditions, the analyte ions were sorbed by the sorbent at pH 5.5 and then eluted with 1.0 mL of 1.0 mol L(-1) HNO(3). The preconcentration factor was 100 for a 100mL sample volume. The limits of detection (LOD) obtained for uranium(VI) and thorium(IV) were 0.3 microg L(-1). The maximum sorption capacity of the modified MCM-41 was found to be 47 and 49 mg g(-1) for uranium(VI) and thorium(IV), respectively. The sorbent exhibited good stability, reusability, high adsorption capacity and fast rate of equilibrium for sorption/desorption of uranium and thorium ions. The applicability of the synthesized sorbent was examined using CRM and real water samples.

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

PubMed

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.

Extractive procedure for uranium determination in water samples by liquid scintillation counting.

PubMed

Gomez Escobar, V; Vera Tomé, F; Lozano, J C; Martín Sánchez, A

1998-07-01

An extractive procedure for uranium determination using liquid scintillation counting with the URAEX cocktail is described. Interference from radon and a strong influence of nitrate ion were detected in this procedure. Interference from radium, thorium and polonium emissions were very low when optimal operating conditions were reached. Quenching effects were considered and the minimum detectable activity was evaluated for different sample volumes. Isotopic analysis of samples can be performed using the proposed method. Comparisons with the results obtained with the general procedure used in alpha spectrometry with passivated implanted planar silicon detectors showed good agreement. The proposed procedure is thus suitable for uranium determination in water samples and can be considered as an alternative to the laborious conventional chemical preparations needed for alpha spectrometry methods using semiconductor detectors.

SEPARATION OF URANIUM FROM THORIUM

DOEpatents

Hellman, N.N.

1959-07-01

A process is presented for separating uranium from thorium wherein the ratio of thorium to uranium is between 100 to 10,000. According to the invention the thoriumuranium mixture is dissolved in nitric acid, and the solution is prepared so as to obtain the desired concentration within a critical range of from 4 to 8 N with regard to the total nitrate due to thorium nitrate, with or without nitric acid or any nitrate salting out agent. The solution is then contacted with an ether, such as diethyl ether, whereby uranium is extracted into ihe organic phase while thorium remains in the aqueous phase.

Nanostructured Metal Oxide Sorbents for the Collection and Recovery of Uranium from Seawater

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chouyyok, Wilaiwan; Warner, Cynthia L.; Mackie, Katherine E.

2016-02-07

The ability to collect uranium from seawater offers the potential for a long-term green fuel supply for nuclear energy. However, extraction of uranium, and other trace minerals, is challenging due to the high ionic strength and low mineral concentrations in seawater. Herein we evaluate the use of nanostructured metal oxide sorbents for the collection and recovery of uranium from seawater. Chemical affinity, chemical adsorption capacity and kinetics of preferred sorbent materials were evaluated. High surface area manganese and iron oxide nanomaterials showed excellent performance for uranium collection from seawater. Inexpensive nontoxic carbonate solutions were demonstrated to be an effective andmore » environmental benign method of stripping the uranium from the metal oxide sorbents. Various formats for the utilization of the nanostructured metals oxide sorbent materials are discussed including traditional and nontraditional methods such as magnetic separation. Keywords: Uranium, nano, manganese, iron, sorbent, seawater, magnetic, separations, nuclear energy« less

Micro-PIXE characterisation of uranium occurrence in the coal zones and the mudstones of the Springbok Flats Basin, South Africa

NASA Astrophysics Data System (ADS)

Nxumalo, V.; Kramers, J.; Mongwaketsi, N.; Przybyłowicz, W. J.

2017-08-01

Uranium occurrence and characterisation in the coal samples of the upper coal zones of the Vryheid Formation and mudstones of the Volksrust Formation was investigated using micro-PIXE (Proton-Induced X-ray Emission) and proton backscattering spectrometry (BS) in conjunction with the nuclear microprobe. Two styles of uranium mineralisation in the Springbok Flats Basin were found: syngenetic mineralisation in which uranium occurs organically bound with coal matrix, with no discrete uranium minerals formed, and epigenetic mineralisation in which uranium occurs in veins that are filled with coffinite with botryoidal texture in the mudstones of the Volksrust Formation, overlying the coal zones. Micro-PIXE analysis made it possible to map out trace elements (including uranium) associated with the coals at low levels of detection, which other techniques such as SEM-EDS and ore microscopy failed. This information will help in better understanding of the best extraction methods to be employed to recover uranium from the coals of the Springbok Flats Basin.

Characterization of uranium bearing material using x-ray fluorescence and direct gamma-rays measurement techniques

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mujaini, M., E-mail: madihah@uniten.edu.my; Chankow, N.; Yusoff, M. Z.

2016-01-22

Uranium ore can be easily detected due to various gamma-ray energies emitted from uranium daughters particularly from {sup 238}U daughters such as {sup 214}Bi, {sup 214}Pb and {sup 226}Ra. After uranium is extracted from uranium ore, only low energy gamma-rays emitted from {sup 235}U may be detected if the detector is placed in close contact to the specimen. In this research, identification and characterization of uranium bearing materials is experimentally investigated using direct measurement of gamma-rays from {sup 235}U in combination with the x-ray fluorescence (XRF) technique. Measurement of gamma-rays can be conducted by using high purity germanium (HPGe) detectormore » or cadmium telluride (CdTe) detector while a {sup 57}Coradioisotope-excited XRF spectrometer using CdTe detector is used for elemental analysis. The proposed technique was tested with various uranium bearing specimens containing natural, depleted and enriched uranium in both metallic and powder forms.« less

RECOVERY OF URANIUM BY AROMATIC DITHIOCARBAMATE COMPLEXING

DOEpatents

Neville, O.K.

1959-08-11

A selective complexing organic solvent extraction process is presented for the separation of uranium values from an aqueous nitric acid solution of neutron irradiated thorium. The process comprises contacting the solution with an organic aromatic dithiccarbamaie and recovering the resulting urancdithiccarbamate complex with an organic solvent such as ethyl acetate.

40 CFR 440.34 - New source performance standards (NSPS).

Code of Federal Regulations, 2011 CFR

2011-07-01

... uranium ore, excluding mines using in situ leach methods, shall not exceed: Effluent characteristic... for the extraction of uranium or from mines and mills using in situ leach methods. The Agency... Subcategory § 440.34 New source performance standards (NSPS). Except as provided in subpart L of this part any...

40 CFR 440.34 - New source performance standards (NSPS).

Code of Federal Regulations, 2010 CFR

2010-07-01

... uranium ore, excluding mines using in situ leach methods, shall not exceed: Effluent characteristic... for the extraction of uranium or from mines and mills using in situ leach methods. The Agency... Subcategory § 440.34 New source performance standards (NSPS). Except as provided in subpart L of this part any...

Investigations into the Effect of Current Velocity on Amidoxime-Based Polymeric Uranium Adsorbent Performance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gill, Gary A.; Kuo, Li-Jung; Strivens, Jonathan E.

2015-12-01

The Fuel Resources Program at the U.S. Department of Energy’s (DOE), Office of Nuclear Energy (DOE-NE) is developing adsorbent technology to extract uranium from seawater. This technology is being developed to provide a sustainable and economically viable supply of uranium fuel for nuclear reactors (DOE, 2010). Among the key environmental variables to understand for adsorbent deployment in the coastal ocean is what effect flow-rates or linear velocity has on uranium adsorption capacity. The goal is to find a flow conditions that optimize uranium adsorption capacity in the shortest exposure time. Understanding these criteria will be critical in choosing a locationmore » for deployment of a marine adsorbent farm. The objective of this study was to identify at what linear velocity the adsorption kinetics for uranium extraction starts to drop off due to limitations in mass transport of uranium to the surface of the adsorbent fibers. Two independent laboratory-based experimental approaches using flow-through columns and recirculating flumes for adsorbent exposure were used to assess the effect of flow-rate (linear velocity) on the kinetic uptake of uranium on amidoxime-based polymeric adsorbent material. Time series observations over a 56 day period were conducted with flow-through columns over a 35-fold range in linear velocity from 0.29 to 10.2 cm/s, while the flume study was conducted over a narrower 11-fold range, from 0.48 to 5.52 cm/s. These ranges were specifically chosen to focus on the lower end of oceanic currents and expand above and below the linear velocity of ~ 2.5 cm/s adopted for marine testing of adsorbent material at PNNL.« less

Immobilization of uranium in contaminated soil by natural apatite addition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mrdakovic Popic, Jelena; Stojanovic, Mirjana; Milosevic, Sinisa

2007-07-01

Available in abstract form only. Full text of publication follows: The goal of this study was to evaluate the effectiveness of Serbian natural mineral apatite as soil additive for reducing the migration of uranium from contaminated sediments. In laboratory study we investigated the sorption properties of domestic apatite upon different experimental conditions, such as pH, adsorbent mass, reaction period, concentration of P{sub 2}O{sub 5} in apatite, solid/liquid ratio. In second part of study, we did the quantification of uranium in soil samples, taken from uranium mine site 'Kalna', by sequential extraction method. The same procedure was, also, used for uraniummore » determination in contaminated soil samples after apatite addition, in order to determine the changes in U distribution in soil fraction. The obtained results showed the significant level of immobilization (96.7%) upon certain conditions. Increase of %P{sub 2}O{sub 5} in apatite and process of mechano-chemical activation led to increase of immobilization capacity from 17.50% till 91.64%. The best results for uranium binding were obtained at pH 5.5 and reaction period 60 days (98.04%) The sequential extraction showed the presence of uranium (48.2%) in potentially available soil fractions, but with the apatite addition uranium content in these fractions decreased (30.64%), what is considering environmental aspect significant fact. In situ immobilization of radionuclide using inexpensive sequestering agents, such as apatite, is very adequate for big contaminated areas of soil with low level of contamination. This investigation study on natural apatite from deposit 'Lisina' Serbia was the first one of this type in our country. Key words: apatite, uranium, immobilization, soil, contamination. (authors)« less

Development of practical decontamination process for the removal of uranium from gravel.

PubMed

Kim, Ilgook; Kim, Gye-Nam; Kim, Seung-Soo; Choi, Jong-Won

2018-01-01

In this study, a practical decontamination process was developed to remove uranium from gravel using a soil washing method. The effects of critical parameters including particle size, H 2 SO 4 concentration, temperature, and reaction time on uranium removal were evaluated. The optimal condition for two-stage washing of gravel was found to be particle size of 1-2 mm, 1.0 M H 2 SO 4 , temperature of 60°C, and reaction time of 3 h, which satisfied the required uranium concentration for self-disposal. Furthermore, most of the extracted uranium was removed from the waste solution by precipitation, implying that the treated solution can be reused as washing solution. These results clearly demonstrated that our proposed process can be indeed a practical technique to decontaminate uranium-polluted gravel.

Progress in understanding uranium(IV) speciation and dynamics in biologically reduced sediments: Research at molecular to centimeter scales by the SLAC SFA program

NASA Astrophysics Data System (ADS)

Bargar, J.; Williams, K. H.; Campbell, K. M.; Stubbs, J. E.; Suvorova, E.; Lezama-Pacheco, J. S.; Alessi, D.; Stylo, M.; Handley, K. M.; Bernier-Latmani, R.; Cerrato, J.; Davis, J. A.; Fox, P. M.; Giammar, D.; Long, P. E.

2011-12-01

The chemical and physical forms of U(IV) in reduced sediments, as well as the biogeochemical processes by which they form and transform, profoundly influence the stability of reduced U(IV) species and the behavior of uranium in biostimulated aquifers. Obtaining such information in field sediments is important because biogeochemical field conditions and their time dependence are difficult to replicate in the laboratory. The majority of contaminated aquifers in which bioremediation is of potential interest, including the Old Rifle, CO IFRC site, exhibit relatively low uranium sediment concentrations, i.e., < 10 ppm, presenting a formidable challenge to the use of spectroscopy and microscopy techniques that typically require 10-fold or higher uranium loadings. We have developed an in-situ column technique to study U(IV) species and evolving microbial communities in the Old Rifle aquifer and to correlate them with changes in trace and major ion groundwater composition during biostimulation treatments. Sediments were examined using x-ray and electron microscopy, x-ray absorption spectroscopy (XAS), and chemical extractions. XAS analysis showed that U(IV) occurred predominantly or exclusively as monomeric U(IV) complexes coordinated to oxo (or similar N/C) neighbors, and is associated with biomass or Fe sulfides. Even in the latter case, U(IV) was not coordinated directly to S neighbors. Sediment-hosted monomeric U(IV) complexes were found to partially transform into uraninite in the aquifer over a subsequent 12 month period. This work establishes the importance of monomeric U(IV) complexes in subsurface sediments at the Old Rifle site and provides a conceptual framework in which previously observed U(IV) reduction products can be related. These experiments also establish that U(IV) species are dynamic in aquifers and can undergo non-oxidative transformation reactions. These new results have important implications for uranium reactive transport models, long-term assessment of remediation technologies, and understanding natural uranium reduction in aquifers.

A preliminary report on the rapid fluorimetric determination of uranium in low-grade ores

USGS Publications Warehouse

Grimaldi, F.S.; Levine, Harry

1950-01-01

A simple and very rapid fluorimetric procedure is described for the determination of uranium in low-grade shale and phosphate ores. The best working range is from 0.001 to about 0.04 percent U. The procedure employs batch extraction of uranium nitrate by ethyl acetate, using aluminum nitrate as the salting agent, prior to the visual fluorimetric estimation. The procedure is especially designed to save reagents; only 9.5 g of aluminum nitrate and 10 ml of ethyl acetate being used for one analysis. The solution of the sample by means of a fusion with NaOH-NaNO3 flux is rapid. After fusion the sample is immediately extracted without removing silica and other hydrolytic precipitates. Aluminum nitrate very effectively ties up fluoride and phosphate, thus eliminating steps required for their removal.

Temperature Dependence of Uranium and Vanadium Adsorption on Amidoxime-Based Adsorbents in Natural Seawater

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuo, Li-Jung; Gill, Gary A.; Tsouris, Costas

Recent advances in the development of amidoxime-based adsorbents have made it highly promising for seawater uranium extraction. However, there is a great need to understand the influence of temperature on the uranium sequestration performance of the adsorbents in natural seawater. Here in this work, the apparent enthalpy and entropy of the sorption of uranium (VI) and vanadium (V) with amidoxime-based adsorbents were determined in natural seawater tests at 8, 20, and 31 °C that cover a broad range of ambient seawater temperature. The sorption of U was highly endothermic, producing apparent enthalpies of 57 ± 6.0 and 59 ± 11more » kJ mol -1 and apparent entropies of 314 ± 21 and 320 ± 36 J K-1 mol -1, respectively, for two adsorbent formulations. In contrast, the sorption of V showed a much smaller temperature sensitivity, producing apparent enthalpies of 6.1 ± 5.9 and -11 ± 5.7 kJ mol -1 and apparent entropies of 164 ± 20 and 103 ± 19 J K -1 mol -1, respectively. This new thermodynamic information suggests that amidoxime-based adsorbents will deliver significantly increased U adsorption capacities and improved selectivity in warmer waters. A separate field study of seawater uranium adsorption conducted in a warm seawater site (Miami, FL, USA) confirm the observed strong temperature effect on seawater uranium mining. Lastly, this strong temperature dependence demonstrates that the warmer the seawater where the amidoxime-based adsorbents are deployed the greater the yield for seawater uranium extraction.« less

Temperature Dependence of Uranium and Vanadium Adsorption on Amidoxime-Based Adsorbents in Natural Seawater

DOE PAGES

Kuo, Li-Jung; Gill, Gary A.; Tsouris, Costas; ...

2018-01-16

Recent advances in the development of amidoxime-based adsorbents have made it highly promising for seawater uranium extraction. However, there is a great need to understand the influence of temperature on the uranium sequestration performance of the adsorbents in natural seawater. Here in this work, the apparent enthalpy and entropy of the sorption of uranium (VI) and vanadium (V) with amidoxime-based adsorbents were determined in natural seawater tests at 8, 20, and 31 °C that cover a broad range of ambient seawater temperature. The sorption of U was highly endothermic, producing apparent enthalpies of 57 ± 6.0 and 59 ± 11more » kJ mol -1 and apparent entropies of 314 ± 21 and 320 ± 36 J K-1 mol -1, respectively, for two adsorbent formulations. In contrast, the sorption of V showed a much smaller temperature sensitivity, producing apparent enthalpies of 6.1 ± 5.9 and -11 ± 5.7 kJ mol -1 and apparent entropies of 164 ± 20 and 103 ± 19 J K -1 mol -1, respectively. This new thermodynamic information suggests that amidoxime-based adsorbents will deliver significantly increased U adsorption capacities and improved selectivity in warmer waters. A separate field study of seawater uranium adsorption conducted in a warm seawater site (Miami, FL, USA) confirm the observed strong temperature effect on seawater uranium mining. Lastly, this strong temperature dependence demonstrates that the warmer the seawater where the amidoxime-based adsorbents are deployed the greater the yield for seawater uranium extraction.« less

Toxicity of Uranium Adsorbent Materials using the Microtox Toxicity Test

DOE Office of Scientific and Technical Information (OSTI.GOV)

Park, Jiyeon; Jeters, Robert T.; Gill, Gary A.

2015-10-01

The Marine Sciences Laboratory at the Pacific Northwest National Laboratory evaluated the toxicity of a diverse range of natural and synthetic materials used to extract uranium from seawater. The uranium adsorbent materials are being developed as part of the U. S. Department of Energy, Office of Nuclear Energy, Fuel Resources Program. The goal of this effort was to identify whether deployment of a farm of these materials into the marine environment would have any toxic effects on marine organisms.

ALKALINE CARBONATE LEACHING PROCESS FOR URANIUM EXTRACTION

DOEpatents

Thunaes, A.; Brown, E.A.; Rabbitts, A.T.

1957-11-12

A process for the leaching of uranium from high carbonate ores is presented. According to the process, the ore is leached at a temperature of about 200 deg C and a pressure of about 200 p.s.i.g. with a solution containing alkali carbonate, alkali permanganate, and bicarbonate ion, the bicarbonate ion functionlng to prevent premature formation of alkali hydroxide and consequent precipitation of a diuranate. After the leaching is complete, the uranium present is recovered by precipitation with NaOH.

Assessment of nonpoint source chemical loading potential to watersheds containing uranium waste dumps and human health hazards associated with uranium exploration and mining, Red, White, and Fry Canyons, southeastern Utah, 2007

USGS Publications Warehouse

Beisner, Kimberly R.; Marston, Thomas M.; Naftz, David L.; Snyder, Terry; Freeman, Michael L.

2010-01-01

During May, June, and July 2007, 58 solid-phase samples were collected from abandoned uranium mine waste dumps, background sites, and adjacent streambeds in Red, White, and Fry Canyons in southeastern Utah. The objectives of this sampling program were to (1) assess the nonpoint-source chemical loading potential to ephemeral and perennial drainage basins from uranium waste dumps and (2) assess potential effects on human health due to recreational activities on and around uranium waste dumps on Bureau of Land Management property. Uranium waste-dump samples were collected using solid-phase sampling protocols. After collection, solid-phase samples were homogenized and extracted in the laboratory using a leaching procedure. Filtered (0.45 micron) water samples were obtained from the field leaching procedure and were analyzed for major and trace elements at the Inductively Coupled Plasma-Mass Spectrometry Metals Analysis Laboratory at the University of Utah. A subset of the solid-phase samples also were digested with strong acids and analyzed for major ions and trace elements at the U.S. Geological Survey Geologic Division Laboratory in Denver, Colorado. For the initial ranking of chemical loading potential for uranium waste dumps, results of leachate analyses were compared with existing aquatic-life and drinking-water-quality standards. To assess potential effects on human health, solid-phase digestion values for uranium were compared to soil screening levels (SSL) computed using the computer model RESRAD 6.5 for a probable concentration of radium. One or more chemical constituents exceeded aquatic life and drinking-water-quality standards in approximately 64 percent (29/45) of the leachate samples extracted from uranium waste dumps. Most of the uranium waste dump sites with elevated trace-element concentrations in leachates were located in Red Canyon. Approximately 69 percent (31/45) of the strong acid digestible soil concentration values were greater than a calculated SSL. Uranium waste dump sites with elevated leachate and total digestible concentrations may need to be further investigated to determine the most appropriate remediation method.

40 CFR 440.34 - New source performance standards (NSPS).

Code of Federal Regulations, 2013 CFR

2013-07-01

... underground, that produce uranium ore, excluding mines using in situ leach methods, shall not exceed: Effluent... leach process for the extraction of uranium or from mines and mills using in situ leach methods. The... Vanadium Ores Subcategory § 440.34 New source performance standards (NSPS). Except as provided in subpart L...

40 CFR 440.34 - New source performance standards (NSPS).

Code of Federal Regulations, 2012 CFR

2012-07-01

... underground, that produce uranium ore, excluding mines using in situ leach methods, shall not exceed: Effluent... leach process for the extraction of uranium or from mines and mills using in situ leach methods. The... Vanadium Ores Subcategory § 440.34 New source performance standards (NSPS). Except as provided in subpart L...

40 CFR 440.34 - New source performance standards (NSPS).

Code of Federal Regulations, 2014 CFR

2014-07-01

... underground, that produce uranium ore, excluding mines using in situ leach methods, shall not exceed: Effluent... leach process for the extraction of uranium or from mines and mills using in situ leach methods. The... Vanadium Ores Subcategory § 440.34 New source performance standards (NSPS). Except as provided in subpart L...

EVALUATION OF AUSTRALIAN RUM JUNGLE URANIUM CONCENTRATE FOR USE AS NLO REFINERY FEED

DOE Office of Scientific and Technical Information (OSTI.GOV)

Collopy, T.J.; Huntington, C.W.; Blum, J.F.

1956-01-20

A laboratory evaluation of Australian Rum Jungle uranium concentrate showed that the uracium can be satisfactorily extracted by 33.5% TBP-kerosene from an aqueous acid slurry of the material, and that impurities in the aqueous uranyl nitrate product obtained by re-extraetion from the organic phase approach NL0 tolerance specifications. The uranium values in the organic product were not completely re-extracted at room temperatare (l0th stage organic, 1.6 g/l U); however, it was assumed that reextraction will be complete under pulse column conditions (150 deg F). The results of the Pilot Plant evaluation of Rum Jungle uranium concentrate (Lot No. 1) indicatedmore » that this material can be processed employing NLO refinery conditions. The aqueous uranyl nitrate product from the test met all impurity specifications except those for manganese and nickel. The high chloride content of this lot of concentrate will mske blending necessary in order to meet NLO feed material specifications. The blending will alan lessen the tendencies toward metallic contamination of the OK liquor observed in these tests. (auth)« less

Role of U(VI) Adsorption in U(VI) Reduction by Geobacter Species.

DOE Office of Scientific and Technical Information (OSTI.GOV)

None, None

2009-03-09

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.

Symposium on the reprocessing of irradiated fuels. Book 2, Session IV

DOE Office of Scientific and Technical Information (OSTI.GOV)

None

1958-12-31

Book two of this conference has a single-focused session IV entitled Nonaqueous Processing, with 8 papers. The session deals with fluoride volatility processes and pyrometallurgical or pyrochemical processes. The latter involves either an oxide drossing or molten metal extraction or fused salt extraction technique and results in only partial decontamination. Fluoride volatility processes appear to be especially favorable for recovery of enriched uranium and decontamination factors of 10/sup 7/ to 10/sup 8/ would be achieved by simpler means than those employed in solvent extraction. Data from lab research on the BrF/sub 3/ process and the ClF/sub 3/ process are givenmore » and discussed and pilot plant experience is described, all in connection with natural uranium or slightly enriched uranium processing. Fluoride volatility processes for enriched or high alloy fuels are described step by step. The economic and engineering considerations of both types of nonaqueous processing are treated separately and as fully as present knowledge allows. A comprehensive review of the chemistry of pyrometallurgical processes is included.« less

Impact of pore size on the sorption of uranyl under seawater conditions

DOE PAGES

Mayes, Richard T.; Gorka, Joanna; Dai, Sheng

2016-04-05

The extraction of uranium from seawater has received significant interest recently, because of the possibility of a near-limitless supply of uranium to fuel the nuclear power industry. While sorbent development has focused primarily on polymeric sorbents, nanomaterials represent a new area that has the potential to surpass the current polymeric sorbents, because of the high surface areas that are possible. Mesoporous carbon materials are a stable, high-surface-area material capable of extracting various chemical species from a variety of environments. Herein, we report the use of a dual templating process to understand the effect of pore size on the adsorption ofmore » uranyl ions from a uranyl brine consisting of seawater-relevant sodium, chloride, and bicarbonate ions. It was found that pore size played a more significant role in the effective use of the grafted polymer, leading to higher uranium capacities than the surface area. Furthermore, the pore size must be tailored to meet the demands of the extraction medium and analyte metal to achieve efficacy as an adsorbent.« less

Accumulation of uranium by immobilized persimmon tannin

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sakaguchi, Takashi; Nakajima, Akira

1994-01-01

We have discovered that the extracted juice of unripe astringent persimmon fruit, designated as kakishibu or shibuol, has an extremely high affinity for uranium. To develop efficient adsorbents for uranium, we tried to immobilize kakishibu (persimmon tannin) with various aldehydes and mineral acids. Persimmon tannin immobilized with glutaraldehyde can accumulate 1.71 g (14 mEq U) of uranium per gram of the adsorbent. The uranium accumulating capacity of this adsorbent is several times greater than that of commercially available chelating resins (2-3 mEq/g). Immobilized persimmon tannin has the most favorable features for uranium recovery; high selective adsorption ability, rapid adsorption rate,more » and applicability in both column and batch systems. The uranium retained on immobilized persimmon tannin can be quantitatively and easily eluted with a very dilute acid, and the adsorbent can thus be easily recycled in the adsorption-desorption process. Immobilized persimmon tannin also has a high affinity for thorium. 23 refs., 13 figs., 7 tabs.« less

Volumetric determination of uranium titanous sulfate as reductant before oxidimetric titration

USGS Publications Warehouse

Wahlberg, J.S.; Skinner, D.L.; Rader, L.F.

1957-01-01

Need for a more rapid volumetric method for the routine determination of uranium in uranium-rich materials has led to the development of a method that uses titanous sulfate as a reductant before oxidimetric titration. Separation of the hydrogen sulfide group is not necessary. Interfering elements precipitated by cupferron are removed by automatic filtrations made simultaneously rather than by the longer chloroform extraction method. Uranium is reduced from VI to IV by addition of an excess of titanous sulfate solution, cupric ion serving as an indicator by forming red metallic copper when reduction is complete. The copper is reoxidized by addition of mercuric perchlorate. The reduced uranium is then determined by addition of excess ferric sulfate and titration with ceric sulfate. The method has proved to be rapid, accurate, and economical.

Effect of biofouling on the performance of amidoxime-based polymeric uranium adsorbents

DOE PAGES

Park, Jiyeon; Gill, Gary A.; Strivens, Jonathan E.; ...

2016-01-27

Here, the Marine Science Laboratory at the Pacific Northwest National Laboratory evaluated the impact of biofouling on uranium adsorbent performance. A surface modified polyethylene adsorbent fiber provided by Oak Ridge National Laboratory, AF adsorbent, was tested either in the presence or absence of light to simulate deployment in shallow or deep marine environments. 42-day exposure tests in column and flume settings showed decreased uranium uptake by biofouling. Uranium uptake was reduced by up to 30 %, in the presence of simulated sunlight, which also increased biomass accumulation and altered the microbial community composition on the fibers. These results suggest thatmore » deployment below the photic zone would mitigate the effects of biofouling, resulting in greater yields of uranium extracted from seawater.« less

Industrial Production of Uranium; PRODUCCION INDUSTRIAL DE URANIO

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pedregal, J.D.

1956-01-01

The purity requirements of uranium and the necessity of purifying the uranium compounds previous to its metallurgical treatment are briefly discussed as an introduction to the different methods reduction to the metal. The methods which are used by the Junta de Energia Nuclear are indicated. (tr-auth)

Extractive scintillating polymer sensors for trace-level detection of uranium in contaminated ground water.

PubMed

Duval, Christine E; DeVol, Timothy A; Husson, Scott M

2016-12-01

This contribution describes the synthesis of robust extractive scintillating resin and its use in a flow-cell detector for the direct detection of uranium in environmental waters. The base poly[(4-methyl styrene)-co-(4-vinylbenzyl chloride)-co-(divinylbenzene)-co-(2-(1-napthyl)-4-vinyl-5-phenyloxazole)] resin contains covalently bound fluorophores. Uranium-binding functionality was added to the resin by an Arbuzov reaction followed by hydrolysis via strong acid or trimethylsilyl bromide (TMSBr)-mediated methanolysis. The resin was characterized by Fourier-transform infrared spectroscopy and spectrofluorometry. Fluorophore degradation was observed in the resin hydrolyzed by strong acid, while the resin hydrolyzed by TMSBr-mediated methanolysis maintained luminosity and showed hydrogen bonding-induced Stokes' shift of ∼100 nm. The flow cell detection efficiency for uranium of the TMSBr-mediated methanolysis resin was evaluated at pH 4, 5 and 6 in DI water containing 500 Bq L -1 uranium-233 and demonstrated flow cell detection efficiencies of 23%, 16% and 7%. Experiments with pH 4, synthetic groundwater with 50 Bq L -1 uranium-233 exhibited a flow cell detection efficiency of 17%. The groundwater measurements show that the resins can concentrate the uranyl cation from waters with high concentrations of competitor ions at near-neutral pH. Findings from this research will lay the groundwork for development of materials for real-time environmental sensing of alpha- and beta-emitting radionuclides. Copyright © 2016 Elsevier B.V. All rights reserved.

Uranium content and leachable fraction of fluorspars

USGS Publications Warehouse

Landa, E.R.; Councell, T.B.

2000-01-01

Much attention in the radiological health community has recently focused on the management and regulation of naturally occurring radioactive materials. Although uranium-bearing minerals are present in a variety of fluorspar deposits, their potential consideration as naturally occurring radioactive materials has received only limited recognition. The uranium content of 28 samples of acid- and cryolite-grade (>97% CaF2) fluorspar from the National Defense Stockpile was found to range from 120 to 24,200 ??g kg-1, with a mean of 2,145 ??g kg-1. As a point of comparison, the average concentration of uranium in the upper crust of the earth is about 2,500 ??g kg-1. Leachability of this uranium was assessed by means of the Toxicity Characteristic Leaching Procedure (TCLP). The TCLP extractable fraction ranged from 1 to 98%, with a mean of 24% of the total uranium. The typically low concentrations of uranium seen in these materials probably reflects the removal of uranium-bearing mineral phases during the beneficiation of the crude fluorspar ore to achieve industrial specifications. Future NORM studies should examine crude fluorspar ores and flotation tailings.

URANIUM EXTRACTION

DOEpatents

Harrington, C.D.; Opie, J.V.

1958-07-01

The recovery of uranium values from uranium ore such as pitchblende is described. The ore is first dissolved in nitric acid, and a water soluble nitrate is added as a salting out agent. The resulting feed solution is then contacted with diethyl ether, whereby the bulk of the uranyl nitrate and a portion of the impurities are taken up by the ether. This acid ether extract is then separated from the aqueous raffinate, and contacted with water causing back extractioa of the uranyl nitrate and impurities into the water to form a crude liquor. After separation from the ether extract, this crude liquor is heated to about 118 deg C to obtain molten uranyl nitrate hexahydratc. After being slightly cooled the uranyl nitrate hexahydrate is contacted with acid free diethyl ether whereby the bulk of the uranyl nitrate is dissolved into the ethcr to form a neutral ether solution while most of the impurities remain in the aqueous waste. After separation from the aqueous waste, the resultant ether solution is washed with about l0% of its volume of water to free it of any dissolved impurities and is then contacted with at least one half its volume of water whereby the uranyl nitrate is extracted into the water to form an aqueous product solution.

Extraction study on uranyl nitrate for energy applications

NASA Astrophysics Data System (ADS)

Giri, R.; Nath, G.

2017-07-01

Due to the ever-growing demand of energy nuclear reactor materials and the nuclear energy are now considered to be the most critical materials and source of energy for future era. Deposition of nuclear wastes in different industry, nuclear power sector are very much toxic in open environment which are hazardous to living being. There are different methods for extraction and reprocessing of these materials which are cost effective and tedious process. Ultrasonic assisted solvent extraction process is a most efficient and economical way for extraction of such type materials. The presence of third phase in mixing of extractants-diluent pair with aqueous phase imposes the problems in extraction of nuclear reactor materials. The appropriate solvent mixture in proper concentration is an important step in the solvent extraction process. Study of thermo-physical properties helps in selecting an optimum blend for extraction process. In the present work, the extraction of uranium with the binary mixture of Methyl Ethyl Ketone (MEK) and Kerosene was investigated and discussed with the variation of ultrasonic frequency for different temperatures. The result shows that the low frequency and low temperature is suitable environment for extraction. The extraction of uranium by this method is found to be a better result for extraction study in laboratory scale as well as industrial sector.

Uranium decay daughters from isolated mines: Accumulation and sources.

PubMed

Cuvier, A; Panza, F; Pourcelot, L; Foissard, B; Cagnat, X; Prunier, J; van Beek, P; Souhaut, M; Le Roux, G

2015-11-01

This study combines in situ gamma spectrometry performed at different scales, in order to accurately locate the contamination pools, to identify the concerned radionuclides and to determine the distribution of the contaminants from soil to bearing phase scale. The potential mobility of several radionuclides is also evaluated using sequential extraction. Using this procedure, an accumulation area located downstream of a former French uranium mine and concentrating a significant fraction of radioactivity is highlighted. We report disequilibria in the U-decay chains, which are likely related to the processes implemented on the mining area. Coupling of mineralogical analyzes with sequential extraction allow us to highlight the presence of barium sulfate, which may be the carrier of the Ra-226 activities found in the residual phase (Ba(Ra)SO4). In contrast, uranium is essentially in the reducible fraction and potentially trapped in clay-iron coatings located on the surface of minerals. Copyright © 2015 Elsevier Ltd. All rights reserved.

Effects of Uranium Oxides on Some of the Algae Native to Eglin Air Force Base, Florida.

DTIC Science & Technology

1982-06-01

Chlorella , and Selenastrum were not identified from the collections after microscopic examination. 4. MOBILITY OF DEPLETED URANIUM BY DISSOLUTION IN NATURAL...processes. A similar finding nas been previously reported for Chlorella regularis (Sakaguchi, Horikoshi, and Nakajima, 1978). In addition, uranium

EXTRACTION OF URANIUM

DOEpatents

Kesler, R.D.; Rabb, D.D.

1959-07-28

An improved process is presented for recovering uranium from a carnotite ore. In the improved process U/sub 2/O/sub 5/ is added to the comminuted ore along with the usual amount of NaCl prior to roasting. The amount of U/sub 2/O/ sub 5/ is dependent on the amount of free calcium oxide and the uranium in the ore. Specifically, the desirable amount of U/sub 2/O/sub 5/ is 3.2% for each 1% of CaO, and 5 to 6% for each 1% of uranium. The mixture is roasted at about 1560 deg C for about 30 min and then leached with a 3 to 9% aqueous solution of sodium carbonate.

Isotopic analysis of uranium in natural waters by alpha spectrometry

USGS Publications Warehouse

Edwards, K.W.

1968-01-01

A method is described for the determination of U234/U238 activity ratios for uranium present in natural waters. The uranium is coprecipitated from solution with aluminum phosphate, extracted into ethyl acetate, further purified by ion exchange, and finally electroplated on a titanium disc for counting. The individual isotopes are determined by measurement of the alpha-particle energy spectrum using a high resolution low-background alpha spectrometer. Overall chemical recovery of about 90 percent and a counting efficiency of 25 percent allow analyses of water samples containing as little as 0.10 ?g/l of uranium. The accuracy of the method is limited, on most samples, primarily by counting statistics.

COORDINATION COMPOUND-SOLVENT EXTRACTION PROCESS FOR URANIUM RECOVERY

DOEpatents

Reas, W.H.

1959-03-10

A method is presented for the separation of uranium from aqueous solutions containing a uranyl salt and thorium. Thc separation is effected by adding to such solutions an organic complexing agent, and then contacting the solution with an organic solvent in which the organic complexing agent is soluble. By use of the proper complexing agent in the proper concentrations uranium will be complexed and subsequently removed in the organic solvent phase, while the thorium remains in the aqueous phase. Mentioned as suitable organic complexing agents are antipyrine, bromoantipyrine, and pyramidon.

PLUTONIUM RECOVERY FROM NEUTRON-BOMBARDED URANIUM FUEL

DOEpatents

Moore, R.H.

1962-04-10

A process of recovering plutonium from neutronbombarded uranium fuel by dissolving the fuel in equimolar aluminum chloride-potassium chloride; heating the mass to above 700 deg C for decomposition of plutonium tetrachloride to the trichloride; extracting the plutonium trichloride into a molten salt containing from 40 to 60 mole % of lithium chloride, from 15 to 40 mole % of sodium chloride, and from 0 to 40 mole % of potassium chloride or calcium chloride; and separating the layer of equimolar chlorides containing the uranium from the layer formed of the plutonium-containing salt is described. (AEC)

Potential Aquifer Vulnerability in Regions Down-Gradient from ...

EPA Pesticide Factsheets

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 rocks and transporting it in low concentrations to a chemical redox interface where it is deposited in an ore zone typically containing the uranium minerals uraninite, pitchblende, and/or coffinite; various iron sulfides; native selenium; clays; and calcite. In situ recovery (ISR) of these uranium ores is a process of contacting the uranium mineral deposit with leaching (lixiviant) fluids via injection of the lixiviant into wells drilled into the subsurface aquifer that hosts uranium ore, while other extraction wells pump the dissolved uranium after dissolution of the uranium minerals. Environmental concerns during and after ISR include water quality impacts from: 1) potential excursions of leaching solutions away from the injection zone into down-dip, underlying, or overlying aquifers; 2) potential migration of uranium and its decay products (e.g., Ra, Rn, Pb); and, 3) potential migration of redox-sensitive trace metals (e.g., Fe, Mn, Mo, Se, V), metalloids (e.g., As), and anions (e.g., sulfate). This review describes the geochemical processes that control roll-front uranium transport and fate in groundwater systems, identifies potential aquifer vulnerabilities to ISR operations, identifies

Experiments and Modeling of Uranium Adsorption in the Presence of Other Ions in Simulated Seawater

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ladshaw, Austin; Das, Sadananda; Liao, Wei-Po

2015-11-19

Seawater contains uranium at an average concentration of 3.3 ppb, as well as a variety of other ions at either overwhelmingly higher or similar concentrations, which complicate the recovery of uranium. This report describes an investigation of the effects of various factors such as uranium speciation and presence of salts including sodium, calcium, magnesium, and bicarbonate, as well as trace elements such as vanadium on uranium adsorption kinetics in laboratory experiments. Adsorption models are also developed to describe the experimental data of uranium extraction from seawater. Results show that the presence of calcium and magnesium significantly slows down the uraniummore » adsorption kinetics. Vanadium can replace uranium from amidoxime-based adsorbent in the presence of sodium in the solution. Results also show that bicarbonate in the solution strongly competes with amidoxime for binding uranium, and thus slows down the uranium adsorption kinetics. Developed on the basis of the experimental findings, the model is capable of describing the effects of pH, ionic strength, temperature, and concentration of various species. The results of this work are useful in the understanding of the important factors that control the adsorbent capacity and kinetics of uranium uptake by amidoxime-based adsorbents.« less

Evaluation of terrestrial plants extracts for uranium sorption and characterization of potent phytoconstituents.

PubMed

Sharma, Sunita; Singh, Bikram; Thulasidas, S K; Kulkarni, Madhuri J; Natarajan, V; Manchanda, Vijay K

2016-01-01

Sorption capacity of four plants (Funaria hygrometrica, Musa acuminata, Brassica juncea and Helianthus annuus) extracts/fractions for uranium, a radionuclide was investigated by EDXRF and tracer studies. The maximum sorption capacity, i.e., 100% (complete sorption) was observed in case of Musa acuminata extract and fractions. Carbohydrate, proteins, phenolics and flavonoids contents in the active fraction (having maximum sorption capacity) were also determined. Further purification of the most active fraction provided three pure molecules, mannitol, sorbitol and oxo-linked potassium oxalate. The characterization of isolated molecules was achieved by using FTIR, NMR, GC-MS, MS-MS, and by single crystal-XRD analysis. Of three molecules, oxo-linked potassium oxalate was observed to have 100% sorption activity. Possible binding mechanism of active molecule with the uranyl cation has been purposed.

Analysis of the 2H-evaporator scale samples (HTF-17-56, -57)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hay, M.; Coleman, C.; Diprete, D.

Savannah River National Laboratory analyzed scale samples from both the wall and cone sections of the 242-16H Evaporator prior to chemical cleaning. The samples were analyzed for uranium and plutonium isotopes required for a Nuclear Criticality Safety Assessment of the scale removal process. The analysis of the scale samples found the material to contain crystalline nitrated cancrinite and clarkeite. Samples from both the wall and cone contain depleted uranium. Uranium concentrations of 16.8 wt% 4.76 wt% were measured in the wall and cone samples, respectively. The ratio of plutonium isotopes in both samples is ~85% Pu-239 and ~15% Pu-238 bymore » mass and shows approximately the same 3.5 times higher concentration in the wall sample versus the cone sample as observed in the uranium concentrations. The mercury concentrations measured in the scale samples were higher than previously reported values. The wall sample contains 19.4 wt% mercury and the cone scale sample 11.4 wt% mercury. The results from the current scales samples show reasonable agreement with previous 242-16H Evaporator scale sample analysis; however, the uranium concentration in the current wall sample is substantially higher than previous measurements.« less

Determination of uranium isotopic composition and 236U content of soil samples and hot particles using inductively coupled plasma mass spectrometry.

PubMed

Boulyga, S F; Becker, J S

2001-07-01

As a result of the accident at the Chernobyl nuclear power plant (NPP) the environment was contaminated with spent nuclear fuel. The 236U isotope was used in this study to monitor the spent uranium from nuclear fallout in soil samples collected in the vicinity of the Chernobyl NPP. Nuclear track radiography was applied for the identification and extraction of hot radioactive particles from soil samples. A rapid and sensitive analytical procedure was developed for uranium isotopic ratio measurement in environmental samples based on double-focusing inductively coupled plasma mass spectrometry (DF-ICP-MS) with a MicroMist nebulizer and a direct injection high-efficiency nebulizer (DIHEN). The performance of the DF-ICP-MS with a quartz DIHEN and plasma shielded torch was studied. Overall detection efficiencies of 4 x 10(-4) and 10(-3) counts per atom were achieved for 238U in DF-ICP-QMS with the MicroMist nebulizer and DIHEN, respectively. The rate of formation of uranium hydride ions UH+/U+ was 1.2 x 10(-4) and 1.4 x 10(-4), respectively. The precision of short-term measurements of uranium isotopic ratios (n = 5) in 1 microg L(-1) NBS U-020 standard solution was 0.11% (238U/235U) and 1.4% (236U/238U) using a MicroMist nebulizer and 0.25% (235U/238U) and 1.9% (236U/P38U) using a DIHEN. The isotopic composition of all investigated Chernobyl soil samples differed from those of natural uranium; i.e. in these samples the 236U/238U ratio ranged from 10(-5) to 10(-3). Results obtained with ICP-MS, alpha- and gamma-spectrometry showed differences in the migration properties of spent uranium, plutonium, and americium. The isotopic ratio of uranium was also measured in hot particles extracted from soil samples.

Removal of Trace Elements by Cupric Oxide Nanoparticles from Uranium In Situ Recovery Bleed Water and Its Effect on Cell Viability

PubMed Central

Schilz, Jodi R.; Reddy, K. J.; Nair, Sreejayan; Johnson, Thomas E.; Tjalkens, Ronald B.; Krueger, Kem P.; Clark, Suzanne

2015-01-01

In situ recovery (ISR) is the predominant method of uranium extraction in the United States. During ISR, uranium is leached from an ore body and extracted through ion exchange. The resultant production bleed water (PBW) contains contaminants such as arsenic and other heavy metals. Samples of PBW from an active ISR uranium facility were treated with cupric oxide nanoparticles (CuO-NPs). CuO-NP treatment of PBW reduced priority contaminants, including arsenic, selenium, uranium, and vanadium. Untreated and CuO-NP treated PBW was used as the liquid component of the cell growth media and changes in viability were determined by the MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) assay in human embryonic kidney (HEK 293) and human hepatocellular carcinoma (Hep G2) cells. CuO-NP treatment was associated with improved HEK and HEP cell viability. Limitations of this method include dilution of the PBW by growth media components and during osmolality adjustment as well as necessary pH adjustment. This method is limited in its wider context due to dilution effects and changes in the pH of the PBW which is traditionally slightly acidic however; this method could have a broader use assessing CuO-NP treatment in more neutral waters. PMID:26132311

Assessment of nonpoint source chemical loading potential to watersheds containing uranium waste dumps associated with uranium exploration and mining, San Rafael Swell, Utah

USGS Publications Warehouse

Freeman, Michael L.; Naftz, David L.; Snyder, Terry; Johnson, Greg

2008-01-01

During July and August of 2006, 117 solid-phase samples were collected from abandoned uranium waste dumps, geologic background sites, and adjacent streambeds in the San Rafael Swell, in southeastern Utah. The objective of this sampling program was to assess the nonpoint source chemical loading potential to ephemeral and perennial watersheds from uranium waste dumps on Bureau of Land Management property. Uranium waste dump samples were collected using solid-phase sampling protocols. After collection, solid-phase samples were homogenized and extracted in the laboratory using a field leaching procedure. Filtered (0.45 micron) water samples were obtained from the field leaching procedure and were analyzed for Ag, As, Ba, Be, Cd, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Sb, Se, U, V, and Zn at the Inductively Coupled Plasma-Mass Spectrometry Metals Analysis Laboratory at the University of Utah, Salt Lake City, Utah and for Hg at the U.S. Geological Survey National Water Quality Laboratory, Denver, Colorado. For the initial ranking of chemical loading potential of suspect uranium waste dumps, leachate analyses were compared with existing aquatic life and drinking-water-quality standards and the ratio of samples that exceeded standards to the total number of samples was determined for each element having a water-quality standard for aquatic life and drinking-water. Approximately 56 percent (48/85) of the leachate samples extracted from uranium waste dumps had one or more chemical constituents that exceeded aquatic life and drinking-water-quality standards. Most of the uranium waste dump sites with elevated trace-element concentrations in leachates were along Reds Canyon Road between Tomsich Butte and Family Butte. Twelve of the uranium waste dump sites with elevated trace-element concentrations in leachates contained three or more constituents that exceeded drinking-water-quality standards. Eighteen of the uranium waste dump sites had three or more constituents that exceeded trace-element concentrations for aquatic life water-quality standards. The proximity of the uranium waste dumps in the Tomsich Butte area near Muddy Creek, coupled with the elevated concentration of trace elements, increases the offsite impact potential to water resources. Future assessment and remediation priority of these areas may be done by using GIS-based risk-mapping techniques, such as Sensitive Catchment Integrated Mapping and Analysis Project.

The behaviour of tributyl phosphate in an organic diluent

NASA Astrophysics Data System (ADS)

Leay, Laura; Tucker, Kate; Del Regno, Annalaura; Schroeder, Sven L. M.; Sharrad, Clint A.; Masters, Andrew J.

2014-09-01

Tributyl phosphate (TBP) is used as a complexing agent in the Plutonium Uranium Extraction (PUREX) liquid-liquid phase extraction process for recovering uranium and plutonium from spent nuclear reactor fuel. Here, we address the molecular and microstructure of the organic phases involved in the extraction process, using molecular dynamics to show that when TBP is mixed with a paraffinic diluent, the TBP self-assembles into a bi-continuous phase. The underlying self-association of TBP is driven by intermolecular interaction between its polar groups, resulting in butyl moieties radiating out into the organic solvent. Simulation predicts a TBP diffusion constant that is anomalously low compared to what might normally be expected for its size; experimental nuclear magnetic resonance (NMR) studies also indicate an extremely low diffusion constant, consistent with a molecular aggregation model. Simulation of TBP at an oil/water interface shows the formation of a bilayer system at low TBP concentrations. At higher concentrations, a bulk bi-continuous structure is observed linking to this surface bilayer. We suggest that this structure may be intimately connected with the surprisingly rapid kinetics of the interfacial mass transport of uranium and plutonium from the aqueous to the organic phase in the PUREX process.

Successful Coupling of a Bis-Amidoxime Uranophile with a Hydrophilic Backbone for Selective Uranium Sequestration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Piechowicz, Marek; Abney, Carter W.; Thacker, Nathan C.

The amidoxime group (-RNH2NOH) has long been used to extract uranium from seawater on account of its high affinity toward uranium. The development of tunable sorbent materials for uranium sequestration remains a research priority as well as a significant challenge. Herein, we report the design, synthesis, and uranium sorption properties of bis-amidoxime-functionalized polymeric materials (BAP 1–3). Bifunctional amidoxime monomers were copolymerized with an acrylamide cross-linker to obtain bis-amidoxime incorporation as high as 2 mmol g–1 after five synthetic steps. The resulting sorbents were able to uptake nearly 600 mg of uranium per gram of polymer after 37 days of contactmore » with a seawater simulant containing 8 ppm uranium. Moreover, the polymeric materials exhibited low vanadium uptake with a maximum capacity of 128 mg of vanadium per gram of polymer. This computationally predicted and experimentally realized selectivity of uranium over vanadium, nearly 5 to 1 w/w, is one of the highest reported to date and represents an advancement in the rational design of sorbent materials with high uptake capacity and selectivity.« less

The determination of uranium (IV) in apatite

USGS Publications Warehouse

Clarke, Roy S.; Altschuler, Zalman S.

1956-01-01

Geologic and mineralogic evidence indicate that the uranium present in apatite may proxy for calcium in the mineral structure as U(IV). An experimental investigation was conducted and chemical evidence was obtained that establishes the presence of U(IV) in apatite. The following analytical procedure was developed for the determination of U(IV). Carbonate-fluorapatite is dissolved in cold 1.5M orthophosphoric acid and fluorapatite is dissolved in cold 1.2M hydrochloric acid containing 1.5 g of hydroxylamine hydrochloride per 100 ml. Uranium (IV) is precipitated by cupferron using titanium as a carrier. The uranium in the precipitate is separated by use of the ethyl acetate extraction procedure and determined fluorimetrically. The validity and the limitations of the method have been established by spike experiments.

Combined transuranic-strontium extraction process

DOEpatents

Horwitz, E.P.; Dietz, M.L.

1992-12-08

The transuranic (TRU) elements neptunium, plutonium and americium can be separated together with strontium from nitric acid waste solutions in a single process. An extractant solution of a crown ether and an alkyl(phenyl)-N,N-dialkylcarbanylmethylphosphine oxide in an appropriate diluent will extract the TRU's together with strontium, uranium and technetium. The TRU's and the strontium can then be selectively stripped from the extractant for disposal. 3 figs.

Combined transuranic-strontium extraction process

DOEpatents

Horwitz, E. Philip; Dietz, Mark L.

1992-01-01

The transuranic (TRU) elements neptunium, plutonium and americium can be separated together with strontium from nitric acid waste solutions in a single process. An extractant solution of a crown ether and an alkyl(phenyl)-N,N-dialkylcarbanylmethylphosphine oxide in an appropriate diluent will extract the TRU's together with strontium, uranium and technetium. The TRU's and the strontium can then be selectively stripped from the extractant for disposal.

Laser fluorometric analysis of plants for uranium exploration

USGS Publications Warehouse

Harms, T.F.; Ward, F.N.; Erdman, J.A.

1981-01-01

A preliminary test of biogeochemical exploration for locating uranium occurrences in the Marfa Basin, Texas, was conducted in 1978. Only 6 of 74 plant samples (mostly catclaw mimosa, Mimosa biuncifera) contained uranium in amounts above the detection limit (0.4 ppm in the ash) of the conventional fluorometric method. The samples were then analyzed using a Scintrex UA-3 uranium analyzer* * Use of trade names in this paper is for descriptive purposes only and does not constitute endorsement by the U.S. Geological Survey. - an instrument designed for direct analysis of uranium in water, and which can be conveniently used in a mobile field laboratory. The detection limit for uranium in plant ash (0.05 ppm) by this method is almost an order of magnitude lower than with the fluorometric conventional method. Only 1 of the 74 samples contained uranium below the detection limit of the new method. Accuracy and precision were determined to be satisfactory. Samples of plants growing on mineralized soils and nonmineralized soils show a 15-fold difference in uranium content; whereas the soils themselves (analyzed by delayed neutron activation analysis) show only a 4-fold difference. The method involves acid digestion of ashed tissue, extraction of uranium into ethyl acetate, destruction of the ethyl acetate, dissolution of the residue in 0.005% nitric acid, and measurement. ?? 1981.

Nuclear Fuel Reprocessing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Harold F. McFarlane; Terry Todd

2013-11-01

Reprocessing is essential to closing nuclear fuel cycle. Natural uranium contains only 0.7 percent 235U, the fissile (see glossary for technical terms) isotope that produces most of the fission energy in a nuclear power plant. Prior to being used in commercial nuclear fuel, uranium is typically enriched to 3–5% in 235U. If the enrichment process discards depleted uranium at 0.2 percent 235U, it takes more than seven tonnes of uranium feed to produce one tonne of 4%-enriched uranium. Nuclear fuel discharged at the end of its economic lifetime contains less one percent 235U, but still more than the natural ore.more » Less than one percent of the uranium that enters the fuel cycle is actually used in a single pass through the reactor. The other naturally occurring isotope, 238U, directly contributes in a minor way to power generation. However, its main role is to transmute into plutoniumby neutron capture and subsequent radioactive decay of unstable uraniumand neptuniumisotopes. 239Pu and 241Pu are fissile isotopes that produce more than 40% of the fission energy in commercially deployed reactors. It is recovery of the plutonium (and to a lesser extent the uranium) for use in recycled nuclear fuel that has been the primary focus of commercial reprocessing. Uraniumtargets irradiated in special purpose reactors are also reprocessed to obtain the fission product 99Mo, the parent isotope of technetium, which is widely used inmedical procedures. Among the fission products, recovery of such expensive metals as platinum and rhodium is technically achievable, but not economically viable in current market and regulatory conditions. During the past 60 years, many different techniques for reprocessing used nuclear fuel have been proposed and tested in the laboratory. However, commercial reprocessing has been implemented along a single line of aqueous solvent extraction technology called plutonium uranium reduction extraction process (PUREX). Similarly, hundreds of types of reactor fuels have been irradiated for different purposes, but the vast majority of commercial fuel is uranium oxide clad in zirconium alloy tubing. As a result, commercial reprocessing plants have relatively narrow technical requirements for used nuclear that is accepted for processing.« less

A selective electromembrane extraction of uranium (VI) prior to its fluorometric determination in water.

PubMed

Davarani, Saied Saeed Hosseiny; Moazami, Hamid Reza; Keshtkar, Ali Reza; Banitaba, Mohammad Hossein; Nojavan, Saeed

2013-06-14

A novel method for the selective electromembrane extraction (EME) of U(6+) prior to fluorometric determination has been proposed. The effect of extraction conditions including supported liquid membrane (SLM) composition, extraction time and extraction voltage were investigated. An SLM composition of 1% di-2-ethyl hexyl phosphonic acid in nitrophenyl octyl ether (NPOE) showed good selectivity, recovery and enrichment factor. The best performance was achieved at an extraction potential of 80 volts and an extraction time of 14 minutes Under the optimized conditions, a linear range from 1 to 1000 ng mL(-1) and LOD of 0.1 ng mL(-1) were obtained for the determination of U(6+). The EME method showed good performance in sample cleanup and the reduction of the interfering effects of Mn(2+), Zn(2+), Cd(2+), Ni(2+), Fe(3+), Co(2+), Cu(2+), Cl(-) and PO4(3-) ions during fluorometric determination of uranium in real water samples. The recoveries above 54% and enrichment factors above 64.7 were obtained by the proposed method for real sample analysis. Copyright © 2013 Elsevier B.V. All rights reserved.

Column bioleaching of uranium embedded in granite porphyry by a mesophilic acidophilic consortium.

PubMed

Qiu, Guanzhou; Li, Qian; Yu, Runlan; Sun, Zhanxue; Liu, Yajie; Chen, Miao; Yin, Huaqun; Zhang, Yage; Liang, Yili; Xu, Lingling; Sun, Limin; Liu, Xueduan

2011-04-01

A mesophilic acidophilic consortium was enriched from acid mine drainage samples collected from several uranium mines in China. The performance of the consortium in column bioleaching of low-grade uranium embedded in granite porphyry was investigated. The influences of several chemical parameters on uranium extraction in column reactor were also investigated. A uranium recovery of 96.82% was achieved in 97 days column leaching process including 33 days acid pre-leaching stage and 64 days bioleaching stage. It was reflected that indirect leaching mechanism took precedence over direct. Furthermore, the bacterial community structure was analyzed by using Amplified Ribosomal DNA Restriction Analysis. The results showed that microorganisms on the residual surface were more diverse than that in the solution. Acidithiobacillus ferrooxidans was the dominant species in the solution and Leptospirillum ferriphilum on the residual surface. Copyright © 2011 Elsevier Ltd. All rights reserved.

Effects of ammonium on uranium partitioning and kaolinite mineral dissolution.

PubMed

Emerson, Hilary P; Di Pietro, Silvina; Katsenovich, Yelena; Szecsody, Jim

2017-02-01

Ammonia gas injection is a promising technique for the remediation of uranium within the vadose zone. It can be used to manipulate the pH of a system and cause co-precipitation processes that are expected to remove uranium from the aqueous phase and decrease leaching from the solid phase. The work presented in this paper explores the effects of ammonium and sodium hydroxide on the partitioning of uranium and dissolution of the kaolinite mineral in simplified synthetic groundwaters using equilibrium batch sorption and sequential extraction experiments. It shows that there is a significant increase in uranium removal in systems with divalent cations present in the aqueous phase but not in sodium chloride synthetic groundwaters. Further, the initial conditions of the aqueous phase do not affect the dissolution of kaolinite. However, the type of base treatment does have an effect on mineral dissolution. Published by Elsevier Ltd.

Investigations into Alternative Desorption Agents for Amidoxime-Based Polymeric Uranium Adsorbents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gill, Gary A.; Kuo, Li-Jung; Strivens, Jonathan E.

2015-06-01

Amidoxime-based polymeric braid adsorbents that can extract uranium (U) from seawater are being developed to provide a sustainable supply of fuel for nuclear reactors. A critical step in the development of the technology is to develop elution procedures to selectively remove U from the adsorbents and to do so in a manner that allows the adsorbent material to be reused. This study investigates use of high concentrations of bicarbonate along with targeted chelating agents as an alternative means to the mild acid elution procedures currently in use for selectively eluting uranium from amidoxime-based polymeric adsorbents.

An Investigation on the Persistence of Uranium Hydride during Storage of Simulant Nuclear Waste Packages.

PubMed

Stitt, C A; Harker, N J; Hallam, K R; Paraskevoulakos, C; Banos, A; Rennie, S; Jowsey, J; Scott, T B

2015-01-01

Synchrotron X-rays have been used to study the oxidation of uranium and uranium hydride when encapsulated in grout and stored in de-ionised water for 10 months. Periodic synchrotron X-ray tomography and X-ray powder diffraction have allowed measurement and identification of the arising corrosion products and the rates of corrosion. The oxidation rates of the uranium metal and uranium hydride were slower than empirically derived rates previously reported for each reactant in an anoxic water system, but without encapsulation in grout. This was attributed to the grout acting as a physical barrier limiting the access of oxidising species to the uranium surface. Uranium hydride was observed to persist throughout the 10 month storage period and industrial consequences of this observed persistence are discussed.

An Investigation on the Persistence of Uranium Hydride during Storage of Simulant Nuclear Waste Packages

PubMed Central

Harker, N. J.; Hallam, K. R.; Paraskevoulakos, C.; Banos, A.; Rennie, S.; Jowsey, J.

2015-01-01

Synchrotron X-rays have been used to study the oxidation of uranium and uranium hydride when encapsulated in grout and stored in de-ionised water for 10 months. Periodic synchrotron X-ray tomography and X-ray powder diffraction have allowed measurement and identification of the arising corrosion products and the rates of corrosion. The oxidation rates of the uranium metal and uranium hydride were slower than empirically derived rates previously reported for each reactant in an anoxic water system, but without encapsulation in grout. This was attributed to the grout acting as a physical barrier limiting the access of oxidising species to the uranium surface. Uranium hydride was observed to persist throughout the 10 month storage period and industrial consequences of this observed persistence are discussed. PMID:26176551

Potential aquifer vulnerability in regions down-gradient from uranium in situ recovery (ISR) sites.

PubMed

Saunders, James A; Pivetz, Bruce E; Voorhies, Nathan; Wilkin, Richard T

2016-12-01

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 important in leaching uranium from source rocks and transporting it in low concentrations to a chemical redox interface where it is deposited in an ore zone typically containing the uranium minerals uraninite, pitchblende, and/or coffinite; various iron sulfides; native selenium; clays; and calcite. In situ recovery (ISR) of uranium ores is a process of contacting the uranium mineral deposit with leaching and oxidizing (lixiviant) fluids via injection of the lixiviant into wells drilled into the subsurface aquifer that hosts uranium ore, while other extraction wells pump the dissolved uranium after dissolution of the uranium minerals. Environmental concerns during and after ISR include water quality degradation from: 1) potential excursions of leaching solutions away from the injection zone into down-gradient, underlying, or overlying aquifers; 2) potential migration of uranium and its decay products (e.g., Ra, Rn, Pb); and, 3) potential mobilization and migration of redox-sensitive trace metals (e.g., Fe, Mn, Mo, Se, V), metalloids (e.g., As), and anions (e.g., sulfate). This review describes the geochemical processes that control roll-front uranium transport and fate in groundwater systems, identifies potential aquifer vulnerabilities to ISR operations, identifies data gaps in mitigating these vulnerabilities, and discusses the hydrogeological characterization involved in developing a monitoring program. Published by Elsevier Ltd.

EXTRACTION METHOD FOR SEPARATING URANIUM, PLUTONIUM, AND FISSION PRODUCTS FROM COMPOSITIONS CONTAINING SAME

DOEpatents

Seaborg, G.T.

1957-10-29

Methods for separating plutonium from the fission products present in masses of neutron irradiated uranium are reported. The neutron irradiated uranium is first dissolved in an aqueous solution of nitric acid. The plutonium in this solution is present as plutonous nitrate. The aqueous solution is then agitated with an organic solvent, which is not miscible with water, such as diethyl ether. The ether extracts 90% of the uraryl nitrate leaving, substantially all of the plutonium in the aqueous phase. The aqueous solution of plutonous nitrate is then oxidized to the hexavalent state, and agitated with diethyl ether again. In the ether phase there is then obtained 90% of plutonium as a solution of plutonyl nitrate. The ether solution of plutonyl nitrate is then agitated with water containing a reducing agent such as sulfur dioxide, and the plutonium dissolves in the water and is reduced to the plutonous state. The uranyl nitrate remains in the ether. The plutonous nitrate in the water may be recovered by precipitation.

Remediation of a uranium-contamination in ground water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Woerner, Joerg; Margraf, Sonja; Hackel, Walter

2007-07-01

The former production site of NUKEM where nuclear fuel-elements were developed and handled from 1958 to 1988 was situated in the centre of an industrial park for various activities of the chemical and metallurgical industry. The size of the industrially used part is about 300.000 m{sup 2}. Regulatory routine controls showed elevated CHC (Chlorinated Hydro-Carbons) values of the ground water at the beginning of the 1990's in an area which represented about 80.000 m{sup 2} down-gradient of locations where CHC compounds were stored and handled. Further investigations until 1998 proved that former activities on the NUKEM site, like the UF{submore » 6} conversion process, were of certain relevance. The fact that several measured values were above the threshold values made the remediation of the ground water mandatory. This was addressed in the permission given by the Ministry for Nuclear Installations and Environment of Hesse according to chap. 7 of the German atomic law in October 2000. Ground water samples taken in an area of about 5.000 m{sup 2} showed elevated values of total Uranium activity up to between 50 and 75 Bq/l in 2002. Furthermore in an area of another 20.000 m{sup 2} the samples were above threshold value. In this paper results of the remediation are presented. The actual alpha-activities of the ground waters of the remediation wells show values of 3 to 9 Bq/l which are dominated by 80 to 90 % U-234 activity. The mass-share of total Uranium for this nuclide amounts to 0,05% on average. The authority responsible for conventional water utilisation defined target values for remediation: 20 {mu}g/l for dissolved Uranium and 10 {mu}g/l for CHC. Both values have not yet been reached for an area of about 10.000 m{sup 2}. The remediation process by extracting water from four remediation wells has proved its efficiency by reduction of the starting concentrations by a factor of 3 to 6. Further pumping will be necessary especially in that area of the site where the contaminations were found later during soil remediation activities. Only two wells have been in operation since July 2002 when the remediation technique was installed and an apparatus for direct gamma-spectroscopic measurement of the accumulated activities on the adsorbers was qualified. Two further remediation wells have been in operation since August 2006, when the installed remediation technique was about to be doubled from a throughput of 5 m{sup 3}/h to 10 m{sup 3}/h. About 20.000 m{sup 3} of ground water have been extracted since from these two wells and the decrease of their Uranium concentrations behaves similar to that of the two other wells being extracted since the beginning of remediation. Both, total Uranium-concentrations and the weight-share of the nuclides U-234, U-235 and U-238 are measured by ICP-MS (Inductively Coupled Plasma - Mass Spectrometry) besides measurements of Uranium-Alpha-Activities in addition to the measurement of CHC components of which PCE (Per-chlor-Ethene) is dominant in the contaminated area. CHC compounds are measured by GC (Gas Chromatography). Down-gradient naturally attenuated products are detected in various compositions. Overall 183.000 m{sup 3} of ground water have been extracted. Using a pump and treat method 11 kg Uranium have been collected on an ion-exchange material based on cellulose, containing almost 100 MBq U-235 activity, and almost 15 kg of CHC, essentially PCE, were collected on GAC (Granules of Activated Carbon). Less than 3% of the extracted Uranium have passed the adsorber-system of the remediation plant and were adsorbed by the sewage sludge of the industrial site's waste water treatment. The monthly monitoring of 19 monitoring wells shows that an efficient artificial barrier was built up by the water extraction. The Uranium contamination of two ground water plumes has drastically been reduced by the used technique dependent on the amounts of extracted water. The concentration of the CHC contamination has changed depending on the location of temporal pumping. Thereby maximum availability of this contaminant for the remediation process is ensured. If locations with unchanged water quality are detected electrochemical parameters of the water or hydro-geologic data of the aquifer have to be taken into further consideration to improve the process of remediation. (authors)« less

Bioremediation of Uranium-Contaminated Groundwater using Engineered Injection and Extraction

NASA Astrophysics Data System (ADS)

Greene, J. A.; Neupauer, R.; Ye, M.; Kasprzyk, J. R.; Mays, D. C.; Curtis, G. P.

2017-12-01

During in-situ remediation of contaminated groundwater, a treatment chemical is injected into the contaminated groundwater to react with and degrade the contaminant, with reactions occurring where the treatment chemical contacts the contaminant. Traditional in-situ groundwater remediation relies on background groundwater flow for spreading of treatment chemicals into contaminant plumes. Engineered Injection and Extraction (EIE), in which time-varying induced flow fields are used to actively spread the treatment chemical into the contaminant plume, has been developed to increase contact between the contaminant and treatment chemical, thereby enhancing contaminant degradation. EIE has been investigated for contaminants that degrade through irreversible bimolecular reaction with a treatment chemical, but has not been investigated for a contaminant governed by reversible reactions. Uranium primarily occurs in its aqueous, mobile form, U(VI), in the environment but can be bioreduced to its sparingly soluble, immobile form, U(IV), by iron reducing bacteria stimulated by an acetate amendment. In this study, we investigate the ability of EIE to facilitate and sustain favorable conditions to immobilize uranium during remediation, and to prevent re-mobilization of uranium into the aqueous phase after active remediation has ended. Simulations in this investigation are conducted using a semi-synthetic model based on physical and chemical conditions at the Naturita Uranium Mill Tailings Remedial Action (UMTRA) site in southwestern Colorado and the Old Rifle UMTRA site in western Colorado. The EIE design is optimized for the synthetic model using the Borg multi-objective evolutionary algorithm.

Determination of U isotope ratios in sediments using ICP-QMS after sample cleanup with anion-exchange and extraction chromatography.

PubMed

Zheng, Jian; Yamada, Masatoshi

2006-01-15

The determination of uranium is important for environmental radioactivity monitoring, which investigates the releases of uranium from nuclear facilities and of naturally occurring radioactive materials by the coal, oil, natural gas, mineral, ore refining and phosphate fertilizer industries, and it is also important for studies on the biogeochemical behavior of uranium in the environment. In this paper, we describe a quadrupole ICP-MS (ICP-QMS)-based analytical procedure for the accurate determination of U isotope ratios ((235)U/(238)U atom ratio and (234)U/(238)U activity ratio) in sediment samples. A two-stage sample cleanup using anion-exchange and TEVA extraction chromatography was employed in order to obtain accurate and precise (234)U/(238)U activity ratios. The factors that affect the accuracy and precision of U isotope ratio analysis, such as detector dead time, abundance sensitivity, dwell time and mass bias were carefully evaluated and corrected. With natural U, a precision lower than 0.5% R.S.D. for (235)U/(238)U atom ratio and lower than 2.0% R.S.D. for (234)U/(238)U activity ratio was obtained with less than 90 ng uranium. The developed analytical method was validated using an ocean sediment reference material and applied to an investigation into the uranium isotopic compositions in a sediment core in a brackish lake in the vicinity of U-related nuclear facilities in Japan.

Recovery of Uranium from Seawater: Preparation and Development of Polymer-Supported Extractants

DOE Office of Scientific and Technical Information (OSTI.GOV)

Spiro, Alexandratos

2013-12-01

A new series of polymer-supported extractants is proposed for the removal and recovery of uranium from seawater. The objective is to produce polymers with improved stability, loading capacity, and sorption kinetics compared to what is found with amidoximes. The target ligands are diphosphonates and aminomethyldiphosphonates. Small molecule analogues, especially of aminomethyldiphos-phonates, have exceptionally high stability constants for the uranyl ion. The polymeric diphosphonates will have high affinities due to their ability to form six-membered rings with the uranyl ion while the aminomethyldiphosphonates may have yet higher affinities due to possible tridentate coordination and their greater acidity. A representative set ofmore » the polymers to be prepared are indicated.« less

Hydrogeology of an ancient arid closed basin: implications for tabular sandstone-hosted uranium deposits

USGS Publications Warehouse

Sanford, R.F.

1990-01-01

Hydrogeologic modeling shows that tabular-type uranium deposits in the Grants uranium region of the San Juan basin, New Mexico, formed in zones of ascending and discharging regional ground-water flow. The association of either lacustrine mudstone or actively subsiding structures and uranium deposits can best be explained by the occurrence of lakes at topographic depressions where ground water having different sources and compositions is likely to converge, mix, and discharge. Ascending and discharging flow also explains the association of uranium deposits with underlying evaporites and suggests a brine interface. The simulations contradict previous suggestions that ground water moved downward in the mudflat. -Author

Microwave-assisted of dispersive liquid-liquid microextraction and spectrophotometric determination of uranium after optimization based on Box-Behnken design and chemometrics methods.

PubMed

Niazi, Ali; Khorshidi, Neda; Ghaemmaghami, Pegah

2015-01-25

In this study an analytical procedure based on microwave-assisted dispersive liquid-liquid microextraction (MA-DLLME) and spectrophotometric coupled with chemometrics methods is proposed to determine uranium. In the proposed method, 4-(2-pyridylazo) resorcinol (PAR) is used as a chelating agent, and chloroform and ethanol are selected as extraction and dispersive solvent. The optimization strategy is carried out by using two level full factorial designs. Results of the two level full factorial design (2(4)) based on an analysis of variance demonstrated that the pH, concentration of PAR, amount of dispersive and extraction solvents are statistically significant. Optimal condition for three variables: pH, concentration of PAR, amount of dispersive and extraction solvents are obtained by using Box-Behnken design. Under the optimum conditions, the calibration graphs are linear in the range of 20.0-350.0 ng mL(-1) with detection limit of 6.7 ng mL(-1) (3δB/slope) and the enrichment factor of this method for uranium reached at 135. The relative standard deviation (R.S.D.) is 1.64% (n=7, c=50 ng mL(-1)). The partial least squares (PLS) modeling was used for multivariate calibration of the spectrophotometric data. The orthogonal signal correction (OSC) was used for preprocessing of data matrices and the prediction results of model, with and without using OSC, were statistically compared. MA-DLLME-OSC-PLS method was presented for the first time in this study. The root mean squares error of prediction (RMSEP) for uranium determination using PLS and OSC-PLS models were 4.63 and 0.98, respectively. This procedure allows the determination of uranium synthesis and real samples such as waste water with good reliability of the determination. Copyright © 2014. Published by Elsevier B.V.

A new formulation containing calixarene molecules as an emergency treatment of uranium skin contamination.

PubMed

Spagnul, Aurélie; Bouvier-Capely, Céline; Phan, Guillaume; Rebière, François; Fattal, Elias

2010-09-01

Cutaneous contamination represents the second highest contamination pathway in the nuclear industry. Despite that the entry of actinides such as uranium into the body through intact or wounded skin can induce a high internal exposure, no specific emergency treatment for cutaneous contamination exists. In the present work, an innovative formulation dedicated to uranium skin decontamination was developed. The galenic form consists in an oil-in-water nanoemulsion, which contains a tricarboxylic calixarene known for its high uranium affinity and selectivity. The physicochemical characterization of this topical form revealed that calixarene molecules are located at the surface of the dispersed oil droplets of the nanoemulsion, being thus potentially available for uranium chelation. It was demonstrated in preliminary in vitro experiments by using an adapted ultrafiltration method that the calixarene nanoemulsion was able to extract and retain more than 80% of uranium from an aqueous uranyl nitrate contamination solution. First ex vivo experiments carried out in Franz diffusion cells on pig ear skin explants during 24 h showed that the immediate application of the calixarene nanoemulsion on a skin contaminated by a uranyl nitrate solution allowed a uranium transcutaneous diffusion decrease of about 98% through intact and excoriated skins. The calixarene nanoemulsion developed in this study thus seems to be an efficient emergency system for uranium skin decontamination.

Process for the extraction of technetium from uranium

DOEpatents

Gong, Cynthia-May S.; Poineau, Frederic; Czerwinski, Kenneth R.

2010-12-21

A spent fuel reprocessing method contacts an aqueous solution containing Technetium(V) and uranyl with an acidic solution comprising hydroxylamine hydrochloride or acetohydroxamic acid to reduce Tc(V) to Tc(II, and then extracts the uranyl with an organic phase, leaving technetium(II) in aqueous solution.

Reclamation with Recovery of Radionuclides and Toxic Metals from Contaminated Materials, Soils, and Wastes

NASA Technical Reports Server (NTRS)

Francis, A. J.; Dodge, C. J.

1993-01-01

A process has been developed at Brookhaven National Laboratory (BNL) for the removal of metals and radionuclides from contaminated materials, soils, and waste sites. In this process, citric acid, a naturally occurring organic complexing agent, is used to extract metals such as Ba, Cd, Cr, Ni, Zn, and radionuclides Co, Sr, Th, and U from solid wastes by formation of water soluble, metal-citrate complexes. Citric acid forms different types of complexes with the transition metals and actinides, and may involve formation of a bidentate, tridentate, binuclear, or polynuclear complex species. The extract containing radionuclide/metal complex is then subjected to microbiological degradation followed by photochemical degradation under aerobic conditions. Several metal citrate complexes are biodegraded, and the metals are recovered in a concentrated form with the bacterial biomass. Uranium forms binuclear complex with citric acid and is not biodegraded. The supernatant containing uranium citrate complex is separated and upon exposure to light, undergoes rapid degradation resulting in the formation of an insoluble, stable polymeric form of uranium. Uranium is recovered as a precipitate (polyuranate) in a concentrated form for recycling or for appropriate disposal. This treatment process, unlike others which use caustic reagents, does not create additional hazardous wastes for disposal and causes little damage to soil which can then be returned to normal use.

Sorption behavior of uranium(VI) on a biotite mineral

DOE Office of Scientific and Technical Information (OSTI.GOV)

Idemitsu, K.; Obata, K.; Furuya, H.

1995-12-31

Biotite has the most important role for the sorption of radionuclides in granitic rocks. Experiments on the sorption of uranium(VI) on biotite were conducted to understand the fundamental controls on uranium sorption on biotite mineral, including the effects of pH and uranium concentration in solution. Biotite powder (mesh 32--60) were washed with 1N HCl for a week and were rinsed twice with deionized water for a week. This HCl treatment was necessary to avoid the effects by other minerals. The agreement between surface adsorption coefficient, Ka, of both biotites with and without HCl treatment was within one order of magnitude.more » The peak Ka value was in the range of 0.1 to 0.01 cm{sup 3}/cm{sup 2} around pH 6. A comparison of aqueous uranium speciations and sorption results indicates that neutral uranyl hydroxide could be an important species sorbed on the biotite. Sequential desorption experiments with KCl and HCl solutions were also carried out after sorption experiments to investigate sorption forms of uranium. Approximately 20% of uranium in solution were sorbed on the biotite as an exchangeable ion. The fraction of exchangeable uranium had a little dependence on pH. The other uranium could not be extracted even by 6N HCl solution. It is possible that most of the uranium could be precipitated as U(IV) via Fe(II) reduction on the biotite surface.« less

SEPARATION PROCESS FOR THORIUM SALTS

DOEpatents

Bridger, G.L.; Whatley, M.E.; Shaw, K.G.

1957-12-01

A process is described for the separation of uranium, thorium, and rare earths extracted from monazite by digesting with sulfuric acid. By carefully increasing the pH of the solution, stepwise, over the range 0.8 to 5.5, a series of selective precipitations will be achieved, with the thorium values coming out at lower pH, the rare earths at intermediate pH and the uranium last. Some mixed precipitates will be obtained, and these may be treated by dissolving in HNO/sub 3/ and contacting with dibutyl phosphate, whereby thorium or uranium are taken up by the organic phase while the rare earths preferentially remain in the aqueous solution.

Mobilization of radionuclides from uranium mill tailings and related waste materials in anaerobic environments

USGS Publications Warehouse

Landa, E.R.

2003-01-01

Specific extraction studies in our laboratory have shown that iron and manganese oxide- and alkaline earth sulfate minerals are important hosts of radium in uranium mill tailings. Iron- and sulfate-reducing bacteria may enhance the release of radium (and its analog barium) from uranium mill tailings, oil field pipe scale [a major technologically enhanced naturally occurring radioactive material (TENORM) waste], and jarosite (a common mineral in sulfuric acid processed-tailings). These research findings are reviewed and discussed in the context of nuclear waste forms (such as barium sulfate matrices), radioactive waste management practices, and geochemical environments in the Earth's surficial and shallow subsurface regions.

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

NASA Astrophysics Data System (ADS)

Stange, Gary Michael

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

SEPARATION OF URANYL AND RUTHENIUM VALUES BY THE TRIBUTYL PHOSPHATE EXTRACTION PROCESS

DOEpatents

Wilson, A.S.

1961-05-01

A process is given for separating uranyl values from ruthenium values contained in an aqueous 3 to 4 M nitric acid solution. After the addition of hydrogen peroxide to obtain a concentration of 0.3 M, the uranium is selectively extracted with kerosene-diluted tributyl phosphate.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kautsky, Mark; Miller, David

This annual report evaluates the performance of the groundwater remediation system at the Shiprock, New Mexico, Disposal Site (Shiprock site) for the period April 2015 through March 2016. The Shiprock site, a former uranium-ore processing facility remediated under the Uranium Mill Tailings Radiation Control Act, is managed by the U.S. Department of Energy (DOE) Office of Legacy Management. This annual report is based on an analysis of groundwater quality and groundwater level data obtained from site monitoring wells and the groundwater flow rates associated with the extraction wells, drains, and seeps. Background The Shiprock mill operated from 1954 to 1968more » on property leased from the Navajo Nation. Remediation of surface contamination, including stabilization of mill tailings in an engineered disposal cell, was completed in 1986. During mill operation, nitrate, sulfate, uranium, and other milling-related constituents leached into underlying sediments and contaminated groundwater in the area of the mill site. In March 2003, DOE initiated active remediation of groundwater at the site using extraction wells and interceptor drains. At that time, DOE developed a baseline performance report that established specific performance standards for the Shiprock site groundwater remediation system. The Shiprock site is divided into two distinct areas: the floodplain and the terrace. The floodplain remediation system consists of two groundwater extraction wells, a seep collection drain, and two collection trenches (Trench 1 and Trench 2). The terrace remediation system consists of nine groundwater extraction wells, two collection drains (Bob Lee Wash and Many Devils Wash), and a terrace drainage channel diversion structure. All extracted groundwater is pumped into a lined evaporation pond on the terrace. Compliance Strategy and Remediation Goals As documented in the Groundwater Compliance Action Plan, the U.S. Nuclear Regulatory Commission–approved compliance strategy for the floodplain is natural flushing supplemented by active remediation. The contaminants of concern (COCs) at the site are ammonia (total as nitrogen), manganese, nitrate (nitrate + nitrite as nitrogen), selenium, strontium, sulfate, and uranium. The compliance standards for nitrate, selenium, and uranium are listed in Title 40 Code of Federal Regulations Part 192. Regulatory standards are not available for ammonia, manganese, and sulfate; remediation goals for these constituents are either risk-based alternate cleanup standards or background levels. These standards and background levels apply only to the compliance strategy for the floodplain. The compliance strategy for the terrace is to eliminate exposure pathways at the washes and seeps and to apply supplemental standards in the western section.« less

Fermentation and Hydrogen Metabolism Affect Uranium Reduction by Clostridia

DOE PAGES

Gao, Weimin; Francis, Arokiasamy J.

2013-01-01

Previously, it has been shown that not only is uranium reduction under fermentation condition common among clostridia species, but also the strains differed in the extent of their capability and the pH of the culture significantly affected uranium(VI) reduction. In this study, using HPLC and GC techniques, metabolic properties of those clostridial strains active in uranium reduction under fermentation conditions have been characterized and their effects on capability variance of uranium reduction discussed. Then, the relationship between hydrogen metabolism and uranium reduction has been further explored and the important role played by hydrogenase in uranium(VI) and iron(III) reduction by clostridiamore » demonstrated. When hydrogen was provided as the headspace gas, uranium(VI) reduction occurred in the presence of whole cells of clostridia. This is in contrast to that of nitrogen as the headspace gas. Without clostridia cells, hydrogen alone could not result in uranium(VI) reduction. In alignment with this observation, it was also found that either copper(II) addition or iron depletion in the medium could compromise uranium reduction by clostridia. In the end, a comprehensive model was proposed to explain uranium reduction by clostridia and its relationship to the overall metabolism especially hydrogen (H 2 ) production.« less

URANIUM RECOVERY PROCESS

DOEpatents

Hyman, H.H.; Dreher, J.L.

1959-07-01

The recovery of uranium from the acidic aqueous metal waste solutions resulting from the bismuth phosphate carrier precipitation of plutonium from solutions of neutron irradiated uranium is described. The waste solutions consist of phosphoric acid, sulfuric acid, and uranium as a uranyl salt, together with salts of the fission products normally associated with neutron irradiated uranium. Generally, the process of the invention involves the partial neutralization of the waste solution with sodium hydroxide, followed by conversion of the solution to a pH 11 by mixing therewith sufficient sodium carbonate. The resultant carbonate-complexed waste is contacted with a titanated silica gel and the adsorbent separated from the aqueous medium. The aqueous solution is then mixed with sufficient acetic acid to bring the pH of the aqueous medium to between 4 and 5, whereby sodium uranyl acetate is precipitated. The precipitate is dissolved in nitric acid and the resulting solution preferably provided with salting out agents. Uranyl nitrate is recovered from the solution by extraction with an ether such as diethyl ether.

High resolution remote sensing information identification for characterizing uranium mineralization setting in Namibia

NASA Astrophysics Data System (ADS)

Zhang, Jie-Lin; Wang, Jun-hu; Zhou, Mi; Huang, Yan-ju; Xuan, Yan-xiu; Wu, Ding

2011-11-01

The modern Earth Observation System (EOS) technology takes important role in the uranium geological exploration, and high resolution remote sensing as one of key parts of EOS is vital to characterize spectral and spatial information of uranium mineralization factors. Utilizing satellite high spatial resolution and hyperspectral remote sensing data (QuickBird, Radarsat2, ASTER), field spectral measurement (ASD data) and geological survey, this paper established the spectral identification characteristics of uranium mineralization factors including six different types of alaskite, lower and upper marble of Rössing formation, dolerite, alkali metasomatism, hematization and chloritization in the central zone of Damara Orogen, Namibia. Moreover, adopted the texture information identification technology, the geographical distribution zones of ore-controlling faults and boundaries between the different strata were delineated. Based on above approaches, the remote sensing geological anomaly information and image interpretation signs of uranium mineralization factors were extracted, the metallogenic conditions were evaluated, and the prospective areas have been predicted.

Multiple recycle of REMIX fuel at VVER-1000 operation in closed fuel cycle

NASA Astrophysics Data System (ADS)

Alekseev, P. N.; Bobrov, E. A.; Chibinyaev, A. V.; Teplov, P. S.; Dudnikov, A. A.

2015-12-01

The basic features of loading the VVER-1000 core with a new variant of REMIX fuel (REgenerated MIXture of U-Pu oxides) are considered during its multiple recycle in a closed nuclear fuel cycle. The fuel composition is produced on the basis of the uranium-plutonium regenerate extracted at processing the spent nuclear fuel (SNF) from a VVER-1000, depleted uranium, and the fissionable material: 235U as a part of highly enriched uranium (HEU) from warheads superfluous for defense purposes or 233U accumulated in thorium blankets of fusion (electronuclear) neutron sources or fast reactors. Production of such a fuel assumes no use of natural uranium in addition. When converting a part of the VVER-1000 reactors to the closed fuel cycle based on the REMIX technology, the consumption of natural uranium decreases considerably, and there is no substantial degradation of the isotopic composition of plutonium or change in the reactor-safety characteristics at the passage from recycle to recycle.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rao, Linfeng

A literature survey has been conducted to collect information on the International R&D activities in the extraction of uranium from seawater for the period from the 1960s till the year of 2010. The reported activities, on both the laboratory scale bench experiments and the large scale marine experiments, were summarized by country/region in this report. Among all countries where such activities have been reported, Japan has carried out the most advanced large scale marine experiments with the amidoxime-based system, and achieved the collection efficiency (1.5 g-U/kg-adsorbent for 30 days soaking in the ocean) that could justify the development of industrialmore » scale marine systems to produce uranium from seawater at the price competitive with those from conventional uranium resources. R&D opportunities are discussed for improving the system performance (selectivity for uranium, loading capacity, chemical stability and mechanical durability in the sorption-elution cycle, and sorption kinetics) and making the collection of uranium from seawater more economically competitive.« less

Distribution of trace elements in drilling chip samples around a roll-type uranium deposit, San Juan Basin, New Mexico

USGS Publications Warehouse

Day, H.C.; Spirakis, C.S.; Zech, R.S.; Kirk, A.R.

1983-01-01

Chip samples from rotary drilling in the vicinity of a roll-type uranium deposit in the southwestern San Juan Basin were split into a whole-washed fraction, a clay fraction, and a heavy mineral concentrate fraction. Analyses of these fractions determined that cutting samples could be used to identify geochemical halos associated with this ore deposit. In addition to showing a distribution of selenium, uranium, vanadium, and molybdenum similar to that described by Harshman (1974) in uranium roll-type deposits in Wyoming, South Dakota, and Texas, the chemical data indicate a previously unrecognized zinc anomaly in the clay fraction downdip of the uranium ore.

Separation by solvent extraction

DOEpatents

Holt, Jr., Charles H.

1976-04-06

17. A process for separating fission product values from uranium and plutonium values contained in an aqueous solution, comprising adding an oxidizing agent to said solution to secure uranium and plutonium in their hexavalent state; contacting said aqueous solution with a substantially water-immiscible organic solvent while agitating and maintaining the temperature at from -1.degree. to -2.degree. C. until the major part of the water present is frozen; continuously separating a solid ice phase as it is formed; separating a remaining aqueous liquid phase containing fission product values and a solvent phase containing plutonium and uranium values from each other; melting at least the last obtained part of said ice phase and adding it to said separated liquid phase; and treating the resulting liquid with a new supply of solvent whereby it is practically depleted of uranium and plutonium.

Determination of the oxidation state of uranium in apatite and phosphorite deposits

USGS Publications Warehouse

Clarke, R.S.; Altschuler, Z.S.

1958-01-01

Geological and mineralogical evidence indicate that the uranium present in apatite may proxy for calcium in the mineral structure as U(IV). An experimental investigation was conducted and chemical evidence was obtained that establishes the presence of U(IV) in apatite. The following analytical procedure was developed for the determination of U(IV). Carbonatefluorapatite is dissolved in 1.5 M orthophosphoric acid at a temperature of 5??C or slightly below and fluorapatite is dissolved in cold 1.2 M hydrochloric acid (approximately 5??C) containing 1.5 g of hydroxylamine hydrochloride per 100 ml. Uranium(IV) is precipitated by cupferron using titanium as a carrier. The uranium in the precipitate is separated by use of the ethyl acetate extraction procedure and determined fluorimetrically. The validity and the limitations of the method have been established by spike experiments. ?? 1958.

Processes affecting transport of uranium in a suboxic aquifer

USGS Publications Warehouse

Davis, J.A.; Curtis, G.P.; Wilkins, M.J.; Kohler, M.; Fox, P.; Naftz, D.L.; Lloyd, J.R.

2006-01-01

At the Naturita site in Colorado, USA, groundwaters were sampled and analyzed for chemical composition and by culture and culture-independent microbiological techniques. In addition, sediments were extracted with a dilute sodium carbonate solution to determine quantities of labile uranium within the sediments. Samples from the upgradient portion of the contaminated aquifer, where very little dissolved Fe(II) is found in the groundwater, have uranium content that is controlled by U(VI) adsorption and few metal-reducing bacteria are observed. In the extreme downgradient portion of the aquifer, where dissolved Fe(II) is observed, uranium content of the sediments includes significant quantities of reduced U(IV) and diverse populations of Fe(III)-reducing bacteria were present in the subsurface with the potential of reducing U(VI) to U(IV). ?? 2006 Elsevier Ltd. All rights reserved.

Guinea’s 2008 Military Coup and Relations with the United States

DTIC Science & Technology

2009-07-16

Guinea’s extractive industry sector is of financial and strategic interest to the United States. In addition to gold, diamonds, uranium , and potential...agency’s legal mandate and authorities have not been clearly defined, and the CNDD has not publicly outlined how the agency is meant to interact with...Guinea’s economy relies heavily on primary commodity exports, notably bauxite (used to produce aluminum), gold, diamonds, uranium , and iron ore

Nuclear Proliferation in the Middle East: Implications for the Superpowers,

DTIC Science & Technology

1982-01-01

when Israeli nuclear scientists began extracting low grade uranium from phosphate deposits in the Negev Desert. With the encouragement of Chaim... Negev -and concomitantly assisted in de- signing the research facilities associated with the reactor. By the time the reactor went critical in 1964, a...deposits in the Negev . Since the early 1970s, an esti- mated 40-50 tons of uranium oxide has been produced annually.1 6 In addition, unconfirmed

Sensitivity of geological, geochemical and hydrologic parameters in complex reactive transport systems for in-situ uranium bioremediation

NASA Astrophysics Data System (ADS)

Yang, G.; Maher, K.; Caers, J.

2015-12-01

Groundwater contamination associated with remediated uranium mill tailings is a challenging environmental problem, particularly within the Colorado River Basin. To examine the effectiveness of in-situ bioremediation of U(VI), acetate injection has been proposed and tested at the Rifle pilot site. There have been several geologic modeling and simulated contaminant transport investigations, to evaluate the potential outcomes of the process and identify crucial factors for successful uranium reduction. Ultimately, findings from these studies would contribute to accurate predictions of the efficacy of uranium reduction. However, all these previous studies have considered limited model complexities, either because of the concern that data is too sparse to resolve such complex systems or because some parameters are assumed to be less important. Such simplified initial modeling, however, limits the predictive power of the model. Moreover, previous studies have not yet focused on spatial heterogeneity of various modeling components and its impact on the spatial distribution of the immobilized uranium (U(IV)). In this study, we study the impact of uncertainty on 21 parameters on model responses by means of recently developed distance-based global sensitivity analysis (DGSA), to study the main effects and interactions of parameters of various types. The 21 parameters include, for example, spatial variability of initial uranium concentration, mean hydraulic conductivity, and variogram structures of hydraulic conductivity. DGSA allows for studying multi-variate model responses based on spatial and non-spatial model parameters. When calculating the distances between model responses, in addition to the overall uranium reduction efficacy, we also considered the spatial profiles of the immobilized uranium concentration as target response. Results show that the mean hydraulic conductivity and the mineral reaction rate are the two most sensitive parameters with regard to the overall uranium reduction. But in terms of spatial distribution of immobilized uranium, initial conditions of uranium concentration and spatial uncertainty in hydraulic conductivity also become important. These analyses serve as the first step of further prediction practices of the complex uranium transport and reaction systems.

Environmental radioactivity assessment around old uranium mining sites near Mangualde (Viseu), Portugal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Carvalho, Fernando P.; Torres, Lubelia M.; Oliveira, Joao M.

2007-07-01

Uranium ore was extracted in the surroundings of Mangualde city, North of Portugal, in the mines of Cunha Baixa, Quinta do Bispo and Espinho until a few years ago. Mining waste, milling tailings and acid mine waters are the on site remains of this extractive activity. Environmental radioactivity measurements were performed in and around these sites in order to assess the dispersal of radionuclides from uranium mining waste and the spread of acidic waters resulting from the in situ uranium leaching with sulphuric acid. Results show migration of acid waters into groundwater around the Cunha Baixa mine. This groundwater ismore » tapped by irrigation wells in the agriculture area near the Cunha Baixa village. Water from wells displayed uranium ({sup 238}U) concentrations up to 19x10{sup 3} mBq L{sup -1} and sulphate ion concentrations up to 1070 mg L{sup -1}. These enhanced concentrations are positively correlated with low water pH, pointing to a common origin for radioactivity, dissolved sulphate, and acidity in underground mining works. Radionuclide concentrations were determined in horticulture and farm products from this area also and results suggest low soil to plant transfer of radionuclides and low food chain transfer of radionuclides to man. Analysis of aerosols in surface air showed re suspension of dust from mining and milling waste heaps. Therefore, it is recommended to maintain mine water treatment and to plan remediation of these mine sites in order to prevent waste dispersal in the environment. (authors)« less

Assessing ligand selectivity for uranium over vanadium ions to aid in the discovery of superior adsorbents for extraction of UO 2 2+ from seawater

DOE PAGES

Ivanov, Alexander S.; Bryantsev, Vyacheslav S.

2016-06-06

Uranium is used as the basic fuel for nuclear power plants, which generate significant amounts of electricity and have life cycle carbon emissions that are as low as renewable energy sources. However, the extraction of this valuable energy commodity from the ground remains controversial, mainly because of environmental and health impacts. Alternatively, seawater offers an enormous uranium resource that may be tapped at minimal environmental cost. Nowadays, amidoxime polymers are the most widely utilized sorbent materials for large-scale extraction of uranium from seawater, but they are not perfectly selective for uranyl, UO 2 2+. In particular, the competition between UOmore » 2 2+ and VO 2+/VO2+ cations poses a significant challenge to the effi-cient mining of UO 2 2+. Thus, screening and rational design of more selective ligands must be accomplished. One of the key components in achieving this goal is the establishment of computational techniques capable of assessing ligand selec-tivity trends. Here, we report an approach based on quantum chemical calculations that achieves high accuracy in repro-ducing experimental aqueous stability constants for VO 2+/VO 2+ complexes with ten different oxygen donor lig-ands. The predictive power of the developed computational protocol was demonstrated for amidoxime-type ligands, providing greater insights into new design strategies for the development of the next generation of adsorbents with high selectivity toward UO 2 2+over VO 2+/VO 2+ ions. Furthermore, the results of calculations suggest that alkylation of amidox-ime moieties present in poly(acrylamidoxime) sorbents can be a potential route to better discrimination between the uranyl and competing vanadium ions within seawater.« less

Extracting uranium from seawater: Promising AI series adsorbents

DOE PAGES

Das, Sadananda; Oyola, Y.; Mayes, Richard T.; ...

2015-11-10

A series of adsorbent (AI10 through AI17) were successfully developed at ORNL by radiation induced graft polymerization (RIGP) of acrylonitrile (AN) and vinylphosphonic acid (VPA) (at different mole/mole ratios) onto high surface area polyethylene fiber, with higher degree of grafting which ranges from 110 300%. The grafted nitrile groups were converted to amidoxime groups by reaction with 10 wt% hydroxylamine at 80 C for 72 hours. The amidoximated adsorbents were then conditioned with 0.44M KOH at 80 C followed by screening at ORNL with simulated seawater spiked with 8 ppm uranium. Uranium adsorption capacity in simulated seawater screening ranged frommore » 171-187 g-U/kg-ads irrespective of %DOG. The performance of the adsorbents for uranium adsorption in natural seawater was also carried out using flow-through-column at Pacific Northwest National Laboratory (PNNL). The three hours KOH conditioning was better for higher uranium uptake than one hour. The adsorbent AI11 containing AN and VPA at the mole ration of 3.52, emerged as the potential candidate for higher uranium adsorption (3.35 g-U/Kg-ads.) after 56 days of exposure in the seawater in the flow-through-column. The rate vanadium adsorption over uranium was linearly increased throughout the 56 days exposure. The total vanadium uptake was ~5 times over uranium after 56 days.« less

Extracting uranium from seawater: Promising AI series adsorbents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Das, Sadananda; Oyola, Y.; Mayes, Richard T.

A series of adsorbent (AI10 through AI17) were successfully developed at ORNL by radiation induced graft polymerization (RIGP) of acrylonitrile (AN) and vinylphosphonic acid (VPA) (at different mole/mole ratios) onto high surface area polyethylene fiber, with higher degree of grafting which ranges from 110 300%. The grafted nitrile groups were converted to amidoxime groups by reaction with 10 wt% hydroxylamine at 80 C for 72 hours. The amidoximated adsorbents were then conditioned with 0.44M KOH at 80 C followed by screening at ORNL with simulated seawater spiked with 8 ppm uranium. Uranium adsorption capacity in simulated seawater screening ranged frommore » 171-187 g-U/kg-ads irrespective of %DOG. The performance of the adsorbents for uranium adsorption in natural seawater was also carried out using flow-through-column at Pacific Northwest National Laboratory (PNNL). The three hours KOH conditioning was better for higher uranium uptake than one hour. The adsorbent AI11 containing AN and VPA at the mole ration of 3.52, emerged as the potential candidate for higher uranium adsorption (3.35 g-U/Kg-ads.) after 56 days of exposure in the seawater in the flow-through-column. The rate vanadium adsorption over uranium was linearly increased throughout the 56 days exposure. The total vanadium uptake was ~5 times over uranium after 56 days.« less

Extracting Uranium from Seawater: Promising AI Series Adsorbents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Das, S.; Oyola, Y.; Mayes, R. T.

A new series of adsorbents (AI10 through AI17) were successfully developed at ORNL by radiation induced graft polymerization (RIGP) of acrylonitrile (AN) and vinylphosphonic acid (VPA) (at different mole to mole ratios) onto high surface area polyethylene fiber, with high degrees of grafting (DOG) varying from 110 to 300%. The grafted nitrile groups were converted to amidoxime groups by reaction with 5 wt % hydroxylamine at 80 °C for 72 h. The amidoximated adsorbents were then conditioned with 0.44 M KOH at 80 °C followed by screening at ORNL with prescreening brine spiked with 8 ppm uranium. Uranium adsorption capacitiesmore » in prescreening ranged from 171 to 187 g-U/kg-ads irrespective of percent DOG. The performance of the adsorbents with respect to uranium adsorption in natural seawater was also investigated using flow-throughcolumn testing at the Pacific Northwest National Laboratory (PNNL). Three hours of KOH conditioning led to higher uranium uptake than 1 h of conditioning. The adsorbent AI11, containing AN and VPA at the mole ratio of 3.52, emerged as the potential candidate for the highest uranium adsorption (3.35 g-U/kg-ads.) after 56 days of exposure in seawater flow-through-columns. The rate of vanadium adsorption over uranium linearly increased throughout the 56 days of exposure. The total mass of vanadium uptake was ~5 times greater than uranium after 56 days.« less

Uranium in well drinking water of Kabul, Afghanistan and its effective, low-cost depuration using Mg-Fe based hydrotalcite-like compounds.

PubMed

Kato, Masashi; Azimi, Mohammad Daud; Fayaz, Said Hafizullah; Shah, Muhammad Dawood; Hoque, Md Zahirul; Hamajima, Nobuyuki; Ohnuma, Shoko; Ohtsuka, Tomomi; Maeda, Masao; Yoshinaga, Masafumi

2016-12-01

Toxic elements in drinking water have great effects on human health. However, there is very limited information about toxic elements in drinking water in Afghanistan. In this study, levels of 10 elements (chromium, nickel, copper, arsenic, cadmium, antimony, barium, mercury, lead and uranium) in 227 well drinking water samples in Kabul, Afghanistan were examined for the first time. Chromium (in 0.9% of the 227 samples), arsenic (7.0%) and uranium (19.4%) exceeded the values in WHO health-based guidelines for drinking-water quality. Maximum chromium, arsenic and uranium levels in the water samples were 1.3-, 10.4- and 17.2-fold higher than the values in the guidelines, respectively. We next focused on uranium, which is the most seriously polluted element among the 10 elements. Mean ± SD (138.0 ± 1.4) of the 238 U/ 235 U isotopic ratio in the water samples was in the range of previously reported ratios for natural source uranium. We then examined the effect of our originally developed magnesium (Mg)-iron (Fe)-based hydrotalcite-like compounds (MF-HT) on adsorption for uranium. All of the uranium-polluted well water samples from Kabul (mean ± SD = 190.4 ± 113.9 μg/L; n = 11) could be remediated up to 1.2 ± 1.7 μg/L by 1% weight of our MF-HT within 60 s at very low cost (<0.001 cents/day/family) in theory. Thus, we demonstrated not only elevated levels of some toxic elements including natural source uranium but also an effective depurative for uranium in well drinking water from Kabul. Since our depurative is effective for remediation of arsenic as shown in our previous studies, its practical use in Kabul may be encouraged. Copyright © 2016 Elsevier Ltd. All rights reserved.

Speciation of plutonium and other metals under UREX process conditIONS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paulenova, Alena; Tkac, Peter; Matteson, Brent S.

2007-07-01

The extractability of various Pu and Np species into tri-n-butyl phosphate (TBP) was investigated. The concentration effects of aceto-hydroxamic acid, nitric acid and nitrate on the distribution ratio of U, Pu and Np were investigated. The considerable ability of AHA to form complexes with the studied elements even under strong acidic conditions was found. While the difference in the extraction of uranyl in the presence and absence of AHA is minimal, extraction yields of Pu and Np decrease significantly. The UV-Vis-NIR and FT-IR spectroscopic investigations of uranium, plutonium, and neptunium species in the presence and absence of AHA in bothmore » aqueous and organic extraction phase were also performed. Spectroscopic analysis showed that the organic phase can contain a substantial amount of metal-hydroxamate species. A solvated ternary complex of uranium UO{sub 2}.AHA.NO{sub 3}.2TBP was observed only after prolonged contact between the aqueous and organic phases, whereas the plutonium hydroxamate species, presumably Pu(AHA){sub x}(NO{sub 3}){sub 4-x}.2TBP, appeared in the organic phase after a four minute extraction. (authors)« less

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

PubMed

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

2015-04-09

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. Copyright © 2014 Elsevier B.V. All rights reserved.

Role of U(VI) Reduction by Geobacter species

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lovely, Derrick

2008-12-23

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 uraniummore » 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.« less

10 CFR Appendix J to Part 110 - Illustrative List of Uranium Conversion Plant Equipment and Plutonium Conversion Plant Equipment...

Code of Federal Regulations, 2010 CFR

2010-01-01

... reactors, flame tower reactors, liquid centrifuges, distillation columns and liquid-liquid extraction... to UF6 is performed by exothermic reaction with fluorine in a tower reactor. UF6 is condensed from..., flame tower reactors, liquid centrifuges, distillation columns and liquid-liquid extraction columns. Hot...

3 CFR 13617 - Executive Order 13617 of June 25, 2012. Blocking Property of the Government of the Russian...

Code of Federal Regulations, 2013 CFR

2013-01-01

... Extracted From Nuclear Weapons 13617 Order 13617 Presidential Documents Executive Orders Executive Order... to the Disposition of Highly Enriched Uranium Extracted From Nuclear Weapons By the authority vested... accumulation of a large volume of weapons-usable fissile material in the territory of the Russian Federation...

10 CFR 171.16 - Annual fees: Materials licensees, holders of certificates of compliance, holders of sealed source...

Code of Federal Regulations, 2011 CFR

2011-01-01

... in devices used in industrial measuring systems, including x-ray fluorescence analyzers [Program Code... of ores containing source material for extraction of metals other than uranium or thorium, including.... 4 Other facilities include licenses for extraction of metals, heavy metals, and rare earths. 5 There...

10 CFR 171.16 - Annual fees: Materials licensees, holders of certificates of compliance, holders of sealed source...

Code of Federal Regulations, 2010 CFR

2010-01-01

... contained in devices used in industrial measuring systems, including x-ray fluorescence analyzers [Program... ores containing source material for extraction of metals other than uranium or thorium, including.... 4 Another license includes licenses for extraction of metals, heavy metals, and rare earths. 5 There...

Structural clues to UO₂²⁺/VO₂⁺ competition in seawater extraction using amidoxime-based extractants.

PubMed

Kelley, Steven P; Barber, Patrick S; Mullins, Peter H K; Rogers, Robin D

2014-10-25

Here we present the first structural comparison of amidoxime complexes of UO2(2+) and VO2(+) (the main competitor in the extraction of uranium from seawater using amidoxime-based sorbents) using a 4,5-di(amidoxime)-functionalized imidazole ligand. The amidoxime groups resist tautomerization in both cases and quite different coordination modes (chelating vs. bridging) are observed.

METHOD OF DISSOLVING REFRACTORY ALLOYS

DOEpatents

Helton, D.M.; Savolainen, J.K.

1963-04-23

This patent relates to the dissolution of alloys of uranium with zirconium, thorium, molybdenum, or niobium. The alloy is contacted with an anhydrous solution of mercuric chloride in a low-molecular-weight monohydric alcohol to produce a mercury-containing alcohol slurry. The slurry is then converted to an aqueous system by adding water and driving off the alcohol. The resulting aqueous slurry is electrolyzed in the presence of a mercury cathode to remove the mercury and produce a uranium-bearing aqueous solution. This process is useful for dissolving irradiated nuclear reactor fuels for radiochemical reprocessing by solvent extraction. In addition, zirconium-alloy cladding is selectively removed from uranium dioxide fuel compacts by this means. (AEC)

Spent nuclear fuel recycling with plasma reduction and etching

DOEpatents

Kim, Yong Ho

2012-06-05

A method of extracting uranium from spent nuclear fuel (SNF) particles is disclosed. Spent nuclear fuel (SNF) (containing oxides of uranium, oxides of fission products (FP) and oxides of transuranic (TRU) elements (including plutonium)) are subjected to a hydrogen plasma and a fluorine plasma. The hydrogen plasma reduces the uranium and plutonium oxides from their oxide state. The fluorine plasma etches the SNF metals to form UF₆ and PuF₄. During subjection of the SNF particles to the fluorine plasma, the temperature is maintained in the range of 1200-2000 deg K to: a) allow any PuF₆ (gas) that is formed to decompose back to PuF₄ (solid), and b) to maintain stability of the UF₆. Uranium (in the form of gaseous UF₆) is easily extracted and separated from the plutonium (in the form of solid PuF₄). The use of plasmas instead of high temperature reactors or flames mitigates the high temperature corrosive atmosphere and the production of PuF₆ (as a final product). Use of plasmas provide faster reaction rates, greater control over the individual electron and ion temperatures, and allow the use of CF₄ or NF₃ as the fluorine sources instead of F₂ or HF.

Study of uranium oxidation states in geological material.

PubMed

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.

Use of Sodium Dithionite as Part of a More Efficient Groundwater Restoration Method Following In-situ Recovery of Uranium at the Smith-Ranch Highland Site in Wyoming

NASA Astrophysics Data System (ADS)

Harris, R.; Reimus, P. W.; Ware, D.; Williams, K.; Chu, D.; Perkins, G.; Migdissov, A. A.; Bonwell, C.

2017-12-01

Uranium is primarily mined for nuclear power production using an aqueous extraction technique called in-situ recovery (ISR). ISR can pollute groundwater with residual uranium and other heavy metals. Reverse osmosis and groundwater sweep are currently used to restore groundwater after ISR mining, but are not permanent solutions. Sodium dithionite is being tested as part of a method to more permanently restore groundwater after ISR mining at the Smith-Ranch Highland site in Wyoming. Sodium dithionite is a chemical reductant that can reduce sediments that were oxidized during ISR. The reduced sediments can reduce soluble uranium (VI) in the groundwater to insoluble uranium (IV). Laboratory studies that use sodium dithionite to treat sediments and waters from the site may help predict how it will behave during a field deployment. An aqueous batch experiment showed that sodium dithionite reduced uranium in post-mined untreated groundwater from 38 ppm to less than 1 ppm after 1 day. A sediment reduction batch experiment showed that sodium dithionite-treated sediments were capable of reducing uranium in post-mined untreated groundwater from 38 ppm to 2 ppm after 7 days. One column experiment is showing post-mined sodium dithionite-treated sediments are capable of reducing uranium in post-mined groundwater for over 30 pore volumes past the initial injection. While these results are promising for field deployments of sodium dithionite, another column experiment with sodium dithionite-treated sediments containing uranium rich organic matter is showing net production of uranium instead of uranium uptake. Sodium dithionite appears to liberate uranium from the organic matter. Another sediment reduction experiment is being conducted to further investigate this hypothesis. These experiments are helping guide plans for field deployments of sodium dithionite at uranium ISR mining sites.

Control of a laser inertial confinement fusion-fission power plant

DOEpatents

Moses, Edward I.; Latkowski, Jeffery F.; Kramer, Kevin J.

2015-10-27

A laser inertial-confinement fusion-fission energy power plant is described. The fusion-fission hybrid system uses inertial confinement fusion to produce neutrons from a fusion reaction of deuterium and tritium. The fusion neutrons drive a sub-critical blanket of fissile or fertile fuel. A coolant circulated through the fuel extracts heat from the fuel that is used to generate electricity. The inertial confinement fusion reaction can be implemented using central hot spot or fast ignition fusion, and direct or indirect drive. The fusion neutrons result in ultra-deep burn-up of the fuel in the fission blanket, thus enabling the burning of nuclear waste. Fuels include depleted uranium, natural uranium, enriched uranium, spent nuclear fuel, thorium, and weapons grade plutonium. LIFE engines can meet worldwide electricity needs in a safe and sustainable manner, while drastically shrinking the highly undesirable stockpiles of depleted uranium, spent nuclear fuel and excess weapons materials.

APPLICATION OF FORMOHYDROXAMIC ACID IN NUCLEAR PROCESSING: SYNTHESIS AND COMPLEXATION WITH TECHNETIUM-99

DOE Office of Scientific and Technical Information (OSTI.GOV)

Amber Wright; Edward Mausolf; Keri Campbell

2010-05-01

Acetohydroxamic acid (AHA) is an organic ligand planned for use in the Uranium Extraction (UREX) process. It reduces neptunium and plutonium, and the resultant hydrophilic complexes are separated from uranium by extraction with tributyl phosphate (TBP) in a hydrocarbon diluent. AHA undergoes hydrolysis to acetic acid which will impede the recycling of nitric acid. During recent discussions of the UREX process, it has been proposed to replace AHA by formohydroxamic acid (FHA). FHA will undergo hydrolysis to formic acid which is volatile, thus allowing the recycling of nitric acid. The reported reduction potentials of AHA and pertechnetate (TcO{sub 4}{sup -})more » indicated that it may be possible for AHA to reduce technetium, altering its fate in the fuel cycle. At UNLV, it has been demonstrated that TcO{sub 4}{sup -} undergoes reductive nitrosylation by AHA under a variety of conditions. The resulting divalent technetium is complexed by AHA to form the pseudo-octahedral trans-aquonitrosyl (diacetohydroxamic)-technetium(II) complex ([Tc{sup II}(NO)(AHA){sub 2}H{sub 2}O]{sup +}). In this paper, we are reporting the synthesis of FHA and its complex formation with technetium along with the characterization of FHA crystals achieved by NMR and IR spectroscopy. Two experiments were conducted to investigate the complexation of FHA with Tc and the results were compared with previous data on AHA. The first experiment involved the elution of Tc from a Reillex HP anion exchange resin, and the second one monitored the complexation of technetium with FHA by UV-visible spectrophotometry.« less

Uranium reduction and resistance to reoxidation under iron-reducing and sulfate-reducing conditions.

PubMed

Boonchayaanant, Benjaporn; Nayak, Dipti; Du, Xin; Criddle, Craig S

2009-10-01

Oxidation and mobilization of microbially-generated U(IV) is of great concern for in situ uranium bioremediation. This study investigated the reoxidation of uranium by oxygen and nitrate in a sulfate-reducing enrichment and an iron-reducing enrichment derived from sediment and groundwater from the Field Research Center in Oak Ridge, Tennessee. Both enrichments were capable of reducing U(VI) rapidly. 16S rRNA gene clone libraries of the two enrichments revealed that Desulfovibrio spp. are dominant in the sulfate-reducing enrichment, and Clostridium spp. are dominant in the iron-reducing enrichment. In both the sulfate-reducing enrichment and the iron-reducing enrichment, oxygen reoxidized the previously reduced uranium but to a lesser extent in the iron-reducing enrichment. Moreover, in the iron-reducing enrichment, the reoxidized U(VI) was eventually re-reduced to its previous level. In both, the sulfate-reducing enrichment and the iron-reducing enrichment, uranium reoxidation did not occur in the presence of nitrate. The results indicate that the Clostridium-dominated iron-reducing communities created conditions that were more favorable for uranium stability with respect to reoxidation despite the fact that fewer electron equivalents were added to these systems. The likely reason is that more of the added electrons are present in a form that can reduce oxygen to water and U(VI) back to U(IV).

National Uranium Resource Evaluation, Tularosa Quadrangle, New Mexico

DOE Office of Scientific and Technical Information (OSTI.GOV)

Berry, V.P.; Nagy, P.A.; Spreng, W.C.

1981-12-01

Uranium favorability of the Tularosa Quadrangle, New Mexico, was evaluated to a depth of 1500 m using National Uranium Resource Evaluation criteria. Uranium occurrences reported in the literature were located, sampled, and described in detail. Areas of anomalous radioactivity, interpreted from an aerial radiometric survey, and geochemical anomalies, interpreted from hydrogeochemical and stream-sediment reconnaissance, were also investigated. Additionally, several hundred rock samples were studied in thin section, and supplemental geochemical analyses of rock and water samples were completed. Fluorometric analyses were completed for samples from the Black Range Primitive Area to augment previously available geochemical data. Subsurface favorability was evaluatedmore » using gamma-ray logs and descriptive logs of sample cuttings. One area of uranium favorability was delineated, based on the data made available from this study. This area is the Nogal Canyon cauldron margin zone. Within the zone, characterized by concentric and radial fractures, resurgent doming, ring-dike volcanism, and intracauldron sedimentation, uranium conentration is confined to magmatic-hydrothermal and volcanogenic uranium deposits.« less

Bacterial leaching of waste uranium materials.

PubMed

Barbic, F F; Bracilović, D M; Krajincanić, B V; Lucić, J L

1976-01-01

The effect of ferrobacteria and thiobacteria on the leaching of waste uranium materials from which 70-80% of uranium was previously leached by classical chemical hydrometallurgical procedure has been investigated. The bacteria used are found in the ore and the mine water of Zletovska River locality, Yugoslavia. Parameters of biological leaching were examined in the laboratory. Leaching conditions were changed with the aim of increasing the amount of uranium leached. The effect of pyrite added to the waste materials before the beginning of leaching has also been examined. Uranium leaching is directly proportional to the composition and number of ferrobacteria and thiobacteria, and increased by almost twice the value obtained from the same starting materials without using bacteria. Increased sulphuric acid concentrations stimulate considerably the rate of leaching. Uranium leaching is increased up to 20% while sulphuric acid consumption is simultaneously decreased by the addition of pyrite. Uranium concentrations in starting waste materials used for leaching were extremely low (0.0278 and 0.372% U) but about 60% recovery of uranium was obtained, with relatively low consumption of sulphuric acid.

Pyroprocessing of Fast Flux Test Facility Nuclear Fuel

DOE Office of Scientific and Technical Information (OSTI.GOV)

B.R. Westphal; G.L. Fredrickson; G.G. Galbreth

Used nuclear fuel from the Fast Flux Test Facility (FFTF) was recently transferred to the Idaho National Laboratory and processed by pyroprocessing in the Fuel Conditioning Facility. Approximately 213 kg of uranium from sodium-bonded metallic FFTF fuel was processed over a one year period with the equipment previously used for the processing of EBR-II used fuel. The peak burnup of the FFTF fuel ranged from 10 to 15 atom% for the 900+ chopped elements processed. Fifteen low-enriched uranium ingots were cast following the electrorefining and distillation operations to recover approximately 192 kg of uranium. A material balance on the primarymore » fuel constituents, uranium and zirconium, during the FFTF campaign will be presented along with a brief description of operating parameters. Recoverable uranium during the pyroprocessing of FFTF nuclear fuel was greater than 95% while the purity of the final electrorefined uranium products exceeded 99%.« less

Pyroprocessing of fast flux test facility nuclear fuel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Westphal, B.R.; Wurth, L.A.; Fredrickson, G.L.

Used nuclear fuel from the Fast Flux Test Facility (FFTF) was recently transferred to the Idaho National Laboratory and processed by pyroprocessing in the Fuel Conditioning Facility. Approximately 213 kg of uranium from sodium-bonded metallic FFTF fuel was processed over a one year period with the equipment previously used for the processing of EBR-II used fuel. The peak burnup of the FFTF fuel ranged from 10 to 15 atom% for the 900+ chopped elements processed. Fifteen low-enriched uranium ingots were cast following the electrorefining and distillation operations to recover approximately 192 kg of uranium. A material balance on the primarymore » fuel constituents, uranium and zirconium, during the FFTF campaign will be presented along with a brief description of operating parameters. Recoverable uranium during the pyroprocessing of FFTF nuclear fuel was greater than 95% while the purity of the final electro-refined uranium products exceeded 99%. (authors)« less

77 FR 53198 - Environmental Impacts Statements; Notice of Availability

Federal Register 2010, 2011, 2012, 2013, 2014

2012-08-31

..., Fluoride Extraction Process and Depleted Uranium Deconversion Plant, License Application to Construct... River National Forest Oil and Gas Leasing, Eagle, Garfield, Gunnison, Mesa, Moffat, Pitkin, Rio Blanco...

DISTRIBUTION OF URANIUM, ZIRCONIUM, NIOBIUM, RUTHENIUM AND CERIUM BETWEEN NITRIC ACID SOLUTIONS AND 10% TLA-5% OCTYL ALCOHOL/SHELL SOL-T

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lopez-Menchero, E.; Centeno, J.; Magni, G.

1962-03-01

The extraction of traces of Ru, Zr, Nb, Ce, and U at low concentrations (5 mg/l in aqueous solution) from nitric acid solutions using trilauryl amine (TLA) has been experimentally studied. TLA will eventually be used for final purification of plutonium. Room-temperature data on plutonium contaminant distribution between aqueous solutions of varying nitric acid concentrations and a Shellsol-T solution containing l0% TlA and 5% octyl alcohol are presented. Within the temperature and nitric acid concentration ranges tested, the extractability of uranium increased with increased acid concentrations, although acid concentration in the aqueous phase had no effect on the decontamination factorsmore » for the main fission products. (H.G.G.)« less

Comparison of the Kinetic Rate Law Parameters for the Dissolution of Natural and Synthetic Autunite in the Presence of Aqueous Bicarbonate Ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gudavalli, Ravi; Katsenovich, Yelena; Wellman, Dawn M.

2013-08-02

Bicarbonate is one of the most significant components within the uranium geochemical cycle. In aqueous solutions, bicarbonate forms strong complexes with uranium. As such, aqueous bicarbonate may significantly increase the rate of uranium release from uranium minerals. Quantifying the relationship of aqueous bicarbonate concentration to the rate of uranium release during dissolution is critical to understanding the long-term fate of uranium within the environment. Single-pass flow-through (SPTF) experiments were conducted to estimate the rate of uranium release from Na meta-autunite as a function of bicarbonate (0.0005-0.003 M) under the pH range of 6-11 and a temperature range of 5-60oC. Consistentmore » with the results of previous investigation, the rate of uranium release exhibited minimal dependency on temperature; but were strongly dependent on pH. Increasing aqueous bicarbonate concentrations afforded comparable increases in the rate of release of uranium. Most notably under low pH conditions the aqueous bicarbonate resulted in up to 370 fold increases in the rate of uranium release in relative to the rate of uranium release in the absence of bicarbonate. However, the effect of aqueous bicarbonate on the release of uranium was significantly less under higher pH conditions. It is postulated that at high pH values, surface sites are saturated with carbonate, thus the addition of more bicarbonate would have less effect on uranium release.« less

Quantifying Dimer and Trimer Formation by Tri- n -butyl Phosphates in n -Dodecane: Molecular Dynamics Simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vo, Quynh N.; Dang, Liem X.; Nilsson, Mikael

2016-07-21

Tri-n-butyl phosphate (TBP), a representative of neutral organophosphorous ligands, is an important extractant used in solvent extraction process for the recovery of uranium and plutonium from spent nuclear fuel. Microscopic pictures of TBP isomerism and its behavior in n-dodecane diluent were investigated utilizing MD simulations with previously optimized force field parameters for TBP and n-dodecane. Potential Mean Force (PMF) calculations on a single TBP molecule show seven probable TBP isomers. Radial Distribution Functions (RDF) of TBP suggests the existence of TBP trimers at high TBP concentrations in addition to dimers. 2D PMF calculations were performed to determine the angle andmore » distance criteria for TBP trimers. The dimerization and trimerization constants of TBP in n-dodecane were obtained and match our own experimental values using FTIR technique. The new insights into the conformational behaviors of TBP molecule as a monomer and as part of an aggregate could greatly aid the understanding of the complexation between TBP and metal ions in solvent extraction system. The U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences funded the work performed by LXD.« less

First-Principles Integrated Adsorption Modeling for Selective Capture of Uranium from Seawater by Polyamidoxime Sorbent Materials

DOE PAGES

Ladshaw, Austin P.; Ivanov, Alexander S.; Das, Sadananda; ...

2018-03-27

Nuclear power is a relatively carbon-free energy source that has the capacity to be utilized today in an effort to stem the tides of global warming. The growing demand for nuclear energy, however, could put significant strain on our uranium ore resources, and the mining activities utilized to extract that ore can leave behind long-term environmental damage. A potential solution to enhance the supply of uranium fuel is to recover uranium from seawater using amidoximated adsorbent fibers. This technology has been studied for decades but is currently plagued by the material’s relatively poor selectivity of uranium over its main competitormore » vanadium. In this work, we investigate the binding schemes between uranium, vanadium, and the amidoxime functional groups on the adsorbent surface. Using quantum chemical methods, binding strengths are approximated for a set of complexation reactions between uranium and vanadium with amidoxime functionalities. Those approximations are then coupled with a comprehensive aqueous adsorption model developed in this work to simulate the adsorption of uranium and vanadium under laboratory conditions. Experimental adsorption studies with uranium and vanadium over a wide pH range are performed, and the data collected are compared against simulation results to validate the model. It was found that coupling ab initio calculations with process level adsorption modeling provides accurate predictions of the adsorption capacity and selectivity of the sorbent materials. Furthermore, this work demonstrates that this multiscale modeling paradigm could be utilized to aid in the selection of superior ligands or ligand compositions for the selective capture of metal ions. Furthermore, this first-principles integrated modeling approach opens the door to the in silico design of next-generation adsorbents with potentially superior efficiency and selectivity for uranium over vanadium in seawater.« less

First-Principles Integrated Adsorption Modeling for Selective Capture of Uranium from Seawater by Polyamidoxime Sorbent Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ladshaw, Austin P.; Ivanov, Alexander S.; Das, Sadananda

Nuclear power is a relatively carbon-free energy source that has the capacity to be utilized today in an effort to stem the tides of global warming. The growing demand for nuclear energy, however, could put significant strain on our uranium ore resources, and the mining activities utilized to extract that ore can leave behind long-term environmental damage. A potential solution to enhance the supply of uranium fuel is to recover uranium from seawater using amidoximated adsorbent fibers. This technology has been studied for decades but is currently plagued by the material’s relatively poor selectivity of uranium over its main competitormore » vanadium. In this work, we investigate the binding schemes between uranium, vanadium, and the amidoxime functional groups on the adsorbent surface. Using quantum chemical methods, binding strengths are approximated for a set of complexation reactions between uranium and vanadium with amidoxime functionalities. Those approximations are then coupled with a comprehensive aqueous adsorption model developed in this work to simulate the adsorption of uranium and vanadium under laboratory conditions. Experimental adsorption studies with uranium and vanadium over a wide pH range are performed, and the data collected are compared against simulation results to validate the model. It was found that coupling ab initio calculations with process level adsorption modeling provides accurate predictions of the adsorption capacity and selectivity of the sorbent materials. Furthermore, this work demonstrates that this multiscale modeling paradigm could be utilized to aid in the selection of superior ligands or ligand compositions for the selective capture of metal ions. Furthermore, this first-principles integrated modeling approach opens the door to the in silico design of next-generation adsorbents with potentially superior efficiency and selectivity for uranium over vanadium in seawater.« less

First-Principles Integrated Adsorption Modeling for Selective Capture of Uranium from Seawater by Polyamidoxime Sorbent Materials.

PubMed

Ladshaw, Austin P; Ivanov, Alexander S; Das, Sadananda; Bryantsev, Vyacheslav S; Tsouris, Costas; Yiacoumi, Sotira

2018-04-18

Nuclear power is a relatively carbon-free energy source that has the capacity to be utilized today in an effort to stem the tides of global warming. The growing demand for nuclear energy, however, could put significant strain on our uranium ore resources, and the mining activities utilized to extract that ore can leave behind long-term environmental damage. A potential solution to enhance the supply of uranium fuel is to recover uranium from seawater using amidoximated adsorbent fibers. This technology has been studied for decades but is currently plagued by the material's relatively poor selectivity of uranium over its main competitor vanadium. In this work, we investigate the binding schemes between uranium, vanadium, and the amidoxime functional groups on the adsorbent surface. Using quantum chemical methods, binding strengths are approximated for a set of complexation reactions between uranium and vanadium with amidoxime functionalities. Those approximations are then coupled with a comprehensive aqueous adsorption model developed in this work to simulate the adsorption of uranium and vanadium under laboratory conditions. Experimental adsorption studies with uranium and vanadium over a wide pH range are performed, and the data collected are compared against simulation results to validate the model. It was found that coupling ab initio calculations with process level adsorption modeling provides accurate predictions of the adsorption capacity and selectivity of the sorbent materials. Furthermore, this work demonstrates that this multiscale modeling paradigm could be utilized to aid in the selection of superior ligands or ligand compositions for the selective capture of metal ions. Therefore, this first-principles integrated modeling approach opens the door to the in silico design of next-generation adsorbents with potentially superior efficiency and selectivity for uranium over vanadium in seawater.

Concentration of Uranium Radioisotopes in Albanian Drinking Waters Measured by Alpha Spectrometry

NASA Astrophysics Data System (ADS)

Bylyku, Elida; Cfarku, Florinda; Deda, Antoneta; Bode, Kozeta; Fishka, Kujtim

2010-01-01

Uranium is a radioactive material that is frequently found in rocks and soil. When uranium decays, it changes into different elements that are also radioactive, including radon, a gas that is known to cause a lung cancer. The main concern with uranium in drinking water is harm to the kidneys. Public water systems are required to keep uranium levels at or below 500 mBq per liter to protect against kidney damage. Such an interest is needed due to safety, regulatory compliance and disposal issue for uranium in the environment since uranium is included as an obligatory controlled radionuclide in the European Legislation (Directive 98/83 CE of Council of 03.11.1998). The aim of this work is to measure the levels of uranium in drinking and drilled well waters in Albania. At first each sample was measured for total Alpha and total Beta activity. The samples with the highest levels of total alpha activity were chosen for the determination of uranium radioisotopes by alpha spectrometry. A radiochemical procedure using extraction with TBP (Tri-Butyl-Phosphate) is used in the presence of U232 as a yield tracer. Thin sources for alpha spectrometry are prepared by electrodepositing on to stainless steel discs. The results of the U238 activity measured in the different samples, depending from their geological origin range between 0.55-13.87 mBq/l. All samples measured results under the European Directive limits for U238 (5-500 mBq/1), Dose Coefficients according to Directive 96/29 EURATOM.

An evaluation of uranium-series dating of fossil echinoids from southern California Pleistocene marine terraces

USGS Publications Warehouse

Muhs, D.R.; Kennedy, G.L.

1985-01-01

Fossil sea urchins (Strongylocentrotus) from Pleistocene marine terraces on the southern California Channel Islands have been dated by the uranium-series method in order to test the suitability of echinoids for dating marine terraces. Results indicate that urchin plates and spines do not behave as closed systems with respect to both uranium and thorium. Calculated ages based on these data do not agree with uranium-series ages (120,000 and 127,000 yrs) obtained previously from corals from the same localities. Thus, fossil sea urchins (Strongylocentrotus) are not considered suitable for uraniumseries dating of Pleistocene marine terrace deposits. ?? 1985.

10 CFR Appendix J to Part 110 - Illustrative List of Uranium Conversion Plant Equipment and Plutonium Conversion Plant Equipment...

Code of Federal Regulations, 2011 CFR

2011-01-01

... reactors, flame tower reactors, liquid centrifuges, distillation columns and liquid-liquid extraction... UF4 to UF6 is performed by exothermic reaction with fluorine in a tower reactor. UF6 is condensed from..., flame tower reactors, liquid centrifuges, distillation columns and liquid-liquid extraction columns. Hot...

77 FR 38457 - Blocking Property of the Government of the Russian Federation Relating to the Disposition of...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-06-27

... Extracted From Nuclear Weapons #0; #0; #0; Presidential Documents #0; #0; #0;#0;Federal Register / Vol. 77... Federation Relating to the Disposition of Highly Enriched Uranium Extracted From Nuclear Weapons By the... the accumulation of a large volume of weapons-usable fissile material in the territory of the Russian...

Caulobacter crescentus as a Whole-Cell Uranium Biosensor▿ †

PubMed Central

Hillson, Nathan J.; Hu, Ping; Andersen, Gary L.; Shapiro, Lucy

2007-01-01

We engineered a strain of the bacterium Caulobacter crescentus to fluoresce in the presence of micromolar levels of uranium at ambient temperatures when it is exposed to a hand-held UV lamp. Previous microarray experiments revealed that several Caulobacter genes are significantly upregulated in response to uranium but not in response to other heavy metals. We designated one of these genes urcA (for uranium response in caulobacter). We constructed a reporter that utilizes the urcA promoter to produce a UV-excitable green fluorescent protein in the presence of the uranyl cation, a soluble form of uranium. This reporter is specific for uranium and has little cross specificity for nitrate (<400 μM), lead (<150 μM), cadmium (<48 μM), or chromium (<41.6 μM). The uranium reporter construct was effective for discriminating contaminated groundwater samples (4.2 μM uranium) from uncontaminated groundwater samples (<0.1 μM uranium) collected at the Oak Ridge Field Research Center. In contrast to other uranium detection methodologies, the Caulobacter reporter strain can provide on-demand usability in the field; it requires minimal sample processing and no equipment other than a hand-held UV lamp, and it may be sprayed directly on soil, groundwater, or industrial surfaces. PMID:17905881

Purification of uranium alloys by differential solubility of oxides and production of purified fuel precursors

DOEpatents

McLean, II, William; Miller, Philip E.

1997-01-01

A method for purifying metallic alloys of uranium for use as nuclear reactor fuels in which the metal alloy is first converted to an oxide and then dissolved in nitric acid. Initial removal of metal oxide impurities not soluble in nitric acid is accomplished by filtration or other physical means. Further purification can be accomplished by carbonate leaching of uranyl ions from the partially purified solution or using traditional methods such as solvent extraction.

Purification of uranium alloys by differential solubility of oxides and production of purified fuel precursors

DOEpatents

McLean, W. II; Miller, P.E.

1997-12-16

A method is described for purifying metallic alloys of uranium for use as nuclear reactor fuels in which the metal alloy is first converted to an oxide and then dissolved in nitric acid. Initial removal of metal oxide impurities not soluble in nitric acid is accomplished by filtration or other physical means. Further purification can be accomplished by carbonate leaching of uranyl ions from the partially purified solution or using traditional methods such as solvent extraction. 3 figs.

Application of neodymium isotope ratio measurements for the origin assessment of uranium ore concentrates.

PubMed

Krajkó, Judit; Varga, Zsolt; Yalcintas, Ezgi; Wallenius, Maria; Mayer, Klaus

2014-11-01

A novel procedure has been developed for the measurement of (143)Nd/(144)Nd isotope ratio in various uranium-bearing materials, such as uranium ores and ore concentrates (UOC) in order to evaluate the usefulness and applicability of variations of (143)Nd/(144)Nd isotope ratio for provenance assessment in nuclear forensics. Neodymium was separated and pre-concentrated by extraction chromatography and then the isotope ratios were measured by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). The method was validated by the measurement of standard reference materials (La Jolla, JB-2 and BCR-2) and the applicability of the procedure was demonstrated by the analysis of uranium samples of world-wide origin. The investigated samples show distinct (143)Nd/(144)Nd ratio depending on the ore type, deposit age and Sm/Nd ratio. Together with other characteristics of the material in question, the Nd isotope ratio is a promising signature for nuclear forensics and suggests being indicative of the source material, the uranium ore. Copyright © 2014 The Authors. Published by Elsevier B.V. All rights reserved.

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

PubMed

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

2014-08-01

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

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

USGS Publications Warehouse

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

2014-01-01

Recent restrictions on uranium mining within the Grand Canyon watershed have drawn attention to scientific data gaps in evaluating the possible effects of ore extraction to human populations as well as wildlife communities in the area. Tissue contaminant concentrations, one of the most basic data requirements to determine exposure, are not available for biota from any historical or active uranium mines in the region. The Canyon Uranium Mine is under development, providing a unique opportunity to characterize concentrations of uranium and other trace elements, as well as radiation levels in biota, found in the vicinity of the mine before ore extraction begins. Our study objectives were to identify contaminants of potential concern and critical contaminant exposure pathways for ecological receptors; conduct biological surveys to understand the local food web and refine the list of target species (ecological receptors) for contaminant analysis; and collect target species for contaminant analysis prior to the initiation of active mining. Contaminants of potential concern were identified as arsenic, cadmium, chromium, copper, lead, mercury, nickel, selenium, thallium, uranium, and zinc for chemical toxicity and uranium and associated radionuclides for radiation. The conceptual exposure model identified ingestion, inhalation, absorption, and dietary transfer (bioaccumulation or bioconcentration) as critical contaminant exposure pathways. The biological survey of plants, invertebrates, amphibians, reptiles, birds, and small mammals is the first to document and provide ecological information on .200 species in and around the mine site; this study also provides critical baseline information about the local food web. Most of the species documented at the mine are common to ponderosa pine Pinus ponderosa and pinyon–juniper Pinus–Juniperus spp. forests in northern Arizona and are not considered to have special conservation status by state or federal agencies; exceptions are the locally endemic Tusayan flameflower Phemeranthus validulus, the long-legged bat Myotis volans, and the Arizona bat Myotis occultus. The most common vertebrate species identified at the mine site included the Mexican spadefoot toad Spea multiplicata, plateau fence lizard Sceloporus tristichus, violetgreen swallow Tachycineta thalassina, pygmy nuthatch Sitta pygmaea, purple martin Progne subis, western bluebird Sialia mexicana, deermouse Peromyscus maniculatus, valley pocket gopher Thomomys bottae, cliff chipmunk Tamias dorsalis, black-tailed jackrabbit Lepus californicus, mule deer Odocoileus hemionus, and elk Cervus canadensis. A limited number of the most common species were collected for contaminant analysis to establish baseline contaminant and radiological concentrations prior to ore extraction. These empirical baseline data will help validate contaminant exposure pathways and potential threats from contaminant exposures to ecological receptors. Resource managers will also be able to use these data to determine the extent to which local species are exposed to chemical and radiation contamination once the mine is operational and producing ore. More broadly, these data could inform resource management decisions on mitigating chemical and radiation exposure of biota at high-grade uranium breccia pipes throughout the Grand Canyon watershed.

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

PubMed Central

Thorgersen, Michael P.; Lancaster, W. Andrew; Rajeev, Lara; Ge, Xiaoxuan; Vaccaro, Brian J.; Poole, Farris L.; Arkin, Adam P.; Mukhopadhyay, Aindrila

2016-01-01

ABSTRACT 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. IMPORTANCE Widespread uranium contamination from industrial sources poses hazards to human health and to the environment. Herein, 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. While other bacteria have been shown to bind U(VI) on their S-layer, we demonstrate here an example of U(IV) bound by an S-layer complex. The UBC provides a potential tool for the microbiological sequestration of uranium for the cleaning of contaminated environments. PMID:27913415

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thorgersen, Michael P.; Lancaster, W. Andrew; Rajeev, Lara

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 hadmore » 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 an S-layer complex. The UBC provides a potential tool for the microbiological sequestration of uranium for the cleaning of contaminated environments.« less

U redox fronts and kaolinisation in basement-hosted unconformity-related U ores of the Athabasca Basin (Canada): late U remobilisation by meteoric fluids

NASA Astrophysics Data System (ADS)

Mercadier, Julien; Cuney, Michel; Cathelineau, Michel; Lacorde, Mathieu

2011-02-01

Proterozoic basement-hosted unconformity-related uranium deposits of the Athabasca Basin (Saskatchewan, Canada) were affected by significant uranium redistribution along oxidation-reduction redox fronts related to cold and late meteoric fluid infiltration. These redox fronts exhibit the same mineralogical and geochemical features as the well-studied uranium roll-front deposits in siliclastic rocks. The primary hydrothermal uranium mineralisation (1.6-1.3 Ga) of basement-hosted deposits is strongly reworked to new disseminated ores comprising three distinctly coloured zones: a white-green zone corresponding to the previous clay-rich alteration halo contemporaneous with hydrothermal ores, a uranium front corresponding to the uranium deposition zone of the redox front (brownish zone, rich in goethite) and a hematite-rich red zone marking the front progression. The three zones directly reflect the mineralogical zonation related to uranium oxides (pitchblende), sulphides, iron minerals (hematite and goethite) and alumino-phosphate-sulphate (APS) minerals. The zoning can be explained by processes of dissolution-precipitation along a redox interface and was produced by the infiltration of cold (<50°C) meteoric fluids to the hydrothermally altered areas. U, Fe, Ca, Pb, S, REE, V, Y, W, Mo and Se were the main mobile elements in this process, and their distribution within the three zones was, for most of them, directly dependent on their redox potential. The elements concentrated in the redox fronts were sourced by the alteration of previously crystallised hydrothermal minerals, such as uranium oxides and light rare earth element (LREE)-rich APS. The uranium oxides from the redox front are characterised by LREE-enriched patterns, which differ from those of unconformity-related ores and clearly demonstrate their distinct conditions of formation. Uranium redox front formation is thought to be linked to fluid circulation episodes initiated during the 400-300 Ma period during uplift and erosion of the Athabasca Basin when it was near the Equator and to have been still active during the last million years. A major kaolinisation event was caused by changes in the fluid circulation regime, reworking the primary uranium redox fronts and causing the redistribution of elements originally concentrated in the uranium-enriched meteoric-related redox fronts.

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

PubMed

Thorgersen, Michael P; Lancaster, W Andrew; Rajeev, Lara; Ge, Xiaoxuan; Vaccaro, Brian J; Poole, Farris L; Arkin, Adam P; Mukhopadhyay, Aindrila; Adams, Michael W W

2017-02-15

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. Herein, 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. While other bacteria have been shown to bind U(VI) on their S-layer, we demonstrate here an example of U(IV) bound by an S-layer complex. The UBC provides a potential tool for the microbiological sequestration of uranium for the cleaning of contaminated environments. Copyright © 2017 American Society for Microbiology.

Uraniferous Phosphates: Resource, Security Risk, or Contaminant

DOE Office of Scientific and Technical Information (OSTI.GOV)

LeMone, D.V.; Goodell, Ph.C.; Gibbs, S.G.

2008-07-01

The escalation of the price of uranium (U) yellow cake (summer high = $130/0.454 kg (lb) has called into question the continuing availability of sufficient stockpiles and ores to process. As was developed during the years following World War II, the establishment and maintenance of a strategic inventory is a reasonable consideration for today. Therefore, it becomes critical to look at potential secondary resources beyond the classical ore suites now being utilized. The most economically viable future secondary source seems to be the byproducts of the beneficiation of phosphoric acids derived from phosphate ores. Phosphorous (P) is an essential nutrientmore » for plants; its deficiency can result in highly restrictive limitations in crop productivity. Acidic soils in tropical and subtropical regions of the world are often P deficient with high P-sorption (fixation) capacities. To correct this deficiency, efficient water-soluble P fertilizers are required. The use of raw phosphate rocks not only adds phosphate but also its contained contaminants, including uranium to the treated land. Another immediate difficulty is phosphogypsum, the standard byproduct of simple extraction. It, for practical purposes, has been selectively classified as TENORM by regulators. The imposition of these standards presents major current and future disposal and re-utilization problems. Therefore, establishing an economically viable system that allows for uranium byproduct extraction from phosphoric acids is desirable. Such a system would be dependent on yellow cake base price stability, reserve estimates, political conditions, nation-state commitment, and dependence on nuclear energy. The accumulation of yellow cake from the additional extraction process provides a valuable commodity and allows the end acid to be a more environmentally acceptable product. The phosphogypsum already accumulated, as well as that which is in process, will not make a viable component for a radiation disposal devise (RDD). Concern for weapon proliferation by rogue nation states from the byproduct production of yellowcake is an unlikely scenario. To extract the fissile U-235 (0.07%) isotope from the yellowcake (99.3%) requires the erection of a costly major gaseous diffusion or a cascading centrifuge facility. Such a facility would be extremely difficult to mask. Therefore, from a diminished security risk and positive economic and environmental viewpoints, the utilization of a phosphoric acid beneficiation process extracting uranium is desirable. (authors)« less

Uranium in NIMROC standard igneous rock samples

NASA Technical Reports Server (NTRS)

Rowe, M. W.; Herndon, J. M.

1976-01-01

Results are reported for analysis of the uranium in multiple samples of each of six igneous-rock standards (dunite, granite, lujavrite, norite, pyroxenite, and syenite) prepared as geochemical reference standards for elemental and isotopic compositions. Powdered rock samples were examined by measuring delayed neutron emission after irradiation with a flux of the order of 10 to the 13th power neutrons/sq cm per sec in a nuclear reactor. The measurements are shown to compare quite favorably with previous uranium determinations for other standard rock samples.

LEACHING OF URANIUM ORES USING ALKALINE CARBONATES AND BICARBONATES AT ATMOSPHERIC PRESSURE

DOEpatents

Thunaes, A.; Brown, E.A.; Rabbits, A.T.; Simard, R.; Herbst, H.J.

1961-07-18

A method of leaching uranium ores containing sulfides is described. The method consists of adding a leach solution containing alkaline carbonate and alkaline bicarbonate to the ore to form a slurry, passing the slurry through a series of agitators, passing an oxygen containing gas through the slurry in the last agitator in the series, passing the same gas enriched with carbon dioxide formed by the decomposition of bicarbonates in the slurry through the penultimate agitator and in the same manner passing the same gas increasingly enriched with carbon dioxide through the other agitators in the series. The conditions of agitation is such that the extraction of the uranium content will be substantially complete before the slurry reaches the last agitator.

Electron-beam-driven RI separator for SCRIT (ERIS) at RIKEN RI beam factory

NASA Astrophysics Data System (ADS)

Ohnishi, T.; Ichikawa, S.; Koizumi, K.; Kurita, K.; Miyashita, Y.; Ogawara, R.; Tamaki, S.; Togasaki, M.; Wakasugi, M.

2013-12-01

We constructed a radioactive isotope (RI) separator named ERIS (electron-beam-driven RI separator for SCRIT) for the SCRIT (Self-Confinement RI Target) electron scattering facility at RIKEN RI Beam Factory (RIBF). In ERIS, production rate of fission products in the photofission of uranium is estimated to be 2.2 ×1011 fissions/s with 30 g of uranium and a 1-kW electron beam. During the commissioning of ERIS, the mass resolution and overall efficiency, including ionization, extraction, and transmission, were found to be 1660 and 21%, respectively, using natural xenon gas. The preparation of uranium carbide (UC2) RI production targets is described from which a 132Sn beam was successfully separated in our first attempt at RI production.

Analysis of Tank 38H (HTF-38-16-80, 81) and Tank 43H (HTF-43-16-82, 83) Samples for Support of the Enrichment Control and Corrosion Control Programs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hay, M.

2016-10-24

SRNL analyzed samples from Tank 38H and Tank 43H to support ECP and CCP. The total uranium in the Tank 38H surface sample was 57.6 mg/L, while the sub-surface sample was 106 mg/L. The Tank 43H samples ranged from 50.0 to 51.9 mg/L total uranium. The U-235 percentage was consistent for all four samples at 0.62%. The total uranium and percent U-235 results appear consistent with recent Tank 38H and Tank 43H uranium measurements. The Tank 38H plutonium results show a large difference between the surface and sub-surface sample concentrations and somewhat higher concentrations than previous samples. The Pu-238 concentrationmore » is more than forty times higher in the Tank 38H sub-surface sample than the surface sample. The surface and sub-surface Tank 43H samples contain similar plutonium concentrations and are within the range of values measured on previous samples. The four samples analyzed show silicon concentrations somewhat higher than the previous sample with values ranging from 104 to 213 mg/L.« less

Ferric ion as a scavenging agent in a solvent extraction process

DOEpatents

Bruns, Lester E.; Martin, Earl C.

1976-01-01

Ferric ions are added into the aqueous feed of a plutonium scrap recovery process that employs a tributyl phosphate extractant. Radiolytic degradation products of tributyl phosphate such as dibutyl phosphate form a solid precipitate with iron and are removed from the extraction stages via the waste stream. Consequently, the solvent extraction characteristics are improved, particularly in respect to minimizing the formation of nonstrippable plutonium complexes in the stripping stages. The method is expected to be also applicable to the partitioning of plutonium and uranium in a scrap recovery process.

Plutonium and uranium determination in environmental samples: combined solvent extraction-liquid scintillation method.

PubMed

McDowell, W J; Farrar, D T; Billings, M R

1974-12-01

A method for the determination of uranium and plutonium by a combined high-resolution liquid scintillation-solvent extraction method is presented. Assuming a sample count equal to background count to be the detection limit, the lower detection limit for these and other alpha-emitting nuclides is 1.0 dpm with a Pyrex sample tube, 0.3 dpm with a quartz sample tube using present detector shielding or 0.02 d.p.m. with pulse-shape discrimination. Alpha-counting efficiency is 100%. With the counting data presented as an alpha-energy spectrum, an energy resolution of 0.2-0.3 MeV peak half-width and an energy identification to +/-0.1 MeV are possible. Thus, within these limits, identification and quantitative determination of a specific alpha-emitter, independent of chemical separation, are possible. The separation procedure allows greater than 98% recovery of uranium and plutonium from solution containing large amounts of iron and other interfering substances. In most cases uranium, even when present in 10(8)-fold molar ratio, may be quantitatively separated from plutonium without loss of the plutonium. Potential applications of this general analytical concept to other alpha-counting problems are noted. Special problems associated with the determination of plutonium in soil and water samples are discussed. Results of tests to determine the pulse-height and energy-resolution characteristics of several scintillators are presented. Construction of the high-resolution liquid scintillation detector is described.

Nuclear and chemical safety analysis: Purex Plant 1970 thorium campaign

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boldt, A.L.; Oberg, G.C.

The purpose of this document is to discuss the flowsheet and the related processing equipment with respect to nuclear and chemical safety. The analyses presented are based on equipment utilization and revised piping as outlined in the design criteria. Processing of thorium and uranium-233 in the Purex Plant can be accomplished within currently accepted levels of risk with respect to chemical and nuclear safety if minor instrumentation changes are made. Uranium-233 processing is limited to a rate of about 670 grams per hour by equipment capacities and criticality safety considerations. The major criticality prevention problems result from the potential accumulationmore » of uranium-233 in a solvent phase in E-H4 (ICU concentrator), TK-J1 (IUC receiver), and TK-J21 (2AF pump tank). The same potential problems exist in TK-J5 (3AF pump tank) and TK-N1 (3BU receiver), but the probabilities of reaching a critical condition are not as great. In order to prevent the excessive accumulation of uranium-233 in any of these vessels by an extraction mechanism, it is necessary to maintain the uranium-233 and salting agent concentrations below the point at which a critical concentration of uranium-233 could be reached in a solvent phase.« less

Extraction of U(VI) from oxalate solutions using tetradecylammonium oxalate (in Russian)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuzina, M.G.; Lipovskii, A.A.

1973-07-01

The extraction of U(VI) from oxalate solutions at various pH values was studied. It was shown that, as a function of the extractant and uranium concentration ratios, the latter was extracted in the form of different acido and hydroxyacido complexes. With excess extractant, the compounds were (R/sub 4/N)/ sub 2/UO/sub 2/Ox/sub 2/ at lo w pH values of the aqueous solution and (R/sub 4/ N)/sub 2/UO/sub 2/Ox(OH)/sub 2/ at h igh values. When there was a deficit of the extractant, different hydroxyacido complexes were formed. (tr-auth)

Investigations Into the Reusability of Amidoxime-Based Polymeric Uranium Adsorbents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuo, Li-Jung; Gill, Gary A.; Strivens, Jonathan E.

Significant advancements in amidoxime-based polymeric adsorbents to extract uranium from seawater are achieved in recent years. The success of uranium adsorbent development can help provide a sustainable supply of fuel for nuclear reactors. To bring down the production cost of this new technology, in addition to the development of novel adsorbents with high uranium capacity and manufacture cost, the development of adsorbent re-using technique is critical because it can further reduce the cost of the adsorbent manufacture. In our last report, the use of high concentrations of bicarbonate solution (3M KHCO3) was identified as a cost-effective, environmental friendly method tomore » strip uranium from amidoxime-based polymeric adsorbents. This study aims to further improve the method for high recovery of uranium capacity in re-uses and to evaluate the performance of adsorbents after multiple re-use cycles. Adsorption of dissolved organic matter (DOM) on the uranium adsorbents during seawater exposure can hinder the uranium adsorption and slow down the adsorption rate. An additional NaOH rinse (0.5 M NaOH, room temperature) was applied after the 3 M KHCO3 elution to remove natural organic matter from adsorbents. The combination of 3 M KHCO3 elution and 0.5 M NaOH rinse significantly improves the recovery of uranium adsorption capacity in the re-used adsorbents. In the first re-use, most ORNL adsorbents tested achieve ~100% recovery by using 3 M KHCO3 elution + 0.5 M NaOH rinse approach, in comparison to 54% recovery when only 3 M KHCO3 elution was applied. A significant drop in capacity was observed when the adsorbents went through more than one re-use. FTIR spectra revealed that degradation of amidoxime ligands occurs during seawater exposure, and is more significant the longer the exposure time. Significantly elevated ratios of Ca/U and Mg/U in re-used adsorbents support the decrease in abundance of amidoxime ligands and increase carboxylate group from FT-IR analysis. The impact of the length of seawater exposure cycle in adsorbent re-use was evaluated by comparing the adsorption capacity for a common adsorbent formulation (ORNL AI8 formulation) under different exposure cycle (28 days and 42 days). Adsorbents with a 28 days seawater exposure cycle had higher recovery of uranium capacity than adsorbent with 42 days of seawater exposure. Under different cumulative seawater exposure time, the adsorbent with 28 days seawater exposure cycle also had less amidoxime ligands degradation than the adsorbent with 42 days seawater exposure cycle. These observations support the negative impact of prolonged seawater exposure on amidoxime ligands stability. Recovery of uranium capacity in re-uses also varies across different adsorbent formulations. Among three different ORNL adsorbents tested (AI8, AF8, AF1-DMSO), AI8 had the best recovery in each re-use, followed by AF8 and then AF1-DMSO. This demonstrates that continuing efforts on developing new adsorbents with high capacity and stability is critical. The overall performance of adsorbents in multiple re-use cycles can be evaluated by calculation total harvestable uranium, the summation of adsorbed uranium from each seawater exposure cycle. In this assessment, the ORNL AI8 braid with 28 days seawater exposure cycle can reach total harvestable uranium 10g Uranium/kg adsorbent in ~140 days; while the same type of braid but with 42 days seawater exposure cycle reach the same level in ~170 days. Notably, the performance of total harvestable uranium also varies among different adsorbent formulations (AI8 > AF1-DMSO > AF8). Short seawater exposure cycle is associated with high re-use frequency. The development of low-cost offshore adsorbent deployment/extraction is essential for high frequency reuse operation. This study also highlights the importance to examine the re-use performance of newly developed uranium adsorbents for selection of optimal adsorbents for ocean deployment.« less

Ion Mobility Spectrometer Field Test

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, Nicholas; McLain, Derek; Steeb, Jennifer

The Morpho Saffran Itemizer 4DX Ion Mobility Spectrometer previously used to detect uranium signatures in FY16 was used at the former New Brunswick Facility, a past uranium facility located on site at Argonne National Laboratory. This facility was chosen in an attempt to detect safeguards relevant signatures and has a history of processing uranium at various enrichments, chemical forms, and purities; various chemicals such as nitric acid, uranium fluorides, phosphates and metals are present at various levels. Several laboratories were sampled for signatures of nuclear activities around the laboratory. All of the surfaces that were surveyed were below background levelsmore » of the radioanalytical instrumentation and determined to be radiologically clean.« less

Chronic Exposure to Uranium from Gestation: Effects on Behavior and Neurogenesis in Adulthood

PubMed Central

Dinocourt, Céline; Culeux, Cécile; Legrand, Marie; Elie, Christelle; Lestaevel, Philippe

2017-01-01

Uranium exposure leads to cerebral dysfunction involving for instance biochemical, neurochemical and neurobehavioral effects. Most studies have focused on mechanisms in uranium-exposed adult animals. However, recent data on developing animals have shown that the developing brain is also sensitive to uranium. Models of uranium exposure during brain development highlight the need to improve our understanding of the effects of uranium. In a model in which uranium exposure began from the first day of gestation, we studied the neurobehavioral consequences as well as the progression of hippocampal neurogenesis in animals from dams exposed to uranium. Our results show that 2-month-old rats exposed to uranium from gestational day 1 displayed deficits in special memory and a prominent depressive-like phenotype. Cell proliferation was not disturbed in these animals, as shown by 5-bromo-2′deoxyuridine (BrdU)/neuronal specific nuclear protein (NeuN) immunostaining in the dentate gyrus. However, in some animals, the pyramidal cell layer was dispersed in the CA3 region. From our previous results with the same model, the hypothesis of alterations of neurogenesis at prior stages of development is worth considering, but is probably not the only one. Therefore, further investigations are needed to correlate cerebral dysfunction and its underlying mechanistic pathways. PMID:28513543

Assessment of a Hydroxyapatite Permeable Reactive Barrier to Remediate Uranium at the Old Rifle Site Colorado.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moore, Robert C.; Szecsody, James; Rigali, Mark J.

We have performed an initial evaluation and testing program to assess the effectiveness of a hydroxyapatite (Ca10(PO4)6(OH)2) permeable reactive barrier and source area treatment to decrease uranium mobility at the Department of Energy (DOE) former Old Rifle uranium mill processing site in Rifle, western Colorado. Uranium ore was processed at the site from the 1940s to the 1970s. The mill facilities at the site as well as the uranium mill tailings previously stored there have all been removed. Groundwater in the alluvial aquifer beneath the site still contains elevated concentrations of uranium, and is currently used for field tests tomore » study uranium behavior in groundwater and investigate potential uranium remediation technologies. The technology investigated in this work is based on in situ formation of apatite in sediment to create a subsurface apatite PRB and also for source area treatment. The process is based on injecting a solution containing calcium citrate and sodium into the subsurface for constructing the PRB within the uranium plume. As the indigenous sediment micro-organisms biodegrade the injected citrate, the calcium is released and reacts with the phosphate to form hydroxyapatite (precipitate). This paper reports on proof-of-principle column tests with Old Rifle sediment and synthetic groundwater.« less

Reconnaissance for uraniferous rocks in northwestern Colorado, southwestern Wyoming, and northeastern Utah

USGS Publications Warehouse

Beroni, E.P.; McKeown, F.A.

1952-01-01

Previous discoveries and studies of radioactive lignites of Tertiary age in North Dakota, South Dakota, Montana, and Wyoming led the Geological Survey in 1950 to do reconnaissance in the Green River and Uinta Basin of Wyoming and Utah, where similar lignites were believed to be present. Because of the common association of uranium with copper deposits and the presence of such deposits in the Uinta Basin, several areas containing copper-uranium minerals were also examined. No deposits commercially exploitable under present conditions were found. Samples of coal from the Bear River formation at Sage, Wyo., assayed 0.004 to 0.013 percent uranium in the ash; in the old Uteland copper mine in Uinta County, Utah, 0.007 to 0.017 percent uranium; in a freshwater limestone, Duchesne County, Utah, as much as 0.019 percent uranium; and in the Mesaverde formation at the Snow and Bonniebell claims near Jensen, Uintah County, Utah, 0.003 to 0.090 percent uranium. Maps were made and samples were taken at the Skull Creek carnotite deposits in Moffat County, Colo. (0.006 to 0.16 percent uranium); at the Fair-U claims in Routt County, Colo. (0.002 to 0.040 percent uranium); and at the Lucky Strike claims near Kremmling in Grand County, Colo. (0.006 to 0.018 percent uranium).

Chronic Exposure to Uranium from Gestation: Effects on Behavior and Neurogenesis in Adulthood.

PubMed

Dinocourt, Céline; Culeux, Cécile; Legrand, Marie; Elie, Christelle; Lestaevel, Philippe

2017-05-17

Uranium exposure leads to cerebral dysfunction involving for instance biochemical, neurochemical and neurobehavioral effects. Most studies have focused on mechanisms in uranium-exposed adult animals. However, recent data on developing animals have shown that the developing brain is also sensitive to uranium. Models of uranium exposure during brain development highlight the need to improve our understanding of the effects of uranium. In a model in which uranium exposure began from the first day of gestation, we studied the neurobehavioral consequences as well as the progression of hippocampal neurogenesis in animals from dams exposed to uranium. Our results show that 2-month-old rats exposed to uranium from gestational day 1 displayed deficits in special memory and a prominent depressive-like phenotype. Cell proliferation was not disturbed in these animals, as shown by 5-bromo-2'deoxyuridine (BrdU)/neuronal specific nuclear protein (NeuN) immunostaining in the dentate gyrus. However, in some animals, the pyramidal cell layer was dispersed in the CA3 region. From our previous results with the same model, the hypothesis of alterations of neurogenesis at prior stages of development is worth considering, but is probably not the only one. Therefore, further investigations are needed to correlate cerebral dysfunction and its underlying mechanistic pathways.

Uranium: A Dentist's perspective

PubMed Central

Toor, R. S. S.; Brar, G. S.

2012-01-01

Uranium is a naturally occurring radionuclide found in granite and other mineral deposits. In its natural state, it consists of three isotopes (U-234, U-235 and U-238). On an average, 1% – 2% of ingested uranium is absorbed in the gastrointestinal tract in adults. The absorbed uranium rapidly enters the bloodstream and forms a diffusible ionic uranyl hydrogen carbonate complex (UO2HCO3+) which is in equilibrium with a nondiffusible uranyl albumin complex. In the skeleton, the uranyl ion replaces calcium in the hydroxyapatite complex of the bone crystal. Although in North India, there is a risk of radiological toxicity from orally ingested natural uranium, the principal health effects are chemical toxicity. The skeleton and kidney are the primary sites of uranium accumulation. Acute high dose of uranyl nitrate delays tooth eruption, and mandibular growth and development, probably due to its effect on target cells. Based on all previous research and recommendations, the role of a dentist is to educate the masses about the adverse effects of uranium on the overall as well as the dental health. The authors recommended that apart from the discontinuation of the addition of uranium to porcelain, the Public community water supplies must also comply with the Environmental Protection Agency (EPA) standards of uranium levels being not more than 30 ppb (parts per billion). PMID:24478959

METHOD OF PROCESSING MONAZITE SAND

DOEpatents

Welt, M.A.; Smutz, M.

1958-08-26

A process is described for recovering thorium, uranium, and rare earth values from monazite sand. The monazite sand is first digested with sulfuric acid and the resulting "monazite sulfate" solution is adjusted to a pH of between 0.4 and 3.0, and oxalate anions are added causing precipitation of the thorium and the rare earths as the oxalates. The oxalate precipitate is separated from the uranium containing supernatant solution, and is dried and calcined to the oxides. The thorium and rare earth oxides are then dissolved in nitric acid and the solution is contacted with tribntyl phosphate whereby an organic extract phase containing the cerium and thorium values is obtained, together with an aqueous raffinate containing the other rare earth values. The organic phase is then separated from the aqueous raffinate and the cerium and thorium are back extracted with an aqueous medium.

Erythrocytes of uranium miners: the activity of the pentose phosphate pathway

PubMed Central

Vích, Z.; Novosad, F.; Brychtová, V.

1970-01-01

Vích, Z., Novosad, F., and Brychtová, V. (1970).Brit. J. industr. Med.,27, 287-290. Erythrocytes of uranium miners: the activity of the pentose phosphate pathway. The functioning of erythrocytes was studied by determination of the activity of the pentose phosphate pathway in 431 individuals - 221 uranium miners, 42 employees of a uranium ore trimming station (30 of whom were exposed), 36 former uranium miners, 32 coal miners, and 100 persons not working in mines and with no previous exposure. In the groups exposed to long-term occupational radiation, the activity of the pentose phosphate cycle was found to be enhanced. This finding was interpreted as evidence for a change in the functional state of the erythrocytes in exposed persons due to the effects of radiation on the genesis of red cells in the bone marrow. PMID:5448126

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.

PubMed

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.

Survey Study of Trunk Materials for Direct ATRP Grafting

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saito, Tomonori; Chatterjee, Sabornie; Johnson, Joseph C.

2015-02-01

In previous study, we demonstrated a new method to prepare polymeric fiber adsorbents via a chemical-grafting method, namely atom-transfer radical polymerization (ATRP), and identified parameters affecting their uranium adsorption capacity. However, ATRP chemical grafting in the previous study still utilized conventional radiation-induced graft polymerization (RIGP) to introduce initiation sites on fibers. Therefore, the objective of the present study is to perform survey study of trunk fiber materials for direct ATRP chemical grafting method without RIGP for the preparation of fiber adsorbents for uranium recovery from seawater.

Materials. Section 1 of Symposium on the peaceful uses of atomic energy in Australia, 1958, held in Sydney, in June 1958

DOE Office of Scientific and Technical Information (OSTI.GOV)

None

The environments of the known uranium occurences in South Australia arc described, and the relation of uranium mineralization with sodic granitic rocks is emphasized. The problems in designing equipment for radiometric prospecting are reviewed. The fabrication and properties of BeO, UO/sub 2/, ThO/sub 2/, and mixed oxides are discussed. The use of pulsing in a uranium extraction pilot plant ion exchange column is described. The wetting of metals by liquid metals is reviewed with emphasis on liquid sodium. The geological nature, extent, and future prospects of minerals with atomic energy applications, occurring in New South Wales are outlined. The developmentmore » of a process for uranium recovery from Mary Kathleen ores is described. Techniques and processes involved in locating, mining, and concentrating davidite-type ores at Radium Hill, South Australia are described. The uranium deposits of the Northern Territory, Australia, are classified and described. The flotation behavior of the simple oxide minerals, uraninite and the colloform variety is discussed. The Port Pirie Treatment Plant for uranium recovery from refractory Radium Hill concentrates is described. The plant utilizes the sulfuric acid-ion exchange process. The uranium deposits of Queensland are described. the details of the production of uranium ore concentrates at Rum jungle near Darwin, Australia, are given. A brief account of the use of neutron diffraction analysis in crystallography is given, and the neutron spectrometers installed on the High Flux Australian Research Reactor are described. (T.R.H.)« less

Synthesis, Development, and Testing of High-Surface-Area Polymer-Based Adsorbents for the Selective Recovery of Uranium from Seawater

DOE PAGES

Oyola, Yatsandra; Janke, Christopher J.; Dai, Sheng

2016-02-29

The ocean contains uranium with an approximate concentration of 3.34 ppb, which can serve as an incredible supply source to sustain nuclear energy in the United States. Unfortunately, technology currently available to recover uranium from seawater is not efficient enough and mining uranium on land is still more economical. For this study, we have developed polymer-based adsorbents with high uranium adsorption capacities by grafting amidoxime onto high-surface-area polyethylene (PE) fibers. Various process conditions have been screened, in combination with developing a rapid testing protocol (<24 h), to optimize the process. These adsorbents are synthesized through radiation-induced grafting of acrylonitrile (AN)more » and methacrylic acid (MAA) onto PE fibers, followed by the conversion of nitriles to amidoximes and basic conditioning. In addition, the uranium adsorption capacity, measured in units of g U/kg ads, is greatly increased by reducing the diameter of the PE fiber or changing its morphology. An increase in the surface area of the PE polymer fiber allows for more grafting sites that are positioned in more-accessible locations, thereby increasing access to grafted molecules that would normally be located in the interior of a fiber with a larger diameter. Polymer fibers with hollow morphologies are able to adsorb beyond 1 order of magnitude more uranium from simulated seawater than current commercially available adsorbents. Finally, several high-surface-area fibers were tested in natural seawater and were able to extract 5–7 times more uranium than any adsorbent reported to date.« less

Estimation and mapping of uranium content of geological units in France.

PubMed

Ielsch, G; Cuney, M; Buscail, F; Rossi, F; Leon, A; Cushing, M E

2017-01-01

In France, natural radiation accounts for most of the population exposure to ionizing radiation. The Institute for Radiological Protection and Nuclear Safety (IRSN) carries out studies to evaluate the variability of natural radioactivity over the French territory. In this framework, the present study consisted in the evaluation of uranium concentrations in bedrocks. The objective was to provide estimate of uranium content of each geological unit defined in the geological map of France (1:1,000,000). The methodology was based on the interpretation of existing geochemical data (results of whole rock sample analysis) and the knowledge of petrology and lithology of the geological units, which allowed obtaining a first estimate of the uranium content of rocks. Then, this first estimate was improved thanks to some additional information. For example, some particular or regional sedimentary rocks which could present uranium contents higher than those generally observed for these lithologies, were identified. Moreover, databases on mining provided information on the location of uranium and coal/lignite mines and thus indicated the location of particular uranium-rich rocks. The geological units, defined from their boundaries extracted from the geological map of France (1:1,000,000), were finally classified into 5 categories based on their mean uranium content. The map obtained provided useful data for establishing the geogenic radon map of France, but also for mapping countrywide exposure to terrestrial radiation and for the evaluation of background levels of natural radioactivity used for impact assessment of anthropogenic activities. Copyright © 2016 Elsevier Ltd. All rights reserved.

Redox behavior of uranium at the nanoporous aluminum oxide-water interface: implications for uranium remediation.

PubMed

Jung, Hun Bok; Boyanov, Maxim I; Konishi, Hiromi; Sun, Yubing; Mishra, Bhoopesh; Kemner, Kenneth M; Roden, Eric E; Xu, Huifang

2012-07-03

Sorption-desorption experiments show that the majority (ca. 80-90%) of U(VI) presorbed to mesoporous and nanoporous alumina could not be released by extended (2 week) extraction with 50 mM NaHCO(3) in contrast with non-nanoporous α alumina. The extent of reduction of U(VI) presorbed to aluminum oxides was semiquantitatively estimated by comparing the percentages of uranium desorbed by anoxic sodium bicarbonate between AH(2)DS-reacted and unreacted control samples. X-ray absorption spectroscopy confirmed that U(VI) presorbed to non-nanoporous alumina was rapidly and completely reduced to nanoparticulate uraninite by AH(2)DS, whereas reduction of U(VI) presorbed to nanoporous alumina was slow and incomplete (<5% reduction after 1 week). The observed nanopore size-dependent redox behavior of U has important implications in developing efficient remediation techniques for the subsurface uranium contamination because the efficiency of in situ bioremediation depends on how effectively and rapidly U(VI) bound to sediment or soil can be converted to an immobile phase.

Multiple recycle of REMIX fuel at VVER-1000 operation in closed fuel cycle

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alekseev, P. N.; Bobrov, E. A., E-mail: evgeniybobrov89@rambler.ru; Chibinyaev, A. V.

2015-12-15

The basic features of loading the VVER-1000 core with a new variant of REMIX fuel (REgenerated MIXture of U–Pu oxides) are considered during its multiple recycle in a closed nuclear fuel cycle. The fuel composition is produced on the basis of the uranium–plutonium regenerate extracted at processing the spent nuclear fuel (SNF) from a VVER-1000, depleted uranium, and the fissionable material: {sup 235}U as a part of highly enriched uranium (HEU) from warheads superfluous for defense purposes or {sup 233}U accumulated in thorium blankets of fusion (electronuclear) neutron sources or fast reactors. Production of such a fuel assumes no usemore » of natural uranium in addition. When converting a part of the VVER-1000 reactors to the closed fuel cycle based on the REMIX technology, the consumption of natural uranium decreases considerably, and there is no substantial degradation of the isotopic composition of plutonium or change in the reactor-safety characteristics at the passage from recycle to recycle.« less

Characterization and Testing of Amidoxime-Based Adsorbent Materials to Extract Uranium from Natural Seawater

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuo, Li-Jung; Janke, Christopher J.; Wood, Jordana R.

Extraction of uranium (U) from seawater for use as a nuclear fuel is a significant challenge due to the low concentration of U in seawater (~3.3 ppb) and difficulties to selectively extract U from the background of major and trace elements in seawater. The Pacific Northwest National Laboratory (PNNL)’s Marine Sciences Laboratory (MSL) has been serving as a marine test site for determining performance characteristics (adsorption capacity, adsorption kinetics, and selectivity) of novel amidoxime-based polymeric adsorbents developed at Oak Ridge National Laboratory (ORNL) under natural seawater exposure conditions. This manuscript describes the performance of three formulations (38H, AF1, AI8) ofmore » amidoxime-based polymeric adsorbents produced at ORNL in MSL’s ambient seawater testing facility. The adsorbents were produced in two forms, fibrous material (40-100 mg samples) and braided material (5-10 g samples), and exposed to natural seawater using flow-through columns and recirculating flumes. All three formulations demonstrated high 56 day uranium adsorption capacity (>3 g U/kg adsorbent). The AF1 formulation had the best uranium adsorption performance, with a 56 day capacity of 3.9 g U/ kg adsorbent, a saturation capacity of 5.4 g U/kg adsorbent, and ~25 days half-saturation time. The two exposure methods, flowthrough columns and flumes, were demonstrated to produce similar performance results, providing confidence that the test methods were reliable, that scaling up from 10’s of mg quantities of exposure in flow-through columns to gram quantities in flumes produced similar results, and confirm that the manufacturing process produces a homogeneous adsorbent. Adsorption kinetics appear to be element specific, with half-saturation times ranging from minutes for the major cations in seawater, to 8-10 weeks for V and Fe. Reducing the exposure time provides a potential pathway to improve the adsorption capacity of U by reducing the V/U ratio on the adsorbent.« less

Characterization and testing of amidoxime-based adsorbent materials to extract uranium from natural seawater

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuo, Li-Jung; Janke, Christopher James; Wood, Jordana

Extraction of uranium (U) from seawater for use as a nuclear fuel is a significant challenge due to the low concentration of U in seawater (~3.3 ppb) and difficulties to selectively extract U from the background of major and trace elements in seawater. The Pacific Northwest National Laboratory (PNNL) s Marine Sciences Laboratory (MSL) has been serving as a marine test site for determining performance characteristics (adsorption capacity, adsorption kinetics, and selectivity) of novel amidoxime-based polymeric adsorbents developed at Oak Ridge National Laboratory (ORNL) under natural seawater exposure conditions. This report describes the performance of three formulations (38H, AF1, AI8)more » of amidoxime-based polymeric adsorbent produced at ORNL in MSL s ambient seawater testing facility. The adsorbents were produced in two forms, fibrous material (40-100 mg samples) and braided material (5-10 g samples), exposed to natural seawater using flow-through columns and recirculating flumes. All three formulations demonstrated high 56 day uranium adsorption capacity (>3 gU/kg adsorbent). The AF1 formulation had the best uranium adsorption performance, with 56-day capacity of 3.9 g U/kg adsorbent, saturation capacity of 5.4 g U/kg adsorbent, and ~25 days half-saturation time. The two exposure methods, flow-through columns and flumes were demonstrated to produce similar performance results, providing confidence that the test methods were reliable, that scaling up from 10 s of mg quantities of exposure in flow-through columns to gram quantities in flumes produced similar results, and that the manufacturing process produces a homogenous adsorbent. Adsorption kinetics appear to be element specific, with half-saturation times ranging from minutes for the major cations in seawater to 8-10weeks for V and Fe. Reducing the exposure time provides a potential pathway to improve the adsorption capacity of U by reducing the V/U ratio on the adsorbent.« less

Characterization and testing of amidoxime-based adsorbent materials to extract uranium from natural seawater

DOE PAGES

Kuo, Li-Jung; Janke, Christopher James; Wood, Jordana; ...

2015-11-19

Extraction of uranium (U) from seawater for use as a nuclear fuel is a significant challenge due to the low concentration of U in seawater (~3.3 ppb) and difficulties to selectively extract U from the background of major and trace elements in seawater. The Pacific Northwest National Laboratory (PNNL) s Marine Sciences Laboratory (MSL) has been serving as a marine test site for determining performance characteristics (adsorption capacity, adsorption kinetics, and selectivity) of novel amidoxime-based polymeric adsorbents developed at Oak Ridge National Laboratory (ORNL) under natural seawater exposure conditions. This report describes the performance of three formulations (38H, AF1, AI8)more » of amidoxime-based polymeric adsorbent produced at ORNL in MSL s ambient seawater testing facility. The adsorbents were produced in two forms, fibrous material (40-100 mg samples) and braided material (5-10 g samples), exposed to natural seawater using flow-through columns and recirculating flumes. All three formulations demonstrated high 56 day uranium adsorption capacity (>3 gU/kg adsorbent). The AF1 formulation had the best uranium adsorption performance, with 56-day capacity of 3.9 g U/kg adsorbent, saturation capacity of 5.4 g U/kg adsorbent, and ~25 days half-saturation time. The two exposure methods, flow-through columns and flumes were demonstrated to produce similar performance results, providing confidence that the test methods were reliable, that scaling up from 10 s of mg quantities of exposure in flow-through columns to gram quantities in flumes produced similar results, and that the manufacturing process produces a homogenous adsorbent. Adsorption kinetics appear to be element specific, with half-saturation times ranging from minutes for the major cations in seawater to 8-10weeks for V and Fe. Reducing the exposure time provides a potential pathway to improve the adsorption capacity of U by reducing the V/U ratio on the adsorbent.« less

Metabolomics reveals dose effects of low-dose chronic exposure to uranium in rats: identification of candidate biomarkers in urine samples.

PubMed

Grison, Stéphane; Favé, Gaëlle; Maillot, Matthieu; Manens, Line; Delissen, Olivia; Blanchardon, Éric; Dublineau, Isabelle; Aigueperse, Jocelyne; Bohand, Sandra; Martin, Jean-Charles; Souidi, Maâmar

2016-01-01

Data are sparse about the potential health risks of chronic low-dose contamination of humans by uranium (natural or anthropogenic) in drinking water. Previous studies report some molecular imbalances but no clinical signs due to uranium intake. In a proof-of-principle study, we reported that metabolomics is an appropriate method for addressing this chronic low-dose exposure in a rat model (uranium dose: 40 mg L -1 ; duration: 9 months, n = 10). In the present study, our aim was to investigate the dose-effect pattern and identify additional potential biomarkers in urine samples. Compared to our previous protocol, we doubled the number of rats per group (n = 20), added additional sampling time points (3 and 6 months) and included several lower doses of natural uranium (doses used: 40, 1.5, 0.15 and 0.015 mg L -1 ). LC-MS metabolomics was performed on urine samples and statistical analyses were made with SIMCA-P+ and R packages. The data confirmed our previous results and showed that discrimination was both dose and time related. Uranium exposure was revealed in rats contaminated for 9 months at a dose as low as 0.15 mg L -1 . Eleven features, including the confidently identified N1-methylnicotinamide, N1-methyl-2-pyridone-5-carboxamide and 4-hydroxyphenylacetylglycine, discriminated control from contaminated rats with a specificity and a sensitivity ranging from 83 to 96 %, when combined into a composite score. These findings show promise for the elucidation of underlying radiotoxicologic mechanisms and the design of a diagnostic test to assess exposure in urine, in a dose range experimentally estimated to be above a threshold between 0.015 and 0.15 mg L -1 .

Cell metal interactions: A comparison of natural uranium to other common metals in renal cells and bone osteoblasts

NASA Astrophysics Data System (ADS)

Milgram, S.; Carrière, M.; Thiebault, C.; Berger, P.; Khodja, H.; Gouget, B.

2007-07-01

Uranium acute intoxication has been documented to induce nephrotoxicity. Kidneys are the main target organs after short term exposures to high concentrations of the toxic, while chronic exposures lead to its accumulation in the skeleton. In this paper, chemical toxicity of uranium is investigated for rat osteoblastic bone cells and compared to results previously obtained on renal cells. We show that bone cells are less sensitive to uranium than renal cells. The influence of the chemical form on U cytotoxicity is demonstrated. For both cell types, a comparison of uranium toxicity with other metals or metalloids toxicities (Mn, Ni, Co, Cu, Zn, Se and Cd) permits classification of Cd, Zn, Se IV and Cu as the most toxic and Ni, Se VI, Mn and U as the least toxic. Chemical toxicity of natural uranium proves to be far less than that of cadmium. To try to explain the differences in sensitivities observed between metals and different cell types, cellular accumulations in cell monolayers are quantified by inductively coupled plasma-mass spectroscopy (ICP-MS), function of time or function of dose: lethal doses which simulate acute intoxications and sub-lethal doses which are more realistic with regard to environmentally metals concentrations. In addition to being more resistant, bone cells accumulated much more uranium than did renal cells. Moreover, for both cell models, Mn, U-citrate and U-bicarbonate are strongly accumulated whereas Cu, Zn and Ni are weakly accumulated. On the other hand, a strong difference in Cd behaviour between the two cell types is shown: whereas Cd is very weakly accumulated in bone cells, it is very strongly accumulated in renal cells. Finally, elemental distribution of the toxics is determined on a cellular scale using nuclear microprobe analysis. For both renal and osteoblastic cells, uranium was accumulated in as intracellular precipitates similar to those observed previously by SEM/EDS.

Cancer incidence and nuclear facilities in Ukraine: a community-based study.

PubMed

Bazyka, D A; Prysyazhnyuk, A Ye; Romanenko, A Ye; Fedorenko, Z P; Gudzenko, N A; Fuzik, M M; Khukhrianska, O M; Trotsyuk, N K; Gulak, L O; Goroch, Ye L; Sumkina, Ye V

2012-07-01

The study goal was to investigate malignant tumors incidence in 5 Ukrainian cities with nuclear hazardous enterprises: extractive, processing enterprises of uranium ore (Zhovti Wody and Dniprodzerzhynsk of Dnipropetrovsk region) and nuclear power stations (Energodar of Zaporizhska region, Pivdennoukrainsk of Mykolayivska region, Netishyn of Khmelnytska region). average annual population of the cities under study in 2003-2008 was 439 600 persons. Total and specific cancer incidence was investigated. Site specific incidence was analyzed for malignancies proved to be radiosensitive in previous studies: trachea, bronchus and lung, breast, kidney, thyroid cancer and leukemia. Data on cancer cases were received in National Cancer Registry of Ukraine (National Cancer Institute). There was used the data of the State Statistics Committee of Ukraine on the size of the studied population by gender - age groups. Standardized incidence ratio of cancer at a whole and for each of five specific forms of malignancies were calculated for the population of each city and group of cities depending on the nature of industrial activity. During the observed period there were registered 9 381 cancer cases in inhabitants of Ukrainian cities with radiation hazardous facilities. There was stated that cancer incidence rate in population of 5 cities significantly exceeded national and regional levels. Among specific forms of malignancy there were observed excess of lung, trachea, bronchus, breast, kidney cancer and leukemia in population of extractive, processing uranium ore cities. No excess of thyroid cancer was identified. In cities with nuclear power station there were registered excess of kidney cancer. Results of the study suggest the necessity to explore the role of various factors in forming the identified cancer incidence features in the Ukrainian population living near the nuclear power facilities.

Utilizing hydrologic, statistical, and geochemical tools to assess uranium mobility in surface and near-surface environments

NASA Astrophysics Data System (ADS)

Naftz, D. L.; Walton-Day, K. E.; Fuller, C.; Dam, W. L.; Briggs, M. A.; Snyder, T.

2015-12-01

Legacy uranium (U) mining and processing activities have resulted in soil and water contamination on Federal, state, and tribal lands in the western United States. Sites include legacy mill sites associated with U extraction now managed by the Department of Energy and thousands of waste dumps associated with U exploration, mining, and processing. Recently (2012), over 400,000 hectares of federally managed land in northern Arizona was withdrawn from consideration of mining for a 20-year period to protect the Grand Canyon watershed from potentially adverse effects of U mineral exploration and development. Ore from active and recently active U mines in the Colorado Plateau, the Henry Mountains Complex, and the Arizona Strip is transported to the only currently (2015) active conventional mill site in the western United States, located in Utah. Previous and ongoing U.S. Geological Survey assessments to examine U mobility at a variety of legacy and active sites associated with ore exploration, extraction, and processing will be presented as field-scale examples. Topics associated with site investigations will include: (1) offsite migration of radionuclides associated with the operation of the White Mesa U mill; (2) long-term contaminant transport from legacy U waste dumps on Bureau of Land Management regulated land in Utah; (3) application of incremental soil sampling techniques to determine pre- and post-mining radionuclide levels associated with planned and operating U mines in northern Arizona; (4) application of fiber optic digital temperature sensing equipment to identify areas where shallow groundwater containing elevated U levels may be discharging to a river adjacent to a reclaimed mill site in central Wyoming; and (5) field-scale manipulation of groundwater chemistry to limit U migration from a legacy upgrader site in southeastern Utah.

FISSION PRODUCT REMOVAL FROM ORGANIC SOLUTIONS

DOEpatents

Moore, R.H.

1960-05-10

The decontamination of organic solvents from fission products and in particular the treatment of solvents that were used for the extraction of uranium and/or plutonium from aqueous acid solutions of neutron-irradiated uranium are treated. The process broadly comprises heating manganese carbonate in air to a temperature of between 300 and 500 deg C whereby manganese dioxide is formed; mixing the manganese dioxide with the fission product-containing organic solvent to be treated whereby the fission products are precipitated on the manganese dioxide; and separating the fission product-containing manganese dioxide from the solvent.

Uraniferous opal, Virgin Valley, Nevada: conditions of formation and implications for uranium exploration

USGS Publications Warehouse

Zielinski, R.A.

1982-01-01

Uraniferous, fluorescent opal, which occurs in tuffaceous sedimentary rocks at Virgin Valley, Nevada, records the temperature and composition of uranium-rich solutions as well as the time of uranium-silica coprecipitation. Results are integrated with previous geologic and geochronologic data for the area to produce a model for uranium mobility that may be used to explore for uranium deposits in similar geologic settings. Uraniferous opal occurs as replacements of diatomite, or silicic air-fall ash layers in tuffaceous lakebeds of the Virgin Valley Formation (Miocene) of Merriam (1907). Fission-track radiography shows uranium to be homogeneously dispersed throughout the opal structure, suggesting coprecipitation of dissolved uranium and silica gel. Fluid inclusions preserved within opal replacements of diatomite have homogenization temperatures in the epithermal range and are of low salinity. Four samples of opal from one locality all have U-Pb apparent ages which suggest uraniferous opal precipitation in late Pliocene time. These ages correspond to a period of local, normal faulting, and highangle faults may have served as vertical conduits for transport of deep, thermalized ground water to shallower levels. Lateral migration of rising solutions occurred at intersections of faults with permeable strata. Silica and some uranium were dissolved from silica-rich host strata of 5-20 ppm original uranium content and reprecipitated as the solutions cooled. The model predicts that in similar geologic settings, ore-grade concentrations of uranium will occur in permeable strata that intersect high-angle faults and that contain uranium source rocks as well as efficient reductant traps for uranium. In the absence of sufficient quantities of reductant materials, uranium will be flushed from the system or will accumulate in low-grade disseminated hosts such as uraniferous opal. ?? 1982.

Quantification of Kinetic Rate Law Parameters of Uranium Release from Sodium Autunite as a Function of Aqueous Bicarbonate Concentrations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gudavalli, Ravi; Katsenovich, Yelena; Wellman, Dawn M.

2013-09-05

ABSTRACT: Hydrogen carbonate is one of the most significant components within the uranium geochemical cycle. In aqueous solutions, hydrogen carbonate forms strong complexes with uranium. As such, aqueous bicarbonate may significantly increase the rate of uranium release from uranium minerals. Quantifying the relationship of aqueous hydrogen carbonate solutions to the rate of uranium release during dissolution is critical to understanding the long-term fate of uranium within the environment. Single-pass flow-through (SPTF) experiments were conducted to estimate the rate of uranium release from Na meta-autunite as a function of bicarbonate solutions (0.0005-0.003 M) under the pH range of 6-11 and temperaturesmore » of 5-60oC. Consistent with the results of previous investigation, the rate of uranium release from sodium autunite exhibited minimal dependency on temperature; but were strongly dependent on pH and increasing concentrations of bicarbonate solutions. Most notably at pH 7, the rate of uranium release exhibited 370 fold increases relative to the rate of uranium release in the absence of bicarbonate. However, the effect of increasing concentrations of bicarbonate solutions on the release of uranium was significantly less under higher pH conditions. It is postulated that at high pH values, surface sites are saturated with carbonate, thus the addition of more bicarbonate would have less effect on uranium release. Results indicate the activation energies were unaffected by temperature and bicarbonate concentration variations, but were strongly dependent on pH conditions. As pH increased from 6 to 11, activation energy values were observed to decrease from 29.94 kJ mol-1 to 13.07 kJ mol-1. The calculated activation energies suggest a surface controlled dissolution mechanism.« less

Effect of metal sulfide pulp density on gene expression of electron transporters in Acidithiobacillus sp. FJ2.

PubMed

Fatemi, Faezeh; Miri, Saba; Jahani, Samaneh

2017-05-01

In Acidithiobacillus ferrooxidans, one of the most important bioleaching bacterial species, the proteins encoded by the rus operon are involved in the electron transfer from Fe 2+ to O 2 . To obtain further knowledge about the mechanism(s) involved in the adaptive responses of the bacteria to growth on the different uranium ore pulp densities, we analyzed the expression of the four genes from the rus operon by real-time PCR, when Acidithiobacillus sp. FJ2 was grown in the presence of different uranium concentrations. The uranium bioleaching results showed the inhibitory effects of the metal pulp densities on the oxidation activity of the bacteria which can affect Eh, pH, Fe oxidation and uranium extractions. Gene expression analysis indicated that Acidithiobacillus sp. FJ2 tries to survive in the stress with increasing in the expression levels of cyc2, cyc1, rus and coxB, but the metal toxicity has a negative effect on the gene expression in different pulp densities. These results indicated that Acidithiobacillus sp. FJ2 could leach the uranium even in high pulp density (50%) by modulation in rus operon gene responses.

The social costs of uranium mining in the US Colorado Plateau cohort, 1960-2005.

PubMed

Jones, Benjamin A

2017-05-01

Long-term social costs associated with underground uranium mining are largely unknown. This study estimated health costs of Native American and white (Hispanic and non-Hispanic origin) uranium miners in the US Public Health Service Colorado Plateau cohort study. Elevated uranium miner person-years of life lost (PYLL) were calculated from the most recent study of the Colorado Plateau cohort over 1960-2005. Nine causes of death categories were included. Costs to society of miner PYLL were monetized using the value of a statistical life-year approach. Costs over 1960-2005 totaled $2 billion USD [95% CI: $1.8, $2.2], or $2.9 million per elevated miner death. This corresponds to $43.1 million [95%: $38.7, $48.7] in annual costs. Lung cancer was the most costly cause of death at $1.4 billion [95%: $1.3, $1.5]. Absolute health costs were largest for white miners, but Native Americans had larger costs per elevated death. Annual excess mortality over 1960-2005 averaged 366.4 per 100,000 miners; 404.6 (white) and 201.5 per 100,000 (Native American). This research advances our understanding of uranium extraction legacy impacts, particularly among indigenous populations.

Tc-99 Decontamination From Heat Treated Gaseous Diffusion Membrane -Phase I

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oji, L.; Wilmarth, B.; Restivo, M.

2017-03-13

Uranium gaseous diffusion cascades represent a significant environmental challenge to dismantle, containerize and dispose as low-level radioactive waste. Baseline technologies rely on manual manipulations involving direct access to technetium-contaminated piping and materials. There is a potential to utilize novel thermal decontamination technologies to remove the technetium and allow for on-site disposal of the very large uranium converters. Technetium entered these gaseous diffusion cascades as a hexafluoride complex in the same fashion as uranium. Technetium, as the isotope Tc-99, is an impurity that follows uranium in the first cycle of the Plutonium and Uranium Extraction (PUREX) process. The technetium speciation ormore » exact form in the gas diffusion cascades is not well defined. Several forms of Tc-99 compounds, mostly the fluorinated technetium compounds with varying degrees of volatility have been speculated by the scientific community to be present in these cascades. Therefore, there may be a possibility of using thermal desorption, which is independent of the technetium oxidation states, to perform an in situ removal of the technetium as a volatile species and trap the radionuclide on sorbent traps which could be disposed as low-level waste.« less

Development and Validation of Capabilities to Measure Thermal Properties of Layered Monolithic U-Mo Alloy Plate-Type Fuel

NASA Astrophysics Data System (ADS)

Burkes, Douglas E.; Casella, Andrew M.; Buck, Edgar C.; Casella, Amanda J.; Edwards, Matthew K.; MacFarlan, Paul J.; Pool, Karl N.; Smith, Frances N.; Steen, Franciska H.

2014-07-01

The uranium-molybdenum (U-Mo) alloy in a monolithic form has been proposed as one fuel design capable of converting some of the world's highest power research reactors from the use of high enriched uranium to low enriched uranium. One aspect of the fuel development and qualification process is to demonstrate appropriate understanding of the thermal-conductivity behavior of the fuel system as a function of temperature and expected irradiation conditions. The purpose of this paper is to verify functionality of equipment installed in hot cells for eventual measurements on irradiated uranium-molybdenum (U-Mo) monolithic fuel specimens, refine procedures to operate the equipment, and validate models to extract the desired thermal properties. The results presented here demonstrate the adequacy of the equipment, procedures, and models that have been developed for this purpose based on measurements conducted on surrogate depleted uranium-molybdenum (DU-Mo) alloy samples containing a Zr diffusion barrier and clad in aluminum alloy 6061 (AA6061). The results are in excellent agreement with thermal property data reported in the literature for similar U-Mo alloys as a function of temperature.

An alternative procedure for uranium analysis in drinking water using AQUALIX columns: application to varied French bottled waters.

PubMed

Bouvier-Capely, C; Bonthonneau, J P; Dadache, E; Rebière, F

2014-01-01

The general population is chronically exposed to uranium ((234)U, (235)U, and (238)U) and polonium ((210)Po) mainly through day-to-day food and beverage intake. The measurement of these naturally-occurring radionuclides in drinking water is important to assess their health impact. In this work the applicability of calix[6]arene-derivatives columns for uranium analysis in drinking water was investigated. A simple and effective method was proposed on a specific column called AQUALIX, for the separation and preconcentration of U from drinking water. This procedure is suitable for routine analysis and the analysis time is considerably shortened (around 4h) by combining the separation on AQUALIX with fast ICP-MS measurement. This new method was tested on different French bottled waters (still mineral water, sparkling mineral water, and spring water). Then, the case of simultaneous presence of uranium and polonium in water was considered due to interferences in alpha spectrometry measurement. A protocol was proposed using a first usual step of spontaneous deposition of polonium on silver disc in order to separate Po, followed by the uranium extraction on AQUALIX column before alpha spectrometry counting. © 2013 Published by Elsevier B.V.

Preconcentration and determination of rare-earth elements in iron-rich water samples by extraction chromatography and plasma source mass spectrometry (ICP-MS).

PubMed

Hernández González, Carolina; Cabezas, Alberto J Quejido; Díaz, Marta Fernández

2005-11-15

A 100-fold preconcentration procedure based on rare-earth elements (REEs) separation from water samples with an extraction chromatographic column has been developed. The separation of REEs from matrix elements (mainly Fe, alkaline and alkaline-earth elements) in water samples was performed loading the samples, previously acidified to pH 2.0 with HNO(3), in a 2ml column preconditioned with 20ml 0.01M HNO(3). Subsequently, REEs were quantitatively eluted with 20ml 7M HNO(3). This solution was evaporated to dryness and the final residue was dissolved in 10ml 2% HNO(3) containing 1mugl(-1) of cesium used as internal standard. The solution was directly analysed by inductively coupled plasma mass spectrometry (ICP-MS), using ultrasonic nebulization, obtaining quantification limits ranging from 0.05 to 0.10 ngl(-1). The proposed method has been applied to granitic waters running through fracture fillings coated by iron and manganese oxy-hydroxides in the area of the Ratones (Cáceres, Spain) old uranium mine.

SOLVENT EXTRACTION PROCESS FOR THE RECOVERY OF METALS FROM PHOSPHORIC ACID

DOEpatents

Bailes, R.H.; Long, R.S.

1958-11-01

> A solvent extraction process is presented for recovering metal values including uranium, thorium, and other lanthanide and actinide elements from crude industrial phosphoric acid solutions. The process conslsts of contacting said solution with an immisclble organic solvent extractant containing a diluent and a material selected from the group consisting of mono and di alkyl phosphates, alkyl phosphonates and alkyl phosphites. The uranlum enters the extractant phase and is subsequently recovered by any of the methods known to the art. Recovery is improved if the phosphate solution is treated with a reducing agent such as iron or aluminum powder prior to the extraction step.

Materials and Methods for Streamlined Laboratory Analysis of Environmental Samples, FY 2016 Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Addleman, Raymond S.; Naes, Benjamin E.; McNamara, Bruce K.

The International Atomic Energy Agency (IAEA) relies upon laboratory analysis of environmental samples (typically referred to as “swipes”) collected during on-site inspections of safeguarded facilities to support the detection and deterrence of undeclared activities. Unfortunately, chemical processing and assay of the samples is slow and expensive. A rapid, effective, and simple extraction process and analysis method is needed to provide certified results with improved timeliness at reduced costs (principally in the form of reduced labor), while maintaining or improving sensitivity and efficacy. To address these safeguard needs the Pacific Northwest National Laboratory (PNNL) explored and demonstrated improved methods for environmentalmore » sample (ES) analysis. Improvements for both bulk and particle analysis were explored. To facilitate continuity and adoption, the new sampling materials and processing methods will be compatible with existing IAEA protocols for ES analysis. PNNL collaborated with Oak Ridge National Laboratory (ORNL), which performed independent validation of the new bulk analysis methods and compared performance to traditional IAEA’s Network of Analytical Laboratories (NWAL) protocol. ORNL efforts are reported separately. This report describes PNNL’s FY 2016 progress, which was focused on analytical application supporting environmental monitoring of uranium enrichment plants and nuclear fuel processing. In the future the technology could be applied to other safeguard applications and analytes related to fuel manufacturing, reprocessing, etc. PNNL’s FY 2016 efforts were broken into two tasks and a summary of progress, accomplishments and highlights are provided below. Principal progress and accomplishments on Task 1, Optimize Materials and Methods for ICP-MS Environmental Sample Analysis, are listed below. • Completed initial procedure for rapid uranium extraction from ES swipes based upon carbonate-peroxide chemistry (delivered to ORNL for evaluation). • Explored improvements to carbonate-peroxide rapid uranium extraction chemistry. • Evaluated new sampling materials and methods (in collaboration with ORNL). • Demonstrated successful ES extractions from standard and novel swipes for a wide range uranium compounds of interest including UO 2F 2 and UO 2(NO 3) 2, U 3O 8 and uranium ore concentrate. • Completed initial discussions with commercial suppliers of PTFE swipe materials. • Submitted one manuscript for publication. Two additional drafts are being prepared. Principal progress and accomplishments on Task 2, Optimize Materials and Methods for Direct SIMS Environmental Sample Analysis, are listed below. • Designed a SIMS swipe sample holder that retrofits into existing equipment and provides simple, effective, and rapid mounting of ES samples for direct assay while enabling automation and laboratory integration. • Identified preferred conductive sampling materials with better performance characteristics. • Ran samples on the new PNNL NWAL equivalent Cameca 1280 SIMS system. • Obtained excellent agreement between isotopic ratios for certified materials and direct SIMS assay of very low levels of LEU and HEU UO 2F 2 particles on carbon fiber sampling material. Sample activities range from 1 to 500 CPM (uranium mass on sample is dependent upon specific isotope ratio but is frequently in the subnanogram range). • Found that the presence of the UF molecular ions, as measured by SIMS, provides chemical information about the particle that is separate from the uranium isotopics and strongly suggests that those particles originated from an UF6 enrichment activity. • Submitted one manuscript for publication. Another manuscript is in preparation.« less

Uptake and speciation of uranium in synthetic gypsum (CaSO4•2H2O): Applications to radioactive mine tailings.

PubMed

Lin, Jinru; Sun, Wei; Desmarais, Jacques; Chen, Ning; Feng, Renfei; Zhang, Patrick; Li, Dien; Lieu, Arthur; Tse, John S; Pan, Yuanming

2018-01-01

Phosphogypsum formed from the production of phosphoric acid represents by far the biggest accumulation of gypsum-rich wastes in the world and commonly contains elevated radionuclides, including uranium, as well as other heavy metals and metalloids. Therefore, billions-of-tons of phosphogypsum stockpiled worldwide not only possess serious environmental problems but also represent a potential uranium resource. Gypsum is also a major solid constituent in many other types of radioactive mine tailings, which stems from the common usage of sulfuric acid in extraction processes. Therefore, management and remediation of radioactive mine tailings as well as future beneficiation of uranium from phosphogysum all require detailed knowledge about the nature and behavior of uranium in gypsum. However, little is known about the uptake mechanism or speciation of uranium in gypsum. In this study, synthesis experiments suggest an apparent pH control on the uptake of uranium in gypsum at ambient conditions: increase in U from 16 μg/g at pH = 6.5 to 339 μg/g at pH = 9.5. Uranium L 3 -edge synchrotron X-ray absorption spectroscopic analyses of synthetic gypsum show that uranyl (UO 2 ) 2+ at the Ca site is the dominant species. The EXAFS fitting results also indicate that uranyl in synthetic gypsum occurs most likely as carbonate complexes and yields an average U-O distance ∼0.25 Å shorter than the average Ca-O distance, signifying a marked local structural distortion. Applications to phosphogypsum from the New Wales phosphoric acid plant (Florida, USA) and uranium mine tailings from the Key Lake mill (Saskatchewan, Canada) show that gypsum is an important carrier of uranium over a wide range of pH and controls the fate of this radionuclide in mine tailings. Also, development of new technologies for recovering U from phosphogypsum in the future must consider lattice-bound uranyl in gypsum. Copyright © 2017 Elsevier Ltd. All rights reserved.

Determination of (236)U and transuranium elements in depleted uranium ammunition by alpha-spectrometry and ICP-MS.

PubMed

Desideri, D; Meli, M A; Roselli, C; Testa, C; Boulyga, S F; Becker, J S

2002-11-01

It is well known that ammunition containing depleted uranium (DU) was used by NATO during the Balkan conflict. To evaluate the origin of DU (the enrichment of natural uranium or the reprocessing of spent nuclear fuel) it is necessary to directly detect the presence of activation products ((236)U, (239)Pu, (240)Pu, (241)Am, and (237)Np) in the ammunition. In this work the analysis of actinides by alpha-spectrometry was compared with that by inductively coupled plasma mass spectrometry (ICP-MS) after selective separation of ultratraces of transuranium elements from the uranium matrix. (242)Pu and (243)Am were added to calculate the chemical yield. Plutonium was separated from uranium by extraction chromatography, using tri- n-octylamine (TNOA), with a decontamination factor higher than 10(6); after elution plutonium was determined by ICP-MS ((239)Pu and (240)Pu) and alpha-spectrometry ((239+240)Pu) after electroplating. The concentration of Pu in two DU penetrator samples was 7 x 10(-12) g g(-1) and 2 x 10(-11) g g(-1). The (240)Pu/(239)Pu isotope ratio in one penetrator sample (0.12+/-0.04) was significantly lower than the (240)Pu/(239)Pu ratios found in two soil samples from Kosovo (0.35+/-0.10 and 0.27+/-0.07). (241)Am was separated by extraction chromatography, using di(2-ethylhexyl)phosphoric acid (HDEHP), with a decontamination factor as high as 10(7). The concentration of (241)Am in the penetrator samples was 2.7 x 10(-14) g g(-1) and <9.4 x 10(-15) g g(-1). In addition (237)Np was detected at ultratrace levels. In general, ICP-MS and alpha-spectrometry results were in good agreement. The presence of anthropogenic radionuclides ((236)U, (239)Pu,(240)Pu, (241)Am, and (237)Np) in the penetrators indicates that at least part of the uranium originated from the reprocessing of nuclear fuel. Because the concentrations of radionuclides are very low, their radiotoxicological effect is negligible.

Physico-Chemical Heterogeneity of Organic-Rich Sediments in the Rifle Aquifer, CO: Impact on Uranium Biogeochemistry.

PubMed

Janot, Noémie; Lezama Pacheco, Juan S; Pham, Don Q; O'Brien, Timothy M; Hausladen, Debra; Noël, Vincent; Lallier, Florent; Maher, Kate; Fendorf, Scott; Williams, Kenneth H; Long, Philip E; Bargar, John R

2016-01-05

The Rifle alluvial aquifer along the Colorado River in west central Colorado contains fine-grained, diffusion-limited sediment lenses that are substantially enriched in organic carbon and sulfides, as well as uranium, from previous milling operations. These naturally reduced zones (NRZs) coincide spatially with a persistent uranium groundwater plume. There is concern that uranium release from NRZs is contributing to plume persistence or will do so in the future. To better define the physical extent, heterogeneity and biogeochemistry of these NRZs, we investigated sediment cores from five neighboring wells. The main NRZ body exhibited uranium concentrations up to 100 mg/kg U as U(IV) and contains ca. 286 g of U in total. Uranium accumulated only in areas where organic carbon and reduced sulfur (as iron sulfides) were present, emphasizing the importance of sulfate-reducing conditions to uranium retention and the essential role of organic matter. NRZs further exhibited centimeter-scale variations in both redox status and particle size. Mackinawite, greigite, pyrite and sulfate coexist in the sediments, indicating that dynamic redox cycling occurs within NRZs and that their internal portions can be seasonally oxidized. We show that oxidative U(VI) release to the aquifer has the potential to sustain a groundwater contaminant plume for centuries. NRZs, known to exist in other uranium-contaminated aquifers, may be regionally important to uranium persistence.

Bidentate organophosphorus solvent extraction process for actinide recovery and partition

DOEpatents

Schulz, Wallace W.

1976-01-01

A liquid-liquid extraction process for the recovery and partitioning of actinide values from acidic nuclear waste aqueous solutions, the actinide values including trivalent, tetravalent and hexavalent oxidation states is provided and includes the steps of contacting the aqueous solution with a bidentate organophosphorous extractant to extract essentially all of the actinide values into the organic phase. Thereafter the respective actinide fractions are selectively partitioned into separate aqueous solutions by contact with dilute nitric or nitric-hydrofluoric acid solutions. The hexavalent uranium is finally removed from the organic phase by contact with a dilute sodium carbonate solution.

Study of Pulsed Columns with the System. Uranyl Nitrate-Nitric Acid-Water- Tributylphosphate; ETUDE DES COLONNES A PULSATIONS A L'AIDE DU SYSTEME NITRATE D'URANYLE-ACIDE NITRIQUEEAU-TRIBUTYLPHOSPHATE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Durandet, J.; Defives, D.; Choffe, B.

1959-10-31

The performsnce of a pulsed column with perforated plates was studied with the aid of a uranyl nitrate-nitric acid --water --tributyl phosphate system. The extraction of uranium from an aqueous acidic solution by an organic solvent and the extraction of uranium from organic solutions by water were the two cases investigated. The variation of the efficiency and the capacity of the pulsed column was determined as a function of the pulse amplitude and frequency, of the total flow rate, of the diameter of the holes, and of the choice of dispersed phase. The results showed that for a given amplitudemore » and total flow rate the efficiency has a maximum with an increase in frequency. (J.S.R.)« less

Reconnaissance for radioactive deposits in eastern Alaska, 1952

USGS Publications Warehouse

Nelson, Arthur Edward; West, Walter S.; Matzko, John J.

1954-01-01

Reconnaissance for radioactive deposits was conducted in selected areas of eastern Alaska during 1952. Examination of copper, silver, and molybdenum occurrences and of a reported nickel prospect in the Slana-Nabesna and Chisana districts in the eastern Alaska Range revealed a maximum radioactivity of about 0.003 percent equivalent uranium. No appreciable radioactivity anomolies were indicated by aerial and foot traverses in the area. Reconnaissance for possible lode concentrations of uranium minerals in the vicinity of reported fluoride occurrences in the Hope Creek and Miller House-Circle Hot Springs areas of the Circle quadrangle and in the Fortymile district found a maximum of 0.055 percent equivalent uranium in a float fragment of ferruginous breccia in the Hope Creek area; analysis of samples obtained in the vicinity of the other fluoride occurrences showed a maximum of only 0.005 percent equivalent uranium. No uraniferous loads were discovered in the Koyukuk-Chandalar region, nor was the source of the monazite, previously reported in the placer concentrates from the Chandalar mining district, located. The source of the uranotheorianite in the placers at Gold Bench on the South Fork of the Koyukuk River was not found during a brief reconaissance, but a placer concentrate was obtained that contains 0.18 percent equivalent uranium. This concentrate is about ten times more radioactive than concentrates previously available from the area.

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

PubMed

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 limiting the mobility of uranium in the presence of dissolved and/or solid-phase oxidants. The results of this field study confirmed those of previous laboratory studies which suggested that reoxidation of uranium under nitrate-reducing conditions can be substantially limited by preferential oxidation of reduced sulfur-bearing species. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

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

DOE PAGES

Paradis, Charles J.; Jagadamma, Sindhu; Watson, David B.; ...

2016-02-11

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. Here 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)more » 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 limiting the mobility of uranium in the presence of dissolved and/or solid-phase oxidants. Lastly, the results of this field study confirmed those of previous laboratory studies which suggested that reoxidation of uranium under nitrate-reducing conditions can be substantially limited by preferential oxidation of reduced sulfur-bearing species.« less

Quantification of kinetic rate law parameters for the dissolution of natural autunite in the presence of aqueous bicarbonate ions at high concentrations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gudavalli, Ravi; Katsenovich, Yelena; Wellman, Dawn

Uranium is a key contaminant of concern in the groundwater at 91 waste sites at 18 U.S. Department of Energy (DOE) facilities within the United States and is a potential source of groundwater contamination and a risk to human health and the environment through discharges to surface water. Dissolved inorganic carbon (bicarbonate/carbonate) has a high affinity for complexing with uranium that is present as sorbed or unique uranium-bearing mineral phases within the sedimentary matrix. This process can result in the formation of soluble uranyl carbonate aqueous species, which are mobile under circumneutral pH conditions. This study was conducted to quantifymore » the rate of release of uranium from the autunite mineral, (Ca[(UO 2)(PO 4)] 2∙3H 2O), that was formed during polyphosphate injection to remediate uranium; the dissolution of uranium was studied as a function of the aqueous bicarbonate concentration, ranging from 25 to 100 mM. Experiments were carried out in the pH range from 7 to 11 in the temperature range of 23-90°C via single-pass flow-through testing. Consistent with the results of previous studies (Gudavalli et al., 2013 a, b), the rate of uranium release from autunite exhibited minimal dependency on temperature, but was strongly dependent on pH and increasing concentrations of bicarbonate in the solution. Data obtained during these experiments were compared with results of previous experiments conducted using a low-concentration range of bicarbonate solutions (0.5-3.0 mM). An 8- to 30 fold increase in the rate of uranium release was observed in the presence of high bicarbonate concentrations at pH 7-8 compared to low bicarbonate values, while at pH 9-11, there was only a 5-fold increase in uranium rate of release with an increase in bicarbonate concentrations. The rate of uranium release was calculated to be between 5.18 x 10 -8 and 1.69 x 10 -7 mol m -2 s -1. The activation energy values at high and low bicarbonate concentrations were similar, with ratio values in the range of 0.6-1.0.« less

Quantification of kinetic rate law parameters for the dissolution of natural autunite in the presence of aqueous bicarbonate ions at high concentrations.

PubMed

Gudavalli, Ravi; Katsenovich, Yelena; Wellman, Dawn

2018-05-02

Uranium is a key contaminant of concern in the groundwater at U.S. Department of Energy (DOE) facilities within the United States and is a potential source of groundwater contamination and a risk to human health and the environment through discharges to surface water. Dissolved inorganic carbon (bicarbonate/carbonate) has a high affinity for complexing with uranium that is present as sorbed or unique uranium-bearing mineral phases within the sedimentary matrix. This process can result in the formation of soluble uranyl carbonate aqueous species, which are mobile under circumneutral pH conditions. This study was conducted to quantify the rate of release of uranium from the autunite mineral, (Ca[(UO 2 )(PO 4 )] 2 •3H 2 O), that was formed during polyphosphate injection to remediate uranium; the dissolution of uranium was studied as a function of the aqueous bicarbonate concentration, ranging from 25 to 100 mM. Experiments were carried out in the pH range from 7 to 11 in the temperature range of 23-90 °C via single-pass flow-through testing. Consistent with the results of previous studies (Gudavalli et al., 2013a, 2013b), the rate of uranium release from autunite exhibited minimal dependency on temperature, but was strongly dependent on pH and increasing concentrations of bicarbonate in the solution. Data obtained during these experiments were compared with results of previous experiments conducted using a low-concentration range of bicarbonate solutions (0.5-3.0 mM). An 8- to 30-fold increase in the rate of uranium release was observed in the presence of high bicarbonate concentrations at pH 7-8 compared to low bicarbonate values, while at pH 9-11, there was only a 5-fold increase in uranium rate of release with an increase in bicarbonate concentrations. The rate of uranium release was calculated to be between 5.18 × 10 -8 and 1.69 × 10 -7  mol m -2 s -1 . The activation energy values at high and low bicarbonate concentrations were similar, with ratio values in the range of 0.6-1.0. Copyright © 2018 Elsevier Ltd. All rights reserved.

Meta-analysis of depleted uranium levels in the Balkan region.

PubMed

Besic, Larisa; Muhovic, Imer; Asic, Adna; Kurtovic-Kozaric, Amina

2017-06-01

In recent years, contradicting data has been published on the connection between the presence of depleted uranium and an increased cancer incidence among military personnel deployed in the Balkans during the 1992-1999 wars. This has led to numerous research articles investigating possible depleted uranium contamination of the afflicted regions of the Balkan Peninsula, namely Bosnia & Herzegovina, Serbia, Kosovo and Montenegro. The aim of this study was to collect data from previously published reports investigating the levels of depleted uranium in the Balkans and to present the data in the form of a meta-analysis. This would provide a clear image of the extent of depleted uranium contamination after the Balkan conflict. In addition, we tested the hypothesis that there is a correlation between the levels of depleted uranium and the assumed depleted uranium-related health effects. Our results suggest that the majority of the examined sites contain natural uranium, while the area of Kosovo appears to be most heavily afflicted by depleted uranium pollution, followed by Bosnia & Herzegovina. Furthermore, the results indicate that it is not possible to make a valid correlation between the health effects and depleted uranium-contaminated areas. We therefore suggest a structured collaborative plan of action where long-term monitoring of the residents of depleted uranium-afflicted areas would be performed. In conclusion, while the possibility of depleted uranium toxicity in post-conflict regions appears to exist, there currently exists no definitive proof of such effects, due to insufficient studies of potentially afflicted populations, in addition to the lack of a common epidemiological approach in the reviewed literature. Copyright © 2017 Elsevier Ltd. All rights reserved.

Selectivity in Ligand Binding to Uranyl Compounds: A Synthetic, Structural, Thermodynamic and Computational Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arnold, John

The uranyl cation (UO 2 2+) is the most abundant form of uranium on the planet. It is estimated that 4.5 billion tons of uranium in this form exist in sea water. The ability to bind and extract the uranyl cation from aqueous solution while separating it from other elements would provide a limitless source of nuclear fuel. A large body of research concerns the selective recognition and extraction of uranyl. A stable molecule, the cation has a linear O=U=O geometry. The short U-O bonds (1.78 Å) arise from the combination of uranium 5f/6d and oxygen 2p orbitals. Due tomore » the oxygen moieties being multiply bonded, these sites were not thought to be basic enough for Lewis acidic coordination to be a viable approach to sequestration. We believe that the goal of developing a practical system for uranium separation from seawater will not be attained without new insights into our existing fundamental knowledge of actinide chemistry. We posit that detailed studies of the kinetic and thermodynamic factors that influence interactions between f-elements and ligands with a range of donor atoms is essential to any major advance in this important area. The goal of this research is thus to broaden the coordination chemistry of the uranyl ion by studying new ligand systems via synthetic, structural, thermodynamic and computational methods. We anticipate that this fundamental science will find use beyond actinide separation technologies in areas such as nuclear waste remediation and nuclear materials.« less

Geochemical investigations by the U.S. Geological Survey on uranium mining, milling, and environmental restoration

USGS Publications Warehouse

Landa, Edward R.; Cravotta, Charles A.; Naftz, David L.; Verplanck, Philip L.; Nordstrom, D. Kirk; Zielinski, Robert A.

2000-01-01

Recent research by the U.S. Geological Survey has characterized contaminant sources and identified important geochemical processes that influence transport of radionuclides from uranium mining and milling wastes. 1) Selective extraction studies indicated that alkaline earth sulfates and hydrous ferric oxides are important hosts of 226Ra in uranium mill tailings. The action of sulfate-reducing and ironreducing bacteria on these phases was shown to enhance release of radium, and this adverse result may temper decisions to dispose of uranium mill tailings in anaerobic environments. 2) Field studies have shown that although surface-applied sewage sludge/wood chip amendments aid in revegetating pyritic spoil, the nitrogen in sludge leachate can enhance pyrite oxidation, acidification of groundwater, and the consequent mobilization of metals and radionuclides. 3) In a U.S. Environmental Protection Agencyfunded study, three permeable reactive barriers consisting of phosphate-rich material, zero-valent iron, or amorphous ferric oxyhydroxide have been installed at an abandoned uranium upgrader facility near Fry Canyon, UT. Preliminary results indicate that each of the permeable reactive barriers is removing the majority of the uranium from the groundwater. 4) Studies on the geochemistry of rare earth elements as analogues for actinides such as uranium and thorium in acid mine drainage environments indicate high mobility under acid-weathering conditions but measurable attenuation associated with iron and aluminum colloid formation. Mass balances from field and laboratory studies are being used to quantify the amount of attenuation. 5) A field study in Colorado demonstrated the use of 234U/238U isotopic ratio measurements to evaluate contamination of shallow groundwater with uranium mill effluent.

RECONNAISSANCE FOR URANIUM IN ASPHALT-BEARING ROCKS IN THE WESTERN UNITED STATES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hail, W.J. Jr.

1957-01-01

An appraisal of asphait-bearing rocks as potential sources of uranium was made during 1953 and 1954 in 45 areas in Calif., Utah, Wyo., Mont., N. Mex., Tex., Okla., and Mo. A total of 202 samples from these areas was analyzed for uranium. The oldest rocks sampled are Ordovician in age, and the youngest are Recent. Although none of the deposits are of value at this time as a source of U, some of the deposits may constitute a low-grade U resource, but recovery of the U will depend upon the primary use of the asphalt. Significant amounts of U lnmore » the ash of oil extracted from these rocks were found in samples from 7 of the 45 areas examined. These areas are Chalome Creek, McKittrick, Edna, and Los Alamos Calif.; Vernal, Utah; Sulphur, Okla.; and Ellis, Mo. The average U content in the ash of the extracted oil of samples from these 7 areas ranges from 0.028 to 0.376%. All except the Chalone Creek area contain large estimated reserves of asphalt-bearing rock, ranging from 15 million to almost 2 billion tons. The average U content of samples from 13 additiomal areas ranges from 0.020 to 0.06B% in the ash of the extracted oil. Many of these areas contain very large reserves of asphalt-bearing rocks. It is believed that most of the asphalt deposits are oil residues, and that the U was introduced during or after the late stages of oil movement and loss of the lighter oil fractions. (auth)« less

The discovery and character of Pleistocene calcrete uranium deposits in the Southern High Plains of west Texas, United States

USGS Publications Warehouse

Van Gosen, Bradley S.; Hall, Susan M.

2017-12-18

This report describes the discovery and geology of two near-surface uranium deposits within calcareous lacustrine strata of Pleistocene age in west Texas, United States. Calcrete uranium deposits have not been previously reported in the United States. The west Texas uranium deposits share characteristics with some calcrete uranium deposits in Western Australia—uranium-vanadium minerals hosted by nonpedogenic calcretes deposited in saline lacustrine environments.In the mid-1970s, Kerr-McGee Corporation conducted a regional uranium exploration program in the Southern High Plains province of the United States, which led to the discovery of two shallow uranium deposits (that were not publicly reported). With extensive drilling, Kerr-McGee delineated one deposit of about 2.1 million metric tons of ore with an average grade of 0.037 percent U3O8 and another deposit of about 0.93 million metric tons of ore averaging 0.047 percent U3O8.The west-Texas calcrete uranium-vanadium deposits occur in calcareous, fine-grained sediments interpreted to be deposited in saline lakes formed during dry interglacial periods of the Pleistocene. The lakes were associated with drainages upstream of a large Pleistocene lake. Age determinations of tephra in strata adjacent to one deposit indicate the host strata is middle Pleistocene in age.Examination of the uranium-vanadium mineralization by scanning-electron microscopy indicated at least two generations of uranium-vanadium deposition in the lacustrine strata identified as carnotite and a strontium-uranium-vanadium mineral. Preliminary uranium-series results indicate a two-component system in the host calcrete, with early lacustrine carbonate that was deposited (or recrystallized) about 190 kilo-annum, followed much later by carnotite-rich crusts and strontium-uranium-vanadium mineralization in the Holocene (about 5 kilo-annum). Differences in initial 234U/238U activity ratios indicate two separate, distinct fluid sources.

Organic tissues, graphite, and hydrocarbons in host rocks of the Rum Jungle Uranium Field, northern Australia

USGS Publications Warehouse

Foster, C.B.; Robbins, E.I.; Bone, Y.

1990-01-01

The Rum Jungle Uranium field consists of at least six early Proterozoic deposits that have been mined either for uranium and/or the associated base and precious metals. Organic matter in the host rocks of the Whites Formation and Coomalie Dolomite is now predominantly graphite, consistent with the metamorphic history of these rocks. For nine samples, the mean total organic carbon content is high (3.9 wt%) and ranged from 0.33 to 10.44 wt%. Palynological extracts from the host rocks include black, filamentous, stellate (Eoastrion-like), and spherical morphotypes, which are typical of early Proterozoic microbiota. The colour, abundance, and shapes of these morphotypes reflect the thermal history, organic richness, and probable lacustrine biofacies of the host rocks. Routine analysis of rock thin sections and of palynological residues shows that mineral grains in some of the host rocks are coated with graphitized organic matter. The grain coating is presumed to result from ultimate thermal degradation of a petroleum phase that existed prior to metamorphism. Hydrocarbons are, however, still present in fluid inclusions within carbonates of the Coomalie Dolomite and lower Whites Formation. The fluid inclusions fluoresce dull orange in blue-light excitation and their hydrocarbon content is confirmed by gas chromatography of whole-rock extracts. Preliminary analysis of the oil suggests that it is migrated, and because it has escaped graphitization through metamorphism it is probably not of early Proterozoic age. The presence of live oil is consistent with fluid inclusion data that suggest subsequent, low-temperature brine migration through the rocks. The present observations support earlier suggestions that organic matter in the host formations trapped uranium to form protore. Subsequent fluid migrations probably brought additional uranium and other metals to these formations, and the organic matter provided a reducing environment for entrapment. ?? 1990.

Uranium distribution and 'excessive' U-He ages in iron meteoritic troilite

NASA Technical Reports Server (NTRS)

Fisher, D. E.

1985-01-01

Fission tracking techniques were used to measure the uranium distribution in meteoritic troilite and graphite. The obtained fission tracking data showed a heterogeneous distribution of tracks with a significant portion of track density present in the form of uranium clusters at least 10 microns in size. The matrix containing the clusters was also heterogeneous in composition with U concentrations of about 0.2-4.7 ppb. U/He ages could not be estimated on the basis of the heterogeneous U distributions, so previously reported estimates of U/He ages in the presolar range are probably invalid.

Grants Mining District

EPA Pesticide Factsheets

The Grants Mineral Belt was the focus of uranium extraction and production activities from the 1950s until the late 1990s. EPA is working with state, local, and federal partners to assess and address health risks and environmental effects of the mines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Parker, B. F.; Hohloch, S.; Pankhurst, J. R.

Vanadium is the main competitor for uranium extraction from seawater, and V( iv ) comprises a minor but important portion of this. V( iv ) undergoes redox reactions with oximes and amidoxime ligands under seawater-relevant conditions, leading to V( v ) complexes and loss of oxime functional groups.

Design of extraction system in BRing at HIAF

NASA Astrophysics Data System (ADS)

Ruan, Shuang; Yang, Jiancheng; Zhang, Jinquan; Shen, Guodong; Ren, Hang; Liu, Jie; Shangguan, Jingbing; Zhang, Xiaoying; Zhang, Jingjing; Mao, Lijun; Sheng, Lina; Yin, Dayu; Wang, Geng; Wu, Bo; Yao, Liping; Tang, Meitang; Cai, Fucheng; Chen, Xiaoqiang

2018-06-01

The Booster Ring (BRing), which is the key part of HIAF (High Intensity heavy ion Accelerator Facility) complex at IMP (Institute of Modern Physics, Chinese Academy of Sciences), can provide uranium (A / q = 7) beam with a wide extraction energy range of 200-800 MeV/u. To fulfill a flexible beam extraction for multi-purpose experiments, both fast and slow extraction systems will be accommodated in the BRing. The fast extraction system is used for extracting short bunched beam horizontally in single-turn. The slow extraction system is used to provide quasi-continuous beam by the third order resonance and RF-knockout scheme. To achieve a compact structure, the two extraction systems are designed to share the same extraction channel. The general design of the fast and slow extraction systems and simulation results are discussed in this paper.

Carbothermic synthesis of 820 μm uranium nitride kernels: Literature review, thermodynamics, analysis, and related experiments

NASA Astrophysics Data System (ADS)

Lindemer, T. B.; Voit, S. L.; Silva, C. M.; Besmann, T. M.; Hunt, R. D.

2014-05-01

The US Department of Energy is developing a new nuclear fuel that would be less susceptible to ruptures during a loss-of-coolant accident. The fuel would consist of tristructural isotropic coated particles with uranium nitride (UN) kernels with diameters near 825 μm. This effort explores factors involved in the conversion of uranium oxide-carbon microspheres into UN kernels. An analysis of previous studies with sufficient experimental details is provided. Thermodynamic calculations were made to predict pressures of carbon monoxide and other relevant gases for several reactions that can be involved in the conversion of uranium oxides and carbides into UN. Uranium oxide-carbon microspheres were heated in a microbalance with an attached mass spectrometer to determine details of calcining and carbothermic conversion in argon, nitrogen, and vacuum. A model was derived from experiments on the vacuum conversion to uranium oxide-carbide kernels. UN-containing kernels were fabricated using this vacuum conversion as part of the overall process. Carbonitride kernels of ∼89% of theoretical density were produced along with several observations concerning the different stages of the process.

Determination of depleted uranium, pyridostigmine bromide and its metabolite in plasma and urine following combined administration in rats.

PubMed

Abu-Qare, A W; Abou-Donia, M B

2001-09-01

A simple and reliable method was developed for the quantification of depleted uranium, the anti nerve agent drug pyridostigmine bromide (PB;3-dimethylaminocarbonyloxy-N-methyl pyridinium bromide) and its metabolite N-methyl-3-hydroxypyridinium bromide in rat plasma and urine. The method involved using solid phase extraction and spectrophotometric determination of uranium, and high performance liquid chromatography (HPLC) with reversed phase C(18) column, and UV detection at 280 nm for PB and its metabolite. Uranium was derivatized using dibenzoylmethane (DBM) then the absorbance was measured at 405 nm. PB and its metabolite were separated using a gradient of 1--40% acetonitrile in 0.1% triflouroacetic acid water solution (pH 3.2) at a flow rate of 0.8 ml/min in a period of 14 min. Limits of detection were 2 ng/ml for uranium and 50 ng/ml for PB and its metabolite. Limits of quantitation were between 10 and 100 ng/ml for uranium and the other two analytes, respectively. Average percentage recovery of five spiked plasma samples were 83.7+/-8.6, 76.8+/-6.7, 79.1+/-7.1, and from urine 82.7+/-8.6, 79.3+/-9.5 and 78.0+/-6.2, for depleted uranium, PB and N-methyl-3-hydroxypyridinium bromide, respectively. The relationship between peak areas and concentration was linear for standards between 100 and 1000 ng/ml for all three analytes. This method was applied to analyze the above chemicals and metabolites following combined administration in rats.

High pressure elasticity and thermal properties of depleted uranium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jacobsen, M. K., E-mail: mjacobsen@lanl.gov; Velisavljevic, N., E-mail: nenad@lanl.gov

2016-04-28

Studies of the phase diagram of uranium have revealed a wealth of high pressure and temperature phases. Under ambient conditions the crystal structure is well defined up to 100 gigapascals (GPa), but very little information on thermal conduction or elasticity is available over this same range. This work has applied ultrasonic interferometry to determine the elasticity, mechanical, and thermal properties of depleted uranium to 4.5 GPa. Results show general strengthening with applied load, including an overall increase in acoustic thermal conductivity. Further implications are discussed within. This work presents the first high pressure studies of the elasticity and thermal properties ofmore » depleted uranium metal and the first real-world application of a previously developed containment system for making such measurements.« less

Investigation of sulphur isotope variation due to different processes applied during uranium ore concentrate production.

PubMed

Krajkó, Judit; Varga, Zsolt; Wallenius, Maria; Mayer, Klaus; Konings, Rudy

The applicability and limitations of sulphur isotope ratio as a nuclear forensic signature have been studied. The typically applied leaching methods in uranium mining processes were simulated for five uranium ore samples and the n ( 34 S)/ n ( 32 S) ratios were measured. The sulphur isotope ratio variation during uranium ore concentrate (UOC) production was also followed using two real-life sample sets obtained from industrial UOC production facilities. Once the major source of sulphur is revealed, its appropriate application for origin assessment can be established. Our results confirm the previous assumption that process reagents have a significant effect on the n ( 34 S)/ n ( 32 S) ratio, thus the sulphur isotope ratio is in most cases a process-related signature.

High pressure elasticity and thermal properties of depleted uranium

DOE PAGES

Jacobsen, M. K.; Velisavljevic, N.

2016-04-28

Studies of the phase diagram of uranium have revealed a wealth of high pressure and temperature phases. Under ambient conditions the crystal structure is well defined up to 100 gigapascals (GPa), but very little information on thermal conduction or elasticity is available over this same range. This work has applied ultrasonic interferometry to determine the elasticity, mechanical, and thermal properties of depleted uranium to 4.5 GPa. Results show general strengthening with applied load, including an overall increase in acoustic thermal conductivity. Further implications are discussed within. Lastly, this work presents the first high pressure studies of the elasticity and thermalmore » properties of depleted uranium metal and the first real-world application of a previously developed containment system for making such measurements.« less

Removing oxygen from a solvent extractant in an uranium recovery process

DOEpatents

Hurst, Fred J.; Brown, Gilbert M.; Posey, Franz A.

1984-01-01

An improvement in effecting uranium recovery from phosphoric acid solutions is provided by sparging dissolved oxygen contained in solutions and solvents used in a reductive stripping stage with an effective volume of a nonoxidizing gas before the introduction of the solutions and solvents into the stage. Effective volumes of nonoxidizing gases, selected from the group consisting of argon, carbon dioxide, carbon monoxide, helium, hydrogen, nitrogen, sulfur dioxide, and mixtures thereof, displace oxygen from the solutions and solvents thereby reduce deleterious effects of oxygen such as excessive consumption of elemental or ferrous and accumulation of complex iron phosphates or cruds.

Recovery of Uranium from Seawater: Modified Polyacrylonitrile Fibers as Selective Extractants

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alexandratos, Spiro D.

2017-03-15

A new bifunctional fiber has been prepared and found to have a significant loading capacity of uranium from real seawater. The fiber support is polyacrylonitrile and bifunctionality is provided by amidoxime and either diethylenetriamine (DETA) or ethylenediamine (EDA) ligands. The key feature is adjusting the hydrophilic /lipophilic balance within the fiber and this was best accomplished by partially acetylating or carboxylating EDA ligands. The bifunctional carboxylated EDA /AO fiber had a loading capacity of 3.83 mg U/g fiber at the Pacific Northwest National Laboratory with a 21 day contact time in real seawater.

Analysis of Tank 38H (HTF-38-17-52, -53) and Tank 43H (HTF-43-17-54, -55) Samples for Support of the Enrichment Control and Corrosion Control Programs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hay, M.; Coleman, C.; Diprete, D.

SRNL analyzed samples from Tank 38H and Tank 43H to support ECP and CCP. The total uranium in the Tank 38H surface sample was 41.3 mg/L while the sub-surface sample was 43.5 mg/L. The Tank 43H samples contained total uranium concentrations of 28.5 mg/L in the surface sample and 28.1 mg/L in the sub-surface sample. The U-235 percentage ranged from 0.62% to 0.63% for the Tank 38H samples and Tank 43H samples. The total uranium and percent U-235 results in the table appear slightly lower than recent Tank 38H and Tank 43H uranium measurements. The plutonium results in the tablemore » show a large difference between the surface and sub-surface sample concentrations for Tank 38H. The Tank 43H plutonium results closely match the range of values measured on previous samples. The Cs-137 results for the Tank 38H surface and sub-surface samples show similar concentrations slightly higher than the concentrations measured in recent samples. The Cs-137 results for the two Tank 43H samples also show similar concentrations within the range of values measured on previous samples. The four samples show silicon concentrations somewhat lower than the previous samples with values ranging from 124 to 168 mg/L.« less

Extracellular reduction of uranium via Geobacter conductive pili as a protective cellular mechanism.

PubMed

Cologgi, Dena L; Lampa-Pastirk, Sanela; Speers, Allison M; Kelly, Shelly D; Reguera, Gemma

2011-09-13

The in situ stimulation of Fe(III) oxide reduction by Geobacter bacteria leads to the concomitant precipitation of hexavalent uranium [U(VI)] from groundwater. Despite its promise for the bioremediation of uranium contaminants, the biological mechanism behind this reaction remains elusive. Because Fe(III) oxide reduction requires the expression of Geobacter's conductive pili, we evaluated their contribution to uranium reduction in Geobacter sulfurreducens grown under pili-inducing or noninducing conditions. A pilin-deficient mutant and a genetically complemented strain with reduced outer membrane c-cytochrome content were used as controls. Pili expression significantly enhanced the rate and extent of uranium immobilization per cell and prevented periplasmic mineralization. As a result, pili expression also preserved the vital respiratory activities of the cell envelope and the cell's viability. Uranium preferentially precipitated along the pili and, to a lesser extent, on outer membrane redox-active foci. In contrast, the pilus-defective strains had different degrees of periplasmic mineralization matching well with their outer membrane c-cytochrome content. X-ray absorption spectroscopy analyses demonstrated the extracellular reduction of U(VI) by the pili to mononuclear tetravalent uranium U(IV) complexed by carbon-containing ligands, consistent with a biological reduction. In contrast, the U(IV) in the pilin-deficient mutant cells also required an additional phosphorous ligand, in agreement with the predominantly periplasmic mineralization of uranium observed in this strain. These findings demonstrate a previously unrecognized role for Geobacter conductive pili in the extracellular reduction of uranium, and highlight its essential function as a catalytic and protective cellular mechanism that is of interest for the bioremediation of uranium-contaminated groundwater.

Feasibility Study on the Use of On-line Multivariate Statistical Process Control for Safeguards Applications in Natural Uranium Conversion Plants

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ladd-Lively, Jennifer L

2014-01-01

The objective of this work was to determine the feasibility of using on-line multivariate statistical process control (MSPC) for safeguards applications in natural uranium conversion plants. Multivariate statistical process control is commonly used throughout industry for the detection of faults. For safeguards applications in uranium conversion plants, faults could include the diversion of intermediate products such as uranium dioxide, uranium tetrafluoride, and uranium hexafluoride. This study was limited to a 100 metric ton of uranium (MTU) per year natural uranium conversion plant (NUCP) using the wet solvent extraction method for the purification of uranium ore concentrate. A key component inmore » the multivariate statistical methodology is the Principal Component Analysis (PCA) approach for the analysis of data, development of the base case model, and evaluation of future operations. The PCA approach was implemented through the use of singular value decomposition of the data matrix where the data matrix represents normal operation of the plant. Component mole balances were used to model each of the process units in the NUCP. However, this approach could be applied to any data set. The monitoring framework developed in this research could be used to determine whether or not a diversion of material has occurred at an NUCP as part of an International Atomic Energy Agency (IAEA) safeguards system. This approach can be used to identify the key monitoring locations, as well as locations where monitoring is unimportant. Detection limits at the key monitoring locations can also be established using this technique. Several faulty scenarios were developed to test the monitoring framework after the base case or normal operating conditions of the PCA model were established. In all of the scenarios, the monitoring framework was able to detect the fault. Overall this study was successful at meeting the stated objective.« less

Selective recovery of uranium from Ca-Mg uranates by chlorination

NASA Astrophysics Data System (ADS)

Pomiro, Federico J.; Gaviría, Juan P.; Quinteros, Raúl D.; Bohé, Ana E.

2017-07-01

A chlorination process is proposed for the uranium extraction and separation using Calciumsbnd Magnesium uranates such as starting reactants which were obtained by precipitation from uranyl nitrate solutions with calcium hydroxide. The study is based on thermodynamic and reaction analysis using chlorine gas as chlorination agent. The results showed that the chlorination reaction of Ca uranate is more feasible to occur than the Mg uranate. The products obtained after chlorination reactions were washed with deionized water to remove the chlorides produced and analyzed. The XRD patterns of the washed products indicated that the chlorination between 400 and 500 °C result in a single phase of calcium uranate (CaUO4) as reaction product. The formation of U3O8 and MgU3O10 was observed at temperatures between 600 °C and 700 °C for 8 hs. The optimal conditions to recover uranium were 3 l h-1 of chlorine and 10 hs of reaction at 700 °C being U3O8 the single uranium product obtained.

Rapid fusion method for the determination of refractory thorium and uranium isotopes in soil samples

DOE PAGES

Maxwell, Sherrod L.; Hutchison, Jay B.; McAlister, Daniel R.

2015-02-14

Recently, approximately 80% of participating laboratories failed to accurately determine uranium isotopes in soil samples in the U.S Department of Energy Mixed Analyte Performance Evaluation Program (MAPEP) Session 30, due to incomplete dissolution of refractory particles in the samples. Failing laboratories employed acid dissolution methods, including hydrofluoric acid, to recover uranium from the soil matrix. The failures illustrate the importance of rugged soil dissolution methods for the accurate measurement of analytes in the sample matrix. A new rapid fusion method has been developed by the Savannah River National Laboratory (SRNL) to prepare 1-2 g soil sample aliquots very quickly, withmore » total dissolution of refractory particles. Soil samples are fused with sodium hydroxide at 600 ºC in zirconium crucibles to enable complete dissolution of the sample. Uranium and thorium are separated on stacked TEVA and TRU extraction chromatographic resin cartridges, prior to isotopic measurements by alpha spectrometry on cerium fluoride microprecipitation sources. Plutonium can also be separated and measured using this method. Batches of 12 samples can be prepared for measurement in <5 hours.« less

In-situ evidence for uranium immobilization and remobilization

USGS Publications Warehouse

Senko, John M.; Istok, Jonathan D.; Suflita, Joseph M.; Krumholz, Lee R.

2002-01-01

The in-situ microbial reduction and immobilization of uranium was assessed as a means of preventing the migration of this element in the terrestrial subsurface. Uranium immobilization (putatively identified as reduction) and microbial respiratory activities were evaluated in the presence of exogenous electron donors and acceptors with field push−pull tests using wells installed in an anoxic aquifer contaminated with landfill leachate. Uranium(VI) amended at 1.5 μM was reduced to less than 1 nM in groundwater in less than 8 d during all field experiments. Amendments of 0.5 mM sulfate or 5 mM nitrate slowed U(VI) immobilization and allowed for the recovery of 10% and 54% of the injected element, respectively, as compared to 4% in the unamended treatment. Laboratory incubations confirmed the field tests and showed that the majority of the U(VI) immobilized was due to microbial reduction. In these tests, nitrate treatment (7.5 mM) inhibited U(VI) reduction, and nitrite was transiently produced. Further push−pull tests were performed in which either 1 or 5 mM nitrate was added with 1.0 μM U(VI) to sediments that already contained immobilized uranium. After an initial loss of the amendments, the concentration of soluble U(VI) increased and eventually exceeded the injected concentration, indicating that previously immobilized uranium was remobilized as nitrate was reduced. Laboratory experiments using heat-inactivated sediment slurries suggested that the intermediates of dissimilatory nitrate reduction (denitrification or dissimilatory nitrate reduction to ammonia), nitrite, nitrous oxide, and nitric oxide were all capable of oxidizing and mobilizing U(IV). These findings indicate that in-situ subsurface U(VI) immobilization can be expected to take place under anaerobic conditions, but the permanence of the approach can be impaired by disimilatory nitrate reduction intermediates that can mobilize previously reduced uranium.

Laboratory column experiments and transport modeling to evaluate retardation of uranium in an aquifer downgradient of a uranium in-situ recovery site

DOE PAGES

Dangelmayr, Martin A.; Reimus, Paul W.; Wasserman, Naomi L.; ...

2017-05-01

The purpose of this study was to determine the attenuation potential and retardation of uranium in sediments taken from boreholes at the Smith-Ranch Highland in-situ recovery (ISR) site. Five column experiments with four different sediments were conducted to study the effects of variable mineralogy and alkalinity on uranium breakthrough. Uranium transport was modeled with PHREEQC using a generalized composite surface complexation model (GC SCM) with one, two, and, three generic surfaces, respectively. Reactive surface areas were approximated with PEST using BET derived surface areas to constrain fitting parameters. Uranium breakthrough was delayed by a factor of 1.68, 1.69 and 1.47more » relative to the non-reactive tracer for three of the 5 experiments at an alkalinity of 540 mg/l. A sediment containing smectite and kaolinite retained uranium by a factor of 2.80 despite a lower measured BET surface area. Decreasing alkalinity to 360 mg/l from 540 mg/l increased retardation by a factor of 4.26. Model fits correlated well to overall BET surface area in the three columns where clay content was less than 1%. For the sediment with clay, models consistently understated uranium retardation when reactive surface sites were restricted by BET results. Calcite saturation was shown to be a controlling factor for uranium desorption as the pH of the system changes. A pH of 6 during a secondary background water flush remobilized previously sorbed uranium resulting in a secondary uranium peak at twice the influent concentrations. Furthermore, this study demonstrates the potential of GC SCM models to predict uranium transport in sediments with homogenous mineral composition, but highlights the need for further research to understand the role of sediment clay composition and calcite saturation in uranium transport.« less

Laboratory column experiments and transport modeling to evaluate retardation of uranium in an aquifer downgradient of a uranium in-situ recovery site

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dangelmayr, Martin A.; Reimus, Paul W.; Wasserman, Naomi L.

The purpose of this study was to determine the attenuation potential and retardation of uranium in sediments taken from boreholes at the Smith-Ranch Highland in-situ recovery (ISR) site. Five column experiments with four different sediments were conducted to study the effects of variable mineralogy and alkalinity on uranium breakthrough. Uranium transport was modeled with PHREEQC using a generalized composite surface complexation model (GC SCM) with one, two, and, three generic surfaces, respectively. Reactive surface areas were approximated with PEST using BET derived surface areas to constrain fitting parameters. Uranium breakthrough was delayed by a factor of 1.68, 1.69 and 1.47more » relative to the non-reactive tracer for three of the 5 experiments at an alkalinity of 540 mg/l. A sediment containing smectite and kaolinite retained uranium by a factor of 2.80 despite a lower measured BET surface area. Decreasing alkalinity to 360 mg/l from 540 mg/l increased retardation by a factor of 4.26. Model fits correlated well to overall BET surface area in the three columns where clay content was less than 1%. For the sediment with clay, models consistently understated uranium retardation when reactive surface sites were restricted by BET results. Calcite saturation was shown to be a controlling factor for uranium desorption as the pH of the system changes. A pH of 6 during a secondary background water flush remobilized previously sorbed uranium resulting in a secondary uranium peak at twice the influent concentrations. Furthermore, this study demonstrates the potential of GC SCM models to predict uranium transport in sediments with homogenous mineral composition, but highlights the need for further research to understand the role of sediment clay composition and calcite saturation in uranium transport.« less

Simplified behaviors from increased heterogeneity: I. 2-D uranium transport experiments at the decimeter scale.

PubMed

Miller, Andrew W; Rodriguez, Derrick R; Honeyman, Bruce D

2013-05-01

Intermediate scale tank studies were conducted to examine the effects of physical heterogeneity of aquifer material on uranium desorption and subsequent transport in order to bridge the scaling gap between bench and field scale systems. Uranium contaminated sediment from a former uranium mill field site was packed into two 2-D tanks with internal dimensions of 2.44×1.22×0.076 m (tank 1) and 2.44×0.61×0.076 m (tank 2). Tank 1 was packed in a physically homogenous manner, and tank 2 was packed with long lenses of high and low conductivities resulting in different flow fields within the tanks. Chemical gradients within the flow domain were altered by temporal changes in influent water chemistry. The uranium source was desorption from the sediment. Despite the physical differences in the flow fields, there were minimal differences in global uranium leaching behavior between the two tanks. The dominant uranium species in both tanks over time and space was Ca2UO2(CO3)3(0). However, the uranium/alkalinity relationships varied as a function of time in tank 1 and were independent of time in tank 2. After planned stop-flow events, small, short-lived rebounds were observed in tank 1 while no rebound of uranium concentrations was observed in tank 2. Despite appearing to be in local equilibrium with respect to uranium desorption, a previously derived surface complexation model was insufficient to describe uranium partitioning within the flow domain. This is the first in a pair of papers; the companion paper presents an intermediate scale 3-D tank experiment and inter-tank comparisons. For these systems, physical heterogeneity at or above the decimeter scale does not affect global scale uranium desorption and transport. Instead, uranium fluxes are controlled by chemistry dependent desorption patterns induced by changing the influent ionic composition. Published by Elsevier B.V.

Simplified behaviors from increased heterogeneity: I. 2-D uranium transport experiments at the decimeter scale

NASA Astrophysics Data System (ADS)

Miller, Andrew W.; Rodriguez, Derrick R.; Honeyman, Bruce D.

2013-05-01

Intermediate scale tank studies were conducted to examine the effects of physical heterogeneity of aquifer material on uranium desorption and subsequent transport in order to bridge the scaling gap between bench and field scale systems. Uranium contaminated sediment from a former uranium mill field site was packed into two 2-D tanks with internal dimensions of 2.44 × 1.22 × 0.076 m (tank 1) and 2.44 × 0.61 × 0.076 m (tank 2). Tank 1 was packed in a physically homogenous manner, and tank 2 was packed with long lenses of high and low conductivities resulting in different flow fields within the tanks. Chemical gradients within the flow domain were altered by temporal changes in influent water chemistry. The uranium source was desorption from the sediment. Despite the physical differences in the flow fields, there were minimal differences in global uranium leaching behavior between the two tanks. The dominant uranium species in both tanks over time and space was Ca2UO2(CO3)30. However, the uranium/alkalinity relationships varied as a function of time in tank 1 and were independent of time in tank 2. After planned stop-flow events, small, short-lived rebounds were observed in tank 1 while no rebound of uranium concentrations was observed in tank 2. Despite appearing to be in local equilibrium with respect to uranium desorption, a previously derived surface complexation model was insufficient to describe uranium partitioning within the flow domain. This is the first in a pair of papers; the companion paper presents an intermediate scale 3-D tank experiment and inter-tank comparisons. For these systems, physical heterogeneity at or above the decimeter scale does not affect global scale uranium desorption and transport. Instead, uranium fluxes are controlled by chemistry dependent desorption patterns induced by changing the influent ionic composition.

Bacterial diversity and composition of an alkaline uranium mine tailings-water interface.

PubMed

Khan, Nurul H; Bondici, Viorica F; Medihala, Prabhakara G; Lawrence, John R; Wolfaardt, Gideon M; Warner, Jeff; Korber, Darren R

2013-10-01

The microbial diversity and biogeochemical potential associated with a northern Saskatchewan uranium mine water-tailings interface was examined using culture-dependent and -independent techniques. Morphologically-distinct colonies from uranium mine water-tailings and a reference lake (MC) obtained using selective and non-selective media were selected for 16S rRNA gene sequencing and identification, revealing that culturable organisms from the uranium tailings interface were dominated by Firmicutes and Betaproteobacteria; whereas, MC organisms mainly consisted of Bacteroidetes and Gammaproteobacteria. Ion Torrent (IT) 16S rRNA metagenomic analysis carried out on extracted DNA from tailings and MC interfaces demonstrated the dominance of Firmicutes in both of the systems. Overall, the tailings-water interface environment harbored a distinct bacterial community relative to the MC, reflective of the ambient conditions (i.e., total dissolved solids, pH, salinity, conductivity, heavy metals) dominating the uranium tailings system. Significant correlations among the physicochemical data and the major bacterial groups present in the tailings and MC were also observed. Presence of sulfate reducing bacteria demonstrated by culture-dependent analyses and the dominance of Desulfosporosinus spp. indicated by Ion Torrent analyses within the tailings-water interface suggests the existence of anaerobic microenvironments along with the potential for reductive metabolic processes.

Novel poly(imide dioxime) sorbents: Development and testing for enhanced extraction of uranium from natural seawater

DOE Office of Scientific and Technical Information (OSTI.GOV)

Das, Sadananda; Brown, Suree; Mayes, Richard T.

2016-04-09

We synthesized a new series of amidoxime-based polymer adsorbents at the Oak Ridge National Laboratory (ORNL) by electron beam induced grafting of acrylonitrile and itaconic acid onto polyethylene fiber. We also demonstrate hydroxylamine derivatives of poly(acrylonitrile) (PAN) moiety to possess two kinds of functional groups: open-chain amidoxime and cyclic imide dioxime. The open-chain amidoxime is shown to convert to imide dioxime on heat treatment in the presence of an aprotic solvent, like dimethylsulfoxide (DMSO). Furthermore, the formation of amidoxime and imide dioxime was confirmed by 13C CP-MAS spectra. The adsorbents were evaluated for uranium adsorption efficiency at ORNL with simulatedmore » seawater spiked with 8 ppm uranium and 5 gallon seawater in a batch reactor, and in flow-through columns with natural seawater at the Marine Science Laboratory (MSL) of Pacific Northwest National Laboratory (PNNL) at Sequim Bay, WA. The DMSO-heat-treated sorbents adsorbed uranium as high as 4.48 g-U/kg-ads. from seawater. Experimental evidence is presented that the poly(imide dioxime) is primarily responsible for enhanced uranium adsorption capacity from natural seawater. The conjugated system in the imide dioxime ligand possesses increased electron donation ability, which is believed to significantly enhance the uranyl coordination in seawater.« less

Reduction of uranium by cytochrome c3 of Desulfovibrio vulgaris

USGS Publications Warehouse

Lovley, D.R.; Widman, P.K.; Woodward, J.C.; Phillips, E.J.P.

1993-01-01

The mechanism for U(VI) reduction by Desulfovibrio vulgaris (Hildenborough) was investigated. The H2-dependent U(VI) reductase activity in the soluble fraction of the cells was lost when the soluble fraction was passed over a cationic exchange column which extracted cytochrome c3. Addition of cytochrome c3 back to the soluble fraction that had been passed over the cationic exchange column restored the U(VI)-reducing capacity. Reduced cytochrome c3 was oxidized by U(VI), as was a c-type cytochrome(s) in whole-cell suspensions. When cytochrome c3 was combined with hydrogenase, its physiological electron donor, U(VI) was reduced in the presence of H2. Hydrogenase alone could not reduce U(VI). Rapid U(VI) reduction was followed by a subsequent slow precipitation of the U(IV) mineral uraninite. Cytochrome c3 reduced U(VI) in a uranium-contaminated surface water and groundwater. Cytochrome c3 provides the first enzyme model for the reduction and biomineralization of uranium in sedimentary environments. Furthermore, the finding that cytochrome c3 can catalyze the reductive precipitation of uranium may aid in the development of fixed-enzyme reactors and/or organisms with enhanced U(VI)-reducing capacity for the bioremediation of uranium- contaminated waters and waste streams.

10 CFR 170.31 - Schedule of fees for materials licenses and other regulatory services, including inspections, and...

Code of Federal Regulations, 2011 CFR

2011-01-01

..., including x-ray fluorescence analyzers.4 Application [Program Code(s): 22140] $1,200 D. All other special... extraction of metals other than uranium or thorium, including licenses authorizing the possession of...

Breccia-pipe uranium mining in northern Arizona; estimate of resources and assessment of historical effects

USGS Publications Warehouse

Bills, Donald J.; Brown, Kristin M.; Alpine, Andrea E.; Otton, James K.; Van Gosen, Bradley S.; Hinck, Jo Ellen; Tillman, Fred D.

2011-01-01

About 1 million acres of Federal land in the Grand Canyon region of Arizona were temporarily withdrawn from new mining claims in July 2009 by the Secretary of the Interior because of concern that increased uranium mining could have negative impacts on the land, water, people, and wildlife. During a 2-year interval, a Federal team led by the Bureau of Land Management is evaluating the effects of withdrawing these lands for extended periods. As part of this team, the U.S. Geological Survey (USGS) conducted a series of short-term studies to examine the historical effects of breccia-pipe uranium mining in the region. The USGS studies provide estimates of uranium resources affected by the possible land withdrawal, examine the effects of previous breccia-pipe mining, summarize water-chemistry data for streams and springs, and investigate potential biological pathways of exposure to uranium and associated contaminants. This fact sheet summarizes results through December 2009 and outlines further research needs.

Biotechnology for the extractive metals industries

NASA Astrophysics Data System (ADS)

Brierley, James A.

1990-01-01

Biotechnology is an alternative process for the extraction of metals, the beneficiation of ores, and the recovery of metals from aqueous systems. Currently, microbial-based processes are used for leaching copper and uranium, enhancing the recovery of gold from refractory ores, and treating industrial wastewater to recover metal values. Future developments, emanating from fundamental and applied research and advances through genetic engineering, are expected to increase the use and efficiency of these biotechnological processes.

RELATIONSHIP OF URANIUM ORE DEPOSITS TO PETROLEUM AND GAS-BEARING STRUCTURES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Russell, R.T.

eposits are located on producing or breached oil and gas structures, or in the immediate vicinity of such structures. Individual deposits associated with these structures contain ore reserves which may exceed one million tons. Data derived from a study of the known deposits should be useful in evaluating the potentiality of other areas where similar structural relations and abnormal radioactivity are known to exist. Uranium deposits located in producing oil or gas fields include a deposit of more than one million tons of uranium ore on a single salt dome in Texas, and uranium deposits in the Poison Basin, Wyoming,more » which are situated over a producing naturalgas structure, having a potential of 100,000 to 200,000 tons. Important uranium mining districts are also located near producing oil fields or near structures which may have contained oil at some time in the past. The Gas Hills district to Wyoming is on the flanks of a breached anticline and within one mile of natural-gas seeps. Deposits in the Brown's Park formation near Maybell, Colorado, are witin 10 miles of producing oil wells and natural-gas seeps are known within one mile of some of the uranium mines; and at Morrison, Colorado, uranium ore is associated with tar seeps. On th Colorado Plateau, large ore bodies with total reserves of at least 30 million tons of 0.3% U/sub 3/O/sub 8/ ore in the Ambrosia Lake district near Grants, New Mexico, and produce ore associated with asphaltite.'' The uraniferous asphaltite'' ore at Temple Mountain, Utah has been known for nearly 50 years. At both Circle Cliffs and the Inter- River area in Utah, uranium ore is associated with asphaltic material on anticlinal structures. Many other deposits are on breached strucIn Wyoming, uranium deposits in Tertiary sandstone and arkose generally lack carbon trash, but are located near oil or gas structures that contain hydrocarbons and natural gases capable of precititating uranium. Also, many uranium deposits on the Colorado Plateau have insufficient plant remains present to be the fixing agent for uranium, but petroleum and/or natural gas are proposed as possible extractants. The hydrogen sulfide contaned in natural gas or dissolved in oil-field water has been a factor in the formation of some uranium deposits. Oil-type structural traps must have been effective in localizing both petroleum and uranium ore in some districts. Although petroleum may contain small amounts of uranium, it is doubtful if either oil or natural gas are important transporting agents for uranium. Careful consideration of these various factors will provide a basis upon which to evaluate more effectively many ore producing areas. (auth)« less

A top-down assessment of energy, water and land use in uranium mining, milling, and refining

DOE Office of Scientific and Technical Information (OSTI.GOV)

E. Schneider; B. Carlsen; E. Tavrides

2013-11-01

Land, water and energy use are key measures of the sustainability of uranium production into the future. As the most attractive, accessible deposits are mined out, future discoveries may prove to be significantly, perhaps unsustainably, more intensive consumers of environmental resources. A number of previous attempts have been made to provide empirical relationships connecting these environmental impact metrics to process variables such as stripping ratio and ore grade. These earlier attempts were often constrained by a lack of real world data and perform poorly when compared against data from modern operations. This paper conditions new empirical models of energy, watermore » and land use in uranium mining, milling, and refining on contemporary data reported by operating mines. It shows that, at present, direct energy use from uranium production represents less than 1% of the electrical energy produced by the once-through fuel cycle. Projections of future energy intensity from uranium production are also possible by coupling the empirical models with estimates of uranium crustal abundance, characteristics of new discoveries, and demand. The projections show that even for the most pessimistic of scenarios considered, by 2100, the direct energy use from uranium production represents less than 3% of the electrical energy produced by the contemporary once-through fuel cycle.« less

Validation of gamma-ray detection techniques for safeguards monitoring at natural uranium conversion facilities

NASA Astrophysics Data System (ADS)

Dewji, S. A.; Lee, D. L.; Croft, S.; Hertel, N. E.; Chapman, J. A.; McElroy, R. D.; Cleveland, S.

2016-07-01

Recent IAEA circulars and policy papers have sought to implement safeguards when any purified aqueous uranium solution or uranium oxides suitable for isotopic enrichment or fuel fabrication exists. Under the revised policy, IAEA Policy Paper 18, the starting point for nuclear material under safeguards was reinterpreted, suggesting that purified uranium compounds should be subject to safeguards procedures no later than the first point in the conversion process. In response to this technical need, a combination of simulation models and experimental measurements were employed to develop and validate concepts of nondestructive assay monitoring systems in a natural uranium conversion plant (NUCP). In particular, uranyl nitrate (UO2(NO3)2) solution exiting solvent extraction was identified as a key measurement point (KMP), where gamma-ray spectroscopy was selected as the process monitoring tool. The Uranyl Nitrate Calibration Loop Equipment (UNCLE) facility at Oak Ridge National Laboratory was employed to simulate the full-scale operating conditions of a purified uranium-bearing aqueous stream exiting the solvent extraction process in an NUCP. Nondestructive assay techniques using gamma-ray spectroscopy were evaluated to determine their viability as a technical means for drawing safeguards conclusions at NUCPs, and if the IAEA detection requirements of 1 significant quantity (SQ) can be met in a timely way. This work investigated gamma-ray signatures of uranyl nitrate circulating in the UNCLE facility and evaluated various gamma-ray detector sensitivities to uranyl nitrate. These detector validation activities include assessing detector responses to the uranyl nitrate gamma-ray signatures for spectrometers based on sodium iodide, lanthanum bromide, and high-purity germanium detectors. The results of measurements under static and dynamic operating conditions at concentrations ranging from 10-90 g U/L of natural uranyl nitrate are presented. A range of gamma-ray lines is examined, including attenuation for transmission measurement of density and concentration. It was determined that transmission-corrected gamma-ray spectra provide a reliable way to monitor the 235U concentration of uranyl nitrate solution in transfer pipes in NUCPs. Furthermore, existing predictive and analysis methods are adequate to design and realize practical designs. The 137Cs transmission source employed in this work is viable but not optimal for 235U densitometry determination. Validated simulations assessed the viability of 133Ba and 57Co as alternative densitometry sources. All three gamma-ray detectors are viable for monitoring natural uranium feed; although high-purity germanium is easiest to interpret, it is, however, the least attractive as an installation instrument. Overall, for monitoring throughput in a facility such as UNCLE, emulating the uranium concentration and pump speeds of the Springfields conversion facility in the United Kingdom, an uncertainty of less than 0.17% is required in order to detect the diversion of 1 SQ of uranyl nitrate through changes in uranium concentration over an accountancy period of one year with a detection probability of 50%. Although calibrated gamma-ray detection systems are capable of determining the concentration of uranium content in NUCPs, it is only in combination with verifiable operator declarations and supporting data, such as flow rate and enrichment, that safeguards conclusions can be drawn.

Analysis of Tank 38H (HTF-38-16-26, 27) and Tank 43H (HTF-43-16-28, 29) Samples for Support of the Enrichment Control and Corrosion Control Programs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hay, M. S.

Savannah River National Laboratory analyzed samples from Tank 38H and Tank 43H to support Enrichment Control Program and Corrosion Control Program. The total uranium in the Tank 38H samples ranged from 20.5 to 34.0 mg/L while the Tank 43H samples ranged from 47.6 to 50.6 mg/L. The U-235 percentage ranged from 0.62% to 0.64% over the four samples. The total uranium and percent U-235 results appear consistent with previous Tank 38H and Tank 43H uranium measurements. The Tank 38H plutonium results show a large difference between the surface and sub-surface sample concentrations and a somewhat higher concentration than previous sub-surfacemore » samples. The two Tank 43H samples show similar plutonium concentrations and are within the range of values measured on previous samples. The plutonium results may be biased high due to the presence of plutonium contamination in the blank samples from the cell sample preparations. The four samples analyzed show silicon concentrations ranging from 47.9 to 105 mg/L.« less

Characterization of PAH matrix with monazite stream containing uranium, gadolinium and iron

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pal, Sangita, E-mail: sangpal@barc.gov.in; Goswami, D.; Meena, Sher Singh

2016-05-23

Uranium (U) gadolinium (Gd) and iron (Fe) containing alkaline waste simulated effluent (relevant to alkaline effluent of monazite ore) has been treated with a novel amphoteric resin viz, Polyamidehydroxamate (PAH) containing amide and hydroxamic acid groups. The resin has been synthesized in an eco-friendly manner by polymerization nad conversion to functional groups characterized by FT-IR spectra and architectural overview by SEM. Coloration of the loaded matrix and de-coloration after extraction of uranium is the special characteristic of the matrix. Effluent streams have been analyzed by ICP-AES, U loaded PAH has been characterized by FT-IR, EXAFS, Gd and Fe by X-raymore » energy values of EDXRF at 6.053 KeVand 6.405 KeV respectively. The remarkable change has been observed in Mössbauer spectrum of Fe-loaded PAH samples.« less

Uranium extraction from TRISO-coated fuel particles using supercritical CO2 containing tri-n-butyl phosphate.

PubMed

Zhu, Liyang; Duan, Wuhua; Xu, Jingming; Zhu, Yongjun

2012-11-30

High-temperature gas-cooled reactors (HTGRs) are advanced nuclear systems that will receive heavy use in the future. It is important to develop spent nuclear fuel reprocessing technologies for HTGR. A new method for recovering uranium from tristructural-isotropic (TRISO-) coated fuel particles with supercritical CO(2) containing tri-n-butyl phosphate (TBP) as a complexing agent was investigated. TRISO-coated fuel particles from HTGR fuel elements were first crushed to expose UO(2) pellet fuel kernels. The crushed TRISO-coated fuel particles were then treated under O(2) stream at 750°C, resulting in a mixture of U(3)O(8) powder and SiC shells. The conversion of U(3)O(8) into solid uranyl nitrate by its reaction with liquid N(2)O(4) in the presence of a small amount of water was carried out. Complete conversion was achieved after 60 min of reaction at 80°C, whereas the SiC shells were not converted by N(2)O(4). Uranyl nitrate in the converted mixture was extracted with supercritical CO(2) containing TBP. The cumulative extraction efficiency was above 98% after 20 min of online extraction at 50°C and 25 MPa, whereas the SiC shells were not extracted by TBP. The results suggest an attractive strategy for reprocessing spent nuclear fuel from HTGR to minimize the generation of secondary radioactive waste. Copyright © 2012 Elsevier B.V. All rights reserved.

Direct observation of pure pentavalent uranium in U2O5 thin films by high resolution photoemission spectroscopy.

PubMed

Gouder, T; Eloirdi, R; Caciuffo, R

2018-05-29

Thin films of the elusive intermediate uranium oxide U 2 O 5 have been prepared by exposing UO 3 precursor multilayers to atomic hydrogen. Electron photoemission spectra measured about the uranium 4f core-level doublet contain sharp satellites separated by 7.9(1) eV from the 4f main lines, whilst satellites characteristics of the U(IV) and U(VI) oxidation states, expected respectively at 6.9(1) and 9.7(1) eV from the main 4f lines, are absent. This shows that uranium ions in the films are in a pure pentavalent oxidation state, in contrast to previous investigations of binary oxides claiming that U(V) occurs only as a metastable intermediate state coexisting with U(IV) and U(VI) species. The ratio between the 5f valence band and 4f core-level uranium photoemission intensities decreases by about 50% from UO 2 to U 2 O 5 , which is consistent with the 5f  2 (UO 2 ) and 5f  1 (U 2 O 5 ) electronic configurations of the initial state. Our studies conclusively establish the stability of uranium pentoxide.

Effects of nitrate on the stability of uranium in a bioreduced region of the subsurface.

PubMed

Wu, Wei-Min; Carley, Jack; Green, Stefan J; Luo, Jian; Kelly, Shelly D; Van Nostrand, Joy; Lowe, Kenneth; Mehlhorn, Tonia; Carroll, Sue; Boonchayanant, Benjaporn; Löfller, Frank E; Watson, David; Kemner, Kenneth M; Zhou, Jizhong; Kitanidis, Peter K; Kostka, Joel E; Jardine, Philip M; Criddle, Craig S

2010-07-01

The effects of nitrate on the stability of reduced, immobilized uranium were evaluated in field experiments at a U.S. Department of Energy site in Oak Ridge, TN. Nitrate (2.0 mM) was injected into a reduced region of the subsurface containing high levels of previously immobilized U(IV). The nitrate was reduced to nitrite, ammonium, and nitrogen gas; sulfide levels decreased; and Fe(II) levels increased then deceased. Uranium remobilization occurred concomitant with nitrite formation, suggesting nitrate-dependent, iron-accelerated oxidation of U(IV). Bromide tracer results indicated changes in subsurface flowpaths likely due to gas formation and/or precipitate. Desorption-adsorption of uranium by the iron-rich sediment impacted uranium mobilization and sequestration. After rereduction of the subsurface through ethanol additions, background groundwater containing high levels of nitrate was allowed to enter the reduced test zone. Aqueous uranium concentrations increased then decreased. Clone library analyses of sediment samples revealed the presence of denitrifying bacteria that can oxidize elemental sulfur, H(2)S, Fe(II), and U(IV) (e.g., Thiobacillus spp.), and a decrease in relative abundance of bacteria that can reduce Fe(III) and sulfate. XANES analyses of sediment samples confirmed changes in uranium oxidation state. Addition of ethanol restored reduced conditions and triggered a short-term increase in Fe(II) and aqueous uranium, likely due to reductive dissolution of Fe(III) oxides and release of sorbed U(VI). After two months of intermittent ethanol addition, sulfide levels increased, and aqueous uranium concentrations gradually decreased to <0.1 microM.

Measurement of dielectric constant of organic solvents by indigenously developed dielectric probe

NASA Astrophysics Data System (ADS)

Keshari, Ajay Kumar; Rao, J. Prabhakar; Rao, C. V. S. Brahmmananda; Ramakrishnan, R.; Ramanarayanan, R. R.

2018-04-01

The extraction, separation and purification of actinides (uranium and plutonium) from various matrices are an important step in nuclear fuel cycle. One of the separation process adopted in an industrial scale is the liquid-liquid extraction or solvent extraction. Liquid-liquid extraction uses a specific ligand/extractant in conjunction with suitable diluent. Solvent extraction or liquid-liquid extraction, involves the partitioning of the solute between two immiscible phases. In most cases, one of the phases is aqueous, and the other one is an organic solvent. The solvent used in solvent extraction should be selective for the metal of interest, it should have optimum distribution ratio, and the loaded metal from the organic phase should be easily stripped under suitable experimental conditions. Some of the important physical properties which are important for the solvent are density, viscosity, phase separation time, interfacial surface tension and the polarity of the extractant.

Bioaccessibility of U, Th and Pb in particulate matter from an abandoned uranium mine

NASA Astrophysics Data System (ADS)

Millward, Geoffrey; Foulkes, Michael; Henderson, Sam; Blake, William

2016-04-01

Currently, there are approximately 150 uranium mines in Europe at various stages of either operation, development, decommissioning, restoration or abandonment (wise-uranium.com). The particulate matter comprising the mounds of waste rock and mill tailings poses a risk to human health through the inadvertent ingestion of particles contaminated with uranium and thorium, and their decay products, which exposes recipients to the dual toxicity of heavy elements and their radioactive emissions. We investigated the bioaccessibility of 238U, 232Th and 206,214,210Pb in particulate samples taken from a contaminated, abandoned uranium mine in South West England. Sampling included a mine shaft, dressing floor and waste heap, as well as soils from a field used for grazing. The contaminants were extracted using the in-vitro Unified Bioaccessibility Research Group of Europe Method (UBM) in order to mimic the digestion processes in the human stomach (STOM) and the combined stomach and gastrointestinal tract (STOM+INT). Analyses of concentrations of U, Th and Pb in the extracts were by ICP-MS and the activity concentrations of radionuclides were determined on the same particles, before and after extraction, using gamma spectroscopy. 'Total' concentrations of U, Th and Pb for all samples were in the range 57 to 16,200, 0.28 to 3.8 and 69 to 4750 mg kg-1, respectively. For U and Pb the concentrations in the STOM fraction were lower than the total and STOM+INT fractions were even lower. However, for Th the STOM+INT fractions were higher than the STOM due to the presence of Th carbonate species within the gastrointestinal fluid. Activity concentrations for 214Pb and 210Pb, including total, STOM and STOM+INT, were in the range 180 to <1 Bq g-1 for the dressing floor and waste heap and 18 to <1 Bq g-1 for the grazing land. Estimates of the bioaccessible fractions (BAFs) of 238U in the most contaminated samples were 39% and 8% in the STOM and STOM+INT, respectively, whereas the respective BAFs for 232Th were 3% and 9%. For stable 206Pb the STOM and STOM+INT BAFs were 16% and 3% for the most contaminated samples, whereas those from the field had 44% in the STOM fraction and 17% in the STOM+INT fraction. The BAFs for 214Pb and 210Pb were the same as 206Pb. Dose estimates were made for the contaminants together with radioactive doses in order to assess potential risk to human health.

10 CFR 37.5 - Definitions.

Code of Federal Regulations, 2014 CFR

2014-01-01

... discrete surface wastes resulting from uranium solution extraction processes. Underground ore bodies... the ratio of the total activity of each radionuclide to the category 1 threshold for that radionuclide and adding the ratios together. If the sum is equal to or exceeds 1, the quantity would be considered...

First experimental results of a cryogenic stopping cell with short-lived, heavy uranium fragments produced at 1000 MeV/u

NASA Astrophysics Data System (ADS)

Purushothaman, S.; Reiter, M. P.; Haettner, E.; Dendooven, P.; Dickel, T.; Geissel, H.; Ebert, J.; Jesch, C.; Plass, W. R.; Ranjan, M.; Weick, H.; Amjad, F.; Ayet, S.; Diwisch, M.; Estrade, A.; Farinon, F.; Greiner, F.; Kalantar-Nayestanaki, N.; Knöbel, R.; Kurcewicz, J.; Lang, J.; Moore, I. D.; Mukha, I.; Nociforo, C.; Petrick, M.; Pfützner, M.; Pietri, S.; Prochazka, A.; Rink, A.-K.; Rinta-Antila, S.; Scheidenberger, C.; Takechi, M.; Tanaka, Y. K.; Winfield, J. S.; Yavor, M. I.

2013-11-01

A cryogenic stopping cell (CSC) has been commissioned with 238U projectile fragments produced at 1000 MeV/u. The spatial isotopic separation in flight was performed with the FRS applying a monoenergetic degrader. For the first time, a stopping cell was operated with exotic nuclei at cryogenic temperatures (70 to 100 K). A helium stopping gas density of up to 0.05\\ \\text{mg/cm}^3 was used, about two times higher than reached before for a stopping cell with RF ion repelling structures. An overall efficiency of up to 15%, a combined ion survival and extraction efficiency of about 50%, and extraction times of 24 ms were achieved for heavy α-decaying uranium fragments. Mass spectrometry with a multiple-reflection time-of-flight mass spectrometer has demonstrated the excellent cleanliness of the CSC. This setup has opened a new field for the spectroscopy of short-lived nuclei.

Actinium radioisotope products of enhanced purity

DOEpatents

Meikrantz, David Herbert; Todd, Terry Allen; Tranter, Troy Joseph; Horwitz, E. Philip

2010-06-15

A product includes actinium-225 (.sup.225Ac) and less than about 1 microgram (.mu.g) of iron (Fe) per millicurie (mCi) of actinium-225. The product may have a radioisotopic purity of greater than about 99.99 atomic percent (at %) actinium-225 and daughter isotopes of actinium-225, and may be formed by a method that includes providing a radioisotope mixture solution comprising at least one of uranium-233 (.sup.233U) and thorium-229 (.sup.229Th), extracting the at least one of uranium-233 and thorium-229 into an organic phase, substantially continuously contacting the organic phase with an aqueous phase, substantially continuously extracting actinium-225 into the aqueous phase, and purifying the actinium-225 from the aqueous phase. In some embodiments, the product may include less than about 1 nanogram (ng) of iron per millicurie (mCi) of actinium-225, and may include less than about 1 microgram (.mu.g) each of magnesium (Mg), Chromium (Cr), and manganese (Mn) per millicurie (mCi) of actinium-225.

EXTRACTION OF URANIUM

DOEpatents

Schmieding, E.G.; Ruehle, A.E.

1961-04-11

A method is given for extracting metal values from an aqueous feed wherein the aqueous feed is passed countercurrent to an organic extractant through a plurality of decanting zones and a portion of the mixture contained in each decanting zone is recycled through a mixing zone associated therewith. The improvement consists of passing more solvent from the top of one decanting zone to the bottom of the preceding decanting zone than can rise to the top thereof and recycling that portion of the solvent that does not rise to the top back to the first named decanting zone through its associated mixing zone.

Capacity of Lemna gibba L. (duckweed) for uranium and arsenic phytoremediation in mine tailing waters.

PubMed

Mkandawire, Martin; Taubert, Barbara; Dudel, E Gert

2004-01-01

The potential of Lemna gibba L. to clean uranium and arsenic contamination from mine surface waters was investigated in wetlands of two former uranium mines in eastern Germany and in laboratory hydroponic culture. Water and plants were sampled and L gibba growth and yield were monitored in tailing ponds from the field study sites. Contaminant accumulation, growth and yield experiments were conducted in the laboratory using synthetic tailing water. Mean background concentrations of the surface waters were 186.0+/-81.2 microg l(-1) uranium and 47.0+/-21.3 microg l(-1) arsenic in Site one and 293.7+/-121.3 microg l(-1) uranium and 41.37+/-24.7 microg l(-1) arsenic in Site two. The initial concentration of both uranium and arsenic in the culture solutions was 100 microg l(-1). The plant samples were either not leached, leached with deionized H2O or ethylenediaminetetracetic (EDTA). The results revealed high bioaccumulation coefficients for both uranium and arsenic. Uranium and arsenic content of L gibba dry biomass of the field samples were as follows: nonleached samples > deionized H2O leached (insignificant ANOVA p = 0.05) > EDTA leached. The difference in both arsenic and uranium enrichment were significantly high between the nonleached and the other two lead samples tested at ANOVA p > 0.001. Estimated mean L gibba density in surface water was 85,344.8+/-1843.4 fronds m(-2) (approximately 1319.7 g m(-2)). The maximum specific growth rate was 0.47+/-0.2 d(-1), which exceeded reported specific growth rates for L gibba in the literature. Average yield was estimated at 20.2+/-6.7 g m(-2) d(-1), giving approximately 73.6+/-21.4 t ha(-1) y(-1) as the annual yield. The highest accumulations observed were 896.9+/-203.8 mg kg(-1) uranium and 1021.7+/-250.8 mg kg(-1) arsenic dry biomass for a 21-d test period in the laboratory steady-state experiments. The potential extractions from surface waters with L gibba L. were estimated to be 662.7 kg uranium ha(-1) yr(-1) and 751.9 kg arsenic ha(-1) yr(-1) under the above conditions.

Carbon-free induction furnace

DOEpatents

Holcombe, Cressie E.; Masters, David R.; Pfeiler, William A.

1985-01-01

An induction furnace for melting and casting highly pure metals and alloys such as uranium and uranium alloys in such a manner as to minimize contamination of the melt by carbon derived from the materials and the environment within the furnace. The subject furnace is constructed of carbon free materials and is housed within a conventional vacuum chamber. The furnace comprises a ceramic oxide crucible for holding the charge of metal or alloy. The heating of the crucible is achieved by a plasma-sprayed tungsten susceptor surrounding the crucible which, in turn, is heated by an RF induction coil separated from the susceptor by a cylinder of inorganic insulation. The furnace of the present invention is capable of being rapidly cycled from ambient temperatures to about 1650.degree. C. for effectively melting uranium and uranium alloys without the attendant carbon contamination problems previously encountered when using carbon-bearing furnace materials.

Non-carbon induction furnace

DOEpatents

Holcombe, C.E.; Masters, D.R.; Pfeiler, W.A.

1984-01-06

The present invention is directed to an induction furnace for melting and casting highly pure metals and alloys such as uranium and uranium alloys in such a manner as to minimize contamination of the melt by carbon derived from the materials and the environment within the furnace. The subject furnace is constructed of non-carbon materials and is housed within a conventional vacuum chamber. The furnace comprises a ceramic oxide crucible for holding the charge of metal or alloys. The heating of the crucible is achieved by a plasma-sprayed tungsten susceptor surrounding the crucible which, in turn, is heated by an rf induction coil separated from the susceptor by a cylinder of inorganic insulation. The furnace of the present invention is capable of being rapidly cycled from ambient temperatures to about 1650/sup 0/C for effectively melting uranium and uranium alloys without the attendant carbon contamination problems previously encountered when using carbon-bearing furnace materials.

Solvent wash solution

DOEpatents

Neace, J.C.

1984-03-13

A process is claimed for removing diluent degradation products from a solvent extraction solution, which has been used to recover uranium and plutonium from spent nuclear fuel. A wash solution and the solvent extraction solution are combined. The wash solution contains (a) water and (b) up to about, and including, 50 vol % of at least one-polar water-miscible organic solvent based on the total volume of the water and the highly-polar organic solvent. The wash solution also preferably contains at least one inorganic salt. The diluent degradation products dissolve in the highly-polar organic solvent and the organic solvent extraction solvent do not dissolve in the highly-polar organic solvent. The highly-polar organic solvent and the extraction solvent are separated.

Solvent wash solution

DOEpatents

Neace, James C.

1986-01-01

Process for removing diluent degradation products from a solvent extraction solution, which has been used to recover uranium and plutonium from spent nuclear fuel. A wash solution and the solvent extraction solution are combined. The wash solution contains (a) water and (b) up to about, and including, 50 volume percent of at least one-polar water-miscible organic solvent based on the total volume of the water and the highly-polar organic solvent. The wash solution also preferably contains at least one inorganic salt. The diluent degradation products dissolve in the highly-polar organic solvent and the organic solvent extraction solvent do not dissolve in the highly-polar organic solvent. The highly-polar organic solvent and the extraction solvent are separated.

Concept Feasibility Report for Electroplating Zirconium onto Uranium Foil - Year 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Coffey, Greg W.; Meinhardt, Kerry D.; Joshi, Vineet V.

2015-03-01

The Fuel Fabrication Capability within the U.S. High Performance Research Reactor Conversion Program is funded through the National Nuclear Security Administration (NNSA) NA-26 (Office of Material Management and Minimization). An investigation was commissioned to determine the feasibility of using electroplating techniques to apply a coating of zirconium onto depleted uranium/molybdenum alloy (U-10Mo). Electroplating would provide an alternative method to the existing process of hot roll-bonding zirconium foil onto the U-10Mo fuel foil during the fabrication of fuel elements for high-performance research reactors. The objective of this research was to develop a reproducible and scalable plating process that will produce amore » uniform, 25 μm thick zirconium metal coating on U-10Mo foil. In previous work, Pacific Northwest National Laboratory (PNNL) established a molten salt electroplating apparatus and protocol to plate zirconium metal onto molybdenum foil (Coffey 2015). During this second year of the research, PNNL furthered this work by moving to the U-10Mo alloy system (90 percent uranium:10 percent molybdenum). The original plating apparatus was disassembled and re-assembled in a laboratory capable of handling low-level radioactive materials. Initially, the work followed the previous year’s approach, and the salt bath composition was targeted at the eutectic composition (LiF:NaF:ZrF4 = 26:37:37 mol%). Early results indicated that the formation of uranium fluoride compounds would be problematic. Other salt bath compositions were investigated in order to eliminate the uranium fluoride production (LiF:NaF = 61:39 mol% and LiF:NaF:KF = 46.5:11.5:42 mol% ). Zirconium metal was used as the crucible for the molten salt. Three plating methods were used—isopotential, galvano static, and pulsed plating. The molten salt method for zirconium metal application provided high-quality plating on molybdenum in PNNL’s previous work. A key advantage of this approach is that plating can be performed under conditions that would greatly reduce the quantity of intermetallics that form at the interface between the zirconium and U-10Mo; unlike roll bonding, the molten salt plating approach would allow for complete coverage of the U-10Mo foil with zirconium. When utilizing the experimental parameters developed for zirconium plating onto molybdenum, a uranium fluoride reaction product was formed at the Zr/U-10Mo interface. By controlling the initial plating potential, the uranium fluoride could be prevented; however, the targeted zirconium thickness (25 ±12.5 μm) could not be achieved while maintaining 100% coverage.« less

Environmental site description for a Uranium Atomic Vapor Laser Isotope Separation (U-AVLIS) production plant at the Paducah Gaseous Diffusion Plant site

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marmer, G.J.; Dunn, C.P.; Moeller, K.L.

Uranium enrichment in the United States has utilized a diffusion process to preferentially enrich the U-235 isotope in the uranium product. The U-AVLIS process is based on electrostatic extraction of photoionized U-235 atoms from an atomic vapor stream created by electron-beam vaporization of uranium metal alloy. The U-235 atoms are ionized when precisely tuned laser light -- of appropriate power, spectral, and temporal characteristics -- illuminates the uranium vapor and selectively photoionizes the U-235 isotope. A programmatic document for use in screening DOE site to locate a U-AVLIS production plant was developed and implemented in two parts. The first partmore » consisted of a series of screening analyses, based on exclusionary and other criteria, that identified a reasonable number of candidate sites. These sites were subjected to a more rigorous and detailed comparative analysis for the purpose of developing a short list of reasonable alternative sites for later environmental examination. This environmental site description (ESD) provides a detailed description of the PGDP site and vicinity suitable for use in an environmental impact statement (EIS). The report is based on existing literature, data collected at the site, and information collected by Argonne National Laboratory (ANL) staff during a site visit. 65 refs., 15 tabs.« less

Uranium delivery and uptake in a montane wetland, north-central Colorado, USA

USGS Publications Warehouse

Schumann, R. Randall; Zielinski, Robert A.; Otton, James K.; Pantea, Michael P.; Orem, William H.

2017-01-01

Comprehensive sampling of peat, underlying lakebed sediments, and coexisting waters of a naturally uraniferous montane wetland are combined with hydrologic measurements to define the important controls on uranium (U) supply and uptake. The major source of U to the wetland is groundwater flowing through locally fractured and faulted granite gneiss of Proterozoic age. Dissolved U concentrations in four springs and one seep ranged from 20 to 83 ppb (μg/l). Maximum U concentrations are ∼300 ppm (mg/kg) in lakebed sediments and >3000 ppm in peat. Uranium in lakebed sediments is primarily stratabound in the more organic-rich layers, but samples of similar organic content display variable U concentrations. Post-depositional modifications include variable additions of U delivered by groundwater. Uranium distribution in peat is heterogeneous and primarily controlled by proximity to groundwater-fed springs and seeps that act as local point sources of U, and by proximity to groundwater directed along the peat/lakebeds contact. Uranium is initially sorbed on various organic components of peat as oxidized U(VI) present in groundwater. Selective extractions indicate that the majority of sorbed U remains as the oxidized species despite reducing conditions that should favor formation of U(IV). Possible explanations are kinetic hindrances related to strong complex formation between uranyl and humic substances, inhibition of anaerobic bacterial activity by low supply of dissolved iron and sulfate, and by cold temperatures.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luther, Erik Paul; Leckie, Rafael M.; Dombrowski, David E.

This supplemental report describes fuel fabrication efforts conducted for the Idaho National Laboratory Trade Study for the TREAT Conversion project that is exploring the replacement of the HEU (Highly Enriched Uranium) fuel core of the TREAT reactor with LEU (Low Enriched Uranium) fuel. Previous reports have documented fabrication of fuel by the “upgrade” process developed at Los Alamos National Laboratory. These experiments supplement an earlier report that describes efforts to increase the graphite content of extruded fuel and minimize cracking.

Supervised Machine Learning for Regionalization of Environmental Data: Distribution of Uranium in Groundwater in Ukraine

NASA Astrophysics Data System (ADS)

Govorov, Michael; Gienko, Gennady; Putrenko, Viktor

2018-05-01

In this paper, several supervised machine learning algorithms were explored to define homogeneous regions of con-centration of uranium in surface waters in Ukraine using multiple environmental parameters. The previous study was focused on finding the primary environmental parameters related to uranium in ground waters using several methods of spatial statistics and unsupervised classification. At this step, we refined the regionalization using Artifi-cial Neural Networks (ANN) techniques including Multilayer Perceptron (MLP), Radial Basis Function (RBF), and Convolutional Neural Network (CNN). The study is focused on building local ANN models which may significantly improve the prediction results of machine learning algorithms by taking into considerations non-stationarity and autocorrelation in spatial data.

Interactions of vanadium( iv ) with amidoxime ligands: redox reactivity

DOE PAGES

Parker, B. F.; Hohloch, S.; Pankhurst, J. R.; ...

2018-01-01

Vanadium is the main competitor for uranium extraction from seawater, and V( iv ) comprises a minor but important portion of this. V( iv ) undergoes redox reactions with oximes and amidoxime ligands under seawater-relevant conditions, leading to V( v ) complexes and loss of oxime functional groups.

Trace elements and Pb isotopes in soils and sediments impacted by uranium mining.

PubMed

Cuvier, A; Pourcelot, L; Probst, A; Prunier, J; Le Roux, G

2016-10-01

The purpose of this study is to evaluate the contamination in As, Ba, Co, Cu, Mn, Ni, Sr, V, Zn and REE, in a high uranium activity (up to 21,000Bq∙kg(-1)) area, downstream of a former uranium mine. Different geochemical proxies like enrichment factor and fractions from a sequential extraction procedure are used to evaluate the level of contamination, the mobility and the availability of the potential contaminants. Pb isotope ratios are determined in the total samples and in the sequential leachates to identify the sources of the contaminants and to determine the mobility of radiogenic Pb in the context of uranium mining. In spite of the large uranium contamination measured in the soils and the sediments (EF≫40), trace element contamination is low to moderate (2

Extracting uranium from seawater: Promising AF series adsorbents

DOE PAGES

Das, Sadananda; Oyola, Y.; Mayes, Richard T.; ...

2015-11-02

Here, a new family of high surface area polyethylene fiber adsorbents (AF series) was recently developed at the Oak Ridge National Laboratory (ORNL). The AF series of were synthesized by radiation-induced graft polymerization of acrylonitrile and itaconic acid (at different monomer/co-monomer mol ratios) onto high surface area polyethylene fibers. The degree of grafting (%DOG) of AF series adsorbents was found to be 154 354%. The grafted nitrile groups were converted to amidoxime groups by treating with hydroxylamine. The amidoximated adsorbents were then conditioned with 0.44M KOH at 80 C followed by screening at ORNL with simulated seawater spiked with 8more » ppm uranium. Uranium adsorption capacity in simulated seawater screening ranged from 170-200 g-U/kg-ads irrespective of %DOG. A monomer/co-monomer mol ratio in the range of 7.57-10.14 seemed to be optimum for highest uranium loading capacity. Subsequently, the adsorbents were also tested with natural seawater at Pacific Northwest National Laboratory (PNNL) using flow-through exposure uptake experiments to determine uranium loading capacity with varying KOH conditioning time at 80 C. The highest adsorption capacity of AF1 measured after 56 days of marine testing was demonstrated as 3.9 g-U/kg-adsorbent and 3.2 g-U/kg-adsorbent for 1hr and 3hrs of KOH conditioning at 80 C, respectively. Based on capacity values of several AF1 samples, it was observed that changing KOH conditioning from 3hrs to 1hr at 80 C resulted in 22-27% increase in uranium loading capacity in seawater.« less

Extracting uranium from seawater: Promising AF series adsorbents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Das, Sadananda; Oyola, Y.; Mayes, Richard T.

Here, a new family of high surface area polyethylene fiber adsorbents (AF series) was recently developed at the Oak Ridge National Laboratory (ORNL). The AF series of were synthesized by radiation-induced graft polymerization of acrylonitrile and itaconic acid (at different monomer/co-monomer mol ratios) onto high surface area polyethylene fibers. The degree of grafting (%DOG) of AF series adsorbents was found to be 154 354%. The grafted nitrile groups were converted to amidoxime groups by treating with hydroxylamine. The amidoximated adsorbents were then conditioned with 0.44M KOH at 80 C followed by screening at ORNL with simulated seawater spiked with 8more » ppm uranium. Uranium adsorption capacity in simulated seawater screening ranged from 170-200 g-U/kg-ads irrespective of %DOG. A monomer/co-monomer mol ratio in the range of 7.57-10.14 seemed to be optimum for highest uranium loading capacity. Subsequently, the adsorbents were also tested with natural seawater at Pacific Northwest National Laboratory (PNNL) using flow-through exposure uptake experiments to determine uranium loading capacity with varying KOH conditioning time at 80 C. The highest adsorption capacity of AF1 measured after 56 days of marine testing was demonstrated as 3.9 g-U/kg-adsorbent and 3.2 g-U/kg-adsorbent for 1hr and 3hrs of KOH conditioning at 80 C, respectively. Based on capacity values of several AF1 samples, it was observed that changing KOH conditioning from 3hrs to 1hr at 80 C resulted in 22-27% increase in uranium loading capacity in seawater.« less

Significance of breeding in fast nuclear reactors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Raza, S.M.; Abidi, S.B.M.

1983-12-01

Only breeder reactors--nuclear power plants that produce more fuel than they consume--are capable in principle of extracting the maximum amount of fission energy contained in uranium ore, thus offering a practical long-term solution to uranium supply problems. Uranium would then constitute a virtually inexhaustible fuel reserve for the world's future energy needs. The ultimate argument for breeding is to conserve the energy resources available to mankind. A long-term role for nuclear power with fast reactors is proven to be economically viable, environmentally acceptable and capable of wide scale exploitation in many countries. In this paper, various suggestions pertaining to themore » fuel fabrication route, fuel cycle economics, studies of the physics of fast nuclear reactors and of engineering design simplifications are presented. Fast reactors contain no moderator and inherently require enriched fuel. In general, the main aim is to suggest an improvement in the understanding of the safety and control characteristics of fast breeder power reactors. Development work is also being devoted to new carbide and nitride fuels, which are likely to exhibit breeding characteristics superior to those of the oxides of plutonium and uranium.« less

Biogenic non-crystalline U(IV) revealed as major component in uranium ore deposits

NASA Astrophysics Data System (ADS)

Bhattacharyya, Amrita; Campbell, Kate M.; Kelly, Shelly D.; Roebbert, Yvonne; Weyer, Stefan; Bernier-Latmani, Rizlan; Borch, Thomas

2017-06-01

Historically, it is believed that crystalline uraninite, produced via the abiotic reduction of hexavalent uranium (U(VI)) is the dominant reduced U species formed in low-temperature uranium roll-front ore deposits. Here we show that non-crystalline U(IV) generated through biologically mediated U(VI) reduction is the predominant U(IV) species in an undisturbed U roll-front ore deposit in Wyoming, USA. Characterization of U species revealed that the majority (~58-89%) of U is bound as U(IV) to C-containing organic functional groups or inorganic carbonate, while uraninite and U(VI) represent only minor components. The uranium deposit exhibited mostly 238U-enriched isotope signatures, consistent with largely biotic reduction of U(VI) to U(IV). This finding implies that biogenic processes are more important to uranium ore genesis than previously understood. The predominance of a relatively labile form of U(IV) also provides an opportunity for a more economical and environmentally benign mining process, as well as the design of more effective post-mining restoration strategies and human health-risk assessment.

Biogenic non-crystalline U(IV) revealed as major component in uranium ore deposits

PubMed Central

Bhattacharyya, Amrita; Campbell, Kate M.; Kelly, Shelly D.; Roebbert, Yvonne; Weyer, Stefan; Bernier-Latmani, Rizlan; Borch, Thomas

2017-01-01

Historically, it is believed that crystalline uraninite, produced via the abiotic reduction of hexavalent uranium (U(VI)) is the dominant reduced U species formed in low-temperature uranium roll-front ore deposits. Here we show that non-crystalline U(IV) generated through biologically mediated U(VI) reduction is the predominant U(IV) species in an undisturbed U roll-front ore deposit in Wyoming, USA. Characterization of U species revealed that the majority (∼58-89%) of U is bound as U(IV) to C-containing organic functional groups or inorganic carbonate, while uraninite and U(VI) represent only minor components. The uranium deposit exhibited mostly 238U-enriched isotope signatures, consistent with largely biotic reduction of U(VI) to U(IV). This finding implies that biogenic processes are more important to uranium ore genesis than previously understood. The predominance of a relatively labile form of U(IV) also provides an opportunity for a more economical and environmentally benign mining process, as well as the design of more effective post-mining restoration strategies and human health-risk assessment. PMID:28569759

Acetaminophen induces xenobiotic-metabolizing enzymes in rat: Impact of a uranium chronic exposure.

PubMed

Rouas, Caroline; Souidi, Maâmar; Grandcolas, Line; Grison, Stephane; Baudelin, Cedric; Gourmelon, Patrick; Pallardy, Marc; Gueguen, Yann

2009-11-01

The extensive use of uranium in civilian and military applications increases the risk of human chronic exposure. Uranium is a slightly radioactive heavy metal with a predominantly chemical toxicity, especially in kidney but also in liver. Few studies have previously shown some effects of uranium on xenobiotic-metabolizing enzymes (XME) that might disturb drug pharmacokinetic. The aim of this study was to determine whether a chronic (9 months) non-nephrotoxic low dose exposure to depleted uranium (DU, 1mg/rat/day) could modify the liver XME, using a single non-hepatotoxic acetaminophen (APAP) treatment (50mg/kg). Most of XME analysed were induced by APAP treatment at the gene expression level but at the protein level only CYP3A2 was significantly increased 3h after APAP treatment in DU-exposed rats whereas it remained at a basal level in unexposed rats. In conclusion, these results showed that a chronic non-nephrotoxic DU exposure specially modify CYP3A2 after a single therapeutic APAP treatment. Copyright © 2009 Elsevier B.V. All rights reserved.

Biogenic non-crystalline U (IV) revealed as major component in uranium ore deposits

DOE PAGES

Bhattacharyya, Amrita; Campbell, Kate M.; Kelly, Shelly D.; ...

2017-06-01

Historically, it is believed that crystalline uraninite, produced via the abiotic reduction of hexavalent uranium (U (VI)) is the dominant reduced U species formed in low-temperature uranium roll-front ore deposits. Here we show that non-crystalline U (IV) generated through biologically mediated U (VI) reduction is the predominant U (IV) species in an undisturbed U roll-front ore deposit in Wyoming, USA. Characterization of U species revealed that the majority (~58-89%) of U is bound as U (IV) to C-containing organic functional groups or inorganic carbonate, while uraninite and U (VI) represent only minor components. The uranium deposit exhibited mostly 238U-enriched isotopemore » signatures, consistent with largely biotic reduction of U (VI) to U (IV). This finding implies that biogenic processes are more important to uranium ore genesis than previously understood. The predominance of a relatively labile form of U (IV) also provides an opportunity for a more economical and environmentally benign mining process, as well as the design of more effective post-mining restoration strategies and human health-risk assessment.« less

Biogenic non-crystalline U(IV) revealed as major component in uranium ore deposits.

PubMed

Bhattacharyya, Amrita; Campbell, Kate M; Kelly, Shelly D; Roebbert, Yvonne; Weyer, Stefan; Bernier-Latmani, Rizlan; Borch, Thomas

2017-06-01

Historically, it is believed that crystalline uraninite, produced via the abiotic reduction of hexavalent uranium (U (VI) ) is the dominant reduced U species formed in low-temperature uranium roll-front ore deposits. Here we show that non-crystalline U (IV)  generated through biologically mediated U (VI)  reduction is the predominant U (IV)  species in an undisturbed U roll-front ore deposit in Wyoming, USA. Characterization of U species revealed that the majority (∼58-89%) of U is bound as U (IV) to C-containing organic functional groups or inorganic carbonate, while uraninite and U (VI) represent only minor components. The uranium deposit exhibited mostly 238 U-enriched isotope signatures, consistent with largely biotic reduction of U (VI) to U (IV) . This finding implies that biogenic processes are more important to uranium ore genesis than previously understood. The predominance of a relatively labile form of U (IV) also provides an opportunity for a more economical and environmentally benign mining process, as well as the design of more effective post-mining restoration strategies and human health-risk assessment.

Biogenic non-crystalline U (IV) revealed as major component in uranium ore deposits

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bhattacharyya, Amrita; Campbell, Kate M.; Kelly, Shelly D.

Historically, it is believed that crystalline uraninite, produced via the abiotic reduction of hexavalent uranium (U (VI)) is the dominant reduced U species formed in low-temperature uranium roll-front ore deposits. Here we show that non-crystalline U (IV) generated through biologically mediated U (VI) reduction is the predominant U (IV) species in an undisturbed U roll-front ore deposit in Wyoming, USA. Characterization of U species revealed that the majority (~58-89%) of U is bound as U (IV) to C-containing organic functional groups or inorganic carbonate, while uraninite and U (VI) represent only minor components. The uranium deposit exhibited mostly 238U-enriched isotopemore » signatures, consistent with largely biotic reduction of U (VI) to U (IV). This finding implies that biogenic processes are more important to uranium ore genesis than previously understood. The predominance of a relatively labile form of U (IV) also provides an opportunity for a more economical and environmentally benign mining process, as well as the design of more effective post-mining restoration strategies and human health-risk assessment.« less

Biogenic non-crystalline U(IV) revealed as major component in uranium ore deposits

USGS Publications Warehouse

Bhattacharyya, Amrita; Campbell, Kate M.; Kelly, Shelly; Roebbert, Yvonne; Weyer, Stefan; Bernier-Latmani, Rizlan; Borch, Thomas

2017-01-01

Historically, it is believed that crystalline uraninite, produced via the abiotic reduction of hexavalent uranium (U(VI)) is the dominant reduced U species formed in low-temperature uranium roll-front ore deposits. Here we show that non-crystalline U(IV) generated through biologically mediated U(VI) reduction is the predominant U(IV) species in an undisturbed U roll-front ore deposit in Wyoming, USA. Characterization of U species revealed that the majority (∼58-89%) of U is bound as U(IV)to C-containing organic functional groups or inorganic carbonate, while uraninite and U(VI) represent only minor components. The uranium deposit exhibited mostly 238U-enriched isotope signatures, consistent with largely biotic reduction of U(VI) to U(IV). This finding implies that biogenic processes are more important to uranium ore genesis than previously understood. The predominance of a relatively labile form of U(IV) also provides an opportunity for a more economical and environmentally benign mining process, as well as the design of more effective post-mining restoration strategies and human health-risk assessment.

Application of phytoextraction for uranium contaminated soil in korea

NASA Astrophysics Data System (ADS)

Ryu, Y.; Han, Y.; Lee, M.

2013-12-01

The soils having high concentration of uranium, sampled from Goesan Deokpyungri area in Korea, were identified with the uranium removal efficiency of phytoextraction by using several plants. According to the results of physicochemical properties, uranium concentration from soil was 28.85mg/kg, pH 5.43 and soil texture was "Sand". Results of SEP(Sequential Extraction Procedure) test, uranium concentrations ratio of soil in the status of exchangeable/carbonate was 13.4%. Five plants such as Lettuce (Lactuca sativa L.), Chinese cabbage (Brassica campestris L.), Sweet potato (Ipomoea batatas (L.) Lam), Radish (Raphanus sativus), Sesame (Perilla frutescens var. japonica) were cultivated during 56 days in phytotron. All the cultivation processes were conducted in a growth chamber at 25 degrees celsius, 70% relative humidity, 4000 Lux illumination (16 hours/day) and CO2 concentration of 600 ppm. Four times at intervals of 2 weeks leaves and roots collected were analyzed for uranium concentration. Ranges of uranium concentration of the roots and leaves from the five plants were measured to 206.81-721.22μg/kg and 3.45-10.21μg/kg respectively. The majority of uranium was found to accumulate in the roots. Uranium concentration in the leaves, regardless of the type of plants were presented below standard of drinking water(30μg/l) by U.S EPA. Phytoextraction pot experiments with citric acid were conducted. Citric acid as chelating agent was applied to soil to enhance uranium accumulation in five crop plants. 6 days before harvest crops, Each citric acid 25mM and 50mM was injected into the soil by 300ml. After injecting citric acid 25mM , pH of the soil was reduced to 4.95. Uranium concentration of leaves and roots collected from five plants was increased to 2-4times and 7-30times compared to control soil. Injected with citric acid 50mM , pH of the soil was reduced to 4.79. Uranium concentration of leaves and roots collected from five plants was increased to 3-10times and 10-50times compared to control soil. The results of TOC (Total Organic Carbon content), CEC (Cation Exchange Capacity), T-N and T-P analysis of the soil with citric acid 25mM and 50mM were similar to control soil. Finally, the chelating agent was effective to use a citric acid 50mM .

Separation techniques for the clean-up of radioactive mixed waste for ICP-AES/ICP-MS analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Swafford, A.M.; Keller, J.M.

1993-03-17

Two separation techniques were investigated for the clean-up of typical radioactive mixed waste samples requiring elemental analysis by Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES) or Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). These measurements frequently involve regulatory or compliance criteria which include the determination of elements on the EPA Target Analyte List (TAL). These samples usually consist of both an aqueous phase and a solid phase which is mostly an inorganic sludge. Frequently, samples taken from the waste tanks contain high levels of uranium and thorium which can cause spectral interferences in ICP-AES or ICP-MS analysis. The removal of these interferences ismore » necessary to determine the presence of the EPA TAL elements in the sample. Two clean-up methods were studied on simulated aqueous waste samples containing the EPA TAL elements. The first method studied was a classical procedure based upon liquid-liquid extraction using tri-n- octylphosphine oxide (TOPO) dissolved in cyclohexane. The second method investigated was based on more recently developed techniques using extraction chromatography; specifically the use of a commercially available Eichrom TRU[center dot]Spec[trademark] column. Literature on these two methods indicates the efficient removal of uranium and thorium from properly prepared samples and provides considerable qualitative information on the extraction behavior of many other elements. However, there is a lack of quantitative data on the extraction behavior of elements on the EPA Target Analyte List. Experimental studies on these two methods consisted of determining whether any of the analytes were extracted by these methods and the recoveries obtained. Both methods produced similar results; the EPA target analytes were only slightly or not extracted. Advantages and disadvantages of each method were evaluated and found to be comparable.« less

Validation of gamma-ray detection techniques for safeguards monitoring at natural uranium conversion facilities

DOE PAGES

Dewji, Shaheen A.; Lee, Denise L.; Croft, Stephen; ...

2016-03-28

Recent IAEA circulars and policy papers have sought to implement safeguards when any purified aqueous uranium solution or uranium oxides suitable for isotopic enrichment or fuel fabrication exists. Under the revised policy, IAEA Policy Paper 18, the starting point for nuclear material under safeguards was reinterpreted, suggesting that purified uranium compounds should be subject to safeguards procedures no later than the first point in the conversion process. In response to this technical need, a combination of simulation models and experimental measurements were employed to develop and validate concepts of nondestructive assay monitoring systems in a natural uranium conversion plant (NUCP).more » In particular, uranyl nitrate (UO 2(NO 3) 2) solution exiting solvent extraction was identified as a key measurement point (KMP), where gamma-ray spectroscopy was selected as the process monitoring tool. The Uranyl Nitrate Calibration Loop Equipment (UNCLE) facility at Oak Ridge National Laboratory was employed to simulate the full-scale operating conditions of a purified uranium-bearing aqueous stream exiting the solvent extraction process in an NUCP. Nondestructive assay techniques using gamma-ray spectroscopy were evaluated to determine their viability as a technical means for drawing safeguards conclusions at NUCPs, and if the IAEA detection requirements of 1 significant quantity (SQ) can be met in a timely way. This work investigated gamma-ray signatures of uranyl nitrate circulating in the UNCLE facility and evaluated various gamma-ray detector sensitivities to uranyl nitrate. These detector validation activities include assessing detector responses to the uranyl nitrate gamma-ray signatures for spectrometers based on sodium iodide, lanthanum bromide, and high-purity germanium detectors. The results of measurements under static and dynamic operating conditions at concentrations ranging from 10–90 g U/L of natural uranyl nitrate are presented. A range of gamma-ray lines is examined, including attenuation for transmission measurement of density and concentration. It was determined that transmission-corrected gamma-ray spectra provide a reliable way to monitor the 235U concentration of uranyl nitrate solution in transfer pipes in NUCPs. Furthermore, existing predictive and analysis methods are adequate to design and realize practical designs. The 137Cs transmission source employed in this work is viable but not optimal for 235U densitometry determination. Validated simulations assessed the viability of 133Ba and 57Co as alternative densitometry sources. All three gamma-ray detectors are viable for monitoring natural uranium feed; although high-purity germanium is easiest to interpret, it is, however, the least attractive as an installation instrument. Overall, for monitoring throughput in a facility such as UNCLE, emulating the uranium concentration and pump speeds of the Springfields conversion facility in the United Kingdom, an uncertainty of less than 0.17% is required in order to detect the diversion of 1 SQ of uranyl nitrate through changes in uranium concentration over an accountancy period of one year with a detection probability of 50%. As a result, calibrated gamma-ray detection systems are capable of determining the concentration of uranium content in NUCPs, it is only in combination with verifiable operator declarations and supporting data, such as flow rate and enrichment, that safeguards conclusions can be drawn.« less

Redox-Active vs Redox-Innocent: A Comparison of Uranium Complexes Containing Diamine Ligands.

PubMed

Pattenaude, Scott A; Mullane, Kimberly C; Schelter, Eric J; Ferrier, Maryline G; Stein, Benjamin W; Bone, Sharon E; Lezama Pacheco, Juan S; Kozimor, Stosh A; Fanwick, Phillip E; Zeller, Matthias; Bart, Suzanne C

2018-05-11

Uranium complexes ( Mes DAE) 2 U(THF) (1-DAE) and Cp 2 U( Mes DAE) (2-DAE) ( Mes DAE = [ArN-CH 2 CH 2 -NAr]; Ar = 2,4,6-trimethylphenyl (Mes)), bearing redox-innocent diamide ligands, have been synthesized and characterized for a full comparison with previously published, redox-active diimine complexes, ( Mes DAB Me ) 2 U(THF) (1-DAB) and Cp 2 U( Mes DAB Me ) (2-DAB) ( Mes DAB Me = [ArN═C(Me)C(Me)═NAr]; Ar = Mes). These redox-innocent analogues maintain an analogous steric environment to their redox-active ligand counterparts to facilitate a study aimed at determining the differing electronic behavior around the uranium center. Structural analysis by X-ray crystallography showed 1-DAE and 2-DAE have a structural environment very similar to 1-DAB and 2-DAB, respectively. The main difference occurs with coordination of the ene-backbone to the uranium center in the latter species. Electronic absorption spectroscopy reveals these new DAE complexes are nearly identical to each other. X-ray absorption spectroscopy suggests all four species contain +4 uranium ions. The data also indicates that there is an electronic difference between the bis(diamide)-THF uranium complexes as opposed to those that only contain one diamide and two cyclopentadienyl rings. Finally, magnetic measurements reveal that all complexes display temperature-dependent behavior consistent with uranium(IV) ions that do not include ligand radicals. Overall, this study determines that there is no significant bonding difference between the redox-innocent and redox-active ligand frameworks on uranium. Furthermore, there are no data to suggest covalent bonding character using the latter ligand framework on uranium, despite what is known for transition metals.

Further evaluations of the toxicity of irradiated advanced heavy water reactor fuels.

PubMed

Edwards, Geoffrey W R; Priest, Nicholas D

2014-11-01

The neutron economy and online refueling capability of heavy water moderated reactors enable them to use many different fuel types, such as low enriched uranium, plutonium mixed with uranium, or plutonium and/or U mixed with thorium, in addition to their traditional natural uranium fuel. However, the toxicity and radiological protection methods for fuels other than natural uranium are not well established. A previous paper by the current authors compared the composition and toxicity of irradiated natural uranium to that of three potential advanced heavy water fuels not containing plutonium, and this work uses the same method to compare irradiated natural uranium to three other fuels that do contain plutonium in their initial composition. All three of the new fuels are assumed to incorporate plutonium isotopes characteristic of those that would be recovered from light water reactor fuel via reprocessing. The first fuel investigated is a homogeneous thorium-plutonium fuel designed for a once-through fuel cycle without reprocessing. The second fuel is a heterogeneous thorium-plutonium-U bundle, with graded enrichments of U in different parts of a single fuel assembly. This fuel is assumed to be part of a recycling scenario in which U from previously irradiated fuel is recovered. The third fuel is one in which plutonium and Am are mixed with natural uranium. Each of these fuels, because of the presence of plutonium in the initial composition, is determined to be considerably more radiotoxic than is standard natural uranium. Canadian nuclear safety regulations require that techniques be available for the measurement of 1 mSv of committed effective dose after exposure to irradiated fuel. For natural uranium fuel, the isotope Pu is a significant contributor to the committed effective dose after exposure, and thermal ionization mass spectrometry is sensitive enough that the amount of Pu excreted in urine is sufficient to estimate internal doses, from all isotopes, as low as 1 mSv. In addition, if this method is extended so that Pu is also measured, then the combined amount of Pu and Pu is sufficiently high in the thorium-plutonium fuel that a committed effective dose of 1 mSv would be measurable. However, the fraction of Pu and Pu in the other two fuels is sufficiently low that a 1 mSv dose would remain below the detection limit using this technique. Thus new methods, such as fecal measurements of Pu (or other alpha emitters), will be required to measure exposure to these new fuels.

Sequential extraction procedure for determination of uranium, thorium, radium, lead and polonium radionuclides by alpha spectrometry in environmental samples

NASA Astrophysics Data System (ADS)

Oliveira, J. M.; Carvalho, F. P.

2006-01-01

A sequential extraction technique was developed and tested for common naturally-occurring radionuclides. This technique allows the extraction and purification of uranium, thorium, radium, lead, and polonium radionuclides from the same sample. Environmental materials such as water, soil, and biological samples can be analyzed for those radionuclides without matrix interferences in the quality of radioelement purification and in the radiochemical yield. The use of isotopic tracers (232U, 229Th, 224Ra, 209Po, and stable lead carrier) added to the sample in the beginning of the chemical procedure, enables an accurate control of the radiochemical yield for each radioelement. The ion extraction procedure, applied after either complete dissolution of the solid sample with mineral acids or co-precipitation of dissolved radionuclide with MnO2 for aqueous samples, includes the use of commercially available pre-packed columns from Eichrom® and ion exchange columns packed with Bio-Rad resins, in altogether three chromatography columns. All radioactive elements but one are purified and electroplated on stainless steel discs. Polonium is spontaneously plated on a silver disc. The discs are measured using high resolution silicon surface barrier detectors. 210Pb, a beta emitter, can be measured either through the beta emission of 210Bi, or stored for a few months and determined by alpha spectrometry through the in-growth of 210Po. This sequential extraction chromatography technique was tested and validated with the analysis of certified reference materials from the IAEA. Reproducibility was tested through repeated analysis of the same homogeneous material (water sample).

Centrifugal contactor operations for UREX process flowsheet. An update

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pereira, Candido; Vandegrift, George F.

2014-08-01

The uranium extraction (UREX) process separates uranium, technetium, and a fraction of the iodine from the other components of the irradiated fuel in nitric acid solution. In May 2012, the time, material, and footprint requirements for treatment of 260 L batches of a solution containing 130 g-U/L were evaluated for two commercial annular centrifugal contactors from CINC Industries. These calculated values were based on the expected volume and concentration of fuel arising from treatment of a single target solution vessel (TSV). The general conclusions of that report were that a CINC V-2 contactor would occupy a footprint of 3.2 mmore » 2 (0.25 m x 15 m) if each stage required twice the nominal footprint of an individual stage, and approximately 1,131 minutes or nearly 19 hours is required to process all of the feed solution. A CINC V-5 would require approximately 9.9 m 2 (0.4 m x 25 m) of floor space but would require only 182 minutes or ~ 3 hours to process the spent target solution. Subsequent comparison with the Modular Caustic Side Solvent Extraction Unit (MCU) at Savannah River Site (SRS) in October 2013 suggested that a more compact arrangement is feasible, and the linear dimension for the CINC V-5 may be reduced to about 8 m; a comparable reduction for the CINC V-2 yields a length of 5 m. That report also described an intermediate-scale (10 cm) contactor design developed by Argonne in the early 1980s that would better align with the SHINE operations as they stood in May 2012. In this report, we revisit the previous evaluation of contactor operations after discussions with CINC Industries and analysis of the SHINE process flow diagrams for the cleanup of the TSV, which were not available at the time of the first assessment.« less

Spatial Distribution of an Uranium-Respiring Betaproteobacterium at the Rifle, CO Field Research Site

PubMed Central

Koribanics, Nicole M.; Tuorto, Steven J.; Lopez-Chiaffarelli, Nora; McGuinness, Lora R.; Häggblom, Max M.; Williams, Kenneth H.; Long, Philip E.; Kerkhof, Lee J.

2015-01-01

The Department of Energy’s Integrated Field-Scale Subsurface Research Challenge Site (IFRC) at Rifle, Colorado was created to address the gaps in knowledge on the mechanisms and rates of U(VI) bioreduction in alluvial sediments. Previous studies at the Rifle IFRC have linked microbial processes to uranium immobilization during acetate amendment. Several key bacteria believed to be involved in radionuclide containment have been described; however, most of the evidence implicating uranium reduction with specific microbiota has been indirect. Here, we report on the cultivation of a microorganism from the Rifle IFRC that reduces uranium and appears to utilize it as a terminal electron acceptor for respiration with acetate as electron donor. Furthermore, this bacterium constitutes a significant proportion of the subsurface sediment community prior to biostimulation based on TRFLP profiling of 16S rRNA genes. 16S rRNA gene sequence analysis indicates that the microorganism is a betaproteobacterium with a high similarity to Burkholderia fungorum. This is, to our knowledge, the first report of a betaproteobacterium capable of uranium respiration. Our results indicate that this microorganism occurs commonly in alluvial sediments located between 3-6 m below ground surface at Rifle and may play a role in the initial reduction of uranium at the site. PMID:25874721

Spatial distribution of an uranium-respiring betaproteobacterium at the Rifle, CO field research site

DOE PAGES

Koribanics, Nicole M.; Tuorto, Steven J.; Lopez-Chiaffarelli, Nora; ...

2015-04-13

The Department of Energy’s Integrated Field-Scale Subsurface Research Challenge Site (IFRC) at Rifle, Colorado was created to address the gaps in knowledge on the mechanisms and rates of U(VI) bioreduction in alluvial sediments. Previous studies at the Rifle IFRC have linked microbial processes to uranium immobilization during acetate amendment. Several key bacteria believed to be involved in radionuclide containment have been described; however, most of the evidence implicating uranium reduction with specific microbiota has been indirect. Here, we report on the cultivation of a microorganism from the Rifle IFRC that reduces uranium and appears to utilize it as a terminalmore » electron acceptor for respiration with acetate as electron donor. Furthermore, this bacterium constitutes a significant proportion of the subsurface sediment community prior to biostimulation based on TRFLP profiling of 16S rRNA genes. 16S rRNA gene sequence analysis indicates that the microorganism is a betaproteobacterium with a high similarity to Burkholderia fungorum. This is, to our knowledge, the first report of a betaproteobacterium capable of uranium respiration. Our results indicate that this microorganism occurs commonly in alluvial sediments located between 3-6 m below ground surface at Rifle and may play a role in the initial reduction of uranium at the site.« less

Global Uranium And Thorium Resources: Are They Adequate To Satisfy Demand Over The Next Half Century?

NASA Astrophysics Data System (ADS)

Lambert, I. B.

2012-04-01

This presentation will consider the adequacy of global uranium and thorium resources to meet realistic nuclear power demand scenarios over the next half century. It is presented on behalf of, and based on evaluations by, the Uranium Group - a joint initiative of the OECD Nuclear Energy Agency and the International Atomic Energy Agency, of which the author is a Vice Chair. The Uranium Group produces a biennial report on Uranium Resources, Production and Demand based on information from some 40 countries involved in the nuclear fuel cycle, which also briefly reviews thorium resources. Uranium: In 2008, world production of uranium amounted to almost 44,000 tonnes (tU). This supplied approximately three-quarters of world reactor requirements (approx. 59,000 tU), the remainder being met by previously mined uranium (so-called secondary sources). Information on availability of secondary sources - which include uranium from excess inventories, dismantling nuclear warheads, tails and spent fuel reprocessing - is incomplete, but such sources are expected to decrease in market importance after 2013. In 2008, the total world Reasonably Assured plus Inferred Resources of uranium (recoverable at less than 130/kgU) amounted to 5.4 million tonnes. In addition, it is clear that there are vast amounts of uranium recoverable at higher costs in known deposits, plus many as yet undiscovered deposits. The Uranium Group has concluded that the uranium resource base is more than adequate to meet projected high-case requirements for nuclear power for at least half a century. This conclusion does not assume increasing replacement of uranium by fuels from reprocessing current reactor wastes, or by thorium, nor greater reactor efficiencies, which are likely to ameliorate future uranium demand. However, progressively increasing quantities of uranium will need to be mined, against a backdrop of the relatively small number of producing facilities around the world, geopolitical uncertainties and strong opposition to growth of nuclear power in a number of quarters - it is vital that the market provides incentives for exploration and development of environmentally sustainable mining operations. Thorium: World Reasonably Assured plus Inferred Resources of thorium are estimated at over 2.2 million tonnes, in hard rock and heavy mineral sand deposits. At least double this amount is considered to occur in as yet undiscovered thorium deposits. Currently, demand for thorium is insignificant, but even a major shift to thorium-fueled reactors would not make significant inroads into the huge resource base over the next half century.

INTERACTIONS AMONG PHOSPHATE AMENDMENTS, MICROBES AND URANIUM MOBILITY IN CONTAMINATED SEDIMENTS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Knox, A

2007-08-30

The use of sequestering agents for the transformation of radionuclides in low concentrations in contaminated soils/sediments offers considerable potential for long-term environmental cleanup. This study evaluated the influence of four phosphate amendments and two microbial amendments on U availability. The synchrotron X-ray fluorescence mapping of the untreated U-contaminated sediment showed that U was closely associated with Mn. All tested phosphate amendments reduced aqueous U concentration more than 90%, likely due to formation of insoluble phosphate precipitates. The addition of A. piechaudii and P. putida alone were found to reduce U concentrations 63% and 31% respectively. Uranium sorption in phosphate treatmentsmore » was significantly reduced in the presence of microbes. However, increased microbial activity in the treated sediment led to reduction of phosphate effectiveness. The average U concentration in 1 M MgCl{sub 2} extract from U amended sediment was 437 {micro}g/kg, but in the same sediment without microbes (autoclaved sediment), the extractable U concentration was only 103 {micro}g/kg. When the autoclaved amended sediment was treated with autoclaved biological apatite, U concentration in the 1 M MgCl{sub 2} extract was {approx}0 {micro}g/kg. Together these tests suggest that microbes may enhance U leaching and reduce phosphate amendment remedial effectiveness.« less

A brief history of the American radium industry and its ties to the scientific community of its early twentieth century

USGS Publications Warehouse

Landa, E.R.

1993-01-01

Federally funded remedial action projects are presently underway in New Jersey and Colorado at sites containing 226Ra and other radionuclides from radium-uranium ore extraction plants that operated during the early twentieth century. They are but the latest chapter in the story of an American industry that emerged and perished in the span of three decades. Major extraction plants were established in or near Denver (CO), Pittsburgh (PA), and New York City (NY) to process radium from ore that came largely from the carnotite deposits of western Colorado and eastern Utah. The staffs of these plants included some of the finest chemists and physicists in the nation, and the highly-refined radium products found a variety of uses in medicine and industry. The discovery of high-grade pitchblende ores in the Belgian Congo and the subsequent opening of an extraction plant near Antwerp, Belgium, in 1992, however, created an economic climate that put an end to the American radium industry. The geologic, chemical, and engineering information gathered during this era formed the basis of the uranium industry of the later part of the century, while the tailings and residues came to be viewed as environmental problems during the same period.

Analysis of tank 38H (HTF-38-17-18, -19) and tank 43H (HTF-43-17-20, -21) samples for support of the enrichment control and corrosion control programs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hay, M. S.; Coleman, C. J.; Diprete, D. P.

SRNL analyzed samples from Tank 38H and Tank 43H to support ECP and CCP. The total uranium in the Tank 38H samples ranged from 53.7 mg/L for the surface sample to 57.0 mg/L in the sub-surface sample. The Tank 43H samples showed uranium concentrations of 46.2 mg/L for the surface sample and 45.7 mg/L in the sub-surface sample. The U-235 percentage was 0.63% in the Tank 38H samples and 0.62% in the Tank 43H samples. The total uranium and percent U-235 results appear consistent with recent Tank 38H and Tank 43H uranium measurements. The plutonium results for the Tank 38Hmore » surface sample are slightly higher than recent sample results, while the Tank 43H plutonium results are within the range of values measured on previous samples. The Cs-137 results for the Tank 38H surface and subsurface samples are slightly higher than the concentrations measured in recent samples. The Cs-137 results for the two Tank 43H samples are within the range of values measured on previous samples. The comparison of the sum of the cations in each sample versus the sum of the anions shows a difference of 23% for the Tank 38H surface sample and 18% for the Tank 43H surface sample. The four samples show silicon concentrations somewhat lower than the previous samples with values ranging from 80.2 to 105 mg/L.« less

Simultaneous spectrophotometric determination of trace amounts of uranium, thorium, and zirconium using the partial least squares method after their preconcentration by alpha-benzoin oxime modified Amberlite XAD-2000 resin.

PubMed

Ghasemi, Jahan B; Zolfonoun, E

2010-01-15

A new solid phase extraction method for separation and preconcentration of trace amounts of uranium, thorium, and zirconium in water samples is proposed. The procedure is based on the adsorption of U(VI), Th(IV) and Zr(IV) ions on a column of Amberlite XAD-2000 resin loaded with alpha-benzoin oxime prior to their simultaneous spectrophotometric determination with Arsenazo III using orthogonal signal correction partial least squares method. The enrichment factor for preconcentration of uranium, thorium, and zirconium was found to be 100. The detection limits for U(VI), Th(IV) and Zr(IV) were 0.50, 0.54, and 0.48microgL(-1), respectively. The precision of the method, evaluated as the relative standard deviation obtained by analyzing a series of 10 replicates, was below 4% for all elements. The practical applicability of the developed sorbent was examined using synthetic seawater, natural waters and ceramic samples.

Microbial biogeochemistry of uranium mill tailings

USGS Publications Warehouse

Landa, Edward R.

2005-01-01

Uranium mill tailings (UMT) are the crushed ore residues from the extraction of uranium (U) from ores. Among the radioactive wastes associated with the nuclear fuel cycle, UMT are unique in terms of their volume and their limited isolation from the surficial environment. For this latter reason, their management and long-term fate has many interfaces with environmental microbial communities and processes. The interactions of microorganisms with UMT have been shown to be diverse and with significant consequences for radionuclide mobility and bioremediation. These radionuclides are associated with the U-decay series. The addition of organic carbon and phosphate is required to initiate the reduction of the U present in the groundwater down gradient of the mills. Investigations on sediment and water from the U-contaminated aquifer, indicates that the addition of a carbon source stimulates the rate of U removal by microbial reduction. Moreover, most attention with respect to passive or engineered removal of U from groundwaters focuses on iron-reducing and sulfate-reducing bacteria.

Reconnaissance soil geochemistry at the Riverton Uranium Mill Tailings Remedial Action Site, Fremont County, Wyoming

USGS Publications Warehouse

Smith, David B.; Sweat, Michael J.

2012-01-01

Soil samples were collected and chemically analyzed from the Riverton Uranium Mill Tailings Remedial Action Site, which lies within the Wind River Indian Reservation in Fremont County, Wyoming. Nineteen soil samples from a depth of 0 to 5 centimeters were collected in August 2011 from the site. The samples were sieved to less than 2 millimeters and analyzed for 44 major and trace elements following a near-total multi-acid extraction. Soil pH was also determined. The geochemical data were compared to a background dataset consisting of 160 soil samples previously collected from the same depth throughout the State of Wyoming as part of another ongoing study by the U.S. Geological Survey. Risk from potentially toxic elements in soil from the site to biologic receptors and humans was estimated by comparing the concentration of these elements with soil screening values established by the U.S. Environmental Protection Agency. All 19 samples exceeded the carcinogenic human health screening level for arsenic in residential soils of 0.39 milligrams per kilogram (mg/kg), which represents a one-in-one-million cancer risk (median arsenic concentration in the study area is 2.7 mg/kg). All 19 samples also exceeded the lead and vanadium screening levels for birds. Eighteen of the 19 samples exceeded the manganese screening level for plants, 13 of the 19 samples exceeded the antimony screening level for mammals, and 10 of 19 samples exceeded the zinc screening level for birds. However, these exceedances are also found in soils at most locations in the Wyoming Statewide soil database, and elevated concentrations alone are not necessarily cause for alarm. Uranium and thorium, two other elements of environmental concern, are elevated in soils at the site as compared to the Wyoming dataset, but no human or ecological soil screening levels have been established for these elements.

PROTECTIVELY COVERED ARTICLE AND METHOD OF MANUFACTURE

DOEpatents

Plott, R.F.

1958-10-28

A method of casting a protective jacket about a ura nium fuel element that will bond completely to the uranium without the use of stringers or supports that would ordinarily produce gaps in the cast metal coating and bond is presented. Preformed endcaps of alumlnum alloyed with 13% silicon are placed on the ends of the uranium fuel element. These caps will support the fuel element when placed in a mold. The mold is kept at a ing alloy but below that of uranium so the cast metal jacket will fuse with the endcaps forming a complete covering and bond to the fuel element, which would otherwise oxidize at the gaps or discontinuities lefi in the coating by previous casting methods.

U(VI) Reduction by Biogenic and Abiotic Hydroxycarbonate Green Rusts: Impacts on U(IV) Speciation and Stability Over Time

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yan, Sen; Boyanov, Maxim I.; Mishra, Bhoopesh

Green rusts (GRs) are redox active Fe II-Fe III minerals that form in the environment via various biotic and abiotic processes. Although both biogenic (BioGR) and abiotic (ChemGR) GRs have been shown to reduce U VI, the dynamics of the transformations and the speciation and stability of the resulting U IV phases are poorly understood. We used carbonate extraction and XAFS spectroscopy to investigate the products of U VI reduction by BioGR and ChemGR. The results show that both GRs can rapidly remove U VI from synthetic groundwater via reduction to U IV. The initial products in the ChemGR systemmore » are solids-associated U IV-carbonate complexes that gradually transform to nanocrystalline uraninite over time, leading to a decrease in the proportion of carbonate-extractable U from ~95% to ~10%. In contrast, solid-phase U IV atoms in the BioGR system remain relatively extractable, non-uraninite U IV species over the same reaction period. The presence of calcium and carbonate in groundwater significantly increase the extractability of U IV in the BioGR system. Furthermore, these data provide new insights into the transformations of U under anoxic conditions in groundwater that contains calcium and carbonate, and have major implications for predicting uranium stability within redox dynamic environments and designing approaches for the remediation of uranium-contaminated groundwater.« less

U(VI) Reduction by Biogenic and Abiotic Hydroxycarbonate Green Rusts: Impacts on U(IV) Speciation and Stability Over Time

DOE PAGES

Yan, Sen; Boyanov, Maxim I.; Mishra, Bhoopesh; ...

2018-04-09

Green rusts (GRs) are redox active Fe II-Fe III minerals that form in the environment via various biotic and abiotic processes. Although both biogenic (BioGR) and abiotic (ChemGR) GRs have been shown to reduce U VI, the dynamics of the transformations and the speciation and stability of the resulting U IV phases are poorly understood. We used carbonate extraction and XAFS spectroscopy to investigate the products of U VI reduction by BioGR and ChemGR. The results show that both GRs can rapidly remove U VI from synthetic groundwater via reduction to U IV. The initial products in the ChemGR systemmore » are solids-associated U IV-carbonate complexes that gradually transform to nanocrystalline uraninite over time, leading to a decrease in the proportion of carbonate-extractable U from ~95% to ~10%. In contrast, solid-phase U IV atoms in the BioGR system remain relatively extractable, non-uraninite U IV species over the same reaction period. The presence of calcium and carbonate in groundwater significantly increase the extractability of U IV in the BioGR system. Furthermore, these data provide new insights into the transformations of U under anoxic conditions in groundwater that contains calcium and carbonate, and have major implications for predicting uranium stability within redox dynamic environments and designing approaches for the remediation of uranium-contaminated groundwater.« less

A procedure for quantitation of total oxidized uranium for bioremediation studies

USGS Publications Warehouse

Elias, Dwayne A.; Senko, John M.; Krumholz, Lee R.

2003-01-01

A procedure was developed for the quantitation of complexed U(VI) during studies on U(VI) bioremediation. These studies typically involve conversion of soluble or complexed U(VI) (oxidized) to U(IV) (the reduced form which is much less soluble). Since U(VI) freely exchanges between material adsorbed to the solid phase and the dissolved phase, uranium bioremediation experiments require a mass balance of U in both its soluble and adsorbed forms as well as in the reduced sediment bound phase. We set out to optimize a procedure for extraction and quantitation of sediment bound U(VI). Various extractant volumes to sediment ratios were tested and it was found that between 1:1 to 8:1 ratios (v/w) there was a steady increase in U(VI) recovered, but no change with further increases in v/w ratio.Various strengths of NaHCO3, Na-EDTA, and Na-citrate were used to evaluate complexed U(VI) recovery, while the efficiency of a single versus repeated extraction steps was compared with synthesized uranyl-phosphate and uranyl-hydroxide. Total recovery with 1 M NaHCO3 was 95.7% and 97.9% from uranyl-phosphate and uranyl-hydroxide, respectively, compared to 80.7% and 89.9% using 450 mM NaHCO3. Performing the procedure once yielded an efficiency of 81.1% and 92.3% for uranyl-phosphate and uranyl-hydroxide, respectively, as compared to three times. All other extractants yielded 7.9–82.0% in both experiments.

Variations in the uranium isotopic compositions of uranium ores from different types of uranium deposits

NASA Astrophysics Data System (ADS)

Uvarova, Yulia A.; Kyser, T. Kurt; Geagea, Majdi Lahd; Chipley, Don

2014-12-01

Variations in 238U/235U and 234U/238U ratios were measured in uranium minerals from a spectrum of uranium deposit types, as well as diagenetic phosphates in uranium-rich basins and peraluminous rhyolites and associated autunite mineralisation from Macusani Meseta, Peru. Mean δ238U values of uranium minerals relative to NBL CRM 112-A are 0.02‰ for metasomatic deposits, 0.16‰ for intrusive, 0.18‰ for calcrete, 0.18‰ for volcanic, 0.29‰ for quartz-pebble conglomerate, 0.29‰ for sandstone-hosted, 0.44‰ for unconformity-type, and 0.56‰ for vein, with a total range in δ238U values from -0.30‰ to 1.52‰. Uranium mineralisation associated with igneous systems, including low-temperature calcretes that are sourced from U-rich minerals in igneous systems, have low δ238U values of ca. 0.1‰, near those of their igneous sources, whereas uranium minerals in basin-hosted deposits have higher and more variable values. High-grade unconformity-related deposits have δ238U values around 0.2‰, whereas lower grade unconformity-type deposits in the Athabasca, Kombolgie and Otish basins have higher δ238U values. The δ234U values for most samples are around 0‰, in secular equilibrium, but some samples have δ234U values much lower or higher than 0‰ associated with addition or removal of 234U during the past 2.5 Ma. These δ238U and δ234U values suggest that there are at least two different mechanisms responsible for 238U/235U and 234U/238U variations. The 234U/238U disequilibria ratios indicate recent fluid interaction with the uranium minerals and preferential migration of 234U. Fractionation between 235U and 238U is a result of nuclear-field effects with enrichment of 238U in the reduced insoluble species (mostly UO2) and 235U in oxidised mobile species as uranyl ion, UO22+, and its complexes. Therefore, isotopic fractionation effects should be reflected in 238U/235U ratios in uranium ore minerals formed either by reduction of uranium to UO2 or chemical precipitation in the form of U6+ minerals. The δ238U values of uranium ore minerals from a variety of deposits are controlled by the isotopic signature of the uranium source, the efficiency of uranium reduction in the case of UO2 systems, and the degree to which uranium was previously removed from the fluid, with less influence from temperature of ore formation and later alteration of the ore. Uranium isotopes are potentially superb tracers of redox in natural systems.

Remote Sensing Detecting for Hydrocarbon Microseepage and Relationship with the Uranium Mineralization in Dongsheng Area, Ordos Basin, China

NASA Astrophysics Data System (ADS)

Zhu, M.; Liu, D.; Gao, Y.

2005-12-01

The Ordos Basin is located at the central area of northern China with an area of about 250,000 km2. It is well known "a basin of energy resources" of China for its large reserves of coal, oil and gas. A large-scale sandstone-type uranium metallogenic belt has been found recently in Zhiluo Formation of middle Jurassic in Dongsheng area in the northeastern part of the basin. The ore-forming mechanism remains unsolved so far. There is a hypothesis that the uranium precipitation was related to a hydrocarbon migration from the central basin. In order to explore the evidences of ever existed hydrocarbon microseepage and migration in this area, several indices such as the Iron Oxide Index, Ferrous Index, Clay Mineral Index, Mineral Composite Index, and Ferrous Transfer Percentage Index have been derived. Thorium Normalization of aeroradiometric data and fusion of aeroradiometric and TM data have been carried out as well. Therefore, the subaerial oxide and reduced area, uranium outmigrated and immigrated area, and ancient recharge and discharge of groundwater are thus delineated. As a result, two hydrocarbon microseepage belts in Dongsheng area have been extracted by combining the methods mentioned above. One is in the northern of Dongsheng along a nearly east-westward fault zone and the other one is in the southern of Dongsheng uranium mineralization belt along a nearly northwestward fault zone. The study suggests that the subaerial reduced area was related to hydrocarbon microseepage and the hydrocarbon migration along the fault and fracture zone or penetrable strata played an important role for uranium deposition in Zhiluo Formation near the northwestward fault zone.

Extracting Uranium from Seawater: Promising AF Series Adsorbents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Das, S.; Oyola, Y.; Mayes, Richard T.

A new family of high-surface-area polyethylene fiber adsorbents named the AF series was recently developed at the Oak Ridge National Laboratory (ORNL). The AF series adsorbents were synthesized by radiation-induced graft polymerization of acrylonitrile and itaconic acid (at different monomer/comonomer mol ratios) onto high surface area polyethylene fibers. The degree of grafting (%DOG) of AF series adsorbents was found to be 154-354%. The grafted nitrile groups were converted to amidoxime groups by treating with hydroxylamine. The amidoximated adsorbents were then conditioned with 0.44 M KOH at 80 °C followed by screening at ORNL with sodium-based synthetic aqueous solution, spiked withmore » 8 ppm uranium. The uranium adsorption capacity in simulated seawater screening ranged from 170 to 200 g-U/kg-ads irrespective of %DOG. A monomer/comonomer molar ratio in the range of 7.57-10.14 seemed to be optimum for highest uranium loading capacity. Subsequently, the adsorbents were also tested with natural seawater at Pacific Northwest National Laboratory (PNNL) using flow-through column experiments to determine uranium loading capacity with varying KOH conditioning times at 80 °C. The highest adsorption capacity of AF1 measured after 56 days of marine testing was demonstrated as 3.9 g-U/kg-adsorbent and 3.2 g-U/kg-adsorbent for 1 and 3 h of KOH conditioning at 80 °C, respectively. Based on capacity values of several AF1 samples, it was observed that changing KOH conditioning from 1 to 3 h at 80 °C resulted in a 22-27% decrease in uranium adsorption capacity in seawater.« less

The Effects of Radiation Chemistry on Solvent Extraction: 1. Conditions in Acidic Solution and a Review of TBP Radiolysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bruce J. Mincher; Guiseppe Modolo; Strephen P. Mezyk

2009-01-01

Solvent extraction is the most commonly used process scale separation technique for nuclear applications and it benefits from more than 60 years of research and development and proven experience at the industrial scale. Advanced solvent extraction processes for the separation of actinides and fission products from dissolved nuclear fuel are now being investigated worldwide by numerous groups (US, Europe, Russia, Japan etc.) in order to decrease the radiotoxic inventories of nuclear waste. While none of the advanced processes have yet been implemented at the industrial scale their development studies have sometimes reached demonstration tests at the laboratory scale. Most ofmore » the partitioning strategies rely on the following four separations: 1. Partitioning of uranium and/or plutonium from spent fuel dissolution liquors. 2. Separation of the heat generating fission products such as strontium and cesium. 3. Coextraction of the trivalent actinides and lanthanides. 4. Separation of the trivalent actinides from the trivalent lanthanides. Tributylphosphate (TBP) in the first separation is the basis of the PUREX, UREX and COEX processes, developed in Europe and the US, whereas monoamides as alternatives for TBP are being developed in Japan and India. For the second separation, many processes were developed worldwide, including the use of crown-ether extractants, like the FPEX process developed in the USA, and the CCD-PEG process jointly developed in the USA and Russia for the partitioning of cesium and strontium. In the third separation, phosphine oxides (CMPOs), malonamides, and diglycolamides are used in the TRUEX, DIAMEX and the ARTIST processes, respectively developed in US, Europe and Japan. Trialkylphosphine oxide(TRPO) developed in China, or UNEX (a mixture of several extractants) jointly developed in Russia and the USA allow all actinides to be co-extracted from acidic radioactive liquid waste. For the final separation, soft donor atom-containing ligands such as the bistriazinylbipyridines (BTBPs) or dithiophosphinic acids have been developed in Europe and China to selectively extract the trivalent actinides. However, in the TALSPEAK process developed in the USA, the separation is based on the relatively high affinity of aminopolycarboxylic acid complexants such as DTPA for trivalent actinides over lanthanides. In the DIDPA, SETFICS and the GANEX processes, developed in Japan and France, the group separation is accomplished in a reverse TALSPEAK process. A typical scenario is shown in Figure 1 for the UREX1a (Uranium Extraction version 1a) process. The initial step is the TBP extraction for the separation of recyclable uranium. The second step partitions the short-lived, highly radioactive cesium and strontium to minimize heat loading in the high-level waste repository. The third step is a group separation of the trivalent actinides and lanthanides with the last step being partitioning of the trivalent lanthanides from the actinides.« less

Characterization and Extraction of Uranium Contamination Perched within the Deep Vadose Zone at the Hanford Site, Washington State

NASA Astrophysics Data System (ADS)

Williams, B. A.; Rohay, V. J.; Benecke, M. W.; Chronister, G. B.; Doornbos, M. H.; Morse, J.

2012-12-01

A highly contaminated perched water zone has been discovered in the deep vadose zone above the unconfined aquifer during drilling of wells to characterize groundwater contamination within the 200 East Area of the U.S. Department of Energy's Hanford Site in southeast Washington. The perched water, which contains nitrate, uranium, and technetium-99 at concentrations that have exceeded 100,000 μg/L, 70,000 μg/L, and 45,000 pCi/L respectively, is providing contamination to the underlying unconfined aquifer. A perched zone extraction well has been installed and is successfully recovering the contaminated perched water as an early remedial measure to reduce impacts to the unconfined aquifer. The integration and interpretation of various borehole hydrogeologic, geochemical, and geophysical data sets obtained during drilling facilitated the delineation of the perching horizon and determination of the nature and extent of the perched contamination. Integration of the borehole geologic and geophysical logs defined the structural elevation and thickness of the perching low permeability silt interval. Borehole geophysical moisture logs, gamma logs, and sample data allowed detailed determination of the elevation and thickness of the oversaturated zone above the perching horizon, and the extent and magnitude of the radiological uranium contamination within the perching interval. Together, these data sets resolved the nature of the perching horizon and the location and extent of the contaminated perched water within the perching zone, allowing an estimation of remaining contaminant extent. The resulting conceptual model indicates that the contaminated perched water is contained within a localized sand lens deposited in a structural low on top of a semi-regional low-permeability silt layer. The top of the sand lens is approximately 72 m (235 ft) below ground surface; the maximum thickness of the sand lens is approximately 3 m (10 ft). The lateral and vertical extent of the perched water is limited to the presence of the sand lens and is approximately 4.6 m (15 ft) above the unconfined aquifer. Liquid wastes containing uranium and technetium-99 that were discharged decades ago to nearby engineered structures for subsurface infiltration and that leaked from single shell storage tanks have migrated vertically and laterally and are accumulating within this sand layer above the perching silt which forms a natural barrier that slows contaminant migration to the aquifer. Extraction of the contaminated perched water began in August 2011 using an automated pumping system installed in a well screened within the perched zone. As of August 1, 2012, approximately 52,000 gallons of perched water containing 115 kg of nitrate, 11.4 kg of uranium and 0.102 mg of technetium-99 have been removed from this zone.

Solubility limits of dibutyl phosphoric acid in uranium-nitric acid solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pierce, R.A.

2000-01-04

The Savannah River Site has enriched uranium (EU) solution that has been stored since being purified in its solvent extraction processes. The concentrations in solution are approximately 6 g/L U and 0.1 M nitric acid. Residual tributylphosphate in solution has slowly hydrolyzed to form dibutyl phosphoric acid (HDBP) at concentrations averaging 30--50 mg/L. Dibutyl phosphoric acid, in turn, is in equilibrium with (HDBP){sub 2} and DBP{sup {minus}}. Uranium can form compounds with the dibutylphosphate ion (DBP{sup {minus}}) which have limited solubility, thereby creating a nuclear criticality safety issue. Literature reports and earlier SRTC tests have shown that it is feasiblemore » to precipitate U-DBP solid during the storage and processing of EU solutions. As a result, a series of solubility experiments were run at nitric acid concentrations from 0--4.0 M HNO{sub 3}, uranium at 0--90 g/L, and temperatures from 0--30 C. The data shows temperature and nitric acid concentration dependence consistent with what would be expected. With respect to uranium concentration, U-DBP solubility passes through a minimum between 6 and 12 g/L U at the acid concentrations and temperatures studied. However, the minimum shows a slight shift toward lower uranium concentrations at lower nitric acid concentrations. The shifts in solubility are strongly dependent upon the overall ionic strength of the solution. The data also reveal a shift to higher DBP solubility above 0.5 M HNO{sub 3} for both 6 g/L and 12 g/L uranium solutions. Analysis of U-DBP solids from the tests identified distinct differences between precipitates from less than 0.5 M solutions and those from greater than 4 M acid. Analyses identified UO{sub 2}(DBP){sub 2} as the dominant compound present at low acid concentrations in accordance with literature reports. As the acid concentration increases, the crystalline UO{sub 2}(DBP){sub 2} shows molecular substitutions and an increase in amorphous content.« less

Mortality in a Combined Cohort of Uranium Enrichment Workers

PubMed Central

Yiin, James H.; Anderson, Jeri L.; Daniels, Robert D.; Bertke, Stephen J.; Fleming, Donald A.; Tollerud, David J.; Tseng, Chih-Yu; Chen, Pi-Hsueh; Waters, Kathleen M.

2017-01-01

Objective To examine the patterns of cause-specific mortality and relationship between internal exposure to uranium and specific causes in a pooled cohort of 29,303 workers employed at three former uranium enrichment facilities in the United States with follow-up through 2011. Methods Cause-specific standardized mortality ratios (SMRs) for the full cohort were calculated with the U.S. population as referent. Internal comparison of the dose-response relation between selected outcomes and estimated organ doses was evaluated using regression models. Results External comparison with the U.S. population showed significantly lower SMRs in most diseases in the pooled cohort. Internal comparison showed positive associations of absorbed organ doses with multiple myeloma, and to a lesser degree with kidney cancer. Conclusion In general, these gaseous diffusion plant workers had significantly lower SMRs than the U.S. population. The internal comparison however, showed associations between internal organ doses and diseases associated with uranium exposure in previous studies. PMID:27753121

The paradox of uranium development: A Polanyian analysis of social movements surrounding the Pinon Ridge Uranium Mill

NASA Astrophysics Data System (ADS)

Malin, Stephanie A.

Renewal of nuclear energy development has been proposed as one viable solution for reducing greenhouse gas emissions and impacts of climate change. This discussion became concrete as the first uranium mill proposed since the end of the Cold War, the Pinon Ridge Uranium Mill, received state permits in January 2011 to process uranium in southwest Colorado's Paradox Valley. Though environmental contamination from previous uranium activity caused one local community to be bulldozed to the ground, local support for renewed uranium activity emerges among local residents in communities like Nucla, Naturita, and Bedrock, Colorado. Regionally, however, a coalition of organized, oppositionbased grassroots groups fights the decision to permit the mill. Combined, these events allow social scientists a natural laboratory through which to view social repercussions of nuclear energy development. In this dissertation, I use a Polanyian theoretical framework to analyze social, political-economic, and environmental contexts of social movements surrounding PR Mill. My overarching research problem is: How might Polanyian double movement theory be applied to and made empirically testable within the social and environmental context of uranium development? I intended this analysis to inform energy policy debates regarding renewable energy. In Chapter 1, I found various forms of social dislocation lead to two divergent social movement outcomes. Economic social dislocation led to strong mill support among most local residents, according to archival, in-depth interview, and survey data. On the other hand, residents in regional communities experienced two other types of social dislocation -- another kind of economic dislocation, related to concern over boom-bust economies, and environmental health dislocations related to uranium exposure, creating conditions for a regional movement in opposition to PR Mill. In Chapter 2, I focus on regulations and find that two divergent social movements -- a support movement locally and a countermovement against the mill regionally -- emerge also as a result of strong faith in regulations, regulators, and Energy Fuels countered by marked distrust in regulations, regulators, and Energy Fuels, respectively. In Chapter 3, I advance Polanyi's double movement theory by comparing different emergent social movements surrounding uranium, showing that historically different circumstances surrounding uranium can help create conditions for divergent social movements.

Visualizing fossilization using laser ablation-inductively coupled plasma-mass spectrometry maps of trace elements in Late Cretaceous bones

USGS Publications Warehouse

Koenig, A.E.; Rogers, R.R.; Trueman, C.N.

2009-01-01

Elemental maps generated by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) provide a previously unavailable high-resolution visualization of the complex physicochemical conditions operating within individual bones during the early stages of diagenesis and fossilization. A selection of LA-ICP-MS maps of bones collected from the Late Cretaceous of Montana (United States) and Madagascar graphically illustrate diverse paths to recrystallization, and reveal unique insights into geochemical aspects of taphonomic history. Some bones show distinct gradients in concentrations of rare earth elements and uranium, with highest concentrations at external bone margins. Others exhibit more intricate patterns of trace element uptake related to bone histology and its control on the flow paths of pore waters. Patterns of element uptake as revealed by LA-ICP-MS maps can be used to guide sampling strategies, and call into question previous studies that hinge upon localized bulk samples of fossilized bone tissue. LA-ICP-MS maps also allow for comparison of recrystallization rates among fossil bones, and afford a novel approach to identifying bones or regions of bones potentially suitable for extracting intact biogeochemical signals. ?? 2009 Geological Society of America.

3 CFR - Continuation of the National Emergency With Respect to the Risk of Nuclear Proliferation Created...

Code of Federal Regulations, 2013 CFR

2013-01-01

... to the Risk of Nuclear Proliferation Created by the Accumulation of Weapons-Usable Fissile Material... Proliferation Created by the Accumulation of Weapons-Usable Fissile Material in the Territory of the Russian... Disposition of Highly Enriched Uranium Extracted from Nuclear Weapons, dated February 18, 1993, and related...

3 CFR - Continuation of the National Emergency With Respect to the Risk of Nuclear Proliferation Created...

Code of Federal Regulations, 2011 CFR

2011-01-01

... to the Risk of Nuclear Proliferation Created by the Accumulation of Weapons-usable Fissile Material... Proliferation Created by the Accumulation of Weapons-usable Fissile Material in the Territory of the Russian... Disposition of Highly Enriched Uranium Extracted from Nuclear Weapons, dated February 18, 1993, and related...

75 FR 34919 - Continuation of the National Emergency With Respect To the Risk of Nuclear Proliferation Created...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-06-18

... To the Risk of Nuclear Proliferation Created By the Accumulation of Weapons-usable Fissile Material... Risk of Nuclear Proliferation Created By the Accumulation of Weapons-usable Fissile Material In the... Russian Federation Concerning the Disposition of Highly Enriched Uranium Extracted from Nuclear Weapons...

77 FR 37261 - Continuation of the National Emergency With Respect to the Risk of Nuclear Proliferation Created...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-06-21

... National Emergency With Respect to the Risk of Nuclear Proliferation Created by the Accumulation of Weapons... Extracted from Nuclear Weapons, dated February 18, 1993, and related contracts and agreements (collectively... derived from nuclear weapons to low enriched uranium for peaceful commercial purposes. The order invoked...

Processing fissile material mixtures containing zirconium and/or carbon

DOEpatents

Johnson, Michael Ernest; Maloney, Martin David

2013-07-02

A method of processing spent TRIZO-coated nuclear fuel may include adding fluoride to complex zirconium present in a dissolved TRIZO-coated fuel. Complexing the zirconium with fluoride may reduce or eliminate the potential for zirconium to interfere with the extraction of uranium and/or transuranics from fission materials in the spent nuclear fuel.

The oxidative corrosion of carbide inclusions at the surface of uranium metal during exposure to water vapour.

PubMed

Scott, T B; Petherbridge, J R; Harker, N J; Ball, R J; Heard, P J; Glascott, J; Allen, G C

2011-11-15

The reaction between uranium and water vapour has been well investigated, however discrepancies exist between the described kinetic laws, pressure dependence of the reaction rate constant and activation energies. Here this problem is looked at by examining the influence of impurities in the form of carbide inclusions on the reaction. Samples of uranium containing 600 ppm carbon were analysed during and after exposure to water vapour at 19 mbar pressure, in an environmental scanning electron microscope (ESEM) system. After water exposure, samples were analysed using secondary ion mass spectrometry (SIMS), focused ion beam (FIB) imaging and sectioning and transmission electron microscopy (TEM) with X-ray diffraction (micro-XRD). The results of the current study indicate that carbide particles on the surface of uranium readily react with water vapour to form voluminous UO(3) · xH(2)O growths at rates significantly faster than that of the metal. The observation may also have implications for previous experimental studies of uranium-water interactions, where the presence of differing levels of undetected carbide may partly account for the discrepancies observed between datasets. Crown Copyright © 2011. Published by Elsevier B.V. All rights reserved.

XAS and TRLIF spectroscopy of uranium and neptunium in seawater.

PubMed

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

2015-03-28

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

Experimental design and optimization of leaching process for recovery of valuable chemical elements (U, La, V, Mo, Yb and Th) from low-grade uranium ore.

PubMed

Zakrzewska-Koltuniewicz, Grażyna; Herdzik-Koniecko, Irena; Cojocaru, Corneliu; Chajduk, Ewelina

2014-06-30

The paper deals with experimental design and optimization of leaching process of uranium and associated metals from low-grade, Polish ores. The chemical elements of interest for extraction from the ore were U, La, V, Mo, Yb and Th. Sulphuric acid has been used as leaching reagent. Based on the design of experiments the second-order regression models have been constructed to approximate the leaching efficiency of elements. The graphical illustrations using 3-D surface plots have been employed in order to identify the main, quadratic and interaction effects of the factors. The multi-objective optimization method based on desirability approach has been applied in this study. The optimum condition have been determined as P=5 bar, T=120 °C and t=90 min. Under these optimal conditions, the overall extraction performance is 81.43% (for U), 64.24% (for La), 98.38% (for V), 43.69% (for Yb) and 76.89% (for Mo) and 97.00% (for Th). Copyright © 2014 Elsevier B.V. All rights reserved.

Environmental proteomics reveals early microbial community responses to biostimulation at a uranium- and nitrate-contaminated site.

PubMed

Chourey, Karuna; Nissen, Silke; Vishnivetskaya, Tatiana; Shah, Manesh; Pfiffner, Susan; Hettich, Robert L; Löffler, Frank E

2013-10-01

High-performance MS instrumentation coupled with improved protein extraction techniques enables metaproteomics to identify active members of soil and groundwater microbial communities. Metaproteomics workflows were applied to study the initial responses (i.e. 4 days post treatment) of the indigenous aquifer microbiota to biostimulation with emulsified vegetable oil (EVO) at a uranium-contaminated site. Members of the Betaproteobacteria (i.e. Dechloromonas, Ralstonia, Rhodoferax, Polaromonas, Delftia, Chromobacterium) and the Firmicutes dominated the biostimulated aquifer community. Proteome characterization revealed distinct differences between the microbial biomass collected from groundwater influenced by biostimulation and groundwater collected upgradient of the EVO injection points. In particular, proteins involved in ammonium assimilation, EVO degradation, and polyhydroxybutyrate granule formation were prominent following biostimulation. Interestingly, the atypical NosZ of Dechloromonas spp. was highly abundant, suggesting active nitrous oxide (N2 O) respiration. c-Type cytochromes were barely detected, as was citrate synthase, a biomarker for hexavalent uranium reduction activity, suggesting that uranium reduction has not commenced 4 days post EVO amendment. Environmental metaproteomics identified microbial community responses to biostimulation and elucidated active pathways demonstrating the value of this technique as a monitoring tool and for complementing nucleic acid-based approaches. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrometallurgical methods of recovery of scandium from the wastes of various technologies

NASA Astrophysics Data System (ADS)

Molchanova, T. V.; Akimova, I. D.; Smirnov, K. M.; Krylova, O. K.; Zharova, E. V.

2017-03-01

The recovery of scandium from the wastes of the production of uranium, titanium, iron-vanadium, and alumina is studied. The applied acid schemes of scandium transfer to a solution followed by ion-exchange recovery and extraction concentration of scandium ensure the precipitation of crude scandium oxides containing up to 5% Sc2O3. Scandium oxides of 99.96-99.99% purity are formed after additional refining of these crude oxides according to an extraction technology using a mixture 15% multiradical phosphine oxide or Cyanex-925 + 15% tributyl phosphate in kerosene.

Natural radionuclide and plutonium content in Black Sea bottom sediments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Strezov, A.; Stoilova, T.; Yordanova, I.

1996-01-01

The content of uranium, thorium, radium, lead, polonium, and plutonium in bottom sediments and algae from two locations at the Bulgarian Black Sea coast have been determined. Some parent:progeny ratios for evaluation of the geochemical behavior of the nuclides have been estimated as well. The extractable and total uranium and thorium are determined by two separate radiochemical procedures to differentiate the more soluble chemical forms of the elements and to estimate the potential hazard for the biosphere and for humans. No distinct seasonal variation as well as no significant change in total and extractable uranium (also for {sup 226}Ra) contentmore » is observed. The same is valid for extractable thorium while the total thorium content in the first two seasons is slightly higher. Our data show that {sup 210}Po content is accumulated more in the sediments than {sup 210}Pb, and the evaluated disequilibria suggest that the two radionuclides belong to more recent sediment layers deposited in the slime samples compared to the silt ones for the different seasons. The obtained values for plutonium are in the lower limits of the data cited in literature, which is quite clear as there are no plutonium discharge facilities at the Bulgarian Black Sea coast. The obtained values for the activity ratio {sup 238}Pu: {sup 239+240}Pu are higher for Bjala sediments compared to those of Kaliakra. The ratio values are out of the variation range for the global contamination with weapon tests fallout plutonium which is probably due to Chernobyl accident contribution. The dependence of natural radionuclide content on the sediment type as well as the variation of nuclide accumulation for two types of algae in two sampling locations for five consecutive seasons is evaluated. No serious contamination with natural radionuclides in the algae is observed. 38 refs., 6 figs., 7 tabs.« less

MOLECULAR SIEVES ADSORB IODINE-131 FROM AIR

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wahlgren, M.A.; Meinke, W.W.

1957-09-01

Consideration has been given to the problem of separating and estimating U, Po, nnd other alpha emitters (in order to provide analytical methods for their routine determination in conformity with the draft agreement on the Harwell effluent). Uranium may be ether extracted from solutions of NH/sub 4/NO/sub 3/ as salting out agent at pH1 with an efficiency of 98 to 99%. The deposition of Po on Ag foil is a specific method for this element and under prescribed conditions similar extraction efficiencies may be obtained. An adequate separation from all "other alpha emitters" is obtained and methods for the estimationmore » of these are discussed. A comprehensive scheme involving a preliminary activity concentration step has been elaborated. U, Po, and the majority of the "other alpha emitters" are precipitated as their tannin complexes at pH8 using Ca(OH)/sub 2/, the calcium-tannin complex acting as a carrier. That part of the activity remaining in solution is determined as in the total activity method, previously described. From the solution of the precipitate, Po is first separated by electrodeposition, and then U by ether extraction in the presence of NH/sub 4/NO/sub 3/. The majority of the "other alpha emitters" still in the aqueous NH/sub 4/NO/sub 3/ solution are collected on a second calcium-tannin precipitate, while the small part remaining in solution after this operation is obtained by direct evaporation. (auth)« less

Unraveling uranium induced oxidative stress related responses in Arabidopsis thaliana seedlings. Part II: responses in the leaves and general conclusions.

PubMed

Vanhoudt, Nathalie; Cuypers, Ann; Horemans, Nele; Remans, Tony; Opdenakker, Kelly; Smeets, Karen; Bello, Daniel Martinez; Havaux, Michel; Wannijn, Jean; Van Hees, May; Vangronsveld, Jaco; Vandenhove, Hildegarde

2011-06-01

The cellular redox balance seems an important modulator under heavy metal stress. While for other heavy metals these processes are well studied, oxidative stress related responses are also known to be triggered under uranium stress but information remains limited. This study aimed to further unravel the mechanisms by which plants respond to uranium stress. Seventeen-day-old Arabidopsis thaliana seedlings, grown on a modified Hoagland solution under controlled conditions, were exposed to 0, 0.1, 1, 10 and 100 μM uranium for 1, 3 and 7 days. While in Part I of this study oxidative stress related responses in the roots were discussed, this second Part II discusses oxidative stress related responses in the leaves and general conclusions drawn from the results of the roots and the leaves will be presented. As several responses were already visible following 1 day exposure, when uranium concentrations in the leaves were negligible, a root-to-shoot signaling system was suggested in which plastids could be important sensing sites. While lipid peroxidation, based on the amount of thiobarbituric acid reactive compounds, was observed after exposure to 100 μM uranium, affecting membrane structure and function, a transient concentration dependent response pattern was visible for lipoxygenase initiated lipid peroxidation. This transient character of uranium stress responses in leaves was emphasized by results of lipoxygenase (LOX2) and antioxidative enzyme transcript levels, enzyme capacities and glutathione concentrations both in time as with concentration. The ascorbate redox balance seemed an important modulator of uranium stress responses in the leaves as in addition to the previous transient responses, the total ascorbate concentration and ascorbate/dehydroascorbate redox balance increased in a concentration and time dependent manner. This could represent either a slow transient response or a stable increase with regard to plant acclimation to uranium stress. Copyright © 2011 Elsevier Ltd. All rights reserved.

SEPARATION OF RUTHENIUM FROM AQUEOUS SOLUTIONS

DOEpatents

Callis, C.F.; Moore, R.L.

1959-09-01

>The separation of ruthenium from aqueous solutions containing uranium plutonium, ruthenium, and fission products is described. The separation is accomplished by providing a nitric acid solution of plutonium, uranium, ruthenium, and fission products, oxidizing plutonium to the hexavalent state with sodium dichromate, contacting the solution with a water-immiscible organic solvent, such as hexone, to extract plutonyl, uranyl, ruthenium, and fission products, reducing with sodium ferrite the plutonyl in the solvent phase to trivalent plutonium, reextracting from the solvent phase the trivalent plutonium, ruthenium, and some fission products with an aqueous solution containing a salting out agent, introducing ozone into the aqueous acid solution to oxidize plutonium to the hexavalent state and ruthenium to ruthenium tetraoxide, and volatizing off the ruthenium tetraoxide.

Evaluation of the suitability of neural network method for prediction of uranium activity ratio in environmental alpha spectra.

PubMed

Einian, Mohammad Reza; Aghamiri, Seyed Mahmood Reza; Ghaderi, Reza

2015-11-01

Applying Artificial Neural Network to an alpha spectrometry system is a good idea to discriminate the composition of environmental and non-environmental materials by the estimation of the (234)U/(238)U activity ratio. Because it eliminates limitations of classical approaches by the extraction the desired information from the average of a partial uranium raw spectrum. The network was trained by an alpha spectrum library which was developed in this work. The results indicated that there was a small difference between the target values and the predictions. These results were acceptable, because the thickness of samples and the inferring elements were different in the real library. Copyright © 2015 Elsevier Ltd. All rights reserved.

Distribution of Pd, Ag & U in the SiC Layer of an Irradiated TRISO Fuel Particle

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thomas M. Lillo; Isabella J. van Rooyen

2014-08-01

The distribution of silver, uranium and palladium in the silicon carbide (SiC) layer of an irradiated TRISO fuel particle was studied using samples extracted from the SiC layer using focused ion beam (FIB) techniques. Transmission electron microscopy in conjunction with energy dispersive x-ray spectroscopy was used to identify the presence of the specific elements of interest at grain boundaries, triple junctions and precipitates in the interior of SiC grains. Details on sample fabrication, errors associated with measurements of elemental migration distances and the distances migrated by silver, palladium and uranium in the SiC layer of an irradiated TRISO particle frommore » the AGR-1 program are reported.« less

The role of water in unconventional in situ energy resource extraction technologies: Chapter 7 in Food, energy, and water: The chemistry connection

USGS Publications Warehouse

Gallegos, Tanya J.; Bern, Carleton R.; Birdwell, Justin E.; Haines, Seth S.; Engle, Mark A.

2015-01-01

Global trends toward developing new energy resources from lower grade, larger tonnage deposits that are not generally accessible using “conventional” extraction methods involve variations of subsurface in situ extraction techniques including in situ oil-shale retorting, hydraulic fracturing of petroleum reservoirs, and in situ recovery (ISR) of uranium. Although these methods are economically feasible and perhaps result in a smaller above-ground land-use footprint, there remain uncertainties regarding potential subsurface impacts to groundwater. This chapter provides an overview of the role of water in these technologies and the opportunities and challenges for water reuse and recycling.

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

USGS Publications Warehouse

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

2010-01-01

This chapter compiles available chemical and radiation toxicity information for plants and animals from the scientific literature on naturally occurring uranium and associated radionuclides. Specifically, chemical and radiation hazards associated with radionuclides in the uranium decay series including uranium, thallium, thorium, bismuth, radium, radon, protactinium, polonium, actinium, and francium were the focus of the literature compilation. In addition, exposure pathways and a food web specific to the segregation areas were developed. Major biological exposure pathways considered were ingestion, inhalation, absorption, and bioaccumulation, and biota categories included microbes, invertebrates, plants, fishes, amphibians, reptiles, birds, and mammals. These data were developed for incorporation into a risk assessment to be conducted as part of an environmental impact statement for the Bureau of Land Management, which would identify representative plants and animals and their relative sensitivities to exposure of uranium and associated radionuclides. This chapter provides pertinent information to aid in the development of such an ecological risk assessment but does not estimate or derive guidance thresholds for radionuclides associated with uranium. Previous studies have not attempted to quantify the risks to biota caused directly by the chemical or radiation releases at uranium mining sites, although some information is available for uranium mill tailings and uranium mine closure activities. Research into the biological impacts of uranium exposure is strongly biased towards human health and exposure related to enriched or depleted uranium associated with the nuclear energy industry rather than naturally occurring uranium associated with uranium mining. Nevertheless, studies have reported that uranium and other radionuclides can affect the survival, growth, and reproduction of plants and animals. Exposure to chemical and radiation hazards is influenced by a plant’s or an animal’s life history and surrounding environment. Various species of plants, invertebrates, fishes, amphibians, reptiles, birds, and mammals found in the segregation areas that are considered species of concern by State and Federal agencies were included in the development of the site-specific food web. The utilization of subterranean habitats (burrows in uranium-rich areas, burrows in waste rock piles or reclaimed mining areas, mine tunnels) in the seasonally variable but consistently hot, arid environment is of particular concern in the segregation areas. Certain species of reptiles, amphibians, birds, and mammals in the segregation areas spend significant amounts of time in burrows where they can inhale or ingest uranium and other radionuclides through digging, eating, preening, and hibernating. Herbivores may also be exposed though the ingestion of radionuclides that have been aerially deposited on vegetation. Measured tissues concentrations of uranium and other radionuclides are not available for any species of concern in the segregation areas. The sensitivity of these animals to uranium exposure is unknown based on the existing scientific literature, and species-specific uranium presumptive effects levels were only available for two endangered fish species known to inhabit the segregation areas. Overall, the chemical toxicity data available for biological receptors of concern were limited, although chemical and radiation toxicity guidance values are available from several sources. However, caution should be used when directly applying these values to northern Arizona given the unique habitat and life history strategies of biological receptors in the segregation areas and the fact that some guidance values are based on models rather than empirical (laboratory or field) data. No chemical toxicity information based on empirical data is available for reptiles, birds, or wild mammals; therefore, the risks associated with uranium and other radionuclides are unknown for these biota.

Host rocks and their alterations as related to uranium-bearing veins in the United States

USGS Publications Warehouse

Walker, George W.

1956-01-01

This paper, dealing with the different kinds of host rocks and their alterations associated with uranium-bearing veins in the United States, is a chapter of a comprehensive report entitled , "Geology of uranium-bearing vein deposits in the United States," in preparation by George W. Walker, Frank W. Osterwald, and others. The comprehensive report will include detailed information on tectonic and structural setting, kinds of host rocks, wall-rock alteration, mineralogy, physical characteristics, processes of deposition, and concepts of origin of uraniferous veins; but, because it will not be completed until sometime in the future, some chapters of the report are being transmitted as they are finished. Part of an introductory chapter to the comprehensive report entitled, "Classification and distribution of uranium-bearing veins in the United States" (Walker and Osterwald, 1956) has already been transmitted; several of the terms used herein are defined in the introductory chapter. Data included in this chapter demonstrate that uranium-bearing veins are: 1) in rocks of nearly all textural, chemical, and mineralogic types; 2) most abundant in holocrystalline, commonly equigranular, igeneous and metamorphic rocks characterized by a moderate to high silica content and and by similar physical properties. Although some of the physiochemical properties of the host rocks are discussed in terms of favorability or nonfavoribility for uranium deposition, the principal purpose of this chapter is to establish the petroloic environment in which uranium-bearing veins have been found. Because favorability or nonfavorability of host rocks is related complexly to the chemistry of ore solutions and to methods or uranium transport and deposition, several hypothetical processes of transport and deposition have been referred to briefly; these and other hypotheses will be outlines and discussed in greater detail in a subsequent chapter. The compilation of data leading to this report and its preparation by a member of the Uranium Research and Resource Section, U.S. Geological Survey, was done on behalf of the Division of Raw Materials, U.S. Atomic Energy Commission. The report is based on both published and unpublished information collected principally by personnel of the U.S. Geological Survey, the U.S. Atomic Energy Commission or its predecessor organization, the Manhattan Engineer District, and to a lesser extent by staff members of other Federal or State agencies and by geologists in private industry. Information concerning foreign uranium-bearing vein deposits has been extracted almost exclusively from published reports; references to these and other data are included at appropriate places.

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

USGS Publications Warehouse

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 simulate the upper limit of dissolved oxygen in recharge water. Overall about 9% of total uranium removed from solution during biostimulation was remobilized. Release of U during oxic elution was a continuous process over 140 days with dissolved uranium concentrations about 0.2 and 0.8 aM for columns with and without ferrous iron addition, respectively. Uranium remaining on the sediment was in the reduced form. The prolonged period of biostimulation and concomitant sulfate reduction appears to limit the rate of U(IV) oxidative remobilization in contrast to a large release observed for columns in previous studies that did not undergo sulfate reduction. Although continued sulfate reduction may cause decreased permeability from precipitation of iron sulfide, the greater apparent stability of the sequestered U(IV) provided by the sustained biostimulation should be considered in design of field scale remediation efforts. Remobilization of uranium following biostimulated reduction should be tested further at the field scale.

The U.S. Army Chemical Corps and a Future Within AFRICOM

DTIC Science & Technology

2009-03-01

pollution of surface and coastal waters; poaching of elephants for ivory • Namibia: diamonds, copper, uranium, gold, silver, lead, tin, lithium...desertification; wildlife populations (such as elephant , hippopotamus, giraffe, and lion) threatened because of poaching and habitat destruction...extraction and refining region; chemical runoff into watersheds; poaching seriously threatens rhinoceros, elephant , antelope, and large cat populations

10 CFR Appendix I to Part 110 - Illustrative List of Reprocessing Plant Components Under NRC Export Licensing Authority

Code of Federal Regulations, 2014 CFR

2014-01-01

... dissolution, solvent extraction, and process liquor storage. There may also be equipment for thermal denitration of uranium nitrate, conversion of plutonium nitrate to oxide metal, and treatment of fission product waste liquor to a form suitable for long term storage or disposal. However, the specific type and...

10 CFR Appendix I to Part 110 - Illustrative List of Reprocessing Plant Components Under NRC Export Licensing Authority

Code of Federal Regulations, 2013 CFR

2013-01-01

... dissolution, solvent extraction, and process liquor storage. There may also be equipment for thermal denitration of uranium nitrate, conversion of plutonium nitrate to oxide metal, and treatment of fission product waste liquor to a form suitable for long term storage or disposal. However, the specific type and...

10 CFR Appendix I to Part 110 - Illustrative List of Reprocessing Plant Components Under NRC Export Licensing Authority

Code of Federal Regulations, 2012 CFR

2012-01-01

... dissolution, solvent extraction, and process liquor storage. There may also be equipment for thermal denitration of uranium nitrate, conversion of plutonium nitrate to oxide metal, and treatment of fission product waste liquor to a form suitable for long term storage or disposal. However, the specific type and...

Improving the Estimates of Waste from the Recycling of Used Nuclear Fuel - 13410

DOE Office of Scientific and Technical Information (OSTI.GOV)

Phillips, Chris; Willis, William; Carter, Robert

2013-07-01

Estimates are presented of wastes arising from the reprocessing of 50 GWD/tonne, 5 year and 50 year cooled used nuclear fuel (UNF) from Light Water Reactors (LWRs), using the 'NUEX' solvent extraction process. NUEX is a fourth generation aqueous based reprocessing system, comprising shearing and dissolution in nitric acid of the UNF, separation of uranium and mixed uranium-plutonium using solvent extraction in a development of the PUREX process using tri-n-butyl phosphate in a kerosene diluent, purification of the plutonium and uranium-plutonium products, and conversion of them to uranium trioxide and mixed uranium-plutonium dioxides respectively. These products are suitable for usemore » as new LWR uranium oxide and mixed oxide fuel, respectively. Each unit process is described and the wastes that it produces are identified and quantified. Quantification of the process wastes was achieved by use of a detailed process model developed using the Aspen Custom Modeler suite of software and based on both first principles equilibrium and rate data, plus practical experience and data from the industrial scale Thermal Oxide Reprocessing Plant (THORP) at the Sellafield nuclear site in the United Kingdom. By feeding this model with the known concentrations of all species in the incoming UNF, the species and their concentrations in all product and waste streams were produced as the output. By using these data, along with a defined set of assumptions, including regulatory requirements, it was possible to calculate the waste forms, their radioactivities, volumes and quantities. Quantification of secondary wastes, such as plant maintenance, housekeeping and clean-up wastes, was achieved by reviewing actual operating experience from THORP during its hot operation from 1994 to the present time. This work was carried out under a contract from the United States Department of Energy (DOE) and, so as to enable DOE to make valid comparisons with other similar work, a number of assumptions were agreed. These include an assumed reprocessing capacity of 800 tonnes per year, the requirement to remove as waste forms the volatile fission products carbon-14, iodine-129, krypton-85, tritium and ruthenium-106, the restriction of discharge of any water from the facility unless it meets US Environmental Protection Agency drinking water standards, no intentional blending of wastes to lower their classification, and the requirement for the recovered uranium to be sufficiently free from fission products and neutron-absorbing species to allow it to be re-enriched and recycled as nuclear fuel. The results from this work showed that over 99.9% of the radioactivity in the UNF can be concentrated via reprocessing into a fission-product-containing vitrified product, bottles of compressed krypton storage and a cement grout containing the tritium, that together have a volume of only about one eighth the volume of the original UNF. The other waste forms have larger volumes than the original UNF but contain only the remaining 0.1% of the radioactivity. (authors)« less

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

NASA Astrophysics Data System (ADS)

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 non-fractionating oxidation, is occurring within this zone. Thus, release of uranium from the NRZs may play a critical role in the persistence of groundwater contamination at these sites.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ivanov, Alexander S.; Bryantsev, Vyacheslav S.

Uranium is used as the basic fuel for nuclear power plants, which generate significant amounts of electricity and have life cycle carbon emissions that are as low as renewable energy sources. However, the extraction of this valuable energy commodity from the ground remains controversial, mainly because of environmental and health impacts. Alternatively, seawater offers an enormous uranium resource that may be tapped at minimal environmental cost. Nowadays, amidoxime polymers are the most widely utilized sorbent materials for large-scale extraction of uranium from seawater, but they are not perfectly selective for uranyl, UO 2 2+. In particular, the competition between UOmore » 2 2+ and VO 2+/VO2+ cations poses a significant challenge to the effi-cient mining of UO 2 2+. Thus, screening and rational design of more selective ligands must be accomplished. One of the key components in achieving this goal is the establishment of computational techniques capable of assessing ligand selec-tivity trends. Here, we report an approach based on quantum chemical calculations that achieves high accuracy in repro-ducing experimental aqueous stability constants for VO 2+/VO 2+ complexes with ten different oxygen donor lig-ands. The predictive power of the developed computational protocol was demonstrated for amidoxime-type ligands, providing greater insights into new design strategies for the development of the next generation of adsorbents with high selectivity toward UO 2 2+over VO 2+/VO 2+ ions. Furthermore, the results of calculations suggest that alkylation of amidox-ime moieties present in poly(acrylamidoxime) sorbents can be a potential route to better discrimination between the uranyl and competing vanadium ions within seawater.« less

Energy balance for uranium recovery from seawater

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schneider, E.; Lindner, H.

The energy return on investment (EROI) of an energy resource is the ratio of the energy it ultimately produces to the energy used to recover it. EROI is a key viability measure for a new recovery technology, particularly in its early stages of development when financial cost assessment would be premature or highly uncertain. This paper estimates the EROI of uranium recovery from seawater via a braid adsorbent technology. In this paper, the energy cost of obtaining uranium from seawater is assessed by breaking the production chain into three processes: adsorbent production, adsorbent deployment and mooring, and uranium elution andmore » purification. Both direct and embodied energy inputs are considered. Direct energy is the energy used by the processes themselves, while embodied energy is used to fabricate their material, equipment or chemical inputs. If the uranium is used in a once-through fuel cycle, the braid adsorbent technology EROI ranges from 12 to 27, depending on still-uncertain performance and system design parameters. It is highly sensitive to the adsorbent capacity in grams of U captured per kg of adsorbent as well as to potential economies in chemical use. This compares to an EROI of ca. 300 for contemporary terrestrial mining. It is important to note that these figures only consider the mineral extraction step in the fuel cycle. At a reference performance level of 2.76 g U recovered per kg adsorbent immersed, the largest energy consumers are the chemicals used in adsorbent production (63%), anchor chain mooring system fabrication and operations (17%), and unit processes in the adsorbent production step (12%). (authors)« less

Dibutyl Phosphoric Acid Solubility in High-Acid, Uranium-Bearing Solutions at SRS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pierce, R.A.

1998-10-02

The Savannah River Site has enriched uranium (EU) solution which has been stored for almost 10 years since being purified in the second uranium cycle of the H area solvent extraction process. The concentrations in solution are approximately 6 g/L U and about 0.1 M nitric acid. Residual tributylphosphate in the solutions has slowly hydrolyzed to form dibutyl phosphoric acid (HDBP) at concentrations averaging 50 mg/L. Uranium is known to form compounds with the dibutylphosphate ion (DBP) which have limited solubility. The potential to form uranium-DBP solids raises a nuclear criticality safety issue. Prior SRTC tests (WSRC-TR-98-00188) showed that U-DBPmore » solids precipitate at concentrations potentially attainable during the storage of enriched uranium solutions. Furthermore, evaporation of the existing EUS solution without additional acidification could result in the precipitation of U-DBP solids if the DBP concentration in the resulting solution exceeds 110 mg/L at ambient temperature. The same potential exists for evaporation of unwashed 1CU solutions. As a follow-up to the earlier studies, SRTC studied the solubility limits for solutions containing acid concentrations above 0.5M HNO3. The data obtained in these tests reveals a shift to higher levels of DBP solubility above 0.5M HNO3 for both 6 g/L and 12 g/L uranium solutions. Analysis of U-DBP solids from the tests identified a mixture of different molecular structures for the solids created. The analysis distinguished UO2(DBP)2 as the dominant compound present at low acid concentrations. As the acid concentration increases, the crystalline UO2(DBP)2 shows molecular substitutions and an increase in amorphous content. Further analysis by methods not available at SRS will be needed to better identify the specific compounds present. This data indicates that acidification prior to evaporation can be used to increase the margin of safety for the storage of the EUS solutions. Subsequent experimentation evaluated options for absorbing HDBP from solution using either activated carbon or anion exchange resin. The activated carbon outperformed the anion exchange resin. Activated carbon absorbs DBP rapidly and has demonstrated the capability of absorbing 15 mg of DBP per gram of activated carbon. Analytical results also show that activated carbon absorbs uranium up to 17 mg per gram of carbon. It is speculated that the uranium absorbed is part of a soluble U-DBP complex that has been absorbed. Additional testing must still be performed to 1) establish absorption limits for uranium for anion exchange resin, 2) evaluate desorption characteristics of uranium and DBP, and 3) study the possibility of re-using the absorbent.« less

Mobilities of uranium and mercury ions in helium

NASA Technical Reports Server (NTRS)

Johnsen, R.; Biondi, M. A.

1972-01-01

The mobilities of mass-identified U(+) and Hg (+) ions in helium were determined in a drift tube-mass spectrometer. For uranium ions, a reduced mobility value is obtained at 305 K and a standard gas density of 2.69 x 10 to the 19th power/cu cm. The mobility of mercury ions is in agreement with two previous determinations. The effect of fast ion injection in drift mobility measurements is discussed, and a technique to circumvent these problems is described. The results are compared with existing theories of ion mobilities.

United States Transuranium and Uranium Registries. Annuary report, February 1, 2004 - June 30, 2005

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alldredge, J. Richard; Ehrhart, Susan M.; Eliston, James T.

2006-05-31

Three events of significance to the U. S. Transuranium and Uranium Registries (USTUR) occurred during this reporting period: 1. The search for a new Associate Director was successful in that Dr. Anthony C. (Tony) James was appointed to the position, 2. A five-year grant for the operation of the USTUR was approved by the U. S. Department of Energy; the previous grant cycles were for three years, 3. I retired from the USTUR Directorship on July 1, 2005 and Tony James became the new Director.

PROCESS FOR PRODUCING ALKYL ORTHOPHOSPHORIC ACID EXTRACTANTS

DOEpatents

Grinstead, R.R.

1962-01-23

A process is given for producing superior alkyl orthophosphoric acid extractants for use in solvent extraction methods to recover and purify various metals such as uranium and vanadium. The process comprises slurrying P/sub 2/O/ sub 5/ in a solvent diluent such as kerosene, benzene, isopropyl ether, and the like. An alipbatic alcohol having from nine to seventeen carbon atoms, and w- hcrein ihc OH group is situated inward of the terminal carbon atoms, is added to the slurry while the reaction temperature is mainiained below 60 deg C. The alcohol is added in the mole ratio of about 2 to l, alcohol to P/sub 2/O/sub 5/. A pyrophosphate reaotion product is formed in the slurry-alcohol mixture. Subsequently, the pyrophosphate reaction product is hydrolyzed with dilute mineral acid to produce the desired alkyl orthophosphoric aeid extractant. The extraetant may then be separated and utilized in metal-recovery, solvent- extraction processes. (AEC)

Linking Chaotic Advection with Subsurface Biogeochemical Processes

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Development of a reactive zone technology for simultaneous in situ immobilisation of radium and uranium

NASA Astrophysics Data System (ADS)

Burghardt, D.; Kassahun, A.

2005-12-01

Simultaneous in situ immobilisation of uranium (U) and radium (226Ra) by injectible amounts of grey cast iron (gcFe), nano-scale iron (naFe) and a gcFe/MnO2 mixture (1:1) was studied in batch and column tests. Both 0.5 g/L naFe and gcFe are effective in 226Ra and U removal from mine water, whereas MnO2 addition clearly increased the efficiency of gcFe for 226Ra and U immobilisation. In a column test with 0.6 wt% gcFe/MnO2 mixture (1:1), neither 226Ra nor U was detected in the effluent after replacement of 45 pore volumes. A sequential extraction under flow condition revealed 226Ra to be mostly occluded in manganese oxides. Uranium was mostly sorbed onto poorly crystalline iron hydroxides, but a significant part was found to be occluded in manganese oxides also. The results of this study suggest that MnO2 promotes iron hydroxide formation under slightly reducing environmental conditions resulting in an increased pollutant retention capacity.

Critical analysis of world uranium resources

USGS Publications Warehouse

Hall, Susan; Coleman, Margaret

2013-01-01

The U.S. Department of Energy, Energy Information Administration (EIA) joined with the U.S. Department of the Interior, U.S. Geological Survey (USGS) to analyze the world uranium supply and demand balance. To evaluate short-term primary supply (0–15 years), the analysis focused on Reasonably Assured Resources (RAR), which are resources projected with a high degree of geologic assurance and considered to be economically feasible to mine. Such resources include uranium resources from mines currently in production as well as resources that are in the stages of feasibility or of being permitted. Sources of secondary supply for uranium, such as stockpiles and reprocessed fuel, were also examined. To evaluate long-term primary supply, estimates of uranium from unconventional and from undiscovered resources were analyzed. At 2010 rates of consumption, uranium resources identified in operating or developing mines would fuel the world nuclear fleet for about 30 years. However, projections currently predict an increase in uranium requirements tied to expansion of nuclear energy worldwide. Under a low-demand scenario, requirements through the period ending in 2035 are about 2.1 million tU. In the low demand case, uranium identified in existing and developing mines is adequate to supply requirements. However, whether or not these identified resources will be developed rapidly enough to provide an uninterrupted fuel supply to expanded nuclear facilities could not be determined. On the basis of a scenario of high demand through 2035, 2.6 million tU is required and identified resources in operating or developing mines is inadequate. Beyond 2035, when requirements could exceed resources in these developing properties, other sources will need to be developed from less well-assured resources, deposits not yet at the prefeasibility stage, resources that are currently subeconomic, secondary sources, undiscovered conventional resources, and unconventional uranium supplies. This report’s analysis of 141 mines that are operating or are being actively developed identifies 2.7 million tU of in-situ uranium resources worldwide, approximately 2.1 million tU recoverable after mining and milling losses were deducted. Sixty-four operating mines report a total of 1.4 million tU of in-situ RAR (about 1 million tU recoverable). Seventy-seven developing mines/production centers report 1.3 million tU in-situ Reasonably Assured Resources (RAR) (about 1.1 million tU recoverable), which have a reasonable chance of producing uranium within 5 years. Most of the production is projected to come from conventional underground or open pit mines as opposed to in-situ leach mines. Production capacity in operating mines is about 76,000 tU/yr, and in developing mines is estimated at greater than 52,000 tU/yr. Production capacity in operating mines should be considered a maximum as mines seldom produce up to licensed capacity due to operational difficulties. In 2010, worldwide mines operated at 70 percent of licensed capacity, and production has never exceeded 89 percent of capacity. The capacity in developing mines is not always reported. In this study 35 percent of developing mines did not report a target licensed capacity, so estimates of future capacity may be too low. The Organisation for Economic Co-operation and Development’s Nuclear Energy Agency (NEA) and International Atomic Energy Agency (IAEA) estimate an additional 1.4 million tU economically recoverable resources, beyond that identified in operating or developing mines identified in this report. As well, 0.5 million tU in subeconomic resources, and 2.3 million tU in the geologically less certain inferred category are identified worldwide. These agencies estimate 2.2 million tU in secondary sources such as government and commercial stockpiles and re-enriched uranium tails. They also estimate that unconventional uranium supplies (uraniferous phosphate and black shale deposits) may contain up to 7.6 million tU. Although unconventional resources are currently subeconomic, the improvement of extraction techniques or the production of coproducts may make extraction of uranium from these types of deposits profitable. A large undiscovered resource base is reported by these agencies, however this class of resource should be considered speculative and will require intensive exploration programs to adequately define them as mineable. These resources may all contribute to uranium supply that would fuel the world nuclear fleet well beyond that calculated in this report. Production of resources in both operating and developing uranium mines is subject to uncertainties caused by technical, legal, regulatory, and financial challenges that combined to create long timelines between deposit discovery and mine production. This analysis indicates that mine development is proceeding too slowly to fully meet requirements for an expanded nuclear power reactor fleet in the near future (to 2035), and unless adequate secondary or unconventional resources can be identified, imbalances in supply and demand may occur.

Uranium and other contaminants in hair from the parents of children with congenital anomalies in Fallujah, Iraq

PubMed Central

2011-01-01

Background Recent reports have drawn attention to increases in congenital birth anomalies and cancer in Fallujah Iraq blamed on teratogenic, genetic and genomic stress thought to result from depleted Uranium contamination following the battles in the town in 2004. Contamination of the parents of the children and of the environment by Uranium and other elements was investigated using Inductively Coupled Plasma Mass Spectrometry. Hair samples from 25 fathers and mothers of children diagnosed with congenital anomalies were analysed for Uranium and 51 other elements. Mean ages of the parents was: fathers 29.6 (SD 6.2); mothers: 27.3 (SD 6.8). For a sub-group of 6 women, long locks of hair were analysed for Uranium along the length of the hair to obtain information about historic exposures. Samples of soil and water were also analysed and Uranium isotope ratios determined. Results Levels of Ca, Mg, Co, Fe, Mn, V, Zn, Sr, Al, Ba, Bi, Ga, Pb, Hg, Pd and U (for mothers only) were significantly higher than published mean levels in an uncontaminated population in Sweden. In high excess were Ca, Mg, Sr, Al, Bi and Hg. Of these only Hg can be considered as a possible cause of congenital anomaly. Mean levels for Uranium were 0.16 ppm (SD: 0.11) range 0.02 to 0.4, higher in mothers (0.18 ppm SD 0.09) than fathers (0.11 ppm; SD 0.13). The highly unusual non-normal Fallujah distribution mean was significantly higher than literature results for a control population Southern Israel (0.062 ppm) and a non-parametric test (Mann Whitney-Wilcoxon) gave p = 0.016 for this comparison of the distribution. Mean levels in Fallujah were also much higher than the mean of measurements reported from Japan, Brazil, Sweden and Slovenia (0.04 ppm SD 0.02). Soil samples show low concentrations with a mean of 0.76 ppm (SD 0.42) and range 0.1-1.5 ppm; (N = 18). However it may be consistent with levels in drinking water (2.28 μgL-1) which had similar levels to water from wells (2.72 μgL-1) and the river Euphrates (2.24 μgL-1). In a separate study of a sub group of mothers with long hair to investigate historic Uranium excretion the results suggested that levels were much higher in the past. Uranium traces detected in the soil samples and the hair showed slightly enriched isotopic signatures for hair U238/U235 = (135.16 SD 1.45) compared with the natural ratio of 137.88. Soil sample Uranium isotope ratios were determined after extraction and concentration of the Uranium by ion exchange. Results showed statistically significant presence of enriched Uranium with a mean of 129 with SD5.9 (for this determination, the natural Uranium 95% CI was 132.1 < Ratio < 144.1). Conclusions Whilst caution must be exercised about ruling out other possibilities, because none of the elements found in excess are reported to cause congenital diseases and cancer except Uranium, these findings suggest the enriched Uranium exposure is either a primary cause or related to the cause of the congenital anomaly and cancer increases. Questions are thus raised about the characteristics and composition of weapons now being deployed in modern battlefields PMID:21888647

Sensitivity analysis of high resolution gamma-ray detection for safeguards monitoring at natural uranium conversion facilities

DOE PAGES

Dewji, Shaheen A.; Croft, Stephen; Hertel, Nolan E.

2016-12-16

Under the policies proposed by recent International Atomic Energy Agency (IAEA) circulars and policy papers, implementation of safeguards exists when any purified aqueous uranium solution or uranium oxides suitable for isotopic enrichment or fuel fabrication exists. Under IAEA Policy Paper 18, the starting point for nuclear material under safeguards was reinterpreted, suggesting that purified uranium compounds should be subject to safeguards procedures no later than the first point in the conversion process. In response to this technical need, a combination of simulation models and experimental measurements were employed in previous work to develop and validate gamma-ray nondestructive assay monitoring systemsmore » in a natural uranium conversion plant (NUCP). In particular, uranyl nitrate (UO 2(NO 3) 2) solution exiting solvent extraction was identified as a key measurement point (KMP). Passive nondestructive assay techniques using high resolution gamma-ray spectroscopy were evaluated to determine their viability as a technical means for drawing safeguards conclusions at NUCPs, and if the IAEA detection requirements of 1 significant quantity (SQ) can be met in a timely manner. Building upon the aforementioned previous validation work on detector sensitivity to varying concentrations of uranyl nitrate via a series of dilution measurements, this work investigates detector response parameter sensitivities to gamma-ray signatures of uranyl nitrate. The full energy peak efficiency of a detection system is dependent upon the sample, geometry, absorption, and intrinsic efficiency parameters. Perturbation of these parameters translates into corresponding variations of the 185.7 keV peak area of the 235U in uranyl nitrate. Such perturbations in the assayed signature impact the quality or versatility of the safeguards conclusions drawn. Given the potentially high throughput of uranyl nitrate in NUCPs, the ability to assay 1 SQ of material requires uncertainty «1%. Accounting for material self-shielding properties, pipe thickness, and source-detector orientation is instrumental in determining the robustness of gamma-ray detection in the process monitoring of uranyl nitrate in NUCPs. Monte Carlo models and ray-tracing models were employed to determine the sensitivity of the detected 185.7 keV photon to self-shielding properties, pipe thickness, and source-detector geometry. Considering the implementation of the detection of 1 SQ, diversion of 1 SQ becomes essentially undetectable given the systematic uncertainty, in addition to considerations such as propagating uncertainties due to pipe offset/position, as well as minor variations in pipe thickness. Consequently, pipe thickness was the most sensitive variable in affecting full energy efficiency of the 185.7 keV signature peak with up to 8% variation in efficiency for ±0.5 mm changes in Schedule 40 304L stainless steel piping. Furthermore, computation of the attenuation correction factor of the uranyl nitrate solution [CF(AT) (i.e. εsample)] using Parker's method using with the approximation for the geometrical factor κ≈π/4 was validated through experimental, Monte Carlo and ray-tracing calculations for a uranyl nitrate filled transfer pipe segment. Furthermore, quantifying sensitivity in detector position, as well as voiding effects due to bubbly flow or laminar flow with an air gap in the uranyl nitrate becomes increasingly important as considerations from (static) design-scale measurements translate into (dynamic) field operations tests.« less

Sensitivity analysis of high resolution gamma-ray detection for safeguards monitoring at natural uranium conversion facilities

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dewji, Shaheen A.; Croft, Stephen; Hertel, Nolan E.

Under the policies proposed by recent International Atomic Energy Agency (IAEA) circulars and policy papers, implementation of safeguards exists when any purified aqueous uranium solution or uranium oxides suitable for isotopic enrichment or fuel fabrication exists. Under IAEA Policy Paper 18, the starting point for nuclear material under safeguards was reinterpreted, suggesting that purified uranium compounds should be subject to safeguards procedures no later than the first point in the conversion process. In response to this technical need, a combination of simulation models and experimental measurements were employed in previous work to develop and validate gamma-ray nondestructive assay monitoring systemsmore » in a natural uranium conversion plant (NUCP). In particular, uranyl nitrate (UO 2(NO 3) 2) solution exiting solvent extraction was identified as a key measurement point (KMP). Passive nondestructive assay techniques using high resolution gamma-ray spectroscopy were evaluated to determine their viability as a technical means for drawing safeguards conclusions at NUCPs, and if the IAEA detection requirements of 1 significant quantity (SQ) can be met in a timely manner. Building upon the aforementioned previous validation work on detector sensitivity to varying concentrations of uranyl nitrate via a series of dilution measurements, this work investigates detector response parameter sensitivities to gamma-ray signatures of uranyl nitrate. The full energy peak efficiency of a detection system is dependent upon the sample, geometry, absorption, and intrinsic efficiency parameters. Perturbation of these parameters translates into corresponding variations of the 185.7 keV peak area of the 235U in uranyl nitrate. Such perturbations in the assayed signature impact the quality or versatility of the safeguards conclusions drawn. Given the potentially high throughput of uranyl nitrate in NUCPs, the ability to assay 1 SQ of material requires uncertainty «1%. Accounting for material self-shielding properties, pipe thickness, and source-detector orientation is instrumental in determining the robustness of gamma-ray detection in the process monitoring of uranyl nitrate in NUCPs. Monte Carlo models and ray-tracing models were employed to determine the sensitivity of the detected 185.7 keV photon to self-shielding properties, pipe thickness, and source-detector geometry. Considering the implementation of the detection of 1 SQ, diversion of 1 SQ becomes essentially undetectable given the systematic uncertainty, in addition to considerations such as propagating uncertainties due to pipe offset/position, as well as minor variations in pipe thickness. Consequently, pipe thickness was the most sensitive variable in affecting full energy efficiency of the 185.7 keV signature peak with up to 8% variation in efficiency for ±0.5 mm changes in Schedule 40 304L stainless steel piping. Furthermore, computation of the attenuation correction factor of the uranyl nitrate solution [CF(AT) (i.e. εsample)] using Parker's method using with the approximation for the geometrical factor κ≈π/4 was validated through experimental, Monte Carlo and ray-tracing calculations for a uranyl nitrate filled transfer pipe segment. Furthermore, quantifying sensitivity in detector position, as well as voiding effects due to bubbly flow or laminar flow with an air gap in the uranyl nitrate becomes increasingly important as considerations from (static) design-scale measurements translate into (dynamic) field operations tests.« less

Sensitivity analysis of high resolution gamma-ray detection for safeguards monitoring at natural uranium conversion facilities

NASA Astrophysics Data System (ADS)

Dewji, S. A.; Croft, S.; Hertel, N. E.

2017-03-01

Under the policies proposed by recent International Atomic Energy Agency (IAEA) circulars and policy papers, implementation of safeguards exists when any purified aqueous uranium solution or uranium oxides suitable for isotopic enrichment or fuel fabrication exists. Under IAEA Policy Paper 18, the starting point for nuclear material under safeguards was reinterpreted, suggesting that purified uranium compounds should be subject to safeguards procedures no later than the first point in the conversion process. In response to this technical need, a combination of simulation models and experimental measurements were employed in previous work to develop and validate gamma-ray nondestructive assay monitoring systems in a natural uranium conversion plant (NUCP). In particular, uranyl nitrate (UO2(NO3)2) solution exiting solvent extraction was identified as a key measurement point (KMP). Passive nondestructive assay techniques using high resolution gamma-ray spectroscopy were evaluated to determine their viability as a technical means for drawing safeguards conclusions at NUCPs, and if the IAEA detection requirements of 1 significant quantity (SQ) can be met in a timely manner. Building upon the aforementioned previous validation work on detector sensitivity to varying concentrations of uranyl nitrate via a series of dilution measurements, this work investigates detector response parameter sensitivities to gamma-ray signatures of uranyl nitrate. The full energy peak efficiency of a detection system is dependent upon the sample, geometry, absorption, and intrinsic efficiency parameters. Perturbation of these parameters translates into corresponding variations of the 185.7 keV peak area of the 235U in uranyl nitrate. Such perturbations in the assayed signature impact the quality or versatility of the safeguards conclusions drawn. Given the potentially high throughput of uranyl nitrate in NUCPs, the ability to assay 1 SQ of material requires uncertainty «1%. Accounting for material self-shielding properties, pipe thickness, and source-detector orientation is instrumental in determining the robustness of gamma-ray detection in the process monitoring of uranyl nitrate in NUCPs. Monte Carlo models and ray-tracing models were employed to determine the sensitivity of the detected 185.7 keV photon to self-shielding properties, pipe thickness, and source-detector geometry. Considering the implementation of the detection of 1 SQ, diversion of 1 SQ becomes essentially undetectable given the systematic uncertainty, in addition to considerations such as propagating uncertainties due to pipe offset/position, as well as minor variations in pipe thickness. Consequently, pipe thickness was the most sensitive variable in affecting full energy efficiency of the 185.7 keV signature peak with up to 8% variation in efficiency for ±0.5 mm changes in Schedule 40 304L stainless steel piping. Furthermore, computation of the attenuation correction factor of the uranyl nitrate solution [CF(AT) (i.e. εsample)] using Parker's method using with the approximation for the geometrical factor κ≈π/4 was validated through experimental, Monte Carlo and ray-tracing calculations for a uranyl nitrate filled transfer pipe segment. Quantifying sensitivity in detector position, as well as voiding effects due to bubbly flow or laminar flow with an air gap in the uranyl nitrate becomes increasingly important as considerations from (static) design-scale measurements translate into (dynamic) field operations tests.

Investigation of the electronic ground states for a reduced pyridine(diimine) uranium series: evidence for a ligand tetraanion stabilized by a uranium dimer.

PubMed

Anderson, Nickolas H; Odoh, Samuel O; Williams, Ursula J; Lewis, Andrew J; Wagner, Gregory L; Lezama Pacheco, Juan; Kozimor, Stosh A; Gagliardi, Laura; Schelter, Eric J; Bart, Suzanne C

2015-04-15

The electronic structures of a series of highly reduced uranium complexes bearing the redox-active pyridine(diimine) ligand, (Mes)PDI(Me) ((Mes)PDI(Me) = 2,6-(2,4,6-Me3-C6H2-N═CMe)2C5H3N) have been investigated. The complexes, ((Mes)PDI(Me))UI3(THF) (1), ((Mes)PDI(Me))UI2(THF)2 (2), [((Mes)PDI(Me))UI]2 (3), and [((Mes)PDI(Me))U(THF)]2 (4), were examined using electronic and X-ray absorption spectroscopies, magnetometry, and computational analyses. Taken together, these studies suggest that all members of the series contain uranium(IV) centers with 5f (2) configurations and reduced ligand frameworks, specifically [(Mes)PDI(Me)](•/-), [(Mes)PDI(Me)](2-), [(Mes)PDI(Me)](3-) and [(Mes)PDI(Me)](4-), respectively. In the cases of 2, 3, and 4 no unpaired spin density was found on the ligands, indicating a singlet diradical ligand in monomeric 2 and ligand electron spin-pairing through dimerization in 3 and 4. Interaction energies, representing enthalpies of dimerization, of -116.0 and -144.4 kcal mol(-1) were calculated using DFT for the monomers of 3 and 4, respectively, showing there is a large stabilization gained by dimerization through uranium-arene bonds. Highlighted in these studies is compound 4, bearing a previously unobserved pyridine(diimine) tetraanion, that was uniquely stabilized by backbonding between uranium cations and the η(5)-pyridyl ring.

High temperature radiance spectroscopy measurements of solid and liquid uranium and plutonium carbides

NASA Astrophysics Data System (ADS)

Manara, D.; De Bruycker, F.; Boboridis, K.; Tougait, O.; Eloirdi, R.; Malki, M.

2012-07-01

In this work, an experimental study of the radiance of liquid and solid uranium and plutonium carbides at wavelengths 550 nm ⩽ λ ⩽ 920 nm is reported. A fast multi-channel spectro-pyrometer has been employed for the radiance measurements of samples heated up to and beyond their melting point by laser irradiation. The melting temperature of uranium monocarbide, soundly established at 2780 K, has been taken as a radiance reference. Based on it, a wavelength-dependence has been obtained for the high-temperature spectral emissivity of some uranium carbides (1 ⩽ C/U ⩽ 2). Similarly, the peritectic temperature of plutonium monocarbide (1900 K) has been used as a reference for plutonium monocarbide and sesquicarbide. The present spectral emissivities of solid uranium and plutonium carbides are close to 0.5 at 650 nm, in agreement with previous literature values. However, their high temperature behaviour, values in the liquid, and carbon-content and wavelength dependencies in the visible-near infrared range have been determined here for the first time. Liquid uranium carbide seems to interact with electromagnetic radiation in a more metallic way than does the solid, whereas a similar effect has not been observed for plutonium carbides. The current emissivity values have also been used to convert the measured radiance spectra into real temperature, and thus perform a thermal analysis of the laser heated samples. Some high-temperature phase boundaries in the systems U-C and Pu-C are shortly discussed on the basis of the current results.

Crystallographic and magnetic structure of UCu{sub 1.5}Sn{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Purwanto, A.; Robinson, R.A.; Nakotte, H.

1996-04-01

We report on the crystallographic and magnetic structures of the antiferromagnet UCu{sub 1.5}Sn{sub 2}, as determined by x-ray and neutron powder diffraction. It crystallizes in the tetragonal CaBe{sub 2}Ge{sub 2} structure type, with space group P/4nmm, and we find no site disorder between two different Sn2{ital c} sites, in contrast with a previous report. UCu{sub 1.5}Sn{sub 2} orders antiferromagnetically with a N{acute e}el temperature of about 110 K. This is unusually high among uranium intermetallics. The uranium moments align along the {ital c} axis in a collinear arrangement but alternating along the {ital c} axis. The low-temperature uranium moment ismore » 2.01{mu}{sub {ital B}}. {copyright} {ital 1996 American Institute of Physics.}« less