Evaluation of various carbon blacks and dispersing agents for use in the preparation of uranium microspheres with carbon

NASA Astrophysics Data System (ADS)

Hunt, R. D.; Johnson, J. A.; Collins, J. L.; McMurray, J. W.; Reif, T. J.; Brown, D. R.

2018-01-01

A comparison study on carbon blacks and dispersing agents was performed to determine their impacts on the final properties of uranium fuel kernels with carbon. The main target compositions in this internal gelation study were 10 and 20 mol % uranium dicarbide (UC2), which is UC1.86, with the balance uranium dioxide. After heat treatment at 1900 K in flowing carbon monoxide in argon for 12 h, the density of the kernels produced using a X-energy proprietary carbon suspension, which is commercially available, ranged from 96% to 100% of theoretical density (TD), with full conversion of UC to UC2 at both carbon concentrations. However, higher carbon concentrations such as a 2.5 mol ratio of carbon to uranium in the feed solutions failed to produce gel spheres with the proprietary carbon suspension. The kernels using our former baseline of Mogul L carbon black and Tamol SN were 90-92% of TD with full conversion of UC to UC2 at a variety of carbon levels. Raven 5000 carbon black and Tamol SN were used to produce 10 mol % UC2 kernels with 95% of TD. However, an increase in the Raven 5000 concentration led to a kernel density below 90% of TD. Raven 3500 carbon black and Tamol SN were used to make very dense kernels without complete conversion to UC2. The selection of the carbon black and dispersing agent is highly dependent on the desired final properties of the target kernels.

Evaluation of various carbon blacks and dispersing agents for use in the preparation of uranium microspheres with carbon

DOE PAGES

Hunt, Rodney Dale; Johnson, Jared A.; Collins, Jack Lee; ...

2017-10-12

A comparison study on carbon blacks and dispersing agents was performed to determine their impacts on the final properties of uranium fuel kernels with carbon. The main target compositions in this internal gelation study were 10 and 20 mol % uranium dicarbide (UC 2), which is UC 1.86, with the balance uranium dioxide. After heat treatment at 1900 K in flowing carbon monoxide in argon for 12 h, the density of the kernels produced using a X-energy proprietary carbon suspension, which is commercially available, ranged from 96% to 100% of theoretical density (TD), with full conversion of UC to UCmore » 2 at both carbon concentrations. However, higher carbon concentrations such as a 2.5 mol ratio of carbon to uranium in the feed solutions failed to produce gel spheres with the proprietary carbon suspension. The kernels using our former baseline of Mogul L carbon black and Tamol SN were 90–92% of TD with full conversion of UC to UC 2 at a variety of carbon levels. Raven 5000 carbon black and Tamol SN were used to produce 10 mol % UC2 kernels with 95% of TD. However, an increase in the Raven 5000 concentration led to a kernel density below 90% of TD. Raven 3500 carbon black and Tamol SN were used to make very dense kernels without complete conversion to UC 2. Lastly, the selection of the carbon black and dispersing agent is highly dependent on the desired final properties of the target kernels.« less

Organic geochemical analysis of sedimentary organic matter associated with uranium

USGS Publications Warehouse

Leventhal, J.S.; Daws, T.A.; Frye, J.S.

1986-01-01

Samples of sedimentary organic matter from several geologic environments and ages which are enriched in uranium (56 ppm to 12%) have been characterized. The three analytical techniqyes used to study the samples were Rock-Eval pyrolysis, pyrolysis-gas chromatography-mass spectrometry, and solid-state C-13 nuclear magnetic resonance (NMR) spectroscopy. In samples with low uranium content, the pyrolysis-gas chromatography products contain oxygenated functional groups (as hydroxyl) and molecules with both aliphatic and aromatic carbon atoms. These samples with low uranium content give measurable Rock-Eval hydrocarbon and organic-CO2 yields, and C-13 NMR values of > 30% aliphatic carbon. In contrast, uranium-rich samples have few hydrocarbon pyrolysis products, increased Rock-Eval organic-CO2 contents and > 70% aromatic carbon contents from C-13 NMR. The increase in aromaticity and decrease in hydrocarbon pyrolysis yield are related to the amount of uranium and the age of the uranium minerals, which correspond to the degree of radiation damage. The three analytical techniques give complementary results. Increase in Rock-Eval organic-CO2 yield correlates with uranium content for samples from the Grants uranium region. Calculations show that the amount of organic-CO2 corresponds to the quantity of uranium chemically reduced by the organic matter for the Grants uranium region samples. ?? 1986.

Compatibility of buffered uranium carbides with tungsten.

NASA Technical Reports Server (NTRS)

Phillips, W. M.

1971-01-01

Results of compatibility tests between tungsten and hyperstoichiometric uranium carbide alloys run at 1800 C for 1000 and 2500 hours. These tests compared tungsten-buffered uranium carbide with tungsten-buffered uranium-zirconium carbide. The zirconium carbide addition appeared to widen the homogeneity range of the uranium carbide, making additional carbon available for reaction. Reaction layers could be formed by either of two diffusion paths, one producing UWC2, while the second resulted in the formation of W2C. UWC2 acts as a diffusion barrier for carbon and slows the growth of the reaction layer with time, while carbon diffusion is relatively rapid in W2C, allowing equilibrium to be reached in less than 2500 hours at a temperature of 1800 C.

Uranium (VI) solubility in carbonate-free ERDA-6 brine

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

Lucchini, Jean-francois; Khaing, Hnin; Reed, Donald T

2010-01-01

When present, uranium is usually an element of importance in a nuclear waste repository. In the Waste Isolation Pilot Plant (WIPP), uranium is the most prevalent actinide component by mass, with about 647 metric tons to be placed in the repository. Therefore, the chemistry of uranium, and especially its solubility in the WIPP conditions, needs to be well determined. Long-term experiments were performed to measure the solubility of uranium (VI) in carbonate-free ERDA-6 brine, a simulated WIPP brine, at pC{sub H+} values between 8 and 12.5. These data, obtained from the over-saturation approach, were the first repository-relevant data for themore » VI actinide oxidation state. The solubility trends observed pointed towards low uranium solubility in WIPP brines and a lack of amphotericity. At the expected pC{sub H+} in the WIPP ({approx} 9.5), measured uranium solubility approached 10{sup -7} M. The objective of these experiments was to establish a baseline solubility to further investigate the effects of carbonate complexation on uranium solubility in WIPP brines.« less

Experimental investigation of the ionization mechanisms of uranium in thermal ionization mass spectrometry in the presence of carbon

NASA Astrophysics Data System (ADS)

Kraiem, M.; Mayer, K.; Gouder, T.; Seibert, A.; Wiss, T.; Thiele, H.; Hiernaut, J.-P.

2010-01-01

Thermal ionization mass spectrometry (TIMS) is a well established instrumental technique for providing accurate and precise isotope ratio measurements of elements with reasonably low first ionization potential. In nuclear safeguards and in environmental research, it is often required to measure the isotope ratios in small samples of uranium. Empirical studies had shown that the ionization yield of uranium and plutonium in a TIMS ion source can be significantly increased in the presence of a carbon source. But, even though carbon appeared crucial in providing high ionization yields, processes taking place on the ionization surface were still not well understood. This paper describes the experimental results obtained from an extended study on the evaporation and ionization mechanisms of uranium occurring on a rhenium mass spectrometry filament in the presence of carbon. Solid state reactions were investigated using X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Additionally, vaporization measurements were performed with a modified-Knudsen cell mass spectrometer for providing information on the neutral uranium species in the vapor phase. Upon heating, under vacuum, the uranyl nitrate sample was found to turn into a uranium carbide compound, independent of the type of carbon used as ionization enhancer. With further heating, uranium carbide leads to formation of single charged uranium metal ions and a small amount of uranium carbide ions. The results are relevant for a thorough understanding of the ion source chemistry of a uranyl nitrate sample under reducing conditions. The significant increase in ionization yield described by many authors on the basis of empirical results can be now fully explained and understood.

Process for electrolytically preparing uranium metal

DOEpatents

Haas, Paul A.

1989-01-01

A process for making uranium metal from uranium oxide by first fluorinating uranium oxide to form uranium tetrafluoride and next electrolytically reducing the uranium tetrafluoride with a carbon anode to form uranium metal and CF.sub.4. The CF.sub.4 is reused in the fluorination reaction rather than being disposed of as a hazardous waste.

Process for electrolytically preparing uranium metal

DOEpatents

Haas, Paul A.

1989-08-01

A process for making uranium metal from uranium oxide by first fluorinating uranium oxide to form uranium tetrafluoride and next electrolytically reducing the uranium tetrafluoride with a carbon anode to form uranium metal and CF.sub.4. The CF.sub.4 is reused in the fluorination reaction rather than being disposed of as a hazardous waste.

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.

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.

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.

Reconnaissance for trace elements in North Dakota and eastern Montana. Part 1. Geology and radioactivity. Part 2. Reserves and summary

USGS Publications Warehouse

Wyant, Donald G.; Beroni, Ernest P.

1950-01-01

The exact mode of origin of the uranium in the lignite is not known. Uranium may have accumulated in swamps at the same time as the organic debris, or it may have been introduced by ground water after the formation of lignite. In either case carbon or carbon compounds apparently caused the precipitation or fixation of uranium. Further work is needed to determine the origin of this type of uranium deposit.

STRIPPING OF URANIUM FROM ORGANIC EXTRACTANTS

DOEpatents

Crouse, D.J. Jr.

1962-09-01

A liquid-liquid extraction method is given for recovering uranium values from uranium-containing solutions. Uranium is removed from a uranium-containing organic solution by contacting said organic solution with an aqueous ammonium carbonate solution substantially saturated in uranium values. A uranium- containing precipitate is thereby formed which is separated from the organic and aqueous phases. Uranium values are recovered from this separated precipitate. (AE C)

The adsorption of methyl iodide on uranium and uranium dioxide: Surface characterization using X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES)

NASA Astrophysics Data System (ADS)

Dillard, J. G.; Moers, H.; Klewe-Nebenius, H.; Kirch, G.; Pfennig, G.; Ache, H. J.

1984-09-01

The adsorption of methyl iodide on uranium and on uranium dioxide has been studied at 25 °C. Surfaces of the substrates were characterized before and after adsorption by X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES). The XPS binding energy results indicate that CH 3I adsorption on uranium yields a carbide-type carbon, UC, and uranium iodide, UI 3. On uranium dioxide the carbon electron binding energy measurements are consistent with the formation of a hydrocarbon, —CH 3-type moiety. The interpretation of XPS and AES spectral features for CH 3I adsorption on uranium suggest that a complex dissociative adsorption reaction takes place. Adsorption of CH 3I on UO 2 occurs via a dissociative process. Saturation coverage occurs on uranium at approximately two langmuir (1 L = 10 -6 Torr s) exposure whereas saturation coverage on uranium dioxide is found at about five langmuir.

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.

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.

Actinide removal from spent salts

DOEpatents

Hsu, Peter C.; von Holtz, Erica H.; Hipple, David L.; Summers, Leslie J.; Adamson, Martyn G.

2002-01-01

A method for removing actinide contaminants (uranium and thorium) from the spent salt of a molten salt oxidation (MSO) reactor is described. Spent salt is removed from the reactor and analyzed to determine the contaminants present and the carbonate concentration. The salt is dissolved in water, and one or more reagents are added to precipitate the thorium as thorium oxide and/or the uranium as either uranium oxide or as a diuranate salt. The precipitated materials are filtered, dried and packaged for disposal as radioactive waste. About 90% of the thorium and/or uranium present is removed by filtration. After filtration, salt solutions having a carbonate concentration >20% can be dried and returned to the reactor for re-use. Salt solutions containing a carbonate concentration <20% require further clean-up using an ion exchange column, which yields salt solutions that contain less than 0.1 ppm of thorium or uranium.

Preparation of carbon coated Fe3O4 nanoparticles for magnetic separation of uranium

NASA Astrophysics Data System (ADS)

Zhang, Xiaofei; Wang, Jun

2018-01-01

Uranium(VI) was removed from aqueous solutions using carbon coated Fe3O4 nanoparticles (Fe3O4@C). Batch experiments were conducted to study the effects of initial pH, shaking time and temperature on uranium sorption efficiency. It was found that the maximum adsorption capacity of the Fe3O4@C toward uranium(VI) was ∼120.20 mg g-1 when the initial uranium(VI) concentration was 100 mg L-1, displaying a high efficiency for the removal of uranium(VI) ions. Kinetics of the uranium(VI) removal is found to follow pseudo-second-order rate equation. In addition, the uranium(VI)-loaded Fe3O4@C nanoparticles can be recovered easily from aqueous solution by magnetic separation and regenerated by acid treatment. Present study suggested that magnetic Fe3O4@C composite particles can be used as an effective and recyclable adsorbent for the removal of uranium(VI) from aqueous solutions.

Method of Making Uranium Dioxide Bodies

DOEpatents

Wilhelm, H. A.; McClusky, J. K.

1973-09-25

Sintered uranium dioxide bodies having controlled density are produced from U.sub.3 O.sub.8 and carbon by varying the mole ratio of carbon to U.sub.3 O.sub.8 in the mixture, which is compressed and sintered in a neutral or slightly oxidizing atmosphere to form dense slightly hyperstoichiometric uranium dioxide bodies. If the bodies are to be used as nuclear reactor fuel, they are subsequently heated in a hydrogen atmosphere to achieve stoichiometry. This method can also be used to produce fuel elements of uranium dioxide -- plutonium dioxide having controlled density.

RECOVERY OF URANIUM FROM CARBONATE LEACH LIQUORS

DOEpatents

Wilson, H.F.

1958-07-01

An improved process is described for the recovery of uranium from vanadifrous ores. In the prior art such ores have been digested with alkali carbonate solutions at a pH of less than 10 and then contacted with a strong base anion exchange resin to separate uranium from vanadium. It has been found that if the exchamge resin feed solution has its pH adjusted to the range 10.8 to 11.8, that vanadium adsorption on the resin is markedly decreased and the separation of uranium from the vanadium is thereby improved.

PROCESSES OF CHLORINATION OF URANIUM OXIDES

DOEpatents

Rosenfeld, S.

1958-09-16

An improvement is described in the process fur making UCl/sub 4/ from uranium oxide and carbon tetrachloride. In that process, oxides of uranium are contacted with carbon tetrachloride vapor at an elevated temperature. It has been fuund that the reaction product and yield are improved if the uranlum oxide charge is disposed in flat trays in the reaction zone, to a depth of not more than 1/2 centimeter.

Uranium-series dated authigenic carbonates and Acheulian sites in southern Egypt

NASA Technical Reports Server (NTRS)

Szabo, B. J.; Mchugh, W. P.; Schaber, G. G.; Breed, C. S.; Haynes, C. V., Jr.

1989-01-01

Field investigations of aggraded paleovalleys, which were identified in southern Egypt using SIR, are discussed. Acheulian artifacts were found in authigenic carbonate deposites along the edges of the paleovalleys. Uranium series dating of 25 carbonate samples shows that widespread carbonate deposition in the area occurred about 45, 141, and 212 thousand years ago. Analysis of the carbonate suggests that the deposition may be related to late Pleistocene humid climates that facilitated human settlement in the region.

Uranium removal from a contaminated effluent using a combined microbial and nanoparticle system.

PubMed

Baiget, Mar; Constantí, Magda; López, M Teresa; Medina, Francesc

2013-09-25

Reduction of soluble uranium(VI) to insoluble uranium(IV) for remediating a uranium-contaminated effluent (EF-03) was examined using a biotic and abiotic integrated system. Shewanella putrefaciens was first used and reduced U(VI) in a synthetic medium but not in the EF-03 effluent sample. Subsequently the growth of autochthonous microorganisms was stimulated with lactate. When lactate was supported on active carbon 77% U(VI) was removed in 4 days. Separately, iron nanoparticles that were 50 nm in diameter reduced U(VI) by 60% in 4 hours. The efficiency of uranium(VI) removal was improved to 96% in 30 min by using a system consisting of lactate and iron nanoparticles immobilized on active carbon. Lactate also stimulated the growth of potential uranium-reducing microorganisms in the EF-03 sample. This system can be efficiently used for the bioremediation of uranium-contaminated effluents. Copyright © 2013 Elsevier B.V. All rights reserved.

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.

PROCESS OF PREPARING URANIUM CARBIDE

DOEpatents

Miller, W.E.; Stethers, H.L.; Johnson, T.R.

1964-03-24

A process of preparing uranium monocarbide is de scribed. Uranium metal is dissolved in cadmium, zinc, cadmium-- zinc, or magnesium-- zinc alloy and a small quantity of alkali metal is added. Addition of stoichiometric amounts of carbon at 500 to 820 deg C then precipitates uranium monocarbide. (AEC)

PRODUCTION OF URANIUM MONOCARBIDE

DOEpatents

Powers, R.M.

1962-07-24

A method of making essentially stoichiometric uranium monocarbide by pelletizing a mixture of uranium tetrafluoride, silicon, and carbon and reacting the mixture at a temperature of approximately 1500 to 1700 deg C until the reaction goes to completion, forming uranium monocarbide powder and volatile silicon tetrafluoride, is described. The powder is then melted to produce uranium monocarbide in massive form. (AEC)

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.

PROCESS FOR RECOVERY OF URANIUM AND VANADIUM FROM CARBONATE SOLUTIONS BY REDUCTION-PRECIPITATION

DOEpatents

Ellis, D.A.; Lindblom, R.O.

1957-09-24

A process employing carbonate leaching of ores and an advantageous methcd of recovering the uranium and vanadium from the leach solution is described. The uranium and vanadium can be precipitated from carbonate leach solutions by reaction with sodium amalgam leaving the leach solution in such a condition that it is economical to replenish for recycling. Such a carbonate leach solution is treated with a dilute sodium amalgam having a sodium concentration within a range of about 0.01 to 0.5% of sodium. Efficiency of the treatment is dependent on at least three additional factors, intimacy of contact of the amalgam with the leach solution, rate of addition of the amalgam and exclusion of oxygen (air).

A wet chemical method for the estimation of carbon in uranium carbides.

PubMed

Chandramouli, V; Yadav, R B; Rao, P R

1987-09-01

A wet chemical method for the estimation of carbon in uranium carbides has been developed, based on oxidation with a saturated solution of sodium dichromate in 9M sulphuric acid, absorption of the evolved carbon dioxide in a known excess of barium hydroxide solution, and titration of the excess of barium hydroxide with standard potassium hydrogen phthalate solution. The carbon content obtained is in good agreement with that obtained by combustion and titration.

Recovery of Uranium from Sodium Carbonate Solutions with Dowex I Anion Exchangers; RECUPERACION DEL URANIO DE SOLUCIONES. DE CARBONATO SODICO MEDIANTE INTERCAMBIO ANIONICO CON RESINA DOWEX I

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

Urgell, M.; Bustamante, J.A.P.; Rodriguez, T.B.

1959-01-01

Synthetic carbonate solutions were used to study the recovery of uranium with Dowex-1. In the first part of the study the capacity of the resin for uranium fixation is investigated as a function of the solution concentration, and the flow velocity. The ideal thickness of the resin bed is investigated. The optimum conditions for elution with various salts and salt mixtures are established. In the last pant, the interference caused by an excess of carbonate and the presence of aluminate or phosphate is considered. (J.S.R.)

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

RECOVERY OF URANIUM AND THORIUM FROM AQUEOUS SOLUTIONS

DOEpatents

Calkins, G.D.

1958-06-10

>A process is described for the recovery of uranium and thorium from monazite sand, which is frequently processed by treating it with a hot sodium hydroxide solution whereby a precipitate forms consisting mainly of oxides or hydroxides of the rare earths, thorium and uranium. The precipitate is dissolved in mineral acid, and the acid solution is then neutralized to a pH value of between 5.2 and 6.2 whereby both the uranium and thorium precipitate as the hydroxides, while substantially all the rare earth metal values present remain in the solution. The uranium and thoriunn can then be separated by dissolving the precipitate in a solution containing a mixture of alkali carbonate and alkali bicarbonate: and contacting the carbonate solution with a strong-base anion exchange resin whereby the uranium values are adsorbed on the resin while the thorium remains in solution.

Carbonate-H2O2 Leaching for Sequestering Uranium from Seawater

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

Pan, Horng-Bin; Weisheng, Liao; Wai, Chien

Uranium adsorbed on amidoxime-based polyethylene fiber in simulated seawater can be quantitatively eluted at room temperature using 1M Na2CO3 containing 0.1 M H2O2. This efficient elution process is probably due to formation of an extremely stable uranyl-peroxo-carbonato complex in the carbonate solution. After washing with water, the sorbent can be reused with little loss of uranium loading capacity. Possible existence of this stable uranyl species in ocean water is also discussed.

Carbonate-H₂O₂ leaching for sequestering uranium from seawater.

PubMed

Pan, Horng-Bin; Liao, Weisheng; Wai, Chien M; Oyola, Yatsandra; Janke, Christopher J; Tian, Guoxin; Rao, Linfeng

2014-07-28

Uranium adsorbed on amidoxime-based polyethylene fiber in simulated seawater can be quantitatively eluted at room temperature using 1 M Na2CO3 containing 0.1 M H2O2. This efficient elution process is probably due to the formation of an extremely stable uranyl-peroxo-carbonato complex in the carbonate solution. After washing with water, the sorbent can be reused with minimal loss of uranium loading capacity. Possible existence of this stable uranyl species in ocean water is also discussed.

PREPARATION OF URANIUM HEXAFLUORIDE

DOEpatents

Lawroski, S.; Jonke, A.A.; Steunenberg, R.K.

1959-10-01

A process is described for preparing uranium hexafluoride from carbonate- leach uranium ore concentrate. The briquetted, crushed, and screened concentrate is reacted with hydrogen fluoride in a fluidized bed, and the uranium tetrafluoride formed is mixed with a solid diluent, such as calcium fluoride. This mixture is fluorinated with fluorine and an inert diluent gas, also in a fluidized bed, and the uranium hexafluoride obtained is finally purified by fractional distillation.

Selective separation of zirconium from uranium in carbonate solutions by ion flotation

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

Jdid, E.A.; Blazy, P.; Mahamadou, A.

1990-05-01

Separation of zirconium from uranium in carbonate media was undertaken by ion flotation. The collector chosen was octylhydroxamic acid (HOHX). It gave a well-flocculated precipitate with zirconium which floated in less than 5 min. The stoichiometry of the reaction is HOHX/Zr = 3.9/1, and the selectivity in the presence of uranium is very high. In fact, for a ratio {Phi} = (HOHX),M/(Zr),M, which is just stoichiometric and is close to 4, the zirconium removal rate reaches 99%, even in industrial media. The loss of uranium is only 0.5% although its concentration is 37.4 g/L. Mechanisms of separation are not affectedmore » by a variation of pH between 6.7 and 9.8, of temperature up to 60{degree}C, and of carbonate concentration within the 15 to 60 g/L Na{sub 2}CO{sub 3} range.« less

Dissolution of Uranium Oxides Under Alkaline Oxidizing Conditions

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

Smith, Steven C.; Peper, Shane M.; Douglas, Matthew

2009-11-01

Bench scale experiments were conducted to determine the dissolution characteristics of uranium oxide powders (UO2, U3O8, and UO3) in aqueous peroxide-carbonate solutions. Experimental parameters included H2O2 concentration, carbonate counter cation (NH4+, Na+, K+, and Rb+), and pH. Results indicate the dissolution rate of UO2 in 1 M (NH4)2CO3 increases linearly with peroxide concentration ranging from 0.05 – 2 M. The three uranium oxide powders exhibited different dissolution patterns however, UO3 exhibited prompt complete dissolution. Carbonate counter cation affected the dissolution kinetics. There is minimal impact of solution pH, over the range 8.8 to 10.6, on initial dissolution rate.

Kinetic study of the carbothermic synthesis of uranium monocarbide microspheres

NASA Astrophysics Data System (ADS)

Mukerjee, S. K.; Dehadraya, J. V.; Vaidya, V. N.; Sood, D. D.

1990-06-01

Uranium monocarbide microspheres were synthesized by carbothermic reduction of porous uranium oxide microspheres with uniformly dispersed carbon black. Kinetics of the reduction was studied under vacuum and flowing inert gas from 1250 to 1550° C. The carbon monoxide gas concentration in the effluent stream during reduction was used to determine the rate of carbide formation. Under vacuum, reduction was found to be controlled by reaction at the reactant-product interface whereas under flowing gas conditions, the diffusion of carbon monoxide gas through the carbide layer was the rate controlling process. The activation energy was 335.1 ± 8.6 and 363.7 ± 7.6 kJ/mol for reduction under vacuum and flowing gas, respectively.

Effects of aqueous uranyl speciation on the kinetics of microbial uranium reduction

DOE PAGES

Belli, Keaton M.; DiChristina, Thomas J.; Van Cappellen, Philippe; ...

2015-02-16

The ability to predict the success of the microbial reduction of soluble U(VI) to highly insoluble U(IV) as an in situ bioremediation strategy is complicated by the wide range of geochemical conditions at contaminated sites and the strong influence of aqueous uranyl speciation on the bioavailability and toxicity of U(VI) to metal-reducing bacteria. In order to determine the effects of aqueous uranyl speciation on uranium bioreduction kinetics, incubations and viability assays with Shewanella putrefaciens strain 200 were conducted over a range of pH and dissolved inorganic carbon (DIC), Ca 2+, and Mg 2+ concentrations. A speciation-dependent kinetic model was developedmore » to reproduce the observed time series of total dissolved uranium concentration over the range of geochemical conditions tested. The kinetic model yielded the highest rate constant for the reduction of uranyl non-carbonate species (i.e., the ‘free’ hydrated uranyl ion, uranyl hydroxides, and other minor uranyl complexes), indicating that they represent the most readily reducible fraction of U(VI) despite being the least abundant uranyl species in solution. In the presence of DIC, Ca 2+, and Mg 2+ is suppressed during the formation of more bioavailable uranyl non-carbonate species and resulted in slower bioreduction rates. At high concentrations of bioavailable U(VI), however, uranium toxicity to S. putrefaciens inhibited bioreduction, and viability assays confirmed that the concentration of non-carbonate uranyl species best predicts the degree of toxicity. The effect of uranium toxicity was accounted for by incorporating the free ion activity model of metal toxicity into the bioreduction rate law. These results demonstrate that, in the absence of competing terminal electron acceptors, uranium bioreduction kinetics can be predicted over a wide range of geochemical conditions based on the bioavailability and toxicity imparted on U(VI) by solution composition. Finally, these findings also imply that the concentration of uranyl non-carbonate species, despite being extremely low, is a determining factor controlling uranium bioreduction at contaminated sites.« less

PROCESS FOR UTILIZING ORGANIC ORTHOPHOSPHATE EXTRACTANTS

DOEpatents

Grinstead, R.R.

1958-11-11

A process is presented for recovering uranium from its ores, the steps comprising producing the uranium in solution in the trivalent state, extracting the uranium from solution in an lmmiscible organic solvent extract phase which lncludes mono and dialkyl orthophosphorlc acid esters having a varying number of carbon atoms on the alkyl substituent, amd recovering the uranium from tbe extract phase.

RECOVERY OF URANIUM FROM ZIRCONIUM-URANIUM NUCLEAR FUELS

DOEpatents

Gens, T.A.

1962-07-10

An improvement was made in a process of recovering uranium from a uranium-zirconium composition which was hydrochlorinated with gsseous hydrogen chloride at a temperature of from 350 to 800 deg C resulting in volatilization of the zirconium, as zirconium tetrachloride, and the formation of a uranium containing nitric acid insoluble residue. The improvement consists of reacting the nitric acid insoluble hydrochlorination residue with gaseous carbon tetrachloride at a temperature in the range 550 to 600 deg C, and thereafter recovering the resulting uranium chloride vapors. (AEC)

Formation and Geological Sequestration of Uranium Nanoparticles in Deep Granitic Aquifer

PubMed Central

Suzuki, Yohey; Mukai, Hiroki; Ishimura, Toyoho; Yokoyama, Takaomi D.; Sakata, Shuhei; Hirata, Takafumi; Iwatsuki, Teruki; Mizuno, Takashi

2016-01-01

The stimulation of bacterial activities that convert hexavalent uranium, U(VI), to tetravalent uranium, U(IV), appears to be feasible for cost-effective remediation of contaminated aquifers. However, U(VI) reduction typically results in the precipitation of U(IV) particles less than 5 nanometers in diameter, except for environmental conditions enriched with iron. Because these tiny particles are mobile and susceptible to oxidative dissolution after the termination of nutrient injection, in situ bioremediation remains to be impractical. Here we show that U(IV) nanoparticles of coffinite (U(SiO4)1−x(OH)4x) formed in fracture-filling calcium carbonate in a granitic aquifer. In situ U-Pb isotope dating demonstrates that U(IV) nanoparticles have been sequestered in the calcium carbonate for at least 1 million years. As the microbiologically induced precipitation of calcium carbonate in aquifer systems worldwide is extremely common, we anticipate simultaneous stimulation of microbial activities for precipitation reactions of calcium carbonate and U(IV) nanoparticles, which leads to long-term sequestration of uranium and other radionuclides in contaminated aquifers and deep geological repositories. PMID:26948389

Formation and Geological Sequestration of Uranium Nanoparticles in Deep Granitic Aquifer.

PubMed

Suzuki, Yohey; Mukai, Hiroki; Ishimura, Toyoho; Yokoyama, Takaomi D; Sakata, Shuhei; Hirata, Takafumi; Iwatsuki, Teruki; Mizuno, Takashi

2016-03-07

The stimulation of bacterial activities that convert hexavalent uranium, U(VI), to tetravalent uranium, U(IV), appears to be feasible for cost-effective remediation of contaminated aquifers. However, U(VI) reduction typically results in the precipitation of U(IV) particles less than 5 nanometers in diameter, except for environmental conditions enriched with iron. Because these tiny particles are mobile and susceptible to oxidative dissolution after the termination of nutrient injection, in situ bioremediation remains to be impractical. Here we show that U(IV) nanoparticles of coffinite (U(SiO4)1-x(OH)4x) formed in fracture-filling calcium carbonate in a granitic aquifer. In situ U-Pb isotope dating demonstrates that U(IV) nanoparticles have been sequestered in the calcium carbonate for at least 1 million years. As the microbiologically induced precipitation of calcium carbonate in aquifer systems worldwide is extremely common, we anticipate simultaneous stimulation of microbial activities for precipitation reactions of calcium carbonate and U(IV) nanoparticles, which leads to long-term sequestration of uranium and other radionuclides in contaminated aquifers and deep geological repositories.

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.

Reactive transport modeling at uranium in situ recovery sites: uncertainties in uranium sorption on iron hydroxides

USGS Publications Warehouse

Johnson, Raymond H.; Tutu, Hlanganani; Brown, Adrian; Figueroa, Linda; Wolkersdorfer, Christian

2013-01-01

Geochemical changes that can occur down gradient from uranium in situ recovery (ISR) sites are important for various stakeholders to understand when evaluating potential effects on surrounding groundwater quality. If down gradient solid-phase material consists of sandstone with iron hydroxide coatings (no pyrite or organic carbon), sorption of uranium on iron hydroxides can control uranium mobility. Using one-dimensional reactive transport models with PHREEQC, two different geochemical databases, and various geochemical parameters, the uncertainties in uranium sorption on iron hydroxides are evaluated, because these oxidized zones create a greater risk for future uranium transport than fully reduced zones where uranium generally precipitates.

Unusual Versatility of the Filamentous, Diazotrophic Cyanobacterium Anabaena torulosa Revealed for Its Survival during Prolonged Uranium Exposure

PubMed Central

Chandwadkar, Pallavi; Nayak, Chandrani

2017-01-01

ABSTRACT Reports on interactions between cyanobacteria and uranyl carbonate are rare. Here, we present an interesting succession of the metabolic responses employed by a marine, filamentous, diazotrophic cyanobacterium, Anabaena torulosa for its survival following prolonged exposure to uranyl carbonate extending up to 384 h at pH 7.8 under phosphate-limited conditions. The cells sequestered uranium (U) within polyphosphates on initial exposure to 100 μM uranyl carbonate for 24 to 28 h. Further incubation until 120 h resulted in (i) significant degradation of cellular polyphosphates causing extensive chlorosis and cell lysis, (ii) akinete differentiation followed by (iii) extracellular uranyl precipitation. X-ray diffraction (XRD) analysis, fluorescence spectroscopy, X-ray absorption near edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) spectroscopy established the identity of the bioprecipitated uranium as a U(VI) autunite-type mineral, which settled at the bottom of the vessel. Surprisingly, A. torulosa cells resurfaced as small green flakes typical of actively growing colonies on top of the test solutions within 192 to 240 h of U exposure. A consolidated investigation using kinetics, microscopy, and physiological and biochemical analyses suggested a role of inducible alkaline phosphatase activity of cell aggregates/akinetes in facilitating the germination of akinetes leading to substantial regeneration of A. torulosa by 384 h of uranyl incubation. The biomineralized uranium appeared to be stable following cell regeneration. Altogether, our results reveal novel insights into the survival mechanism adopted by A. torulosa to resist sustained uranium toxicity under phosphate-limited oxic conditions. IMPORTANCE Long-term effects of uranyl exposure in cyanobacteria under oxic phosphate-limited conditions have been inadequately explored. We conducted a comprehensive examination of the metabolic responses displayed by a marine cyanobacterium, Anabaena torulosa, to cope with prolonged exposure to uranyl carbonate at pH 7.8 under phosphate limitation. Our results highlight distinct adaptive mechanisms harbored by this cyanobacterium that enabled its natural regeneration following extensive cell lysis and uranium biomineralization under sustained uranium exposure. Such complex interactions between environmental microbes such as Anabaena torulosa and uranium over a broader time range advance our understanding on the impact of microbial processes on uranium biogeochemistry. PMID:28258135

Neutron-rich isotope production using a uranium carbide - carbon nanotubes SPES target prototype

NASA Astrophysics Data System (ADS)

Corradetti, S.; Biasetto, L.; Manzolaro, M.; Scarpa, D.; Carturan, S.; Andrighetto, A.; Prete, G.; Vasquez, J.; Zanonato, P.; Colombo, P.; Jost, C. U.; Stracener, D. W.

2013-05-01

The SPES (Selective Production of Exotic Species) project, under development at the Istituto Nazionale di Fisica Nucleare - Laboratori Nazionali di Legnaro (INFN-LNL), is a new-generation Isotope Separation On-Line (ISOL) facility for the production of radioactive ion beams by means of the proton-induced fission of uranium. In the framework of the research on the SPES target, seven uranium carbide discs, obtained by reacting uranium oxide with graphite and carbon nanotubes, were irradiated with protons at the Holifield Radioactive Ion Beam Facility (HRIBF) of Oak Ridge National Laboratory (ORNL). In the following, the yields of several fission products obtained during the experiment are presented and discussed. The experimental results are then compared to those obtained using a standard uranium carbide target. The reported data highlights the capability of the new type of SPES target to produce and release isotopes of interest for the nuclear physics community.

Bioremediation of uranium contamination with enzymatic uranium reduction

USGS Publications Warehouse

Lovley, D.R.; Phillips, E.J.P.

1992-01-01

Enzymatic uranium reduction by Desulfovibrio desulfuricans readily removed uranium from solution in a batch system or when D. desulfuricans was separated from the bulk of the uranium-containing water by a semipermeable membrane. Uranium reduction continued at concentrations as high as 24 mM. Of a variety of potentially inhibiting anions and metals evaluated, only high concentrations of copper inhibited uranium reduction. Freeze-dried cells, stored aerobically, reduced uranium as fast as fresh cells. D. desulfuricans reduced uranium in pH 4 and pH 7.4 mine drainage waters and in uraniumcontaining groundwaters from a contaminated Department of Energy site. Enzymatic uranium reduction has several potential advantages over other bioprocessing techniques for uranium removal, the most important of which are as follows: the ability to precipitate uranium that is in the form of a uranyl carbonate complex; high capacity for uranium removal per cell; the formation of a compact, relatively pure, uranium precipitate.

First-principles study of uranium carbide: Accommodation of point defects and of helium, xenon, and oxygen impurities

NASA Astrophysics Data System (ADS)

Freyss, Michel

2010-01-01

Point defects and volatile impurities (helium, xenon, oxygen) in uranium monocarbide UC are studied by first-principles calculations. Preliminarily, bulk properties of UC and of two other uranium carbide phases, UC2 and U2C3 , are calculated in order to compare them to experimental data and to get confidence in the use of the generalized gradient approximation for this class of compounds. The subsequent study of different types of point defects shows that the carbon sublattice best accommodates the defects. The perturbation of the crystal structure induced by the defects is weak and the interaction between defects is found short range. Interstitial carbon dumbbells possibly play an important role in the diffusion of carbon atoms. The most favorable location of diluted helium, xenon, and oxygen impurities in the UC crystal lattice is then determined. The rare-gas atoms occupy preferably a uranium substitution site or a uranium site in a U-C bivacancy. But their incorporation in UC is, however, not energetically favorable, especially for xenon, suggesting their propensity to diffuse in the material and/or form bubbles. On the other hand, oxygen atoms are very favorably incorporated as diluted atoms in the UC lattice, confirming the easy oxidation of UC. The oxygen atoms preferably occupy a carbon substitution site or the carbon site of a U-C bivacancy. Our results are compared to available experimental data on UC and to similar studies by first-principles calculations for other carbides and nitrides with the rock-salt structure.

Repeated Storage of Respired Carbon in the Equatorial Pacific Ocean Over the Last Three Glacial Cycles

NASA Astrophysics Data System (ADS)

Jacobel, A. W.; McManus, J. F.; Anderson, R. F.; Winckler, G.

2017-12-01

As the largest reservoir of carbon actively exchanging with the atmosphere on glacial-interglacial timescales, the deep ocean has been implicated as the likely location of carbon dioxide sequestration during Pleistocene glaciations. Despite strong theoretical underpinnings for this expectation, it has been challenging to identify unequivocal evidence for respired carbon storage in the paleoceanographic record. Data on the rate of ocean ventilation derived from paired planktonic-benthic foraminifera radiocarbon ages conflict across the equatorial Pacific, and different proxy reconstructions contradict one another about the depth and origin of the watermass containing the respired carbon. Because any change in the storage of respiratory carbon must be accompanied by corresponding changes in dissolved oxygen concentrations, proxy data reflecting bottom water oxygenation are of value in addressing these apparent inconsistencies. We present new records of the redox sensitive metal uranium from the central equatorial Pacific to qualitatively identify intervals associated with respiratory carbon storage over the past 350 kyr. Our data reveal periods of deep ocean authigenic uranium deposition in association with each of the last three glacial maxima. Equatorial Pacific export productivity data show intervals with abundant authigenic uranium are not associated with local productivity increases, indicating episodic precipitation of authigenic uranium does not directly reflect increases in situ microbial respiration, but rather occurs in response to basin-wide decreases in deep water oxygen concentrations. We combine our new data with previously published results to propose a picture of glacial carbon storage and equatorial Pacific watermass structure that is internally consistent. We conclude that respired carbon storage in the Pacific was a persistent feature of Pleistocene glaciations.

HIGH DENSITY NUCLEAR FUEL COMPOSITION

DOEpatents

Litton, F.B.

1962-07-17

ABS>A nuclear fuel consisting essentially of uranium monocarbide and containing 2.2 to 4.6 wt% carbon, 0.1 to 2.3 wt% oxygen, 0.05 to 2.5 wt% nitrogen, and the balance uranium was developed. The maximum oxygen content was less than one-half the carbon content by weight and the carbon, oxygen, and nitrogen are present as a single phase substituted solid solution of UC, C, O, and N. A method of preparing the fuel composition is described. (AEC)

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.

Geochemical, mineralogical and microbiological characteristics of sediment from a naturally reduced zone in a uranium-contaminated aquifer

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

Campbell, Kate M.; Kukkadapu, Ravi K.; Qafoku, Nikolla

2012-05-23

Localized zones or lenses of naturally reduced sediments have the potential to play a significant role in the fate and transport of redox-sensitive metals and metalloids in aquifers. To assess the mineralogy, microbiology, and redox processes that occur in these zones, we examined several cores from a region of naturally occurring reducing conditions in a uranium-contaminated aquifer (Rifle, CO). Sediment samples from a transect of cores ranging from oxic/suboxic Rifle aquifer sediment to naturally reduced sediment were analyzed for uranium and iron content, oxidation state, and mineralogy, reduced sulfur phases, and solid phase organic carbon content using a suite ofmore » analytical and spectroscopic techniques on bulk sediment and size fractions. Solid-phase uranium concentrations were higher in the naturally reduced zone, with a high proportion of the uranium present as reduced U(IV). The sediments were also elevated in reduced sulfur phases and Fe(II), indicating it is very likely that U(VI), Fe(III), and sulfate reduction occurred or is occurring in the sediment. The microbial community was assessed using lipid- and DNA-based techniques, and statistical redundancy analysis was performed to determine correlations between the microbial community and the geochemistry. Increased concentration of solid phase organic carbon and biomass in the naturally reduced sediment suggests that natural bioreduction is stimulated by a zone of increased organic carbon concentration associated with fine-grained material and lower permeability to groundwater flow. Characterization of the naturally bioreduced sediment provides an understanding of the natural processes that occur in the sediment under reducing conditions and how they may impact natural attenuation of radionuclides and other redox sensitive materials. Results also suggest the importance of recalcitrant organic carbon for maintaining reducing conditions and uranium immobilization.« less

Uranium-series dated authigenic carbonates and acheulian sites in southern Egypt

USGS Publications Warehouse

Szabo, B. J.; McHugh, W.P.; Schaber, G.G.; Haynes, C.V.; Breed, C.S.

1989-01-01

Field investigations in southern Egypt have yielded Acheulian artifacts in situ in authigenic carbonate deposits (CaCO3-cemented alluvium) along the edges of nowaggraded paleovalleys (Wadi Arid and Wadi Safsaf). Uranium-series dating of 25 carbonate samples from various localities as far apart as 70 kilometers indicates that widespread carbonate deposition occurred about 45, 141 and 212 ka (thousand years ago). Most of the carbonate appears to have been precipitated from groundwater, which suggests that these three episodes of deposition may be related to late Pleistocene humid climates that facilitated human settlement in this now hyperarid region. Carbonate cements from sediments containing Acheulian artifacts provide a minimum age of 212 ka for early occupation of the paleovalleys.

As-cast uranium-molybdenum based metallic fuel candidates and the effects of carbon addition

NASA Astrophysics Data System (ADS)

Blackwood, Van Stephen

The objective of this research was to develop and recommend a metallic nuclear fuel candidate that lowered the onset temperature of gamma phase formation comparable or better than the uranium-10 wt. pct. molybdenum alloy, offered a solidus temperature as high or higher than uranium-10 wt. pct. zirconium (1250°C), and stabilized the fuel phase against interaction with iron and steel at least as much as uranium-10 wt. pct. zirconium stabilized the fuel phase. Two new as-cast alloy compositions were characterized to assess thermal equilibrium boundaries of the gamma phase field and the effect of carbon addition up to 0.22 wt. pct. The first system investigated was uranium- x wt. pct. M where x ranged between 5-20 wt. pct. M was held at a constant ratio of 50 wt. pct. molybdenum, 43 wt. pct. titanium, and 7 wt. pct. zirconium. The second system investigated was the uranium-molybdenum-tungsten system in the range 90 wt. pct. uranium - 10 wt. pct. molybdenum - 0 wt. pct. tungsten to 80 wt. pct. uranium - 10 wt. pct. molybdenum - 10 wt. pct. tungsten. The results showed that the solidus temperature increased with increased addition of M up to 12.5 wt. pct. for the uranium-M system. Alloy additions of titanium and zirconium were removed from uranium-molybdenum solid solution by carbide formation and segregation. The uranium-molybdenum-tungsten system solidus temperature increased to 1218°C at 2.5 wt. pct. with no significant change in temperature up to 5 wt. pct. tungsten suggesting the solubility limit of tungsten had been reached. Carbides were observed with surrounding areas enriched in both molybdenum and tungsten. The peak solidus temperatures for the alloy systems were roughly the same at 1226°C for the uranium-M system and 1218°C for the uranium-molybdenum-tungsten system. The uranium-molybdenum-tungsten system required less alloy addition to achieve similar solidus temperatures as the uranium-M system.

RECOVERY OF URANIUM FROM AQUEOUS PHOSPHATE-CONTAINING SOLUTIONS

DOEpatents

Igelsrud, I.; Stephen, E.F.

1959-08-11

ABS>A method is presented for recovering hexavalent uranium from an acidic phosphaie solution. A high molecular weight amine, such as a mixture of cccoanut oil amines, is added to the solution in such amount as to give a ratio of about 2000 parts by weight of amine to 1 part by weight of uranium. The uranium is precipitated with the amines and the whole filtered from the solution. The uranium is leached from the amine mass by washing with aqueous sodium carbonate solution; and the amine mixture is available for reuse.

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.

Electron-spectroscopy studies of clean thorium and uranium surfaces. Chemisorption and initial stages of reaction with O2, CO, and CO2

NASA Astrophysics Data System (ADS)

McLean, W.; Colmenares, C. A.; Smith, R. L.; Somorjai, G. A.

1982-01-01

The adsorption of O2, CO, and CO2 on the thorium (111) crystal face and on polycrystalline α-uranium has been investigated by x-ray photoelectron spectroscopy, Auger electron spectroscopy (AES), and secondary-ion mass spectroscopy (SIMS) at 300 K. Oxygen adsorption on both metals resulted in the formation of the metal dioxide. CO and CO2 adsorption on Th(111) produced species derived from atomic carbon and oxygen; the presence of molecular CO was also detected. Only atomic carbon and oxygen were observed on uranium. Elemental depth profiles by AES and SIMS indicated that the carbon produced by the dissociation of CO or CO2 diffused into the bulk of the metals to form a carbide, while the oxygen remained on their surfaces as an oxide.

Unusual Versatility of the Filamentous, Diazotrophic Cyanobacterium Anabaena torulosa Revealed for Its Survival during Prolonged Uranium Exposure.

PubMed

Acharya, Celin; Chandwadkar, Pallavi; Nayak, Chandrani

2017-05-01

Reports on interactions between cyanobacteria and uranyl carbonate are rare. Here, we present an interesting succession of the metabolic responses employed by a marine, filamentous, diazotrophic cyanobacterium, Anabaena torulosa for its survival following prolonged exposure to uranyl carbonate extending up to 384 h at pH 7.8 under phosphate-limited conditions. The cells sequestered uranium (U) within polyphosphates on initial exposure to 100 μM uranyl carbonate for 24 to 28 h. Further incubation until 120 h resulted in (i) significant degradation of cellular polyphosphates causing extensive chlorosis and cell lysis, (ii) akinete differentiation followed by (iii) extracellular uranyl precipitation. X-ray diffraction (XRD) analysis, fluorescence spectroscopy, X-ray absorption near edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) spectroscopy established the identity of the bioprecipitated uranium as a U(VI) autunite-type mineral, which settled at the bottom of the vessel. Surprisingly, A. torulosa cells resurfaced as small green flakes typical of actively growing colonies on top of the test solutions within 192 to 240 h of U exposure. A consolidated investigation using kinetics, microscopy, and physiological and biochemical analyses suggested a role of inducible alkaline phosphatase activity of cell aggregates/akinetes in facilitating the germination of akinetes leading to substantial regeneration of A. torulosa by 384 h of uranyl incubation. The biomineralized uranium appeared to be stable following cell regeneration. Altogether, our results reveal novel insights into the survival mechanism adopted by A. torulosa to resist sustained uranium toxicity under phosphate-limited oxic conditions. IMPORTANCE Long-term effects of uranyl exposure in cyanobacteria under oxic phosphate-limited conditions have been inadequately explored. We conducted a comprehensive examination of the metabolic responses displayed by a marine cyanobacterium, Anabaena torulosa , to cope with prolonged exposure to uranyl carbonate at pH 7.8 under phosphate limitation. Our results highlight distinct adaptive mechanisms harbored by this cyanobacterium that enabled its natural regeneration following extensive cell lysis and uranium biomineralization under sustained uranium exposure. Such complex interactions between environmental microbes such as Anabaena torulosa and uranium over a broader time range advance our understanding on the impact of microbial processes on uranium biogeochemistry. Copyright © 2017 American Society for Microbiology.

Recovery and recycling of uranium from rejected coated particles for compact high temperature reactors

NASA Astrophysics Data System (ADS)

Pai, Rajesh V.; Mollick, P. K.; Kumar, Ashok; Banerjee, J.; Radhakrishna, J.; Chakravartty, J. K.

2016-05-01

UO2 microspheres prepared by internal gelation technique were coated with pyrolytic carbon and silicon carbide using CVD technique. The particles which were not meeting the specifications were rejected. The rejected/failed UO2 based coated particles prepared by CVD technique was used for oxidation and recovery and recycling. The oxidation behaviour of sintered UO2 microspheres coated with different layers of carbon and SiC was studied by thermal techniques to develop a method for recycling and recovery of uranium from the failed/rejected coated particles. It was observed that the complete removal of outer carbon from the spheres is difficult. The crushing of microspheres enabled easier accessibility of oxygen and oxidation of carbon and uranium at 800-1000 °C. With the optimized process of multiple crushing using die & plunger and sieving the broken coated layers, we could recycle around fifty percent of the UO2 microspheres which could be directly recoated. The rest of the particles were recycled using a wet recycling method.

Coupling XRD, EXAFS, and 13C NMR to study the effect of the carbon stoichiometry on the local structure of UC(1±x).

PubMed

Carvajal Nuñez, U; Martel, L; Prieur, D; Lopez Honorato, E; Eloirdi, R; Farnan, I; Vitova, T; Somers, J

2013-10-07

A series of uranium carbide samples, prepared by arc melting with a C/U ratio ranging from 0.96 to 1.04, has been studied by X-ray diffraction (XRD), (13)C nuclear magnetic resonance (NMR), and extended X-ray absorption fine structure (EXAFS). XRD determines phase uniqueness and the increase of the lattice parameter versus the carbon content. In contrast, (13)C NMR detects the different carbon environments in the lattice and in this study, clearly identifies the presence of discrete peaks for carbon in the octahedral lattice site in UC and an additional peak associated with excess carbon in hyperstoichiometric samples. Two peaks associated with different levels of carbon deficiency are detected for all hypostoichiometric compositions. More than one carbon environment is always detected by (13)C NMR. This exemplifies the difficulty in obtaining a perfect stoichiometric uranium monocarbide UC(1.00). The (13)C MAS spectra of uranium carbides exhibit the effects resulting from the carbon content on both the broadening of the peaks and on the Knight shift. An abrupt spectral change occurs between hypo- and hyperstoichiometric samples. The results obtained by EXAFS highlight subtle differences between the different stoichiometries, and in the hyperstoichiometric samples, the EXAFS results are consistent with the excess carbon atoms being in the tetrahedral interstitial position.

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.

MOLDED SEALING ELEMENT

DOEpatents

Bradford, B.W.; Skinner, W.J.

1959-03-24

Molded sealing elements suitable for use under conditions involving exposure to uranium hexafluoride vapor are described. Such sealing elements are made by subjecting graphitic carbons to a preliminary treatment with uranium hexafluoride vapor, and then incorporating polytetrafluorethylene in them. The resulting composition has good wear resistant and frictional properties and is resistant to disintegration by uranium hexafluoride over long periods of exposure.

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/.

KINETICS OF THE DISSOLUTION OF URANIUM DIOXIDE IN CARBONATE-BICARBONATE SOLUTIONS

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

Schortmann, W.E.; DeSesa, M.A.

The kinetics of the dissolution of uranium dioxide in sodium carbonate- sodium bicarbonate solutions were determined. The study was undertaken in order to obtain fundamental information about the commercial carbonate process for leaching uranium from its ores. A rate equation incorporating the effects of surface area oxygen partial pressure, temperature, and reagent concentrations was empirically developed. A mechanism consisting essentially of two consecutive reactions at steady state is proposed. These reactions are the oxidation of U/ sup 4+/ to U/sup 6+/ and the subsequent formation of the uranyl dicarbonate complexion. Depending on the conditions, either or both of these reactionsmore » can determine the over-all rate. The conversion of uranyl dicarbonate to the uranyl tricarbonate complexion is postulated to be very rapid. In the suggested mechanism, the rate-determining phase of the oxidation is the dissociation of adsorbed molecular oxygen. and both the carbonate and bicarbonate ions play equivalent roles in the formation of the uranyl dicarbonate. As indicated by their high activation energies of about 13 and 14 kcal per mole uranium, both reactions are chemical rather than diffusional processes. A mathematical examination of the proposed mechanism produced a rate equation consistent with the experimental information. The credibility of the mechanism was thereby strengthened. (auth)« less

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

PubMed

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

2010-02-01

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

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.

Uranium in granitic magmas: Part 1. Experimental determination of uranium solubility and fluid-melt partition coefficients in the uranium oxide-haplogranite-H 2O-Na 2CO 3 system at 720-770°C, 2 kbar

NASA Astrophysics Data System (ADS)

Peiffert, Chantal; Cuney, Michel; Nguyen-Trung, Chinh

1994-06-01

The solubility of uranium was investigated in both carbonated aqueous fluid and granitic melt in equilibrium in the system haplogranite-uranium oxide-H 2O-Na 2CO 3 (0.5-1 molal) at 720-770°C, 2 kbar, andƒo 2 fixed by Ni-NiO, Fe 3O 4-Fe 2O 3, and Cu 2O-CuO buffers. As complete solid solution exists between UO 2.00 and UO 2.25 (i.e., 75 mol% UO 2 + 25 mol% UO 3), three distinct uranium oxides: UO (2.01 ± 0.01), UO (2.1.0 ± 0.02), and UO (2.25 ± 0.02) were, respectively, obtained at equilibrium, under the three ƒo 2 conditions cited above. Thus, the percentage of U (VI) in uranium oxide increased with increasing log ƒo 2. The thermal decomposition of Na 2CO 3 to CO 2 and Na 2O led to the decrease of the sodium carbonate concentration from 0.5-1 molal to ~10 -2 molal in all aqueous fluids and to the dissolution of Na in the silicate melts. Crystal-free silicate glasses with four agpaitic coefficients, α = ( (Na+K)/Al) = 1.1, 1.3, 1.5, and 1.7 were obtained. The uranium solubility in 10 -2 m aqueous carbonated fluid ((8.1 ± 0.1) ≤ quench pH ≤ (8.9 ± 0.1)) was in the range 1-17 ppm and increased linearly with increasing ƒo 2 according to the expression: log (U) (ppm) = 0.09 ·log ƒo 2 (bar) + 1.47 . This equation is valid for the temperature range 720-770°C and 2 kbar. U(IV) carbonate possibly were major species in aqueous solutions under reducing conditions (Ni-NiO buffer) whereas U(VI) carbonate complexes dominated under higher oxidation conditions (Fe 3O 4-Fe 2O 3, Cu 2O-CuO buffers). The uranium content in silicate glasses varied in a large range (10 2-2 × 10 5 ppm) and log (U) (ppm) increases linearly with both ƒo 2, and α in the range 1.1-1.5 according to the equation log (U) (ppm) = 0.04 log ƒo 2 (bar) + 3.80α -1.34 . This equation is valid for (1)ƒ o 2 ranging from Ni-NiO to Cu 2O-CuO, and (2) the temperature range 720-770°C at 2 kbar. The effect of ƒo 2 on the uranium solubility in silicate melt slightly decreased with increasing α from 1.1 to 1.5. For α in the range 1.5-1.7, the effect of both ƒo 2 and agpaicity index on the uranium solubility was considerably reduced. The temperature variation in the range 720-770°C had no significant effect on the uranium solubility in either aqueous fluid or silicate melt. The partition coefficient (D fluid/melt) of uranium was in the range 10 -4.0-10 -1.5 and depended on both ƒo 2 and α according to the equation log D fluid/melt = 0.05 log ƒo 2 (bar) - 3.78α + 2.84 . The validity conditions of this equation are similar to those of the preceding one. Results obtained in the present study could be used to predict the geochemical behaviour of uranium during magma fractionation and to further understanding of the formation of uranium ore deposits related to partial melting or fractional crystallization of felsic magmas. The genesis of the Kvanefjeld (Ilimaussaq, Greenland) uranium deposit is discussed.

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

PubMed

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

2017-05-05

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

Natural uranium and thorium isotopes in sediment cores off Malaysian ports

NASA Astrophysics Data System (ADS)

Yusoff, Abdul Hafidz; Sabuti, Asnor Azrin; Mohamed, Che Abd Rahim

2015-06-01

Sediment cores collected from three Malaysian marine ports, namely, Kota Kinabalu, Labuan and Klang were analyzed to determine the radioactivities of 234U, 238U, 230Th, 232Th and total organic carbon (TOC) content. The objectives of this study were to determine the factors that control the activity of uranium isotopes and identify the possible origin of uranium and thorium in these areas. The activities of 234U and 238U show high positive correlation with TOC at the middle of sediment core from Kota Kinabalu port. This result suggests that activity of uranium at Kota Kinabalu port was influenced by organic carbon. The 234U/238U value at the upper layer of Kota Kinabalu port was ≥1.14 while the ratio value at Labuan and Klang port was ≤ 1.14. These results suggest a reduction process occurred at Kota Kinabalu port where mobile U(VI) was converted to immobile U(IV) by organic carbon. Therefore, it can be concluded that the major input of uranium at Kota Kinabalu port is by sorptive uptake of authigenic uranium from the water column whereas the major inputs of uranium to Labuan and Klang port are of detrital origin. The ratio of 230Th/232Th was used to estimate the origin of thorium. Low ratio value (lt; 1.5) at Labuan and Klang ports support the suggestion that thorium from both areas were come from detrital input while the high ratio (> 1.5) of 230Th/232Th at Kota Kinabalu port suggest the anthropogenic input of 230Th to this area. The source of 230Th is probably from phosphate fertilizers used in the oil-palm cultivation in Kota Kinabalu that is adjacent to the Kota Kinabalu port.

METHOD OF PRODUCING URANIUM METAL BY ELECTROLYSIS

DOEpatents

Piper, R.D.

1962-09-01

A process is given for making uranium metal from oxidic material by electrolytic deposition on the cathode. The oxidic material admixed with two moles of carbon per one mole of uranium dioxide forms the anode, and the electrolyte is a mixture of from 40 to 75% of calcium fluoride or barium fluoride, 15 to 45% of uranium tetrafluoride, and from 10 to 20% of lithium fluoride or magnesium fluoride; the temperature of the electrolyte is between 1150 and 1175 deg C. (AEC)

Carbothermic Synthesis of 820 m UN Kernels: Literature Review, Thermodynamics, Analysis, and Related Experiments

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

Lindemer, Terrence; Voit, Stewart L; Silva, Chinthaka M

2014-01-01

The U.S. Department of Energy is considering 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 large, dense uranium nitride (UN) kernels. This effort explores many factors involved in using gel-derived uranium oxide-carbon microspheres to make large UN kernels. Analysis of recent studies with sufficient experimental details is provided. Extensive thermodynamic calculations are used to predict carbon monoxide and other pressures for several different reactions that may be involved in conversion of uranium oxides and carbides to UN. Experimentally, the method for making themore » gel-derived microspheres is described. These were used in a microbalance with an attached mass spectrometer to determine details of carbothermic conversion in argon, nitrogen, or vacuum. A quantitative model is derived from experiments for vacuum conversion to an uranium oxide-carbide kernel.« less

Preliminary investigation of the elemental variation and diagenesis of a tabular uranium deposit, La Sal Mine, San Juan County, Utah

USGS Publications Warehouse

Brooks, Robert A.; Campbell, John A.

1976-01-01

Ore in the La Sal mine, San Juan County, Utah, occurs as a typical tabular-type uranium deposit of the-Colorado Plateau. Uranium-vanadium occurs in the Salt Wash Member of the Jurassic Morrison Formation. Chemical and petrographic analyses were used to determine elemental variation and diagenetic aspects across the orebody. Vanadium is concentrated in the dark clay matrix, which constitutes visible ore. Uranium content is greater above the vanadium zone. Calcium, carbonate carbon, and lead show greater than fifty-fold increase across the ore zone, whereas copper and organic carbon show only a several-fold increase. Large molybdenum concentrations are present in and above the tabular layer, and large selenium concentrations occur below the uranium zone within the richest vanadium zone. Iron is enriched in the vanadium horizon. Chromium is depleted from above the ore and strongly enriched below. Elements that vary directly with the vanadium content include magnesium, iron, selenium, zirconium, strontium, titanium, lead, boron, yttrium, and scandium. The diagenetic sequence is as follows: (1) formation of secondary quartz overgrowths as cement; (2) infilling and lining of remaining pores with amber opaline material; (3) formation of vanadium-rich clay matrix, which has replaced overgrowths as well as quartz grains; (4) replacement of overgrowths and detrital grains by calcite; (5) infilling of pores with barite and the introduction of pyrite and marcasite.

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

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

Stewart, B.D.; Mayes, Melanie; Fendorf, Scott

2010-01-01

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

SLURRY SOLVENT EXTRACTION PROCESS FOR THE RECOVERY OF METALS FROM SOLID MATERIALS

DOEpatents

Grinstead, R.R.

1959-01-20

A solvent extraction process is described for recovering uranium from low grade uranium bearing minerals such as carnotit or shale. The finely communited ore is made up as an aqueous slurry containing the necessary amount of acid to solubilize the uranium and simultaneously or subsequently contacted with an organic solvent extractant such as the alkyl ortho-, or pyro phosphoric acids, alkyl phosphites or alkyl phosphonates in combination with a diluent such as kerosene or carbon tetrachlorids. The extractant phase is separated from the slurry and treated by any suitable process to recover the uranium therefrom. One method for recovering the uranium comprises treating the extract with aqueous HF containing a reducing agent such as ferrous sulfate, which reduces the uranium and causes it to be precipitated as uranium tetrafluoride.

URANIUM RECOVERY PROCESS

DOEpatents

Stevenson, J.W.; Werkema, R.G.

1959-07-28

The recovery of uranium from magnesium fluoride slag obtained as a by- product in the production of uranium metal by the bomb reduction prccess is presented. Generally the recovery is accomplished by finely grinding the slag, roasting ihe ground slag air, and leaching the roasted slag with a hot, aqueous solution containing an excess of the sodium bicarbonate stoichiometrically required to form soluble uranium carbonate complex. The roasting is preferably carried out at between 425 and 485 deg C for about three hours. The leaching is preferably done at 70 to 90 deg C and under pressure. After leaching and filtration the uranium may be recovered from the clear leach liquor by any desired method.

Microscopic Fuel Particles Produced by Self-Assembly of Actinide Nanoclusters on Carbon Nanomaterials

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

Na, Chongzheng

2016-10-17

Many consider further development of nuclear power to be essential for sustained development of society; however, the fuel forms currently used are expensive to recycle. In this project, we sought to create the knowledge and knowhow that are needed to produce nanocomposite materials by directly depositing uranium nanoclusters on networks of carbon-­ based nanomaterials. The objectives of the proposed work were to (1) determine the control of uranium nanocluster surface chemistry on nanocomposite formation, (2) determine the control of carbon nanomaterial surface chemistry on nanocomposite formation, and (3) develop protocols for synthesizing uranium-­carbon nanomaterials. After examining a wide variety ofmore » synthetic methods, we show that synthesizing graphene-­supported UO 2 nanocrystals in polar ethylene glycol compounds by polyol reduction under boiling reflux can enable the use of an inexpensive graphene precursor graphene oxide in the production of uranium-carbon nanocomposites in a one-­pot process. We further show that triethylene glycol is the most suitable solvent for producing nanometer-­sized UO 2 crystals compared to monoethylene glycol, diethylene glycol, and polyethylene glycol. Graphene-­supported UO 2 nanocrystals synthesized with triethylene glycol show evidence of heteroepitaxy, which can be beneficial for facilitating heat transfer in nuclear fuel particles. Furthermore, we show that graphene-supported UO 2 nanocrystals synthesized by polyol reduction can be readily stored in alcohols, preventing oxidation from the prevalent oxygen in air. Together, these methods provide a facile approach for preparing and storing graphene-supported UO nanocrystals for further investigation and development under ambient conditions.« less

U/Th dating of carbonate deposits from Constantina (Sevilla), Spain.

PubMed

Alcaraz-Pelegrina, J M; Martínez-Aguirre, A

2007-07-01

Uranium-series method has been applied to continental carbonate deposits from Constantina, Seville, in Spain. All samples analysed were impure carbonates and the leachate-leachate method was used to obtain activity ratios in carbonate fraction. Leachate-residue methods were applied to one of the samples in order to compare with leachate-leachate method, but leachate-residue method assumptions did not meet and ages resulting from leachate-residue methods were not valid. Ages obtained by leachate-leachate method range from 1.8 to 23.5ky BP and are consistent with stratigraphical positions of samples analysed. Initial activity ratios for uranium isotopes are practically constant in this period, thus indicating that no changes in environmental conditions occur between 1.8 and 23.5ky period.

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.

Determination of uranium in clinical and environmental samples by FIAS-ICPMS

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

Karpas, Z.; Lorber, A.; Halicz, L.

Uranium may enter the human body through ingestion or inhalation. Ingestion of uranium compounds through the diet, mainly drinking water, is a common occurrence, as these compounds are present in the biosphere. Inhalation of uranium-containing particles is mainly an occupational safety problem, but may also take place in areas where uranium compounds are abundant. The uranium concentration in urine samples may serve as an indication of the total uranium body content. A method based on flow injection and inductively coupled plasma mass spectrometry (FIAS-ICPMS) was found to be most suitable for determination of uranium in clinical samples (urine and serum),more » environmental samples (seawater, wells and carbonate rocks) and in liquids consumed by humans (drinking water and commercial beverages). Some examples of the application of the FIAS-ICPMS method are reviewed and presented here.« less

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.

DOUBLE-BAKED, SELF-CHANNELLING ELECTRODE

DOEpatents

Piper, R.D.; Leifield, R.F.

1963-03-12

A method is given for making an electrode for use in the electrolytic reduction of uranium oxides to uranium metal in a fused salt electrolyte. Uranlum oxide such as UO/sub 2/ is mixed with somewhat less than the stoichiometric amount of carbon needed for the reduction, and the mixture is baked and crushed to make a nonspherical material. The latter is then mixed with a carbon binder sufficient to satisfy stoichiometry, pressed into a shape such as a cylinder, and baked. (AEC)

Constitutional studies on carbide nuclear fuels for fast breeder reactors. III. The uranium-barium-carbon ternary system at 1400°C, with observations on the uranium-strontium-carbon system

NASA Astrophysics Data System (ADS)

Peatfield, M.; Brett, N. H.; Potter, P. E.

1980-03-01

The ternary system U-Ba-C has been examined at 1400°C and the solid-state compatibility lines established. No compound formation was found to occur and solubility effects were found to be minimal. A tentative examination of compositions in the U-Sr-C system indicates that it is of a similar form to that of the U-Ba-C system.

Fission- and alpha-track study of biogeochemistry of plutonium and uranium in carbonates of bikini and enewetak atolls. Final report

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

Levy, Y.; Friedman, G. M.; Miller, D. S.

1978-12-31

Results of the analysis of uranium concentrations in the 8 coral heads sampled from the Bikini and Enewetak lagoons lead to the following conclusions: (1) no parallel increase in uranium concentration was found in the corals contaminated by Pu and Am; (2) in the noncontaminated corals, the fission track analysis shows wider ranges of uranium concentrations (1.8 to 3.1). Thus, in the corals not contaminated by Pu and Am, uranium concentrations similar to the uranium concentration in the contaminated corals were found; (3) uranium content in all corals analyzed was rather homogeneously distributed, i.e., no hot spots, stars, or areasmore » differing in concentration by more than a few percent were detected by the fission track analyses.« less

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.

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.

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.

Homologation and functionalization of carbon monoxide by a recyclable uranium complex.

PubMed

Gardner, Benedict M; Stewart, John C; Davis, Adrienne L; McMaster, Jonathan; Lewis, William; Blake, Alexander J; Liddle, Stephen T

2012-06-12

Carbon monoxide (CO) is in principle an excellent resource from which to produce industrial hydrocarbon feedstocks as alternatives to crude oil; however, CO has proven remarkably resistant to selective homologation, and the few complexes that can effect this transformation cannot be recycled because liberation of the homologated product destroys the complexes or they are substitutionally inert. Here, we show that under mild conditions a simple triamidoamine uranium(III) complex can reductively homologate CO and be recycled for reuse. Following treatment with organosilyl halides, bis(organosiloxy)acetylenes, which readily convert to furanones, are produced, and this was confirmed by the use of isotopically (13)C-labeled CO. The precursor to the triamido uranium(III) complex is formed concomitantly. These findings establish that, under appropriate conditions, uranium(III) can mediate a complete synthetic cycle for the homologation of CO to higher derivatives. This work may prove useful in spurring wider efforts in CO homologation, and the simplicity of this system suggests that catalytic CO functionalization may soon be within reach.

Homologation and functionalization of carbon monoxide by a recyclable uranium complex

PubMed Central

Gardner, Benedict M.; Stewart, John C.; Davis, Adrienne L.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Liddle, Stephen T.

2012-01-01

Carbon monoxide (CO) is in principle an excellent resource from which to produce industrial hydrocarbon feedstocks as alternatives to crude oil; however, CO has proven remarkably resistant to selective homologation, and the few complexes that can effect this transformation cannot be recycled because liberation of the homologated product destroys the complexes or they are substitutionally inert. Here, we show that under mild conditions a simple triamidoamine uranium(III) complex can reductively homologate CO and be recycled for reuse. Following treatment with organosilyl halides, bis(organosiloxy)acetylenes, which readily convert to furanones, are produced, and this was confirmed by the use of isotopically 13C-labeled CO. The precursor to the triamido uranium(III) complex is formed concomitantly. These findings establish that, under appropriate conditions, uranium(III) can mediate a complete synthetic cycle for the homologation of CO to higher derivatives. This work may prove useful in spurring wider efforts in CO homologation, and the simplicity of this system suggests that catalytic CO functionalization may soon be within reach. PMID:22652572

Formation of unprecedented actinidecarbon triple bonds in uranium methylidyne molecules

PubMed Central

Lyon, Jonathan T.; Hu, Han-Shi; Andrews, Lester; Li, Jun

2007-01-01

Chemistry of the actinide elements represents a challenging yet vital scientific frontier. Development of actinide chemistry requires fundamental understanding of the relative roles of actinide valence-region orbitals and the nature of their chemical bonding. We report here an experimental and theoretical investigation of the uranium methylidyne molecules X3UCH (X = F, Cl, Br), F2ClUCH, and F3UCF formed through reactions of laser-ablated uranium atoms and trihalomethanes or carbon tetrafluoride in excess argon. By using matrix infrared spectroscopy and relativistic quantum chemistry calculations, we have shown that these actinide complexes possess relatively strong UC triple bonds between the U 6d-5f hybrid orbitals and carbon 2s-2p orbitals. Electron-withdrawing ligands are critical in stabilizing the U(VI) oxidation state and sustaining the formation of uranium multiple bonds. These unique UC-bearing molecules are examples of the long-sought actinide-alkylidynes. This discovery opens the door to the rational synthesis of triple-bonded actinidecarbon compounds. PMID:18024591

Calyptogena-cemented rocks and concretions from the eastern part of Nankai accretionary prism: Age and geochemistry of uranium

NASA Astrophysics Data System (ADS)

Lalou, Claude; Fontugne, Michel; Lallemand, Serge E.; Lauriat-Rage, Agnès

1992-04-01

Calyptogena valves included in a carbonate-rich cement, and fragments of a carbonate-rich chimney, have been examined for their stable isotopic (C and O) composition,14C activity and uranium series disequilibrium. The fossil shells were formed essentially with seawater carbon and a negligible contribution of cold seepage organic carbon, as shown by theirδ13C values. This allows the14C method to be used to determine their age. A fairly good concordance between the14C and230Th234U ages of the youngest shells gives confidence in the dating of the older samples using the latter technique. Thus, theCalyptogena are dated at ca. 150,000 and 20,000 yrs B.P. They have been preserved from dissolution by rapid cementation by a supersaturated carbonate solution. The cement is especially rich in uranium (as high as 75 ppm), whose source is seawater; the enrichment is due to local reducing conditions brought about by the bacterial decomposition of the soft tissues of the bivalves shortly after death. TheCalyptogena that probably developed between these two events (the events of ca. 20,000 and 150,000 yrs) have not been preserved from dissolution because, as is presently the case, the cold seepages were undersaturated with calcium carbonate. The two events probably represent periods of intense fluid venting connected with tectonic activity.

PROCESSES OF RECLAIMING URANIUM FROM SOLUTIONS

DOEpatents

Zumwalt, L.R.

1959-02-10

A process is described for reclaiming residual enriched uranium from calutron wash solutions containing Fe, Cr, Cu, Ni, and Mn as impurities. The solution is adjusted to a pH of between 2 and 4 and is contacted with a metallic reducing agent, such as iron or zinc, in order to reduce the copper to metal and thereby remove it from the solution. At the same time the uranium present is reduced to the uranous state The solution is then contacted with a precipitate of zinc hydroxide or barium carbonate in order to precipitate and carry uranium, iron, and chromium away from the nickel and manganese ions in the solution. The uranium is then recovered fronm this precipitate.

Developing uranium dicarbide-graphite porous materials for the SPES project

NASA Astrophysics Data System (ADS)

Biasetto, L.; Zanonato, P.; Carturan, S.; Di Bernardo, P.; Colombo, P.; Andrighetto, A.; Prete, G.

2010-09-01

Uranium carbide dispersed in graphite was produced under vacuum by means of carbothermic reduction of different uranium oxides (UO 2, U 3O 8 and UO 3), using graphite as the source of carbon. The thermal process was monitored by mass spectrometry and the gas evolution confirmed the reduction of the U 3O 8 and UO 3 oxides to UO 2 before the carbothermic reaction, that started to occur at T > 1000 °C. XRD analysis confirmed the formation of α-UC 2 and of a minor amount of UC. The morphology of the produced uranium carbide was not affected by the oxides employed as the source of uranium.

PROCESS FOR THE RECOVERY AND PURIFICATION OF URANIUM DEPOSITS

DOEpatents

Carter, J.M.; Kamen, M.D.

1958-10-14

A process is presented for recovering uranium values from UCl/sub 4/ deposits formed on calutrons. Such deposits are removed from the calutron parts by an aqueous wash solution which then contains the uranium values in addition to the following impurities: Ni, Cu, Fe, and Cr. This impurity bearing wash solution is treated with an oxidizing agent, and the oxidized solution is then treated with ammonia in order to precipitate the uranium as ammonium diuranate. The metal impurities of iron and chromium, which form insoluble hydroxides, are precipitated along with the uranium values. The precipitate is separated from the solution, dissolved in acid, and the solution again treated with ammonia and ammonium carbonate, which results in the precipitation of the metal impurities as hydroxides while the uranium values remain in solution.

Irradiation of organic matter by uranium decay in the Alum Shale, Sweden

NASA Astrophysics Data System (ADS)

Lewan, M. D.; Buchardt, B.

1989-06-01

The Alum Shale of Sweden contains black shales with anomalously high uranium concentrations in excess of 100 ppm. Syngenetic or early diagenetic origin of this uranium indicates that organic matter within these shales has been irradiated by decaying uranium for approximately 500 Ma. Radiation-induced polymerization of alkanes through a free-radical cross-linking mechanism appears to be responsible for major alterations within the irradiated organic matter. Specific radiation-induced alterations include generation of condensate-like oils at reduced yields from hydrous pyrolysis experiments, decrease in atomic H/C ratios of kerogens, decrease in bitumen/organic-carbon ratios, and a relative increase in low-molecular weight triaromatic steroid hydrocarbons. Conversely, stable carbon isotopes of kerogens, reflectance of vitrinite-like macerais, oil-generation kinetics, and isomerization of 20R to 20S αα C 29-steranes were not affected by radiation. The radiation dosage needed to cause the alterations observed in the Alum Shale has been estimated to be in excess of 10 5 Mrads with respect to organic carbon. This value is used to estimate the potential for radiation damage to thermally immature organic matter in black shales through the geological rock record. High potential for radiation damage is not likely in Cenozoic and Mesozoic black shales but becomes more likely in lower Paleozoic and Precambrian black shales.

Improved ion exchange membrane

NASA Technical Reports Server (NTRS)

Rembaum, A.; Yen, S. P. S.; Klein, E.

1975-01-01

Membrane, made from commercially-available hollow fibers, is used in reverse osmosis, or dialysis. Fiber has skin layers which pass only small molecules. Macromolecules cannot penetrate skin. Fibers can also be used to remove other undesirable anions, such as phosphate, sulfate, carbonate, and uranium in form of uranium-sulfate complex.

FUSED SALT PROCESS FOR RECOVERY OF VALUES FROM USED NUCLEAR REACTOR FUELS

DOEpatents

Moore, R.H.

1960-08-01

A process is given for recovering plutonium from a neutron-irradiated uranium mass (oxide or alloy) by dissolving the mass in an about equimolar alkali metalaluminum double chloride, adding aluminum metal to the mixture obtained at a temperature of between 260 and 860 deg C, and separating a uranium-containing metal phase and a plutonium-chloride- and fission-product chloridecontaining salt phase. Dissolution can be expedited by passing carbon tetrachloride vapors through the double salt. Separation without reduction of plutonium from neutron- bombarded uranium and that of cerium from uranium are also discussed.

Spectroscopy and DFT studies of uranyl carbonate, rutherfordine, UO2CO3: a model for uranium transport, carbon dioxide sequestration, and seawater species

NASA Astrophysics Data System (ADS)

Kalashnyk, N.; Perry, D. L.; Massuyeau, F.; Faulques, E.

2017-12-01

Several optical microprobe experiments of the anhydrous uranium carbonate—rutherfordine—are presented in this work and compared to periodic density functional theory results. Rutherfordine is the simplest uranyl carbonate and constitutes an ideal model system for the study of the rich uranium carbonate family relevant for environmental sustainability. Micro-Raman, micro-reflectance, and micro-photoluminescence (PL) spectroscopy studies have been carried out in situ on native, micrometer-sized crystals. The sensitivity of these techniques is sufficient to analyze minute amounts of samples in natural environments without using x-ray analysis. In addition, very intense micro-PL and micro-reflectance spectra that were not reported before add new results on the ground and excited states of this mineral. The optical gap value determined experimentally is found at about 2.6-2.8 eV. Optimized geometry, band structure, and phonon spectra have been calculated. The main vibrational lines are identified and predicted by this theoretical study. This work is pertinent for optical spectroscopy, for identification of uranyl species in various environmental settings, and for nuclear forensic analysis.

Uranium isotope evidence for two episodes of deoxygenation during Oceanic Anoxic Event 2

NASA Astrophysics Data System (ADS)

Clarkson, Matthew O.; Stirling, Claudine H.; Jenkyns, Hugh C.; Dickson, Alexander J.; Porcelli, Don; Moy, Christopher M.; Pogge von Strandmann, Philip A. E.; Cooke, Ilsa R.; Lenton, Timothy M.

2018-03-01

Oceanic Anoxic Event 2 (OAE 2), occurring ˜94 million years ago, was one of the most extreme carbon cycle and climatic perturbations of the Phanerozoic Eon. It was typified by a rapid rise in atmospheric CO2, global warming, and marine anoxia, leading to the widespread devastation of marine ecosystems. However, the precise timing and extent to which oceanic anoxic conditions expanded during OAE 2 remains unresolved. We present a record of global ocean redox changes during OAE 2 using a combined geochemical and carbon cycle modeling approach. We utilize a continuous, high-resolution record of uranium isotopes in pelagic and platform carbonate sediments to quantify the global extent of seafloor anoxia during OAE 2. This dataset is then compared with a dynamic model of the coupled global carbon, phosphorus, and uranium cycles to test hypotheses for OAE 2 initiation. This unique approach highlights an intra-OAE complexity that has previously been underconstrained, characterized by two expansions of anoxia separated by an episode of globally significant reoxygenation coincident with the “Plenus Cold Event.” Each anoxic expansion event was likely driven by rapid atmospheric CO2 injections from multiphase Large Igneous Province activity.

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

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.

An unusual temperature dependence in the oxidation of oxycarbide layers on uranium

NASA Astrophysics Data System (ADS)

Ellis, Walton P.

1981-09-01

An anomalous temperature dependence has been observed for the oxidation kinetics of outermost oxycarbide layers on polycrystalline uranium metal. Normally, oxidation or corrosion reactions are expected to proceed more rapidly as the temperature is elevated. Thus, it came as a surprise when we observed that the removal of the outermost atomic layers of carbon from uranium oxycarbide by O 2 reproducibly proceeds at a much faster rate at 25°C than at 280°C.

An unusual temperature dependence in the oxidation of oxycarbide layers on uranium

NASA Astrophysics Data System (ADS)

Ellis, Walton P.

An anomalous temperature dependence has been observed for the oxidation kinetics of outermost oxycarbide layers on polycrystalline uranium metal. Normally, oxidation or corrosion reactions are expected to proceed more rapidly as the temperature is elevated. Thus, it came as a surprise when we observed that the removal of the outermost atomic layers of carbon from uranium oxycarbide by O 2 reproducibly proceeds at a much faster rate at 25°C than at 280°C.

Chemical analysis of water samples and geophysical logs from cored test holes drilled in the central Oklahoma Aquifer, Oklahoma

USGS Publications Warehouse

Schlottmann, Jamie L.; Funkhouser, Ron A.

1991-01-01

Chemical analyses of water from eight test holes and geophysical logs for nine test holes drilled in the Central Oklahoma aquifer are presented. The test holes were drilled to investigate local occurrences of potentially toxic, naturally occurring trace substances in ground water. These trace substances include arsenic, chromium, selenium, residual alpha-particle activities, and uranium. Eight of the nine test holes were drilled near wells known to contain large concentrations of one or more of the naturally occurring trace substances. One test hole was drilled in an area known to have only small concentrations of any of the naturally occurring trace substances.Water samples were collected from one to eight individual sandstone layers within each test hole. A total of 28 water samples, including four duplicate samples, were collected. The temperature, pH, specific conductance, alkalinity, and dissolved-oxygen concentrations were measured at the sample site. Laboratory determinations included major ions, nutrients, dissolved organic carbon, and trace elements (aluminum, arsenic, barium, beryllium, boron, cadmium, chromium, hexavalent chromium, cobalt, copper, iron, lead, lithium, manganese, mercury, molybdenum, nickel, selenium, silver, strontium, vanadium and zinc). Radionuclide activities and stable isotope (5 values also were determined, including: gross-alpha-particle activity, gross-beta-particle activity, radium-226, radium-228, radon-222, uranium-234, uranium-235, uranium-238, total uranium, carbon-13/carbon-12, deuterium/hydrogen-1, oxygen-18/oxygen-16, and sulfur-34/sulfur-32. Additional analyses of arsenic and selenium species are presented for selected samples as well as analyses of density and iodine for two samples, tritium for three samples, and carbon-14 for one sample.Geophysical logs for most test holes include caliper, neutron, gamma-gamma, natural-gamma logs, spontaneous potential, long- and short-normal resistivity, and single-point resistance. Logs for test-hole NOTS 7 do not include long- and short-normal resistivity, spontaneous-potential, or single-point resistivity. Logs for test-hole NOTS 7A include only caliper and natural-gamma logs.

The removal of uranium (VI) from aqueous solutions onto activated carbon developed from grinded used tire.

PubMed

Belgacem, Ahmed; Rebiai, Rachid; Hadoun, Hocine; Khemaissia, Sihem; Belmedani, Mohamed

2014-01-01

In this study, activated carbon was prepared from waste tire by KOH chemical activation. The pore properties including the BET surface area, pore volume, pore size distribution, and average pore diameter were characterized. BET surface area of the activated carbon was determined as 558 m(2)/g. The adsorption of uranium ions from the aqueous solution using this activated carbon has been investigated. Various physico-chemical parameters such as pH, initial metal ion concentration, and adsorbent dosage level and equilibrium contact time were studied by a batch method. The optimum pH for adsorption was found to be 3. The removal efficiency has also been determined for the adsorption system as a function of initial concentration. The experimental results were fitted to Langmuir, Freundlich, and Dubinin-Radushkevich (D-R) isotherm models. A comparison of best-fitting was performed using the coefficient of correlation and the Langmuir isotherm was found to well represent the measured sorption data. According to the evaluation using the Langmuir equation, the saturated monolayer sorption capacity of uranium ions onto waste tire activated carbon was 158.73 mg/g. The thermodynamic equilibrium constant and the Gibbs free energy were determined and results indicated the spontaneous nature of the adsorption process. Kinetics data were best described by pseudo-second-order model.

Origin of the Mariano Lake uranium deposit, McKinley County, New Mexico

USGS Publications Warehouse

Fishman, Neil S.; Reynolds, Richard L.

1982-01-01

The Mariano Lake uranium deposit, hosted by the Brushy Basin Member of the Jurassic Morrison Formation, occurs in the trough of an east-west trending syncline at the western end of the Smith Lake-Mariano Lake group of uranium deposits near Crownpoint, New Mexico. The orebody, which contains abundant amorphous organic material, is situated on the reduced side of a regional reduction-oxidation (redox) interface. The presence of amorphous organic material suggests the orebody may represent a tabular (primary) deposit, whereas the close proximity of the orebody to the redox interface is suggestive that uranium was secondarily redistributed by oxidative processes from pre-existing tabular orebodies. Uranium contents correlate positively with both organic carbon and vanadium contents. Petrographic evidence and scanning electron microscope-energy dispersive analyses point to uranium residence in the epigentically introduced amorphous organic material, which coats detrital grains and fills voids. Uranium mineralization was preceded by the following diagenetic alterations: precipitation of pyrite (d34S values ranging from-11.0 to-38.2 per mil); precipitation of mixed-layer smectite-illite clays; partial dissolution of some of the detrital feldspar population; and precipitation of quartz and adularia overgrowths. Alterations associated with uranium mineralization include emplacement of amorphous organic material (possibly uranium bearing); destruction of detrital iron-titanium oxide grains; coprecipitation of chlorite and microcrystalline quartz, and precipitation of pyrite and marcasite (d34S values for these sulfides ranging from -29.4 to -41.6 per mil). After mineralization, calcite, dolomite, barite, and kaolinite precipitated, and authigenic iron disulfides were replaced by ferric oxides and hydroxides. Geochemical data (primarily the positive correlation of uranium content to both organic carbon and vanadium contents) and petrographic observations (epigentically introduced amorphous organic matter and uranium residence in this organic matter) indicate that the Mariano Lake orebody is a tabular-type uranium deposit. Oxidative processes have not noticeably redistributed and reconcentrated primary uranium in the immediate vicinity of the deposit nor have they greatly modified geochemical characteristics in the ore. Preservation of the Mariano Lake deposit may not only be related to its position along the synclinal trough, where oxidative destruction of the orebody has been inhibited by stagnation of oxidizing ground waters by the structure, but also due to the deflection of ground waters (resulting from low orebody porosity) around the orebody.

Some Thermodynamic Features of Uranium-Plutonium Nitride Fuel in the Course of Burnup

NASA Astrophysics Data System (ADS)

Rusinkevich, A. A.; Ivanov, A. S.; Belov, G. V.; Skupov, M. V.

2017-12-01

Calculation studies on the effect of carbon and oxygen impurities on the chemical and phase compositions of nitride uranium-plutonium fuel in the course of burnup are performed using the IVTANTHERMO code. It is shown that the number of moles of UN decreases with increasing burnup level, whereas UN1.466, UN1.54, and UN1.73 exhibit a considerable increase. The presence of oxygen and carbon impurities causes an increase in the content of the UN1.466, UN1.54 and UN1.73 phases in the initial fuel by several orders of magnitude, in particular, at a relatively low temperature. At the same time, the presence of impurities abruptly reduces the content of free uranium in unburned fuel. Plutonium in the considered system is contained in form of Pu, PuC, PuC2, Pu2C3, and PuN. Plutonium carbides, as well as uranium carbides, are formed in small amounts. Most of the plutonium remains in the form of nitride PuN, whereas unbound Pu is present only in the areas with a low burnup level and high temperatures.

Long-term in situ oxidation of biogenic uraninite in an alluvial aquifer: impact of dissolved oxygen and calcium.

PubMed

Lezama-Pacheco, Juan S; Cerrato, José M; Veeramani, Harish; Alessi, Daniel S; Suvorova, Elena; Bernier-Latmani, Rizlan; Giammar, Daniel E; Long, Philip E; Williams, Kenneth H; Bargar, John R

2015-06-16

Oxidative dissolution controls uranium release to (sub)oxic pore waters from biogenic uraninite produced by natural or engineered processes, such as bioremediation. Laboratory studies show that uraninite dissolution is profoundly influenced by dissolved oxygen (DO), carbonate, and solutes such as Ca(2+). In complex and heterogeneous subsurface environments, the concentrations of these solutes vary in time and space. Knowledge of dissolution processes and kinetics occurring over the long-term under such conditions is needed to predict subsurface uranium behavior and optimize the selection and performance of uraninite-based remediation technologies over multiyear periods. We have assessed dissolution of biogenic uraninite deployed in wells at the Rifle, CO, DOE research site over a 22 month period. Uraninite loss rates were highly sensitive to DO, with near-complete loss at >0.6 mg/L over this period but no measurable loss at lower DO. We conclude that uraninite can be stable over decadal time scales in aquifers under low DO conditions. U(VI) solid products were absent over a wide range of DO values, suggesting that dissolution proceeded through complexation and removal of oxidized surface uranium atoms by carbonate. Moreover, under the groundwater conditions present, Ca(2+) binds strongly to uraninite surfaces at structural uranium sites, impacting uranium fate.

ANIONIC EXCHANGE PROCESS FOR THE RECOVERY OF URANIUM AND VANADIUM FROM CARBONATE SOLUTIONS

DOEpatents

Bailes, R.H.; Ellis, D.A.; Long, R.S.

1958-12-16

Uranium and vanadium can be economically purified and recovered from non- salt roast carbonate leach liquors by adsorption on a strongly basic anionic exchange resin and subsequent selective elution by one of three alternative methods. Method 1 comprises selectively eluting uranium from the resin with an ammonium sulfate solution followed by eluting vanadium from the resin with either 5 M NaCl, saturated (NH/sub 4/)/sub 2/CO/sub 3/, saturated NaHCO/sub 3/, 1 M NaOH, or saturated S0/sub 2/ solutions. Method II comprises selectively eluting vanadium from the resin with either concentrated NaCl or S0/sub 2/ solutions subsequent to pretreatment of the column with either S0/sub 2/ gas, 1 N HCl, or 0.1 N H/sub 2/8O/sub 4/ followed by eluting uranium from the resin with solutions containing 0.9 M NH/sub 4/Cl or NaCl and 0.1 Cl. Method III comprises flowing the carbonate leac solutlon through a first column of a strongly basic anlonlc exchange resin untll vanadium breakthrough occurs, so that the effluent solution is enriched ln uranium content and the vanadium is chiefly retalned by the resln, absorbing the uranlum from the enriched effluent solution on a second column of a strongly basic anionic exchange resin, pretreating the first column with either 0.1 N HCl, 0.1 H/sub 2/SO/sub 4/, C0/sub 2/ gas, or ammonium sulfate, selectively eluting the vanadlum from the column with saturated S0/sub 2/ solution, pretreatlng the second column with either 0.1 N HCl or S0/sub 2/ gas, selectively eluting residual vanadium from the column with saturated S0/sub 2/ solution, and then eluting the uranium from the column with either 0.1 N HCl and 1 N NaCl orO.l N HCl and 1 N NH/sub 4/Cl.

Comprehensive Evaluation of Soil Near Uranium Tailings, Beishan City, China.

PubMed

Xun, Yan; Zhang, Xinjia; Chaoliang, Chen; Luo, Xuegang; Zhang, Yu

2018-06-01

To evaluate the impact of uranium tailings on soil composition and soil microbial, six soil samples at different distance from the uranium tailings (Beishan City, China) were collected for further analysis. Concentrations of radionuclides ( 238 U and 232 Th), heavy metals (Mn, Cd, Cr, Ni, Zn, and Pb) and organochlorine pesticide were determined by ICP-MS and GC, they were significantly higher than those of the control. And the Average Well Color Development as well as the Shannon, the Evenness, and the Simpson index were calculated to evaluate the soil microbial diversity. The carbon utilization model of soil microbial community was also analyzed by Biolog-eco. All results indicated that uranium tailings leaded to excessive radionuclides and heavy metals, and decreased the diversity of the soil microbial community. Our study will provide a valuable basis for soil quality evaluation around uranium tailing repositories and lay a foundation for the management and recovery of uranium tailings.

Investigation of uranium binding forms in selected German mineral waters.

PubMed

Osman, Alfatih A A; Geipel, Gerhard; Bernhard, Gert; Worch, Eckhard

2013-12-01

Cryogenic time-resolved laser-induced fluorescence spectroscopy was successfully used to identify uranium binding forms in selected German mineral waters of extremely low uranium concentrations (<2.0 μg/L). The measurements were performed at a low temperature of 153 K. The spectroscopic data showed a prevalence of aquatic species Ca2UO2(CO3)3 in all investigated waters, while other uranyl-carbonate complexes, viz, UO2CO3(aq) and UO2(CO3)2 (2-), only existed as minor species. The pH value, alkalinity (CO3 (2-)), and the main water inorganic constituents, specifically the Ca(2+) concentration, showed a clear influence on uranium speciation. Speciation modeling was performed using the most recent thermodynamic data for aqueous complexes of uranium. The modeling results for the main uranium binding form in the investigated waters indicated a good agreement with the spectroscopy measurements.

Patterns and Features of Global Uranium Resources and Production

NASA Astrophysics Data System (ADS)

Wang, Feifei; Song, Zisheng; Cheng, Xianghu; Huanhuan, MA

2017-11-01

With the entry into force of the Paris Agreement, the development of clean and low-carbon energy has become the consensus of the world. Nuclear power is one energy that can be vigorously developed today and in the future. Its sustainable development depends on a sufficient supply of uranium resources. It is of great practical significance to understand the distribution pattern of uranium resources and production. Based on the latest international authoritative reports and data, this paper analysed the distribution of uranium resources, the distribution of resources and production in the world, and the developing tendency in future years. The results show that the distribution of uranium resources is uneven in the world, and the discrepancies between different type deposits is very large. Among them, sandstone-type uranium deposits will become the main type owing to their advantages of wide distribution, minor environmental damage, mature mining technology and high economic benefit.

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.

Molecular Simulations of the Diffusion of Uranyl Carbonate Species in Nanosized Mineral Fractures

NASA Astrophysics Data System (ADS)

Kerisit, S.; Liu, C.

2010-12-01

Uranium is a major groundwater contaminant at uranium processing and mining sites as a result of intentional and accidental discharges of uranium-containing waste products into subsurface environments. Recent characterization has shown that uranium preferentially associates with intragrain and intra-aggregate domains in some of the uranium-contaminated sediments collected from the US Department of Energy Hanford Site [1, 2]. In these sediments, uranium existed as precipitated and/or adsorbed phases in grain micropores with nano- to microscale sizes. Desorption and diffusion characterization studies and continuum-scale modeling indicated that ion diffusion in the microfractures is a major mechanism that led to preferential uranium concentration in the microfracture regions and will control the future mobility of uranium in the subsurface sediments [1, 3-4]. However, the diffusion properties of uranyl species in the intragrain regions, especially at the solid-liquid interface, are still poorly understood. Therefore, a general aim of this work is to provide atomic-level insights into the contribution of microscopic surface effects to the slow diffusion process of uranyl species in porous media with nano- to microsized fractures. In this presentation, we will first present molecular dynamics (MD) simulations of feldspar-water interfaces to investigate their interfacial structure and dynamics and establish a theoretical framework for subsequent simulations of water and ion diffusion at these interfaces [5]. We will then report on MD simulations carried out to probe the effects of confinement and of the presence of the mineral surface on the diffusion of water and electrolyte ions in nanosized feldspar fractures [6]. Several properties of the mineral-water interface were varied, such as the fracture width, the ionic strength of the contacting solution, and the surface charge. Our calculations reveal a 2.0-2.5 nm interfacial region within which the diffusion properties of water and that of the electrolyte ions differ significantly from those in bulk aqueous solutions. We will then present MD simulations of the diffusion of a series of alkaline-earth uranyl carbonate species in aqueous solutions [7]. The MD simulations show that the alkaline-earth uranyl carbonate complexes have distinct water exchange dynamics, which could lead to different reactivities. Finally, we will present recent results on the diffusion and adsorption of uranyl carbonate species in intragrain micropores, modeled with the feldspar-water interfaces mentioned in the above, to help interpret the diffusion behavior of uranium in contaminated sediments. [1] Liu C. et al. Geochim. Cosmochim. Acta 68 4519 (2004) [2] McKinley J. P. et al. Geochim. Cosmochim. Acta 70 1873 (2006) [3] Liu C. et al. Water Resour. Res. 42 W12420 (2006) [4] Ilton E. S. et al. Environ. Sci. Technol. 42 1565 (2009) [5] Kerisit S. et al. Geochim. Cosmochim. Acta 72 1481 (2008) [6] Kerisit S. and Liu C. Environ. Sci. Technol. 43 777 (2009) [7] Kerisit S. and Liu C. Geochim. Cosmochim. Acta 74 4937 (2010)

Hydrogeochemical and stream sediment reconnaissance basic data for Waco NTMS quadrangle, Texas

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

Not Available

1981-07-31

Results of a reconnaissance geochemical survey of the Waco Quadrangle are reported. Field and laboratory data are presented for 218 groundwater and 614 stream sediment samples. Statistical and areal distribution of uranium and possible uranium-related variables are displayed. A generalized geologic map of the survey area is provided, and pertinent geologic factors which may be of significance in evaluating the potential for uranium mineralization are briefly discussed. Groundwater data indicate that uranium concentrations above the 85th percentile occur primarily in the Upper cretaceous units (Navarro, Taylor, and Woodbine Groups) and Lower Cretaceous carbonate units (Fredricksburg and Wilcox Groups). Saline watermore » trends are also prominent in these units. Stream sediment data indicate high uranium concentrations occur in the western portion of the quadrangle. Most of the samples with high uranium values are collected from the Upper and Lower Cretaceous and Tertiary units. Associated with the high uranium values are high concentrations of aluminum, chromium, iron, scandium, yttrium, zinc, and zirconium.« less

METHOD OF FORMING A FUEL ELEMENT FOR A NUCLEAR REACTOR

DOEpatents

Layer, E.H. Jr.; Peet, C.S.

1962-01-23

A method is given for preparing a fuel element for a nuclear reactor. The method includes the steps of sandblasting a body of uranium dioxide to roughen the surface thereof, depositing a thin layer of carbon thereon by thermal decomposition of methane, and cladding the uranium dioxide body with zirconium by gas pressure bonding. (AEC)

The effect of Si and Al concentrations on the removal of U(VI) in the alkaline conditions created by NH3 gas

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

Katsenovich, Yelena P.; Cardona, Claudia; Lapierre, Robert

2016-10-01

Remediation of uranium in the deep unsaturated zone is a challenging task, especially in the presence of oxygenated, high-carbonate alkalinity soil and pore water composition typical for arid and semi-arid environments of the western regions of the U.S. This study evaluates the effect of various pore water constituencies on changes of uranium concentrations in alkaline conditions, created in the presence of reactive gases such as NH3 to effectively mitigate uranium contamination in the vadose zone sediments. This contaminant is a potential source for groundwater pollution through slow infiltration of soluble and highly mobile uranium species towards the water table. Themore » objective of this research was to evaluate uranium sequestration efficiencies in the alkaline synthetic pore water solutions prepared in a broad range of Si, Al, and bicarbonate concentrations typically present in field systems of the western U.S. regions and identify solid uranium-bearing phases that result from ammonia gas treatment. In previous studies (Szecsody et al. 2012; Zhong et al. 2015), although uranium mobility was greatly decreased, solid phases could not be identified at the low uranium concentrations in field-contaminated sediments. The chemical composition of the synthetic pore water used in the experiments varied for silica (5–250 mM), Al3+ (2.8 or 5 mM), HCO3- (0–100 mM) and U(VI) (0.0021–0.0084 mM) in the solution mixture. Experiment results suggested that solutions with Si concentrations higher than 50 mM exhibited greater removal efficiencies of U(VI). Solutions with higher concentrations of bicarbonate also exhibited greater removal efficiencies for Si, Al, and U(VI). Overall, the silica polymerization reaction leading to the formation of Si gel correlated with the removal of U(VI), Si, and Al from the solution. If no Si polymerization was observed, there was no U removal from the supernatant solution. Speciation modeling indicated that the dominant uranium species in the presence of bicarbonate were anionic uranyl carbonate complexes (UO2(CO3)2-2 and UO2(CO3)3-4) and in the absence of bicarbonate in the solution, U(VI) major species appeared as uranyl-hydroxide (UO2(OH)3- and UO2(OH)4-2) species. The model also predicted the formation of uranium solid phases. Uranyl carbonates as rutherfordine [UO2CO3], cejkaite [Na4(UO2)(CO3)3] and hydrated uranyl silicate phases as Na-boltwoodite [Na(UO2)(SiO4)·1.5H2O] were anticipated for most of the synthetic pore water compositions amended from medium (2.9 mM) to high (100 mM) bicarbonate concentrations.« less

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.

SULFIDE METHOD PLUTONIUM SEPARATION

DOEpatents

Duffield, R.B.

1958-08-12

A process is described for the recovery of plutonium from neutron irradiated uranium solutions. Such a solution is first treated with a soluble sullide, causing precipitation of the plutoniunn and uraniunn values present, along with those impurities which form insoluble sulfides. The precipitate is then treated with a solution of carbonate ions, which will dissolve the uranium and plutonium present while the fission product sulfides remain unaffected. After separation from the residue, this solution may then be treated by any of the usual methods, such as formation of a lanthanum fluoride precipitate, to effect separation of plutoniunn from uranium.

Rates and mechanisms of uranyl oxyhydroxide mineral dissolution

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

Reinoso-Maset, Estela; Steefel, Carl I.; Um, Wooyong

Uranyl oxyhydroxide minerals are important weathering products in uranium-contaminated surface and subsurface environments that regulate dissolved uranium concentrations. However, dissolution rates for this class of minerals and associated dissolution mechanisms have not been previously reported for circumneutral pH conditions, particularly for the case of flow through porous media. In this paper, the dissolution rates of K- and Na-compreignacite (K 2(UO 2) 6O 4(OH) 6·8H 2O and Na 2(UO 2) 6O 4(OH) 6·8H 2O respectively) were measured using flow-through columns reacted with two simulated background porewater (BPW) solutions of low and high dissolved total carbonate content (ca. 0.2 and 2.8 mmolmore » L -1). Column materials were characterized before and after reaction with electron microscopy, bulk chemistry, and EXAFS to identify structural and chemical changes during dissolution and to obtain insight into molecular-scale processes. The reactive transport code CrunchFlow was used to calculate overall dissolution rates while accounting for fluid transport and changes in mineral volume and reactive surface area and results were compared to steady-state dissolution rate calculations. In low carbonate BPW systems, interlayer K and Na were initially leached from both minerals, and in Na-compreignacite, K and minor divalent cations from the input solution were incorporated into the mineral structure. Results of characterization analyses suggested that after reaction both K- and Na-compreignacite resembled a disordered K-compreignacite with altered surfaces. A 10-fold increase in dissolved carbonate concentration and corresponding increase in pH (from 6.65 to 8.40) resulted in a net removal of 58-87% of total uranium mass from the columns, compared to <1% net loss in low carbonate BPW systems. Steady-state release of dissolved uranium was not observed with high carbonate solutions and post-reaction characterizations indicated a lack of development of leached or altered surfaces. Dissolution rates (normalized to specific surface area) were about 2.5-3 orders-of-magnitude faster in high versus low carbonate BPW systems, with Na-compreignacite dissolving more rapidly than K-compreignacite under both BPW conditions, possibly due to greater ion exchange (1.57·10 -10 vs. 1.28·10 -13 mol m -2 s -1 [log R = -9.81 and -12.89] and 5.79·10 -10 vs. 3.71·10 -13 mol m -2 s -1 [log R = -9.24 and -12.43] for K- and Na-compreignacite respectively). Experimental and spectroscopic results suggest that the dissolution rate is controlled by bond breaking of a uranyl group and detachment from polyhedral layers of the mineral structure. With higher dissolved carbonate concentrations, this rate-determining step is accelerated by the formation of Ca-uranyl carbonate complexes (dominant species under these conditions), which resulted in an increase of the dissolution rates. Optimization of both dissolution rate and mineral volume fraction in the reactive transport model to account for uranium mass removal during dissolution more accurately reproduced effluent data in high carbonate systems, and resulted in faster overall rates compared with a steady-state dissolution assumption. Finally, this study highlights the importance of coupling reaction and transport processes during the quantification of mineral dissolution rates to accurately predict the fate of contaminants such as uranium in porous geomedia.« less

Rates and mechanisms of uranyl oxyhydroxide mineral dissolution

DOE PAGES

Reinoso-Maset, Estela; Steefel, Carl I.; Um, Wooyong; ...

2017-06-01

Uranyl oxyhydroxide minerals are important weathering products in uranium-contaminated surface and subsurface environments that regulate dissolved uranium concentrations. However, dissolution rates for this class of minerals and associated dissolution mechanisms have not been previously reported for circumneutral pH conditions, particularly for the case of flow through porous media. In this paper, the dissolution rates of K- and Na-compreignacite (K 2(UO 2) 6O 4(OH) 6·8H 2O and Na 2(UO 2) 6O 4(OH) 6·8H 2O respectively) were measured using flow-through columns reacted with two simulated background porewater (BPW) solutions of low and high dissolved total carbonate content (ca. 0.2 and 2.8 mmolmore » L -1). Column materials were characterized before and after reaction with electron microscopy, bulk chemistry, and EXAFS to identify structural and chemical changes during dissolution and to obtain insight into molecular-scale processes. The reactive transport code CrunchFlow was used to calculate overall dissolution rates while accounting for fluid transport and changes in mineral volume and reactive surface area and results were compared to steady-state dissolution rate calculations. In low carbonate BPW systems, interlayer K and Na were initially leached from both minerals, and in Na-compreignacite, K and minor divalent cations from the input solution were incorporated into the mineral structure. Results of characterization analyses suggested that after reaction both K- and Na-compreignacite resembled a disordered K-compreignacite with altered surfaces. A 10-fold increase in dissolved carbonate concentration and corresponding increase in pH (from 6.65 to 8.40) resulted in a net removal of 58-87% of total uranium mass from the columns, compared to <1% net loss in low carbonate BPW systems. Steady-state release of dissolved uranium was not observed with high carbonate solutions and post-reaction characterizations indicated a lack of development of leached or altered surfaces. Dissolution rates (normalized to specific surface area) were about 2.5-3 orders-of-magnitude faster in high versus low carbonate BPW systems, with Na-compreignacite dissolving more rapidly than K-compreignacite under both BPW conditions, possibly due to greater ion exchange (1.57·10 -10 vs. 1.28·10 -13 mol m -2 s -1 [log R = -9.81 and -12.89] and 5.79·10 -10 vs. 3.71·10 -13 mol m -2 s -1 [log R = -9.24 and -12.43] for K- and Na-compreignacite respectively). Experimental and spectroscopic results suggest that the dissolution rate is controlled by bond breaking of a uranyl group and detachment from polyhedral layers of the mineral structure. With higher dissolved carbonate concentrations, this rate-determining step is accelerated by the formation of Ca-uranyl carbonate complexes (dominant species under these conditions), which resulted in an increase of the dissolution rates. Optimization of both dissolution rate and mineral volume fraction in the reactive transport model to account for uranium mass removal during dissolution more accurately reproduced effluent data in high carbonate systems, and resulted in faster overall rates compared with a steady-state dissolution assumption. Finally, this study highlights the importance of coupling reaction and transport processes during the quantification of mineral dissolution rates to accurately predict the fate of contaminants such as uranium in porous geomedia.« less

RECOVERY OF THORIUM AND URANIUM VALUES FROM AQUEOUS SOLUTIONS

DOEpatents

Calkins, G.D.

1958-02-18

This patent deals with the separation and recovery of uranium from monazite sand. After initial treatment of the sand with sodium hydroxide, a precipitate is obtuined which contains the uranium, thorium, rare earths and some phosphorus. This precipitate is then dissolved in nitric acid. The bulk of the rare earths are removed from thls soiution by adding aa excess of alkali carbonate, causing precipitation of the rare earths together with part of the thorium present. The solution still contains a considerable amount of thorium, some rare earths, and practically all of the uranium originally present. Thorium and rare earth values are readily precipitated from such solution, and the uranium values thus isolated, by the addition of an excess hydrogen peroxide. The pH value of the solution is preferably adjusted to at least 9 prior to the addition of the peroxide.

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

Reactivity of formic acid (HCOOD and DCOOH) at uranium and UO 2.0 surfaces

NASA Astrophysics Data System (ADS)

Manner, William L.; Lloyd, Jane A.; Paffett, Mark T.

1999-10-01

Interactions of DCOOH and HCOOD with uranium and UO 2.0 surfaces have been examined using surface-specific techniques of thermal desorption mass spectroscopy (TDMS), X-ray photoelectron spectroscopy (XPS), and static secondary ion mass spectroscopy (SSIMS). On the clean uranium surface, formate is the predominant product following formic acid adsorption at 100 K. A wide range of products is observed after annealing to 200 K, including formate, hydroxyl, O ads, and H ads (D ads) groups. Adsorbed formate decomposes by 300 K increasing the concentration of the remaining surface products. Surface-adsorbed carbon following TDMS measurements remains as the carbide, as indicated from XPS and SSIMS measurements. The only gaseous species created in high yields from the clean surface upon annealing are H 2, HD, and D 2. On the oxide surface (UO 2.0), adsorbed formate groups are more stable toward dissociation in comparison with the clean uranium surface. Between 100 and 300 K the predominant species on the UO 2.0 surface are surface formate and hydroxyl groups. Hydroxyl groups react between 300 and 350 K to release water from the surface. Adsorbed formate groups decompose between 400 and 500 K to release CO and H 2CO (D 2CO) groups from the oxide surface. Carbon was not detected on the oxide surface by XPS or SSIMS after annealing to 500 K, indicating that all carbon-containing species either desorb in the form of CO-containing products or migrate into the surface.

Method for oxygen reduction in a uranium-recovery process. [US DOE patent application

DOEpatents

Hurst, F.J.; Brown, G.M.; Posey, F.A.

1981-11-04

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 iron and accumulation of complex iron phosphates or cruds.

New insight into the ternary complexes of uranyl carbonate in seawater.

PubMed

Beccia, M R; Matara-Aho, M; Reeves, B; Roques, J; Solari, P L; Monfort, M; Moulin, C; Den Auwer, C

2017-11-01

Uranium is naturally present in seawater at trace levels and may in some cases be present at higher concentrations, due to anthropogenic nuclear activities. Understanding uranium speciation in seawater is thus essential for predicting and controlling its behavior in this specific environmental compartment and consequently, its possible impact on living organisms. The carbonato calcic complex Ca 2 UO 2 (CO 3 ) 3 was previously identified as the main uranium species in natural seawater, together with CaUO 2 (CO 3 ) 3 2- . In this work, we further investigate the role of the alkaline earth cation in the structure of the ternary uranyl-carbonate complexes. For this purpose, artificial seawater, free of Mg 2+ and Ca 2+ , using Sr 2+ as a spectroscopic probe was prepared. Combining TRLIF and EXAFS spectroscopy, together with DFT and theoretical thermodynamic calculations, evidence for the presence of Sr alkaline earth counter ion in the complex structure can be asserted. Furthermore, data suggest that when Ca 2+ is replaced by Sr 2+ , SrUO 2 (CO 3 ) 3 2- is the main complex in solution and it occurs with the presence of at least one monodentate carbonate in the uranyl coordination sphere. Copyright © 2017 Elsevier Ltd. All rights reserved.

Uranium(III)-carbon multiple bonding supported by arene δ-bonding in mixed-valence hexauranium nanometre-scale rings.

PubMed

Wooles, Ashley J; Mills, David P; Tuna, Floriana; McInnes, Eric J L; Law, Gareth T W; Fuller, Adam J; Kremer, Felipe; Ridgway, Mark; Lewis, William; Gagliardi, Laura; Vlaisavljevich, Bess; Liddle, Stephen T

2018-05-29

Despite the fact that non-aqueous uranium chemistry is over 60 years old, most polarised-covalent uranium-element multiple bonds involve formal uranium oxidation states IV, V, and VI. The paucity of uranium(III) congeners is because, in common with metal-ligand multiple bonding generally, such linkages involve strongly donating, charge-loaded ligands that bind best to electron-poor metals and inherently promote disproportionation of uranium(III). Here, we report the synthesis of hexauranium-methanediide nanometre-scale rings. Combined experimental and computational studies suggest overall the presence of formal uranium(III) and (IV) ions, though electron delocalisation in this Kramers system cannot be definitively ruled out, and the resulting polarised-covalent U = C bonds are supported by iodide and δ-bonded arene bridges. The arenes provide reservoirs that accommodate charge, thus avoiding inter-electronic repulsion that would destabilise these low oxidation state metal-ligand multiple bonds. Using arenes as electronic buffers could constitute a general synthetic strategy by which to stabilise otherwise inherently unstable metal-ligand linkages.

Identification of Uranyl Minerals Using Oxygen K-Edge X Ray Absorption Spectroscopy

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

Ward, Jesse D.; Bowden, Mark E.; Resch, Charles T.

2016-03-01

Uranium analysis is consistently needed throughout the fuel cycle, from mining to fuel fabrication to environmental monitoring. Although most of the world’s uranium is immobilized as pitchblende or uraninite, there exists a plethora of secondary uranium minerals, nearly all of which contain the uranyl cation. Analysis of uranyl compounds can provide clues as to a sample’s facility of origin and chemical history. X-ray absorption spectroscopy is one technique that could enhance our ability to identify uranium minerals. Although there is limited chemical information to be gained from the uranium X-ray absorption edges, recent studies have successfully used ligand NEXAFS tomore » study the physical chemistry of various uranium compounds. This study extends the use of ligand NEXAFS to analyze a suite of uranium minerals. We find that major classes of uranyl compounds (carbonate, oxyhydroxide, silicate, and phosphate) exhibit characteristic lineshapes in the oxygen K-edge absorption spectra. As a result, this work establishes a library of reference spectra that can be used to classify unknown uranyl minerals.« less

Modeling of point defects and rare gas incorporation in uranium mono-carbide

NASA Astrophysics Data System (ADS)

Chartier, A.; Van Brutzel, L.

2007-02-01

An embedded atom method (EAM) potential has been established for uranium mono-carbide. This EAM potential was fitted on structural properties of metallic uranium and uranium mono-carbide. The formation energies of point defects, as well as activation energies for self migration, have been evaluated in order to cross-check the suitability of the potential. Assuming that the carbon vacancies are the main defects in uranium mono-carbide compounds, the migration paths and energies are consistent with experimental data selected by Catlow[C.R.A. Catlow, J. Nucl. Mater. 60 (1976) 151]. The insertion and migration energies for He, Kr and Xe have also been evaluated with available inter-atomic potentials [H.H. Andersen, P. Sigmund, Nucl. Instr. and Meth. B 38 (1965) 238]. Results show that the most stable defect configuration for rare gases is within uranium vacancies. The migration energy of an interstitial Xe is 0.5 eV, in agreement with the experimental value of 0.5 eV [Hj. Matzke, Science of advanced LMFBR fuels, Solid State Physics, Chemistry and Technology of Carbides, Nitrides and Carbonitrides of Uranium and Plutonium, North-Holland, 1986].

Enhanced uranium immobilization and reduction by Geobacter sulfurreducens biofilms.

PubMed

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

2014-11-01

Biofilms formed by dissimilatory metal reducers are of interest to develop permeable biobarriers for the immobilization of soluble contaminants such as uranium. Here we show that biofilms of the model uranium-reducing bacterium Geobacter sulfurreducens immobilized substantially more U(VI) than planktonic cells and did so for longer periods of time, reductively precipitating it to a mononuclear U(IV) phase involving carbon ligands. The biofilms also tolerated high and otherwise toxic concentrations (up to 5 mM) of uranium, consistent with a respiratory strategy that also protected the cells from uranium toxicity. The enhanced ability of the biofilms to immobilize uranium correlated only partially with the biofilm biomass and thickness and depended greatly on the area of the biofilm exposed to the soluble contaminant. In contrast, uranium reduction depended on the expression of Geobacter conductive pili and, to a lesser extent, on the presence of the c cytochrome OmcZ in the biofilm matrix. The results support a model in which the electroactive biofilm matrix immobilizes and reduces the uranium in the top stratum. This mechanism prevents the permeation and mineralization of uranium in the cell envelope, thereby preserving essential cellular functions and enhancing the catalytic capacity of Geobacter cells to reduce uranium. Hence, the biofilms provide cells with a physically and chemically protected environment for the sustained immobilization and reduction of uranium that is of interest for the development of improved strategies for the in situ bioremediation of environments impacted by uranium contamination. Copyright © 2014, American Society for Microbiology. All Rights Reserved.

Enhanced Uranium Immobilization and Reduction by Geobacter sulfurreducens Biofilms

PubMed Central

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

2014-01-01

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

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.

Uranium association with iron-bearing phases in mill tailings from Gunnar, Canada.

PubMed

Othmane, Guillaume; Allard, Thierry; Morin, Guillaume; Sélo, Madeleine; Brest, Jessica; Llorens, Isabelle; Chen, Ning; Bargar, John R; Fayek, Mostafa; Calas, Georges

2013-11-19

The speciation of uranium was studied in the mill tailings of the Gunnar uranium mine (Saskatchewan, Canada), which operated in the 1950s and 1960s. The nature, quantification, and spatial distribution of uranium-bearing phases were investigated by chemical and mineralogical analyses, fission track mapping, electron microscopy, and X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopies at the U LIII-edge and Fe K-edge. In addition to uranium-containing phases from the ore, uranium is mostly associated with iron-bearing minerals in all tailing sites. XANES and EXAFS data and transmission electron microscopy analyses of the samples with the highest uranium concentrations (∼400-700 mg kg(-1) of U) demonstrate that uranium primarily occurs as monomeric uranyl ions (UO2(2+)), forming inner-sphere surface complexes bound to ferrihydrite (50-70% of the total U) and to a lesser extent to chlorite (30-40% of the total U). Thus, the stability and mobility of uranium at the Gunnar site are mainly influenced by sorption/desorption processes. In this context, acidic pH or alkaline pH with the presence of UO2(2+)- and/or Fe(3+)-complexing agents (e.g., carbonate) could potentially solubilize U in the tailings pore waters.

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

Progress report on the Happy Jack mine, Which Canyon area, San Juan county, Utah

USGS Publications Warehouse

Trites, Albert F.; Chew, Randall T.

1954-01-01

The Happy Jack mine is in the White Canyon area, San Juan county, Utah. Production is from high-grade uranium deposits in the Shinarump conglomerate of the Triassic age. In this area the Shinarump beds range from about 16 to 40 feet in thickness and the lower part of these beds fills an east-trending channel this is note than 750 feet wide and 10 feet deep. The Shinarump conglomerate consists of beds of coarse- to fine-grained quartzose sandstone, conglomerate, siltstone, and claystone. Carbonized wood is abundant in these beds, and in the field it was classified as mineral charcoal and coal. Intra-Shinarump channels, cross-stratification, current lineation, and slumping and compaction structures have been recognized in the mine. Steeply dipping fractures have dominant trends in four directions -- N 65°W, N 60°E, N 85°E, and due north. Uranium occurs as bedded deposits, as replacement bodies in accumulations of "trash", and as replacements of larger fragments of wood. An "ore shoot" is formed where the three types of uranium deposits occur together; these ore shoots appear to be elongate masses with sharp boundaries. Uranium minerals include uraninite, sooty pitchblende(?), and the sulfate--betazippeite, johannite, and uranopilite. Associated with the uraninite are the sulfide minerals covellite, bornite, chalcopyritw, and pyrite. Galena and sphalerite have been found in close association with uranium minerals. The gaunge minerals include: limonite and hematite present in most of the sandstone beds throughout the deposit, jarosite that impregnates much of the sandstone in the outer parts of the mine workings, gypsum that fills many of the fractures, and barite that impregnates the sandstone in at least one part of the mine. Secondary copper minerals, mainly copper sulfates, occur throughout the mine, but most abundant near the adits in the outermost 30 feet of the workings. The minerals comprising the bulk of the country rock include quartz, feldspar, and clay minerals. The amount of uranium minerals deposited in a sandstone bed is believed to have been determined by the position of the bed in the channel, the permeability of the sandstone in the bed, and the amount of carbonized wood and plant remains within the bed. The beds considered most favorable for uranium deposition contain an abundance of claystone and siltstone both as matrix filling and as fragments and pebbles. Suggested exploration guides from uranium ore bodies include the following: (1) interbedded siltstone lenses, (2) claystone and siltstone cement and pabbles, (3) concentrations of "trash", (4) covelllite and bornite, (5) chalcopyrite, and (6) carbonized wood.

Comparison of abundances of chemical elements in mineralized and unmineralized sandstone of the Brushy Basin Member of the Morrison Formation, Smith Lake District, Grants uranium region, New Mexico

USGS Publications Warehouse

Pierson, C.T.; Spirakis, C.S.; Robertson, J.F.

1983-01-01

Statistical treatment of analytical data from the Mariano Lake and Ruby uranium deposits in the Smith Lake district, New Mexico, indicates that organic carbon, arsenic, barium, calcium, cobalt, copper, gallium, iron, lead, manganese, molybdenum, nickel, selenium, strontium, sulfur, vanadium, yttrium, and zirconium are concentrated along with uranium in primary ore. Comparison of the Smith Lake data with information from other primary deposits in the Grants uranium region and elsewhere in the Morrison Formation of the Colorado Plateau suggests that these elements, with the possible exceptions of zirconium and gallium and with the probable addition of aluminum and magnesium, are typically associated with primary, tabular uranium deposits. Chemical differences between the Ruby and Mariano Lake deposits are consistent with the interpretation that the Ruby deposit has been more affected by post-mineralization oxidizing solutions than has the Mariano Lake deposit.

Materials for the Recovery of Uranium from Seawater

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

Abney, Carter W.; Mayes, Richard T.; Saito, Tomonori

More than 1000× uranium exists in the oceans than exists in terrestrial ores. With nuclear power generation expected to increase over the coming decades, access to this unconventional reserve is a matter of energy security. With origins in the mid-1950’s, materials have been developed for the selective recovery of seawater uranium for more than six decades, with a renewed interest in particular since 2010. This review comprehensively surveys materials developed from 2000 – 2016 for recovery of seawater uranium, in particular including recent developments in inorganic materials, polymer adsorbents and related research pertaining to amidoxime, and nanostructured materials such asmore » metal-organic frameworks, porous-organic polymers, and mesoporous carbons. In conclusion, challenges of performing reliable and reproducible uranium adsorption studies are also discussed, as well as the standardization of parameters necessary to ensure valid comparisons between different adsorbents.« less

Materials for the Recovery of Uranium from Seawater

DOE PAGES

Abney, Carter W.; Mayes, Richard T.; Saito, Tomonori; ...

2017-11-22

More than 1000× uranium exists in the oceans than exists in terrestrial ores. With nuclear power generation expected to increase over the coming decades, access to this unconventional reserve is a matter of energy security. With origins in the mid-1950’s, materials have been developed for the selective recovery of seawater uranium for more than six decades, with a renewed interest in particular since 2010. This review comprehensively surveys materials developed from 2000 – 2016 for recovery of seawater uranium, in particular including recent developments in inorganic materials, polymer adsorbents and related research pertaining to amidoxime, and nanostructured materials such asmore » metal-organic frameworks, porous-organic polymers, and mesoporous carbons. In conclusion, challenges of performing reliable and reproducible uranium adsorption studies are also discussed, as well as the standardization of parameters necessary to ensure valid comparisons between different adsorbents.« less

Selective Extraction of Uranium from Liquid or Supercritical Carbon Dioxide

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

Farawila, Anne F.; O'Hara, Matthew J.; Wai, Chien M.

2012-07-31

Current liquid-liquid extraction processes used in recycling irradiated nuclear fuel rely on (1) strong nitric acid to dissolve uranium oxide fuel, and (2) the use of aliphatic hydrocarbons as a diluent in formulating the solvent used to extract uranium. The nitric acid dissolution process is not selective. It dissolves virtually the entire fuel meat which complicates the uranium extraction process. In addition, a solvent washing process is used to remove TBP degradation products, which adds complexity to the recycling plant and increases the overall plant footprint and cost. A liquid or supercritical carbon dioxide (l/sc -CO2) system was designed tomore » mitigate these problems. Indeed, TBP nitric acid complexes are highly soluble in l/sc -CO2 and are capable of extracting uranium directly from UO2, UO3 and U3O8 powders. This eliminates the need for total acid dissolution of the irradiated fuel. Furthermore, since CO2 is easily recycled by evaporation at room temperature and pressure, it eliminates the complex solvent washing process. In this report, we demonstrate: (1) A reprocessing scheme starting with the selective extraction of uranium from solid uranium oxides into a TBP-HNO3 loaded Sc-CO2 phase, (2) Back extraction of uranium into an aqueous phase, and (3) Conversion of recovered purified uranium into uranium oxide. The purified uranium product from step 3 can be disposed of as low level waste, or mixed with enriched uranium for use in a reactor for another fuel cycle. After an introduction on the concept and properties of supercritical fluids, we first report the characterization of the different oxides used for this project. Our extraction system and our online monitoring capability using UV-Vis absorbance spectroscopy directly in sc-CO2 is then presented. Next, the uranium extraction efficiencies and kinetics is demonstrated for different oxides and under different physical and chemical conditions: l/sc -CO2 pressure and temperature, TBP/HNO3 complex used, reductant or complexant used for selectivity, and ionic liquids used as supportive media. To complete the extraction and recovery cycle, we then demonstrate uranium back extraction from the TBP loaded sc-CO2 phase into an aqueous phase and the characterization of the uranium complex formed at the end of this process. Another aspect of this project was to limit proliferation risks by either co-extracting uranium and plutonium, or by leaving plutonium behind by selectively extracting uranium. We report that the former is easily achieved, since plutonium is in the tetravalent or hexavalent oxidation state in the oxidizing environment created by the TBP-nitric acid complex, and is therefore co-extracted. The latter is more challenging, as a reductant or complexant to plutonium has to be used to selectively extract uranium. After undertaking experiments on different reducing or complexing systems (e.g., AcetoHydroxamic Acid (AHA), Fe(II), ascorbic acid), oxalic acid was chosen as it can complex tetravalent actinides (Pu, Np, Th) in the aqueous phase while allowing the extraction of hexavalent uranium in the sc-CO2 phase. Finally, we show results using an alternative media to commonly used aqueous phases: ionic liquids. We show the dissolution of uranium in ionic liquids and its extraction using sc-CO2 with and without the presence of AHA. The possible separation of trivalent actinides from uranium is also demonstrated in ionic liquids using neodymium as a surrogate and diglycolamides as the extractant.« less

Interlaboratory comparison of chemical analysis of uranium mononitride

NASA Technical Reports Server (NTRS)

Merkle, E. J.; Davis, W. F.; Halloran, J. T.; Graab, J. W.

1974-01-01

Analytical methods were established in which the critical variables were controlled, with the result that acceptable interlaboratory agreement was demonstrated for the chemical analysis of uranium mononitride. This was accomplished by using equipment readily available to laboratories performing metallurgical analyses. Agreement among three laboratories was shown to be very good for uranium and nitrogen. Interlaboratory precision of + or - 0.04 percent was achieved for both of these elements. Oxygen was determined to + or - 15 parts per million (ppm) at the 170-ppm level. The carbon determination gave an interlaboratory precision of + or - 46 ppm at the 320-ppm level.

Method for cleaning bomb-reduced uranium derbies

DOEpatents

Banker, John G.; Wigginton, Hubert L.; Beck, David E.; Holcombe, Cressie E.

1981-01-01

The concentration of carbon in uranium metal ingots induction cast from derbies prepared by the bomb-reduction of uranium tetrafluoride in the presence of magnesium is effectively reduced to less than 100 ppm by removing residual magnesium fluoride from the surface of the derbies prior to casting. This magnesium fluoride is removed from the derbies by immersing them in an alkali metal salt bath which reacts with and decomposes the magnesium fluoride. A water quenching operation followed by a warm nitric acid bath and a water rinse removes the residual salt and reaction products from the derbies.

Method for cleaning bomb-reduced uranium derbies

DOEpatents

Banker, J.G.; Wigginton, H.L.; Beck, D.E.; Holcombe, C.E.

The concentration of carbon in uranium metal ingots induction cast from derbies prepared by the bomb-reduction of uranium tetrafluoride in the presence of magnesium is effectively reduced to less than 100 ppM by removing residual magnesium fluoride from the surface of the derbies prior to casting. This magnesium fluoride is removed from the derbies by immersing them in an alkali metal salt bath which reacts with and decomposes the magnesium fluoride. A water quenching operation followed by a warm nitric acid bath and a water rinse removes the residual salt and reaction products from the derbies.

Uranium isotopes distinguish two geochemically distinct stages during the later Cambrian SPICE event

PubMed Central

Dahl, Tais W.; Boyle, Richard A.; Canfield, Donald E.; Connelly, James N.; Gill, Benjamin C.; Lenton, Timothy M.; Bizzarro, Martin

2015-01-01

Anoxic marine zones were common in early Paleozoic oceans (542–400 Ma), and present a potential link to atmospheric pO2 via feedbacks linking global marine phosphorous recycling, primary production and organic carbon burial. Uranium (U) isotopes in carbonate rocks track the extent of ocean anoxia, whereas carbon (C) and sulfur (S) isotopes track the burial of organic carbon and pyrite sulfur (primary long-term sources of atmospheric oxygen). In combination, these proxies therefore reveal the comparative dynamics of ocean anoxia and oxygen liberation to the atmosphere over million-year time scales. Here we report high-precision uranium isotopic data in marine carbonates deposited during the Late Cambrian ‘SPICE’ event, at ca. 499 Ma, documenting a well-defined −0.18‰ negative δ238U excursion that occurs at the onset of the SPICE event’s positive δ13C and δ34S excursions, but peaks (and tails off) before them. Dynamic modelling shows that the different response of the U reservoir cannot be attributed solely to differences in residence times or reservoir sizes - suggesting that two chemically distinct ocean states occurred within the SPICE event. The first ocean stage involved a global expansion of euxinic waters, triggering the spike in U burial, and peaking in conjunction with a well-known trilobite extinction event. During the second stage widespread euxinia waned, causing U removal to tail off, but enhanced organic carbon and pyrite burial continued, coinciding with evidence for severe sulfate depletion in the oceans (Gill et al., 2011). We discuss scenarios for how an interval of elevated pyrite and organic carbon burial could have been sustained without widespread euxinia in the water column (both non-sulfidic anoxia and/or a more oxygenated ocean state are possibilities). Either way, the SPICE event encompasses two different stages of elevated organic carbon and pyrite burial maintained by high nutrient fluxes to the ocean, and potentially sustained by internal marine geochemical feedbacks. PMID:25684783

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 .

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 fissile materials from nuclear wastes

DOEpatents

Forsberg, Charles W.

1999-01-01

A process for recovering fissile materials such as uranium, and plutonium, and rare earth elements, from complex waste feed material, and converting the remaining wastes into a waste glass suitable for storage or disposal. The waste feed is mixed with a dissolution glass formed of lead oxide and boron oxide resulting in oxidation, dehalogenation, and dissolution of metal oxides. Carbon is added to remove lead oxide, and a boron oxide fusion melt is produced. The fusion melt is essentially devoid of organic materials and halogens, and is easily and rapidly dissolved in nitric acid. After dissolution, uranium, plutonium and rare earth elements are separated from the acid and recovered by processes such as PUREX or ion exchange. The remaining acid waste stream is vitrified to produce a waste glass suitable for storage or disposal. Potential waste feed materials include plutonium scrap and residue, miscellaneous spent nuclear fuel, and uranium fissile wastes. The initial feed materials may contain mixtures of metals, ceramics, amorphous solids, halides, organic material and other carbon-containing material.

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.

Theoretical Model for Volume Fraction of UC, 235U Enrichment, and Effective Density of Final U 10Mo Alloy

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

Devaraj, Arun; Prabhakaran, Ramprashad; Joshi, Vineet V.

2016-04-12

The purpose of this document is to provide a theoretical framework for (1) estimating uranium carbide (UC) volume fraction in a final alloy of uranium with 10 weight percent molybdenum (U-10Mo) as a function of final alloy carbon concentration, and (2) estimating effective 235U enrichment in the U-10Mo matrix after accounting for loss of 235U in forming UC. This report will also serve as a theoretical baseline for effective density of as-cast low-enriched U-10Mo alloy. Therefore, this report will serve as the baseline for quality control of final alloy carbon content

Spectroscopic Evidence of Uranium Immobilization in Acidic ...

EPA Pesticide Factsheets

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

Process for recovering uranium

DOEpatents

MacWood, G. E.; Wilder, C. D.; Altman, D.

1959-03-24

A process useful in recovering uranium from deposits on stainless steel liner surfaces of calutrons is presented. The deposit is removed from the stainless steel surface by washing with aqueous nitric acid. The solution obtained containing uranium, chromium, nickel, copper, and iron is treated with an excess of ammonium hydroxide to precipitnte the uranium, iron, and chromium and convert the nickel and copper to soluble ammonio complexions. The precipitated material is removed, dried and treated with carbon tetrachloride at an elevated temperature of about 500 to 600 deg C to form a vapor mixture of UCl/ sub 4/, UCl/sub 5/, FeCl/sub 3/, and CrCl/sub 4/. The UCl/sub 4/ is separated from this vapor mixture by selective fractional condensation at a temperature of about 500 to 400 deg C.

PROCESS FOR RECOVERING URANIUM

DOEpatents

MacWood, G.E.; Wilder, C.D.; Altman, D.

1959-03-24

A process is described for recovering uranium from deposits on stainless steel liner surfaces of calutrons. The deposit is removed from the stainless steel surface by washing with aqueous nitric acid. The solution obtained containing uranium, chromium, nickels copper, and iron is treated with excess of ammonium hydroxide to precipitatc the uranium, irons and chromium and convert thc nickel and copper to soluble ammonia complexions. The precipitated material is removed, dried, and treated with carbon tetrachloride at an elevated temperature of about 500 to 600 deg C to form a vapor mixture of UCl/sub 4/, UCl/sub 5/, FeCl/ sub 3/, and CrCl/sub 4/. The UCl/sub 4/ is separated from this vapor mixture by selective fractional condensation at a temprrature of about 300 to400 deg C.

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

Future World of Illicit Nuclear Trade: Mitigating the Threat

DTIC Science & Technology

2013-07-29

uranium with lasers that is similar to MLIS. 3 Most of the equipment, including four carbon monoxide lasers and vacuum chambers, was delivered. But...Centrifuge Facility 43 Figure 10: Centrifuge Output vs. Goods Required 44 3b Digging Deeper: Laser Enrichment of Uranium 47 Box 3...Major Foreign Assistance to Iran’s Pre-2004 Laser Enrichment Program 50 4. Key Information: The Special Challenge of the Spread of Classified 53

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.

Uranium and organic matters: use of pyrolysis-gas chromatography, carbon, hydrogen, and uranium contents to characterize the organic matter from sandstone-type deposits

USGS Publications Warehouse

Leventhal, Joel S.

1979-01-01

Organic matter seems to play an important role in the genesis of uranium deposits in sandstones in the western United States. Organic materials associated with ore from the Texas coastal plain, Tertiary basins of Wyoming, Grants mineral belt of New Mexico, and the Uravan mineral belt of Utah and Colorado vary widely in physical appearance and chemical composition. Partial characterization of organic materials is achieved by chemical analyses to determine atomic hydrogen-to-carbon (H/C) ratios and by gas chromatographic analyses to determine the molecular fragments evolved during stepwise pyrolysis. From the pyrolysis experiments the organic materials can be classified and grouped: (a) lignites from Texas and Wyoming and (b) hydrogen poor materials, from Grants and Uravan mineral belts and Wyoming; (c) naphthalene-containing materials from Grants mineral belt and Wyoming; and (d) complex and aromatic materials from Uravan, Grants and Wyoming. The organic materials analyzed have atomic H/C ratios that range from approximately 0.3 to at least 1.5. The samples with higher H/C ratios yield pyrolysis products that contain as many as 30 carbon atoms per molecule. Samples with low H/C ratios are commonly more uraniferous and yield mostly methane and low-molecular-weight gases during pyrolysis.

Innovative Elution Processes for Recovering Uranium and Transition Metals from Amidoxime-based Adsorbents

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

Wai, Chien M.

Amidoxime-based polymer fibers are considered one of the most promising materials for sequestering uranium from seawater. The high-surface-area polymer fibers containing amidoxime and carboxylate groups synthesized by Oak Ridge National Lab (ORNL-AF1) show very high uranium adsorption capacities known in the literature. Effective elution of uranium and repeated use of the adsorbent are important factors affecting the cost of producing uranium from seawater using this material. Traditional acid leaching of uranium followed by KOH conditioning of the fiber causes chemical changes and physical damage to the ORNL-AF1 adsorbent. Two alkaline solution leaching methods were developed by this project, one usesmore » a highly concentrated (3 M) potassium bicarbonate solution at pH 8.3 and 40 °C; the other uses a mixture of sodium carbonate and hydrogen peroxide at pH 10.4. Both elution methods do not require KOH conditioning prior to reusing the fiber adsorbent. The conditions of eluting uranium from the amidoxime-based adsorbent using these alkaline solutions are confirmed by thermodynamic calculations. The bicarbonate elution method is selective for uranium recovery compared to other elution methods and causes no chemical change to the fiber material based on FTIR spectroscopy« less

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.

Molecular-scale characterization of uranium sorption by bone apatite materials for a permeable reactive barrier demonstration

USGS Publications Warehouse

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

2003-01-01

Uranium binding to bone charcoal and bone meal apatite materials was investigated using U LIII-edge EXAFS spectroscopy and synchrotron source XRD measurements of laboratory batch preparations in the absence and presence of dissolved carbonate. Pelletized bone char apatite recovered from a permeable reactive barrier (PRB) at Fry Canyon, UT, was also studied. EXAFS analyses indicate that U(VI) sorption in the absence of dissolved carbonate occurred by surface complexation of U(VI) for sorbed concentrations ??? 5500 ??g U(VI)/g for all materials with the exception of crushed bone char pellets. Either a split or a disordered equatorial oxygen shell was observed, consistent with complexation of uranyl by the apatite surface. A second shell of atoms at a distance of 2.9 A?? was required to fit the spectra of samples prepared in the presence of dissolved carbonate (4.8 mM total) and is interpreted as formation of ternary carbonate complexes with sorbed U(VI). A U-P distance at 3.5-3.6 A?? was found for most samples under conditions where uranyl phosphate phases did not form, which is consistent with monodentate coordination of uranyl by phosphate groups in the apatite surface. At sorbed concentrations ??? 5500 ??g U(VI)/g in the absence of dissolved carbonate, formation of the uranyl phosphate solid phase, chernikovite, was observed. The presence of dissolved carbonate (4.8 mM total) suppressed the formation of chernikovite, which was not detected even with sorbed U(VI) up to 12 300 ??g U(VI)/g in batch samples of bone meal, bone charcoal, and reagent-grade hydroxyapatite. EXAFS spectra of bone char samples recovered from the Fry Canyon PRB were comparable to laboratory samples in the presence of dissolved carbonate where U(VI) sorption occurred by surface complexation. Our findings demonstrate that uranium uptake by bone apatite will probably occur by surface complexation instead of precipitation of uranyl phosphate phases under the groundwater conditions found at many U-contaminated sites.

The UC2-x - Carbon eutectic: A laser heating study

NASA Astrophysics Data System (ADS)

Manara, D.; Boboridis, K.; Morel, S.; De Bruycker, F.

2015-11-01

The UC2-x - carbon eutectic has been studied by laser heating and fast multi-wavelength pyrometry under inert atmosphere. The study has been carried out on three compositions, two of which close to the phase boundary of the UC2-x - C miscibility gap (with C/U atomic ratios 2 and 2.1), and one, more crucial, with a large excess of carbon (C/U = 2.82). The first two compositions were synthesised by arc-melting. This synthesis method could not be applied to the last composition, which was therefore completed directly by laser irradiation. The U - C - O composition of the samples was checked by using a combustion method in an ELTRA® analyser. The eutectic temperature, established to be 2737 K ± 20 K, was used as a radiance reference together with the cubic - tetragonal (α → β) solid state transition, fixed at 2050 K ± 20 K. The normal spectral emissivity of the carbon-richer compounds increases up to 0.7, whereas the value 0.53 was established for pure hypostoichiometric uranium dicarbide at the limit of the eutectic region. This increase is analysed in the light of the demixing of excess carbon, and used for the determination of the liquidus temperature (3220 K ± 50 K for UC2.82). Due to fast solid state diffusion, also fostered by the cubic - tetragonal transition, no obvious signs of a lamellar eutectic structure could be observed after quenching to room temperature. The eutectic surface C/UC2-x composition could be qualitatively, but consistently, followed during the cooling process with the help of the recorded radiance spectra. Whereas the external liquid surface is almost entirely constituted by uranium dicarbide, it gets rapidly enriched in demixed carbon upon freezing. Demixed carbon seems to quickly migrate towards the inner bulk during further cooling. At the α → β transition, uranium dicarbide covers again the almost entire external surface.

Electron transfer at the cell-uranium interface in Geobacter spp.

PubMed

Reguera, Gemma

2012-12-01

The in situ stimulation of Fe(III) oxide reduction in the subsurface stimulates the growth of Geobacter spp. and the precipitation of U(VI) from groundwater. As with Fe(III) oxide reduction, the reduction of uranium by Geobacter spp. requires the expression of their conductive pili. The pili bind the soluble uranium and catalyse its extracellular reductive precipitation along the pili filaments as a mononuclear U(IV) complexed by carbon-containing ligands. Although most of the uranium is immobilized by the pili, some uranium deposits are also observed in discreet regions of the outer membrane, consistent with the participation of redox-active foci, presumably c-type cytochromes, in the extracellular reduction of uranium. It is unlikely that cytochromes released from the outer membrane could associate with the pili and contribute to the catalysis, because scanning tunnelling microscopy spectroscopy did not reveal any haem-specific electronic features in the pili, but, rather, showed topographic and electronic features intrinsic to the pilus shaft. Pili not only enhance the rate and extent of uranium reduction per cell, but also prevent the uranium from traversing the outer membrane and mineralizing the cell envelope. As a result, pili expression preserves the essential respiratory activities of the cell envelope and the cell's viability. Hence the results support a model in which the conductive pili function as the primary mechanism for the reduction of uranium and cellular protection in Geobacter spp.

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

Morgan, T.L.; George, W.E.; Hensley, W.K.

As part of the Hydrogeochemical and Stream Sediment Reconnaissance (HSSR) of the National Uranium Resource Evaluation (NURE) sponsored by the US Department of Energy (DOE), the Los Alamos Scientific Laboratory (LASL) conducted a detailed hydrogeochemical survey of well waters in a 4250-km/sup 2/ area near Pie Town in west-central New Mexico. A total of 300 well samples was collected and analyzed for uranium and 23 other elements. The results of these analyses and carbonate and bicarbonate ion concentrations are presented in the Appendixes of this report. Uranium concentrations range from below the detection limit of 0.02 parts per billion (ppB)more » to 293.18 ppB and average 8.71 ppB. Samples containing high levels of uranium were collected from the Largo Creek valley west of Quemado, from a small area about 6 km east of Quemado, from a small area surrounding Pie Town, and from scattered locations in the area surrounding Adams Diggings north of Pie Town. Most of the samples containing high uranium concentrations were collected from wells associated with the volcanic sedimentary facies of the Datil formation. This formation is a likely source of mobile uranium that may be precipitating in the underlying Baca formation, a known uranium host unit. Bicarbonate ion concentration, while proportional to uranium concentration in some cases, is not a strong controlling factor in the uranium concentrations in samples from this area.« less

The Study of Microbial Environmental Processes Related to the Natural Attenuation of Uranium at the Rifle Site using Systems-level Biology

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

Methe, Barbara; Lipton, Mary; Mahadevan, Krishna

Microbes exist in communities in the environment where they are fundamental drivers of global carbon, nutrient and metal cycles. In subsurface environments, they possess significant metabolic potential to affect these global cycles including the transformation of radionuclides. This study examined the influence of microbial communities in sediment zones undergoing biogeochemical cycling of carbon, nutrients and metals including natural attenuation of uranium. This study examined the relationship of both the microbiota (taxonomy) and their metabolic capacity (function) in driving carbon, nutrient and metal cycles including uranium reduction at the Department of Energy (DOE) Rifle Integrated Field Research Challenge (RIFRC). Objectives ofmore » this project were: 1) to apply systems-level biology through application of ‘metaomics’ approaches (collective analyses of whole microbial community DNA, RNA and protein) to the study of microbial environmental processes and their relationship to C, N and metals including the influence of microbial communities on uranium contaminant mobility in subsurface settings undergoing natural attenuation, 2) improve methodologies for data generation using metaomics (collectively metagenomics, metatranscriptomics and proteomics) technologies and analysis and interpretation of that data and 3) use the data generated from these studies towards microbial community-scale metabolic modeling. The strategy for examining these subsurface microbial communities was to generate sequence reads from microbial community DNA (metagenomics or whole genome shotgun sequencing (WGS)) and RNA (metatranscriptomcs or RNAseq) and protein information using proteomics. Results were analyzed independently and through computational modeling. Overall, the community model generated information on the microbial community structure that was observed using metaomic approaches at RIFRC sites and thus provides an important framework for continued community modeling development. The model as created is capable of predicting the response of the community structure in changing environments such as anoxic/oxic conditions or limitations by carbon or nutrients. The ability to more accurately model these responses is critical to understanding carbon and energy flows in an ecosystem is critical towards improving our ability to make predictions that can be used to design more efficient remediation and management strategies, and better understand the implications of environmental perturbations on these ecosystems.« less

Can we predict uranium bioavailability based on soil parameters? Part 1: effect of soil parameters on soil solution uranium concentration.

PubMed

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

2007-01-01

Present study aims to quantify the influence of soil parameters on soil solution uranium concentration for (238)U spiked soils. Eighteen soils collected under pasture were selected such that they covered a wide range for those parameters hypothesised as being potentially important in determining U sorption. Maximum soil solution uranium concentrations were observed at alkaline pH, high inorganic carbon content and low cation exchange capacity, organic matter content, clay content, amorphous Fe and phosphate levels. Except for the significant correlation between the solid-liquid distribution coefficients (K(d), L kg(-1)) and the organic matter content (R(2)=0.70) and amorphous Fe content (R(2)=0.63), there was no single soil parameter significantly explaining the soil solution uranium concentration (which varied 100-fold). Above pH=6, log(K(d)) was linearly related with pH [log(K(d))=-1.18 pH+10.8, R(2)=0.65]. Multiple linear regression analysis did result in improved predictions of the soil solution uranium concentration but the model was complex.

Uranium minerals in Oligocene gypsum near Chadron, Dawes County, Nebraska

USGS Publications Warehouse

Dunham, R.J.

1955-01-01

Carnotite, sabugalite [HAI(UO2)4(PO4)4 • 16H2O] and autunite occur in the basal 25 feet of a 270-foot sequence of nonmarine bedded gypsum and gypsiferous clay in the Brule formation of Oligocene age about 12 miles northeast of Chadron in northeastern Dawes County, Nebraska. Uranium minerals are visible at only two localities and are associated with carbonaceous matter. Elsewhere the basal 25 feet of the gypsum sequence is interbedded with carbonate rocks and is weakly but persistently uraniferous. Uranium probably was emplaced from above by uranyl solutions rich in sulfate.

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

Distribution and potential health risk of groundwater uranium in Korea.

PubMed

Shin, Woosik; Oh, Jungsun; Choung, Sungwook; Cho, Byong-Wook; Lee, Kwang-Sik; Yun, Uk; Woo, Nam-Chil; Kim, Hyun Koo

2016-11-01

Chronic exposure even to extremely low specific radioactivity of natural uranium in groundwater results in kidney problems and potential toxicity in bones. This study was conducted to assess the potential health risk via intake of the groundwater containing uranium, based on the determination of the uranium occurrence in groundwater. The groundwater was investigated from a total of 4140 wells in Korea. Most of the groundwater samples showed neutral pH and (sub-)oxic condition that was influenced by the mixing with shallow groundwater due to long-screened (open) wells. High uranium contents exceeding the WHO guideline level of 30 μg L(-1) were observed in the 160 wells located mainly in the plutonic bedrock regions. The statistical analysis suggested that the uranium component was present in groundwater by desorption and re-dissolution processes. Predominant uranium phases were estimated to uranyl carbonates under the Korean groundwater circumstances. These mobile forms of uranium and oxic condition facilitate the increase of potential health risk downgradient. In particular, long-term intake of groundwater containing >200 μg U L(-1) may induce internal exposure to radiation as well as the effects of chemical toxicity. These high uranium concentrations were found in twenty four sampling wells of rural areas in this study, and they were mainly used for drinking. Therefore, the high-level uranium wells and neighboring areas must be properly managed and monitored to reduce the exposure risk for the residents by drinking groundwater. Copyright © 2016 Elsevier Ltd. All rights reserved.

Interaction of Uranium with Bacterial Cell Surfaces: Inferences from Phosphatase-Mediated Uranium Precipitation.

PubMed

Kulkarni, Sayali; Misra, Chitra Seetharam; Gupta, Alka; Ballal, Anand; Apte, Shree Kumar

2016-08-15

Deinococcus radiodurans and Escherichia coli expressing either PhoN, a periplasmic acid phosphatase, or PhoK, an extracellular alkaline phosphatase, were evaluated for uranium (U) bioprecipitation under two specific geochemical conditions (GCs): (i) a carbonate-deficient condition at near-neutral pH (GC1), and (ii) a carbonate-abundant condition at alkaline pH (GC2). Transmission electron microscopy revealed that recombinant cells expressing PhoN/PhoK formed cell-associated uranyl phosphate precipitate under GC1, whereas the same cells displayed extracellular precipitation under GC2. These results implied that the cell-bound or extracellular location of the precipitate was governed by the uranyl species prevalent at that particular GC, rather than the location of phosphatase. MINTEQ modeling predicted the formation of predominantly positively charged uranium hydroxide ions under GC1 and negatively charged uranyl carbonate-hydroxide complexes under GC2. Both microbes adsorbed 6- to 10-fold more U under GC1 than under GC2, suggesting that higher biosorption of U to the bacterial cell surface under GC1 may lead to cell-associated U precipitation. In contrast, at alkaline pH and in the presence of excess carbonate under GC2, poor biosorption of negatively charged uranyl carbonate complexes on the cell surface might have resulted in extracellular precipitation. The toxicity of U observed under GC1 being higher than that under GC2 could also be attributed to the preferential adsorption of U on cell surfaces under GC1. This work provides a vivid description of the interaction of U complexes with bacterial cells. The findings have implications for the toxicity of various U species and for developing biological aqueous effluent waste treatment strategies. The present study provides illustrative insights into the interaction of uranium (U) complexes with recombinant bacterial cells overexpressing phosphatases. This work demonstrates the effects of aqueous speciation of U on the biosorption of U and the localization pattern of uranyl phosphate precipitated as a result of phosphatase action. Transmission electron microscopy revealed that location of uranyl phosphate (cell associated or extracellular) was primarily influenced by aqueous uranyl species present under the given geochemical conditions. The data would be useful for understanding the toxicity of U under different geochemical conditions. Since cell-associated precipitation of metal facilitates easy downstream processing by simple gravity-based settling down of metal-loaded cells, compared to cumbersome separation techniques, the results from this study are of considerable relevance to effluent treatment using such cells. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

Interaction of Uranium with Bacterial Cell Surfaces: Inferences from Phosphatase-Mediated Uranium Precipitation

PubMed Central

Kulkarni, Sayali; Misra, Chitra Seetharam; Gupta, Alka; Ballal, Anand

2016-01-01

ABSTRACT Deinococcus radiodurans and Escherichia coli expressing either PhoN, a periplasmic acid phosphatase, or PhoK, an extracellular alkaline phosphatase, were evaluated for uranium (U) bioprecipitation under two specific geochemical conditions (GCs): (i) a carbonate-deficient condition at near-neutral pH (GC1), and (ii) a carbonate-abundant condition at alkaline pH (GC2). Transmission electron microscopy revealed that recombinant cells expressing PhoN/PhoK formed cell-associated uranyl phosphate precipitate under GC1, whereas the same cells displayed extracellular precipitation under GC2. These results implied that the cell-bound or extracellular location of the precipitate was governed by the uranyl species prevalent at that particular GC, rather than the location of phosphatase. MINTEQ modeling predicted the formation of predominantly positively charged uranium hydroxide ions under GC1 and negatively charged uranyl carbonate-hydroxide complexes under GC2. Both microbes adsorbed 6- to 10-fold more U under GC1 than under GC2, suggesting that higher biosorption of U to the bacterial cell surface under GC1 may lead to cell-associated U precipitation. In contrast, at alkaline pH and in the presence of excess carbonate under GC2, poor biosorption of negatively charged uranyl carbonate complexes on the cell surface might have resulted in extracellular precipitation. The toxicity of U observed under GC1 being higher than that under GC2 could also be attributed to the preferential adsorption of U on cell surfaces under GC1. This work provides a vivid description of the interaction of U complexes with bacterial cells. The findings have implications for the toxicity of various U species and for developing biological aqueous effluent waste treatment strategies. IMPORTANCE The present study provides illustrative insights into the interaction of uranium (U) complexes with recombinant bacterial cells overexpressing phosphatases. This work demonstrates the effects of aqueous speciation of U on the biosorption of U and the localization pattern of uranyl phosphate precipitated as a result of phosphatase action. Transmission electron microscopy revealed that location of uranyl phosphate (cell associated or extracellular) was primarily influenced by aqueous uranyl species present under the given geochemical conditions. The data would be useful for understanding the toxicity of U under different geochemical conditions. Since cell-associated precipitation of metal facilitates easy downstream processing by simple gravity-based settling down of metal-loaded cells, compared to cumbersome separation techniques, the results from this study are of considerable relevance to effluent treatment using such cells. PMID:27287317

Preliminary Report on the White Canyon Area, San Juan County, Utah

USGS Publications Warehouse

Benson, William Edward Barnes; Trites, A.F.; Beroni, E.P.; Feeger, J.A.

1952-01-01

The White Canyon area in San Juan County, Utah, contains known deposits of copper-uranium ore and is currently being mapped and studied by the Geological Survey. To date, approximately 75 square miles, or about 20 percent of the area, has been mapped on a scale 1 inch=1 mile. The White Canyon area is underlain by more than 2,000 feet of sedimentary rocks, Carboniferous to Jurassic(?) in age. The area is on the flank of the Elk Ridge anticline, and the strata have a regional dip of 1 deg to 2 deg SW. The Shinarump conglomerate of Late Triassic age is the principal ore-bearing formation. The Shinarump consists of lenticular beds of sandstone, conglomeratic sandstone, clay, and siltstone, and ranges in thickness from a feather edge to as much as 75 feet. Locally the sandstones contain silicified and carbonized wood and fragments of charcoal. These vegetal remains are especially common in channel-fill deposits. Jointing is prominent in the western part of the area, and apparently affects all formations. Adjacent to the joints some of the redbeds in the sequence are bleached. Deposits of copper-uranium minerals have been found in the Moenkopi, Shinarump, and Chinle formations, but the only production of ore has been from the Shinarump conglomerate. The largest concentration of these minerals is in the lower third of the Shinarump, and the deposits seem to be controlled in part by ancient channel fills and in part by fractures. Locally precipitation of the copper and uranium minerals apparently has been aided by charcoal and clays. Visible uranium minerals include both hard and soft pitchblende and secondary hydrosulfates, phosphates, and silicates. In addition, unidentified uranium compounds are present in carbonized wood and charcoal, and in veinlets of hydrocarbons. Base-metal sulfides have been identified in all prospects that extend beyond the oxidized zone. Secondary copper minerals in the oxidized zone include the hydrous sulfates and carbonates, and possibly chrysocolla. The principal gangue minerals are quartz, clay minerals, chlorite, oxides of iron and manganese, alunite, calcite, gypsum, pyrite, allophane, gibbsite, opal, and chalcedony. The origin of the copper-uranium ores has not been determined, but the association of many deposits with fractures, the mineralogic assemblage, and a lead-uranium age determination of 50 to 60 million years for the pitchblende in the Happy Jack mine favor the hypothesis that the ores are of hydrothermal origin and were deposited in early Tertiary time. Criteria believed to be the most useful in prospecting for new deposits are (1) visible uranium minerals; (2) visible copper minerals; (3) alunite; (4) hydrocarbons; and (5) bleaching of the underlying Moenkopi formation.

Weathering and evaporation controls on dissolved uranium concentrations in groundwater - A case study from northern Burundi.

PubMed

Post, V E A; Vassolo, S I; Tiberghien, C; Baranyikwa, D; Miburo, D

2017-12-31

The potential use of groundwater for potable water supply can be severely compromised by natural contaminants such as uranium. The environmental mobility of uranium depends on a suite of factors including aquifer lithology, redox conditions, complexing agents, and hydrological processes. Uranium concentrations of up to 734μg/L are found in groundwater in northern Burundi, and the objective of the present study was to identify the causes for these elevated concentrations. Based on a comprehensive data set of groundwater chemistry, geology, and hydrological measurements, it was found that the highest dissolved uranium concentrations in groundwater occur near the shores of Lake Tshohoha South and other smaller lakes nearby. A model is proposed in which weathering and evapotranspiration during groundwater recharge, flow and discharge exert the dominant controls on the groundwater chemical composition. Results of PHREEQC simulations quantitatively confirm this conceptual model and show that uranium mobilization followed by evapo-concentration is the most likely explanation for the high dissolved uranium concentrations observed. The uranium source is the granitic sand, which was found to have a mean elemental uranium content of 14ppm, but the exact mobilization process could not be established. Uranium concentrations may further be controlled by adsorption, especially where calcium-uranyl‑carbonate complexes are present. Water and uranium mass balance calculations for Lake Tshohoha South are consistent with the inferred fluxes and show that high‑uranium groundwater represents only a minor fraction of the overall water input to the lake. These findings highlight that the evaporation effects that cause radionuclide concentrations to rise to harmful levels in groundwater discharge areas are not only confined to arid regions, and that this should be considered when selecting suitable locations for water supply wells. Copyright © 2017 Elsevier B.V. All rights reserved.

The role of extracellular DNA in uranium precipitation and biomineralisation.

PubMed

Hufton, Joseph; Harding, John H; Romero-González, Maria E

2016-10-26

Bacterial extra polymeric substances (EPS) have been associated with the extracellular precipitation of uranium. Here we report findings on the biomineralisation of uranium, with extracellular DNA (eDNA) used as a model biomolecule representative of EPS. The complexation and precipitation of eDNA with uranium were investigated as a function of pH, ionic strength and varying concentrations of reactants. The role of phosphate moieties in the biomineralisation mechanism was studied by enzymatically releasing phosphate (ePO 4 ) from eDNA compared to abiotic phosphate (aPO 4 ). The eDNA-uranium precipitates and uranium minerals obtained were characterised by Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FT-IR) spectroscopy, Scanning Electron Microscopy-Energy Dispersive X-Ray analysis (SEM-EDX), X-Ray Powder Diffraction (XRD) and X-Ray Photoelectron Spectroscopy (XPS). ATR-FT-IR showed that at pH 5, the eDNA-uranium precipitation mechanism was predominantly mediated by interactions with phosphate moieties from eDNA. At pH 2, the uranium interactions with eDNA occur mainly through phosphate. The solubility equilibrium was dependent on pH with the formation of precipitate reduced as the pH increased. The XRD data confirmed the formation of a uranium phosphate precipitate when synthesised using ePO 4 . XPS and SEM-EDX studies showed the incorporation of carbon and nitrogen groups from the enzymatic orthophosphate hydrolysis on the obtained precipitated. These results suggested that the removal of uranium from solution occurs via two mechanisms: complexation by eDNA molecules and precipitation of a uranium phosphate mineral of the type (UO 2 HPO 4 )·xH 2 O by enzymatic orthophosphate hydrolysis. This demonstrated that eDNA from bacterial EPS is a key contributor to uranium biomineralisation.

Release of U(VI) from spent biosorbent immobilized in cement concrete blocks

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

Venkobachar, C.; Iyengar, L.; Mishra, U.K.

1995-12-01

This paper deals with cementation as the method for the disposal of spent biosorbent, Ganoderma lucidum (a wood rotting macrofungi) after it is used for the removal of Uranium. Results on the uranium release during the curing of cement-concrete (CC) blocks indicated that placing the spent sorbent at the center of the blocks during their casting yields better immobilization of uranium as compared to the homogeneous mixing of the spent sorbent with the cement. Short term leach tests indicated that the uranium release was negligible in simulated seawater, 1.8% in 0.2 N sodium carbonate and 6.0% in 0.2 N HCl.more » The latter two leachates were used to represent the extreme environmental conditions. It was observed that the presence of the spent biosorbent up to 5% by weight did not affect the compressive strength of CC blocks. Thus cementation technique is suitable for the immobilization of uranium loaded biosorbent for its ultimate disposal.« less

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.

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

Preparation of UC0.07-0.10N0.90-0.93 spheres for TRISO coated fuel particles

NASA Astrophysics Data System (ADS)

Hunt, R. D.; Silva, C. M.; Lindemer, T. B.; Johnson, J. A.; Collins, J. L.

2014-05-01

The US Department of Energy is considering 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 dense uranium nitride (UN) kernels with diameters of 650 or 800 μm. The objectives of this effort are to make uranium oxide microspheres with adequately dispersed carbon nanoparticles and to convert these microspheres into UN spheres, which could be then sintered into kernels. Recent improvements to the internal gelation process were successfully applied to the production of uranium gel spheres with different concentrations of carbon black. After the spheres were washed and dried, a simple two-step heat profile was used to produce porous microspheres with a chemical composition of UC0.07-0.10N0.90-0.93. The first step involved heating the microspheres to 2023 K in a vacuum, and in the second step, the microspheres were held at 1873 K for 6 h in flowing nitrogen.

Immobilization of uranium in biofilm microorganisms exposed to groundwater seeps over granitic rock tunnel walls in Olkiluoto, Finland

NASA Astrophysics Data System (ADS)

Krawczyk-Bärsch, Evelyn; Lünsdorf, Heinrich; Pedersen, Karsten; Arnold, Thuro; Bok, Frank; Steudtner, Robin; Lehtinen, Anne; Brendler, Vinzenz

2012-11-01

In an underground rock characterization facility, the ONKALO tunnel in Finland, massive 5-10-mm thick biofilms were observed attached to tunnel walls where groundwater was seeping from bedrock fractures at a depth of 70 m. In laboratory experiments performed in a flow cell with detached biofilms to study the effect of uranium on the biofilm, uranium was added to the circulating groundwater (CGW) obtained from the fracture feeding the biofilm. The final uranium concentration in the CGW was adjusted to 4.25 × 10-5 M, in the range expected from a leaking spent nuclear fuel (SNF) canister in a future underground repository. The effects were investigated using microelectrodes to measure pH and Eh, time-resolved laser fluorescence spectroscopy (TRLFS), energy-filtered transmission electron microscopy (EF-TEM), and electron energy-loss spectroscopy (EELS) studies and thermodynamic calculations were utilized as well. The results indicated that the studied biofilms constituted their own microenvironments, which differed significantly from that of the CGW. A pH of 5.37 was recorded inside the biofilm, approximately 3.5 units lower than the pH observed in the CGW, due to sulfide oxidation to sulfuric acid in the biofilm. Similarly, the Eh of +73 mV inside the biofilm was approximately 420 mV lower than the Eh measured in the CGW. Adding uranium increased the pH in the biofilm to 7.27 and reduced the Eh to -164 mV. The changes of Eh and pH influenced the bioavailability of uranium, since microbial metabolic processes are sensitive to metals and their speciation. EF-TEM investigations indicated that uranium in the biofilm was immobilized intracellularly in microorganisms by the formation of metabolically mediated uranyl phosphate, similar to needle-shaped autunite (Ca[UO2]2[PO4]2·2-6H2O) or meta-autunite (Ca[UO2]2[PO4]2·10-12H2O). In contrast, TRLFS studies of the contaminated CGW identified aqueous uranium carbonate species, likely (Ca2UO2[CO3]3), formed due to the high concentration of carbonate in the CGW. The results agreed with thermodynamic calculations of the theoretically predominant field of uranium species, formed in the uranium-contaminated CGW at the measured geochemical parameters. This investigation clearly demonstrated that biological systems must be considered as a part of natural systems that can significantly influence radionuclide behavior. The results improve our understanding of the mechanisms of biofilm response to radionuclides in relation to safety assessments of SNF repositories.

Radioactive mineral spring precipitates, their analytical and statistical data and the uranium connection

USGS Publications Warehouse

Cadigan, R.A.; Felmlee, J.K.

1982-01-01

Major radioactive mineral springs are probably related to deep zones of active metamorphism in areas of orogenic tectonism. The most common precipitate is travertine, a chemically precipitated rock composed chiefly of calcium carbonate, but also containing other minerals. The mineral springs are surface manifestations of hydrothermal conduit systems which extend downward many kilometers to hot source rocks. Conduits are kept open by fluid pressure exerted by carbon dioxide-charged waters rising to the surface propelled by heat and gas (CO2 and steam) pressure. On reaching the surface, the dissolved carbon dioxide is released from solution, and calcium carbonate is precipitated. Springs also contain sulfur species (for example, H2S and HS-), and radon, helium and methane as entrained or dissolved gases. The HS- ion can react to form hydrogen sulfide gas, sulfate salts, and native sulfur. Chemical salts and native sulfur precipitate at the surface. The sulfur may partly oxidize to produce detectable sulfur dioxide gas. Radioactivity is due to the presence of radium-226, radon-222, radium-228, and radon-220, and other daughter products of uranium-238 and thorium-232. Uranium and thorium are not present in economically significant amounts in most radioactive spring precipitates. Most radium is coprecipitated at the surface with barite. Barite (barium sulfate) forms in the barium-containing spring water as a product of the oxidation of sulfur species to sulfate ions. The relatively insoluble barium sulfate precipitates and removes much of the radium from solution. Radium coprecipitates to a lesser extent with manganese-barium- and iron-oxy hydroxides. R-mode factor analysis of abundances of elements suggests that 65 percent of the variance of the different elements is affected by seven factors interpreted as follows: (1) Silica and silicate contamination and precipitation; (2) Carbonate travertine precipitation; (3) Radium coprecipitation; (4) Evaporite precipitation; (5) Hydrous limonite precipitation and coprecipitated elements including uranium; (6) Rare earth elements deposited with detrital contamination (?); (7) Metal carbonate adsorption and precipitation. Economically recoverable minerals occurring at some localities in spring precipitates are ores of iron, manganese, sulfur, tungsten and barium and ornamental travertine. Continental radioactive mineral springs occur in areas of crustal thickening caused by overthrusting of crustal plates, and intrusion and metamorphism. Sedimentary rocks on the lower plate are trapped between the plates and form a zone of metamorphism. Connate waters, carbonate rocks and organic-carbon-bearing rocks react to extreme pressure and temperature to produce carbon dioxide, and steam. Fractures are forced open by gas and fluid pressures. Deep-circulating meteoric waters then come in contact with the reactive products, and a hydrothermal cell forms. When hot mineral-charged waters reach the surface they form the familiar hot mineral springs. Hot springs also occur in relation to igneous intrusive action or volcanism both of which may be products of the crustal plate overthrusting. Uranium and thorium in the sedimentary rocks undergoing metamorphism are sometimes mobilized, but mobilization is generally restricted to an acid hydrothermal environment; much is redeposited in favorable environments in the metamorphosed sediments. Radium and radon, which are highly mobile in both acid and alkaline aqueous media move upward into the hydrothermal cell and to the surface.

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.

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.

Argonne explains nuclear recycling in 4 minutes

ScienceCinema

Willit, Jim; Williamson, Mark; Haynes, Amber

2018-05-30

Currently, when using nuclear energy only about five percent of the uranium used in a fuel rod gets fissioned for energy; after that, the rods are taken out of the reactor and put into permanent storage. There is a way, however, to use almost all of the uranium in a fuel rod. Recycling used nuclear fuel could produce hundreds of years of energy from just the uranium we've already mined, all of it carbon-free. Problems with older technology put a halt to recycling used nuclear fuel in the United States, but new techniques developed by scientists at Argonne National Laboratory address many of those issues. For more information, visit http://www.anl.gov/energy/nuclear-energy.

Methods for making a porous nuclear fuel element

DOEpatents

Youchison, Dennis L; Williams, Brian E; Benander, Robert E

2014-12-30

Porous nuclear fuel elements for use in advanced high temperature gas-cooled nuclear reactors (HTGR's), and to processes for fabricating them. Advanced uranium bi-carbide, uranium tri-carbide and uranium carbonitride nuclear fuels can be used. These fuels have high melting temperatures, high thermal conductivity, and high resistance to erosion by hot hydrogen gas. Tri-carbide fuels, such as (U,Zr,Nb)C, can be fabricated using chemical vapor infiltration (CVI) to simultaneously deposit each of the three separate carbides, e.g., UC, ZrC, and NbC in a single CVI step. By using CVI, the nuclear fuel may be deposited inside of a highly porous skeletal structure made of, for example, reticulated vitreous carbon foam.

Solid-phase data from cores at the proposed Dewey Burdock uranium in-situ recovery mine, near Edgemont, South Dakota

USGS Publications Warehouse

Johnson, Raymond H.; Diehl, Sharon F.; Benzel, William M.

2013-01-01

This report releases solid-phase data from cores at the proposed Dewey Burdock uranium in-situ recovery site near Edgemont, South Dakota. These cores were collected by Powertech Uranium Corporation, and material not used for their analyses were given to the U.S. Geological Survey for additional sampling and analyses. These additional analyses included total carbon and sulfur, whole rock acid digestion for major and trace elements, 234U/238U activity ratios, X-ray diffraction, thin sections, scanning electron microscopy analyses, and cathodoluminescence. This report provides the methods and data results from these analyses along with a short summary of observations.

Spectroscopic evidence of uranium immobilization in acidic wetlands by natural organic matter and plant roots.

PubMed

Li, Dien; Kaplan, Daniel I; Chang, Hyun-Shik; Seaman, John C; Jaffé, Peter R; Koster van Groos, Paul; Scheckel, Kirk G; Segre, Carlo U; Chen, Ning; Jiang, De-Tong; Newville, Matthew; Lanzirotti, Antonio

2015-03-03

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

Spectroscopic evidence of uranium immobilization in acidic wetlands by natural organic matter and plant roots

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

Li, Dien; Kaplan, Daniel I.; Chang, Hyun-Shik

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

Spectroscopic evidence of uranium immobilization in acidic wetlands by natural organic matter and plant roots

DOE PAGES

Li, Dien; Kaplan, Daniel I.; Chang, Hyun-Shik; ...

2015-03-03

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

Uranium(IV) adsorption by natural organic matter in anoxic sediments

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

Bone, Sharon E.; Dynes, James J.; Cliff, John

Uranium is an important carbon-free fuel source and environmental contaminant that accumulates in the tetravalent state, U(IV), in anoxic sediments, such as ore deposits, marine basins, and contaminated aquifers. However, little is known about the speciation of U(IV) in low-temperature geochemical environments, inhibiting the development of a conceptual model of U behavior. Until recently, U(IV) was assumed to exist predominantly as the sparingly soluble mineral uraninite (UO 2+x) in anoxic sediments; however, studies now show that this is not often the case. Yet a model of U(IV) speciation in the absence of mineral formation under field-relevant conditions has not yetmore » been developed. Uranium(IV) speciation controls its reactivity, particularly its susceptibility to oxidative mobilization, impacting its distribution and toxicity. Here we show adsorption to organic carbon and organic carbon-coated clays dominate U(IV) speciation in an organic-rich natural substrate under field-relevant conditions. Whereas previous research assumed that U(IV) speciation is dictated by the mode of reduction (i.e., whether reduction is mediated by microbes or by inorganic reductants), our results demonstrate that mineral formation can be diminished in favor of adsorption, regardless of reduction pathway. Projections of U transport and bioavailability, and thus its threat to human and ecosystem health, must consider U(IV) adsorption to organic matter within the sediment environment.« less

Uranium(IV) adsorption by natural organic matter in anoxic sediments

DOE PAGES

Bone, Sharon E.; Dynes, James J.; Cliff, John; ...

2017-01-09

Uranium is an important carbon-free fuel source and environmental contaminant that accumulates in the tetravalent state, U(IV), in anoxic sediments, such as ore deposits, marine basins, and contaminated aquifers. However, little is known about the speciation of U(IV) in low-temperature geochemical environments, inhibiting the development of a conceptual model of U behavior. Until recently, U(IV) was assumed to exist predominantly as the sparingly soluble mineral uraninite (UO 2+x) in anoxic sediments; however, studies now show that this is not often the case. Yet a model of U(IV) speciation in the absence of mineral formation under field-relevant conditions has not yetmore » been developed. Uranium(IV) speciation controls its reactivity, particularly its susceptibility to oxidative mobilization, impacting its distribution and toxicity. Here we show adsorption to organic carbon and organic carbon-coated clays dominate U(IV) speciation in an organic-rich natural substrate under field-relevant conditions. Whereas previous research assumed that U(IV) speciation is dictated by the mode of reduction (i.e., whether reduction is mediated by microbes or by inorganic reductants), our results demonstrate that mineral formation can be diminished in favor of adsorption, regardless of reduction pathway. Projections of U transport and bioavailability, and thus its threat to human and ecosystem health, must consider U(IV) adsorption to organic matter within the sediment environment.« less

A STUDY OF THE ACIDOSIS, BLOOD UREA, AND PLASMA CHLORIDES IN URANIUM NEPHRITIS IN THE DOG, AND OF THE PROTECTIVE ACTION OF SODIUM BICARBONATE.

PubMed

Goto, K

1917-05-01

1. The presence of an acidosis in dogs with experimental uranium nephritis is demonstrable by the Van Slyke-Stillman-Cullen method and that of Marriott. It is detected more readily by the former method. 2. This acidosis is associated with increase in the blood urea and plasma chlorides and with the appearance of albumin and casts in the urine. 3. The oral administration of sodium bicarbonate diminishes the acidosis, the increase in plasma chlorides, the amount of albumin and casts in the urine, and, to a lesser degree, the increase in the blood urea following the administration of uranium. It also diminishes the severity of the changes produced by uranium in the kidneys. 4. The oral administration of sodium bicarbonate to normal dogs raises the carbon dioxide content of the plasma as determined by the. Van Slyke-Stillman-Cullen method.

Reconnaissance of uranium and copper deposits in parts of New Mexico, Colorado, Utah, Idaho, and Wyoming

USGS Publications Warehouse

Gott, Garland B.; Erickson, Ralph L.

1952-01-01

Because of the common association of uranium and copper in several of the commercial uranium deposits in the Colorado Plateau Province, a reconnaissance was made of several known deposits of copper disseminated through sandstone to determine whether they might be a source of uranium. In order to obtain more information regarding the relationship between copper, uranium and carbonaceous materials, some of the uraniferious asphaltrite deposits in the Shinarump conglomerate along the west flank of the San Rafael Swell were also investigated briefly. During this reconnaissance 18 deposits were examined in New Mexico, eight in Utah, two in Idaho, and one each in Wyoming and Colorado. No uranium deposits of commercial grade are associated with the copper deposits that were examined. The uraniferous asphaltites in the Shinarump conglomerate of Triassic age on the west flank of the San Rafael Swell, however, are promising from the standpoint of commercial uranium production. Spectrographic analyses of crude oil, asphalt, and bituminous shales show a rather consistent suite of trace metals including vanadium, nickel, copper, cobalt, chromium, lead zinc, and molybdenum. The similarity of the metal assemblage, including uranium of the San Rafael Swell asphaltites, to the metal assemblage in crude oil and other bituminous materials suggests that these metals were concentrated in the asphaltites from petroleum. However, the hypothesis that uranium minerals were already present before the hydrocarbons were introduced and that some sort of replacement or uranium minerals by carbon compounds was effected after the petroleum migrated into the uranium deposit should not be disregarded. The widespread association of uranium with asphaltic material suggests that it also may have been concentrated by some agency connected with the formation of petroleum. The problem of the association of uranium and other trace metals with hydrocarbons should be studied further both in the field and in the laboratory.

Determination of irradiated reactor uranium in soil samples in Belarus using 236U as irradiated uranium tracer.

PubMed

Mironov, Vladislav P; Matusevich, Janna L; Kudrjashov, Vladimir P; Boulyga, Sergei F; Becker, J Sabine

2002-12-01

This work presents experimental results on the distribution of irradiated reactor uranium from fallout after the accident at Chernobyl Nuclear Power Plant (NPP) in comparison to natural uranium distribution in different soil types. Oxidation processes and vertical migration of irradiated uranium in soils typical of the 30 km relocation area around Chernobyl NPP were studied using 236U as the tracer for irradiated reactor uranium and inductively coupled plasma mass spectrometry as the analytical method for uranium isotope ratio measurements. Measurements of natural uranium yielded significant variations of its concentration in upper soil layers from 2 x 10(-7) g g(-1) to 3.4 x 10(-6) g g(-1). Concentrations of irradiated uranium in the upper 0-10 cm soil layers at the investigated sampling sites varied from 5 x 10(-12) g g(-1) to 2 x 10(-6) g g(-1) depending on the distance from Chernobyl NPP. In the majority of investigated soil profiles 78% to 97% of irradiated "Chernobyl" uranium is still contained in the upper 0-10 cm soil layers. The physical and chemical characteristics of the soil do not have any significant influence on processes of fuel particle destruction. Results obtained using carbonate leaching of 236U confirmed that more than 60% of irradiated "Chernobyl" uranium is still in a tetravalent form, ie. it is included in the fuel matrix (non-oxidized fuel UO2). The average value of the destruction rate of fuel particles determined for the Western radioactive trace (k = 0.030 +/- 0.005 yr(-1)) and for the Northern radioactive trace (k = 0.035 + 0.009 yr(-1)) coincide within experimental errors. Use of leaching of fission products in comparison to leaching of uranium for study of the destruction rate of fuel particles yielded poor coincidence due to the fact that use of fission products does not take into account differences in the chemical properties of fission products and fuel matrix (uranium).

Long-term anoxia and release of ancient, labile carbon upon thaw of Pleistocene permafrost

USGS Publications Warehouse

Ewing, Stephanie A.; O'Donnell, Jonathan A.; Aiken, George R.; Butler, Kenna D.; Butman, David; Windham-Myers, Lisamarie; Kanevskiy, Mikhail

2015-01-01

The fate of permafrost carbon upon thaw will drive feedbacks to climate warming. Here we consider the character and context of dissolved organic carbon (DOC) in yedoma permafrost cores from up to 20 m depth in central Alaska. We observed high DOC concentrations (4 to 129 mM) and consistent low molecular weight organic acid concentrations in three cores. We estimate a DOC production rate of 12 µmol DOC m−2 yr−1 based on model ages of up to ~200 kyr derived from uranium isotopes. Acetate C accounted for 24 ± 1% of DOC in all samples. This proportion suggests long-term anaerobiosis and is likely to influence thaw outcomes due to biolability of acetate upon release in many environments. The combination of uranium isotopes, ammonium concentrations, and calcium concentrations explained 86% of the variation in thaw water DOC concentrations, suggesting that DOC production may be related to both reducing conditions and mineral dissolution over time.

Mineral and energy resources of the Roswell Resource Area, East-Central New Mexico

USGS Publications Warehouse

Bartsch-Winkler, Susan B.; Donatich, Alessandro J.

1995-01-01

The sedimentary formations of the Roswell Resource Area have significant mineral and energy resources. Some of the pre-Pennsylvanian sequences in the Northwestern Shelf of the Permian Basin are oil and gas reservoirs, and Pennsylvanian rocks in Tucumcari Basin are reservoirs of oil and gas as well as source rocks for oil and gas in Triassic rocks. Pre-Permian rocks also contain minor deposits of uranium and vanadium, limestone, and gases. Hydrocarbon reservoirs in Permian rocks include associated gases such as carbon dioxide, helium, and nitrogen. Permian rocks are mineralized adjacent to the Lincoln County porphyry belt, and include deposits of copper, uranium, manganese, iron, polymetallic veins, and Mississippi-Valley-type lead-zinc. Industrial minerals in Permian rocks include fluorite, barite, potash, halite, polyhalite, gypsum, anhydrite, sulfur, limestone, dolomite, brine deposits (iodine and bromine), aggregate (sand), and dimension stone. Doubly terminated quartz crystals, called 'Pecos diamonds' and collected as mineral specimens, occur in Permian rocks along the Pecos River. Mesozoic sedimentary rocks are hosts for copper, uranium, and small quantities of gold-silver-tellurium veins, as well as significant deposits of oil and gas, carbon dioxide, asphalt, coal, and dimension stone. Mesozoic rocks contain limited amounts of limestone, gypsum, petrified wood, and clay. Tertiary rocks host ore deposits commonly associated with intrusive rocks, including platinum-group elements, iron skarns, manganese, uranium and vanadium, molybdenum, polymetallic vein deposits, gold-silver-tellurium veins, and thorium-rare-earth veins. Museum-quality quartz crystals are associated with Tertiary intrusive rocks. Industrial minerals in Tertiary rocks include fluorite, vein- and bedded-barite, caliche, limestone, and aggregate. Tertiary and Quaternary sediments host important placer deposits of gold and titanium, and occurrences of silver and uranium. Important industrial commodities include caliche, limestone and dolomite, and aggregate. Quaternary basalt contains sub-ore-grade uranium, scoria, and clay deposits.

Finding Paleoclimates Using Pedogenic Carbonates

NASA Astrophysics Data System (ADS)

Garapaty, C.; Bella Pratt, K.; Blisniuk, K.

2016-12-01

Carbonate rinds naturally form on the undersides of clasts in desert soil. These carbonate rinds can be used to determine past climates in these environments because they contain certain radioactive isotopes and stable isotopes. Radioactive isotopes can provide the age of soil formation because carbonate rinds only form after the soil. When the carbonates are forming on the rock, in desert soil, they trap miniscule amounts of uranium which will radioactively decay into thorium. Therefore, the uranium to thorium ratio found when the carbonates are analyzed can accurately give you the date of the sample. On the other hand stable isotopes help determine the average temperature at the time the carbonate was formed. The oxygen in the CO3- (carbonate) are usually 16O and 18O. The ratio of 16O to 18O can give you the temperature of the environment when the carbonates formed. This ratio depends on temperature because water with 16O evaporates first since it is lighter and 18O precipitates more easily because it is heavier. Evaporation, precipitation, and temperature change, easily alters the concentration of the ratio of 16O to 18O so it is easy to calculate the temperature, in that area and at that time, from it. The samples I worked on are from the Sonoran Desert in Southern California. I used a microscope, tweezers and a small pick to remove the carbonate from the clast and remove the biotite and other contamination from the carbonate. Later, we wash the samples by hand and by using an ultrasonic machine to make them even cleaner by washing away any loose material. We had to remove the biotite and wash away the loose material because the carbonates need to be clean in order for us to analyze it accurately.

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.

HIGH TEMPERATURE REFRACTORY COATING FOR GRAPHITE MOLDS

DOEpatents

Stoddard, S.D.

1958-10-21

An improved foundry mold coating for use with graphite molds used in the casting of uranium is presented. The refractory mold coating serves to keep the molten uranium from contact with graphite of the mold and thus prevents carbon pickup by the molten metal. The refractory coating is made by dry mixing certain specific amounts of aluminum oxide, bentonite, Tennessee ball clay, and a soluble silicate salt. Water is then added to the mixture and the suspension thus formed is applied by spraying onto the mold.

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.

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.

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

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.

Structural changes in amber due to uranium mineralization.

PubMed

Havelcová, Martina; Machovič, Vladimír; Mizera, Jiří; Sýkorová, Ivana; René, Miloš; Borecká, Lenka; Lapčák, Ladislav; Bičáková, Olga; Janeček, Oldřich; Dvořák, Zdeněk

2016-07-01

The presence of uranium, with a bulk mass fraction of about 1.5 wt% and radiolytic alterations are a feature of Cenomanian amber from Křižany, at the northeastern edge of the North Bohemian Cretaceous uranium ore district. Pores and microcracks in the amber were filled with a mineral admixture, mainly in the form of Zr-Y-REE enriched uraninite. As a result of radiolytic alterations due to the presence of uranium, structural changes were observed in the Křižany amber in comparison with a reference amber from Nové Strašecí in central Bohemia; this was of similar age and botanical origin but did not contain elevated levels of uranium. Structural changes involved an increase in aromaticity due to dehydroaromatization of aliphatic cyclic hydrocarbons, loss of oxygen functional groups, an increase in the degree of polymerization, crosslinking of CC bonds, formation of a three-dimensional hydrocarbon network in the bulk organic matrix, and carbonization of the organic matrix around the uraninite infill. Copyright © 2016 Elsevier Ltd. All rights reserved.

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.

Estimation of uranium migration parameters in sandstone aquifers.

PubMed

Malov, A I

2016-03-01

The chemical composition and isotopes of carbon and uranium were investigated in groundwater samples that were collected from 16 wells and 2 sources in the Northern Dvina Basin, Northwest Russia. Across the dataset, the temperatures in the groundwater ranged from 3.6 to 6.9 °C, the pH ranged from 7.6 to 9.0, the Eh ranged from -137 to +128 mV, the total dissolved solids (TDS) ranged from 209 to 22,000 mg L(-1), and the dissolved oxygen (DO) ranged from 0 to 9.9 ppm. The (14)C activity ranged from 0 to 69.96 ± 0.69 percent modern carbon (pmC). The uranium content in the groundwater ranged from 0.006 to 16 ppb, and the (234)U:(238)U activity ratio ranged from 1.35 ± 0.21 to 8.61 ± 1.35. The uranium concentration and (234)U:(238)U activity ratio increased from the recharge area to the redox barrier; behind the barrier, the uranium content is minimal. The results were systematized by creating a conceptual model of the Northern Dvina Basin's hydrogeological system. The use of uranium isotope dating in conjunction with radiocarbon dating allowed the determination of important water-rock interaction parameters, such as the dissolution rate:recoil loss factor ratio Rd:p (a(-1)) and the uranium retardation factor:recoil loss factor ratio R:p in the aquifer. The (14)C age of the water was estimated to be between modern and >35,000 years. The (234)U-(238)U age of the water was estimated to be between 260 and 582,000 years. The Rd:p ratio decreases with increasing groundwater residence time in the aquifer from n × 10(-5) to n × 10(-7) a(-1). This finding is observed because the TDS increases in that direction from 0.2 to 9 g L(-1), and accordingly, the mineral saturation indices increase. Relatively high values of R:p (200-1000) characterize aquifers in sandy-clayey sediments from the Late Pleistocene and the deepest parts of the Vendian strata. In samples from the sandstones of the upper part of the Vendian strata, the R:p value is ∼ 24, i.e., sorption processes are expressed more weakly, and uranium is possibly desorbed from the sediments. Overall, these results provide a better understanding of the evolution of uranium isotopes in groundwater systems. Copyright © 2015 Elsevier Ltd. All rights reserved.

Hydrocarbon-mediated gold and uranium concentration in the Witwatersrand Basin, South Africa

NASA Astrophysics Data System (ADS)

Fuchs, Sebastian; Williams-Jones, Anthony; Schumann, Dirk; Couillard, Martin; Murray, Andrew

2016-04-01

The Witwatersrand deposits in South Africa represent the largest repository of gold in the World and a major resource of uranium. The genesis of the gold and uranium ores in the quartz-pebble conglomerates (reefs), however, is still a matter of considerable discussion. Opinion has been divided over whether they represent paleo-placers that have been partly remobilised by hydrothermal fluids or if the mineralisation is entirely hydrothermal in origin. In addition, recently published models have proposed a syngenetic origin for the gold involving bacterially-mediated precipitation from meteoric water and shallow seawater. An important feature of the gold and uranium mineralisation in the reefs is the strong spatial association with organic matter. In some reefs, up to 70% of the gold and almost the entire uranium resource is spatially associated with pyrobitumen seams, suggesting a genetic relationship of the gold-uranium mineralisation with hydrocarbons. Here we report results of a study of the Carbon Leader Reef, using high-resolution scanning and transmission electron microscopy (SEM / TEM) and LA-ICP-MS that provide new insights into the role of hydrocarbons in the concentration of the gold and uranium. A detailed examination revealed gold monocrystals containing numerous rounded or elliptical inclusions filled with pyrobitumen. We interpret these inclusions to record the crystallisation of the gold around droplets of a hydrocarbon liquid that migrated through the Witwatersrand basin, and was converted to pyrobitumen by being heated. We propose that the gold was transported in a hydrothermal fluid as a bisulphide complex and that this fluid mixed with the hydrocarbon liquid to form a water-oil emulsion. The interaction between the two fluids caused a sharp reduction in fO2 at the water-oil interface, which destabilised the gold-bisulphide complexes, causing gold monocrystals to precipitate around the oil droplets. In contrast to the gold, uraninite, the principal uranium mineral, occurs as complex-shaped grains that represent aggregates containing billions of uraninite nanocrystals (5 - 7 nm in diameter), which grew in situ in the pyrobitumen matrix or more likely its liquid precursor (Fuchs et al., 2015). This in situ growth of isolated nanocrystalline aggregates shows that uranium was mobilised and concentrated by liquid hydrocarbons, and that uraninite nanocrystals were released from the oils during the conversion of oil to pyrobitumen. Our study provides new insights into the complex mechanisms of ore formation in the Witwatersrand Supergroup and compelling evidence that hydrocarbons played a major role in the concentration of the gold and uranium. It does not rule out the possibility that gold and uranium were introduced into the Witwatersrand Basin as detrital grains but shows that mobilisation of gold and uranium by hydrothermal fluids and hydrocarbon liquids, respectively, and the mixing of these fluids, were essential to ore formation. Fuchs, S., Schumann, D., Williams-Jones, A.E., Vali, H., 2015. The growth and concentration of uranium and titanium minerals in hydrocarbons of the Carbon Leader Reef, Witwatersrand Supergroup, South Africa. Chemical Geology 393-394, 55-66.

Methods for manufacturing porous nuclear fuel elements for high-temperature gas-cooled nuclear reactors

DOEpatents

Youchison, Dennis L [Albuquerque, NM; Williams, Brian E [Pocoima, CA; Benander, Robert E [Pacoima, CA

2010-02-23

Methods for manufacturing porous nuclear fuel elements for use in advanced high temperature gas-cooled nuclear reactors (HTGR's). Advanced uranium bi-carbide, uranium tri-carbide and uranium carbonitride nuclear fuels can be used. These fuels have high melting temperatures, high thermal conductivity, and high resistance to erosion by hot hydrogen gas. Tri-carbide fuels, such as (U,Zr,Nb)C, can be fabricated using chemical vapor infiltration (CVI) to simultaneously deposit each of the three separate carbides, e.g., UC, ZrC, and NbC in a single CVI step. By using CVI, a thin coating of nuclear fuel may be deposited inside of a highly porous skeletal structure made, for example, of reticulated vitreous carbon foam.

Porous nuclear fuel element for high-temperature gas-cooled nuclear reactors

DOEpatents

Youchison, Dennis L [Albuquerque, NM; Williams, Brian E [Pacoima, CA; Benander, Robert E [Pacoima, CA

2011-03-01

Porous nuclear fuel elements for use in advanced high temperature gas-cooled nuclear reactors (HTGR's), and to processes for fabricating them. Advanced uranium bi-carbide, uranium tri-carbide and uranium carbonitride nuclear fuels can be used. These fuels have high melting temperatures, high thermal conductivity, and high resistance to erosion by hot hydrogen gas. Tri-carbide fuels, such as (U,Zr,Nb)C, can be fabricated using chemical vapor infiltration (CVI) to simultaneously deposit each of the three separate carbides, e.g., UC, ZrC, and NbC in a single CVI step. By using CVI, the nuclear fuel may be deposited inside of a highly porous skeletal structure made of, for example, reticulated vitreous carbon foam.

Porous nuclear fuel element with internal skeleton for high-temperature gas-cooled nuclear reactors

DOEpatents

Youchison, Dennis L.; Williams, Brian E.; Benander, Robert E.

2013-09-03

Porous nuclear fuel elements for use in advanced high temperature gas-cooled nuclear reactors (HTGR's), and to processes for fabricating them. Advanced uranium bi-carbide, uranium tri-carbide and uranium carbonitride nuclear fuels can be used. These fuels have high melting temperatures, high thermal conductivity, and high resistance to erosion by hot hydrogen gas. Tri-carbide fuels, such as (U,Zr,Nb)C, can be fabricated using chemical vapor infiltration (CVI) to simultaneously deposit each of the three separate carbides, e.g., UC, ZrC, and NbC in a single CVI step. By using CVI, the nuclear fuel may be deposited inside of a highly porous skeletal structure made of, for example, reticulated vitreous carbon foam.

The Gas Hills uranium district and some probable controls for ore deposition

USGS Publications Warehouse

Zeller, Howard Davis

1957-01-01

Uranium deposits occur in the upper coarse-grained facies of the Wind River formation of Eocene age in the Gas Hills district of the southern part of the Wind River Basin. Some of the principal deposits lie below the water table in the unoxidized zone and consist of uraninite and coffinite occurring as interstitial fillings in irregular blanket-like bodies. In the near-surface deposits that lie above the water table, the common yellow uranium minerals consist of uranium phosphates, silicates, and hydrous oxides. The black unoxidized uraninite -coffinite ores show enrichment of molybdenum, arsenic, and selenium when compared to the barren sandstone. Probable geologic controls for ore deposits include: 1) permeable sediments that allowed passage of ore-bearing solutions; 2) numerous faults that acted as impermeable barriers impounding the ore -bearing solutions; 3) locally abundant pyrite, carbonaceous material, and natuial gas containing hydrogen sulfide that might provide a favorable environment for precipitation of uranium. Field and laboratory evidence indicate that the uranium deposits in the Gas Hills district are very young and related to the post-Miocene to Pleistocene regional tilting to the south associated with the collapse of the Granite Mountains fault block. This may have stopped or reversed ground water movement from a northward (basinward) direction and alkaline ground water rich in carbonate could have carried the uranium into the favorable environment that induced precipitation.

The short-term reduction of uranium by nanoscale zero-valent iron (nZVI): role of oxide shell, reduction mechanism and the formation of U( v )-carbonate phases

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

Tsarev, Sergey; Collins, Richard N.; Ilton, Eugene S.

Nanoscale zero-valent iron (nZVI) is a potential remediation agent for uranium-contaminated groundwaters, however, a complete mechanistic understanding of the processes that lead to uranium immobilization has yet to be achieved. In this study, the short-term anoxic reaction of U(VI) with fresh, (anoxic) aged and corroded nZVI particles was investigated under aqueous conditions conducive to the formation of thermodynamically stable U(VI)-Ca-CO3 ternary aqueous complexes. The first stage of the reaction between U(VI) and nZVI was assigned to sorption processes with the formation of surface U(VI)-carbonate complexes. Aged nZVI removed U(VI) faster than either fresh or corroded nZVI and it is hypothesizedmore » that U reduction initially occurs through the transfer of one electron from Fe(II) in the nZVI surface oxide layer. Evidence for reduction to U(V) was obtained through X-ray photoelectron spectroscopy and by determination of U-O bond distances of ~2.05 Å and 2.27 Å by U LIII-edge X-ray absorption spectroscopy detection of U-O bond distances at ~2.05 Å and 2.27 Å with these distances , similar to thoseat observed for the U(V) site in the mixed U(V)/U(VI) carbonate mineral wyartite. Scanning transmission electron microscopy also demonstrated that U was present as a nanoparticulate phase after one day of reaction, rather than a surface complex. Further reduction to U(IV), as observed in previous studies, would appear to be rate-limiting and coincident with the transformation of this meta-stable U-carbonate phase to uraninite (UO2).« less

U(VI) adsorption on aquifer sediments at the Hanford Site.

PubMed

Um, Wooyong; Serne, R Jeffrey; Brown, Christopher F; Last, George V

2007-08-15

Aquifer sediments collected via split-spoon sampling in two new groundwater wells in the 200-UP-1 operable unit at the Hanford Site were characterized and showed typical Ringold Unit E Formation properties dominated by gravel and sand. High iron-oxide content in Fe oxide/clay coatings caused the highest U(VI) adsorption as quantified by batch K(d) values, indicating iron oxides are the key solid adsorbent in the 200-UP-1 sediments that affect U(VI) fate and mobility. Even though U(VI) adsorption on the gravel-sized fraction of the sediments is considered to be negligible, careful characterization should be conducted to determine U(VI) adsorption on gravel, because of presence of Fe oxides coatings and diffusion-controlled adsorption into the gravel particles' interior surfaces. A linear adsorption isotherm was observed up to 10(-6) M (238 microg/L) of total U(VI) concentration in batch U(VI) adsorption tests with varying total U(VI) concentrations in spiked groundwater. U(VI) adsorption decreased with increasing concentrations of dissolved carbonate, because strong anionic aqueous uranium-carbonate complexes formed at high pH and high alkalinity conditions. Noticeable uranium desorption hysteresis was observed in a flow-through column experiment, suggesting that desorption K(d) values for aged uranium-contaminated sediments at the Hanford Site can be larger than adsorption K(d) values determined in short-term laboratory experiments and slow uranium release from contaminated sediments into the groundwater is expected.

Magnesium transport extraction of transuranium elements from LWR fuel

DOEpatents

Ackerman, John P.; Battles, James E.; Johnson, Terry R.; Miller, William E.; Pierce, R. Dean

1992-01-01

A process of separating transuranium actinide values from uranium values present in spent nuclear oxide fuels which contain rare earth and noble metal fission products. The oxide fuel is reduced with Ca metal in the presence of CaCl.sub.2 and a U-Fe alloy containing not less than about 84% by weight uranium at a temperature in the range of from about 800.degree. C. to about 850.degree. C. to produce additional uranium metal which dissolves in the U-Fe alloy raising the uranium concentration and having transuranium actinide metals and rare earth fission product metals and the noble metal fission products dissolved therein. The CaCl.sub.2 having CaO and fission products of alkali metals and the alkali earth metals and iodine dissolved therein is separated and electrolytically treated with a carbon electrode to reduce the CaO to Ca metal while converting the carbon electrode to CO and CO.sub.2. The Ca metal and CaCl.sub.2 is recycled to reduce additional oxide fuel. The U-Fe alloy having transuranium actinide metals and rare earth fission product metals and the noble metal fission products dissolved therein is contacted with Mg metal which takes up the actinide and rare earth fission product metals. The U-Fe alloy retains the noble metal fission products and is stored while the Mg is distilled and recycled leaving the transuranium actinide and rare earth fission products isolated.

Performance and Mechanism of Uranium Adsorption from Seawater to Poly(dopamine)-Inspired Sorbents.

PubMed

Wu, Fengcheng; Pu, Ning; Ye, Gang; Sun, Taoxiang; Wang, Zhe; Song, Yang; Wang, Wenqing; Huo, Xiaomei; Lu, Yuexiang; Chen, Jing

2017-04-18

Developing facile and robust technologies for effective enrichment of uranium from seawater is of great significance for resource sustainability and environmental safety. By exploiting mussel-inspired polydopamine (PDA) chemistry, diverse types of PDA-functionalized sorbents including magnetic nanoparticle (MNP), ordered mesoporous carbon (OMC), and glass fiber carpet (GFC) were synthesized. The PDA functional layers with abundant catechol and amine/imine groups provided an excellent platform for binding to uranium. Due to the distinctive structure of PDA, the sorbents exhibited multistage kinetics which was simultaneously controlled by chemisorption and intralayer diffusion. Applying the diverse PDA-modified sorbents for enrichment of low concentration (parts per billion) uranium in laboratory-prepared solutions and unpurified seawater was fully evaluated under different scenarios: that is, by batch adsorption for MNP and OMC and by selective filtration for GFC. Moreover, high-resolution X-ray photoelectron spectroscopic and extended X-ray absorption fine structure studies were performed for probing the underlying coordination mechanism between PDA and U(VI). The catechol hydroxyls of PDA were identified as the main bidentate ligands to coordinate U(VI) at the equatorial plane. This study assessed the potential of versatile PDA chemistry for development of efficient uranium sorbents and provided new insights into the interaction mechanism between PDA and uranium.

Trivalent uranium phenylchalcogenide complexes: exploring the bonding and reactivity with CS2 in the Tp*2UEPh series (E = O, S, Se, Te).

PubMed

Matson, Ellen M; Breshears, Andrew T; Kiernicki, John J; Newell, Brian S; Fanwick, Phillip E; Shores, Matthew P; Walensky, Justin R; Bart, Suzanne C

2014-12-15

The trivalent uranium phenylchalcogenide series, Tp*2UEPh (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate, E = O (1), S (2), Se (3), Te (4)), has been synthesized to investigate the nature of the U-E bond. All compounds have been characterized by (1)H NMR, infrared and electronic absorption spectroscopies, and in the case of 4, X-ray crystallography. Compound 4 was also studied by SQUID magnetometry. Computational studies establish Mulliken spin densities for the uranium centers ranging from 3.005 to 3.027 (B3LYP), consistent for uranium-chalcogenide bonds that are primarily ionic in nature, with a small covalent contribution. The reactivity of 2-4 toward carbon disulfide was also investigated and showed reversible CS2 insertion into the U(III)-E bond, forming Tp*2U(κ(2)-S2CEPh) (E = S (5), Se (6), Te (7)). Compound 5 was characterized crystallographically.

Processing and fabrication of mixed uranium/refractory metal carbide fuels with liquid-phase sintering

NASA Astrophysics Data System (ADS)

Knight, Travis W.; Anghaie, Samim

2002-11-01

Optimization of powder processing techniques were sought for the fabrication of single-phase, solid-solution mixed uranium/refractory metal carbide nuclear fuels - namely (U, Zr, Nb)C. These advanced, ultra-high temperature nuclear fuels have great potential for improved performance over graphite matrix, dispersed fuels tested in the Rover/NERVA program of the 1960s and early 1970s. Hypostoichiometric fuel samples with carbon-to-metal ratios of 0.98, uranium metal mole fractions of 5% and 10%, and porosities less than 5% were fabricated. These qualities should provide for the longest life and highest performance capability for these fuels. Study and optimization of processing methods were necessary to provide the quality assurance of samples for meaningful testing and assessment of performance for nuclear thermal propulsion applications. The processing parameters and benefits of enhanced sintering by uranium carbide liquid-phase sintering were established for the rapid and effective consolidation and formation of a solid-solution mixed carbide nuclear fuel.

Distribution of uranium in the Bisbee district, Cochise County, Arizona

USGS Publications Warehouse

Wallace, Stewart R.

1956-01-01

The Bisbee district has been an important source of copper for many years, and substantial amounts of lead and zinc ore and minor amounts of manganese ore have been mined during certain periods. The copper deposits occur both as low-grade disseminated ore in the Sacramento Hill stock and as massive sulfide (and secondary oxide and carbonate) replacement bodies in Paleozoic limestones that are intruded by the stock and related igneous bodies. The lead-zinc production has come almost entirely from limestone replacement bodies. The disseminated ore exhibits no anomalous radioactivity, and samples from the Lavender pit contain from 0.002 to less than 0.001 percent equivalent uranium. The limestone replacement ores are distinctly radioactive and stoping areas can be readily distinguished from from unmineralized ground on the basis of radioactivity alone. The equivalent uranium content of the copper replacement ores ranges from 0.002 to 0.014 percent and averages about 0.005 percent; the lead-zinc replacement ores average more than 0.007 percent equivalent uranium. Most of the uranium in the copper ores of the district is retained in the smelter slag of a residual concentrate; the slag contains about 0.009 percent equivalent uranium. Uranium carried off each day by acid mine drainage is roughly equal to 1 percent of that being added to the slag dump. Although the total amount of uranium in the district is large, no minable concentrations of ore-grade material are known; samples of relatively high-grade material represent only small fractions of tons at any one locality.

Vapor core propulsion reactors

NASA Technical Reports Server (NTRS)

Diaz, Nils J.

1991-01-01

Many research issues were addressed. For example, it became obvious that uranium tetrafluoride (UF4) is a most preferred fuel over uranium hexafluoride (UF6). UF4 has a very attractive vaporization point (1 atm at 1800 K). Materials compatible with UF4 were looked at, like tungsten, molybdenum, rhenium, carbon. It was found that in the molten state, UF4 and uranium attacked most everything, but in the vapor state they are not that bad. Compatible materials were identified for both the liquid and vapor states. A series of analyses were established to determine how the cavity should be designed. A series of experiments were performed to determine the properties of the fluid, including enhancement of the electrical conductivity of the system. CFD's and experimental programs are available that deal with most of the major issues.

Some observations on uranium carbide alloy/tungsten compatibility

NASA Technical Reports Server (NTRS)

Phillips, W. M.

1972-01-01

Chemical compatibility between both pure and thoriated tungsten and uranium carbide alloys was studied at 1800 C for up to 3300 hours. Alloying with zirconium carbide appeared to widen the homogeneity range of uranium carbide, making additional carbon available for reaction with the tungsten. Reaction layers were formed both by vapor phase reaction and by physical contact, producing either or both UWC2 and W2C, dependent upon the phases present in the starting fuel alloy. Formation of UWC2 results in slow growth of the reaction layer with time, while W2C reaction layers grow rapidly, allowing equilibrium to be reached in less than 2500 hours at 1800 C. The presence of a thermal gradient had no effect on the reactions observed nor did the presence of thoria in the tungsten clad.

Some observations on uranium carbide alloy/tungsten compatibility.

NASA Technical Reports Server (NTRS)

Phillips, W. M.

1972-01-01

Results of chemical compatibility tests between both pure tungsten and thoriated tungsten run at 1800 C for up to 3300 hours with uranium carbide alloys. Alloying with zirconium carbide appeared to widen the homogeneity range of uranium carbide, making additional carbon available for reaction with the tungsten. Reaction layers were formed both by vapor phase reaction and by physical contact, producing either or both UWC2 and W2C, depending upon the phases present in the starting fuel alloy. Formation of UWC2 results in slow growth of the reaction layer with time, while W2C reaction layers grow rapidly, allowing equilibrium to be reached in less than 2500 hours at 1800 C. Neither the presence of a thermal gradient nor the presence of thoria in the tungsten clad affect the reactions observed.

Process for converting magnesium fluoride to calcium fluoride

DOEpatents

Kreuzmann, A.B.; Palmer, D.A.

1984-12-21

This invention is a process for the conversion of magnesium fluoride to calcium fluoride whereby magnesium fluoride is decomposed by heating in the presence of calcium carbonate, calcium oxide or calcium hydroxide. Magnesium fluoride is a by-product of the reduction of uranium tetrafluoride to form uranium metal and has no known commercial use, thus its production creates a significant storage problem. The advantage of this invention is that the quality of calcium fluoride produced is sufficient to be used in the industrial manufacture of anhydrous hydrogen fluoride, steel mill flux or ceramic applications.

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.

Formation of uranium and cerium nitrides by the reaction of carbides with NH 3 and N 2/H 2 stream

NASA Astrophysics Data System (ADS)

Nakagawa, Takashi; Matsuoka, Hirotaka; Sawa, Masaji; Hirota, Masayuki; Miyake, Masanobu; Katsura, Masahiro

1997-08-01

UC or CeC 2 were converted into U 2N 3 or CeN by the use of NH 3 or an N 2/H 2 gas mixture. A stream of NH 3 works not only as a nitriding agent but also as a carbon clearing agent due to its high nitriding and hydriding activities. When the carbide is converted into nitride, carbon is liberated. Some experiments were performed in order to examine the role of the carbon activity of carbon materials (amorphous carbon or graphite) in the formation of CH 4.

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.

Potential for U sequestration with select minerals and sediments via base treatment.

PubMed

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

2018-06-13

Temporary base treatment is a potential remediation technique for heavy metals through adsorption, precipitation, and co-precipitation with minerals. Manipulation of pH with ammonia gas injection may be especially useful for vadose zone environments as it does not require addition of liquids that would increase the flux towards groundwater. In this research, we conducted laboratory batch experiments to evaluate the changes in uranium mobility and mineral dissolution with base treatments including sodium hydroxide, ammonium hydroxide, and ammonia gas. Our data show that partitioning of uranium to the solid phase increases by several orders of magnitude following base treatment in the presence of different minerals and natural sediments from the Hanford site. The presence of dissolved calcium and carbonate play an important role in precipitation and co-precipitation of uranium at elevated pH. In addition, significant incongruent dissolution of bulk mineral phases occurs and likely leads to precipitation of secondary mineral phases. These secondary phases may remove uranium via adsorption, precipitation, and co-precipitation processes and may coat uranium phases with low solubility minerals as the pH returns to natural conditions. Copyright © 2018 Elsevier Ltd. All rights reserved.

Leaching under Oxygen Pressure with Carbonate Solution Reduction by Hydrogen; LIXIVIATION OXYDANTE DES PECHBLENDES ET PRECIPITATION DE L'URANIUM PAR L'HYDROGENE. APPLICATION AUX MINERAIS PAUVRES FRANCAIS

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

Balaceanu, J.C.; Coussemant, F.; Mouret, P.

1959-10-31

A study was made of the basic characteristics of the leaching with carbonate solution under oxygen pressure and of the catalytic hydrogen reduction of low-grade French ores. Pure U/sub 3/O/sub 8/ was used in the investigations on leaching. The effects of oxygen pressure, temperature, initial surface of the oxide, surfuce during the course of the reaction, and concentration of the carbonate solution were determined. It was shown that the heterogeneous reactions involve a constant surface and two steps. A pilot plant experiment was made on a number of low-grade French ores. With ores the leaching is not sensitive to oxygenmore » pressure. Dilute solutions of sodium uranyl carbonate are obtained from the leaching. The uranium can be precipitated as an oxide of a lower valent state by catalytic reduction with hydrogen. The study of this step was made on pure solutions of sodium uranyl carbonate in the presence of nickel and platinum catalysts. The reaction is strongly modified by the presence of even low concentrations of sodium bicarbonate. The reaction velocity increases with hydrogen pressure up to 5 atm, but then becomes independent of the pressure. The precipitation is accelerated by an increase in temperature. (J.S.R.)« less

Infrared Lasers in Chemistry.

ERIC Educational Resources Information Center

John, Phillip

1982-01-01

Selected infrared laser chemistry topics are discussed including carbon dioxide lasers, infrared quanta and molecules, laser-induced chemistry, structural isomerization (laser purification, sensitized reactions, and dielectric breakdown), and fundamental principles of laser isotope separation, focusing on uranium isotope separation. (JN)

Chemistry Notes.

ERIC Educational Resources Information Center

School Science Review, 1983

1983-01-01

Presents chemistry experiments, laboratory procedures, demonstrations, and classroom materials/activities. These include: experiments on colloids, processing of uranium ore, action of heat on carbonates; color test for phenols and aromatic amines; solvent properties of non-electrolytes; stereoscopic applications/methods; a valency balance;…

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

PubMed

Schierz, A; Zänker, H

2009-04-01

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

Impurity characterization of magnesium diuranate using simultaneous TG-DTA-FTIR measurements

NASA Astrophysics Data System (ADS)

Raje, Naina; Ghonge, Darshana K.; Hemantha Rao, G. V. S.; Reddy, A. V. R.

2013-05-01

Current studies describe the application of simultaneous thermogravimetry-differential thermal analysis - evolved gas analysis techniques for the compositional characterization of magnesium diuranate (MDU) with respect to the impurities present in the matrix. The stoichiometric composition of MDU was identified as MgU2O7ṡ3H2O. Presence of carbonate and sulphate as impurities in the matrix was confirmed through the evolved gas analysis using Fourier Transformation Infrared Spectrometry detection. Carbon and magnesium hydroxide content present as impurities in magnesium diuranate have been determined quantitatively using TG and FTIR techniques and the results are in good agreement. Powder X-ray diffraction analysis of magnesium diuranate suggests the presence of magnesium hydroxide as impurity in the matrix. Also these studies confirm the formation of magnesium uranate, uranium sesquioxide and uranium dioxide above 1000 °C, due to the decomposition of magnesium diuranate.

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.

Summary of the mineralogy of the Colorado Plateau uranium ores

USGS Publications Warehouse

Weeks, Alice D.; Coleman, Robert Griffin; Thompson, Mary E.

1956-01-01

In the Colorado Plateau uranium has been produced chiefly from very shallow mines in carnotite ores (oxidized vanadiferous uranium ores) until recent deeper mining penetrated black unoxidized ores in water-saturated rocks and extensive exploration has discovered many deposits of low to nonvanadiferous ores. The uranium ores include a wide range from highly vanadiferous and from as much as one percent to a trace of copper, and contain a small amount of iron and traces of lead, zinc, molybdenum, cobalt, nickel, silver, manganese, and other metals. Recent investigation indicates that the carnotite ores have been derived by progressive oxidation of primary (unoxidized) black ores that contain low-valent uranium and vanadium oxides and silicates. The uranium minerals, uraninite and coffinite, are associated with coalified wood or other carbonaceous material. The vanadium minerals, chiefly montroseite, roscoelite, and other vanadium silicates, occur in the interstices of the sandstone and in siltstone and clay pellets as well as associated with fossil wood. Calcite, dolomite, barite and minor amounts of sulfides, arsenides, and selenides occur in the unoxidized ore. Partially oxidized vanadiferous ore is blue black, purplish brown, or greenish black in contrast to the black or dark gray unoxidized ore. Vanadium combines with uranium to form rauvite. The excess vanadium is present in corvusite, fernandinite, melanovanadite and many other quadrivalent and quinquevalent vanadium minerals as well as in vanadium silicates. Pyrite and part or all of the calcite are replaced by iron oxides and gypsum. In oxidized vanadiferous uranium ores the uranium is fixed in the relatively insoluble minerals carnotite and tyuyamunite, and the excess vanadium commonly combines with one or more of the following: calcium, sodium, potassium, magnesium, aluminum, iron, copper, manganese, or barium, or rarely it forms the hydrated pentoxide. The relatively stable vanadium silicates are little affected by oxidation. The unoxidized nonvanadiferous ores contain uraninite and coffinite in close association with coalified wood and iron and copper sulfides, and traces of many other sulfides, arsenides and selenides. The oxidized nonvanadiferous ores differ from the vanadiferous ores because, in the absence of vanadium to complex the uranium, a great variety of secondary yellow and greenish-yellow uranyl minerals are formed. The uranyl sulfates and carbonates are more common than the oxides, phosphates, arsenates, and silicates. Because the sulfates and carbonates are much less stable that carnotite, the oxidized nonvanadiferous ores occure only as halos around cores of unoxidized ore and do not form large oxidized deposits close to the surface of the ground as carnotite ores. Oxidation has taken place since the lowering of the water table in the present erosion cycle. Because of local structures and the highly lenticular character of the fluviatile host rocks perched water tables and water-saturated lenses of sandstone are common high above the regional water table. Unoxidized ore has been preserved in these water-saturated rocks and the boundary between oxidized and unoxidized ore is very irregular.

Uranium mineralization and unconformities: how do they correlate? - A look beyond the classic unconformity-type deposit model?

NASA Astrophysics Data System (ADS)

Markwitz, Vanessa; Porwal, Alok; Campbell McCuaig, T.; Kreuzer, Oliver P.

2010-05-01

Uranium deposits are usually classified based on the characteristics of their host rocks and geological environments (Dahlkamp, 1993; OECD/NEA Red Book and IAEA, 2000; Cuney, 2009). The traditional unconformity-related deposit types are the most economical deposits in the world, with the highest grades amongst all uranium deposit types. In order to predict undiscovered uranium deposits, there is a need to understand the spatial association of uranium mineralization with structures and unconformities. Hydrothermal uranium deposits develop by uranium enriched fluids from source rocks, transported along permeable pathways to their depositional environment. Unconformities are not only separating competent from incompetent sequences, but provide the physico-chemical gradient in the depositional environment. They acted as important fluid flow pathways for uranium to migrate not only for surface-derived oxygenated fluids, but also for high oxidized metamorphic and magmatic fluids, dominated by their geological environment in which the unconformities occur. We have carried out comprehensive empirical spatial analyses of various types of uranium deposits in Australia, and first results indicate that there is a strong spatial correlation between unconformities and uranium deposits, not only for traditional unconformity-related deposits but also for other styles. As a start we analysed uranium deposits in Queensland and in particular Proterozoic metasomatic-related deposits in the Mount Isa Inlier and Late Carboniferous to Early Permian volcanic-hosted uranium occurrences in Georgetown and Charters Towers Regions show strong spatial associations with contemporary and older unconformities. The Georgetown Inlier in northern Queensland consists of a diverse range of rocks, including Proterozoic and early Palaeozoic metamorphic rocks and granites and late Palaeozoic volcanic rocks and related granites. Uranium-molybdenum (+/- fluorine) mineralization in the Georgetown inlier varies from strata- to structure-bound and occurs above regional unconformities. The Proterozoic basins in the Mount Isa Inlier rest unconformably on Palaeoproterozoic basement accompanied by volcanic and igneous rocks, which were deformed and metamorphosed in the Mesoproterozoic. Uranium occurrences in the Western Succession of Mount Isa are either hosted in clastic metasediments or mafic volcanics that belong to the Palaeoproterozoic Eastern Creek Volcanics. Uranium and vanadium mineralization occur in metasomatised and hematite-magnetite-carbonate alteration zones, bounded by major faults and regional unconformities. The results of this study highlight the importance of unconformities in uranium minerals systems as possible fluid pathways and/or surfaces of physico-chemical contrast that could have facilitated the precipitation of uranium, not only in classical unconformity style uranium deposits but in several other styles of uranium mineralization as well. References Cuney, M., 2009. The extreme diversity of uranium deposits. Mineralium Deposita, 44, 3-9. Dahlkamp, F. J., 1993. Uranium ore deposits. Springer, Berlin, p 460. OECD / NEA Red Book & IAEA, 2000. Uranium 1999: Resources, Production and Demand. OECD Nuclear Energy Agency and International Atomic Energy Agency, Paris.

Evaluating Uranium Isotopes in Carbonates and Implications for Reconstructing Marine Paleoredox Conditions

NASA Astrophysics Data System (ADS)

Aharony, Ofer; Gubser, Steven S.; Maldacena, Juan; Ooguri, Hirosi; Oz, Yaron

2016-12-01

Uranium isotope ratios (238U/235U, reported as δ238U) have emerged as a promising proxy for marine redox conditions. This proxy relies on isotopic fractionation that occurs during reduction of soluble U(VI) to insoluble U(IV), wherein 238U is preferentially reduced and incorporated via authigenic processes into anoxic sediments, leaving the residual seawater U and resulting carbonates 238U-depleted. Because carbonates are generally well preserved in the rock record, they are useful archives of seawater chemistry throughout Earth history, including δ238U. In principle, the long residence time of U in the ocean permits quantitative inferences of global paleoredox conditions using carbonate δ238U records. To assess the performance of the proxy, we compile all published δ238U measurements from carbonate rocks and sediments, which span the Cryogenian through the modern. The potential for δ238U to serve as a quantitative, global paleoredox proxy is supported by reproducible trends across depositional environments and paleogeographic regions in the Cryogenian non-glacial interlude and across the Permian-Triassic and Triassic-Jurassic boundaries, although carbonates deposited in deeper waters (>200 m) may be subject to local effects. Using a box model, we highlight the key levers associated with seawater δ238U and the timescales of such variability. Like all sedimentary archives, carbonate rocks are prone to diagenetic alteration and additional controls that cause δ238U in carbonates to deviate from global seawater values. Specifically, the U isotopic composition of carbonate sediments can be influenced by diagenesis, carbonate mineralogy, dolomitization, detrital input, local organic matter deposition, and pore water chemistry. We evaluate indicators of these factors in the context of a diagenetic model to assess the sensitivity of carbonate δ238U to local syndepositional or post-depositional processes. These results improve the framework for interpreting carbonate δ238U records and reconstructing past changes in the oxygenation of the Earth's oceans.

Dissolution of Uranium(IV) Oxide in Solutions of Ammonium Carbonate and Hydrogen Peroxide

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

Smith, Steven C.; Peper, Shane M.; Douglas, Matthew

2009-09-12

Understanding the dissolution characteristics of uranium oxides is of fundamental scientific interest. Bench scale experiments were conducted to determine the optimal dissolution parameters of uranium(IV) oxide (UO2) powder in solutions of ammonium carbonate [(NH4)2CO3] and hydrogen peroxide (H2O2). Experimental parameters included variable peroxide and carbonate concentrations, and temperature. Results indicate the dissolution rate of UO2 in 1 M (NH4)2CO3 increases linearly with peroxide concentration ranging from 0.05 – 2 M (1:1 to 40:1 mol ratio H2O2:U), with no apparent maximum rate reached under the limited conditions used in our study. Temperature ranging studies show the dissolution rate of UO2 inmore » 1 M (NH4)2CO3 and 0.1 M H2O2 (2:1 mol ratio H2O2:U) increases linearly from 15 °C to 60 °C, again with no apparent maximum rate reached. Dissolution of UO2 in solutions with constant [H2O2] and [(NH4)2CO3] ranging from 0.5 to 2 M showed no difference in rate; however dissolution was significantly reduced in 0.05 M (NH4)2CO3 solution. The results of this study demonstrate the influence of [H2O2], [(NH4)2CO3], and temperature on the dissolution of UO2 in peroxide-containing (NH4)2CO3 solutions. Future studies are planned to elucidate the solution and solid state complexes in these systems.« less

Development of Novel Sorbents for Uranium Extraction from Seawater

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

Lin, Wenbin; Taylor-Pashow, Kathryn

2014-01-08

As the uranium resource in terrestrial ores is limited, it is difficult to ensure a long-term sustainable nuclear energy technology. The oceans contain approximately 4.5 billion tons of uranium, which is one thousand times the amount of uranium in terrestrial ores. Development of technologies to recover the uranium from seawater would greatly improve the uranium resource availability, sustaining the fuel supply for nuclear energy. Several methods have been previously evaluated including solvent extraction, ion exchange, flotation, biomass collection, and adsorption; however, none have been found to be suitable for reasons such as cost effectiveness, long term stability, and selectivity. Recentmore » research has focused on the amidoxime functional group as a promising candidate for uranium sorption. Polymer beads and fibers have been functionalized with amidoxime functional groups, and uranium adsorption capacities as high as 1.5 g U/kg adsorbent have recently been reported with these types of materials. As uranium concentration in seawater is only ~3 ppb, great improvements to uranium collection systems must be made in order to make uranium extraction from seawater economically feasible. This proposed research intends to develop transformative technologies for economic uranium extraction from seawater. The Lin group will design advanced porous supports by taking advantage of recent breakthroughs in nanoscience and nanotechnology and incorporate high densities of well-designed chelators into such nanoporous supports to allow selective and efficient binding of uranyl ions from seawater. Several classes of nanoporous materials, including mesoporous silica nanoparticles (MSNs), mesoporous carbon nanoparticles (MCNs), meta-organic frameworks (MOFs), and covalent-organic frameworks (COFs), will be synthesized. Selective uranium-binding liagnds such as amidoxime will be incorporated into the nanoporous materials to afford a new generation of sorbent materials that will be evaluated for their uranium extraction efficiency. The initial testing of these materials for uranium binding will be carried out in the Lin group, but more detailed sorption studies will be carried out by Dr. Taylor-Pashow of Savannah River National Laboratory in order to obtain quantitative uranyl sorption selectivity and kinetics data for the proposed materials. The proposed nanostructured sorbent materials are expected to have higher binding capacities, enhanced extraction kinetics, optimal stripping efficiency for uranyl ions, and enhanced mechanical and chemical stabilities. This transformative research will significantly impact uranium extraction from seawater as well as benefit DOE’s efforts on environmental remediation by developing new materials and providing knowledge for enriching and sequestering ultralow concentrations of other metals.« less

Oxidative Uranium Release from Anoxic Sediments under Diffusion-Limited Conditions.

PubMed

Bone, Sharon E; Cahill, Melanie R; Jones, Morris E; Fendorf, Scott; Davis, James; Williams, Kenneth H; Bargar, John R

2017-10-03

Uranium (U) contamination occurs as a result of mining and ore processing; often in alluvial aquifers that contain organic-rich, reduced sediments that accumulate tetravalent U, U(IV). Uranium(IV) is sparingly soluble, but may be mobilized upon exposure to nitrate (NO 3 - ) and oxygen (O 2 ), which become elevated in groundwater due to seasonal fluctuations in the water table. The extent to which oxidative U mobilization can occur depends upon the transport properties of the sediments, the rate of U(IV) oxidation, and the availability of inorganic reductants and organic electron donors that consume oxidants. We investigated the processes governing U release upon exposure of reduced sediments to artificial groundwater containing O 2 or NO 3 - under diffusion-limited conditions. Little U was mobilized during the 85-day reaction, despite rapid diffusion of groundwater within the sediments and the presence of nonuraninite U(IV) species. The production of ferrous iron and sulfide in conjunction with rapid oxidant consumption suggested that the sediments harbored large concentrations of bioavailable organic carbon that fueled anaerobic microbial respiration and stabilized U(IV). Our results suggest that seasonal influxes of O 2 and NO 3 - may cause only localized mobilization of U without leading to export of U from the reducing sediments when ample organic carbon is present.

Comparison of high-density carbon implosions in unlined uranium versus gold hohlraums

NASA Astrophysics Data System (ADS)

Dewald, Eduard; Meezan, Nathan; Tommasini, Riccardo; Khan, Shahab; MacKinnon, Andrew; Berzak Hopkins, Laura; Divol, Laurent; Lepape, Sebastien; Moore, Alastair; Schneider, Marilyn; Pak, Arthur; Nikroo, Abbas; Landen, Otto

2016-10-01

In Inertial Confinement Fusion (ICF) implosions, laser energy is converted to x-ray radiation in hohlraums with High-Z walls. At radiation temperatures near 300 eV relevant for ICF experiments, the radiative losses in heating the wall are lower for U than for Au hohlraums. Furthermore, the intensity of the ``M-band'' x-rays with photon energies h ν >1.8 keV is lower for uranium, allowing for reduced capsule dopant concentrations employed to minimize inner ablator preheat and hence keep favorable fuel/ablator interface Atwood numbers. This in turn improves the ablator rocket efficiency and reduces the risk of polluting the hot-spot with emissive dopant material. The first uranium vacuum hohlraum experiments on the National Ignition Facility (NIF) with undoped high-density carbon (HDC, or diamond) capsules have demonstrated 30% lower ``M-band'' intensity relative to Au, resulting in lower inflight ablator thickness due to reduced preheat. In addition, fusion neutron yields are 2x higher in U than in Au hohlraums for D2-gas filled capsule implosions at ICF relevant velocities of 380 +/-20 km/s. These results have led the NIF ICF implosions to routinely employ U hohlraums. Prepared by LLNL under Contract DE-AC52-07NA27344.

Impact of natural organic matter on uranium transport through saturated geologic materials: from molecular to column scale.

PubMed

Yang, Yu; Saiers, James E; Xu, Na; Minasian, Stefan G; Tyliszczak, Tolek; Kozimor, Stosh A; Shuh, David K; Barnett, Mark O

2012-06-05

The risk stemming from human exposure to actinides via the groundwater track has motivated numerous studies on the transport of radionuclides within geologic environments; however, the effects of waterborne organic matter on radionuclide mobility are still poorly understood. In this study, we compared the abilities of three humic acids (HAs) (obtained through sequential extraction of a peat soil) to cotransport hexavalent uranium (U) within water-saturated sand columns. Relative breakthrough concentrations of U measured upon elution of 18 pore volumes increased from undetectable levels (<0.001) in an experiment without HAs to 0.17 to 0.55 in experiments with HAs. The strength of the HA effect on U mobility was positively correlated with the hydrophobicity of organic matter and NMR-detected content of alkyl carbon, which indicates the possible importance of hydrophobic organic matter in facilitating U transport. Carbon and uranium elemental maps collected with a scanning transmission X-ray microscope (STXM) revealed uneven microscale distribution of U. Such molecular- and column-scale data provide evidence for a critical role of hydrophobic organic matter in the association and cotransport of U by HAs. Therefore, evaluations of radionuclide transport within subsurface environments should consider the chemical characteristics of waterborne organic substances, especially hydrophobic organic matter.

Epithermal uranium deposits in a volcanogenic context: the example of Nopal 1 deposit, Sierra de Pena Blanca, Mexico

NASA Astrophysics Data System (ADS)

Calas, G.; Angiboust, S.; Fayek, M.; Camacho, A.; Allard, T.; Agrinier, P.

2009-12-01

The Peña Blanca molybdenum-uranium field (Chihuahua, Mexico) exhibits over 100 airborne anomalies hosted in tertiary ignimbritic ash-flow tuffs (44 Ma) overlying the Pozos conglomerate and a sequence of Cretaceous carbonate rocks. Uranium occurrences are associated with breccia zones at the intersection of two or more fault systems. Periodic reactivation of these structures associated with Basin and Range and Rio Grande tectonic events resulted in the mobilization of U and other elements by meteoric fluids heated by geothermal activity. Trace element geochemistry (U, Th, REE) provides evidence for local mobilization of uranium under oxidizing conditions. In addition, O- and H-isotope geochemistry of kaolinite, smectite, opal and calcite suggests that argillic alteration proceeded at shallow depth with meteoric water at 25-75 °C. Focussed along breccia zones, fluids precipitated several generations of pyrite and uraninite together with kaolinite, as in the Nopal 1 mine, indicating that mineralization and hydrothermal alteration of volcanic tuffs are contemporaneous. Low δ34S values (~ -24.5 ‰) of pyrites intimately associated with uraninite suggest that the reducing conditions at the origin of the U-mineralization arise from biological activity. Later, the uplift of Sierra Pena Blanca resulted in oxidation and remobilization of uranium, as confirmed by the spatial distribution of radiation-induced defect centers in kaolinites. These data show that tectonism and biogenic reducing conditions can play a major role in the formation and remobilization of uranium in epithermal deposits. By comparison with the other uranium deposits at Sierra Pena Blanca and nearby Sierra de Gomez, Nopal 1 deposit is one of the few deposits having retained a reduced uranium mineralization.

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.

A study of contaminated soils near Crucea-Botus, ana uranium mine (East Carpathians, Romania): metal distribution and partitioning of natural actinides with implications for vegetation uptake

NASA Astrophysics Data System (ADS)

Petrescu, L.; Bilal, E.

2012-04-01

Between 1962 and 2009, National Company of Uranium - CNU, the former Romanian Rare Metals Mining Company, mined over 1,200,000 tones of pitchblende ore in the East Carpathians (Crucea-Botušana area, Bistrita Mountains). The exploration and mining facilities include 32 adits, situated between 780 and 1040 m above sea level. Radioactive waste resulted from mining are disposed next to the mining facilities. Mine dumps (32) cover an area of 364,000 square meters and consist of waste rock (rocks with sub-economic mineralization) and gangue minerals. Older dumps (18) have been already naturally reclaimed by forest vegetation, which played an important role in stabilizing the waste dump cover and in slowing down the uranium migration processes. The soils samples have been collected from different mine dumps in the Crucea-Botušana uranium deposit, mainly from 1, 4, 5, 6, 8, 9, 1/30 and 950 mine waste galleries. Soil samples were collected from the upper part and slope at each mine dump, from the vegetation root zones. Total uranium concentration in soils collected from Crucea-Botušana site ranged from 6.10 to 680.70 ppm, with a mean of 52.48 ppm (dry wt.). Total thorium varies between 7.70 and 115.30 ppm (dry wt.). This indicates that the adsorption of the radioactive elements by the soils is high and variable, influenced by the ore dump - sample relationship. The sequential extraction has emphasized the fact that the uranium is associated with all the mineral fractions present in the soil samples. A great percentage of U can be found in the carbonate (21.77%), organic (15.04%) and oxides fractions (15.88%) - in accordance with the high absorbed/adsorbed properties of this element. The percentage of uranium detected in the exchangeable fraction is rather small - 2.16%. It is also to be expected that the uranium should be irreversible adsorbed by the organic matter and by the clay minerals due to its ionic radius and to its positive charge. The fact that 21.77% of the total uranium can be found in the specifically absorbed and carbonate bound fraction, indicated the important role played by the carbonates in the retention of U; one the other hand this fraction is liable to release the uranium if the pH should happen to change. Thorium appear in high-enough concentration in the soil is scarcely available because 70.29% is present in residual fraction, and about 21.78% in the crystalline iron oxides occluded fraction and organically and secondary sulfide bound fraction. This is certainly due to the fact that this naturally occurring radionuclide can be associated with relatively insoluble mineral phases like alumino-silicates and refractory oxides. Its association with the organic matter (10.93%) suggests that it can form soluble organic complexes that can facilitate its removal by the stream waters. Grounded on these results, we were able to prove that the examined mine dumps can represent an impact on the environment, which constitute an argument in favor of the initiation of a program of remedying the quality of the environment from this mining zone. Although from our research it resulted that the natural actinides does not concentrate in the exchangeable fraction (Th) or it concentrates very little in it (U), the isolation of the mineral fraction of soil rich in U and Th helps us in the future identification of the links between the bioavailability and the pedogenesis, connections which control the cycle of the radioactive metals.

Adsorbent Alkali Conditioning for Uranium Adsorption from Seawater. Adsorbent Performance and Technology Cost Evaluation

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

Tsouris, Costas; Mayes, Richard T.; Janke, Christopher James

The Fuel Resources program of the Fuel Cycle Research and Development program of the Office of Nuclear Energy (NE) is focused on identifying and implementing actions to assure that nuclear fuel resources are available in the United States. An immense source of uranium is seawater, which contains an estimated amount of 4.5 billion tonnes of dissolved uranium. This unconventional resource 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 uranium recovery from seawater.more » The goal is to develop advanced adsorbents to reduce the seawater uranium recovery technology cost and uncertainties. Under this program, Oak Ridge National Laboratory (ORNL) has developed a new amidoxime-based adsorbent of high surface area, which tripled the uranium capacity of leading Japanese adsorbents. Parallel efforts have been focused on the optimization of the physicochemical and operating parameters used during the preparation of the adsorbent for deployment. A set of parameters that need to be optimized are related to the conditioning of the adsorbent with alkali solution, which is necessary prior to adsorbent deployment. Previous work indicated that alkali-conditioning parameters significantly affect the adsorbent performance. Initiated in 2014, this study had as a goal to determine optimal parameters such as base type and concentration, temperature, and duration of conditioning that maximize the uranium adsorption performance of amidoxime functionalized adsorbent, while keeping the cost of uranium production low. After base-treatment at various conditions, samples of adsorbent developed at ORNL were tested in this study with batch simulated seawater solution of 8-ppm uranium concentration, batch seawater spiked with uranium nitrate at 75-100 ppb uranium, and continuous-flow natural seawater at the Pacific Northwest National Laboratory (PNNL). Fourier Transform Infrared (FTIR) spectroscopy, Nuclear Magnetic Resonance (NMR) spectroscopy, Scanning Electron Microscopy (SEM), and elemental analysis were used to characterize the adsorbent at different stages of adsorbent preparation and treatment. The study can be divided into two parts: (A) investigation of optimal parameters for KOH adsorbent conditioning and (B) investigation of other possible agents for alkali conditioning, including cost analysis on the basis of uranium production. In the first part of the study, tests with simulated seawater containing 8 ppm uranium showed that the uranium adsorption capacity increased with an increase in the KOH concentration and conditioning time and temperature at each of the KOH concentrations used. FTIR and solid state NMR studies indicated that KOH conditioning converts the amidoxime functional groups into more hydrophilic carboxylate. The longer the KOH conditioning time, up to three hours, the higher was the loading capacity from the simulated seawater solution which is composed of only uranyl, sodium, chloride, and carbonate ions. Marine testing with natural seawater, on the other hand, showed that the uranium adsorption capacity of the adsorbent increased with KOH conditioning temperature, and gradually decreased with increasing KOH conditioning time from one hour to three hours at 80 C. This behavior is due to the conversion of amidoxime to carboxylate. The carboxylate groups are needed to increase the hydrophilicity of the adsorbent; however, conversion of a significant amount of amidoxime to carboxylate leads to loss in selectivity toward uranyl ions. Thus, there is an optimum KOH conditioning time for each temperature at which an optimum ratio between amidoxime and carboxylate is reached. For the case of base conditioning with 0.44 M KOH at 80 C, the optimal conditioning time is 1 hour, with respect to the highest uranium loading capacity from natural seawater. Uptake of other metal ions such as V, Fe, and Cu follows the same trend as that of uranium. Also, the uptake of Ca, Mg, and Zn ions increased with increasing KOH conditioning time, probably due to formation of more carboxylates, which leads to conversion of uranium-selective binding sites to less selective sites. In the second part of the study, inorganic based reagents such as sodium hydroxide (NaOH), sodium carbonate (Na 2CO 3), cesium hydroxide (CsOH), as well as organic based reagents such as ammonium hydroxide (AOH), tetramethylammonium hydroxide (TMAOH), tetraethylammonium hydroxide (TEAOH), triethylmethylammonium hydroxide (TEMAOH), tetrapropylammonium hydroxide (TPAOH) and tetrabutylammonium hydroxide (TBAOH), in addition to KOH, were used for alkaline conditioning. NaOH has emerged as a better reagent for alkaline conditioning of amidoxime-based adsorbent because of higher uranium uptake capacity, higher uranium uptake selectivity ...« less

Uranium in Surface Waters and Sediments Affected by Historical Mining in the Denver West 1:100,000 Quadrangle, Colorado

USGS Publications Warehouse

Zielinski, Robert A.; Otton, James K.; Schumann, R. Randall; Wirt, Laurie

2008-01-01

Geochemical sampling of 82 stream waters and 87 stream sediments within mountainous areas immediately west of Denver, Colorado, was conducted by the U.S. Geological Survey in October 1994. The primary purpose was to evaluate regionally the effects of geology and past mining on the concentration and distribution of uranium. The study area contains uranium- and thorium-rich bedrock, numerous noneconomic occurrences of uranium minerals, and several uranium deposits of variable size and production history. During the sampling period, local streams had low discharge and were more susceptible to uranium-bearing acid drainage originating from historical mines of base- and precious-metal sulfides. Results indicated that the spatial distribution of Precambrian granites and metamorphic rocks strongly influences the concentration of uranium in stream sediments. Within-stream transport increases the dispersion of uranium- and thorium rich mineral grains derived primarily from granitic source rocks. Dissolved uranium occurs predominantly as uranyl carbonate complexes, and concentrations ranged from less than 1 to 65 micrograms per liter. Most values were less than 5 micrograms per liter, which is less than the current drinking water standard of 30 micrograms per liter and much less than locally applied aquatic-life toxicity standards of several hundred micrograms per liter. In local streams that are affected by uranium-bearing acid mine drainage, dissolved uranium is moderated by dilution and sorptive uptake by stream sediments. Sorbents include mineral alteration products and chemical precipitates of iron- and aluminum-oxyhydroxides, which form where acid drainage enters streams and is neutralized. Suspended uranium is relatively abundant in some stream segments affected by nearby acid drainage, which likely represents mobilization of these chemical precipitates. The 234U/238U activity ratio of acid drainage (0.95-1.0) is distinct from that of local surface waters (more than 1.05), and this distinctive isotopic composition may be preserved in iron-oxyhydroxide precipitates of acid drainage origin. The study area includes a particularly large vein-type uranium deposit (Schwartzwalder mine) with past uranium production. Stream water and sediment collected downstream from the mine's surface operations have locally anomalous concentrations of uranium. Fine-grained sediments downstream from the mine contain rare minute particles (10-20 micrometers) of uraninite, which is unstable in a stream environment and thus probably of recent origin related to mining. Additional rare particles of very fine grained (less than 5 micrometer) barite likely entered the stream as discharge from settling ponds in which barite precipitation was formerly used to scavenge dissolved radium from mine effluent.

Preliminary report on uranium deposits in the Miller Hill area, Carbon County, Wyoming

USGS Publications Warehouse

Love, J.D.

1953-01-01

A sequence of radioactive rocks of Miocene (?) age, the Browns Park formation, in the Miller Hill area of southern Wyoming is more than 1,000 feet thick. The formation crops out in an area of approximately 600 square miles, and consists of a basal conglomerate, tuffs, tuffaceous limy sandstones, and thin persistent radioactive algal limestones. Uranium is concentrated in both algal limestones and in tuffaceous limy sandstones. The uranium is believed to have been deposited. at least in part with the sediments, rather than to have come in at a later date. The highest uranium values were found in a widespread algal limestone bed, which contains as much as 0. 15 percent uranium. Values of 0.01 percent uranium or more were obtained from 8 samples taken from approximately 220 feet of stratigraphic section in the Browns Park formation. This is the first reported occurrence of limestone source rock from Wyoming that has been found to contain a commercial grade of uranium. The economic possibilities of the area have not been determined adequately and no estimates of tonnage are warranted at the present time. An airborne radiometric survey was made by the Geophysics Branch of the Geological Survey, of the west half of the area, recommended by the writer for investigation. Ground check of all anomalies reported at that time showed that they were in localities where the background radiation was much higher than average. Additional localities with high background radiation were found on the ground in the area east of that which was flown.

The Nopal 1 Uranium Deposit: an Overview

NASA Astrophysics Data System (ADS)

Calas, G.; Allard, T.; Galoisy, L.

2007-05-01

The Nopal 1 natural analogue is located in the Pena Blanca uranium district, about 50 kms north of Chihuahua City, Mexico. The deposit is hosted in tertiary ignimbritic ash-flow tuffs, dated at 44 Ma (Nopal and Colorados formations), and overlying the Pozos conglomerate formation and a sequence of Cretaceous carbonate rocks. The deposit is exposed at the ground surface and consists of a near vertical zone extending over about 100 m with a diameter of 40 m. An interesting characteristic is that the primary mineralization has been exposed above the water table, as a result of the uplift of the Sierra Pena Blanca, and subsequently oxidized with a remobilization of hexavalent uranium. The primary mineralization has been explained by various genetic models. It is associated to an extensive hydrothermal alteration of the volcanic tuffs, locally associated to pyrite and preserved by an intense silicification. Several kaolinite parageneses occur in fissure fillings and feldspar pseudomorphs, within the mineralized breccia pipe and the barren surrounding rhyolitic tuffs. Smectites are mainly developed in the underlying weakly welded tuffs. Several radiation-induced defect centers have been found in these kaolinites providing a unique picture of the dynamics of uranium mobilization (see Allard et al., this session). Another evidence of this mobilization is given by the spectroscopy of uranium-bearing opals, which show characteristic fluorescence spectra of uranyl groups sorbed at the surface of silica. By comparison with the other uranium deposits of the Sierra Pena Blanca and the nearby Sierra de Gomez, the Nopal 1 deposit is original, as it is one of the few deposits hving retained a reduced uranium mineralization.

The separation of lanthanides and actinides in supercritical fluid carbon dioxide

DOE PAGES

Mincher, Bruce J.; Wai, Chien M.; Fox, Robert V.; ...

2015-10-28

Supercritical fluid carbon dioxide presents an attractive alternative to conventional solvents for recovery of the actinides and lanthanides. Carbon dioxide is a good solvent for fluorine and phosphate-containing ligands, including the traditional tributylphosphate ligand used in process-scale uranium separations. Actinide and lanthanide oxides may even be directly dissolved in carbon dioxide containing the complexes formed between these ligands and mineral acids, obviating the need for large volumes of acids for leaching and dissolution, and the corresponding organic liquid–liquid solvent extraction solutions. As a result, examples of the application of this novel technology for actinide and lanthanide separations are presented.

Uranium Anodic Dissolution under Slightly Alkaline Conditions Progress Report Full-Scale Demonstration with DU Foil

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

Gelis, A.; Brown, M. A.; Wiedmeyer, S.

2014-02-18

Argonne National Laboratory (Argonne) is developing an alternative method for digesting irradiated low enriched uranium (LEU) foil targets to produce 99Mo in neutral/alkaline media. This method consists of the electrolytic dissolution of irradiated uranium foil in sodium bicarbonate solution, followed by precipitation of base-insoluble fission and activation products, and uranyl-carbonate species with CaO. The addition of CaO is vital for the effective anion exchange separation of 99MoO 4 2- from the fission products, since most of the interfering anions (e.g., CO 3 2-) are removed from the solution, while molybdate remains in solution. An anion exchange is used to retainmore » and to purify the 99Mo from the filtrate. The electrochemical dissolver has been designed and fabricated in 304 stainless-steel (SS), and tested for the dissolution of a full-size depleted uranium (DU) target, wrapped in Al foil. Future work will include testing with low-burn-up DU foil at Argonne and later with high-burn-up LEU foils at Oak Ridge National Laboratory.« less

Geochemistry of vanadium in an epigenetic, sandstone-hosted vanadium- uranium deposit, Henry Basin, Utah

USGS Publications Warehouse

Wanty, R.B.; Goldhaber, M.B.; Northrop, H.R.

1990-01-01

The epigenetic Tony M vanadium-uranium orebody in south-central Utah is hosted in fluvial sandstones of the Morrison Formation (Upper Jurassic). Measurements of the relative amounts of V+3 and V +4 in ore minerals show that V+3 is more abundant. Thermodynamic calculations show that vanadium was more likely transported to the site of mineralization as V+4. The ore formed as V+4 was reduced by hydrogen sulfide, followed by hydrolysis and precipitation of V+3 in oxide minerals or chlorite. Uranium was transported as uranyl ion (U+6), or some complex thereof, and reduced by hydrogen sulfide, forming coffinite. Detrital organic matter in the rocks served as the carbon source for sulfate-reducing bacteria. Vanadium most likely was derived from the dissolution of iron-titanium oxides. Uranium probably was derived from the overlying Brushy Basin Member of the Morrison Formation. Previous studies have shown that the ore formed at the density-stratified interface between a basinal brine and dilute meteoric water. The mineralization processes described above occurred within the mixing zone between these two fluids. -from Authors

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

PubMed

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

2013-01-15

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

Radium isotope quartet in groundwater as a proxy for identification of aquifer rocks and mechanisms of water-rock interactions: examples from the Negev, Israel

NASA Astrophysics Data System (ADS)

Vengosh, A.; Pery, N.; Paytan, A.; Haquin, G.; Elhanani, S.; Pankratov, I.

2006-05-01

Many aquifer systems are composed of multiple rock types. Previous attempts to evaluate the specific aquifer rocks that control the groundwater chemistry and possible flow paths within these multiple lithological systems have used major ion chemistry and isotopic tracers (e.g., strontium isotopes). Here we propose an additional isotopic proxy that is based on the distribution of radium isotopes in groundwater. Radium has four radioactive isotopes that are part of the decay chains of uranium-238, thorium-232, and uranium-235. The abundance of radium isotope quartet (226Ra-half life 1600 y; 228Ra-5.6 y; 224Ra-3.6 d; 223Ra-11.4 d) in groundwater reflects the Th/U ratios in the rocks. Investigation of groundwater from the Negev, Israel, enabled us to discriminate between groundwaters flowing in the Lower Cretaceous Nubian Sandstone and the Upper Cretaceous Judea Group carbonate aquifers. Groundwater flowing in the sandstone aquifer has distinguishably high 228Ra/226Ra and 224Ra/223Ra ratios due to the high Th/U ratio in sandstone. In contrast, the predominance of uranium in carbonate rocks results in low 228Ra/226Ra and 224Ra/223Ra ratios in the associated groundwater. We show that the radium activity in groundwater in the two-aquifer systems is correlated with temperature, dissolved oxygen, and salinity. The increase of radium activity is also associated with changes in the isotopic ratios; 228Ra/226Ra ratios increase and decrease in the sandstone and carbonate aquifers, respectively. Given that the dissolution of radium isotopes depends on their decay constants, the use of the four radium isotopes with different decay constants enabled us to distinguish between dissolution (higher abundance of the long-lived isotopes) and recoil (predominance of the short-lived isotopes) processes. In spite of these isotopic fractionations, the radium isotopic discrimination between carbonate and sandstone aquifers is significant.

National Uranium Resource Evaluation: Marfa Quadrangle, Texas

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

Henry, C D; Duex, T W; Wilbert, W P

1982-09-01

The uranium favorability of the Marfa 1/sup 0/ by 2/sup 0/ Quadrangle, Texas, was evaluated in accordance with criteria established for the National Uranium Resource Evaluation. Surface and subsurface studies, to a 1500 m (5000 ft) depth, and chemical, petrologic, hydrogeochemical, and airborne radiometric data were employed. The entire quadrangle is in the Basin and Range Province and is characterized by Tertiary silicic volcanic rocks overlying mainly Cretaceous carbonate rocks and sandstones. Strand-plain sandstones of the Upper Cretaceous San Carlos Formation and El Picacho Formation possess many favorable characteristics and are tentatively judged as favorable for sandstone-type deposits. The Tertiarymore » Buckshot Ignimbrite contains uranium mineralization at the Mammoth Mine. This deposit may be an example of the hydroauthigenic class; alternatively, it may have formed by reduction of uranium-bearing ground water produced during diagenesis of tuffaceous sediments of the Vieja Group. Although the presence of the deposit indicates favorability, the uncertainty in the process that formed the mineralization makes delineation of a favorable environment or area difficult. The Allen intrusions are favorable for authigenic deposits. Basin fill in several bolsons possesses characteristics that suggest favorability but which are classified as unevaluated because of insufficient data. All Precambrian, Paleozoic, other Mesozoic, and other Cenozoic environments are unfavorable.« less

Effects of uranium concentration on microbial community structure and functional potential.

PubMed

Sutcliffe, Brodie; Chariton, Anthony A; Harford, Andrew J; Hose, Grant C; Greenfield, Paul; Elbourne, Liam D H; Oytam, Yalchin; Stephenson, Sarah; Midgley, David J; Paulsen, Ian T

2017-08-01

Located in the Northern Territory of Australia, Ranger uranium mine is directly adjacent to the UNESCO World Heritage listed Kakadu National Park, with rehabilitation targets needed to ensure the site can be incorporated into the park following the mine's closure in 2026. This study aimed to understand the impact of uranium concentration on microbial communities, in order to identify and describe potential breakpoints in microbial ecosystem services. This is the first study to report in situ deployment of uranium-spiked sediments along a concentration gradient (0-4000 mg U kg -1 ), with the study design maximising the advantages of both field surveys and laboratory manipulative studies. Changes to microbial communities were characterised through the use of amplicon and shotgun metagenomic next-generation sequencing. Significant changes to taxonomic and functional community assembly occurred at a concentration of 1500 mg U kg -1 sediment and above. At uranium concentrations of ≥ 1500 mg U kg -1 , genes associated with methanogenic consortia and processes increased in relative abundance, while numerous significant changes were also seen in the relative abundances of genes involved in nitrogen cycling. Such alterations in carbon and nitrogen cycling pathways suggest that taxonomic and functional changes to microbial communities may result in changes in ecosystem processes and resilience. © 2017 Society for Applied Microbiology and John Wiley & Sons Ltd.

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

PubMed

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

2009-04-01

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

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

Quantitative ion beam analysis of M-C-O systems: application to an oxidized uranium carbide sample

NASA Astrophysics Data System (ADS)

Martin, G.; Raveu, G.; Garcia, P.; Carlot, G.; Khodja, H.; Vickridge, I.; Barthe, M. F.; Sauvage, T.

2014-04-01

A large variety of materials contain both carbon and oxygen atoms, in particular oxidized carbides, carbon alloys (as ZrC, UC, steels, etc.), and oxycarbide compounds (SiCO glasses, TiCO, etc.). Here a new ion beam analysis methodology is described which enables quantification of elemental composition and oxygen concentration profile over a few microns. It is based on two procedures. The first, relative to the experimental configuration relies on a specific detection setup which is original in that it enables the separation of the carbon and oxygen NRA signals. The second concerns the data analysis procedure i.e. the method for deriving the elemental composition from the particle energy spectrum. It is a generic algorithm and is here successfully applied to characterize an oxidized uranium carbide sample, developed as a potential fuel for generation IV nuclear reactors. Furthermore, a micro-beam was used to simultaneously determine the local elemental composition and oxygen concentration profiles over the first microns below the sample surface. This method is adapted to the determination of the composition of M?C?O? compounds with a sensitivity on elemental atomic concentrations around 1000 ppm.

Coating method for graphite

DOEpatents

Banker, John G.; Holcombe, Jr., Cressie E.

1977-01-01

A method of limiting carbon contamination from graphite ware used in induction melting of uranium alloys is provided comprising coating the graphite surface with a suspension of Y.sub.2 O.sub.3 particles in water containing about 1.5 to 4% by weight sodium carboxymethylcellulose.

Coating method for graphite

DOEpatents

Banker, J.G.; Holcombe, C.E. Jr.

1975-11-06

A method of limiting carbon contamination from graphite ware used in induction melting of uranium alloys is provided. The graphite surface is coated with a suspension of Y/sub 2/O/sub 3/ particles in water containing about 1.5 to 4 percent by weight sodium carboxymethylcellulose.

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.

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

Progress report on geologic studies of the Ranger orebodies, Northern Territory, Australia

USGS Publications Warehouse

Nash, J.T.; Frishman, David

1982-01-01

The Ranger No. 1 and No. 3 orebodies contain about 124,000 tonnes U3O8 in highly chloritized metasediments of the lower Proterozoic Cahill Formation within about 500 m of the projected sub-Kombolgie Formation unconformity. In both orebodies, oxidized and reduced uranium minerals occur chiefly in quartzose schists that have highly variable amounts of muscovite, sericite, and chlorite. The effects of several periods of alteration are pervasive in the vicinity of orebodies where biotite and garnet are altered to chlorite, and feldspars to white mica or chlorite. Oxidized uranium minerals, associated with earthy iron oxides, occur from the surface to a depth of about 60 m. Below the oxidized zone, uranium occurs chiefly as uraninite and pitchblende disseminated through thick sections of quartz-chlorite-muscovite schist and has no apparent association with graphite or sulfides. In fact, graphite is rare and sulfides are generally low in abundance (<0.5 percent). Higher ore grades occur in disrupted zones a few centimeters thick and in some quartz-chlorite vein-like zones of uncertain origin. Uranium correlates strongly with chlorite, but not all of the many ages of chlorite have associated uranium. At least five textural varieties of chlorite are present and represent at least 3 ages. Preliminary microprobe analyses suggest that Mg-Fe-Al contents are relatively uniform. Apatite commonly occurs with chlorite. Uranium is not common in carbonate rocks and seems to occur only in disrupted zones that have chlorite alteration. Chloritization and silicification are more widespread and intense in the No. 1 orebody than in the No. 3. In both orebodies, hematite occurs tens to hundreds of meters below the weathered zone, in both altered and largely unaltered rocks, with and without uranium. The structure of the orebodies is outwardly simple, particularly in No. 3; dips are less than 40? on most lithologic contacts. The No. 1 orebody is in a basin-like structure about 400 m wide that probably formed in part by progressive removal of carbonate rocks that are as much as 200 m thick adjacent to the No. 1 orebody and below the No. 3 orebody. Quartz-chlorite breccias have formed in the zone of carbonate thinning; uranium is spotty and low grade in these breccias. Chloritized and uraniferous broken and sheared zones, a few centimeters to a few meters thick, have an unknown attitude but must have small displacement. Blocks of altered Kombolgie sandstone are downfaulted into the No. 3 orebody and locally contain reduced uranium minerals. One or more shear zones 5-30 m thick of crushed and smeared fine to coarse rock fragments occur below the orebodies, and other low-angle shears probably occur in the orebodies. The shear zone dips about 40 o and displacement on it is not known. The footwall rocks generally are less retrograded than those in the hanging wall (orebody) and consist of quartz-biotite-feldspar schists and gneisses flanking the Nanambu Complex. A few scattered fractures in the footwall sequence contain pitchblende of unknown age and origin. Major element chemical analyses confirm the lithologic observations of large changes in composition during multiple stages of alteration. Granitic dikes and pelitic schists have gained Fe and Mg and lost Si, Ca, Na, and K during chloritization. Marbles have gained Si, Al, Fe, and P, and lost Mg, Ca, and K during jasperoid-chlorite alteration. Total net chemical gains and losses in the Ranger No. 1 orebody were huge: equal to about 37 percent of the mass of the ore-bearing rock that will be mined. There were net gains in Si and P and net losses in Al, Fe, Mg, Ca, K, and Na. The geologic age(s) of uranium emplacement are obscure because there are few age criteria. Reduced uranium minerals are younger than 1.8-b.y.-old granite dikes, and some occur locally in 1.65-b.y.-old Kombolgie Formation. Diabase dikes (age not known) are thoroughly chloritized and contain sparse ore minerals. Oxidized ura

Radioactivity and geochemistry of selected mineral-spring waters in the Western United States; basic data and multivariate statistical analysis

USGS Publications Warehouse

Felmlee, J.K.; Cadigan, R.A.

1982-01-01

Multivariate statistical analyses were performed on data from 156 mineral-spring sites in nine Western States to analyze relationships among the various parameters measured in the spring waters. Correlation analysis and R-mode factor analysis indicate that three major factors affect water composition in the spring systems studied: (1) duration of water circulation, (2) depth of water circulation, and (3) partial pressure of carbon dioxide. An examination of factor scores indicates that several types of hydrogeologic systems were sampled. Most of the samples are (1) older water from deeper circulating systems having relatively high salinity, high temperature, and low Eh or (2) younger water from shallower circulating systems having relatively low salinity, low temperature, and high Eh. The rest of the samples are from more complex systems. Any of the systems can have a relatively high or low content of dissolved carbonate species, resulting in a low or high pH, respectively. Uranium concentrations are commonly higher in waters of relatively low temperature and high Eh, and radium concentrations are commonly higher in waters having a relatively high carbonate content (low pH) and, secondarily, relatively high salinity. Water samples were collected and (or) measurements were taken at 156 of the 171 mineral-spring sites visited. Various samples were analyzed for radium, uranium, radon, helium, and radium-228 as well as major ions and numerous trace elements. On-site measurements for physical properties including temperature, specific conductance, pH, Eh, and dissolved oxygen were made. All constituents and properties show a wide range of values. Radium concentrations range from less than 0.01 to 300 picocuries per liter; they average 1.48 picocuries per liter and have an anomaly threshold value of 171 picocuries per liter for the samples studied. Uranium concentrations range from less than 0.01 to 120 micrograms per liter and average 0.26 micrograms per liter; they have an anomaly threshold value of 48.1 micrograms per liter. Radon content ranges from less than 10 to 110,000 picocuries per liter, averages 549 picocuries per liter and has an anomaly threshold of 20,400 picocuries per liter. Helium content ranges from -1,300 to +13,000 parts per billion relative to atmospheric helium; it averages +725 parts per billion and has an anomaly threshold of 10,000 parts per billion. Radium-228 concentrations range from less than 2.0 to 33 picocuries per liter; no anomaly threshold was determined owing to the small number of samples. All of the anomaly thresholds may be somewhat high because the sampling was biased toward springs likely to be radioactive. The statistical variance in radium and uranium concentrations unaccounted for by the identified factors testifies to the complexity of some hydrogeologic systems. Unidentified factors related to geologic setting and the presence of uranium-rich rocks in the systems also affect the observed concentrations of the radioactive elements in the water. The association of anomalous radioactivity in several springs with nearby known uranium occurrences indicates that other springs having anomalous radioactivity may also be associated with uranium occurrences as yet undiscovered.

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.

Granulated activated carbon modified with hydrophobic silica aerogel-potential composite materials for the removal of uranium from aqueous solutions.

PubMed

Coleman, Sabre J; Coronado, Paul R; Maxwell, Robert S; Reynolds, John G

2003-05-15

Aqueous solutions of 100 parts per billion (ppb) uranium at pH 7 were treated with granulated activated carbon (GAC) that had been modified with various formulations of hydrophobic aerogels. The composite materials were found to be superior in removing uranium from a stock solution compared to GAC alone evaluated by a modified ASTM D 3860-98 method for batch testing. The testing results were evaluated using a Freundlich adsorption model. The best performing material has parameters of n = 287 and Kf = 1169 compared to n = 1.00, and Kf = 20 for GAC alone. The composite materials were formed by mixing (CH3O)4Si with the hydrophobic sol-gel precursor, (CH3O)3SiCH2CH2CF3 and with specified modifiers, such as H3PO4, Ca(NO3)2, and (C2H5O)3SiCH2CH2P(O)(OC2H5)2, elation catalysts, and GAC in a supercritical reactor system. After gelation, supercritical extraction, and sieving, the composites were tested. Characterization by FTIR and 31P NMR indicate the formation of phosphate in the case of the H3PO4 and Ca(NO3)2 composites and phosphonic acid related compounds in the phosphonate composite. These composite materials have potential application in the clean up of groundwater at DOE and other facilities.

Iron Mineralogy and Uranium-Binding Environment in the Rhizosphere of a Wetland Soil

EPA Science Inventory

Wetlands mitigate the migration of groundwater contaminants through a series of biogeochemical gradients that enhance multiple contaminant-binding processes. The hypothesis of this study was that wetland plant roots contribute organic carbon and release O₂ within the ...

Microbial links between sulfate reduction and metal retention in uranium- and heavy metal-contaminated soil.

PubMed

Sitte, Jana; Akob, Denise M; Kaufmann, Christian; Finster, Kai; Banerjee, Dipanjan; Burkhardt, Eva-Maria; Kostka, Joel E; Scheinost, Andreas C; Büchel, Georg; Küsel, Kirsten

2010-05-01

Sulfate-reducing bacteria (SRB) can affect metal mobility either directly by reductive transformation of metal ions, e.g., uranium, into their insoluble forms or indirectly by formation of metal sulfides. This study evaluated in situ and biostimulated activity of SRB in groundwater-influenced soils from a creek bank contaminated with heavy metals and radionuclides within the former uranium mining district of Ronneburg, Germany. In situ activity of SRB, measured by the (35)SO(4)(2-) radiotracer method, was restricted to reduced soil horizons with rates of < or =142 +/- 20 nmol cm(-3) day(-1). Concentrations of heavy metals were enriched in the solid phase of the reduced horizons, whereas pore water concentrations were low. X-ray absorption near-edge structure (XANES) measurements demonstrated that approximately 80% of uranium was present as reduced uranium but appeared to occur as a sorbed complex. Soil-based dsrAB clone libraries were dominated by sequences affiliated with members of the Desulfobacterales but also the Desulfovibrionales, Syntrophobacteraceae, and Clostridiales. [(13)C]acetate- and [(13)C]lactate-biostimulated soil microcosms were dominated by sulfate and Fe(III) reduction. These processes were associated with enrichment of SRB and Geobacteraceae; enriched SRB were closely related to organisms detected in soils by using the dsrAB marker. Concentrations of soluble nickel, cobalt, and occasionally zinc declined < or =100% during anoxic soil incubations. In contrast to results in other studies, soluble uranium increased in carbon-amended treatments, reaching < or =1,407 nM in solution. Our results suggest that (i) ongoing sulfate reduction in contaminated soil resulted in in situ metal attenuation and (ii) the fate of uranium mobility is not predictable and may lead to downstream contamination of adjacent ecosystems.

Microbial Links between Sulfate Reduction and Metal Retention in Uranium- and Heavy Metal-Contaminated Soil▿

PubMed Central

Sitte, Jana; Akob, Denise M.; Kaufmann, Christian; Finster, Kai; Banerjee, Dipanjan; Burkhardt, Eva-Maria; Kostka, Joel E.; Scheinost, Andreas C.; Büchel, Georg; Küsel, Kirsten

2010-01-01

Sulfate-reducing bacteria (SRB) can affect metal mobility either directly by reductive transformation of metal ions, e.g., uranium, into their insoluble forms or indirectly by formation of metal sulfides. This study evaluated in situ and biostimulated activity of SRB in groundwater-influenced soils from a creek bank contaminated with heavy metals and radionuclides within the former uranium mining district of Ronneburg, Germany. In situ activity of SRB, measured by the 35SO42− radiotracer method, was restricted to reduced soil horizons with rates of ≤142 ± 20 nmol cm−3 day−1. Concentrations of heavy metals were enriched in the solid phase of the reduced horizons, whereas pore water concentrations were low. X-ray absorption near-edge structure (XANES) measurements demonstrated that ∼80% of uranium was present as reduced uranium but appeared to occur as a sorbed complex. Soil-based dsrAB clone libraries were dominated by sequences affiliated with members of the Desulfobacterales but also the Desulfovibrionales, Syntrophobacteraceae, and Clostridiales. [13C]acetate- and [13C]lactate-biostimulated soil microcosms were dominated by sulfate and Fe(III) reduction. These processes were associated with enrichment of SRB and Geobacteraceae; enriched SRB were closely related to organisms detected in soils by using the dsrAB marker. Concentrations of soluble nickel, cobalt, and occasionally zinc declined ≤100% during anoxic soil incubations. In contrast to results in other studies, soluble uranium increased in carbon-amended treatments, reaching ≤1,407 nM in solution. Our results suggest that (i) ongoing sulfate reduction in contaminated soil resulted in in situ metal attenuation and (ii) the fate of uranium mobility is not predictable and may lead to downstream contamination of adjacent ecosystems. PMID:20363796

Genome-Based Models to Optimize In Situ Bioremediation of Uranium and Harvesting Electrical Energy from Waste Organic Matter

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

Lovley, Derek R

2012-12-28

The goal of this research was to provide computational tools to predictively model the behavior of two microbial communities of direct relevance to Department of Energy interests: 1) the microbial community responsible for in situ bioremediation of uranium in contaminated subsurface environments; and 2) the microbial community capable of harvesting electricity from waste organic matter and renewable biomass. During this project the concept of microbial electrosynthesis, a novel form of artificial photosynthesis for the direct production of fuels and other organic commodities from carbon dioxide and water was also developed and research was expanded into this area as well.

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.

Uranium isotope fractionation in biogenic carbonates: biological effects

NASA Astrophysics Data System (ADS)

Chen, X.; Romaniello, S. J.; Herrmann, A. D.; Anbar, A. D.

2017-12-01

Recent laboratory experiments have demonstrated small but potentially significant isotope fractionation ( 0.10 ‰ for 238U/235U) during uranium (U) incorporation into abiotic calcite and aragonite, with heavier U isotopes preferentially enriched in the precipitates [1]. In contrast, measurements of natural biogenic carbonates to date have not been able to resolve significant U isotopic fractionation from seawater although this might be expected given a typical measurement precision of ± 0.10 ‰. Determining whether or not biogenic carbonates display U isotope fractionation similar to abiotic carbonates could have important implications for understanding the mechanisms of U incorporation into various biogenic carbonates. Furthermore, because most marine carbonates are biogenic, the extent of isotopic fractionation, if any, could have important implications for the interpretation of sedimentary carbonates record similar to effects observed for Cr and B isotopes [2, 3]. To resolve this discrepancy, we utilized a higher precision 238U/235U method which uses larger sample sizes to improve measurement precision of natural samples to ± 0.02 ‰ (2 se, N = 6) [4]. Using this method, we have surveyed 238U/235U in primary biogenic skeletal carbonates including scleractinian corals, green and red algae, and mollusks, as well as non-skeletal carbonates such as stromatolites, ooids, and carbonate sands from the Bahamas, Gulf of California, and French Polynesia. New high-precision U isotopes measurements reveal that biogenic skeletal carbonates are typically 0.02 - 0.08 ‰ heavier than modern seawater. Scleractinian corals display values closest to seawater (- 0.37 ‰), while green algae, red algae, mollusks, and echinoderms display variable but larger extents of fractionation up to 0.08 ‰. The direction and magnitude of U isotope fractionation in these biogenic precipitates are generally consistent with results from abiotic coprecipitation experiments, but may be subject to variations in U speciation and carbonate chemistry at calcification sites. [1] Chen et a., (2016), GCA, 188, 189-207. [2] Wang et a., (2016), Geobiology, 5, 51-64. [3] Pagani et al., (2005) GCA, 69, 953-961. [4] Andersen et al., (2016) CG, 420, 11-22.

Compositions and methods for treating nuclear fuel

DOEpatents

Soderquist, Chuck Z; Johnsen, Amanda M; McNamara, Bruce K; Hanson, Brady D; Smith, Steven C; Peper, Shane M

2013-08-13

Compositions are provided that include nuclear fuel. Methods for treating nuclear fuel are provided which can include exposing the fuel to a carbonate-peroxide solution. Methods can also include exposing the fuel to an ammonium solution. Methods for acquiring molybdenum from a uranium comprising material are provided.

Compositions and methods for treating nuclear fuel

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

Soderquist, Chuck Z; Johnsen, Amanda M; McNamara, Bruce K

Compositions are provided that include nuclear fuel. Methods for treating nuclear fuel are provided which can include exposing the fuel to a carbonate-peroxide solution. Methods can also include exposing the fuel to an ammonium solution. Methods for acquiring molybdenum from a uranium comprising material are provided.

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

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

Mehta, Vrajesh; Maillot, Fabien; Wang, Zheming

Uranyl phosphate solids are often found with uranium ores, and their low solubility makes them promising target phases for in situ remediation of uranium-contaminated subsurface environments. The products and solubility of uranium(VI) precipitated with phosphate can be affected by the pH, dissolved inorganic carbon (DIC) concentration, and co-solute composition (e.g. Na+/Ca2+) of the groundwater. Batch experiments were performed to study the effect of these parameters on the products and extent of uranium precipitation induced by phosphate addition. In the absence of co-solute cations, chernikovite [H3O(UO2)(PO4)•3H2O] precipitated despite uranyl orthophosphate [(UO2)3(PO4)2•4H2O] being thermodynamically more favorable under certain conditions. As determined usingmore » X-ray diffraction, electron microscopy, and laser induced fluorescence spectroscopy, the presence of Na+ or Ca2+ as a co-solute led to the precipitation of sodium autunite ([Na2(UO2)2(PO4)2] and autunite [Ca(UO2)2(PO4)2]), which are structurally similar to chernikovite. In the presence of sodium, the dissolved U(VI) concentrations were generally in agreement with equilibrium predictions of sodium autunite solubility. However, in the calcium-containing systems, the observed concentrations were below the predicted solubility of autunite, suggesting the possibility of uranium adsorption to or incorporation in a calcium phosphate precipitate in addition to the precipitation of autunite.« less

Dynamic leaching studies of 48 MWd/kgU UO2 commercial spent nuclear fuel under oxic conditions

NASA Astrophysics Data System (ADS)

Serrano-Purroy, D.; Casas, I.; González-Robles, E.; Glatz, J. P.; Wegen, D. H.; Clarens, F.; Giménez, J.; de Pablo, J.; Martínez-Esparza, A.

2013-03-01

The leaching of a high-burn-up spent nuclear fuel (48 MWd/KgU) has been studied in a carbonate-containing solution and under oxic conditions using a Continuously Stirred Tank Flow-Through Reactor (CSTR). Two samples of the fuel, one prepared from the centre of the pellet (labelled CORE) and another one from the fuel pellet periphery, enriched with the so-called High Burn-Up Structure (HBS, labelled OUT) have been used.For uranium and actinides, the results showed that U, Np, Am and Cm gave very similar normalized dissolution rates, while Pu showed slower dissolution rates for both samples. In addition, dissolution rates were consistently two to four times lower for OUT sample compared to CORE sample.Considering the fission products release the main results are that Y, Tc, La and Nd dissolved very similar to uranium; while Cs, Sr, Mo and Rb have up to 10 times higher dissolution rates. Rh, Ru and Zr seemed to have lower dissolution rates than uranium. The lowest dissolution rates were found for OUT sample.Three different contributions were detected on uranium release, modelled and attributed to oxidation layer, fines and matrix release.

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.

Mechanisms of uranium interactions with hydroxyapatite: Implications for groundwater remediation

USGS Publications Warehouse

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

2002-01-01

The speciation of U(VI) sorbed to synthetic hydroxyapatite was investigated using a combination of U LIII-edge XAS, synchrotron XRD, batch uptake measurements, and SEM-EDS. The mechanisms of U(VI) removal by apatite were determined in order to evaluate the feasibility of apatitebased in-situ permeable reactive barriers (PRBs). In batch U(VI) uptake experiments with synthetic hydroxyapatite (HA), near complete removal of dissolved uranium (>99.5%) to <0.05 ??M was observed over a range of total U(VI) concentrations up to equimolar of the total P in the suspension. XRD and XAS analyses of U(VI)-reacted HA at sorbed concentrations ???4700 ppm U(VI) suggested that uranium(VI) phosphate, hydroxide, and carbonate solids were not present at these concentrations. Fits to EXAFS spectra indicate the presence of Ca neighbors at 3.81 A??. U-Ca separation, suggesting that U(VI) adsorbs to the HA surfaces as an inner-sphere complex. Uranium(VI) phosphate solid phases were not detected in HA with 4700 ppm sorbed U(VI) by backscatter SEM or EDS, in agreement with the surface complexation process. In contrast, U(VI) speciation in samples that exceeded 7000 ppm sorbed U(VI) included a crystalline uranium(VI) phosphate solid phase, identified as chernikovite by XRD. At these higher concentrations, a secondary, uranium(VI) phosphate solid was detected by SEM-EDS, consistent with chernikovite precipitation. Autunite formation occurred at total U:P molar ratios ???0.2. Our findings provide a basis for evaluating U(VI) sorption mechanisms by commercially available natural apatites for use in development of PRBs for groundwater U(VI) remediation.

Redox Roll-Front Mobilization of Geogenic Uranium by Nitrate Input into Aquifers: Risks for Groundwater Resources.

PubMed

van Berk, Wolfgang; Fu, Yunjiao

2017-01-03

Redox conditions are seen as the key to controlling aqueous uranium concentrations (cU (aq) ). Groundwater data collected by a state-wide groundwater quality monitoring study in Mecklenburg-Western Pomerania (Germany) reveal peak cU (aq) up to 75 μg L -1 but low background uranium concentrations (median cU (aq) < 0.5 μg L -1 ). To characterize the hydrogeochemical processes causing such groundwater contamination by peak cU (aq) , we reanalyzed measured redox potentials and total concentrations of aqueous uranium, nitrate, and sulfate species in groundwater together with their distribution across the aquifer depth and performed semigeneric 2D reactive mass transport modeling which is based on chemical thermodynamics. The combined interpretation of modeling results and measured data reveals that high cU (aq) and its depth-specific distribution depending on redox conditions is a result of a nitrate-triggered roll-front mobilization of geogenic uranium in the studied aquifers which are unaffected by nuclear activities. The modeling results show that groundwater recharge containing (fertilizer-derived) nitrate drives the redox shift from originally reducing toward oxidizing environments, when nitrate input has consumed the reducing capacity of the aquifers, which is present as pyrite, degradable organic carbon, and geogenic U(IV) minerals. This redox shift controls the uranium roll-front mobilization and results in high cU (aq) within the redoxcline. Moreover, the modeling results indicate that peak cU (aq) occurring at this redox front increase along with the temporal progress of such redox conversion within the aquifer.

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 report on the White Canyon area, San Juan county, Utah

USGS Publications Warehouse

Benson, William E.; Trites, Albert F.; Beroni, Ernest P.; Feeger, John A.

1952-01-01

The White Canyon area, in the central part of San Juan County, Utah, consists of approximately two 15-minute quadrangles. Approximately 75 square miles have been mapped by the Geological Survey on a scale of 1 inch equals 1 mile, using a combined aerial photography-plane table method. Structure contours were drawn on top of the Organ Rock member of the Cutler formation. Parts of the Gonway and North Point claims, 1/4 mile east of the Happy Jack mine, were mapped in detail. The principal objectives of the investigations were: (1) to establish ore guides; (2) to select areas favorable for exploration; and (3) to map the general geology and to determine the regional relationships of the uranium deposits. The White Canyon area is comprised of sedimentary rocks of Carboniferous to Jurassic age, more than 2,000 feet thick, having a regional dip of 1° to 2° SW. The nearest igneous rocks are in the Henry Mountains about 7 miles west of the northern part of the area; The Shinarump conglomerate of the late Triassic age, the principal ore horizon in the White Canyon area, consists of lenticular beds of sandstone, conglomeratic sandstone, conglomerate, clay, and siltstone. The Shinarump conglomerate, absent in places, is as much as 75 feet thick. The sandstones locally contain molds of logs and fragments of altered volcanic ash. Some of the logs have been replaced by copper and uranium minerals and iron oxides. The clay and siltstone underlie and are interbedded with the sandstone, and are most common in channels that cut into the underlying Moenkopi formation. The Shinarump conglomerate contains reworked Moenkopi siltstone fragments, clay balls, carbonized wood, and pebbles of quarts, quartzite, and chert. Jointing is prominent in the Western part of the mapped area. The three most prominent joint trends are due east, N. 65°-75° W., and N. 65°-75° E. All joints have vertical dips. The red beds are bleached along some joints, especially those that trend N. 65°-75° W. All uranium ore produced has been from the lower part of the Shinarump conglomerate, where it commonly occurs with copper as disseminations and fracture coatings in sandstone. Uranium and copper minerals also occur in low-grade disseminated deposits in the lower Chinle and in the Moenkopi formation and in veins cutting these formations. Although some uranium deposits occur in Chinarump channels and scours, copper and uranium minerals along fractures suggest that channel control may be secondary. Logs and clay balls apparently have exerted some chemical influences for deposition. The uranium occurs as the oxide in some deposits, and as secondary hydrous sulfates, phosphates, oxides, and silicates in these and several other deposits. Charcoal, iron and manganese oxides, and veinlets of hydrocarbon are abnormally radioactive in most of the deposits. Base-metal sulfides are commonly found inside the oxidized zone. Secondary copper minerals include the hydrous sulfates and carbonate. Gangue minerals include quarts, clay minerals, and manganese oxides, dickite (?), calcite, gypsum, pyrite, and chalcedony (?). Principal wall-rock alteration appears to have been silicification, clay alteration, and bleaching. Most of the shipped ore has contained more than 0.3 percent uranium. The ore also contains copper, commonly in grades lower than 1.0 percent. Criteria believed to be most useful for prospecting for concealed uranium deposits are (1) visible uranium minerals; (2) sulfide minerals; (3) secondary copper minerals; (4) dickite (?); (5) hydrocarbons; and (6) bleaching and alteration of the Moenkopi formation.

The origin of the Avram Iancu U-Ni-Co-Bi-As mineralization, Băiţa (Bihor) metallogenic district, Bihor Mts., Romania

NASA Astrophysics Data System (ADS)

Zajzon, Norbert; Szentpéteri, Krisztián; Szakáll, Sándor; Kristály, Ferenc

2015-10-01

The Băiţa metallogenic district in the Bihor Mountains is a historically important mining area in Romania. Uranium mining took place between 1952 and 1998 from various deposits, but very little is known about the geology and mineralogy of these deposits. In this paper, we describe geology and mineralogy of uranium mineralization of the Avram Iancu uranium mine from waste dump samples collected before complete remediation of the site. Texturally and mineralogically complex assemblages of nickeline, cobaltite-gersdorffite solid solution, native Bi, Bi-sulfosalts, molybdenite, and pyrite-chalcopyrite-sphalerite occur with uraninite, "pitchblende," and brannerite in most of the ore samples. The association of nickel, cobalt, and arsenic with uranium is reminiscent of five-element association of vein type U-Ni-Co-Bi-As deposits; however, the Avram Iancu ores appear to be more replacement-type stratiform/stratabound. Avram Iancu ore samples contain multistage complex, skarn, uranium sulfide, arsenide assemblages that can be interpreted to have been formed in the retrograde cooling stages of the skarn hydrothermal system. This mineralizing system may have built-up along Upper Cretaceous-Paleogene "Banatite" intrusions of diorite-to-granite composition. The intrusions crosscut the underlying uraniferous Permian formations in the stacked NW-verging Biharia Nappe System. The mineralization forms stacked, multilayer replacement horizons, along carbonate-rich lithologies within the metavolcanic (tuffaceous) Muncel Series. Mineral paragenesis and some mineral chemistry suggest moderate-to-high <450, i.e., 350-310 °C, formation temperatures for the uranium sulfide stage along stratigraphically controlled replacement zones and minor veins. Uranium minerals formed abundantly in this early stage and include botryoidal, sooty and euhedral uraninite, brannerite, and coffinite. Later and/or lower-temperature mineral assemblages include heterogeneous, complexly zoned arsenide-sulfarsenide solid solutions associated with minute but abundant uranium minerals. Within the later arsenide-sulfarsenide mineral assemblage, there is great variation in Ni, Co, and S content with generally increasing arsenic content. Uranium minerals in this late-stage assemblage include very fine euhedral uraninite and brannerite inclusions in arsenide-sulfarsenide minerals. Native bismuth and Bi-sulfosalt krupkaite are observed in this As-S-rich assemblage strongly associated with cobaltite.

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

Millennial Variability of Eastern Equatorial Bottom Water Oxygenation and Atmospheric CO2 over the past 100 kyr

NASA Astrophysics Data System (ADS)

Marcantonio, F.; Loveley, M.; Wisler, M.; Hostak, R.; Hertzberg, J. E.; Schmidt, M. W.; Lyle, M. W.

2017-12-01

Storage of respired carbon in the deep ocean may play a significant role in lowering atmospheric CO2 concentrations by about 80 ppm during the last glacial maximum compared to pre-industrial times. The cause of this sequestration and the subsequent release of the deep respired carbon pool at the last termination remains elusive. Within the last glacial period, on millennial timescales, the relationship between the CO2 cycle and any waxing and waning of a deep respired pool also remains unclear. To further our understanding of the millennial variability in the storage of a deep-ocean respired carbon pool during the last glacial, we measure authigenic uranium and 230Th-derived non-lithogenic barium fluxes (xsBa flux) in two high-sedimentation-rate cores from the Panama Basin of the Eastern Equatorial Pacific (EEP) (8JC, 6° 14.0' N, 86° 02.6' W; 1993 m water depth; 17JC 00° 10.8' S, 85° 52.0' W; 2846 m water depth). Sediment authigenic U concentrations are controlled by the redox state of sediments which, in turn, is a function of the rain of organic material from the surface ocean and the oxygen content of bottom waters. At both 8JC and 17JC, the mismatch between xsBa fluxes, a proxy for the reconstruction of oceanic productivity, and authigenic uranium concentrations suggests that the primary control of the latter values is changes in bottom water oxygenation. Peak authigenic uranium concentrations occur during glacial periods MIS 2, 3, and 4, respectively, and are two to three times higher than those during interglacial periods, MIS 1 and 5. EEP bottom waters were likely suboxic during times of the last glacial period when atmospheric CO2 concentrations were at their lowest concentrations. In addition, the pattern of increased deep-water oxygenation during times of higher CO2 during the last glacial is similar to that reported in a study of authigenic U in sediments from the Antarctic Zone of the Southern Ocean (Jaccard et al., 2016). We suggest that a respired carbon pool existed within a large swath of the abyssal Southern and Pacific Oceans throughout the entire last glacial cycle, and that this respired carbon was periodically released through increased ventilation of deep ocean waters. Jaccard et al. (2016) Nature 530, 207-210.

Modeling the UO2 ex-AUC pellet process and predicting the fuel rod temperature distribution under steady-state operating condition

NASA Astrophysics Data System (ADS)

Hung, Nguyen Trong; Thuan, Le Ba; Thanh, Tran Chi; Nhuan, Hoang; Khoai, Do Van; Tung, Nguyen Van; Lee, Jin-Young; Jyothi, Rajesh Kumar

2018-06-01

Modeling uranium dioxide pellet process from ammonium uranyl carbonate - derived uranium dioxide powder (UO2 ex-AUC powder) and predicting fuel rod temperature distribution were reported in the paper. Response surface methodology (RSM) and FRAPCON-4.0 code were used to model the process and to predict the fuel rod temperature under steady-state operating condition. Fuel rod design of AP-1000 designed by Westinghouse Electric Corporation, in these the pellet fabrication parameters are from the study, were input data for the code. The predictive data were suggested the relationship between the fabrication parameters of UO2 pellets and their temperature image in nuclear reactor.

Geographical coincidence of high heat flow, high seismicity, and upwelling, with hydrocarbon deposits, phosphorites, evaporites, and uranium ores.

PubMed

Libby, L M; Libby, W F

1974-10-01

Oil deposits occur in deep sediments, and appear to be organic matter that has been transformed through the action of geothermal heat and pressure. Deep sediments, rich in biological remains, are created by ocean upwelling, caused in part by high geothermal heat flow through the sea bottom. Such regions correlate with enhanced seismic activity. We look for correlations of seismicity, high heat flux, petroleum, uranium, phosphates, and salts, deposited from abundant plant life. These may be useful in discovering more petroleum and coal. We estimate that the known world reserves of petroleum and coal are about 10(-4) of the total of buried biogenic carbon.

Optimized LWIR enhancement of nanosecond and femtosecond LIBS uranium emission

NASA Astrophysics Data System (ADS)

Akpovo, Codjo A.; Ford, Alan; Johnson, Lewis

2016-05-01

A carbon dioxide (CO2) transverse electrical breakdown in atmosphere (TEA), pulsed laser was used to enhance the laser-induced breakdown spectroscopy (LIBS) spectral signatures of uranium under nanosecond (ns) and femtosecond (fs) ablation. The peak areas of both ionic and neutral species increased by one order of magnitude for ns-ablation and two orders of magnitude for fs-ablation over LIBS when the CO2 TEA laser was used with samples of dried solutions of uranyl nitrate hexahydrate (UO2(NO3)2·6H2O) on silicon wafers. Electron temperature and density measurements show that the spectral emission improvement from using the TEA laser comes from plasma reheating.

Geographical Coincidence of High Heat Flow, High Seismicity, and Upwelling, with Hydrocarbon Deposits, Phosphorites, Evaporites, and Uranium Ores

PubMed Central

Libby, L. M.; Libby, W. F.

1974-01-01

Oil deposits occur in deep sediments, and appear to be organic matter that has been transformed through the action of geothermal heat and pressure. Deep sediments, rich in biological remains, are created by ocean upwelling, caused in part by high geothermal heat flow through the sea bottom. Such regions correlate with enhanced seismic activity. We look for correlations of seismicity, high heat flux, petroleum, uranium, phosphates, and salts, deposited from abundant plant life. These may be useful in discovering more petroleum and coal. We estimate that the known world reserves of petroleum and coal are about 10-4 of the total of buried biogenic carbon. Images PMID:16592185

Radium and uranium levels in vegetables grown using different farming management systems.

PubMed

Lauria, D C; Ribeiro, F C A; Conti, C C; Loureiro, F A

2009-02-01

Vegetables grown with phosphate fertilizer (conventional management), with bovine manure fertilization (organic management) and in a mineral nutrient solution (hydroponic) were analyzed and the concentrations of (238)U, (226)Ra and (228)Ra in lettuce, carrots, and beans were compared. Lettuce from hydroponic farming system showed the lowest concentration of radionuclides 0.51 for (226)Ra, 0.55 for (228)Ra and 0.24 for (238)U (Bq kg(-1) dry). Vegetables from organically and conventionally grown farming systems showed no differences in the concentration of radium and uranium. Relationships between uranium content in plants and exchangeable Ca and Mg in soil were found, whereas Ra in vegetables was inversely correlated to the cation exchange capacity of soil, leading to the assumption that by supplying carbonate and cations to soil, liming may cause an increase of U and a decrease of radium uptake by plants. The soil to plant transfer varied from 10(-4) to 10(-2) for (238)U and from 10(-2) to 10(-1) for (228)Ra.

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

Magnesium fluoride reduction-vessel liners. Final report

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

Latham-Brown, C.E.

1986-03-26

The work described in this report details a program that demonstrated a method by which magnesium fluoride, the by-product of the reduction reaction of uranium tetrafluoride to uranium metal could be used to replace the present graphite used to line the reduction vessel. Utilization of magnesium fluoride (MgF2) as a reduction-vessel liner has the potential to decrease carbon contamination and thereby reduce DU derby rejects due to chemistry. Additionally, there would be the elimination of the cost of the graphite crucible liner and the associated disposal costs by replacement with the by-product of the reduction reaction, which is magnesium fluoride.more » The process would ultimately result in reduced manufacturing costs for derby metal and higher yield of finished penetrators. This was to be accomplished in such a manner as to produce uranium metal derbies which would be accommodated into the present Nuclear Metals-Carolina Metals penetrator production process with minimal changes in equipment and procedures.« less

Measurement of carbon distribution in nuclear fuel pin cladding specimens by means of a secondary ion mass spectrometer

NASA Astrophysics Data System (ADS)

Bart, Gerhard; Aerne, Ernst Tino; Burri, Martin; Zwicky, Hans-Urs

1986-11-01

Cladding carburization during irradiation of advanced mixed uranium plutonium carbide fast breeder reactor fuel is possibly a life limiting fuel pin factor. The quantitative assessment of such clad carbon embrittlement is difficult to perform by electron microprobe analysis because of sample surface contamination, and due to the very low energy of the carbon K α X-ray transition. The work presented here describes a method developed at the Swiss Federal Institute for Reactor Research (EIR) to use shielded secondary ion mass spectrometry (SIMS) as an accurate tool to determine radial distribution profiles of carbon in radioactive stainless steel fuel pin cladding. Compared with nuclear microprobe analysis (NMA) [1], which is also an accurate method for carbon analysis, the SIMS method distinguishes itself by its versatility for simultaneous determination of additional impurities.

Geology of the Midnite uranium mine area, Washington: maps, description, and interpretation

USGS Publications Warehouse

Nash, J. Thomas

1977-01-01

Bedrock geology of about 12 km2 near the Midnite mine has been mapped at the surface, in mine exposures, and from drilling, at scales from 1:600 to 1:12,000 and is presented here at 1:12,000 to provide description of the setting of uranium deposits. Oldest rocks in the area are metapelitic and metacarbonate rocks of the Precambrian (Y) Togo Formation. The chief host for uranium deposits is graphitic and pyritic mica phyllite and muscovite schist. Ore also occurs in calc-silicate hornfels and marble at the western edge of a calcareous section about 1,150 m thick. Calcareous rocks of the Togo are probably older than the pelitic as they are interpreted to be near the axis of a broad anticline. The composition and structural position of the calcareous unit suggests correlation with less metamorphosed carbonate-bearing rocks of the Lower Wallace Formation, Belt Supergroup, about 200 km to the east. Basic sills intrusive into the Togo have been metamorphosed to amphibolite. Unmetamorphosed rocks in the mine area are Cretaceous(?) and Eocene igneous rocks. Porphyritic quartz monzonite of Cretaceous age, part of the Loon Lake batholith, is exposed over one third of the mine area. It underlies the roof pendant of Precambrian rocks in which the Midnite mine occurs at depths of generally less than 300 m. The pluton is a two-mica granite and exhibits pegmatitic and aplitic textural features indicative of water saturation and pressure quenching. Eocene intrusive and extrusive rocks in the area provide evidence that the Eocene surface was only a short distance above the present uranium deposits. Speculative hypotheses are presented for penesyngenetic, hydrothermal, and supergene modes of uranium emplacement. The Precambrian Stratigraphy, similar in age and pre-metamorphic lithology to that of rocks hosting large uranium deposits in Saskatchewan and Northern Territory, Australia, suggests the possibility of uranium accumulation along with diagenetic pyrite in carbonaceous muds in a marine shelf environment. This hypothesis is not favored by the author because there is no evidence for stratabound uranium such as high regional radioactivity in the Togo. A hydrothermal mode of uranium emplacement is supported by the close apparent ages of mineralization and plutonism, and by petrology of the pluton. I speculate that uranium may have become enriched in postmagmatic fluids at the top of the pluton, possibly by hydrothermal leaching of soluble uranium associated with magnetite, and diffused outward into metasedimentary wall rocks to create an aureole about 100 m thick containing about 100 ppm uranium. Chemistry of the hydrothermal process is not understood, but uranium does not appear to have been transported by an oxidizing fluid, and the fluid did not produce veining and alteration comparable to that of base-metal sulfide deposits. Uranium in the low-grade protore is believed to have been redistributed into permeable zones in the Tertiary to create ore grades. Geologic and isotopic ages of uranium mineralization, and the small volume of porphyritic quartz monzonite available for leaching, are not supportive of supergene emplacement of uranium.

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.

A literature review of interaction of oxidized uranium species and uranium complexes with soluble organic matter

USGS Publications Warehouse

Jennings, Joan K.; Leventhal, J.S.

1978-01-01

Organic material is commonly found associated with uranium ores in sandstone-type deposits. This review of the literature summarizes the classes and separations of naturally occurring organic material but the emphasis is on soluble organic species. The main class of materials of interest is humic substances which are high-molecular-weight complex molecules that are soluble in alkaline solution. These humic substances are able to solubilize (make soluble) minerals and also to complex [by ion exchange and (or) chelation] many cations. The natural process of soil formation results in both mineral decomposition and element complexing by organic species. Uranium in solution, such as ground water, can form many species with other elements or complexes present depending on Eh and pH. In natural systems (oxidizing Eh, pH 5-9) the uranium is usually present as a complex with hydroxide or carbonate. Thermodynamic data for these species are presented. Interacting metals and organic materials have been observed in nature and studied in the laboratory by many workers in diverse scientific disciplines. The results are not easily compared. Measurements of the degree of complexation are reported as equilibrium stability constant determinations. This type of research has been done for Mn, Fe, Cu, Zn, Pb, Ni, Co, Mg, Ca, Al, and to a limited degree for U. The use of Conditional Stability Constants has given quantitative results in some cases. The methods utilized in experiments and calculations are reviewed.

Effect of bicarbonate on aging and reactivity of nanoscale zerovalent iron (nZVI) toward uranium removal.

PubMed

Hua, Yilong; Wang, Wei; Huang, Xiaoyue; Gu, Tianhang; Ding, Dexin; Ling, Lan; Zhang, Wei-Xian

2018-06-01

Bicarbonate, ubiquitous in natural and waste waters is an important factor regulating the rate and efficiency of pollutant separation and transformation. For example, it can form complexes with U(VI) in the aqueous phase and at the solid-water interface. In this work, we investigated the effect of bicarbonate on the aging of nanoscale zero-valent (nZVI) in the context of U(VI) reduction and removal from wastewater. For fresh nZVI, over 99% aqueous uranium was separated in less than 10 min, of which 83% was reduced from U(VI) to U(IV). When nZVI was aged in water, its activity for U(VI) sequestration and reduction was significantly reduced. Batch experiments showed that for nZVI aged in the presence of 10 mM bicarbonate, only 20.3% uranium was reduced to U(IV) after 6 h reactions. Characterizations of the iron nanoparticles with spherical aberration corrected scanning transmission electron microscopy (Cs-STEM) suggest that in fresh nZVI, uranium was concentrated at the nanoparticle center; whereas in nZVI aged in bicarbonate, uranium was largely deposited on the outer surface of the nanoparticles. Furthermore, aged nZVI without bicarbonate contained more lepidocrocite (γ-FeOOH) while aged nZVI in the presence of bicarbonate had more magnetite/maghemite (Fe 3 O 4 /γ-Fe 2 O 3 ). This could be attributed to the formation of carbonate green rust and pH buffer effect of . Primary mechanisms for U(VI) removal with nZVI include reduction, sorption and/or precipitation. Results demonstrate that bicarbonate alter the aging products of nZVI, and reduces the separation efficiency and reduction capability for uranium removal. Copyright © 2018. Published by Elsevier Ltd.

Uranium biogeochemistry across the redox transition zone of a permanently stratified fjord: Framvaren, Norway

USGS Publications Warehouse

Swarzenski, P.W.; McKee, B.A.; Skei, J.M.; Todd, J.F.

1999-01-01

During August 1995, the vertical concentration profile of dissolved and particulate uranium exhibited strong non-conservative characteristics in the upper 30 m of Framvaren Fjord. There was a pronounced peak in both particulate (> 0.2 ??m; 1.09 nM) and dissolved (< 0.2 ??m; 17.06 nM) uranium in the finely stratified waters at the O2/H2S interface which is positioned well within the euphotic zone at about 20-21 m. Such concentration maxima at the redox boundary are also observed for dissolved organic carbon (DEC), Sr and Ba. Dissolved U levels seen in the water column from 18 m down to 30 m exceeded the high salinity (salinity = 35) U concentrations (13.63 ?? 0.84 nM; Chen, J.H., Edwards, R.L., Wasserburg, G.L., 1986. 238U, 234U and 232Th in seawater. Earth Planet Sci. Lett. 80, 241-251.) observed uniformly in the open ocean. A prolific population of S microbes (e.g., Chromatium, Chlorobium sp.) flourishes at the O2/H2S interface. The source of elevated U at the redox boundary must be due to microbial uptake and subsequent release processes rather than dilution from oceanic uranium. Uranium oxidation state determinations in waters from 1, 22 and 30 m depth reveal that reduced U(IV) is not present in significant abundance, and that the chemical and/or biological reduction of hexavalent uranium is largely inhibited. Our results suggest that U and other trace constituents such as DOC, Sr, Ba, Fe(II), Mn(II) are greatly modified by direct and indirect microbial transformation reactions which are most concentrated across the redox transition zone in Framvaren Fjord.

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.

A Methodology for Characterizing Potential Uranium Transport in Deep Geological Disposal Sites

NASA Astrophysics Data System (ADS)

Dittrich, T. M.; Reimus, P. W.

2013-12-01

In order to make safe and reasonable decisions about radioactive waste disposal in deep geologic sites, it is important to understand the fate and potential transport of long half-life transuranic radionuclides over a wide range of time and distance scales. The objective of this study was to evaluate and demonstrate new experimental methods for quantifying the potential for actinide transport in deep fractured crystalline rock formations. We selected a fractured/weathered granodiorite at the Grimsel Test Site (GTS) in Switzerland as a model system because field experiments involving uranium, as well as other actinides, have already been conducted. Working on this system provides a unique opportunity to compare lab experimental results with field-scale observations. Drilled rock cores and weathered fracture fill material (FFM) from the GTS were shipped to Los Alamos National Laboratory, characterized by x-ray diffraction and microscopy, and used in batch sorption/desorption and column breakthrough experiments. Uranium solutions were made by adding uranium to a synthetic Grimsel groundwater that matched the natural water chemistry found in the GTS groundwater. Batch and breakthrough experiments were conducted using solutions between pH 6.9 and 9.0. All column experiments were conducted using syringe pumps at low flow rate (<0.3 ml h-1) in small columns containing 5 g of material with pore volumes of 2-3 ml. These small columns allow rapid and economical evaluation of sorption/desorption behavior under flowing conditions (and in duplicate or triplicate). Solutions were switched to uranium-free synthetic Grimsel groundwater after equilibration in batch experiments or after near-steady uranium breakthrough occurred in column experiments. The measurement of uranium concentrations as a function of time under these conditions allowed interrogation of desorption rates which we believe control uranium fate and transport over long time and distance scales. Uranium transport was conservative and matched tritium breakthrough for pH 9.0; however, retardation increased when pH was reduced to 7.9 and 6.9. We are currently evaluating uranium adsorption/desorption rates as a function of water chemistry (initial focus on pH), with future testing planned to evaluate the influence of carbonate concentrations, flow rates, mineralogy, bentonite colloids and other actinides (e.g., Am). Figure 1. Uranium breakthrough results for (a) 6.5 μM U, (b) U-free solution, (c) flow rate increased from 0.3 to 0.6 mL h-1, (d) pH increased from 6.8 to 7.2, and (e) pH increased from 7.2 to 8.8.

Neutralisation of an acidic pit lake by alkaline waste products.

PubMed

Allard, Bert; Bäckström, Mattias; Karlsson, Stefan; Grawunder, Anja

2014-01-01

A former open pit where black shale (alum shale) was excavated during 1942-1965 has been water filled since 1966. The water chemistry was dominated by calcium and sulphate and had a pH of 3.2-3.4 until 1997-1998, when pH was gradually increasing. This was due to the intrusion of leachates from alkaline cement waste deposited close to the lake. A stable pH of around 7.5 was obtained after 6-7 years. The chemistry of the pit lake has changed due to the neutralisation. Concentrations of some dissolved metals, notably zinc and nickel, have gone down, as a result of adsorption/co-precipitation on solid phases (most likely iron and aluminium hydroxides), while other metals, notably uranium and molybdenum, are present at elevated levels. Uranium concentration is reaching a minimum of around pH 6.5 and is increasing at higher pH, which may indicate a formation of neutral and anionic uranyl carbonate species at high pH (and total carbonate levels around 1 mM). Weathering of the water-exposed shale is still in progress.

Aerodynamic levitator for in situ x-ray structure measurements on high temperature and molten nuclear fuel materials

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

Weber, J. K. R.; Alderman, O. L. G.; Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439

2016-07-15

An aerodynamic levitator with carbon dioxide laser beam heating was integrated with a hermetically sealed controlled atmosphere chamber and sample handling mechanism. The system enabled containment of radioactive samples and control of the process atmosphere chemistry. The chamber was typically operated at a pressure of approximately 0.9 bars to ensure containment of the materials being processed. Samples 2.5-3 mm in diameter were levitated in flowing gas to achieve containerless conditions. Levitated samples were heated to temperatures of up to 3500 °C with a partially focused carbon dioxide laser beam. Sample temperature was measured using an optical pyrometer. The sample environment wasmore » integrated with a high energy (100 keV) x-ray synchrotron beamline to enable in situ structure measurements to be made on levitated samples as they were heated, melted, and supercooled. The system was controlled from outside the x-ray beamline hutch by using a LabVIEW program. Measurements have been made on hot solid and molten uranium dioxide and binary uranium dioxide-zirconium dioxide compositions.« less

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

Gerczak, Tyler J.; Smith, Kurt R.; Petrie, Christian M.

Tristructural-isotropic (TRISO)–coated particle fuel is a promising advanced fuel concept consisting of a spherical fuel kernel made of uranium oxide and uranium carbide, surrounded by a porous carbonaceous buffer layer and successive layers of dense inner pyrolytic carbon (IPyC), silicon carbide (SiC) deposited by chemical vapor , and dense outer pyrolytic carbon (OPyC). This fuel concept is being considered for advanced reactor applications such as high temperature gas-cooled reactors (HTGRs) and molten salt reactors (MSRs), as well as for accident-tolerant fuel for light water reactors (LWRs). Development and implementation of TRISO fuel for these reactor concepts support the US Departmentmore » of Energy (DOE) Office of Nuclear Energy mission to promote safe, reliable nuclear energy that is sustainable and environmentally friendly. During operation, the SiC layer serves as the primary barrier to metallic fission products and actinides not retained in the kernel. It has been observed that certain fission products are released from TRISO fuel during operation, notably, Ag, Eu, and Sr [1]. Release of these radioisotopes causes safety and maintenance concerns.« less

Aerodynamic levitator for in situ x-ray structure measurements on high temperature and molten nuclear fuel materials

DOE PAGES

Weber, J. K. R.; Tamalonis, A.; Benmore, C. J.; ...

2016-07-01

We integrated an aerodynamic levitator with carbon dioxide laser beam heating with a hermetically sealed controlled atmosphere chamber and sample handling mechanism. The system enabled containment of radioactive samples and control of the process atmosphere chemistry. Furthermore, the chamber was typically operated at a pressure of approximately 0.9 bars to ensure containment of the materials being processed. Samples 2.5-3 mm in diameter were levitated in flowing gas to achieve containerless conditions. Levitated samples were heated to temperatures of up to 3500 °C with a partially focused carbon dioxide laser beam. Sample temperature was measured using an optical pyrometer. The samplemore » environment was integrated with a high energy (100 keV) x-ray synchrotron beamline to enable in situ structure measurements to be made on levitated samples as they were heated, melted, and supercooled. Our system was controlled from outside the x-ray beamline hutch by using a LabVIEW program. Measurements have been made on hot solid and molten uranium dioxide and binary uranium dioxide-zirconium dioxide compositions.« less

Uranium Stable Isotopes: A Proxy For Productivity Or Ocean Oxygenation?

NASA Astrophysics Data System (ADS)

Severmann, S.

2015-12-01

Uranium elemental abundances in sediments have traditionally been used to reconstruct primary productivity and carbon flux in the ocean. 238U/235U isotope compositions, in contrast, are currently understood to reflect the extent of bottom water anoxia in the ocean. A review of our current understanding of authigenic U enrichment mechanism into reducing sediments suggests that a revision of this interpretation is warranted. Specifically, the current interpretation of U isotope effects in suboxic vs. anoxic deposits has not taken into account the well-documented linear relationship with organic C burial rates. Although organic C rain rates (i.e., surface productivity) and bottom water oxygenation are clearly related, distinction between these two environmental controls is conceptually important as it relates to the mechanism of enhanced C burial and ultimately the strength of the biological pump. Here we will review new and existing data to test the hypothesis that the isotope composition of authigenic U in reducing sediments are best described by their relationship with parameters related to organic carbon delivery and burial, rather than bottom water oxygen concentration.

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

PubMed

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

2010-06-28

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

Processing of solid solution, mixed uranium/refractory metal carbides for advanced space nuclear power and propulsion systems

NASA Astrophysics Data System (ADS)

Knight, Travis Warren

Nuclear thermal propulsion (NTP) and space nuclear power are two enabling technologies for the manned exploration of space and the development of research outposts in space and on other planets such as Mars. Advanced carbide nuclear fuels have been proposed for application in space nuclear power and propulsion systems. This study examined the processing technologies and optimal parameters necessary to fabricate samples of single phase, solid solution, mixed uranium/refractory metal carbides. In particular, the pseudo-ternary carbide, UC-ZrC-NbC, system was examined with uranium metal mole fractions of 5% and 10% and corresponding uranium densities of 0.8 to 1.8 gU/cc. Efforts were directed to those methods that could produce simple geometry fuel elements or wafers such as those used to fabricate a Square Lattice Honeycomb (SLHC) fuel element and reactor core. Methods of cold uniaxial pressing, sintering by induction heating, and hot pressing by self-resistance heating were investigated. Solid solution, high density (low porosity) samples greater than 95% TD were processed by cold pressing at 150 MPa and sintering above 2600 K for times longer than 90 min. Some impurity oxide phases were noted in some samples attributed to residual gases in the furnace during processing. Also, some samples noted secondary phases of carbon and UC2 due to some hyperstoichiometric powder mixtures having carbon-to-metal ratios greater than one. In all, 33 mixed carbide samples were processed and analyzed with half bearing uranium as ternary carbides of UC-ZrC-NbC. Scanning electron microscopy, x-ray diffraction, and density measurements were used to characterize samples. Samples were processed from powders of the refractory mono-carbides and UC/UC 2 or from powders of uranium hydride (UH3), graphite, and refractory metal carbides to produce hypostoichiometric mixed carbides. Samples processed from the constituent carbide powders and sintered at temperatures above the melting point of UC showed signs of liquid phase sintering and were shown to be largely solid solutions. Pre-compaction of mixed carbide powders prior to sintering was shown to be necessary to achieve high densities. Hypostoichiometric, samples processed at 2500 K exhibited only the initial stage of sintering and solid solution formation. Based on these findings, a suggested processing methodology is proposed for producing high density, solid solution, mixed carbide fuels. Pseudo-binary, refractory carbide samples hot pressed at 3100 K and 6 MPa showed comparable densities (approximately 85% of the theoretical value) to samples processed by cold pressing and sintering at temperatures of 2800 K.

Radio-Ecological Conditions of Groundwater in the Area of Uranium Mining and Milling Facility - 13525

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

Titov, A.V.; Semenova, M.P.; Seregin, V.A.

2013-07-01

Manmade chemical and radioactive contamination of groundwater is one of damaging effects of the uranium mining and milling facilities. Groundwater contamination is of special importance for the area of Priargun Production Mining and Chemical Association, JSC 'PPMCA', because groundwater is the only source of drinking water. The paper describes natural conditions of the site, provides information on changes of near-surface area since the beginning of the company, illustrates the main trends of contaminators migration and assesses manmade impact on the quality and mode of near-surface and ground waters. The paper also provides the results of chemical and radioactive measurements inmore » groundwater at various distances from the sources of manmade contamination to the drinking water supply areas. We show that development of deposits, mine water discharge, leakages from tailing dams and cinder storage facility changed general hydro-chemical balance of the area, contributed to new (overlaid) aureoles and flows of scattering paragenetic uranium elements, which are much smaller in comparison with natural ones. However, increasing flow of groundwater stream at the mouth of Sukhoi Urulyungui due to technological water infiltration, mixing of natural water with filtration streams from industrial reservoirs and sites, containing elevated (relative to natural background) levels of sulfate-, hydro-carbonate and carbonate- ions, led to the development and moving of the uranium contamination aureole from the undeveloped field 'Polevoye' to the water inlet area. The aureole front crossed the southern border of water inlet of drinking purpose. The qualitative composition of groundwater, especially in the southern part of water inlet, steadily changes for the worse. The current Russian intervention levels of gross alpha activity and of some natural radionuclides including {sup 222}Rn are in excess in drinking water; regulations for fluorine and manganese concentrations are also in excess. Possible ways to improve the situation are considered. (authors)« less

PROCESS OF MAKING SHAPED FUEL FOR NUCLEAR REACTORS

DOEpatents

O'Leary, W.J.; Fisher, E.A.

1964-02-11

A process for making uranium dioxide fuel of great strength, density, and thermal conductivity by mixing it with 0.1 to 1% of a densifier oxide (tin, aluminum, zirconium, ferric, zinc, chromium, molybdenum, titanium, or niobium oxide) and with a plasticizer (0.5 to 3% of bentonite and 0.05 to 2% of methylcellulose, propylene glycol alginate, or ammonium alginate), compacting the mixture obtained, and sintering the bodies in an atmosphere of carbon monoxide or carbon dioxide, with or without hydrogen, or of a nitrogen-hydrogen mixture is described. (AEC)

The effect of hydrogen peroxide on uranium oxide films on 316L stainless steel

NASA Astrophysics Data System (ADS)

Wilbraham, Richard J.; Boxall, Colin; Goddard, David T.; Taylor, Robin J.; Woodbury, Simon E.

2015-09-01

For the first time the effect of hydrogen peroxide on the dissolution of electrodeposited uranium oxide films on 316L stainless steel planchets (acting as simulant uranium-contaminated metal surfaces) has been studied. Analysis of the H2O2-mediated film dissolution processes via open circuit potentiometry, alpha counting and SEM/EDX imaging has shown that in near-neutral solutions of pH 6.1 and at [H2O2] ⩽ 100 μmol dm-3 the electrodeposited uranium oxide layer is freely dissolving, the associated rate of film dissolution being significantly increased over leaching of similar films in pH 6.1 peroxide-free water. At H2O2 concentrations between 1 mmol dm-3 and 0.1 mol dm-3, formation of an insoluble studtite product layer occurs at the surface of the uranium oxide film. In analogy to corrosion processes on common metal substrates such as steel, the studtite layer effectively passivates the underlying uranium oxide layer against subsequent dissolution. Finally, at [H2O2] > 0.1 mol dm-3 the uranium oxide film, again in analogy to common corrosion processes, behaves as if in a transpassive state and begins to dissolve. This transition from passive to transpassive behaviour in the effect of peroxide concentration on UO2 films has not hitherto been observed or explored, either in terms of corrosion processes or otherwise. Through consideration of thermodynamic solubility product and complex formation constant data, we attribute the transition to the formation of soluble uranyl-peroxide complexes under mildly alkaline, high [H2O2] conditions - a conclusion that has implications for the design of both acid minimal, metal ion oxidant-free decontamination strategies with low secondary waste arisings, and single step processes for spent nuclear fuel dissolution such as the Carbonate-based Oxidative Leaching (COL) process.

Anomalous Lead Isotopic Composition of Galena and Age of Altered Uranium Minerals: a Case study of Chauli Deposits, Chatkal-Qurama District, Uzbekistan

NASA Astrophysics Data System (ADS)

Chernyshev, I. V.; Golubev, V. N.; Chugaev, A. V.

2017-11-01

The enrichment of lead isotopic composition of nonuranium minerals, in the first place galena in 206Pb and 207Pb, as compared to common lead is a remarkable feature of uranium deposits. The study of such lead isotopic composition anomalous in 206Pb and 207Pb in uranium minerals provides an opportunity for not only identification of superimposed processes resulting in transformation of uranium ores during deposit history but also calculation of age of these processes under certain model assumptions. Galena from the Chauli deposit in the Chatkal-Qurama district, Uzbekistan, a typical representative of hydrothermal uranium deposits associated with domains of Phanerozoic continental volcanism, has been examined with the highprecision (±0.02%) MC-ICP-MS method. Twenty microsamples of galena were taken from polished sections. Six of them are galena hosted in carbonate adjacent to pitchblende spherulites or filling thin veinlets (approximately 60 μm) cutting pitchblende. Isotopically anomalous lead with 206Pb/204Pb and 207Pb/204Pb values reaching 20.462 and 15.743, respectively, has been found in these six microsamples in contrast to another fourteen in which the Pb-Pb characteristics are consistent with common lead. On the basis of these data and with account for the 292 ± 2 Ma age for the Chauli deposit, the age of epigenetic transformation of uranium ores of this deposit has been estimated. During this process, radiogenic lead partly lost from pitchblende was captured into galena. The obtained date is 170 Ma. In the Chatkal-Qurama district, these epigenetic processes are apparently caused by the interaction of uranium minerals with activated underground water under tectonic activity and relief transformation, which took place from the post-Permian (i.e., after the Chauli formation) to the Jurassic period.

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.

Composite catalyst for carbon monoxide and hydrocarbon oxidation

DOEpatents

Liu, W.; Flytzani-Stephanopoulos, M.

1996-03-19

A method and composition are disclosed for the complete oxidation of carbon monoxide and/or hydrocarbon compounds. The method involves reacting the carbon monoxide and/or hydrocarbons with an oxidizing agent in the presence of a metal oxide composite catalyst. The catalyst is prepared by combining fluorite-type oxygen ion conductors with active transition metals. The fluorite oxide, selected from the group consisting of cerium oxide, zirconium oxide, thorium oxide, hafnium oxide, and uranium oxide, and may be doped by alkaline earth and rare earth oxides. The transition metals, selected from the group consisting of molybdenum, copper, cobalt, manganese, nickel, and silver, are used as additives. The atomic ratio of transition metal to fluorite oxide is less than one.

Composite catalyst for carbon monoxide and hydrocarbon oxidation

DOEpatents

Liu, Wei; Flytzani-Stephanopoulos, Maria

1996-01-01

A method and composition for the complete oxidation of carbon monoxide and/or hydrocarbon compounds. The method involves reacting the carbon monoxide and/or hydrocarbons with an oxidizing agent in the presence of a metal oxide composite catalyst. The catalyst is prepared by combining fluorite-type oxygen ion conductors with active transition metals. The fluorite oxide, selected from the group consisting of cerium oxide, zirconium oxide, thorium oxide, hafnium oxide, and uranium oxide, and may be doped by alkaline earth and rare earth oxides. The transition metals, selected from the group consisting of molybdnum, copper, cobalt, maganese, nickel, and silver, are used as additives. The atomic ratio of transition metal to fluorite oxide is less than one.

Neutron production by stopping 55 MeV deuterons in carbon and heavy water

NASA Astrophysics Data System (ADS)

Lhersonneau, G.; Malkiewicz, T.; Jones, P.; Ketelhut, S.; Trzaska, W. H.

2012-09-01

Neutron production by stopping 55 MeV deuterons in thick carbon and heavy-water targets has been measured by the activation method. The geometry was close to the one defined for the SPIRAL2 uranium-carbide target in the initial phase. A comparative method for obtaining the neutron flux has been used and is presented in detail. The neutron flux generated by 55 MeV deuterons on carbon is 2.3 times the flux at the deuteron energy of 40 MeV. The flux further increases by a factor 1.4 when using a heavy-water target. These results are discussed in the context of an energy upgrade of the SPIRAL2 driver accelerator.

Contributions to the geology of uranium and thorium by the United States Geological Survey and Atomic Energy Commission for the United Nations International Conference on Peaceful Uses of Atomic Energy, Geneva, Switzerland, 1955

USGS Publications Warehouse

Page, Lincoln R.; Stocking, Hobart E.; Smith, Harriet B.

1956-01-01

Within the boundaries of the United States abnormal amounts of uranium have been found in rocks of nearly all geologic ages and lithologic types. Distribution of ore is more restricted. On the Colorado Plateau, the Morrison formation of Jurassic age yields 61.4 percent of the ore produced in the United States, and the Chinle conglomerate and Shinarump formation of Triassic age contribute 26.0 and 5.8 percent, respectively. Clastic, carbonaceous, and carbonate sedimentary rocks of Tertiary, Mesozoic, and Paleozoic ages and veins of Tertiary age are the source of the remaining 6.8 percent.

Acceptance Test Data for BWXT Coated Particle Batch 93164A Defective IPyC Fraction and Pyrocarbon Anisotropy

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

Helmreich, Grant W.; Hunn, John D.; Skitt, Darren J.

2017-02-01

Coated particle fuel batch J52O-16-93164 was produced by Babcock and Wilcox Technologies (BWXT) for possible selection as fuel for the Advanced Gas Reactor Fuel Development and Qualification (AGR) Program’s AGR-5/6/7 irradiation test in the Idaho National Laboratory (INL) Advanced Test Reactor (ATR), or may be used as demonstration production-scale coated particle fuel for other experiments. The tristructural-isotropic (TRISO) coatings were deposited in a 150-mm-diameter production-scale fluidizedbed chemical vapor deposition (CVD) furnace onto 425-μm-nominal-diameter spherical kernels from BWXT lot J52L-16-69316. Each kernel contained a mixture of 15.5%-enriched uranium carbide and uranium oxide (UCO) and was coated with four consecutive CVD layers:more » a ~50% dense carbon buffer layer with 100-μm-nominal thickness, a dense inner pyrolytic carbon (IPyC) layer with 40-μm-nominal thickness, a silicon carbide (SiC) layer with 35-μm-nominal thickness, and a dense outer pyrolytic carbon (OPyC) layer with 40-μm-nominal thickness. The TRISO-coated particle batch was sieved to upgrade the particles by removing over-sized and under-sized material, and the upgraded batch was designated by appending the letter A to the end of the batch number (i.e., 93164A).« less

Evolution of the atomic order and valence state of rare-earth atoms and uranium in a new carbon-metal composite—diphthalocyanine pyrolysate C64H32N16 Me ( Me = Y, La, Ce, Eu, and U)

NASA Astrophysics Data System (ADS)

Sovestnov, A. E.; Kapustin, V. K.; Tikhonov, V. I.; Fomin, E. V.; Chernenkov, Yu. P.

2014-08-01

The structure of a metal-carbon composite formed by the pyrolysis of diphthalocyanine of some rare-earth elements (Y, La, Ce, Eu) and uranium in the temperature range T ann = 800-1700°C has been investigated for the first time by the methods of X-ray diffraction analysis and X-ray line shift. It has been shown that, in the general case, the studied pyrolysates consist of three phases. One phase corresponds to the structure of graphite. The second phase corresponds to nitrides, carbides, and oxides of basic metal elements with a crystallite size ranging from 5 to 100 nm. The third phase is amorphous or consisting of crystallites with a size of ˜1 nm. It has been found that all the basic elements (Y, La, Ce, Eu, U) and incorporated iodine atoms in the third phase are in a chemically bound state. The previously unobserved electronic configurations have been revealed for europium. The possibility of including not only atoms of elements forming diphthalocyanine but also other elements (for example, iodine) in the composite structure is of interest, in particular, for the creation of a thermally, chemically, and radiation resistant metal-carbon matrix for the radioactive waste storage.

Geochemical and mineralogical studies of a South Texas roll-front uranium deposit

USGS Publications Warehouse

Goldhaber, Martin B.; Reynolds, Richard L.

1977-01-01

Core samples from a roll-front uranium deposit in south Texas have been analyzed for iron sulfide content and mineralogy, organic carbon content and the abundance of carbonate, iron, manganese and titanium. Sulfide occurs almost exclusively as the iron disulfides pyrite and marcasite, in concentrations as high as 2 percent of the coarse (>62 ?m) fraction. Marcasite is particularly abundant relative to pyrite in the vicinity of the roll front. Because marcasite precipitation requires acidic pH's and the most likely mechanism for generating a low pH is oxidation of preore sulfide, it is argued that marcasite formation is, at least in part, related to roll-front development. Organic carbon analyses from various representative parts of the deposit are uniformly low (<0.1 percent C). This is taken to imply that sulfate reducing bacteria were not involved in either initial sulfidation of the host rock or during later sulfidization that was related to the ore-forming episode. carbonate minerals, such as calcite, are quite abundant, but appear to have formed after the ore. The overall abundance of iron apparently is not systematically related to position with respect to the roll front, whereas manganese probably is concentrated near the redox interface. Titanium like iron does not show a systematic relationship to position about the roll. However, titanium is systematically more abundant in the fine fraction (462 ?m) relative to the coarse fraction with distance downdip. This reflects a progressively more intense alteration of precursor iron titanium oxide minerals to fine-grained TiO2.

Isotopic Tracers for Delineating Non-Point Source Pollutants in Surface Water

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

Davisson, M L

2001-03-01

This study tested whether isotope measurements of surface water and dissolved constituents in surface water could be used as tracers of non-point source pollution. Oxygen-18 was used as a water tracer, while carbon-14, carbon-13, and deuterium were tested as tracers of DOC. Carbon-14 and carbon-13 were also used as tracers of dissolved inorganic carbon, and chlorine-36 and uranium isotopes were tested as tracers of other dissolved salts. In addition, large databases of water quality measurements were assembled for the Missouri River at St. Louis and the Sacramento-San Joaquin Delta in California to enhance interpretive results of the isotope measurements. Muchmore » of the water quality data has been under-interpreted and provides a valuable resource to investigative research, for which this report exploits and integrates with the isotope measurements.« less

Uranium in groundwater - A synopsis based on a large hydrogeochemical data set.

PubMed

Riedel, Thomas; Kübeck, Christine

2018-02-01

Most of the knowledge on the occurrence of Uranium (U) in groundwater comes from in-situ manipulation experiments in the field, computational modelling studies or from laboratory analyses where individual processes of U mobilization were studied in isolation. Because of Uranium's vital redox chemistry it interacts, often simultaneously, with many other element cycles (e.g., sulfur, carbon, iron, and manganese) making it difficult to predict U concentrations in natural environments. For the present study a large data set was analyzed to predict the occurrence of U in groundwater from basic hydrochemistry. The data set consists of more than 8000 chemical groundwater analyses (including Uranium concentrations) from more than 2000 sampling locations. A strong relation between U concentrations and electric conductivity as well as alkalinity was observed, suggesting that weathering of geogenic source material and desorption from mineral surfaces is the principle mechanism of U release. Except for aquifers with strongly reducing conditions this process leads to a slow but continuous accumulation of U in groundwater in most cases. Importantly, the occurrence of U is modulated by the prevailing redox conditions in an aquifer. Uranium concentrations were moderate under oxic conditions and highest under manganese and nitrate-reducing conditions (heterotrophic as wells as autotrophic nitrate reduction). Only in iron- and sulfate-reducing groundwater the probability of U concentrations above 1 μg l -1 was virtually zero, as these ground waters act as U sinks. The combination of mineral weathering (especially carbonates) with mobilization of U under manganese and nitrate reducing conditions results in the highest risk of detecting U. In contrast, a low risk is associated with low pH (<7) and low mineralization of groundwater, which is the case in granitic catchments, for example. Our results further provide evidence, that agricultural practices such as liming, use of fertilizers and irrigation influence the occurrence of U in groundwater in multiple ways. Accurate management of aquifers underlying farmland will therefore become more and more important in the future. In summary, we find that the vulnerability of an aquifer to elevated U concentrations cannot be explained by a single factor. This complicates efforts to target elevated U concentrations in groundwaters that are abstracted for drinking water production. Copyright © 2017 Elsevier Ltd. All rights reserved.

REFRACTORY COATING FOR GRAPHITE MOLDS

DOEpatents

Stoddard, S.D.

1958-06-24

Refractory coating for graphite molds used in the casting of uranium is described. The coating is an alumino-silicate refractory composition which may be used as a mold surface in solid form or as a coating applied to the graphite mold. The composition consists of a mixture of ball clay, kaolin, alumina cement, alumina, water, sodium silicate, and sodium carbonate.

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

Weydert, M.; Brennan, J.G.; Andersen, R.A.

Reaction of (MeC{sub 5}H{sub 4}){sub 3}UX (X = Cl, MeC{sub 5}H{sub 4}) with t-BuLi affords the tertiary alkyl complex (MeC{sub 5}H{sub 4}){sub 3}U(t-Bu). Despite uranium(IV) generally being the preferred oxidation state in organometallic systems, (MeC{sub 5}H{sub 4}){sub 3}U(t-Bu) reacts with Lewis bases (L = PMe{sub 3}, THF, RCN, RNC) to yield the reduced uranium(III) base adducts (MeC{sub 5}H{sub 4}){sub 3}U(L). Carbon monoxide undergoes migratory insertion into the metal tertiary alkyl bond. The resulting acyl derivative decomposes at 90{degree}C to yield insoluble uranium-containing products and a mixture of tert-butyltoluenes by ring expansion of a methylcyclopentadienyl ligand. Ethylene also undergoes migratory insertionmore » into the metal tertiary alkyl bond. No subsequent insertion of ethylene into the metal carbon bond takes place after the first equivalent has inserted. In marked contrast, reaction of various (MeC{sub 5}H{sub 4}){sub 3}ThX (X = Cl, I, MeC{sub 5}H{sub 4}, O-2,6-Me{sub 2}C{sub 6}H{sub 3}, OTs) compounds with t-BuLi gave intractable materials. However, reaction of the cationic species [(RC{sub 5}H{sub 4}){sub 3}Th](BPh{sub 4}) (R = Me{sub 3}Si, t-Bu) with t-BuLi yields the new thorium hydrides (RC{sub 5}H{sub 4}){sub 3}ThH. 40 refs., 2 figs.« less

Radioactive mineral springs in Delta County, Colorado

USGS Publications Warehouse

Cadigan, Robert A.; Rosholt, John N.; Felmlee, J. Karen

1976-01-01

The system of springs in Delta County, Colo., contains geochemical clues to the nature and location of buried uranium-mineralized rock. The springs, which occur along the Gunnison River and a principal tributary between Delta and Paonia, are regarded as evidence of a still-functioning hydrothermal system. Associated with the springs are hydrogen sulfide and sulfur dioxide gas seeps, carbon dioxide gas-powered geysers, thick travertine deposits including radioactive travertine, and a flowing warm-water (41?C) radioactive well. Geochemical study of the springs is based on surface observations, on-site water-property measurements, and sampling of water, travertine, soft precipitates, and mud. The spring deposits are mostly carbonates, sulfates, sulfides, and chlorides that locally contain notable amounts of some elements, such as arsenic, barium, lithium, and radium. Samples from five localities have somewhat different trace element assemblages even though they are related to the same hydrothermal system. All the spring waters but one are dominated by sodium chloride or sodium bicarbonate. The exception is an acid sulfate water with a pH of 2.9, which contains high concentrations of aluminum and iron. Most of the detectable radioactivity is due to the presence of radium-226, a uranium daughter product, but at least one spring precipitate contains abundant radium-228, a thorium daughter product. The 5:1 ratio of radium-228 to radium-226 suggests the proximity of a vein-type deposit as a source for the radium. The proposed locus of a thorium-uranium mineral deposit is believed to lie in the vicinity of Paonia, Colo. Exact direction and depth are not determinable from data now available.

Genesis of kasolite associated with aplite-pegmatite at Jabal Sayid, Hijaz region, Kingdom of Saudi Arabia

NASA Astrophysics Data System (ADS)

Dawood, Yehia H.; Harbi, Hesham M.; Abd El-Naby, Hamdy H.

2010-01-01

In this study, we report kasolite Pb(UO 2)SiO 4·(H 2O) for the first time as a main uranyl mineral in the mineralized aplite-pegmatite of Jabal Sayid, Hijaz region. It commonly forms clusters of yellow acicular crystals in the voids and fractures. The mineral chemistry and mineralogical characteristics of kasolite were investigated using different techniques. Calcium, iron and phosphorus are detected in kasolite in addition to its major constituents; uranium, lead and silicon. Lead does not exist as a radiogenic product and not even as a substitute for uranium in the mineral structure. Alternatively, galena mineralization could be considered as a source for lead. The fluoride and carbonate complexes played a significant role in the formation of kasolite. High temperature hydrothermal solutions reacted with pre-existing uranium-bearing metamictized accessory minerals such as pyrochlore, U-rich thorite and zircon to form uranous fluoride complexes. These complexes are predominant in reducing environment and at pH 4. When the fluids approached the surface passing through fracture system, the oxygen fugacity ( fO 2) and the pH increased because of the loss of volatile components. At these conditions, uranous fluorides would convert to uranyl fluoride complexes UO 2F 3-. Further decrease in temperature was associated with the decay of the activity of fluorine ion by the dilution of hydrothermal solutions and precipitation of fluorite. At this condition, uranyl-carbonate complexes are favoured. These complexes were combined later with silica and lead to form kasolite.

Net energy payback and CO2 emissions from three midwestern wind farms: An update

USGS Publications Warehouse

White, S.W.

2006-01-01

This paper updates a life-cycle net energy analysis and carbon dioxide emissions analysis of three Midwestern utility-scale wind systems. Both the Energy Payback Ratio (EPR) and CO2 analysis results provide useful data for policy discussions regarding an efficient and low-carbon energy mix. The EPR is the amount of electrical energy produced for the lifetime of the power plant divided by the total amount of energy required to procure and transport the materials, build, operate, and decommission the power plants. The CO2 analysis for each power plant was calculated from the life-cycle energy input data. A previous study also analyzed coal and nuclear fission power plants. At the time of that study, two of the three wind systems had less than a full year of generation data to project the life-cycle energy production. This study updates the analysis of three wind systems with an additional four to eight years of operating data. The EPR for the utility-scale wind systems ranges from a low of 11 for a two-turbine system in Wisconsin to 28 for a 143-turbine system in southwestern Minnesota. The EPR is 11 for coal, 25 for fission with gas centrifuge enriched uranium and 7 for gaseous diffusion enriched uranium. The normalized CO2 emissions, in tonnes of CO2 per GW eh, ranges from 14 to 33 for the wind systems, 974 for coal, and 10 and 34 for nuclear fission using gas centrifuge and gaseous diffusion enriched uranium, respectively. ?? Springer Science+Business Media, LLC 2007.

Geochemistry and migration of contaminants at the Weldon Spring chemical plant site, St. Charles County, Missouri, 1989-91

USGS Publications Warehouse

Schumacher, John G.

1993-01-01

The geochemistry of the shallow aquifer and geochemical controls on the migration of uranium and other constituents from raffinate pits were determined at the Weldon Spring chemical plant site. Surface-water samples from the raffinate pits con- tained large concentrations of calcium, magnesium, sodium, potassium, sulfate, nitrite, lithium, moly- bdenum, strontium, vanadium, and uranium. Analyses of interstitial-water samples from raffinate pit 3 indicated that concentrations of most constituents increased with increasing depth below the water- sediment interface. Nitrate and uranium were not chemically reduced and attenuated within the raffinate pits and can be expected to migrate into the overburden. Laboratory sorption experiments were performed to evaluate the effect of pH value on the sorption of several raffinate constituents by the overburden. No sorption of calcium, sodium, sulfate, nitrate, or lithium was observed. Sorption of molybdenum was dependent on solution pH and sorption of uranium was dependent on solution pH and carbonate concentration. The sorption of uranium and molybdenum was consistent with sorption controlled by oxyhydroxides. The quality of water collected in overburden lysimeters near raffinate pit 4 can be modeled as a mixture of water from raffinate pits 3 and 4, and an uncontaminated com- ponent in a system at equilibrium with ferrihydrite and calcite. Increased constituent concentrations in a perennial spring north of the site were the result of a subsurface connection between the spring and several losing stream segments receiving runoff from the site, in addition to seepage from the raffinate pits.

Preparation of porous magnesium oxide foam and study on its enrichment of uranium

NASA Astrophysics Data System (ADS)

Wang, Yunsheng; Chen, Yuantao; Liu, Chen; Yu, Fang

2018-06-01

Herein, we prepared porous magnesium oxide (MP-MgO) by in situ carbonization and using Mg(NO3)2 as precursor along with P123 as soft template. The BET surface area, and total pore volume of MP-MgO were found to be 14.76 m2 g, 0.15 cm3 g-1, respectively. The adsorption behavior of U (Ⅵ) by the porous MgO was studied by static adsorption experiments, and also the effects of adsorption time, pH of wastewater and U (Ⅵ) concentration were discussed. The results indicated that the optimum pH for MP-MgO was 3.0-4.5, the removal of uranium in this case was mainly due to surface complexation. Through the study, we found that the adsorption capacity of MP-MgO for uranium was more than 2500 mg g-1, the adsorption equilibrium time was about 150 min. Moreover, the kinetic study showed that the process followed the pseudo-first-order model, and the adsorption process was spontaneous and endothermic.

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

A review of the high temperature oxidation of uranium oxides in molten salts and in the solid state to form alkali metal uranates, and their composition and properties

NASA Astrophysics Data System (ADS)

Griffiths, Trevor R.; Volkovich, Vladimir A.

An extensive review of the literature on the high temperature reactions (both in melts and in the solid state) of uranium oxides (UO 2, U 3O 8 and UO 3) resulting in the formation of insoluble alkali metal (Li to Cs) uranates is presented. Their uranate(VI) and uranate(V) compounds are examined, together with mixed and oxygen-deficient uranates. The reactions of uranium oxides with carbonates, oxides, per- and superoxides, chlorides, sulfates, nitrates and nitrites under both oxidising and non-oxidising conditions are critically examined and systematised, and the established compositions of a range of uranate(VI) and (V) compounds formed are discussed. Alkali metal uranates(VI) are examined in detail and their structural, physical, thermodynamic and spectroscopic properties considered. Chemical properties of alkali metal uranates(VI), including various methods for their reduction, are also reported. Errors in the current theoretical treatment of uranate(VI) spectra are identified and the need to develop routes for the preparation of single crystals is stressed.

Synthesis and sintering of UN-UO2 fuel composites

NASA Astrophysics Data System (ADS)

Jaques, Brian J.; Watkins, Jennifer; Croteau, Joseph R.; Alanko, Gordon A.; Tyburska-Püschel, Beata; Meyer, Mitch; Xu, Peng; Lahoda, Edward J.; Butt, Darryl P.

2015-11-01

The design and development of an economical, accident tolerant fuel (ATF) for use in the current light water reactor (LWR) fleet is highly desirable for the future of nuclear power. Uranium mononitride has been identified as an alternative fuel with higher uranium density and thermal conductivity when compared to the benchmark, UO2, which could also provide significant economic benefits. However, UN by itself reacts with water at reactor operating temperatures. In order to reduce its reactivity, the addition of UO2 to UN has been suggested. In order to avoid carbon impurities, UN was synthesized from elemental uranium using a hydride-dehydride-nitride thermal synthesis route prior to mixing with up to 10 wt% UO2 in a planetary ball mill. UN and UN - UO2 composite pellets were sintered in Ar - (0-1 at%) N2 to study the effects of nitrogen concentration on the evolved phases and microstructure. UN and UN-UO2 composite pellets were also sintered in Ar - 100 ppm N2 to assess the effects of temperature (1700-2000 °C) on the final grain morphology and phase concentration.

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

Jaques, Brian J.; Watkins, Jennifer; Croteau, Joseph R.

In this study, the design and development of an economical, accident tolerant fuel (ATF) for use in the current light water reactor (LWR) fleet is highly desirable for the future of nuclear power. Uranium mononitride has been identified as an alternative fuel with higher uranium density and thermal conductivity when compared to the benchmark, UO 2, which could also provide significant economic benefits. However, UN by itself reacts with water at reactor operating temperatures. In order to reduce its reactivity, the addition of UO 2 to UN has been suggested. In order to avoid carbon impurities, UN was synthesized frommore » elemental uranium using a hydride-dehydride-nitride thermal synthesis route prior to mixing with up to 10 wt% UO 2 in a planetary ball mill. UN and UN – UO 2 composite pellets were sintered in Ar – (0–1 at%) N 2 to study the effects of nitrogen concentration on the evolved phases and microstructure. UN and UN-UO 2 composite pellets were also sintered in Ar – 100 ppm N 2 to assess the effects of temperature (1700–2000 °C) on the final grain morphology and phase concentration.« less

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

WANG,YIFENG; XU,HUIFANG

Correctly identifying the possible alteration products and accurately predicting their occurrence in a repository-relevant environment are the key for the source-term calculation in a repository performance assessment. Uraninite in uranium deposits has long been used as a natural analog to spent fuel in a repository because of their chemical and structural similarity. In this paper, a SEM/AEM investigation has been conducted on a partially alternated uraninite sample from a uranium ore deposit of Shinkolobwe of Congo. The mineral formation sequences were identified: uraninite {yields} uranyl hydrates {yields} uranyl silicates {yields} Ca-uranyl silicates or uraninite {yields} uranyl silicates {yields} Ca-uranyl silicates.more » Reaction-path calculations were conducted for the oxidative dissolution of spent fuel in a representative Yucca Mountain groundwater. The predicted sequence is in general consistent with the SEM observations. The calculations also show that uranium carbonate minerals are unlikely to become major solubility-controlling mineral phases in a Yucca Mountain environment. Some discrepancies between model predictions and field observations are observed. Those discrepancies may result from poorly constrained thermodynamic data for uranyl silicate minerals.« less

Design options for improved performance with high-density carbon ablators and low-gas fill hohlraum targets

NASA Astrophysics Data System (ADS)

Berzak Hopkins, L.; Divol, L.; Lepape, S.; Meezan, N. B.; Dewald, E.; Ho, D.; Khan, S.; Pak, A.; Ralph, J.; Ross, J. S.

2016-10-01

Recent simulation-based and experimental work using high-density carbon ablators in unlined uranium hohlraums with 0.3 mg/cc helium fill have demonstrated round implosions with minimal evolution of Legendre moment P2 during burn. To extend this promising work, design studies have been performed to explore potential performance improvements with larger capsules, while maintaining similar case-to-capsule target ratios. We present here the results of these design studies, which will motivate a series of upcoming experiments at the National Ignition Facility. Prepared by LLNL under Contract DE-AC52-07NA27344.

The application of visible absorption spectroscopy to the analysis of uranium in aqueous solutions

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

Colletti, Lisa Michelle; Copping, Roy; Garduno, Katherine

Through assay analysis into an excess of 1 M H 2SO 4 at fixed temperature a technique has been developed for uranium concentration analysis by visible absorption spectroscopy over an assay concentration range of 1.8 – 13.4 mgU/g. Once implemented for a particular spectrophotometer and set of spectroscopic cells this technique promises to provide more rapid results than a classical method such as Davies-Gray (DG) titration analysis. While not as accurate and precise as the DG method, a comparative analysis study reveals that the spectroscopic method can analyze for uranium in well characterized uranyl(VI) solution samples to within 0.3% ofmore » the DG results. For unknown uranium solutions in which sample purity is less well defined agreement between the developed spectroscopic method and DG analysis is within 0.5%. The technique can also be used to detect the presence of impurities that impact the colorimetric analysis, as confirmed through the analysis of ruthenium contamination. Finally, extending the technique to other assay solution, 1 M HNO 3, HCl and Na 2CO 3, has also been shown to be viable. As a result, of the four aqueous media the carbonate solution yields the largest molar absorptivity value at the most intensely absorbing band, with the least impact of temperature.« less

The application of visible absorption spectroscopy to the analysis of uranium in aqueous solutions

DOE PAGES

Colletti, Lisa Michelle; Copping, Roy; Garduno, Katherine; ...

2017-07-18

Through assay analysis into an excess of 1 M H 2SO 4 at fixed temperature a technique has been developed for uranium concentration analysis by visible absorption spectroscopy over an assay concentration range of 1.8 – 13.4 mgU/g. Once implemented for a particular spectrophotometer and set of spectroscopic cells this technique promises to provide more rapid results than a classical method such as Davies-Gray (DG) titration analysis. While not as accurate and precise as the DG method, a comparative analysis study reveals that the spectroscopic method can analyze for uranium in well characterized uranyl(VI) solution samples to within 0.3% ofmore » the DG results. For unknown uranium solutions in which sample purity is less well defined agreement between the developed spectroscopic method and DG analysis is within 0.5%. The technique can also be used to detect the presence of impurities that impact the colorimetric analysis, as confirmed through the analysis of ruthenium contamination. Finally, extending the technique to other assay solution, 1 M HNO 3, HCl and Na 2CO 3, has also been shown to be viable. As a result, of the four aqueous media the carbonate solution yields the largest molar absorptivity value at the most intensely absorbing band, with the least impact of temperature.« less

Uranium Biomineralization By Natural Microbial Phosphatase Activities in the Subsurface

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

Taillefert, Martial

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

A simple-rapid method to separate uranium, thorium, and protactinium for U-series age-dating of materials

PubMed Central

Knight, Andrew W.; Eitrheim, Eric S.; Nelson, Andrew W.; Nelson, Steven; Schultz, Michael K.

2017-01-01

Uranium-series dating techniques require the isolation of radionuclides in high yields and in fractions free of impurities. Within this context, we describe a novel-rapid method for the separation and purification of U, Th, and Pa. The method takes advantage of differences in the chemistry of U, Th, and Pa, utilizing a commercially-available extraction chromatographic resin (TEVA) and standard reagents. The elution behavior of U, Th, and Pa were optimized using liquid scintillation counting techniques and fractional purity was evaluated by alpha-spectrometry. The overall method was further assessed by isotope dilution alpha-spectrometry for the preliminary age determination of an ancient carbonate sample obtained from the Lake Bonneville site in western Utah (United States). Preliminary evaluations of the method produced elemental purity of greater than 99.99% and radiochemical recoveries exceeding 90% for U and Th and 85% for Pa. Excellent purity and yields (76% for U, 96% for Th and 55% for Pa) were also obtained for the analysis of the carbonate samples and the preliminary Pa and Th ages of about 39,000 years before present are consistent with 14C-derived age of the material. PMID:24681438

CONTINUOUS PROCESS FOR PREPARING URANIUM HEXAFLUORIDE FROM URANIUM TETRAFLUORIDE AND OXYGEN

DOEpatents

Adams, J.B.; Bresee, J.C.; Ferris, L.M.

1961-11-21

A process for preparing UF/sub 6/ by reacting UF/sub 4/ and oxygen is described. The UF/sub 4/ and oxygen are continuously introduced into a fluidized bed of UO/sub 2/F/sub 2/ at a temperature of 600 to 900 deg C. The concentration of UF/sub 4/ in the bed is maintained below 25 weight per cent in order to avoid sintering and intermediate compound formation. By-product U0/sub 2/F/sub 2/ is continuously removed from the top of the bed recycled. In an alternative embodiment heat is supplied to the reaction bed by burning carbon monoxide in the bed. The product UF/sub 6/ is filtered to remove entrained particles and is recovered in cold traps and chemical traps. (AEC)

Distribution of selenium, molybdenum and uranium in sediment cores from the Colorado River delta, Baja California, Mexico.

PubMed

Orozco-Durán, A; Daesslé, L W; Gutiérrez-Galindo, E A; Muñoz-Barbosa, A

2012-01-01

The distribution of selenium, molybdenum and uranium was studied in ~1.5 m sediment cores from the Colorado River delta, at the Colorado (CR) and Hardy (HR) riverbeds. Core HR2 showed highest Se, Mo and U concentrations at its bottom (2.3, 0.95 and 1.8 μg g(-1)) within a sandy-silt layer deposited prior to dam construction. In CR5 the highest concentrations of these elements (0.9, 1.4 and 1.7 μg g(-1) respectively) were located at the top of the core within a surface layer enriched in organic carbon. A few samples from HR2 had Se above the probable toxic effect level guidelines.

Surface spectroscopy studies of the oxidation behavior of uranium

NASA Astrophysics Data System (ADS)

Bloch, J.; Atzmony, U.; Dariel, M. P.; Mintz, M. H.; Shamir, N.

1982-02-01

Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) techniques were utilized to study the oxidation behavior of clean uranium surfaces, at very low pressures of various atmospheres (UHV, H 2, O 2, and CO 2), at room temperature. Both for O 2 and CO 2, a precursor chemisorbed oxygen species has been identified at the very initial stage of the oxidation reaction. This chemisorbed oxygen transforms to the oxide form at a rate which depends on the pressure of the oxidizing atmosphere. Residual gaseous carbon compounds which are present even under UHV conditions result in the simultaneous formation of surface carbide which accompanies the initial stage of oxidation. This carbide however decomposes later as oxidation proceeds. Adventitious hydrocarbon adsorption occurs on the formed oxide layer.

Identification of Uranium Minerals in Natural U-Bearing Rocks Using Infrared Reflectance Spectroscopy

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

Beiswenger, Toya N.; Gallagher, Neal B.; Myers, Tanya L.

The identification of minerals, including uranium-bearing minerals, is traditionally a labor-intensive-process using x-ray diffraction (XRD), fluorescence, or other solid-phase and wet chemical techniques. While handheld XRD and fluorescence instruments can aid in field identification, handheld infrared reflectance spectrometers can also be used in industrial or field environments, with rapid, non-destructive identification possible via spectral analysis of the solid’s reflectance spectrum. We have recently developed standard laboratory measurement methods for the infrared (IR) reflectance of solids and have investigated using these techniques for the identification of uranium-bearing minerals, using XRD methods for ground-truth. Due to the rich colors of such species,more » including distinctive spectroscopic signatures in the infrared, identification is facile and specific, both for samples that are pure or are partially composed of uranium (e.g. boltwoodite, schoepite, tyuyamunite, carnotite, etc.) or non-uranium minerals. The method can be used to detect not only pure and partial minerals, but is quite sensitive to chemical change such as hydration (e.g. schoepite). We have further applied statistical methods, in particular classical least squares (CLS) and multivariate curve resolution (MCR) for discrimination of such uranium minerals and two uranium pure chemicals (U3O8 and UO2) against common background materials (e.g. silica sand, asphalt, calcite, K-feldspar) with good success. Each mineral contains unique infrared spectral features; some of the IR features are similar or common to entire classes of minerals, typically arising from similar chemical moieties or functional groups in the minerals: phosphates, sulfates, carbonates, etc. These characteristic 2 infrared bands generate the unique (or class-specific) bands that distinguish the mineral from the interferents or backgrounds. We have observed several cases where the chemical moieties that provide the spectral discrimination in the longwave IR do so by generating upward-going reststrahlen bands in the reflectance data, but the same minerals have other weaker (overtone) bands, sometimes from the same chemical groups, that are manifest as downward-going transmission-type features in the midwave and shortwave infrared.« less

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

Nitrogen reduction and functionalization by a multimetallic uranium nitride complex

NASA Astrophysics Data System (ADS)

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

2017-07-01

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

Mineral and energy resources of the BLM Roswell Resource Area, east-central New Mexico

USGS Publications Warehouse

Bartsch-Winkler, Susan B.

1992-01-01

The sedimentary formations of the Roswell Resource Area have significant mineral and energy resources. Some of the pre-Pennsylvanian sequences in the Northwestern Shelf of the Permian Basin are oil and gas reservoirs, and Pennsylvanian rocks in Tucumcari basin are reservoirs of oil and gas as well as source rocks for oil and gas in Triassic rocks. Pre-Permian rocks also contain minor deposits of uranium and vanadium, limestone, and associated gases. Hydrocarbon reservoirs in Permian rocks include associated gases such as carbon dioxide, helium, and nitrogen. Permian rocks are mineralized adjacent to the Lincoln County porphyry belt, and include deposits of copper, uranium, manganese, iron, polymetallic veins, and Mississippi-valley-type (MVT) lead-zinc. Industrial minerals in Permian rocks include fluorite, barite, potash, halite, polyhalite, gypsum, anhydrite, sulfur, limestone, dolomite, brine deposits (iodine and bromine), aggregate (sand), and dimension stone. Doubly terminated quartz crystals, called "Pecos diamonds" and collected as mineral specimens, occur in Permian rocks along the Pecos River. Mesozoic sedimentary rocks are hosts for copper, uranium, and small quantities of gold-silver-tellurium veins, as well as significant deposits of oil and gas, COa, asphalt, coal, and dimension stone. Mesozoic rocks contain limited amounts of limestone, gypsum, petrified wood, dinosaur remains, and clays. Tertiary rocks host ore deposits commonly associated with intrusive rocks, including platinum group elements, iron skarns, manganese, uranium and vanadium, molybdenum, polymetallic vein deposits, gold-silver- tellurium veins, and thorium-rare earth veins. Museum-quality quartz crystals in Lincoln County were formed in association with intrusive rocks in the Lincoln County porphyry belt. Industrial minerals in Tertiary rocks include fluorite, vein- and bedded-barite, caliche, limestone, and aggregate. Tertiary and Quaternary sediments host important placer deposits of gold and titanium, and minor silver, uranium occurrences, as well as important industrial commodities, including caliche, limestone and dolomite, and aggregate (sand). Quaternary basalt contains sub-ore-grade uranium, scoria, and clay deposits.

Measures of the environmental footprint of the front end of the nuclear fuel cycle

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

E. Schneider; B. Carlsen; E. Tavrides

2013-11-01

Previous estimates of environmental impacts associated with the front end of the nuclear fuel cycle (FEFC) have focused primarily on energy consumption and CO2 emissions. Results have varied widely. This work builds upon reports from operating facilities and other primary data sources to build a database of front end environmental impacts. This work also addresses land transformation and water withdrawals associated with the processes of the FEFC. These processes include uranium extraction, conversion, enrichment, fuel fabrication, depleted uranium disposition, and transportation. To allow summing the impacts across processes, all impacts were normalized per tonne of natural uranium mined as wellmore » as per MWh(e) of electricity produced, a more conventional unit for measuring environmental impacts that facilitates comparison with other studies. This conversion was based on mass balances and process efficiencies associated with the current once-through LWR fuel cycle. Total energy input is calculated at 8.7 x 10- 3 GJ(e)/MWh(e) of electricity and 5.9 x 10- 3 GJ(t)/MWh(e) of thermal energy. It is dominated by the energy required for uranium extraction, conversion to fluoride compound for subsequent enrichment, and enrichment. An estimate of the carbon footprint is made from the direct energy consumption at 1.7 kg CO2/MWh(e). Water use is likewise dominated by requirements of uranium extraction, totaling 154 L/MWh(e). Land use is calculated at 8 x 10- 3 m2/MWh(e), over 90% of which is due to uranium extraction. Quantified impacts are limited to those resulting from activities performed within the FEFC process facilities (i.e. within the plant gates). Energy embodied in material inputs such as process chemicals and fuel cladding is identified but not explicitly quantified in this study. Inclusion of indirect energy associated with embodied energy as well as construction and decommissioning of facilities could increase the FEFC energy intensity estimate by a factor of up to 2.« less

The association of uranium with organic matter in Holocene peat: An experimental leaching study

USGS Publications Warehouse

Zielinski, R.A.; Meier, A.L.

1988-01-01

Uraniferous peat was sampled from surface layers of a Holocene U deposit in northeastern Washington State. Dried, sized, and homogenized peat that contained 5980 ??307 ppm U was subjected to a variety of leaching conditions to determine the nature and strength of U-organic bonding in recently accumulated organic matter. The results complement previous experimental studies of U uptake on peat and suggest some natural or anthropogenic disturbances that are favorable for remobilizing U. The fraction of U leached in 24 h experiments at 25??C ranged from 0 to 95%. The most effective leach solutions contained anions capable of forming stable dissolved complexes with uranyl (UO2+2) cation. These included H2SO4 (pH = 1.5) and concentrated (>0.01 M) solutions of sodium bicarbonate-carbonate (pH = 7.0-10.0), or sodium pyrophosphate (pH = 10). Effective leaching by carbonate and pyrophosphate in the absence of added oxidant, and the insignificant effect of added oxidant (as pressurized O2) strongly suggest that U is initially fixed on organic matter as an oxidized U(VI) species. Uranium is more strongly bound than some other polyvalent cations, based on its resistance to exchange in the presence of large excesses of dissolved Ca2+ and Cu2+. Measurements of the rate of U leaching indicate faster rates in acid solution compared to carbonate solution, and are consisten with simultaneous attack of sites with different affinities for U. Sulfuric acid appears a good choice for commercial extraction of U from mined peat. In situ disturbances such as overliming of peat soils, addition of fertilizers containing pyrophosphate, or incursions of natural carbonate-rich waters could produce significant remobilization of U, and possibly compromise the quality of local domestic water supplies. ?? 1988.

Thorium and Uranium in the Rock Raw Materials Used For the Production of Building Materials

NASA Astrophysics Data System (ADS)

Pękala, Agnieszka

2017-10-01

Thorium and uranium are constant components of all soils and most minerals thereby rock raw materials. They belong to the particularly dangerous elements because of their natural radioactivity. Evaluation of the content of the radioactive elements in the rock raw materials seems to be necessary in the early stage of the raw material evaluation. The rock formations operated from deposits often are accumulated in landfills and slag heaps where the concentration of the radioactive elements can be many times higher than under natural conditions. In addition, this phenomenon may refer to buildings where rock raw materials are often the main components of the construction materials. The global control system of construction products draws particular attention to the elimination of used construction products containing excessive quantities of the natural radioactive elements. In the presented study were determined the content of thorium and uranium in rock raw materials coming from the Bełachatów lignite deposit. The Bełchatów lignite deposit extracts mainly lignite and secondary numerous accompanying minerals with the raw material importance. In the course of the field works within the framework of the carried out work has been tested 92 samples of rocks of varied petrographic composition. There were carried out analyses of the content of the radioactive elements for 50 samples of limestone of the Jurassic age, 18 samples of kaolinite clays, and 24 samples of siliceous raw materials, represented by opoka-rocks, diatomites, gaizes and clastic rocks. The measurement of content of the natural radioactive elements thorium and uranium based on measuring the frequency counts of gamma quantum, recorded separately in measuring channels. At the same time performed measurements on volume patterns radioactive: thorium and uranium. The studies were carried out in Mazar spectrometer on the powdered material. Standardly performed ten measuring cycles, after which were calculated the concentration of radioactive elements in the sample. The highest concentration of thorium and uranium has been found in the clayey raw material. Their value was respectively from 8 to 12 mg/kg for thorium and from 2.3 to 3.5 mg/kg for uranium. In carbonate sediments the content of thorium was at the level from 0.5 to 2.1 mg/kg and uranium from 0.5-2.2 mg/kg. From a group of the siliceous raw materials the diatomite had a highest concentrations of radioactive elements where the content of thorium was from 1.5 to 1.8 mg/kg and uranium from 1.3 to 1.7 mg/kg.

Acceptance Test Data for Candidate AGR-5/6/7 TRISO Particle Batches BWXT Coater Batches 93165 93172 Defective IPyC Fraction and Pyrocarbon Anisotropy

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

Helmreich, Grant W.; Hunn, John D.; Skitt, Darren J.

2017-03-01

Coated particle fuel batches J52O-16-93165, 93166, 93168, 93169, 93170, and 93172 were produced by Babcock and Wilcox Technologies (BWXT) for possible selection as fuel for the Advanced Gas Reactor Fuel Development and Qualification (AGR) Program’s AGR-5/6/7 irradiation test in the Idaho National Laboratory (INL) Advanced Test Reactor (ATR). Some of these batches may alternately be used as demonstration coated particle fuel for other experiments. Each batch was coated in a 150-mm-diameter production-scale fluidized-bed chemical vapor deposition (CVD) furnace. Tristructural isotropic (TRISO) coatings were deposited on 425-μm-nominal-diameter spherical kernels from BWXT lot J52R-16-69317 containing a mixture of 15.5%-enriched uranium carbide andmore » uranium oxide (UCO). The TRISO coatings consisted of four consecutive CVD layers: a ~50% dense carbon buffer layer with 100-μm-nominal thickness, a dense inner pyrolytic carbon (IPyC) layer with 40-μm-nominal thickness, a silicon carbide (SiC) layer with 35-μm-nominal thickness, and a dense outer pyrolytic carbon (OPyC) layer with 40-μmnominal thickness. The TRISO-coated particle batches were sieved to upgrade the particles by removing over-sized and under-sized material, and the upgraded batches were designated by appending the letter A to the end of the batch number (e.g., 93165A).« less

Microbial Metabolic Response to Carbon Sources in a Uranium Contaminated Floodplain

NASA Astrophysics Data System (ADS)

Barragan, L.; Boye, K.; Bargar, J.; Fendorf, S. E.

2016-12-01

In Riverton, Wyoming, uranium (U) from a former ore processing plant, contaminated the groundwater and accumulated in Naturally Reduced Zones (NRZs). The NRZs have now become a secondary source of U and are releasing U into the ground water due to seasonal water table fluctuations. Microorganisms that mediate the mobilization and retention of U are likely to reside in these zones enriched with organic matter that comprises their energy source of carbon (C) for respiration. In this study, we are measuring microbial respiration (basal and substrate induced) by the MicroRespTM system, which is a quick screening method for respiratory activity in natural samples. This can provide information about the microbial community composition at certain depths and insight into their metabolic pathways which may explain U behavior in the ground water. In addition, we are determining elemental composition in the sediments by X-ray fluorescence spectroscopy (XRF) and elemental analysis (EA). Water soluble cations, anions and organic C is determined by inductively coupled plasma (ICP), mass spectrometry, ion chromatography (IC) and non-purgeable organic carbon (NPOC) analyses, respectively. If the behavior of the microbial community in the NRZ environment (enriched in both U and C) differs from that in unsaturated sediments, this can provide crucial clues to understand what causes U to be retained or released from the NRZs. This information will be used to develop and improve models aimed at predicting U mobility in the floodplain groundwater systems.

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

A Uranium-Lead Chronology of Speleothem Deposition in the Canadian Arctic

NASA Astrophysics Data System (ADS)

Gambino, C.; Shakun, J. D.; McGee, D.; Ramezani, J.; Khadivi, S.; Wong, C. I.

2017-12-01

The Artic is one of the fastest warming regions on the planet. Currently much of the Arctic is covered by permafrost, which contains approximately 1,700 gigatons of organic carbon. Permafrost thaw could release a substantial amount of this carbon as greenhouse gases into the atmosphere through microbial decomposition, potentially dramatically amplifying anthropogenic warming. However, the risk of permafrost thaw is uncertain, with models exhibiting a wide range of possibilities. Assessing the stability of permafrost during past interglacial periods enables evaluation of the sensitivity of permafrost to warming. Cave mineral deposits (speleothems) in areas currently covered with permafrost can act as a proxy for past permafrost thaw, as liquid water is one criteria of speleothem growth and thus implies thawed ground conditions. Previous uranium-thorium (U-Th) dating of speleothems (n=67) from a wide range of latitudes and permafrost zones across the southern Canadian Rockies, Northwest Territories, and the northern Yukon suggest deposition during Marine Isotope Stage (MIS) 11 and 13. The majority of U-Th dates of these speleothems, however, exceed the U-Th dating limit of 600 ka. In this study, we apply uranium-lead (U-Pb) geochronology to several of these speleothems to extend the records of speleothem growth further back in time. Initial results include a U-Pb age of 428 ± 14 ka that replicates a previous U-Th age of 416.8 ± 7.9 ka, and U-Pb ages on two other speleothems of 870 ± 100 ka and 1502 ± 30 ka. The results of currently in progress U-Pb analyses and a comparison of results with paleo-temperature and ice volume reconstructions will also be presented.

Uranium mineralization in fluorine-enriched volcanic rocks

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

Burt, D.M.; Sheridan, M.F.; Bikun, J.

1980-09-01

Several uranium and other lithophile element deposits are located within or adjacent to small middle to late Cenozoic, fluorine-rich rhyolitic dome complexes. Examples studied include Spor Mountain, Utah (Be-U-F), the Honeycomb Hills, Utah (Be-U), the Wah Wah Mountains, Utah (U-F), and the Black Range-Sierra Cuchillo, New Mexico (Sn-Be-W-F). The formation of these and similar deposits begins with the emplacement of a rhyolitic magma, enriched in lithophile metals and complexing fluorine, that rises to a shallow crustal level, where its roof zone may become further enriched in volatiles and the ore elements. During initial explosive volcanic activity, aprons of lithicrich tuffsmore » are erupted around the vents. These early pyroclastic deposits commonly host the mineralization, due to their initial enrichment in the lithophile elements, their permeability, and the reactivity of their foreign lithic inclusions (particularly carbonate rocks). The pyroclastics are capped and preserved by thick topaz rhyolite domes and flows that can serve as a source of heat and of additional quantities of ore elements. Devitrification, vapor-phase crystallization, or fumarolic alteration may free the ore elements from the glassy matrix and place them in a form readily leached by percolating meteoric waters. Heat from the rhyolitic sheets drives such waters through the system, generally into and up the vents and out through the early tuffs. Secondary alteration zones (K-feldspar, sericite, silica, clays, fluorite, carbonate, and zeolites) and economic mineral concentrations may form in response to this low temperature (less than 200 C) circulation. After cooling, meteoric water continues to migrate through the system, modifying the distribution and concentration of the ore elements (especially uranium).« less

Groundwater quality of the Gulf Coast aquifer system, Houston, Texas, 2010

USGS Publications Warehouse

Oden, Jeannette H.; Brown, Dexter W.; Oden, Timothy D.

2011-01-01

Gross alpha-particle activities and beta-particle activities for all 47 samples were analyzed at 72 hours after sample collection and again at 30 days after sample collection, allowing for the measurement of the activity of short-lived isotopes. Gross alpha-particle activities reported in this report were not adjusted for activity contributions by radon or uranium and, therefore, are conservatively high estimates if compared to the U.S. Environmental Protection Agency National Primary Drinking Water Regulation for adjusted gross alpha-particle activity. The gross alpha-particle activities at 30 days in the samples ranged from R0.60 to 25.5 picocuries per liter and at 72 hours ranged from 2.58 to 39.7 picocuries per liter, and the "R" preceding the value of 0.60 picocuries per liter refers to a nondetected result less than the sample-specific critical level. Gross beta-particle activities measured at 30 days ranged from 1.17 to 14.4 picocuries per liter and at 72 hours ranged from 1.97 to 4.4 picocuries per liter. Filtered uranium was detected in quantifiable amounts in all of the 47 wells sampled. The uranium concentrations ranged from 0.03 to 42.7 micrograms per liter. One sample was analyzed for carbon-14, and the amount of modern atmospheric carbon was reported as 0.2 percent. Six source-water samples collected from municipal supply wells were analyzed for radium-226, and all of the concentrations were considered detectable concentrations (greater than their associated sample-specific critical level). Three source-water samples collected were analyzed for radon-222, and all of the concentrations were substantially greater than the associated sample-specific critical level.

Uranium deposits of the northern part of the Boulder Batholith, Montana

USGS Publications Warehouse

Becraft, George E.

1955-01-01

Uranium minerals and radioactivity anomalies occur in many silver-lead veins and chalcedony veins and vein zones in the Boulder batholith of southwestern Montanao Pitchblende has been identified in a few silver-lead veins. These veins occupy shear zones along which there is no evidence of large-scale lateral displacement. The wall rock adjacent to the veins is intensely silicified and sencitized quartz monzonite and granodiortte. The veins have yielded substantial quantities of lead, silver, zinc, and gold. The silver-lead veins consist principal1y of galena, spha1erite, tetrahedrite, cha1copyrite and pyrite in a gangue of light to dark gray quartz, altered rock, gouge, and subordinate chalcedony and carbonate minerals. No anomalous radioactivity nor uranium minerals have been found in similar veins in pre-batholithic rocks of the area. Chalcedony veins and vein zones, some of which are ttraniferous, are distinctly different from the silver-lead veins and, with a single except1on, are known only in the batholith. The chalcedony vein zones consist of one or more discontinuous stringers or veins of cha1cedony and microcrystalline quartz in silicified and sericitized quartz monzonite and granodiorite, and in less strongly altered alaskite. On1y small amounts of silver ore have been produced from these chalcedony veins and vein zones. All of the veins are ear1y Tertiary in age, but the silver-lead veins probably are older than the chalcedony veins. Uranium is closely associated with chalcedory and microcrystalline quartz in both types of veins. This association suggests that all of the uranium in the area is of the same age. If so, some of the silver-lead veins must have been reopened during the period of chalcedony vein formation.

Linking AS, SE, V, and MN Behavior to Natural Biostimulated Uranium Cycling

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

Keimowitz, Alison; Ranville, James; Mailloux, Brian

The project “Linking As, Se, V, and Mn behavior to Natural and Biostimulated Uranium Cycling” successfully investigated Arsenic cycling the Rifle Colorado IFRC. This project trained undergraduate and graduate students at the Colorado School of Mines, Vassar College, and Barnard College. This resulted in both undergraduate theses and a PhD thesis and multiple publications. The science was highly successful and we were able to test the main hypotheses. We have shown that (H1) under reducing conditions that promote uranium immobilization arsenic is readily mobilized, that (H2) thioarsenic species are abundant during this mobilization, and (H3) we have examined arsenic mobilizationmore » for site sediment. At the Rifle IFRC Acetate was added during experiments to immobilize Uranium. These experiments successfully immobilized uranium but unfortunately would mobilize arsenic. We developed robust sampling and analysis methods for thioarsenic species. We showed that the mobilization occurred under sulfate reducing conditions and the majority of the arsenic was in the form of thioarsenic species. Previous studies had predicted the presence of thioarsenic species but this study used robust field and laboratory methods to quantitatively determine the presence of thioarsenic species. During stimulation in wells with high arsenic the primary species were trithioarsenate and dithioarsenate. In wells with low levels of arsenic release thioarsenates were absent or minor components. Fortunately after the injection of acetate ended the aquifer would become less reducing and the arsenic concentrations would decrease to pre-injection levels. In aquifers where organic carbon is being added as a remedial method or as a contaminant the transient mobility of arsenic during sulfidogenesis should be considered especially in sulfate rich aquifers as this could impact downgradient water quality.« less

SHEATHING URANIUM

DOEpatents

Colbeck, E.W.

1959-02-01

A method is deseribed for forming a conveniently handled corrosion resistant U articlc comprising pouring molten U into an open-ended corrosion resistant metal eontainer such as Cu and its alloys, Al, or austenitic Ni stainless steel. The exposed surface of the cast U is covered with a metallic packing material such as a brazing flux consisting of Al-Si alloy. The container is sealed iii contact with substantially the entire exposed surface of the packing material. The article is then worked mechanically to reduce the cross section. l3651 A thorium--carbon alloy containing 0.1 to 0.5% by weight carbon, whieh is more resistant to water corrosion than pure thorium metal is presented. The alloy is prepared by fusing thorium metal with the desired amount of carbon at a temperature of about 1850 C. It is found that the carbon is present in the alloy as thorium monocarbide

METHOD OF MAKING FUEL BODIES

DOEpatents

Goeddel, W.V.; Simnad, M.T.

1962-04-24

An improved method of making a fuel body containing carbon for reactors is described. Carbides of uranium and thorium having a particle size of from 100 to 500 microns are mixed with carbon having a particle size that will pass a 200 mesh screen but be retained by a 325 mesh screen, and 10 per cent by weight pitch. The mixture is heated to a temperature of about 700 to 900 deg C, at which point bonding is effected while maintaining it under mechanical pressure of over 3,000 pounds per square inch. The entire compact is heated to a uniform temperature during the process, preferably by electrical resistance of the compact itself. (AEC)

Geology, geochemistry, and geophysics of the Fry Canyon uranium/copper project site, southeastern Utah - Indications of contaminant migration

USGS Publications Warehouse

Otton, James K.; Zielinski, Robert A.; Horton, Robert J.

2010-01-01

The Fry Canyon uranium/copper project site in San Juan County, southeastern Utah, was affected by the historical (1957-68) processing of uranium and copper-uranium ores. Relict uranium tailings and related ponds, and a large copper heap-leach pile at the site represent point sources of uranium and copper to local soils, surface water, and groundwater. This study was designed to establish the nature, extent, and pathways of contaminant dispersion. The methods used in this study are applicable at other sites of uranium mining, milling, or processing. The uranium tailings and associated ponds sit on a bench that is as much as 4.25 meters above the level of the adjacent modern channel of Fry Creek. The copper heap leach pile sits on bedrock just south of this bench. Contaminated groundwater from the ponds and other nearby sites moves downvalley and enters the modern alluvium of adjacent Fry Creek, its surface water, and also a broader, deeper paleochannel that underlies the modern creek channel and adjacent benches and stream terraces. The northern extent of contaminated groundwater is uncertain from geochemical data beyond an area of monitoring wells about 300 meters north of the site. Contaminated surface water extends to the State highway bridge. Some uranium-contaminated groundwater may also enter underlying bedrock of the Permian Cedar Mesa Sandstone along fracture zones. Four dc-resistivity surveys perpendicular to the valley trend were run across the channel and its adjacent stream terraces north of the heap-leach pile and ponds. Two surveys were done in a small field of monitoring wells and two in areas untested by borings to the north of the well field. Bedrock intercepts, salt distribution, and lithologic information from the wells and surface observations in the well field aided interpretation of the geophysical profiles there and allowed interpretation of the two profiles not tested by wells. The geophysical data for the two profiles to the north of the well field suggest that the paleochannel persists at least 900 m to the north of the heap leach and pond sites. Contamination of groundwater beneath the stream terraces may extend at least that far. Fry Creek surface water (six samples), seeps and springs (six samples), and wells (eight samples) were collected during a dry period of April 16-19, 2007. The most uranium-rich (18.7 milligrams per liter) well water on the site displays distinctive Ca-Mg-SO4-dominant chemistry indicating the legacy of heap leaching copper-uranium ores with sulfuric acid. This same water has strongly negative d34S of sulfate (-13.3 per mil) compared to most local waters of -2.4 to -5.4 per mil. Dissolved uranium species in all sampled waters are dominantly U(VI)-carbonate complexes. All waters are undersaturated with respect to U(VI) minerals. The average 234U/238U activity ratio (AR) in four well waters from the site (0.939 + or ? 0.011) is different from that of seven upstream waters (1.235 + or ? 0.069). This isotopic contrast permits quantitative estimates of mixing of site-derived uranium with natural uranium in waters collected downstream. At the time of sampling, uranium in downstream surface water was mostly (about 67 percent) site-derived and subject to further concentration by evaporation. Three monitoring wells located approximately 0.4 kilometer downstream contained dominantly (78-87 percent) site-derived uranium. Distinctive particles of chalcopyrite (CuFeS) and variably weathered pyrite (FeS2) are present in tailings at the stream edge on the site and are identified in stream sediments 1.3 kilometers downstream, based on inspection of polished grain mounts of magnetic mineral separates.

Unconventional energy resources: 2007-2008 review

USGS Publications Warehouse

Warwick, Peter D.; ,

2009-01-01

This paper summarizes five 2007–2008 resource commodity committee reports prepared by the Energy Minerals Division (EMD) of the American Association of Petroleum Geologists. Current United States and global research and development activities related to gas hydrates, gas shales, geothermal resources, oil sands, and uranium resources are included in this review. These commodity reports were written to advise EMD leadership and membership of the current status of research and development of unconventional energy resources. Unconventional energy resources are defined as those resources other than conventional oil and natural gas that typically occur in sandstone and carbonate rocks. Gas hydrate resources are potentially enormous; however, production technologies are still under development. Gas shale, geothermal, oil sand, and uranium resources are now increasing targets of exploration and development, and are rapidly becoming important energy resources that will continue to be developed in the future.

Characteristics of uranium carbonitride microparticles synthesized using different reaction conditions

NASA Astrophysics Data System (ADS)

Silva, Chinthaka M.; Lindemer, Terrence B.; Voit, Stewart R.; Hunt, Rodney D.; Besmann, Theodore M.; Terrani, Kurt A.; Snead, Lance L.

2014-11-01

Three sets of experimental conditions were tested to synthesize uranium carbonitride (UC1-xNx) kernels from gel-derived urania-carbon microspheres. Primarily, three sequences of gases were used, N2 to N2-4%H2 to Ar, Ar to N2 to Ar, and Ar-4%H2 to N2-4%H2 to Ar-4%H2. Physical and chemical characteristics such as geometrical density, phase purity, and chemical compositions of the synthesized UC1-xNx were measured. Single-phase kernels were commonly obtained with densities generally ranging from 85% to 93% TD and values of x as high as 0.99. In-depth analysis of the microstrutures of UC1-xNx has been carried out and is discussed with the objective of large batch fabrication of high density UC1-xNx kernels.

Direct electrochemical reduction of solid uranium oxide in molten fluoride salts

NASA Astrophysics Data System (ADS)

Gibilaro, Mathieu; Cassayre, Laurent; Lemoine, Olivier; Massot, Laurent; Dugne, Olivier; Malmbeck, Rikard; Chamelot, Pierre

2011-07-01

The direct electrochemical reduction of UO 2 solid pellets was carried out in LiF-CaF 2 (+2 mass.% Li 2O) at 850 °C. An inert gold anode was used instead of the usual reactive sacrificial carbon anode. In this case, oxidation of oxide ions present in the melt yields O 2 gas evolution on the anode. Electrochemical characterisations of UO 2 pellets were performed by linear sweep voltammetry at 10 mV/s and reduction waves associated to oxide direct reduction were observed at a potential 150 mV more positive in comparison to the solvent reduction. Subsequent, galvanostatic electrolyses runs were carried out and products were characterised by SEM-EDX, EPMA/WDS, XRD and microhardness measurements. In one of the runs, uranium oxide was partially reduced and three phases were observed: nonreduced UO 2 in the centre, pure metallic uranium on the external layer and an intermediate phase representing the initial stage of reduction taking place at the grain boundaries. In another run, the UO 2 sample was fully reduced. Due to oxygen removal, the U matrix had a typical coral-like structure which is characteristic of the pattern observed after the electroreduction of solid oxides.

Synthesis and sintering of UN-UO 2 fuel composites

DOE PAGES

Jaques, Brian J.; Watkins, Jennifer; Croteau, Joseph R.; ...

2015-06-17

In this study, the design and development of an economical, accident tolerant fuel (ATF) for use in the current light water reactor (LWR) fleet is highly desirable for the future of nuclear power. Uranium mononitride has been identified as an alternative fuel with higher uranium density and thermal conductivity when compared to the benchmark, UO 2, which could also provide significant economic benefits. However, UN by itself reacts with water at reactor operating temperatures. In order to reduce its reactivity, the addition of UO 2 to UN has been suggested. In order to avoid carbon impurities, UN was synthesized frommore » elemental uranium using a hydride-dehydride-nitride thermal synthesis route prior to mixing with up to 10 wt% UO 2 in a planetary ball mill. UN and UN – UO 2 composite pellets were sintered in Ar – (0–1 at%) N 2 to study the effects of nitrogen concentration on the evolved phases and microstructure. UN and UN-UO 2 composite pellets were also sintered in Ar – 100 ppm N 2 to assess the effects of temperature (1700–2000 °C) on the final grain morphology and phase concentration.« less

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

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

Vishnivetskaya, Tatiana A; Brandt, Craig C; Madden, Andrew

2010-01-01

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

Mineral transformation and biomass accumulation associated with uranium bioremediation at Rifle, Colorado

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

Li, L.; Steefel, C.I.; Williams, K.H.

2009-04-20

Injection of organic carbon into the subsurface as an electron donor for bioremediation of redox-sensitive contaminants like uranium often leads to mineral transformation and biomass accumulation, both of which can alter the flow field and potentially bioremediation efficacy. This work combines reactive transport modeling with a column experiment and field measurements to understand the biogeochemical processes and to quantify the biomass and mineral transformation/accumulation during a bioremediation experiment at a uranium contaminated site near Rifle, Colorado. We use the reactive transport model CrunchFlow to explicitly simulate microbial community dynamics of iron and sulfate reducers, and their impacts on reaction rates.more » The column experiment shows clear evidence of mineral precipitation, primarily in the form of calcite and iron monosulfide. At the field scale, reactive transport simulations suggest that the biogeochemical reactions occur mostly close to the injection wells where acetate concentrations are highest, with mineral precipitate and biomass accumulation reaching as high as 1.5% of the pore space. This work shows that reactive transport modeling coupled with field data can be an effective tool for quantitative estimation of mineral transformation and biomass accumulation, thus improving the design of bioremediation strategies.« less

Mineral transformation and biomass accumulation associated with uranium bioremediation at Rifle, Colorado.

PubMed

Li, Li; Steefel, Carl I; Williams, Kenneth H; Wilkins, Michael J; Hubbard, Susan S

2009-07-15

Injection of organic carbon into the subsurface as an electron donor for bioremediation of redox-sensitive contaminants like uranium often leads to mineral transformation and biomass accumulation, both of which can alter the flow field and potentially bioremediation efficacy. This work combines reactive transport modeling with a column experiment and field measurements to understand the biogeochemical processes and to quantify the biomass and mineral transformation/accumulation during a bioremediation experiment at a uranium contaminated site near Rifle, Colorado. We use the reactive transport model CrunchFlow to explicitly simulate microbial community dynamics of iron and sulfate reducers, and their impacts on reaction rates. The column experiment shows clear evidence of mineral precipitation, primarily in the form of calcite and iron monosulfide. At the field scale, reactive transport simulations suggest that the biogeochemical reactions occur mostly close to the injection wells where acetate concentrations are highest, with mineral precipitate and biomass accumulation reaching as high as 1.5% of the pore space. This work shows that reactive transport modeling coupled with field data can bean effective tool for quantitative estimation of mineral transformation and biomass accumulation, thus improving the design of bioremediation strategies.

Wall-rock control of cortain pitchblende deposits in Golden Gate Canyon, Jefferson County, Colorado

USGS Publications Warehouse

Adams, John W.; Stugard, Frederick

1954-01-01

Carbonate veins cutting pre-Cambrian metamorphic rocks in Golden Gate Canyon contain pitchblende and base-metal sulfides. The veins occupy extensive faults of Laramide age but normally contain pitchblende only where the cut hornblende gneiss. At the Union Pacific prospect, which was studied in detail, pitchblende, hermatite, and some ankerite formed in advance of sulfides, except possibly for minor pyrite. Base-metal sulfides and the bulk of ankerite-calcite vein-filling were deposited after the pitchblende. Chemical analyses show a high ferrous iron content in the hornblende gneiss in contrast to low ferrous iron in the adjacent biotite gneiss. It is hypothesized that ferrous iron released by alteration of hornblende was partly oxidized to hematite by the ore-bearing solutions and, contemporaneously, uranium was reduced and deposited as pitchblende. In other veins, biotite or iron sulfides may have been similarly effective in precipitating pitchblende. Apparently both the ferrous ion and the sulfide ion can serve as reducing agents and control pitchblende deposition. It is suggested that conditions particularly favorable for uranium deposition are present where uranium-bearing solutions had access to rocks rich in ferrous iron or pre-existing sulfides.

Development of stripper options for FRIB

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

Marti, F.; Hershcovitch, A.; Momozaki, Y.

2010-09-12

The US Department of Energy Facility for Rare Isotope Beams (FRIB) at Michigan State University includes a heavy ion superconducting linac capable of accelerating all ions up to uranium with energies higher than 200 MeV/u and beam power up to 400 kW. To achieve these goals with present ion source performance it is necessary to accelerate simultaneously two charge states of uranium from the ion source in the first section of the linac. At an energy of approximately 16.5 MeV/u it is planned to strip the uranium beam to reduce the voltage needed in the rest of the linac tomore » achieve the final energy. Up to five different charge states are planned to be accelerated simultaneously after the stripper. The design of the stripper is a challenging problem due to the high power deposited (approximately 0.7 kW) in the stripper media by the beam in a small spot. To assure success of the project we have established a research and development program that includes several options: carbon or diamond foils, liquid lithium films, gas strippers and plasma strippers. We present in this paper the status of the different options.« less

Remediation of Uranium in the Hanford Vadose Zone Using Gas-Transported Reactants: Laboratory Scale Experiments in Support of the Deep Vadose Zone Treatability Test Plan for the Hanford Central Plateau

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

Szecsody, James E.; Truex, Michael J.; Zhong, Lirong

2010-01-04

This laboratory-scale investigation is focused on decreasing mobility of uranium in subsurface contaminated sediments in the vadose zone by in situ geochemical manipulation at low water content. This geochemical manipulation of the sediment surface phases included reduction, pH change (acidic and alkaline), and additions of chemicals (phosphate, ferric iron) to form specific precipitates. Reactants were advected into 1-D columns packed with Hanford 200 area U-contaminated sediment as a reactive gas (for CO2, NH3, H2S, SO2), with a 0.1% water content mist (for NaOH, Fe(III), HCl, PO4) and with a 1% water content foam (for PO4). Uranium is present in themore » sediment in multiple phases that include (in decreasing mobility): aqueous U(VI) complexes, adsorbed U, reduced U(IV) precipitates, rind-carbonates, total carbonates, oxides, silicates, phosphates, and in vanadate minerals. Geochemical changes were evaluated in the ability to change the mixture of surface U phases to less mobile forms, as defined by a series of liquid extractions that dissolve progressively less soluble phases. Although liquid extractions provide some useful information as to the generalized uranium surface phases (and are considered operational definitions of extracted phases), positive identification (by x-ray diffraction, electron microprobe, other techniques) was also used to positively identify U phases and effects of treatment. Some of the changes in U mobility directly involve U phases, whereas other changes result in precipitate coatings on U surface phases. The long-term implication of the U surface phase changes to alter U mass mobility in the vadose zone was then investigated using simulations of 1-D infiltration and downward migration of six U phases to the water table. In terms of the short-term decrease in U mobility (in decreasing order), NH3, NaOH mist, CO2, HCl mist, and Fe(III) mist showed 20% to 35% change in U surface phases. Phosphate addition (mist or foam advected) showed inconsistent change in aqueous and adsorbed U, but significant coating (likely phosphates) on U-carbonates. The two reductive gas treatments (H2S and SO2) showed little change. For long-term decrease in U reduction, mineral phases created that had low solubility (phosphates, silicates) were desired, so NH3, phosphates (mist and foam delivered), and NaOH mist showed the greatest formation of these minerals. In addition, simulations showed the greatest decrease in U mass transport time to reach groundwater (and concentration) for these silicate/phosphate minerals. Advection of reactive gasses was the easiest to implement at the laboratory scale (and presumably field scale). Both mist and foam advection show promise and need further development, but current implementation move reactants shorter distances relative to reactive gasses. Overall, the ammonia and carbon dioxide gas had the greatest overall geochemical performance and ability to implement at field scale. Corresponding mist-delivered technologies (NaOH mist for ammonia and HCl mist for carbon dioxide) performed as well or better geochemically, but are not as easily upscaled. Phosphate delivery by mist was rated slightly higher than by foam delivery simply due to the complexity of foam injection and unknown effect of U mobility by the presence of the surfactant.« less

Microbial Reduction of Fe(III) and U(VI) in Aquifers: Simulations Exploring Coupled Effects of Heterogeneity and Fe(II) Sorption

NASA Astrophysics Data System (ADS)

Scheibe, T. D.; Fang, Y.; Roden, E. E.; Brooks, S. C.; Chien, Y.; Murray, C. J.

2004-05-01

Uranium is a significant groundwater contaminant at many former mining and processing sites. In its oxidized state, U(VI) is soluble and mobile, although strongly retarded by sorption to natural iron oxide surfaces. It has been demonstrated that commonly occurring subsurface microorganisms can reduce uranium and other metals when provided sufficient carbon as an electron donor. Reduced U(IV) precipitates as a solid phase; therefore biostimulation provides a potential strategy for in situ removal from contaminated groundwater. However, these biogeochemical reactions occur in the context of a complex heterogeneous environment in which flow and transport dynamics and abiotic reactions can have significant impacts. We have constructed a high-resolution numerical model of groundwater flow and multicomponent reactive transport that incorporates heterogeneity in hydraulic conductivity and initial Fe(III) distribution, microbial growth and transport dynamics, and effects of sorption or precipitation of biogenic Fe(II) on availability of Fe(III) as an electron acceptor. The biogeochemical reaction models and their parameters are based on laboratory experiments; the heterogeneous field-scale property distributions are based on interpretations of geophysical and other observations at a highly characterized field site. The model is being run in Monte Carlo mode to examine the controls that these factors exert on 1) the initial distribution of sorbed uranium in an oxic environment and 2) the reduction and immobilization of uranium upon introduction of a soluble electron donor.

Molecular dynamics simulation of the diffusion of uranium species in clay pores.

PubMed

Liu, Xiao-yu; Wang, Lu-hua; Zheng, Zhong; Kang, Ming-liang; Li, Chun; Liu, Chun-li

2013-01-15

Molecular dynamics simulations were carried out to investigate the diffusive behavior of aqueous uranium species in montmorillonite pores. Three uranium species (UO(2)(2+), UO(2)CO(3), UO(2)(CO(3))(2)(2-)) were confirmed in both the adsorbed and diffuse layers. UO(2)(CO(3))(3)(4-) was neglected in the subsequent analysis due to its scare occurrence. The species-based diffusion coefficients in montmorillonite pores were then calculated, and compared with the water mobility and their diffusivity in aqueous solution/feldspar nanosized fractures. Three factors were considered that affected the diffusive behavior of the uranium species: the mobility of water, the self-diffusion coefficient of the aqueous species, and the electrostatic forces between the negatively charged surface and charged molecules. The mobility of U species in the adsorbed layer decreased in the following sequence: UO(2)(2+)>UO(2)CO(3)>UO(2)(CO(3))(2)(2-). In the diffuse layer, we obtained the highest diffusion coefficient for UO(2)(CO(3))(2)(2-) with the value of 5.48×10(-10) m(2) s(-1), which was faster than UO(2)(2+). For these two charged species, the influence of electrostatic forces on the diffusion of solutes in the diffuse layer is overwhelming, whereas the influence of self-diffusion and water mobility is minor. Our study demonstrated that the negatively charged uranyl carbonate complex must be addressed in the safety assessment of potential radioactive waste disposal systems. Copyright © 2012 Elsevier B.V. All rights reserved.

A Comparison of Naturally-Occurring and Artificially Stimulated Uranium(VI) Bioreduction in Sediment from a Field-scale Experiment in Rifle, CO

NASA Astrophysics Data System (ADS)

Campbell, K. M.; Williams, K. H.; Lesher, E.; Davis, J. A.; Long, P. E.

2007-12-01

Long-term remediation of uranium (U)-contaminated groundwater poses one of the greatest challenges in the clean-up of impacted sites. One solution is to reduce dissolved U(VI) to insoluble U(IV) precipitates by stimulating indigenous metal reducing bacterial populations in situ. Contamination from a former U mine tailings repository (Rifle, CO) provides a research site to study the efficacy of biostimulated U(VI) reduction at the field scale. Several cores were drilled in June 2007 across a region of naturally-occurring U(VI) bioreduction. The cores represent a cross section of sediment that ranges from minimally reducing to highly reducing. Anaerobic sediment samples from the cores were analyzed for labile U(VI) content by carbonate extraction in anoxic conditions (pH 9.4, 14 mM NaHCO3, 2.8 mM Na2CO¬3). A subset of the same core sections were dried and oxidized by exposure to air for 2 weeks. The carbonate extraction was repeated, and the amount of U(IV) present in the anaerobic sample was calculated by difference between the anoxic and oxidized extractions. An acid extraction was also performed on the oxidized sediments to compare the carbonate extractable and the acid extractable U fractions. The highest U concentrations were found in the highly bioreduced sediment, with the majority of U present as U(IV) (66-92%). The regions of highest bioreduction also correspond to elevated concentrations of solid phase organic carbon, suggesting that natural bioreduction is stimulated by zones of increased organic carbon content. The same field site was then used for an artificially stimulated bioreduction experiment, where the indigenous bacterial community was stimulated by injecting acetate upgradient of the core collection location. Carbonate and acid extractions were performed on core samples taken after the completion of the acetate injection. This work evaluates the composition of the sediment before and after biostimulation as a way of directly comparing the extent of natural U(VI) bioreduction to acetate-stimulated bioreduction in order to facilitate the design of a more effective bioremediation strategy for this site.

Uranium-Series Dating of the East Franklin Mountain's Fault Carbonates in El Paso, Texas

NASA Astrophysics Data System (ADS)

Garcia, V. H.; Ma, L.; Pavlis, T. L.; Hurtado, J. M., Jr.

2017-12-01

Direct dating of fault activity is a fundamentally important part of many paleoseismic studies and has potential implications on the quantity, magnitude, recurrence intervals, and timing of earthquake occurrences in the past and future. Faults in the Rio Grande Rift (RGR) in southern New Mexico and West Texas have often been overlooked in seismic hazard assessments due to inferred low tectonic rates and long recurrence intervals. However, there is geologic evidence from surface ruptures that at least 22 large earthquakes (M > 6.25) have occurred in the RGR within the last 10,000 kyrs. The binational conurbation of the El Paso-Juarez region (home to 2.3 million people) lies in the southern extent of the RGR and is traversed by many Quaternary faults, which pose a potentially catastrophic hazard for the region. One fault in particular, the East Franklin Mountains fault (EFMF), is made up of many smaller fault segments that cross through heavily populated areas of the El Paso-Juarez region. Direct dating of past movement on a central segment of the EFMF is a fundamental and important piece of the puzzle in understanding when and how often seismic activity occurred in the fault. In this study, we applied Uranium-series (U-series) dating of fault carbonates collected from a trench that was dug on the central segment of the EFMF. Fault related calcite precipitants and pedogenic carbonates from a nearby soil profile were collected to (1) constraint the timing of past fault activity and (2) understand the relationship and timing of pedogenic carbonate formation away from the EFMF. U-series dating reveals that pedogenic carbonates collected from colluvial wedges along the fault are approximately half the optically stimulated luminescence age of the deposits, suggesting the U-Series dates record a relatively continuous accumulation of carbonates post-deposition. U-Series dates from within the EFMF, however, provided potentially the best estimates for the age of the most recent seismic event with ages of 10 - 12 kyrs, suggesting this method has potential broader applications in paleoseismic studies.

The Itataia phosphate-uranium deposit (Ceará, Brazil) new petrographic, geochemistry and isotope studies

NASA Astrophysics Data System (ADS)

Veríssimo, César Ulisses Vieira; Santos, Roberto Ventura; Parente, Clóvis Vaz; Oliveira, Claudinei Gouveia de; Cavalcanti, José Adilson Dias; Nogueira Neto, José de Araújo

2016-10-01

The Itataia phosphate-uranium deposit is located in Santa Quitéria, in central Ceará State, northeastern Brazil. Mineralization has occurred in different stages and involves quartz leaching (episyenitization), brecciation and microcrystalline phase formation of concretionary apatite. The last constitutes the main mineral of Itatiaia uranium ore, namely collophane. Collophanite ore occurs in massive bodies, lenses, breccia zones, veins or episyenite in marble layers, calc-silicate rocks and gneisses of the Itataia Group. There are two accepted theories on the origin of the earliest mineralization phase of Itataia ore: syngenetic (primary) - where the ore is derived from a continental source and then deposited in marine and coastal environments; and epigenetic (secondary) - whereby the fluids are of magmatic, metamorphic and meteoric origin. The characterization of pre- or post-deformational mineralization is controversial, since the features of the ore are interpreted as deformation. This investigation conducted isotopic studies and chemical analyses of minerals in marbles and calc-silicate rocks of the Alcantil and Barrigas Formations (Itataia Group), as well as petrographic and structural studies. Analysis of the thin sections shows at least three phosphate mineral phases associated with uranium mineralizaton: (1) A prismatic fluorapatite phase associated with chess-board albite, arfvedsonite and ferro-eckermannite; (2) a second fluorapatite phase with fibrous radial or colloform habits that replaces calcium carbonate in marble, especially along fractures, with minerals such as quartz, chlorite and zeolite also identified in calc-silicate rocks; and (3) an younger phosphate phase of botryoidal apatite (fluorapatite and hydroxyapatite) related with clay minerals and probably others calcium and aluminum phosphates. Detailed isotopic analysis carried out perpendicularly to the mineralized levels and veins in the marble revealed significant variation in isotopic ratios. Mineralized zones exhibit a decrease in δ13C and δ18O isotope values and a higher 87Sr/86Sr ratio toward the center of the vein. In conjunction with petrographic studies, these changes contesting the hypothesis of a sedimentary origin for uranium and suggest a radiogenic Sr input by alkaline to peralkaline fluids from fertile granites of the end of Brasiliano/Pan-African orogeny, located outside the deposit. The origin of the phosphorous is associated with phosphorite deposits in the same depositional environment of the neoproterozoic supracrustal quartz-pelite-carbonate sediments of the Itataia Group. Considering the studies conducted here and available geological data, three main mineralizing events can be identified in Itataia: (1) an initial high temperature event connected with a sodium metasomatism-related uranium episode, taking place in Borborema Province and its African counterpart; (2) a second lower temperature stage, consisting of a multiphase cataclastic/hydrothermal event limited to fault and paleokarst zones; and (3) a third and final event, developed in frankly oxidizing conditions. The last two involving mixing of hydrothermal and meteoric fluids.

Analyzing the impact of reactive transport on the repository performance of TRISO fuel

NASA Astrophysics Data System (ADS)

Schmidt, Gregory

One of the largest determiners of the amount of electricity generated by current nuclear reactors is the efficiency of the thermodynamic cycle used for power generation. Current light water reactors (LWR) have an efficiency of 35% or less for the conversion of heat energy generated by the reactor to electrical energy. If this efficiency could be improved, more power could be generated from equivalent volumes of nuclear fuel. One method of improving this efficiency is to use a coolant flow that operates at a much higher temperature for electricity production. A reactor design that is currently proposed to take advantage of this efficiency is a graphite-moderated, helium-cooled reactor known as a High Temperature Gas Reactor (HTGR). There are significant differences between current LWR's and the proposed HTGR's but most especially in the composition of the nuclear fuel. For LWR's, the fuel elements consist of pellets of uranium dioxide or plutonium dioxide that are placed in long tubes made of zirconium metal alloys. For HTGR's, the fuel, known as TRISO (TRIstructural-ISOtropic) fuel, consists of an inner sphere of fissile material, a layer of dense pyrolytic carbon (PyC), a ceramic layer of silicon carbide (SiC) and a final dense outer layer of PyC. These TRISO particles are then compacted with graphite into fuel rods that are then placed in channels in graphite blocks. The blocks are then arranged in an annular fashion to form a reactor core. However, this new fuel form has unanswered questions on the environmental post-burn-up behavior. The key question for current once-through fuel operations is how these large irradiated graphite blocks with spent fuel inside will behave in a repository environment. Data in the literature to answer this question is lacking, but nevertheless this is an important question that must be answered before wide-spread adoption of HTGR's could be considered. This research has focused on answering the question of how the large quantity of graphite surrounding the spent HTGR fuel will impact the release of aqueous uranium from the TRISO fuel. In order to answer this question, the sorption and partitioning behavior of uranium to graphite under a variety of conditions was investigated. Key systematic variables that were analyzed include solution pH, dissolved carbonate concentration, uranium metal concentration and ionic strength. The kinetics and desorption characteristics of uranium/graphite partitioning were studied as well. The graphite used in these experiments was also characterized by a variety of techniques and conclusions are drawn about the relevant surface chemistry of graphite. This data was then used to generate a model for the reactive transport of uranium in a graphite matrix. This model was implemented with the software code CXTFIT and validated through the use of column studies mirroring the predicted system.

Submarine Atmospheres

DTIC Science & Technology

1990-07-01

Society of Mechanical Engineers . 7 Anonymous (19862) The Toxic Effects of Chronic Exposures to Low Levels of Carbon Dioxide, Report No. 973, Naval...is diesel engine exhaust. It started with uranium miners back in the mid- 60s. Let me just offer the fact that although it is a very complex mixture...reforming this by a modifled diesel engine In the laboratory, were able to produce lesions within the lung that progressed into vesicular emphysema

The water-energy nexus: an earth science perspective

USGS Publications Warehouse

Healy, Richard W.; Alley, William M.; Engle, Mark A.; McMahon, Peter B.; Bales, Jerad D.

2015-01-01

Relevant earth science issues analyzed and discussed herein include freshwater availability; water use; ecosystems health; assessment of saline water resources; assessment of fossil-fuel, uranium, and geothermal resources; subsurface injection of wastewater and carbon dioxide and related induced seismicity; climate change and its effect on water availability and energy production; byproducts and waste streams of energy development; emerging energy-development technologies; and energy for water treatment and delivery.

Dense Medium Ore Concentrates of Bois-Noirs; MINERAIS DES BOIS NOIRS CONCENTRES DE MILIEU DENSE

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

Le Bris, J.; Leduc, M.

1959-01-01

The chemical treatment of uranium concentrates of BoisNoirs ore obtained by heavy medium are discussed. The first part deals with sulfuric acid attack on the concentrate, and the second part with the separation of the solution from residues by filtration. A third part deals with this separation by decantation. The fourth part deals with the carbonation of the pickling solutions obtained. (auth)

Geochronology Database for Central Colorado

USGS Publications Warehouse

Klein, T.L.; Evans, K.V.; deWitt, E.H.

2010-01-01

This database is a compilation of published and some unpublished isotopic and fission track age determinations in central Colorado. The compiled area extends from the southern Wyoming border to the northern New Mexico border and from approximately the longitude of Denver on the east to Gunnison on the west. Data for the tephrochronology of Pleistocene volcanic ash, carbon-14, Pb-alpha, common-lead, and U-Pb determinations on uranium ore minerals have been excluded.

FUEL COMPOSITION FOR NUCLEAR REACTORS

DOEpatents

Andersen, J.C.

1963-08-01

A process for making refractory nuclear fuel elements involves heating uranium and silicon powders in an inert atmosphere to 1600 to 1800 deg C to form USi/sub 3/; adding silicon carbide, carbon, 15% by weight of nickel and aluminum, and possibly also molybdenum and silicon powders; shaping the mixture; and heating to 1700 to 2050 deg C again in an inert atmosphere. Information on obtaining specific compositions is included. (AEC)

A simple-rapid method to separate uranium, thorium, and protactinium for U-series age-dating of materials.

PubMed

Knight, Andrew W; Eitrheim, Eric S; Nelson, Andrew W; Nelson, Steven; Schultz, Michael K

2014-08-01

Uranium-series dating techniques require the isolation of radionuclides in high yields and in fractions free of impurities. Within this context, we describe a novel-rapid method for the separation and purification of U, Th, and Pa. The method takes advantage of differences in the chemistry of U, Th, and Pa, utilizing a commercially-available extraction chromatographic resin (TEVA) and standard reagents. The elution behavior of U, Th, and Pa were optimized using liquid scintillation counting techniques and fractional purity was evaluated by alpha-spectrometry. The overall method was further assessed by isotope dilution alpha-spectrometry for the preliminary age determination of an ancient carbonate sample obtained from the Lake Bonneville site in western Utah (United States). Preliminary evaluations of the method produced elemental purity of greater than 99.99% and radiochemical recoveries exceeding 90% for U and Th and 85% for Pa. Excellent purity and yields (76% for U, 96% for Th and 55% for Pa) were also obtained for the analysis of the carbonate samples and the preliminary Pa and Th ages of about 39,000 years before present are consistent with (14)C-derived age of the material. Copyright © 2014 Elsevier Ltd. All rights reserved.

Investigation of charge stripping scheme for uranium ions at 1-20 MeV/nucleon

NASA Astrophysics Data System (ADS)

Kuboki, Hironori; Harada, Hiroyuki; Saha, Pranab K.

2018-05-01

We investigated a possibility to obtain charge distributions of uranium ions under the conditions to meet the requirements of the booster synchrotron proposed for heavy ion acceleration at J-PARC. The charge distribution is expected to have a width as narrow as possible to realize multi-charge acceleration. The main candidate of stripping material is a carbon foil because we can obtain narrower distributions than gas stripper and a lot of data is available. Besides that, the thickness of the stripping material should be less than 142 μg cm-2 because the energy loss in the stripping material would be compensated by an auxiliary accelerating cavity in the synchrotron ring. We studied the impact energy with which the charge distribution attains equilibrium within this thickness and has the narrowest width. The width is estimated over 1-20 MeV/nucleon by the calculation using the ionization and electron capture cross sections. Scaling factors are introduced to reproduce the experimental data and are determined to be 2.0 and 0.08 for the cross sections of ionization and electron capture, respectively. We concluded that the narrowest width can be obtained at 5.5 MeV/nucleon with a 109-μg cm-2-thick carbon foil.

Uranium(IV) adsorption by natural organic matter in anoxic sediments

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

Bone, Sharon E.; Dynes, James J.; Cliff, John

2017-01-09

Uranium is an important fuel source and a global environmental contaminant. It accumulates in the tetravalent state, U(IV), in anoxic sediments, including ore deposits, marine basins, and contaminated aquifers. However, very little is known about the speciation of U(IV) in low temperature geochemical environments, inhibiting the development of a conceptual model of U behavior. Until recently, U(IV) was assumed to exist predominantly as the sparingly soluble mineral uraninite (UO 2) in anoxic sediments; yet studies now show that UO 2 is not often dominant in these environments. However, a model of U(IV) speciation under environmentally relevant conditions has not yetmore » been developed. Here we show that complexes of U(IV) adsorb on organic carbon and organic carbon-coated clays in an organic-rich natural substrate under field-relevant conditions. Whereas previous research assumed that the U(IV) product depended on the reduction pathway, our results demonstrate that UO 2 formation can be inhibited simply by decreasing the U:solid ratio. Thus, it is the number and type of surface ligands that controls U(IV) speciation subsequent to U(VI) reduction. Projections of U transport and bioavailability, and thus its threat to human and ecosystem health, must consider retention of U(IV) ions within the local sediment environment.« less

Simultaneous determination of uranium carbide dissolution products by capillary zone electrophoresis.

PubMed

Sladkov, Vladimir; Fourest, Blandine

2009-03-20

Separation and simultaneous determination of a number of organic acid anions (oxalate, mellitate, trimellitate and benzoate) and U(VI) with direct UV detection is developed for analysis of uranium carbide (UC) dissolution products by capillary zone electrophoresis (CZE). Reverse polarity mode is used. It is found that complex formation of U(VI) with carbonate, used as a carrier electrolyte, allows U(VI) to be determined, as negatively charged species, in a single run with organic acid anions. Some parameters such as pH value, composition of electrolyte and detection wavelength are optimized. Under the chosen conditions (carbonate buffer (ionic strength of 100 mM), pH 9.8, 0.15 mM tetradecyltrimethylammonium bromide (TTAB)) a complete separation is achieved. Calibration plots are linear in two ranges of concentration for U(VI) ( approximately 1 x 10(-5) to 1 x 10(-3)), mellitate and trimellitate ( approximately 5 x 10(-6) to 5 x 10(-4)), and about one range ( approximately 1 x 10(-4) to 5 x 10(-3)) for oxalate and benzoate. Accuracy of the procedure is checked by the "added-found" method in standard mixture solutions. Relative standard deviation is within the range of 2-10% and the recovery is in the range of 90-110%. This method is applied for the analysis of real UC dissolution samples.

Geology of the Ralston Buttes district, Jefferson County, Colorado: a preliminary report

USGS Publications Warehouse

Sheridan, Douglas M.; Maxwell, Charles H.; Albee, Arden L.; Van Horn, Richard

1956-01-01

The Ralston Buttes district in Jefferson County is one of the most significant new uranium districts located east of the Continental Divide in Colorado. The district is east of the Colorado Front Range mineral belt, along the east front of the range. From November 1953 through October 1956, about 10,000 tons of uranium ore, much of which was high-grade pitchblende-bearing vein material, was shipped from the district. The ore occurs in deposits that range in size from bodies containing less than 50 tons to ore shoots containing over 1,000 tons. The only other mining activity in the area has been a sporadic production of beryl, feldspar, and scrap mica from Precambrian pegmatites, and quarrying of dimension stone, limestone, and clay from sedimentary rocks. Most of the Ralston Buttes district consists of complexly folded Precambrian metamorphic and igneous rocks - gneiss, schist, quartzite, amphibolite, and granodiorite. Paleozoic and Mesozoic sedimentary rocks crop out in the northeastern part of the district. These rocks are cut by northwesterly-trending fault systems of Laramide age and by small bodies of intrusive rocks that are Tertiary in age. The typical uranium deposits in the district are hydrothermal veins occupying openings in Laramide fault breccias or related fractures that cut the Precambrian rocks. Pitchblende and lesser amounts of secondary uranium minerals are associated with sparse base-mental sulfides in a gangue of carbonate minerals, potash feldspar, and, more rarely, quartz. Less common types of deposits consist of pitchblende and secondary uranium minerals that occupy fractures cutting pegmatites and quartz veins. The uranium deposits are concentrated in two areas, the Ralston Creek area and the Golden Gate Canyon area. The deposits in the Ralston Creek area are located along the Rogers fault system, and the deposits in the Golden Gate Canyon area are along the Hurricane Hill fault system. Two geologic factors were important to the localization of the uranium deposits: (1) favorable structural environment and (2) favorable host rocks. The deposits in each of the two major areas are located where a northwesterly-trending Laramide fault system splits into a complex network of faults. Also, most of the deposits appear to be localized where the faults cut Precambrian rocks rich in hornblende, biotite, or garnet and biotite. The ore controls recognized in this relatively new uranium district may have wider application in areas of similar geology elsewhere in the Front Range.

Assessment of calcium addition on the removal of U(VI) in the alkaline conditions created by NH 3 gas

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

Katsenovich, Yelena; Cardona, Claudia; Szecsody, Jim

Remediation of uranium (U) contamination in the deep vadose zone (VZ) sediments abundant in calcite mineral is a challenging task considering the formation of highly stable and mobile uranyl complexes with carbonate and calcium in pore water composition. There is a concern that uranium contamination in the VZ can serve as a continued source for groundwater pollution, creating a risk to human health and the environment through the groundwater pathway. This requires in-situ remediation of the radionuclide-contaminated VZ to convert soluble U species to low solubility precipitates that are stable in the natural environment. Injection of reactive gasses (e.g., NHmore » 3) is a promising technology to decrease U mobility in the unsaturated zone without the addition of liquid amendments. The NH 3 injection creates alkaline conditions that can alter the sediment pore water composition due to a release of elements from minerals (via desorption and dissolution) that are present in the sediment. However, it is not known how VZ pore water constituents (Si, Al 3+, HCO 3 -, and Ca 2 +) would affect U(VI) removal/precipitation in alkaline conditions. This study quantified the role of major pore water constituents typically present in the arid and semi-arid environments of the western regions of the U.S and identified solid uranium-bearing phases that could potentially precipitate from solutions approximating pore water compositions after pH manipulations via ammonia gas injections. Triplicate samples were prepared using six Si (5, 50 100, 150, 200, and 250 mM), six HCO 3 - (0, 3, 25, 50, 75, and 100 mM), and two Ca 2+ (5 and 10 mM) concentrations. The concentration of aluminum and uranium was kept constant at 5 mM and 0.0084 mM, respectively, in all synthetic formulations tested. Results showed that the percentage of U(VI) removal was controlled by the Si/Al molar ratios and Ca 2+ concentrations. Regardless of the bicarbonate concentration tested, the percentage of U(VI) removed increased as the Si/Al ratios were increased. However, higher Ca concentrations correlated with higher U(VI) removal, ranging between 96% and 99%, at low Si/Al ratios. The SEM images of dried precipitates displayed dense amorphous regions high in silica content, where EDS elemental analysis unveiled higher U atomic percentages. The formation of uranyl silicate and carbonate minerals was also predicted by the speciation modeling. XRD analysis revealed the presence of uranyl carbonate mineral phases (andersonite, grimselite); however, uranyl silicates predicted (Na-boltwoodite) were not identified experimentally, possibly due to the amorphous nature of the silica solid phases observed in our experiments.« less

Assessment of calcium addition on the removal of U(VI) in the alkaline conditions created by NH 3 gas

DOE PAGES

Katsenovich, Yelena; Cardona, Claudia; Szecsody, Jim; ...

2018-03-06

Remediation of uranium (U) contamination in the deep vadose zone (VZ) sediments abundant in calcite mineral is a challenging task considering the formation of highly stable and mobile uranyl complexes with carbonate and calcium in pore water composition. There is a concern that uranium contamination in the VZ can serve as a continued source for groundwater pollution, creating a risk to human health and the environment through the groundwater pathway. This requires in-situ remediation of the radionuclide-contaminated VZ to convert soluble U species to low solubility precipitates that are stable in the natural environment. Injection of reactive gasses (e.g., NHmore » 3) is a promising technology to decrease U mobility in the unsaturated zone without the addition of liquid amendments. The NH 3 injection creates alkaline conditions that can alter the sediment pore water composition due to a release of elements from minerals (via desorption and dissolution) that are present in the sediment. However, it is not known how VZ pore water constituents (Si, Al 3+, HCO 3 -, and Ca 2 +) would affect U(VI) removal/precipitation in alkaline conditions. This study quantified the role of major pore water constituents typically present in the arid and semi-arid environments of the western regions of the U.S and identified solid uranium-bearing phases that could potentially precipitate from solutions approximating pore water compositions after pH manipulations via ammonia gas injections. Triplicate samples were prepared using six Si (5, 50 100, 150, 200, and 250 mM), six HCO 3 - (0, 3, 25, 50, 75, and 100 mM), and two Ca 2+ (5 and 10 mM) concentrations. The concentration of aluminum and uranium was kept constant at 5 mM and 0.0084 mM, respectively, in all synthetic formulations tested. Results showed that the percentage of U(VI) removal was controlled by the Si/Al molar ratios and Ca 2+ concentrations. Regardless of the bicarbonate concentration tested, the percentage of U(VI) removed increased as the Si/Al ratios were increased. However, higher Ca concentrations correlated with higher U(VI) removal, ranging between 96% and 99%, at low Si/Al ratios. The SEM images of dried precipitates displayed dense amorphous regions high in silica content, where EDS elemental analysis unveiled higher U atomic percentages. The formation of uranyl silicate and carbonate minerals was also predicted by the speciation modeling. XRD analysis revealed the presence of uranyl carbonate mineral phases (andersonite, grimselite); however, uranyl silicates predicted (Na-boltwoodite) were not identified experimentally, possibly due to the amorphous nature of the silica solid phases observed in our experiments.« less

Production of Low Enriched Uranium Nitride Kernels for TRISO Particle Irradiation Testing

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

McMurray, J. W.; Silva, C. M.; Helmreich, G. W.

2016-06-01

A large batch of UN microspheres to be used as kernels for TRISO particle fuel was produced using carbothermic reduction and nitriding of a sol-gel feedstock bearing tailored amounts of low-enriched uranium (LEU) oxide and carbon. The process parameters, established in a previous study, produced phasepure NaCl structure UN with dissolved C on the N sublattice. The composition, calculated by refinement of the lattice parameter from X-ray diffraction, was determined to be UC 0.27N 0.73. The final accepted product weighed 197.4 g. The microspheres had an average diameter of 797±1.35 μm and a composite mean theoretical density of 89.9±0.5% formore » a solid solution of UC and UN with the same atomic ratio; both values are reported with their corresponding calculated standard error.« less

Methods for determination of radioactive substances in water and fluvial sediments

USGS Publications Warehouse

Thatcher, Leland Lincoln; Janzer, Victor J.; Edwards, Kenneth W.

1977-01-01

Analytical methods for the determination of some of the more important components of fission or neutron activation product radioactivity and of natural radioactivity found in water are reported. The report for each analytical method includes conditions for application of the method, a summary of the method, interferences, required apparatus and reagents, analytical procedures, calculations, reporting of results, and estimation of precision. The fission product isotopes considered are cesium-137, strontium-90, and ruthenium-106. The natural radioelements and isotopes considered are uranium, lead-210, radium-226, radium-228, tritium, and carbon-14. A gross radioactivity survey method and a uranium isotope ratio method are given. When two analytical methods are in routine use for an individual isotope, both methods are reported with identification of the specific areas of application of each. Techniques for the collection and preservation of water samples to be analyzed for radioactivity are discussed.

A Heterobimetallic Complex With an Unsupported Uranium(III)-Aluminum(I) Bond: (CpSiMe3)3U-AlCp* (Cp* = C5Me5)

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

Minasian, Stefan; Krinsky Ph.D., Jamin; Williams, Valerie

2008-07-23

The discovery of molecular metal-metal bonds has been of fundamental importance to the understanding of chemical bonding. For the actinides, examples of unsupported metal-metal bonds are relatively uncommon, consisting of Cp{sub 3}U-SnPh{sub 3}, and several actinide-transition metal complexes. Traditionally, bonding in the f-elements has been described as electrostatic; however, elucidating the degree of covalency is a subject of recent research. In carbon monoxide complexes of the trivalent uranium metallocenes, decreased {nu}{sub CO} values relative to free CO suggest that the U(III) atom acts as a {pi}-donor. Ephritikhine and coworkers have demonstrated that {pi}-accepting ligands can differentiate trivalent lanthanide and actinidemore » ions, an effect that renders this chemistry of interest in the context of nuclear waste separation technology.« less

Research and development on materials for the SPES target

NASA Astrophysics Data System (ADS)

Corradetti, Stefano; Andrighetto, Alberto; Manzolaro, Mattia; Scarpa, Daniele; Vasquez, Jesus; Rossignoli, Massimo; Monetti, Alberto; Calderolla, Michele; Prete, Gianfranco

2014-03-01

The SPES project at INFN-LNL (Istituto Nazionale di Fisica Nucleare - Laboratori Nazionali di Legnaro) is focused on the production of radioactive ion beams. The core of the SPES facility is constituted by the target, which will be irradiated with a 40 MeV, 200 µA proton beam in order to produce radioactive species. In order to efficiently produce and release isotopes, the material constituting the target should be able to work under extreme conditions (high vacuum and temperatures up to 2000 °C). Both neutron-rich and proton-rich isotopes will be produced; in the first case, carbon dispersed uranium carbide (UCx) will be used as a target, whereas to produce p-rich isotopes, several types of targets will have to be irradiated. The synthesis and characterization of different types of material will be reported. Moreover, the results of irradiation and isotopes release tests on different uranium carbide target prototypes will be discussed.

Energy map of southwestern Wyoming, Part B: oil and gas, oil shale, uranium, and solar

USGS Publications Warehouse

Biewick, Laura R.H.; Wilson, Anna B.

2014-01-01

The U.S. Geological Survey (USGS) has compiled Part B of the Energy Map of Southwestern Wyoming for the Wyoming Landscape Conservation Initiative (WLCI). Part B consists of oil and gas, oil shale, uranium, and solar energy resource information in support of the WLCI. The WLCI represents the USGS partnership with other Department of the Interior Bureaus, State and local agencies, industry, academia, and private landowners, all of whom collaborate to maintain healthy landscapes, sustain wildlife, and preserve recreational and grazing uses while developing energy resources in southwestern Wyoming. This product is the second and final part of the Energy Map of Southwestern Wyoming series (also see USGS Data Series 683, http://pubs.usgs.gov/ds/683/), and encompasses all of Carbon, Lincoln, Sublette, Sweetwater, and Uinta Counties, as well as areas in Fremont County that are in the Great Divide and Green River Basins.

METHOD OF MAKING FUEL BODIES

DOEpatents

Goeddel, W.V.; Simnad, M.T.

1963-04-30

This patent relates to a method of making a fuel compact having a matrix of carbon or graphite which carries the carbides of fissile material. A nuclear fuel material selected from the group including uranium and thorium carbides, silicides, and oxides is first mixed both with sufficient finely divided carbon to constitute a matrix in the final product and with a diffusional bonding material selected from the class consisting of zirconium, niobium, molybdenum, titanium, nickel, chromium, and silicon. The mixture is then heated at a temperature of 1500 to 1800 nif- C while maintaining it under a pressure of over about 2,000 pounds per square inch. Preferably, heating is accomplished by the electrical resistance of the compact itself. (AEC)

Two major Cenozoic episodes of phosphogenesis recorded in equatorial Pacific seamount deposits

USGS Publications Warehouse

Hein, J.R.; Hsueh-Wen, Yeh; Gunn, S.H.; Sliter, W.V.; Benninger, L.M.; Chung-Ho, Wang

1993-01-01

The phosphorites occur in a wide variety of forms, but most commonly carbonate fluorapatite (CFA) replaced middle Eocene and older carbonate sediment in a deep water environment (>1000 m). Element ratios distinguish seamount phosphorites from continental margin, plateau, and insular phosphorites. Uranium and thorium contents are low and total rare earch element (REE) contents are generally high. The paleoceanographic conditions initiated and sustained development of phosphorite by accumulation of dissolved phosphorus in the deep sea during relatively stable climatic conditions when oceanic circulation was sluggish. Fluctuations in climate, sealevel, and upwelling that accompanied the climate transitions may have driven cycles of enrichment and depletion of the deep-sea phosphorus reservoir. -from Authors

Characterization of cores from an in-situ recovery mined uranium deposit in Wyoming: Implications for post-mining restoration

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

WoldeGabriel, G.; Boukhalfa, H.; Ware, S. D.

In-situ recovery (ISR) of uranium (U) from sandstone-type roll-front deposits is a technology that involves the injection of solutions that consist of ground water fortified with oxygen and carbonate to promote the oxidative dissolution of U, which is pumped to recovery facilities located at the surface that capture the dissolved U and recycle the treated water. The ISR process alters the geochemical conditions in the subsurface creating conditions that are more favorable to the migration of uranium and other metals associated with the uranium deposit. There is a lack of clear understanding of the impact of ISR mining on themore » aquifer and host rocks of the post-mined site and the fate of residual U and other metals within the mined ore zone. We performed detailed petrographic, mineralogical, and geochemical analyses of several samples taken from about 7 m of core of the formerly the ISR-mined Smith Ranch–Highland uranium deposit in Wyoming. We show that previously mined cores contain significant residual uranium (U) present as coatings on pyrite and carbonaceous fragments. Coffinite was identified in three samples. Core samples with higher organic (> 1 wt.%) and clay (> 6–17 wt.%) contents yielded higher 234U/ 238U activity ratios (1.0–1.48) than those with lower organic and clay fractions. The ISR mining was inefficient in mobilizing U from the carbonaceous materials, which retained considerable U concentrations (374–11,534 ppm). This is in contrast with the deeper part of the ore zone, which was highly depleted in U and had very low 234U/ 238U activity ratios. This probably is due to greater contact with the lixiviant (leaching solution) during ISR mining. EXAFS analyses performed on grains with the highest U and Fe concentrations reveal that Fe is present in a reduced form as pyrite and U occurs mostly as U(IV) complexed by organic matter or as U(IV) phases of carbonate complexes. Moreover, U–O distances of ~ 2.05 Å were noted, indicating the potential formation of other poorly defined U(IV/VI) species. We also noted a small contribution from Udouble bond; length as m-dashO at 1.79 Å, which indicates that U is partially oxidized. There is no apparent U–S or U–Fe interaction in any of the U spectra analyzed. However, SEM analysis of thin sections prepared from the same core material reveals surficial U associated with pyrite which is probably a minor fraction of the total U present as thin coatings on the surface of pyrite. Our data show the presence of different structurally variable uranium forms associated with the mined cores. U associated with carbonaceous materials is probably from the original U mobilization that accumulated in the organic matter-rich areas under reducing conditions during shallow burial diagenesis. U associated with pyrite represents a small fraction of the total U and was likely deposited as a result of chemical reduction by pyrite. Our data suggest that areas rich in carbonaceous materials had limited exposure to the lixiviant solution, continue to be reducing, and still hold significant U resources. Because of their limited access to fluid flow, these areas might not contribute significantly to post-mining U release or attenuation. Areas with pyrite that are accessible to fluids seem to be more reactive and could act as reductants and facilitate U reduction and accumulation, limiting its migration.« less

Characterization of cores from an in-situ recovery mined uranium deposit in Wyoming: Implications for post-mining restoration

DOE PAGES

WoldeGabriel, G.; Boukhalfa, H.; Ware, S. D.; ...

2014-10-08

In-situ recovery (ISR) of uranium (U) from sandstone-type roll-front deposits is a technology that involves the injection of solutions that consist of ground water fortified with oxygen and carbonate to promote the oxidative dissolution of U, which is pumped to recovery facilities located at the surface that capture the dissolved U and recycle the treated water. The ISR process alters the geochemical conditions in the subsurface creating conditions that are more favorable to the migration of uranium and other metals associated with the uranium deposit. There is a lack of clear understanding of the impact of ISR mining on themore » aquifer and host rocks of the post-mined site and the fate of residual U and other metals within the mined ore zone. We performed detailed petrographic, mineralogical, and geochemical analyses of several samples taken from about 7 m of core of the formerly the ISR-mined Smith Ranch–Highland uranium deposit in Wyoming. We show that previously mined cores contain significant residual uranium (U) present as coatings on pyrite and carbonaceous fragments. Coffinite was identified in three samples. Core samples with higher organic (> 1 wt.%) and clay (> 6–17 wt.%) contents yielded higher 234U/ 238U activity ratios (1.0–1.48) than those with lower organic and clay fractions. The ISR mining was inefficient in mobilizing U from the carbonaceous materials, which retained considerable U concentrations (374–11,534 ppm). This is in contrast with the deeper part of the ore zone, which was highly depleted in U and had very low 234U/ 238U activity ratios. This probably is due to greater contact with the lixiviant (leaching solution) during ISR mining. EXAFS analyses performed on grains with the highest U and Fe concentrations reveal that Fe is present in a reduced form as pyrite and U occurs mostly as U(IV) complexed by organic matter or as U(IV) phases of carbonate complexes. Moreover, U–O distances of ~ 2.05 Å were noted, indicating the potential formation of other poorly defined U(IV/VI) species. We also noted a small contribution from Udouble bond; length as m-dashO at 1.79 Å, which indicates that U is partially oxidized. There is no apparent U–S or U–Fe interaction in any of the U spectra analyzed. However, SEM analysis of thin sections prepared from the same core material reveals surficial U associated with pyrite which is probably a minor fraction of the total U present as thin coatings on the surface of pyrite. Our data show the presence of different structurally variable uranium forms associated with the mined cores. U associated with carbonaceous materials is probably from the original U mobilization that accumulated in the organic matter-rich areas under reducing conditions during shallow burial diagenesis. U associated with pyrite represents a small fraction of the total U and was likely deposited as a result of chemical reduction by pyrite. Our data suggest that areas rich in carbonaceous materials had limited exposure to the lixiviant solution, continue to be reducing, and still hold significant U resources. Because of their limited access to fluid flow, these areas might not contribute significantly to post-mining U release or attenuation. Areas with pyrite that are accessible to fluids seem to be more reactive and could act as reductants and facilitate U reduction and accumulation, limiting its migration.« less

Influence of carbon source and inoculum type on anaerobic biomass adhesion on polyurethane foam in reactors fed with acid mine drainage.

PubMed

Rodriguez, Renata P; Zaiat, Marcelo

2011-04-01

This paper analyzes the influence of carbon source and inoculum origin on the dynamics of biomass adhesion to an inert support in anaerobic reactors fed with acid mine drainage. Formic acid, lactic acid and ethanol were used as carbon sources. Two different inocula were evaluated: one taken from an UASB reactor and other from the sediment of a uranium mine. The values of average colonization rates and the maximum biomass concentration (C(max)) were inversely proportional to the number of carbon atoms in each substrate. The highest C(max) value (0.35 g TVS g(-1) foam) was observed with formic acid and anaerobic sludge as inoculum. Maximum colonization rates (v(max)) were strongly influenced by the type of inoculum when ethanol and lactic acid were used. For both carbon sources, the use of mine sediment as inoculum resulted in a v(max) of 0.013 g TVS g(-1) foam day(-1), whereas 0.024 g TVS g(-1) foam day(-1) was achieved with anaerobic sludge. Copyright © 2011 Elsevier Ltd. All rights reserved.

Low-z gas stripper as an alternative to carbon foils for the acceleration of high-power uranium beams

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

Okuno, H.; Hershcovitch, A.; Fukunishi, N.

2011-04-23

The RIKEN accelerator complex started feeding the next-generation exotic beam facility radioisotope beam factory (RIBF) with heavy-ion beams from 2007 after the successful commissioning of RIBF at the end of 2006. Many improvements made from 2007 to 2010 were instrumental in increasing the intensity of various heavy-ion beams. However, the available beam intensity of very heavy ion beams, especially uranium beams, is far below our goal of 1 p{mu}A (6 x 10{sup 12} particles/s). In order to achieve this goal, upgrade programs are already in progress; the programs include the construction of a new 28-GHz superconducting electron cyclotron resonance ionmore » source and a new injector linac. However, the most serious problem, that of a charge stripper for high-power uranium beams, still remains unsolved, despite extensive research and development work using large foils mounted on a rotating cylinder and a N{sup 2} gas stripper. A gas stripper is free from problems related to lifetime, though the equilibrium charge state in this stripper is considerably lower than that in a carbon foil, owing to the absence of the density effect. Nevertheless, the merits of gas strippers motivated us to develop a low-Z gas stripper to achieve a higher equilibrium charge state even in gases. We measured the electron-loss and electron-capture cross sections of uranium ions in He gas as a function of their charge state at 11, 14, and 15 MeV/nucleon. The equilibrium charge states extracted from the intersection of the lines of the two cross sections were promisingly higher than those in N{sub 2} gas by more than 10. Simple simulations of charge development along the stripper thickness were performed by assuming the measured cross sections. The simulation results show that about 1 mg/cm{sup 2} of He gas should be accumulated to achieve a charge state higher than that of N{sub 2} gas, notwithstanding the difficulty in accumulation of this helium amount owing to its fast dispersion. However, we now believe that the following two solutions can overcome this difficulty: a gas cell with a very large differential pumping system and a gas cell with a plasma window. Their merits and demerits are discussed in the paper.« less

Unexpected Interactions of the Cyanobacterial Metallothionein SmtA with Uranium.

PubMed

Acharya, Celin; Blindauer, Claudia A

2016-02-15

Molecules for remediating or recovering uranium from contaminated environmental resources are of high current interest, with protein-based ligands coming into focus recently. Metallothioneins either bind or redox-silence a range of heavy metals, conferring protection against metal stress in many organisms. Here, we report that the cyanobacterial metallothionein SmtA competes with carbonate for uranyl binding, leading to formation of heterometallic (UO2)(n)Zn4SmtA species, without thiol oxidation, zinc loss, or compromising secondary or tertiary structure of SmtA. In turn, only metalated and folded SmtA species were found to be capable of uranyl binding. (1)H NMR studies and molecular modeling identified Glu34/Asp38 and Glu12/C-terminus as likely adventitious, but surprisingly strong, bidentate binding sites. While it is unlikely that these interactions correspond to an evolved biological function of this metallothionein, their occurrence may offer new possibilities for designing novel multipurpose bacterial metallothioneins with dual ability to sequester both soft metal ions including Cu(+), Zn(2+), Cd(2+), Hg(2+), and Pb(2+) and hard, high-oxidation state heavy metals such as U(VI). The concomitant protection from the chemical toxicity of uranium may be valuable for the development of bacterial strains for bio-remediation.

Geochemical features of the ore-bearing medium in uranium deposits in the Khiagda ore field

NASA Astrophysics Data System (ADS)

Kochkin, B. T.; Solodov, I. N.; Ganina, N. I.; Rekun, M. L.; Tarasov, N. N.; Shugina, G. A.; Shulik, L. S.

2017-09-01

The Neogene uranium deposits of the Khiagda ore field (KOF) belong to the paleovalley variety of the hydrogene type and differ from other deposits of this genetic type in the geological and geochemical localization conditions. The contemporary hydrogeochemical setting and microbiological composition of ore-bearing medium are discussed. The redox potential of the medium (Eh is as low as-400 mV) is much lower than those established at other hydrogenic deposits, both ancient Late Mesozoic and young Late Alpine, studied with the same methods in Russia, Uzbekistan, and southern Kazakhstan. The pH of subsurface water (6.86-8.13) differs in significant fluctuations both between neighboring deposits and within individual ore lodes. Hydrogen-forming and denitrifying bacteria are predominant in microbiological populations, whereas sulfate-reducing bacteria are low-active. The consideration of these factors allowed us to describe the mechanism of uranium ore conservation as resulting from the development of the cryolithic zone, which isolates ore lodes from the effect of the external medium. Carbonated water supplied from the basement along fault zones also participates in the formation of the present-day hydrogeochemical setting. Based on the features of the ore-bearing medium, we propose a method of borehole in situ acid leaching to increase the efficiency of mining in the Khiagda ore field.

Spallation studies on shock loaded uranium

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

Tonks, D.L.; Hixson, R.; Gustavsen, R.L.

1997-12-31

Uranium samples at two different purity levels were used for spall strength measurements at three different stress levels. A 50 mm single-stage gas-gun was used to produce planar impact conditions using Z-cut quartz impactors. Samples of depleted uranium were taken from very high purity material and from material that had 300 ppm of carbon added. A pair of shots was done for each impact strength, one member of the pair with VISAR diagnostics and the second with soft recovery for metallographical examination. A series of increasing final stress states were chosen to effectively freeze the microstructural damage at three placesmore » in the development to full spall separation. This allowed determination of the dependence of spall mechanisms on stress level and sample purity. This report will discuss both the results of the metallurgical examination of soft recovered samples and the modeling of the free surface VISAR data. The micrographs taken from the recovered samples show brittle cracking as the spallation failure mechanism. Deformation induced twins are plentiful and obviously play a role in the spallation process. The twins are produced in the initial shock loading and, so, are present already before the fracture process begins. The 1 d characteristics code CHARADE has been used to model the free surface VISAR data.« less

Mechanistic approach for nitride fuel evolution and fission product release under irradiation

NASA Astrophysics Data System (ADS)

Dolgodvorov, A. P.; Ozrin, V. D.

2017-01-01

A model for describing uranium-plutonium mixed nitride fuel pellet burning was developed. Except fission products generating, the model includes impurities of oxygen and carbon. Nitrogen behaviour in nitride fuel was analysed and the nitrogen chemical potential in solid solution with uranium-plutonium nitride was constructed. The chemical program module was tested with the help of thermodynamic equilibrium phase distribution calculation. Results were compared with analogous data in literature, quite good agreement was achieved, especially for uranium sesquinitride, metallic species and some oxides. Calculation of a process of nitride fuel burning was also conducted. Used mechanistic approaches for fission product evolution give the opportunity to find fission gas release fractions and also volumes of intergranular secondary phases. Calculations present that the most massive secondary phases are the oxide and metallic phases. Oxide phase contain approximately 1 % wt of substance over all time of burning with slightly increasing of content. Metallic phase has considerable rising of mass and by the last stage of burning it contains about 0.6 % wt of substance. Intermetallic phase has less increasing rate than metallic phase and include from 0.1 to 0.2 % wt over all time of burning. The highest element fractions of released gaseous fission products correspond to caesium and iodide.

TC-99 Decontaminant from heat treated gaseous diffusion membrane -Phase I, Part B

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

Oji, L.; Restivo, M.; Duignan, M.

2017-11-01

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 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 or exactmore » form in the gaseous 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 or leaching desorption, which is independent of the technetium oxidation states, to perform an insitu removal of the technetium as a volatile species and trap the radionuclide on sorbent traps which could be disposed as low-level waste. Based on the positive results of the first part of this work1 the use of steam as a thermal decontamination agent was further explored with a second piece of used barrier material from a different location. This new series of tests included exposing more of the material surface to the flow of high temperature steam through the change in the reactor design, subjecting it to alternating periods of stream and vacuum, as well as determining if a lower temperature steam, i.e., 121°C (250°F) would be effective, too. Along with these methods, one other simpler method involving the leaching of the Tc-99 contaminated barrier material with a 1.0 M aqueous solution of ammonium carbonate, with and without sonication, was evaluated.« less

Multilinear analysis of Time-Resolved Laser-Induced Fluorescence Spectra of U(VI) containing natural water samples

NASA Astrophysics Data System (ADS)

Višňák, Jakub; Steudtner, Robin; Kassahun, Andrea; Hoth, Nils

2017-09-01

Natural waters' uranium level monitoring is of great importance for health and environmental protection. One possible detection method is the Time-Resolved Laser-Induced Fluorescence Spectroscopy (TRLFS), which offers the possibility to distinguish different uranium species. The analytical identification of aqueous uranium species in natural water samples is of distinct importance since individual species differ significantly in sorption properties and mobility in the environment. Samples originate from former uranium mine sites and have been provided by Wismut GmbH, Germany. They have been characterized by total elemental concentrations and TRLFS spectra. Uranium in the samples is supposed to be in form of uranyl(VI) complexes mostly with carbonate (CO32- ) and bicarbonate (HCO3- ) and to lesser extend with sulphate (SO42- ), arsenate (AsO43- ), hydroxo (OH- ), nitrate (NO3- ) and other ligands. Presence of alkaline earth metal dications (M = Ca2+ , Mg2+ , Sr2+ ) will cause most of uranyl to prefer ternary complex species, e.g. Mn(UO2)(CO3)32n-4 (n ɛ {1; 2}). From species quenching the luminescence, Cl- and Fe2+ should be mentioned. Measurement has been done under cryogenic conditions to increase the luminescence signal. Data analysis has been based on Singular Value Decomposition and monoexponential fit of corresponding loadings (for separate TRLFS spectra, the "Factor analysis of Time Series" (FATS) method) and Parallel Factor Analysis (PARAFAC, all data analysed simultaneously). From individual component spectra, excitation energies T00, uranyl symmetric mode vibrational frequencies ωgs and excitation driven U-Oyl bond elongation ΔR have been determined and compared with quasirelativistic (TD)DFT/B3LYP theoretical predictions to cross -check experimental data interpretation. Note to the reader: Several errors have been produced in the initial version of this article. This new version published on 23 October 2017 contains all the corrections.

Data Validation Package May 2015, Groundwater Sampling at the Shoal, Nevada, Site

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

Findlay, Rick; Kautsky, Mark

The U.S. Department of Energy Office of Legacy Management conducted annual sampling at the Shoal, Nevada, Site (Shoal) in May 2015. Groundwater samples were collected from wells MV-1, MV-2, MV-3, MV-4, MV-5, H-3, HC-1, HC-2d, HC-3, HC-4, HC-5, HC-6, HC-7, HC-8, and HS-1. Sampling was conducted as specified in the Sampling and Analysis Plan for US. Department of Energy Office of Legacy Management Sites (LMS/PRO/S04351, continually updated, http://energy.gov/lm/downloads/sampling-and-analysis-plan-us-department-energy­ office-legacy-management-sites). Monitoring wells MV-1, MV-2, MV-3, MV-4, MV-5, HC-2d, HC-4, HC-5, HC-7, HC-8, and HS-1 were purged prior to sampling using dedicated submersible pumps. At least one well casing volume was removed,more » and field parameters (temperature, pH, and specific conductance) were allowed to stabilize before samples were collected. Samples were collected from wells H-3, HC-1, HC-3, and HC-6 using a depth-specific bailer because these wells are not completed with dedicated submersible pumps. Samples were submitted under Requisition Index Number (RIN) 15057042 to ALS Laboratory Group in Fort Collins, Colorado, for the determination of bromide, gross alpha, gross beta, tritium, uranium isotopes, and total uranium (by mass); and under RIN 15057043 to the University of Arizona for the determination of carbon-14 and iodine-129. A duplicate sample from location MV-2 was included with RIN 15057042. The laboratory results from the 2015 sampling event are consistent with those of previous years with the exception of sample results from well HC-4. This well continues to be the only well with tritium concentrations above the laboratory’s minimum detectable concentration which is attributed to the wells proximity to the nuclear detonation. The tritium concentration (731 picocuries per liter [pCi/L]) is consistent with past results and is below the U.S. Environmental Protection Agency's (EPA) maximum contaminant level (MCL) of 20,000 pCi/L. However, concentrations of gross alpha, uranium, and carbon-14 all increased in the sample from well HC-4 during this sampling event. Concentrations of gross alpha and uranium have been above the EPA MCLs in this well since 2012 and the highest concentrations of gross alpha (60.6 pCi/L) and uranium (110 micrograms per liter) were detected during this sampling event. Refer to the time-concentration plots included with this report. Also see the 2015 Groundwater Monitoring Report Project Shoal Area: Subsurface Corrective Action Unit 447 for additional information on the 2015 sampling results.« less

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

PubMed Central

Kubicki, James D; Halada, Gary P; Jha, Prashant; Phillips, Brian L

2009-01-01

Background Quantum mechanical calculations were performed on a variety of uranium species representing U(VI), U(V), U(IV), U-carbonates, U-phosphates, U-oxalates, U-catecholates, U-phosphodiesters, U-phosphorylated N-acetyl-glucosamine (NAG), and U-2-Keto-3-doxyoctanoate (KDO) with explicit solvation by H2O molecules. These models represent major U species in natural waters and complexes on bacterial surfaces. The model results are compared to observed EXAFS, IR, Raman and NMR spectra. Results Agreement between experiment and theory is acceptable in most cases, and the reasons for discrepancies are discussed. Calculated Gibbs free energies are used to constrain which configurations are most likely to be stable under circumneutral pH conditions. Reduction of U(VI) to U(IV) is examined for the U-carbonate and U-catechol complexes. Conclusion Results on the potential energy differences between U(V)- and U(IV)-carbonate complexes suggest that the cause of slower disproportionation in this system is electrostatic repulsion between UO2 [CO3]35- ions that must approach one another to form U(VI) and U(IV) rather than a change in thermodynamic stability. Calculations on U-catechol species are consistent with the observation that UO22+ can oxidize catechol and form quinone-like species. In addition, outer-sphere complexation is predicted to be the most stable for U-catechol interactions based on calculated energies and comparison to 13C NMR spectra. Outer-sphere complexes (i.e., ion pairs bridged by water molecules) are predicted to be comparable in Gibbs free energy to inner-sphere complexes for a model carboxylic acid. Complexation of uranyl to phosphorus-containing groups in extracellular polymeric substances is predicted to favor phosphonate groups, such as that found in phosphorylated NAG, rather than phosphodiesters, such as those in nucleic acids. PMID:19689800

Permanent human occupation of the central Tibetan Plateau in the early Holocene.

PubMed

Meyer, M C; Aldenderfer, M S; Wang, Z; Hoffmann, D L; Dahl, J A; Degering, D; Haas, W R; Schlütz, F

2017-01-06

Current models of the peopling of the higher-elevation zones of the Tibetan Plateau postulate that permanent occupation could only have been facilitated by an agricultural lifeway at ~3.6 thousand calibrated carbon-14 years before present. Here we report a reanalysis of the chronology of the Chusang site, located on the central Tibetan Plateau at an elevation of ~4270 meters above sea level. The minimum age of the site is fixed at ~7.4 thousand years (thorium-230/uranium dating), with a maximum age between ~8.20 and 12.67 thousand calibrated carbon-14 years before present (carbon-14 assays). Travel cost modeling and archaeological data suggest that the site was part of an annual, permanent, preagricultural occupation of the central plateau. These findings challenge current models of the occupation of the Tibetan Plateau. Copyright © 2017, American Association for the Advancement of Science.

Radionuclides as natural tracers of the interaction between groundwater and surface water in the River Andarax, Spain.

PubMed

Navarro-Martinez, Francisco; Salas Garcia, Alejandro; Sánchez-Martos, Francisco; Baeza Espasa, Antonio; Molina Sánchez, Luis; Rodríguez Perulero, Antonio

2017-12-01

The identification of specific aquifers that supply water to river systems is fundamental to understanding the dynamics of the rivers' hydrochemistry, particularly in arid and semiarid environments where river flow may be discontinuous. There are multiple methods to identify the source of river water. In this study of the River Andarax, in the Southeast of Spain, an analysis of natural tracers (physico-chemical parameters, uranium, radium and radon) in surface water and groundwater indicates that chemical parameters and uranium clearly identify the areas where there is groundwater-surface water interaction. The concentration of uranium found in the river defines two areas: the headwaters with U concentrations of 2 μg L -1 and the lower reaches, with U of 6 μg L -1 . Furthermore, variation in the 234 U/ 238 U isotopic ratio allowed us to detect the influence that groundwater from the carbonate aquifer has on surface water in the headwaters of the river, where the saline content is lower and the water has a calcium bicarbonate facies. The concentration of 226 Ra and 222 Rn are low in the surface waters: <1.6 × 10 -6  μg L -1 and <5.1 × 10 -12  μg L -1 , respectively. There is a slight increase in the lower reaches where the water has a permanent flow, greater salinity and a calcium-magnesium-sulphate facies. All this is favoured by the influence of groundwater from the detritic aquifer on the surface waters. The results of this study indicate the utility in the use of physico-chemical and radiological data conjointly as tracers of groundwater-surface water interaction in semiarid areas where the lithology of aquifers is diverse (carbonate and detritic) and where evaporitic rocks are present. Copyright © 2017 Elsevier Ltd. All rights reserved.

Ab-initio study of C and O impurities in uranium nitride

NASA Astrophysics Data System (ADS)

Lopes, Denise Adorno; Claisse, Antoine; Olsson, Pär

2016-09-01

Uranium nitride (UN) has been considered a potential fuel for Generation IV (GEN-IV) nuclear reactors as well as a possible new fuel for Light Water Reactors (LWR), which would permit an extension of the fuel residence time in the reactor. Carbon and oxygen impurities play a key role in the UN microstructure, influencing important parameters such as creep, swelling, gas release under irradiation, compatibility with structural steel and coolants, and thermal stability. In this work, a systematic study of the electronic structure of UN containing C and O impurities using first-principles calculations by the Density Functional Theory (DFT) method is presented. In order to describe accurately the localized U 5f electrons, the DFT + U formalism was adopted. Moreover, to avoid convergence toward metastable states, the Occupation Matrix Control (OMC) methodology was applied. The incorporation of C and O in the N-vacancy is found to be energetically favorable. In addition, only for O, the incorporation in the interstitial position is energetically possible, showing some degree of solubility for this element in this site. The binding energies show that the pairs (Csbnd Nvac) and (Osbnd Nvac) interact much further than the other defects, which indicate the possible occurrence of vacancy drag phenomena and clustering of these impurities in grain boundaries, dislocations and free surfaces. The migration energy of an impurity by single N-vacancy show that C and O employ different paths during diffusion. Oxygen migration requires significantly lower energy than carbon. This fact is due to flexibility in the Usbnd O chemical bonds, which bend during the diffusion forming a pseudo UO2 coordination. On the other hand, C and N have a directional and inflexible chemical bond with uranium; always requiring the octahedral coordination. These findings provide detailed insight into how these impurities behave in the UN matrix, and can be of great interest for assisting the development of this new nuclear fuel for next-generation reactors.

Microbial carbon cycling in oligotrophic regional aquifers near the Tono Uranium Mine, Japan as inferred from δ13C and Δ14C values of in situ phospholipid fatty acids and carbon sources

USGS Publications Warehouse

Mills, Christopher T.; Amano, Yuki; Slater, Gregory F.; Dias, Robert F.; Iwatsuki, Teruki; Mandernack, Kevin W.

2010-01-01

Microorganisms are ubiquitous in deep subsurface environments, but their role in the global carbon cycle is not well-understood. The natural abundance δ13C and Δ14C values of microbial membrane phospholipid fatty acids (PLFAs) were measured and used to assess the carbon sources of bacteria in sedimentary and granitic groundwaters sampled from three boreholes in the vicinity of the Tono Uranium Mine, Gifu, Japan. Sample storage experiments were performed and drill waters analyzed to characterize potential sources of microbial contamination. The most abundant PLFA structures in all waters sampled were 16:0, 16:1ω7c, cy17:0, and 18:1ω7c. A PLFA biomarker for type II methanotrophs, 18:1ω8c, comprised 3% and 18% of total PLFAs in anoxic sedimentary and granitic waters, respectively, sampled from the KNA-6 borehole. The presence of this biomarker was unexpected given that type II methanotrophs are considered obligate aerobes. However, a bacterium that grows aerobically with CH4 as the sole energy source and which also produces 56% of its total PLFAs as 18:1ω8c was isolated from both waters, providing additional evidence for the presence of type II methanotrophs. The Δ14C values determined for type II methanotroph PLFAs in the sedimentary (−861‰) and granite (−867‰) waters were very similar to the Δ14C values of dissolved inorganic carbon (DIC) in each water (∼−850‰). This suggests that type II methanotrophs ultimately derive all their carbon from inorganic sources, whether directly from DIC and/or from CH4 produced by the reduction of DIC. In contrast, δ13C values of type II PLFAs in the sedimentary (−93‰) and granite (−60‰) waters indicate that these organisms use different carbon assimilation schemes in each environment despite very similar δ13CCH4">δ13CCH4 values (∼−95‰) for each water. The δ13CPLFA values (−28‰ to −45‰) of non-methanotrophic bacteria in the KNA-6 LTL water do not clearly distinguish between heterotrophic and autotrophic metabolisms, but Δ14CPLFAvalues indicate that >65% of total bacteria filtered from the KNA-6 LTL water are heterotrophs. Ancient Δ14C values (∼−1000‰) of some PLFAs suggest that many heterotrophs utilize ancient organic matter, perhaps from lignite seams within the sedimentary rocks. The more negative range of δ13CPLFA values determined for the KNA-6 granitic water (−42‰ to −66‰) are likely the result of a microbial ecosystem dominated by chemolithoautotrophy, perhaps fuelled by abiogenic H2. Results of sample storage experiments showed substantial shifts in microbial community composition and δ13CPLFAvalues (as much as 5‰) during 2–4 days of dark, refrigerated, aseptic storage. However, water samples collected and immediately filtered back in the lab from freshly drilled MSB-2 borehole appeared to maintain the same relative relationships between δ13CPLFA values for sedimentary and granitic host rocks as observed for samples directly filtered under artesian flow from the KNA-6 borehole of the Tono Uranium Mine.

Uranium occurrences in the Golden Gate Canyon and Ralston Creek areas, Jefferson County, Colorado

USGS Publications Warehouse

Adams, John Wagstaff; Gude, A.J.; Beroni, E.P.

1953-01-01

Pitchblende, associated with base-metal sulfides, has been found at nine localities in the northern part of Jefferson County, Colo., in shear zones that cut pre-Cambrian metamorphic and igneous rocks, chiefly hornblende gneiss, biotite schist, and granite pegmatite. The known deposits are in the vicinity of Halston Creek and Golden Gate Canyon, in the foothills of the Colorado Front Range and about 15 miles east of the pitchblende-producing area of the Central City district. Two of the pitchblende occurrences were found by a local prospector in 1949; the seven other deposits were found by Geological Survey. personnel in 1951-52. The pitchblende deposits, with one exception, are in major shear zones that contain veinlike bodies of carbonate-rich breccia that ranges from 1 to 5 feet in thickness. The breccias probably are related to the Laramide faults, or 'breccia reefs' of similar trend, mapped by Loverinq and Goddard (1950). The breccias are composed of fragments of bleached and iron-stained wall rock, usually hornblende gneiss, that have been cut by veins and cemented by carbonate minerals, quartz, and orthoclase(?). Pitchblende and associated ore minerals, chiefly copper sulfides, occur in and along the margins of the breccias and apparently were introduced at a late stage of the carbonate deposition. At one deposit, the Buckman, the pitchblende is in narrow shear zones not closely related to any large breccia bodies. Secondary uranium minerals are subordinate except at the Schwartzwalder mine, where torbernite and metatorbernite are common. Some alteration of pitchblende to non-opaque materials, believed to be hydrated oxides, has been noted in ore from two of the deposits.

Distribution of uranium and thorium in dolomitic gravel fill and shale saprolite

DOE PAGES

Phillips, D. H.; Watson, D. B.

2014-12-05

The objectives of this study were to examine (1) the distribution of U and Th in dolomitic gravel fill and shale saprolite, and (2) the removal of uranium from acidic groundwater by dolomitic gravel through precipitation with amorphous basaluminite at the U.S. DOE Oak Ridge Integrated Field Research Challenge (ORIFRC) field site west of the Oak Ridge Y-12 National Security Complex in East Tennessee. Media reactivity and sustainability are a technical concern with the deployment of any subsurface reactive media. Because the gravel was placed in the subsurface and exposed to contaminated groundwater for over 20 years, it provided amore » unique opportunity to study the solid and water phase geochemical conditions within the media after this length of exposure. This study illustrates that dolomite gravel can remove U from acidic contaminated groundwater with high levels of Al 3+, Ca 2+, NO 3-, and SO 4 2- over the long term. As the groundwater flows through high pH carbonate gravel, U containing amorphous basaluminite precipitates as the pH increases. This is due to an increase in groundwater pH from 3.2 to ~6.5 as it comes in contact with the gravel. Therefore, carbonate gravel could be considered as a possible treatment medium for removal and sequestration ofUand otherpHsensitive metals from acidic contaminated groundwater. Thorium concentrations are also high in the carbonate gravel. Thorium generally shows an inverse relationship with U from the surface down into the deeper saprolite. Barite precipitated in the shallow saprolite directly below the dolomitic gravel from barium present in the acidic contaminated groundwater.« less

Geochemical Characterization of the Upper and Middle Floridan Aquifer System, South Florida

NASA Astrophysics Data System (ADS)

Mirecki, J.; Richardson, E.; Bennett, M.; Hendel, J.

2008-05-01

Our study focus is to characterize the water quality and geochemical environment of the Floridan Aquifer System (FAS) throughout the regional flowpath. A synoptic survey of 21 wells (n=15, upper FAS; n=6 middle FAS) was supplemented by additional samples (n=11) obtained during exploratory well development at 4 aquifer storage recovery (ASR) pilot sites. Synoptic survey samples were analyzed intensively, yielding a dataset that consists of major and trace dissolved constituents (including metals), stable isotopes (δ18O, δ13C, δD, δ34S in sulfate and sulfide), carbon species (carbonate alkalinity and organic carbon), uranium-series radionuclides, nutrients, and selected microbes and pathogens. The objectives of this study are three-fold: 1) to provide baseline water-quality and geochemical information prior to initiation of ASR activities that are part of the Comprehensive Everglades Restoration Plan; 2) to quantify the major controls on geochemical evolution along upper and middle FAS flowpaths using geochemical modeling methods; and 3) to identify areas where water- quality may limit the feasibility of ASR methods in the FAS. Preliminary interpretations water quality changes along the regional FAS flowpath can be summarized as follows. Concentrations of dissolved constituents increase from north to south along the flow path; generally, the upper FAS has lower total dissolved solids than the middle FAS at locations where well pairs were analyzed. The redox environment changes from oxic to strongly anoxic, very close to the recharge area. Redox measurements, dissolved iron, sulfide, and sulfur isotope data are consistent with sulfate-reducing conditions. Uranium-series isotope concentrations and activities generally are below regulatory criteria, with few exceptions in both the upper and middle FAS. Areas with greater radionuclide activity occur primarily at distal flowpath locations or at the coast.

CHEMICAL DIFFERENCES BETWEEN SLUDGE SOLIDS AT THE F AND H AREA TANK FARMS

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

Reboul, S.

2012-08-29

The primary source of waste solids received into the F Area Tank Farm (FTF) was from PUREX processing performed to recover uranium and plutonium from irradiated depleted uranium targets. In contrast, two primary sources of waste solids were received into the H Area Tank Farm (HTF): a) waste from PUREX processing; and b) waste from H-modified (HM) processing performed to recover uranium and neptunium from burned enriched uranium fuel. Due to the differences between the irradiated depleted uranium targets and the burned enriched uranium fuel, the average compositions of the F and H Area wastes are markedly different from onemore » another. Both F and H Area wastes contain significant amounts of iron and aluminum compounds. However, because the iron content of PUREX waste is higher than that of HM waste, and the aluminum content of PUREX waste is lower than that of HM waste, the iron to aluminum ratios of typical FTF waste solids are appreciably higher than those of typical HTF waste solids. Other constituents present at significantly higher concentrations in the typical FTF waste solids include uranium, nickel, ruthenium, zinc, silver, cobalt and copper. In contrast, constituents present at significantly higher concentrations in the typical HTF waste solids include mercury, thorium, oxalate, and radionuclides U-233, U-234, U-235, U-236, Pu-238, Pu-242, Cm-244, and Cm-245. Because of the higher concentrations of Pu-238 in HTF, the long-term concentrations of Th-230 and Ra-226 (from Pu-238 decay) will also be higher in HTF. The uranium and plutonium distributions of the average FTF waste were found to be consistent with depleted uranium and weapons grade plutonium, respectively (U-235 comprised 0.3 wt% of the FTF uranium, and Pu-240 comprised 6 wt% of the FTF plutonium). In contrast, at HTF, U-235 comprised 5 wt% of the uranium, and Pu-240 comprised 17 wt% of the plutonium, consistent with enriched uranium and high burn-up plutonium. X-ray diffraction analyses of various FTF and HTF samples indicated that the primary crystalline compounds of iron in sludge solids are Fe{sub 2}O{sub 3}, Fe{sub 3}O{sub 4}, and FeO(OH), and the primary crystalline compounds of aluminum are Al(OH){sub 3} and AlO(OH). Also identified were carbonate compounds of calcium, magnesium, and sodium; a nitrated sodium aluminosilicate; and various uranium compounds. Consistent with expectations, oxalate compounds were identified in solids associated with oxalic acid cleaning operations. The most likely oxidation states and chemical forms of technetium are assessed in the context of solubility, since technetium-99 is a key risk driver from an environmental fate and transport perspective. The primary oxidation state of technetium in SRS sludge solids is expected to be Tc(IV). In salt waste, the primary oxidation state is expected to be Tc(VII). The primary form of technetium in sludge is expected to be a hydrated technetium dioxide, TcO{sub 2} {center_dot} xH{sub 2}O, which is relatively insoluble and likely co-precipitated with iron. In salt waste solutions, the primary form of technetium is expected to be the very soluble pertechnetate anion, TcO{sub 4}{sup -}. The relative differences between the F and H Tank Farm waste provide a basis for anticipating differences that will occur as constituents of FTF and HTF waste residue enter the environment over the long-term future. If a constituent is significantly more dominant in one of the Tank Farms, its long-term environmental contribution will likely be commensurately higher, assuming the environmental transport conditions of the two Tank Farms share some commonality. It is in this vein that the information cited in this document is provided - for use during the generation, assessment, and validation of Performance Assessment modeling results.« less

Characterization of uranium carbide target materials to produce neutron-rich radioactive beams

NASA Astrophysics Data System (ADS)

Tusseau-Nenez, Sandrine; Roussière, Brigitte; Barré-Boscher, Nicole; Gottberg, Alexander; Corradetti, Stefano; Andrighetto, Alberto; Cheikh Mhamed, Maher; Essabaa, Saïd; Franberg-Delahaye, Hanna; Grinyer, Joanna; Joanny, Loïc; Lau, Christophe; Le Lannic, Joseph; Raynaud, Marc; Saïd, Abdelhakim; Stora, Thierry; Tougait, Olivier

2016-03-01

In the framework of a R&D program aiming to develop uranium carbide (UCx) targets for radioactive nuclear beams, the Institut de Physique Nucléaire d'Orsay (IPNO) has developed an experimental setup to characterize the release of various fission fragments from UCx samples at high temperature. The results obtained in a previous study have demonstrated the feasibility of the method and started to correlate the structural properties of the samples and their behavior in terms of nuclear reaction product release. In the present study, seven UCx samples have been systematically characterized in order to better understand the correlation between their physicochemical characteristics and release properties. Two very different samples, the first one composed of dense UC and the second one of highly porous UCx made of multi-wall carbon nanotubes, were provided by the ActILab (ENSAR) collaboration. The others were synthesized at IPNO. The systems for irradiation and heating necessary for the release studies have been improved with respect to those used in previous studies. The results show that the open porosity is hardly the limiting factor for the fission product release. The homogeneity of the microstructure and the pore size distribution contributes significantly to the increase of the release. The use of carbon nanotubes in place of traditional micrometric graphite particles appears to be promising, even if the homogeneity of the microstructure can still be enhanced.

Uranium(VI) adsorption to ferrihydrite: Application of a surface complexation model

USGS Publications Warehouse

Waite, T.D.; Davis, J.A.; Payne, T.E.; Waychunas, G.A.; Xu, N.

1994-01-01

A study of U(VI) adsorption by ferrihydrite was conducted over a wide range of U(VI) concentrations, pH, and at two partial pressures of carbon dioxide. A two-site (strong- and weak-affinity sites, FesOH and FewOH, respectively) surface complexation model was able to describe the experimental data well over a wide range of conditions, with only one species formed with each site type: an inner-sphere, mononuclear, bidentate complex of the type (FeO2)UO2. The existence of such a surface species was supported by results of uranium EXAFS spectroscopy performed on two samples with U(VI) adsorption density in the upper range observed in this study (10 and 18% occupancy of total surface sites). Adsorption data in the alkaline pH range suggested the existence of a second surface species, modeled as a ternary surface complex with UO2CO30 binding to a bidentate surface site. Previous surface complexation models for U(VI) adsorption have proposed surface species that are identical to the predominant aqueous species, e.g., multinuclear hydrolysis complexes or several U(VI)-carbonate complexes. The results demonstrate that the speciation of adsorbed U(VI) may be constrained by the coordination environment at the surface, giving rise to surface speciation for U(VI) that is significantly less complex than aqueous speciation.

Uncertainty and variability in laboratory derived sorption parameters of sediments from a uranium in situ recovery site

NASA Astrophysics Data System (ADS)

Dangelmayr, Martin A.; Reimus, Paul W.; Johnson, Raymond H.; Clay, James T.; Stone, James J.

2018-06-01

This research assesses the ability of a GC SCM to simulate uranium transport under variable geochemical conditions typically encountered at uranium in-situ recovery (ISR) sites. Sediment was taken from a monitoring well at the SRH site at depths 192 and 193 m below ground and characterized by XRD, XRF, TOC, and BET. Duplicate column studies on the different sediment depths, were flushed with synthesized restoration waters at two different alkalinities (160 mg/l CaCO3 and 360 mg/l CaCO3) to study the effect of alkalinity on uranium mobility. Uranium breakthrough occurred 25% - 30% earlier in columns with 360 mg/l CaCO3 over columns fed with 160 mg/l CaCO3 influent water. A parameter estimation program (PEST) was coupled to PHREEQC to derive site densities from experimental data. Significant parameter fittings were produced for all models, demonstrating that the GC SCM approach can model the impact of carbonate on uranium in flow systems. Derived site densities for the two sediment depths were between 141 and 178 μmol-sites/kg-soil, demonstrating similar sorption capacities despite heterogeneity in sediment mineralogy. Model sensitivity to alkalinity and pH was shown to be moderate compared to fitted site densities, when calcite saturation was allowed to equilibrate. Calcite kinetics emerged as a potential source of error when fitting parameters in flow conditions. Fitted results were compared to data from previous batch and column studies completed on sediments from the Smith-Ranch Highland (SRH) site, to assess variability in derived parameters. Parameters from batch experiments were lower by a factor of 1.1 to 3.4 compared to column studies completed on the same sediments. The difference was attributed to errors in solid-solution ratios and the impact of calcite dissolution in batch experiments. Column studies conducted at two different laboratories showed almost an order of magnitude difference in fitted site densities suggesting that experimental methodology may play a bigger role in column sorption behavior than actual sediment heterogeneity. Our results demonstrate the necessity for ISR sites to remove residual pCO2 and equilibrate restoration water with background geochemistry to reduce uranium mobility. In addition, the observed variability between fitted parameters on the same sediments highlights the need to provide standardized guidelines and methodology for regulators and industry when the GC SCM approach is used for ISR risk assessments.

Uncertainty and variability in laboratory derived sorption parameters of sediments from a uranium in situ recovery site.

PubMed

Dangelmayr, Martin A; Reimus, Paul W; Johnson, Raymond H; Clay, James T; Stone, James J

2018-06-01

This research assesses the ability of a GC SCM to simulate uranium transport under variable geochemical conditions typically encountered at uranium in-situ recovery (ISR) sites. Sediment was taken from a monitoring well at the SRH site at depths 192 and 193 m below ground and characterized by XRD, XRF, TOC, and BET. Duplicate column studies on the different sediment depths, were flushed with synthesized restoration waters at two different alkalinities (160 mg/l CaCO 3 and 360 mg/l CaCO 3 ) to study the effect of alkalinity on uranium mobility. Uranium breakthrough occurred 25% - 30% earlier in columns with 360 mg/l CaCO 3 over columns fed with 160 mg/l CaCO 3 influent water. A parameter estimation program (PEST) was coupled to PHREEQC to derive site densities from experimental data. Significant parameter fittings were produced for all models, demonstrating that the GC SCM approach can model the impact of carbonate on uranium in flow systems. Derived site densities for the two sediment depths were between 141 and 178 μmol-sites/kg-soil, demonstrating similar sorption capacities despite heterogeneity in sediment mineralogy. Model sensitivity to alkalinity and pH was shown to be moderate compared to fitted site densities, when calcite saturation was allowed to equilibrate. Calcite kinetics emerged as a potential source of error when fitting parameters in flow conditions. Fitted results were compared to data from previous batch and column studies completed on sediments from the Smith-Ranch Highland (SRH) site, to assess variability in derived parameters. Parameters from batch experiments were lower by a factor of 1.1 to 3.4 compared to column studies completed on the same sediments. The difference was attributed to errors in solid-solution ratios and the impact of calcite dissolution in batch experiments. Column studies conducted at two different laboratories showed almost an order of magnitude difference in fitted site densities suggesting that experimental methodology may play a bigger role in column sorption behavior than actual sediment heterogeneity. Our results demonstrate the necessity for ISR sites to remove residual pCO2 and equilibrate restoration water with background geochemistry to reduce uranium mobility. In addition, the observed variability between fitted parameters on the same sediments highlights the need to provide standardized guidelines and methodology for regulators and industry when the GC SCM approach is used for ISR risk assessments. Copyright © 2018 Elsevier B.V. All rights reserved.

Ground-water quality and geochemistry, Carson Desert, western Nevada

USGS Publications Warehouse

Lico, Michael S.; Seiler, R.L.

1994-01-01

Aquifers in the Carson Desert are the primary source of drinking water, which is highly variable in chemical composition. In the shallow basin-fill aquifers, water chemistyr varies from a dilute calcium bicarbonate-dominated water beneath the irrigated areas to a saline sodium chloride- dominated water beneath unirrigated areas. Water samples from the shallow aquifers commonly have dissolved solids, chloride, magnesium, sulfate, arsenic, and manganese concentrations that exceed State of Nevada drinking-water standards. Water in the intermediante basin-fill aquifers is a dilute sodium bicarbonate type in the Fallon area and a distinctly more saline sodium chloride type in the Soda Lake-Upsal Hogback area. Dissolved solids, chloride, arsenic, fluoride, and manganese concen- trations commonly exceed drinking-water standards. The basalt aquifer contains a dilute sodium bicarbonate chloride water. Arsenic concentrations exceed standards in all sampled wells. The concen- trations of major constituents in ground water beneath the southern Carson Desert are the result of evapotranspiration and natural geochemical reactions with minerals derived mostly from igneous rocks. Water with higher concentrations of iron and manganese is near thermodynamic equilibrium with siderite and rhodochrosite and indicates that these elements may be limited by the solubility of their respective carbonate minerals. Naturally occurring radionuclides (uranium and radon-222) are present in ground water from the Carson Desert in concen- tratons higher than proposed drinking-water standards. High uranium concentrations in the shallow aquifers may be caused by evaporative concentration and the release of uranium during dissolution of iron and manganese oxides or the oxidation of sedimentary organic matter that typically has elevated uranium concentrations. Ground water in the Carson Desert does not appear to have be contaminated by synthetic organic chemicals.

Evaluation of alternatives for best available technology treatment and retreatment of uranium-contaminated wastewater at the Paducah Gaseous Diffusion Plant C-400 Facility

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

Del Cul, G.D.; Osborne, P.E.; Beck, D.E.

1991-01-01

The Paducah Gaseous Diffusion Plant (PGDP) C-400 Decontamination Facility generates aqueous solutions that originate in drum washing, machine parts and equipment cleaning, and other decontamination processes. The chemical composition of the waste depends on the particular operation involved. In general, the waste contains uranyl, fluoride, carbonate, and nitrate ions, plus soaps, detergents, secondary contaminants, and particulate matter. The uranium content is rather variable ranging between 0.5 and 30 g/l. The main contaminants are fluoride, technetium, uranium, and other heavy metals. The plan included (1) a literature search to support best available technology (BAT) evaluation of treatment alternatives, (2) a qualitymore » assurance/quality control plan, (3) suggestion of alternative treatment options, (4) bench-scale tests studies of the proposed treatment alternatives, and (5) establishment of the final recommendation. The following report records the evaluation of items (1) to (3) of the action plan for the BAT evaluation of alternatives for the treatment and retreatment of uranium-contaminated wastewater at the PGDP C-400 treatment facility. After a thorough literature search, five major technologies were considered: (1) precipitation/coprecipitation, (2) reverse osmosis, (3) ultrafiltration, (4) supported liquid membranes, and (5) ion exchange. Biosorption was also considered, but as it is a fairly new technology with few demonstrations of its capabilities, it is mentioned only briefly in the report. Based on C-400's requirements and facilities, the precipitation/coprecipitation process appears to be the best suited for use at the plant. Four different treatment options using the precipitation/coprecipitation technology are proposed. Bench-scale studies of the four options are suggested. 37 refs.« 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

Soft-Templating Synthesis of Mesoporous Silica-Based Materials for Environmental Applications

NASA Astrophysics Data System (ADS)

Gunathilake, Chamila Asanka

Dissertation research is mainly focus on: 1) the development of mesoporous silica materials with organic pendant and bridging groups (isocyanurate, amidoxime, benzene) and incorporated metal (aluminum, zirconium, calcium, and magnesium) species for high temperature carbon dioxide (CO2) sorption, 2) phosphorous-hydroxy functionalized mesoporous silica materials for water treatment, and 3) amidoxime-modified ordered mesoporous silica materials for uranium sorption under seawater conditions. The goal is to design composite materials for environmental applications with desired porosity, surface area, and functionality by selecting proper metal oxide precursors, organosilanes, tetraethylorthosilicate, (TEOS), and block copolymer templates and by adjusting synthesis conditions. The first part of dissertation presents experimental studies on the merge of aluminum, zirconium, calcium, and magnesium oxides with mesoporous silica materials containing organic pendant (amidoxime) and bridging groups (isocyanurate, benzene) to obtain composite sorbents for CO2 sorption at ambient (0-25 °C) and elevated (60-120 °C) temperatures. These studies indicate that the aforementioned composite sorbents are fairly good for CO2 capture at 25 °C via physisorption mechanism and show a remarkably high affinity toward CO2 chemisorption at 60-120 °C. The second part of dissertation is devoted to silica-based materials with organic functionalities for removal of heavy metal ions such as lead from contaminated water and for recovery of metal ions such as uranium from seawater. First, ordered mesoporous organosilica (OMO) materials with diethylphosphatoethyl and hydroxyphosphatoethyl surface groups were examined for Pb2+ adsorption and showed unprecedented adsorption capacities up to 272 mg/g and 202 mg/g, respectively However, the amidoxime-modified OMO materials were explored for uranium extraction under seawater conditions and showed remarkable capacities reaching 57 mg of uranium per gram of adsorbent.

Evaluation of Sustainability of the Carbon and Silicon Ecosystem: From Nanoparticles to Macroworld

NASA Astrophysics Data System (ADS)

Dolin, V.

Rapid development of nanotechnologies has led to a complicated problem of utilization, storage and treatment of waste nanodevices of silicon and carbon origin. The processes of physico-chemical and biogeochemical destruction of carbon—silicon—uranium nanoparticles of Chernobyl origin has been studied. The period of half-destruction assessed by leaching of different radionuclide from particles is between 5 and 25 years. Natural ecosystems are generally of carbon and silicon origin. The behavior of radionuclide in natural media is observed over a period of 20 years. For the balance calculations we have utilized the Geochemical Transition Factor (GTF) that represents the quantity of substance, which is accumulated by living matter from the area unit. The main part of total carbon is involved in biogeochemical cycles in the forest ecosystem. Anthropogenic activity leads to a considerable imbalance of carbon isotopes. The distribution of carbon isotopes between different biotic levels demonstrates that radiocarbon of artificial emission is substantially less bio-available than those from natural sources. The environmental ability to recovery, lies in decontamination of carbon trophic circuits, is an order of magnitude greater than the rate of natural attenuation and corresponds to the removal of artificial matter from natural silicon media. The modern sustainability of the silicon and carbon ecosystem is determined by an insignificant quantity of artificial matter involved in biogeochemical cycles.

Growth of High Purity Oxygen-Free Silicon by Cold Crucible Techniques.

DTIC Science & Technology

1982-06-01

Liquid Metals (A Review). High Temp.-High Pressures 2(6), 583-586, 1970. 1971 Knights, C.F. and Perkins, R. Levitation Melting of Uranium Mono- Carbide . J...content - typically I PPM or less. c) The crystals grown exhibited a high level of carbon contamination (2-30 PPM ) which we believe, is caused by the...grown from melts confined in the cold crucible exhibit an unusually low oxygen content - typically 1 PPM or less. c.) The crystals grown exhibited a

Incremental Sampling Methodology (ISM). Part 1, Section 2: Principles

DTIC Science & Technology

2012-03-01

Many contaminants adhere to the surfaces of certain minerals  Organic carbon is composed of complex molecules that can act as molecular sponges...hydroxide particles “the iron in a cubic yard of soil [1-1.5 tons] is capable of adsorbing 0.5 to 5 lbs of soluble metals …or organics” (Vance...determine decision outcome!  ISM addresses the problems of both micro- and short-scale heterogeneity Set of co-located samples for uranium (mg/kg) As

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

Electrically Heated Testing of the Kilowatt Reactor Using Stirling Technology (KRUSTY) Experiment Using a Depleted Uranium Core

NASA Technical Reports Server (NTRS)

Briggs, Maxwell H.; Gibson, Marc A.; Sanzi, James

2017-01-01

The Kilopower project aims to develop and demonstrate scalable fission-based power technology for systems capable of delivering 110 kW of electric power with a specific power ranging from 2.5 - 6.5 Wkg. This technology could enable high power science missions or could be used to provide surface power for manned missions to the Moon or Mars. NASA has partnered with the Department of Energys National Nuclear Security Administration, Los Alamos National Labs, and Y-12 National Security Complex to develop and test a prototypic reactor and power system using existing facilities and infrastructure. This technology demonstration, referred to as the Kilowatt Reactor Using Stirling TechnologY (KRUSTY), will undergo nuclear ground testing in the summer of 2017 at the Nevada Test Site. The 1 kWe variation of the Kilopower system was chosen for the KRUSTY demonstration. The concept for the 1 kWe flight system consist of a 4 kWt highly enriched Uranium-Molybdenum reactor operating at 800 degrees Celsius coupled to sodium heat pipes. The heat pipes deliver heat to the hot ends of eight 125 W Stirling convertors producing a net electrical output of 1 kW. Waste heat is rejected using titanium-water heat pipes coupled to carbon composite radiator panels. The KRUSTY test, based on this design, uses a prototypic highly enriched uranium-molybdenum core coupled to prototypic sodium heat pipes. The heat pipes transfer heat to two Advanced Stirling Convertors (ASC-E2s) and six thermal simulators, which simulate the thermal draw of full scale power conversion units. Thermal simulators and Stirling engines are gas cooled. The most recent project milestone was the completion of non-nuclear system level testing using an electrically heated depleted uranium (non-fissioning) reactor core simulator. System level testing at the Glenn Research Center (GRC) has validated performance predictions and has demonstrated system level operation and control in a test configuration that replicates the one to be used at the Device Assembly Facility (DAF) at the Nevada National Security Site. Fabrication, assembly, and testing of the depleted uranium core has allowed for higher fidelity system level testing at GRC, and has validated the fabrication methods to be used on the highly enriched uranium core that will supply heat for the DAF KRUSTY demonstration.

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

Mid-depth respired carbon storage and oxygenation of the eastern equatorial Pacific over the last 25,000 years

NASA Astrophysics Data System (ADS)

Umling, Natalie E.; Thunell, Robert C.

2018-06-01

A growing body of evidence suggests that respired carbon was stored in mid-depth waters (∼1-3 km) during the last glacial maximum (LGM) and released to the atmosphere from upwelling regions during deglaciation. Decreased ventilation, enhanced productivity, and enhanced carbonate dissolution are among the mechanisms that have been cited as possible drivers of glacial CO2 drawdown. However, the relative importance of each of these mechanisms is poorly understood. New approaches to quantitatively constrain bottom water carbonate chemistry and oxygenation provide methods for estimating historic changes in respired carbon storage. While increased CO2 drawdown during the LGM should have resulted in decreased oxygenation and a shift in dissolved inorganic carbon (DIC) speciation towards lower carbonate ion concentrations, this is complicated by the interplay of carbonate compensation, export productivity, and circulation. To disentangle these processes, we use a multiproxy approach that includes boron to calcium (B/Ca) ratios of the benthic foraminifera Cibicidoides wuellerstorfi to reconstruct deep-water carbonate ion concentrations ([CO32-]) and the uranium to calcium (U/Ca) ratio of foraminiferal coatings in combination with benthic foraminiferal carbon isotopes to reconstruct changes in bottom water oxygen concentrations ([O2]) and organic carbon export. Our records indicate that LGM [CO32-] and [O2] was reduced at mid water depths of the eastern equatorial Pacific (EEP), consistent with increased respired carbon storage. Furthermore, our results suggest enhanced mixing of lower Circumpolar Deep Water (LCDW) to EEP mid water depths and provide evidence for the importance of circulation for oceanic-atmospheric CO2 exchange.

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.

In situ synthesis and characterization of uranium carbide using high temperature neutron diffraction

NASA Astrophysics Data System (ADS)

Reiche, H. Matthias; Vogel, Sven C.; Tang, Ming

2016-04-01

We investigated the formation of UCx from UO2+x and graphite in situ using neutron diffraction at high temperatures with particular focus on resolving the conflicting reports on the crystal structure of non-quenchable cubic UC2. The agents were UO2 nanopowder, which closely imitates nano grains observed in spent reactor fuels, and graphite powder. In situ neutron diffraction revealed the onset of the UO2 + 2C → UC + CO2 reaction at 1440 °C, with its completion at 1500 °C. Upon further heating, carbon diffuses into the uranium carbide forming C2 groups at the octahedral sites. This resulting high temperature cubic UC2 phase is similar to the NaCl-type structure as proposed by Bowman et al. Our novel experimental data provide insights into the mechanism and kinetics of formation of UC as well as characteristics of the high temperature cubic UC2 phase which agree with proposed rotational rehybridization found from simulations by Wen et al.

Uranium carbide dissolution in nitric solution: Sonication vs. silent conditions

NASA Astrophysics Data System (ADS)

Virot, Matthieu; Szenknect, Stéphanie; Chave, Tony; Dacheux, Nicolas; Moisy, Philippe; Nikitenko, Sergey I.

2013-10-01

The dissolution of uranium carbide (UC) in nitric acid media is considered by means of power ultrasound (sonication) or magnetic stirring. The induction period required to initiate UC dissolution was found to be dramatically shortened when sonicating a 3 M nitric solution (Ar, 20 kHz, 18 W cm-2, 20 °C). At higher acidity, magnetic stirring offers faster dissolution kinetics compared to sonication. Ultrasound-assisted UC dissolution is found to be passivated after ∼60% dissolution and remains incomplete whatever the acidity which is confirmed by ICP-AES, LECO and SEM-EDX analyses. In general, the kinetics of UC dissolution is linked to the in situ generation of nitrous acid in agreement with the general mechanism of UC dissolution; the nitrous acid formation is reported to be faster under ultrasound at low acidity due to the nitric acid sonolysis. The carbon balance shared between the gaseous, liquid, and solid phases is strongly influenced by the applied dissolution procedure and HNO3 concentration.

Ages and Origins of Calcite and Opal in the Exploratory Studies Facility Tunnel, Yucca Mountain, Nevada

USGS Publications Warehouse

Paces, James B.; Neymark, Leonid A.; Marshall, Brian D.; Whelan, Joseph F.; Peterman, Zell E.

2001-01-01

Deposits of calcite and opal are present as coatings on open fractures and lithophysal cavities in unsaturated-zone tuffs at Yucca Mountain, Nevada, site of a potential high-level radioactive waste repository. Outermost layers of calcite and opal have radiocarbon ages of 16,000 to 44,000 years before present and thorium-230/uranium ages of 28,000 to more than 500,000 years before present. These ages are young relative to the 13-million-year age of the host rocks. Multiple subsamples from the same outer layer typically show a range of ages with youngest ages from the thinnest subsamples. Initial uranium-234/uranium-238 activity ratios between 1 and 9.5 show a distinct negative correlation with thorium-230/uranium age and are greater than 4 for all but one sample younger than 100,000 years before present. These data, along with micrometer-scale layering and distinctive crystal morphologies, are interpreted to indicate that deposits formed very slowly from water films migrating through open cavities. Exchanges of carbon dioxide and water vapor probably took place between downward-migrating liquids and upward-migrating gases at low rates, resulting in oversaturation of mineral constituents at crystal extremities and more or less continuous deposition of very thin layers. Therefore, subsamples represent mixtures of older and younger layers on a scale finer than sampling techniques can resolve. Slow, long-term rates of deposition (less than about 5 millimeters of mineral per million years) are inferred from subsamples of outermost calcite and opal. These growth rates are similar to those calculated assuming that total coating thicknesses of 10 to 40 millimeters accumulated over 12 million years. Calcite has a wide range of delta carbon-13 values from about -8.2 to 8.5 per mil and delta oxygen-18 values from about 10 to 21 per mil. Systematic microsampling across individual mineral coatings indicates basal (older) calcite tends to have the largest delta carbon-13 values and smallest delta oxygen-18 values compared to calcite from intermediate and outer positions. Basal calcite has relatively small strontium-87/strontium-86 ratios, between 0.7105 and 0.7120, that are similar to the initial isotopic compositions of the strontium-rich tuff units, whereas outer calcite has more radiogenic strontium-87/strontium-86 ratios between 0.7115 and 0.7127. Isotopic compositions of strontium, oxygen, and carbon in the outer (youngest) unsaturated-zone calcite are coincident with those measured in Yucca Mountain calcrete, which formed by pedogenic processes. The physical and isotopic data from calcite and opal indicate that they formed from solutions of meteoric origin percolating through a limited network of connected fracture pathways in the unsaturated zone rather than by inundation from ascending ground water originating in the saturated zone. Mineral assemblages, textures, and distributions within the unsaturated zone are distinctly different from those deposited below the water table at Yucca Mountain. The calcite and opal typically are present only on footwall surfaces of a small fraction of fractures and only on floors of a small fraction of lithophysal cavities. The similarities in the carbon, oxygen, and strontium isotopic compositions between fracture calcite and soil-zone calcite, as well as the gradation of textures from detritus-rich micrite in the soil to detritus-free spar 10 to 30 meters below the surface, also support a genetic link between the two depositional environments. Older deposits contain oxygen isotope compositions that indicate elevated temperatures of mineral formation during the early stages of deposition; however, in the youngest deposits these values are consistent with deposition under geothermal gradients similar to modern conditions. Correlations between mineral ages and varying Pleistocene climate conditions are not apparent from the current data. Cumulative evidence from calcite and opal deposits indicate

31 CFR 540.317 - Uranium feed; natural uranium feed.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 31 Money and Finance:Treasury 3 2011-07-01 2011-07-01 false Uranium feed; natural uranium feed...) AGREEMENT ASSETS CONTROL REGULATIONS General Definitions § 540.317 Uranium feed; natural uranium feed. The term uranium feed or natural uranium feed means natural uranium in the form of UF6 suitable for uranium...

31 CFR 540.317 - Uranium feed; natural uranium feed.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 31 Money and Finance: Treasury 3 2010-07-01 2010-07-01 false Uranium feed; natural uranium feed...) AGREEMENT ASSETS CONTROL REGULATIONS General Definitions § 540.317 Uranium feed; natural uranium feed. The term uranium feed or natural uranium feed means natural uranium in the form of UF6 suitable for uranium...

Process for continuous production of metallic uranium and uranium alloys

DOEpatents

Hayden, H.W. Jr.; Horton, J.A.; Elliott, G.R.B.

1995-06-06

A method is described for forming metallic uranium, or a uranium alloy, from uranium oxide in a manner which substantially eliminates the formation of uranium-containing wastes. A source of uranium dioxide is first provided, for example, by reducing uranium trioxide (UO{sub 3}), or any other substantially stable uranium oxide, to form the uranium dioxide (UO{sub 2}). This uranium dioxide is then chlorinated to form uranium tetrachloride (UCl{sub 4}), and the uranium tetrachloride is then reduced to metallic uranium by reacting the uranium chloride with a metal which will form the chloride of the metal. This last step may be carried out in the presence of another metal capable of forming one or more alloys with metallic uranium to thereby lower the melting point of the reduced uranium product. The metal chloride formed during the uranium tetrachloride reduction step may then be reduced in an electrolysis cell to recover and recycle the metal back to the uranium tetrachloride reduction operation and the chlorine gas back to the uranium dioxide chlorination operation. 4 figs.

Process for continuous production of metallic uranium and uranium alloys

DOEpatents

Hayden, Jr., Howard W.; Horton, James A.; Elliott, Guy R. B.

1995-01-01

A method is described for forming metallic uranium, or a uranium alloy, from uranium oxide in a manner which substantially eliminates the formation of uranium-containing wastes. A source of uranium dioxide is first provided, for example, by reducing uranium trioxide (UO.sub.3), or any other substantially stable uranium oxide, to form the uranium dioxide (UO.sub.2). This uranium dioxide is then chlorinated to form uranium tetrachloride (UCl.sub.4), and the uranium tetrachloride is then reduced to metallic uranium by reacting the uranium chloride with a metal which will form the chloride of the metal. This last step may be carried out in the presence of another metal capable of forming one or more alloys with metallic uranium to thereby lower the melting point of the reduced uranium product. The metal chloride formed during the uranium tetrachloride reduction step may then be reduced in an electrolysis cell to recover and recycle the metal back to the uranium tetrachloride reduction operation and the chlorine gas back to the uranium dioxide chlorination operation.

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).

Single crystal structures and theoretical calculations of uranium endohedral metallofullerenes (U@C2n , 2n = 74, 82) show cage isomer dependent oxidation states for U.

PubMed

Cai, Wenting; Morales-Martínez, Roser; Zhang, Xingxing; Najera, Daniel; Romero, Elkin L; Metta-Magaña, Alejandro; Rodríguez-Fortea, Antonio; Fortier, Skye; Chen, Ning; Poblet, Josep M; Echegoyen, Luis

2017-08-01

Charge transfer is a general phenomenon observed for all endohedral mono-metallofullerenes. Since the detection of the first endohedral metallofullerene (EMF), La@C 82 , in 1991, it has always been observed that the oxidation state of a given encapsulated metal is always the same, regardless of the cage size. No crystallographic data exist for any early actinide endohedrals and little is known about the oxidation states for the few compounds that have been reported. Here we report the X-ray structures of three uranium metallofullerenes, U@ D 3h -C 74 , U@ C 2 (5)-C 82 and U@ C 2v (9)-C 82 , and provide theoretical evidence for cage isomer dependent charge transfer states for U. Results from DFT calculations show that U@ D 3h -C 74 and U@ C 2 (5)-C 82 have tetravalent electronic configurations corresponding to U 4+ @ D 3h -C 74 4- and U 4+ @ C 2 (5)-C 82 4- . Surprisingly, the isomeric U@ C 2v (9)-C 82 has a trivalent electronic configuration corresponding to U 3+ @ C 2v (9)-C 82 3- . These are the first X-ray crystallographic structures of uranium EMFs and this is first observation of metal oxidation state dependence on carbon cage isomerism for mono-EMFs.

Behavior of Colorado Plateau uranium minerals during oxidation

USGS Publications Warehouse

Garrels, Robert Minard; Christ, C.L.

1956-01-01

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

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).

Geochemical characterization of groundwater discharging from springs north of the Grand Canyon, Arizona, 2009–2016

USGS Publications Warehouse

Beisner, Kimberly R.; Tillman, Fred D.; Anderson, Jessica R.; Antweiler, Ronald C.; Bills, Donald J.

2017-08-01

A geochemical study was conducted on 37 springs discharging from the Toroweap Formation, Coconino Sandstone, Hermit Formation, Supai Group, and Redwall Limestone north of the Grand Canyon near areas of breccia-pipe uranium mining. Baseline concentrations were established for the elements As, B, Li, Se, SiO2, Sr, Tl, U, and V. Three springs exceeded U.S. Environmental Protection Agency drinking water standards: Fence Spring for arsenic, Pigeon Spring for selenium and uranium, and Willow (Hack) Spring for selenium. The majority of the spring sites had uranium values of less than 10 micrograms per liter (μg/L), but six springs discharging from all of the geologic units studied that are located stratigraphically above the Redwall Limestone had uranium values greater than 10 μg/L (Cottonwood [Tuckup], Grama, Pigeon, Rock, and Willow [Hack and Snake Gulch] Springs). The geochemical characteristics of these six springs with elevated uranium include Ca-Mg-SO4 water type, circumneutral pH, high specific conductance, correlation and multivariate associations between U, Mo, Sr, Se, Li, and Zn, low 87Sr/86Sr, low 234U/238U activity ratios (1.34–2.31), detectable tritium, and carbon isotopic interpretation indicating they may be a mixture of modern and pre-modern waters. Similar geochemical compositions of spring waters having elevated uranium concentrations are observed at sites located both near and away from sites of uranium-mining activities in the present study. Therefore, mining does not appear to explain the presence of elevated uranium concentrations in groundwater at the six springs noted above. The elevated uranium at the six previously mentioned springs may be influenced by iron mineralization associated with mineralized breccia pipe deposits. Six springs discharging from the Coconino Sandstone (Upper Jumpup, Little, Horse, and Slide Springs) and Redwall Limestone (Kanab and Side Canyon Springs) contained water with corrected radiocarbon ages as much as 9,300 years old. Of the springs discharging water with radiocarbon age, Kanab and Side Canyon Springs contain tritium of more than 1.3 picocuries per liter (pCi/L), indicating they may contain a component of modern water recharged after 1952. Springs containing high values of tritium (greater than 5.1 pCi/L), which may suggest a significant component of modern water, include Willow (Hack), Saddle Horse, Cottonwood (Tuckup), Hotel, Bitter, Unknown, Hole in the Wall, and Hanging Springs. Fence and Rider Springs, located on the eastern end of the study area near the Colorado River, have distinctly different geochemical compositions compared to the other springs of the study. Additionally, water from Fence Spring has the highest 87Sr/86Sr for samples analyzed from this study with a value greater than those known in sedimentary rocks from the region. Strontium isotope data likely indicate that water discharging at Fence Spring has interacted with Precambrian basement rocks. Rider Spring had the most depleted values of stable O and H isotopes indicating that recharge, if recent, occurred at higher elevations or was recharged during earlier, cooler-climate conditions.

Risk evaluation of uranium mining: A geochemical inverse modelling approach

NASA Astrophysics Data System (ADS)

Rillard, J.; Zuddas, P.; Scislewski, A.

2011-12-01

It is well known that uranium extraction operations can increase risks linked to radiation exposure. The toxicity of uranium and associated heavy metals is the main environmental concern regarding exploitation and processing of U-ore. In areas where U mining is planned, a careful assessment of toxic and radioactive element concentrations is recommended before the start of mining activities. A background evaluation of harmful elements is important in order to prevent and/or quantify future water contamination resulting from possible migration of toxic metals coming from ore and waste water interaction. Controlled leaching experiments were carried out to investigate processes of ore and waste (leached ore) degradation, using samples from the uranium exploitation site located in Caetité-Bahia, Brazil. In experiments in which the reaction of waste with water was tested, we found that the water had low pH and high levels of sulphates and aluminium. On the other hand, in experiments in which ore was tested, the water had a chemical composition comparable to natural water found in the region of Caetité. On the basis of our experiments, we suggest that waste resulting from sulphuric acid treatment can induce acidification and salinization of surface and ground water. For this reason proper storage of waste is imperative. As a tool to evaluate the risks, a geochemical inverse modelling approach was developed to estimate the water-mineral interaction involving the presence of toxic elements. We used a method earlier described by Scislewski and Zuddas 2010 (Geochim. Cosmochim. Acta 74, 6996-7007) in which the reactive surface area of mineral dissolution can be estimated. We found that the reactive surface area of rock parent minerals is not constant during time but varies according to several orders of magnitude in only two months of interaction. We propose that parent mineral heterogeneity and particularly, neogenic phase formation may explain the observed variation of the reactive mineral surface area. The formation of coatings on dissolving mineral surfaces significantly reduces the amount of surface available to react with fluids. Our results show that negatively charged ion complexes, responsible for U transport, decreases when alkalinity and rock buffer capacity is similarly lower. Carbonate ion pairs however, may increase U mobility when radionuclide concentration is high and rock buffer capacity is low. The present work helps to orient future monitoring of this site in Brazil as well as of other sites where uranium is linked to igneous rock formations, without the presence of sulphides. Monitoring SO4 migration (in acidic leaching uranium sites) seems to be an efficient and simple way to track different hazards, especially in tropical conditions, where the succession of dry and wet periods increases the weathering action of the residual H2SO4. Nevertheless, models of risk evaluation should take into account reactive surface areas and neogenic minerals since they determine the U ion complex formation, which in turn, controls uranium mobility in natural systems. Keywords: uranium mining, reactive mineral surface area, uranium complexes, inverse modelling approach, risk evaluation

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.

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

PubMed

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

2013-04-01

We examine subsurface uranium (U) plumes at two U.S. Department of Energy sites that are located near large river systems and are influenced by groundwater-river hydrologic interaction. Following surface excavation of contaminated materials, both sites were projected to naturally flush remnant uranium contamination to levels below regulatory limits (e.g., 30 μg/L or 0.126 μmol/L; U.S. EPA drinking water standard), with 10 years projected for the Hanford 300 Area (Columbia River) and 12 years for the Rifle site (Colorado River). The rate of observed uranium decrease was much lower than expected at both sites. While uncertainty remains, a comparison of current understanding suggests that the two sites have common, but also different mechanisms controlling plume persistence. At the Hanford 300 A, the persistent source is adsorbed U(VI) in the vadose zone that is released to the aquifer during spring water table excursions. The release of U(VI) from the vadose zone and its transport within the oxic, coarse-textured aquifer sediments is dominated by kinetically-limited surface complexation. Modeling implies that annual plume discharge volumes to the Columbia River are small (

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

NASA Astrophysics Data System (ADS)

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

2013-04-01

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

Kinetics of triscarbonato uranyl reduction by aqueous ferrous iron: a theoretical study.

PubMed

Wander, Matthew C F; Kerisit, Sebastien; Rosso, Kevin M; Schoonen, Martin A A

2006-08-10

Uranium is a pollutant whose mobility is strongly dependent on its oxidation state. While U(VI) in the form of the uranyl cation is readily reduced by a range of natural reductants, by contrast complexation of uranyl by carbonate greatly reduces its reduction potential and imposes increased electron transfer (ET) distances. Very little is known about the elementary processes involved in uranium reduction from U(VI) to U(V) to U(IV) in general. In this study, we examine the theoretical kinetics of ET from ferrous iron to triscarbonato uranyl in aqueous solution. A combination of molecular dynamics (MD) simulations and density functional theory (DFT) electronic structure calculations is employed to compute the parameters that enter into Marcus' ET model, including the thermodynamic driving forces, reorganization energies, and electronic coupling matrix elements. MD simulations predict that two ferrous iron atoms will bind in an inner-sphere fashion to the three-membered carbonate ring of triscarbonato uranyl, forming the charge-neutral ternary Fe(2)UO(2)(CO(3))(3)(H(2)O)(8) complex. Through a sequential proton-coupled electron-transfer mechanism (PCET), the first ET step converting U(VI) to U(V) is predicted by DFT to occur with an electronic barrier that corresponds to a rate on the order of approximately 1 s(-1). The second ET step converting U(V) to U(IV) is predicted to be significantly endergonic. Therefore, U(V) is a stabilized end product in this ET system, in agreement with experiment.

Uranium distribution in the coastal waters and pore waters of Tampa Bay, Florida

USGS Publications Warehouse

Swarzenski, P.W.; Baskaran, M.

2006-01-01

The geochemical reactivity of uranium (238U) and dissolved organic carbon (DOC), Fe, Mn, Ba, and V was investigated in the water column, pore waters, and across a river/estuarine mixing zone in Tampa Bay, Florida. This large estuary is impacted both by diverse anthropogenic activity and by extensive U-rich phosphatic deposits. Thus, the estuarine behavior of uranium may be examined relative to such known U enrichments and anthropogenic perturbations. Dissolved (< 0.45??m) uranium exhibited both removal and enrichment processes across the Alafia River/estuarine mixing zone relative to conservative mixing. Such non-conservative U behavior may be attributed to: i) physical mixing processes within the river; ii) U carrier phase reactivity; and/or iii) fluid exchange processes across sediment/water interface. In the bay proper, U concentrations were ?????2 to 3 times greater than those reported for other estuarine systems and are likely a result of erosional inputs from the extensive, underlying U-rich phosphatic deposits. Whereas dissolved U concentrations generally did not approach seawater values (13.6??nM) along the Alafia River salinity transect, water column U concentrations exceeded 16??nM in select regions of the bay. Within the hydrogeological framework of the bay, such enriched U may also be derived from advective fluid transport processes across the sediment/water interface, such as submarine groundwater discharge (SGD) or hyporheic exchange within coastal rivers. Pore water profiles of U in Tampa Bay show both a flux into and out of bottom sediments, and average, diffusive U pore water fluxes (Jdiff) ranged from - 82.0 to 116.6??mol d- 1. It is likely that negative U fluxes imply seawater entrainment or infiltration (i.e., submarine groundwater recharge), which may contribute to the removal of water column uranium. For comparison, a bay-wide, Ra-derived submarine groundwater discharge estimate for Tampa Bay (8??L m- 2 d- 1) yielded an average, advective (JSGD) U flux of 112.9??mol d- 1. In Tampa Bay, the estuarine distribution of U indicates a strong natural, geologic control that may also be influenced by enhanced fluid transport processes across the sediment/water interface. ?? 2006 Elsevier B.V. All rights reserved.

Attenuation and Transport Mechanisms of Depleted Uranium in Groundwater at Lawrence Livermore National Laboratory Site 300

NASA Astrophysics Data System (ADS)

Danny, K. R.; Taffet, M. J.; Brusseau, M. L. L.; Chorover, J.

2015-12-01

Lawrence Livermore National Laboratory (LLNL) Site 300 was established in 1955 to support weapons research and development. Depleted uranium was used as a proxy for fissile uranium-235 (235U) in open-air explosives tests conducted at Building 812. As a result, oxidized depleted uranium was deposited on the ground, eventually migrating to the underlying sandstone aquifer. Uranium (U) groundwater concentrations exceed the California and Federal Maximum Contaminant Level of 20 pCi L-1 (30 ug L-1). However, the groundwater plume appears to attenuate within 60 m of the source, beyond which no depleted U is detected. This study will determine the relative contribution of physical (e.g. dilution), chemical (e.g. surface adsorption, mineral precipitation), and biological (e.g. biotransformation) processes that contribute to the apparent attenuation of U, which exists as uranyl (UO22+) complexes, at the site. Methods of investigation include evaluating 15 yr of hydrogeologic and chemical data, creating a site conceptual model, and applying equilibrium (e.g. aqueous species complexation, mineral saturation indices) and reactive transport models using Geochemist's WorkbenchTM. Reactive transport results are constrained by direct field observations, including U major ion, and dissolved O2 concentrations, pH, and others, under varying chemical and hydraulic conditions. Aqueous speciation calculations indicate that U primarily exists as anionic CaUO2(CO3)32- or neutral Ca2UO2(CO3)30 species. Additionally, nucleation and growth of Ca/Mg uranyl carbonate solids are predicted to affect attenuation. Initial reactive transport results suggest surface adsorption (e.g. ion exchange, surface complexation) to layer silicate clays is limited under the aqueous geochemical conditions of the site. Current and future work includes XRD analysis of aquifer solids to constrain iron and aluminum (oxy)hydroxides, and coupling advective-dispersive transport with the chemical and physical processes. This work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344. LLNL-ABS-675707.

Preparation and crystal structure of U3Fe2C5: An original uranium-iron carbide

NASA Astrophysics Data System (ADS)

Henriques, M. S.; Paixão, J. A.; Henriques, M. S. C.; Gonçalves, A. P.

2015-09-01

The U3Fe2C5 compound was prepared from the elements by arc-melting, followed by an heat-treatment in an induction furnace, at 1250 °C for 1 h and 1300 °C for 2 h. The crystal structure of this phase was determined by direct methods from single crystal X-ray diffraction data. U3Fe2C5 crystallizes in an original tetragonal crystal structure, with space group I4/mmm, a = 3.4980(3) Å and c = 19.8380(15) Å as lattice constants and two formula units per cell. This new type structure is characterized by the simultaneous presence of isolated and pairs of carbon atoms, the interatomic distances in the pairs being similar to a typical carbon-carbon double bond length found in a molecule. U3Fe2C5 is closely related to UC and UFeC2, and can be seen as build from two (distorted) UFeC2 unit cells and a UC layer.

40 CFR 421.320 - Applicability: Description of the secondary uranium subcategory.

Code of Federal Regulations, 2012 CFR

2012-07-01

... secondary uranium subcategory. 421.320 Section 421.320 Protection of Environment ENVIRONMENTAL PROTECTION... CATEGORY Secondary Uranium Subcategory § 421.320 Applicability: Description of the secondary uranium... uranium (including depleted uranium) by secondary uranium facilities. ...

40 CFR 421.320 - Applicability: Description of the secondary uranium subcategory.

Code of Federal Regulations, 2011 CFR

2011-07-01

... secondary uranium subcategory. 421.320 Section 421.320 Protection of Environment ENVIRONMENTAL PROTECTION... CATEGORY Secondary Uranium Subcategory § 421.320 Applicability: Description of the secondary uranium... uranium (including depleted uranium) by secondary uranium facilities. ...

40 CFR 421.320 - Applicability: Description of the secondary uranium subcategory.

Code of Federal Regulations, 2013 CFR

2013-07-01

... secondary uranium subcategory. 421.320 Section 421.320 Protection of Environment ENVIRONMENTAL PROTECTION... CATEGORY Secondary Uranium Subcategory § 421.320 Applicability: Description of the secondary uranium... uranium (including depleted uranium) by secondary uranium facilities. ...

40 CFR 421.320 - Applicability: Description of the secondary uranium subcategory.

Code of Federal Regulations, 2014 CFR

2014-07-01

... secondary uranium subcategory. 421.320 Section 421.320 Protection of Environment ENVIRONMENTAL PROTECTION... CATEGORY Secondary Uranium Subcategory § 421.320 Applicability: Description of the secondary uranium... uranium (including depleted uranium) by secondary uranium facilities. ...

40 CFR 421.320 - Applicability: Description of the secondary uranium subcategory.

Code of Federal Regulations, 2010 CFR

2010-07-01

... secondary uranium subcategory. 421.320 Section 421.320 Protection of Environment ENVIRONMENTAL PROTECTION... CATEGORY Secondary Uranium Subcategory § 421.320 Applicability: Description of the secondary uranium... uranium (including depleted uranium) by secondary uranium facilities. ...

The removal of uranium onto carbon-supported nanoscale zero-valent iron particles

NASA Astrophysics Data System (ADS)

Crane, Richard A.; Scott, Thomas

2014-12-01

In the current work carbon-supported nanoscale zero-valent iron particles (CS nZVI), synthesised by the vacuum heat treatment of ferric citrate trihydrate absorbed onto carbon black, have been tested for the removal of uranium (U) from natural and synthetic waters. Two types of CS nZVI were tested, one vacuum annealed at 600 °C for 4 h and the other vacuum annealed at 700 °C for 4 h, with their U removal behaviour compared to nZVI synthesised via the reduction of ferrous iron using sodium borohydride. The batch systems were analysed over a 28-day reaction period during which the liquid and nanoparticulate solids were periodically analysed to determine chemical evolution of the solutions and particulates. Results demonstrate a well-defined difference between the two types of CS nZVI, with greater U removal exhibited by the nanomaterial synthesised at 700 °C. The mechanism has been attributed to the CS nZVI synthesised at 700 °C exhibiting (i) a greater proportion of surface oxide Fe2+ to Fe3+ (0.34 compared to 0.28); (ii) a greater conversion of ferric citrate trihydrate [2Fe(C6H5O7)·H2O] to Fe0; and (iii) a larger surface area (108.67 compared to 88.61 m2 g-1). Lower maximum U uptake was recorded for both types of CS nZVI in comparison with the borohydride-reduced nZVI. A lower decrease in solution Eh and DO was also recorded, indicating that less chemical reduction of U was achieved by the CS nZVI. Despite this, lower U desorption in the latter stages of the experiment (>7 days) was recorded for the CS nZVI synthesised at 700 °C, indicating that carbon black in the CS nZVI is likely to have contributed towards U sorption and retention. Overall, it can be stated that the borohydride-reduced nZVI were significantly more effective than CS nZVI for U removal over relatively short timescales (e.g. <48 h), however, they were more susceptible to U desorption over extended time periods.

Paleo-Productivity across the Paleocene-Eocene Thermal Maximum, Walvis Ridge Transect (ODP Sites 1262, 1263, and 1266)

NASA Astrophysics Data System (ADS)

Chun, C. O.; Delaney, M. L.; Zachos, J. C.

2005-12-01

Walvis Ridge transect (Ocean Drilling Program (ODP) Leg 208) provides the first high-resolution depth-transect of deep-sea sediments recovered from the south Atlantic across the P/E boundary. A geographically restricted depth transect (~ 2.2 km, water depths between 2500 and 4770 m) allows us to constrain the surface waters by assuming marine productivity conditions in the overlying water column are similar across all sites. The sediment record will reveal variations for processes that are water-depth dependent. We use the geochemical tracers; biogenic barium, phosphorus, calcium carbonate, and the redox sensitive trace elements manganese and uranium, to reconstruct nutrient burial, paleoproductivity, and bottom water redox chemistry across the Paleocene-Eocene Thermal Maximum (PETM). We calculate our concentrations on a calcium carbonate-free basis to account for dilution by non-carbonate sediments. Trace metal enrichment factors (EFs) are calculated relative to bulk crustal averages. We chose three sites from the depth transect: the shallowest (Site 1263, 2717 m water depth), an intermediate site (Site 1266, 3798 m water depth), and the deepest site (Site 1262, 4755 m water depth). We sampled each site at a sample resolution of ~ 1-2 kyr for 5 m.y. centered at 55 Ma. Uranium EFs at the shallow site exhibits values ~ 5 pre-event and drop to values near crustal averages during and after the carbon isotope excursion (CIE). No dramatic changes in U EFs across the P/E boundary are recorded at the deep and intermediate sites. Mn EFs range between 2.9 -8.6 prior to the event across all three sites, suggesting an oxygenated depositional environment. At the boundary, Mn EFs drop to crustal averages at all sites, then gradually return to pre-event values, indicating more reducing environments during the CIE, a possible explanation for the benthic extinction event (BEE) observed across this transect. Ba excess and reactive phosphorus exhibit decreased concentrations during the CIE with gradual return to pre-event values at the shallowest and deepest sites. We will compare the paleo-productivity and redox chemistry response at the Walvis Ridge sites across the PETM.

Release behavior of uranium in uranium mill tailings under environmental conditions.

PubMed

Liu, Bo; Peng, Tongjiang; Sun, Hongjuan; Yue, Huanjuan

2017-05-01

Uranium contamination is observed in sedimentary geochemical environments, but the geochemical and mineralogical processes that control uranium release from sediment are not fully appreciated. Identification of how sediments and water influence the release and migration of uranium is critical to improve the prevention of uranium contamination in soil and groundwater. To understand the process of uranium release and migration from uranium mill tailings under water chemistry conditions, uranium mill tailing samples from northwest China were investigated with batch leaching experiments. Results showed that water played an important role in uranium release from the tailing minerals. The uranium release was clearly influenced by contact time, liquid-solid ratio, particle size, and pH under water chemistry conditions. Longer contact time, higher liquid content, and extreme pH were all not conducive to the stabilization of uranium and accelerated the uranium release from the tailing mineral to the solution. The values of pH were found to significantly influence the extent and mechanisms of uranium release from minerals to water. Uranium release was monitored by a number of interactive processes, including dissolution of uranium-bearing minerals, uranium desorption from mineral surfaces, and formation of aqueous uranium complexes. Considering the impact of contact time, liquid-solid ratio, particle size, and pH on uranium release from uranium mill tailings, reducing the water content, decreasing the porosity of tailing dumps and controlling the pH of tailings were the key factors for prevention and management of environmental pollution in areas near uranium mines. Copyright © 2017 Elsevier Ltd. All rights reserved.

Uranium, yttrium, and rare earth elements accumulation during the Cretaceous anoxic events in carbonaceous rocks in the Pacific Ocean

NASA Astrophysics Data System (ADS)

Savelyeva, Olga; Philosofova, Tatyana; Bergal-Kuvikas, Olga; Savelyeva, Svetlana

2017-04-01

We have studied the carbonate-siliceous section of paleooceanic Albian-Cenomanian deposits on the Kamchatsky Mys peninsula (Eastern Kamchatka, Russia) [1].The section is represented by a rhythmic alternation of planktonic limestones and jaspers, accumulated in the open ocean environment. The rhythmicity can be attributed to climate variations that reflect a fluctuation of astronomical parameters (Milankovitch cycles) [2, 3].The section contains two beds enriched in organic carbon, corresponding to the two oceanic anoxic events - MCE and OAE2 [3]. The maximum content of organic matter in those beds reaches 68%. Our geochemical studies revealed an enrichment of the carbonaceous rocks in some major and trace elements including PGE, in comparison with the surrounding limestone and jasper [4].The accumulation of the ore elements in carbonaceous beds is caused by euxinic conditions during sedimentation.The content of uranium, yttrium, and rare earth elements in carbonaceous rocks is up to 60, 142 and 312 ppm respectively. Phosphate grains (bone detritus) with microinclusions of yttrium and uranium minerals were revealed in the carbonaceous rocks using the scanning electron microscope. These data prove the hypothesis of the sorbtion of U and Y by phosphate detritus from seawater. Microprobe analysis also showed an increased content of Cu, Zn, V in some pyrite framboids, which indicates that these elements are fixed in rocks by Fe-sulphide phase or organic matter under euxinic conditions. Our research may bring us closer to understanding the mechanism of syngenetic accumulation of metals in the black shales. This work was supported by the RFBR (No. 16-05-00546). [1] Palechek, T.N., Savelyev, D.P., Savelyeva, O.L. (2010) Stratigraphy and Geological Correlation 18, (1) 63-82. [2] Savelyeva, O.L. (2010). Vestnik Kraunts. Nauki o zemle 1 (15), 45-55 (in Russian). [3] Savelyev, D.P., Savelyeva, O.L., Palechek, T.N., Pokrovsky, B.G. (2012) Geophysical Research Abstracts, 14, EGU2012-1940. [4] Savelyeva, O., Palesskiy, S., Savelyev, D. (2015) Goldschmidt Abstracts, 2015. 2779.

Resistance, bioaccumulation and solid phase extraction of uranium (VI) by Bacillus vallismortis and its UV-vis spectrophotometric determination.

PubMed

Ozdemir, Sadin; Oduncu, M Kadir; Kilinc, Ersin; Soylak, Mustafa

2017-05-01

Bioaccumulation, resistance and preconcentration of uranium(VI) by thermotolerant Bacillus vallismortis were investigated in details. The minimum inhibition concentration of (MIC) value of U(VI) was found as 85 mg/L and 15 mg/L in liquid and solid medium, respectively. Furthermore, the effect of various U(VI) concentrations on the growth of bacteria and bioaccumulation on B. vallismortis was examined in the liquid culture media. The growth was not significantly affected in the presence of 1.0, 2.5 and 5.0 mg/L U(VI) up to 72 h. The highest bioaccumulation value at 1 mg/L U(VI) concentration was detected at the 72nd hour (10 mg/g metal/dry bacteria), while the maximum bioaccumulation value at 5 mg/L U(VI) concentration was determined at the 48th hour (50 mg metal/dry bacteria). In addition to these, various concentration of U(VI) on α-amylase production was studied. The α-amylase activities at 0, 1, 2.5 and 5 mg/L U(VI) were found as 3313.2, 3845.2, 3687.1 and 3060.8 U/mg, respectively at 48th. Besides, uranium (VI) ions were preconcentrated with immobilized B. vallismortis onto multiwalled carbon nanotube (MWCNT) and were determined by UV-vis spectrophotometry. The surface macro structure and functionalities of B. vallismortis immobilized onto multiwalled carbon nanotube with and without U(VI) were examined by FT-IR and SEM. The optimum pH and flow rate for the biosorption of U(VI) were 4.0-5.0 and 1.0 mL/min, respectively. The quantitative elution occurred with 5.0 mL of 1 mol/L HCl. The loading capacity of immobilized B. vallismortis was determined as 23.6 mg/g. The certified reference sample was employed for the validation of developed solid phase extraction method. The new validated method was applied to the determination of U(VI) in water samples from Van Lake-Turkey. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

Reiche, Helmut Matthias; Vogel, Sven C.

New in situ data for the U-C system are presented, with the goal of improving knowledge of the phase diagram to enable production of new ceramic fuels. The none quenchable, cubic, δ-phase, which in turn is fundamental to computational methods, was identified. Rich datasets of the formation synthesis of uranium carbide yield kinetics data which allow the benchmarking of modeling, thermodynamic parameters etc. The order-disorder transition (carbon sublattice melting) was observed due to equal sensitivity of neutrons to both elements. This dynamic has not been accurately described in some recent simulation-based publications.

Process for electroslag refining of uranium and uranium alloys

DOEpatents

Lewis, P.S. Jr.; Agee, W.A.; Bullock, J.S. IV; Condon, J.B.

1975-07-22

A process is described for electroslag refining of uranium and uranium alloys wherein molten uranium and uranium alloys are melted in a molten layer of a fluoride slag containing up to about 8 weight percent calcium metal. The calcium metal reduces oxides in the uranium and uranium alloys to provide them with an oxygen content of less than 100 parts per million. (auth)

Detection of depleted uranium in urine of veterans from the 1991 Gulf War.

PubMed

Gwiazda, R H; Squibb, K; McDiarmid, M; Smith, D

2004-01-01

American soldiers involved in "friendly fire" accidents during the 1991 Gulf War were injured with depleted-uranium-containing fragments or possibly exposed to depleted uranium via other routes such as inhalation, ingestion, and/or wound contamination. To evaluate the presence of depleted uranium in these soldiers eight years later, the uranium concentration and depleted uranium content of urine samples were determined by inductively coupled plasma mass spectrometry in (a) depleted uranium exposed soldiers with embedded shrapnel, (b) depleted uranium exposed soldiers with no shrapnel, and (c) a reference group of deployed soldiers not involved in the friendly fire incidents. Uranium isotopic ratios measured in many urine samples injected directly into the inductively coupled plasma mass spectrometer and analyzed at a mass resolution m/delta m of 300 appeared enriched in 235U with respect to natural abundance (0.72%) due to the presence of an interference of a polyatomic molecule of mass 234.81 amu that was resolved at a mass resolution m/delta m of 4,000. The 235U abundance measured on uranium separated from these urines by anion exchange chromatography was clearly natural or depleted. Urine uranium concentrations of soldiers with shrapnel were higher than those of the two other groups, and 16 out of 17 soldiers with shrapnel had detectable depleted uranium in their urine. In depleted uranium exposed soldiers with no shrapnel, depleted uranium was detected in urine samples of 10 out of 28 soldiers. The median uranium concentration of urines with depleted uranium from soldiers without shrapnel was significantly higher than in urines with no depleted uranium, though substantial overlap in urine uranium concentrations existed between the two groups. Accordingly, assessment of depleted uranium exposure using urine must rely on uranium isotopic analyses, since urine uranium concentration is not an unequivocal indicator of depleted uranium presence in soldiers with no embedded shrapnel.

Evidence of Enhanced Respired Carbon in Eastern Equatorial Pacific Deep-Waters over the last 30,000 years

NASA Astrophysics Data System (ADS)

Umling, N. E.; Thunell, R.

2016-12-01

Rapid decreases in glacial deep water reservoir ages have been observed in the Eastern Equatorial Pacific (EEP; this study), North Pacific (Rae et al., 2014), Southwest Pacific (Sikes et al., 2016), and North Atlantic (Skinner et al., 2013). It has been hypothesized that release of a deep ocean 14C-depleted, respired-carbon reservoir to the surface ocean and atmosphere is the most likely mechanism for the observed increases in atmospheric CO2 concentrations recorded in ice cores during the last glacial-interglacial transition (Broecker and Barker, 2007). This study examines whether oxygenation, organic carbon flux, and carbonate chemistry in the EEP deep-waters reflect an increase in respired carbon associated with recorded 14C-depletions using isotopic and trace element records from three Panama Basin cores (2,650-3,200 m water-depth). An increase in glacial deep-water respired carbon storage would result in a shift of DIC speciation towards lower carbonate ion concentrations along with deoxygenation of bottom waters. Specifically, we use the boron to calcium (B/Ca) and uranium to calcium (U/Ca) ratios of the benthic foraminifera Cibicidoides wuellerstorfi to reconstruct deep-water carbonate ion concentration (Yu and Elderfield, 2007; Raizsch et al., 2011). Additionally, bottom water oxygenation is estimated from the difference in δ13C of benthic foraminifera living in pore waters at the anoxic boundary and of those living in bottom water (Δ δ13C; Hoogakker et al., 2015, 2016), while carbon flux was assessed from the U/Ca and Cd/Ca of foraminiferal authigenic coatings.

31 CFR 540.317 - Uranium feed; natural uranium feed.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 31 Money and Finance:Treasury 3 2013-07-01 2013-07-01 false Uranium feed; natural uranium feed... (Continued) OFFICE OF FOREIGN ASSETS CONTROL, DEPARTMENT OF THE TREASURY HIGHLY ENRICHED URANIUM (HEU) AGREEMENT ASSETS CONTROL REGULATIONS General Definitions § 540.317 Uranium feed; natural uranium feed. The...

31 CFR 540.317 - Uranium feed; natural uranium feed.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 31 Money and Finance:Treasury 3 2012-07-01 2012-07-01 false Uranium feed; natural uranium feed... (Continued) OFFICE OF FOREIGN ASSETS CONTROL, DEPARTMENT OF THE TREASURY HIGHLY ENRICHED URANIUM (HEU) AGREEMENT ASSETS CONTROL REGULATIONS General Definitions § 540.317 Uranium feed; natural uranium feed. The...

31 CFR 540.317 - Uranium feed; natural uranium feed.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 31 Money and Finance:Treasury 3 2014-07-01 2014-07-01 false Uranium feed; natural uranium feed... (Continued) OFFICE OF FOREIGN ASSETS CONTROL, DEPARTMENT OF THE TREASURY HIGHLY ENRICHED URANIUM (HEU) AGREEMENT ASSETS CONTROL REGULATIONS General Definitions § 540.317 Uranium feed; natural uranium feed. The...

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

NASA Astrophysics Data System (ADS)

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

2011-05-01

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

Structure of carbonate melts at high pressure

NASA Astrophysics Data System (ADS)

Hudspeth, J.; Sanloup, C.; Cochain, B.; Konopkova, Z.; Afonina, V.; Morgenroth, W.

2015-12-01

Carbonate melts are rare magmas with only a single active volcano (Oldoinyo Lengai,Tanzania [1]). They are of fundamental interest for their role in the Earth's deep carbon cycle and are of immense economic importance due to their affinity for REE strategic metals (niobium, uranium, tantalum, etc). They have remarkable physical properties such as very low viscosity [2] and magmatic temperatures for alkaline carbonate lavas [3] and it has been predicted that their compressibility could be significantly higher than that of silicate melts [4,5]. Despite the atomic structure of carbonate melts being fundamental for controlling their physical and chemical behavior in natural systems, very few structural studies have been reported and these have been largely computational. Here we present initial structural investigations of carbonate melts at mantle pressures using in situ x-ray diffraction in diamond anvil cells. The structure factor S(Q) is transformed to obtain the real space pair distribution function G(R) which describes the local and intermediate range atomic ordering allowing bond length and coordination number changes with pressure to be determined. [1] Krafft and Keller, Science 245:168-170, 1989 [2] Yono et al., Nat. Commun. 5:5091, 2014 [3] Dobson et al., Earth Planet. Sci. Lett. 143:207-215, 1996 [4] Genge et al., Earth Planet. Sci. Lett. 131:225-238, 1995 [5] Jones et al., Rev. Mineral. Geochem. 75:289-322, 2013

Understanding controls on redox processes in floodplain sediments of the Upper Colorado River Basin

DOE PAGES

Noël, Vincent; Boye, Kristin; Kukkadapu, Ravi K.; ...

2017-12-15

Floodplains, heavily used for water supplies, housing, agriculture, mining, and industry, are important repositories of organic carbon, nutrients, and metal contaminants. The accumulation and release of these species is often mediated by redox processes. By understanding the physicochemical, hydrological, and biogeochemical controls on the distribution and variability of sediment redox conditions we can develop conceptual and numerical models of contaminant transport within floodplains. The Upper Colorado River Basin (UCRB) is impacted by former uranium and vanadium ore processing, resulting in contamination by V, Cr, Mn, As, Se, Mo and U. Previous authors have suggested that sediment redox activity occurring withinmore » organic carbon-enriched bodies located below the groundwater level may be regionally important to the maintenance and release of contaminant inventories, particularly uranium. To help assess this hypothesis, vertical distributions of Fe and S redox states and sulfide mineralogy were assessed in sediment cores from three floodplain sites spanning a 250 km transect of the central UCRB. Our results support the hypothesis that organic-enriched reduced sediments are important zones of biogeochemical activity within UCRB floodplains. Furthermore, we found that the presence of organic carbon, together with pore saturation, are the key requirements for maintaining reducing conditions, which were dominated by sulfate-reduction products. Sediment texture was found to be of secondary importance and to moderate the response of the system to external forcing, such as oxidant diffusion. Consequently, fine-grain sediments are relatively resistant to oxidation in comparison to coarser-grained sediments. Exposure to oxidants consumes precipitated sulfides, with a disproportionate loss of mackinawite (FeS) as compared to the more stable pyrite. The accompanying loss of redox buffering capacity creates the potential for release of sequestered radionuclides and metals. Because of their redox reactivity and stores of metals, C, and N, organic-enriched sediments are likely to be important to nutrient and contaminant mobility within UCRB floodplain aquifers.« less

Understanding controls on redox processes in floodplain sediments of the Upper Colorado River Basin

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

Noël, Vincent; Boye, Kristin; Kukkadapu, Ravi K.

Floodplains, heavily used for water supplies, housing, agriculture, mining, and industry, are important repositories of organic carbon, nutrients, and metal contaminants. The accumulation and release of these species is often mediated by redox processes. By understanding the physicochemical, hydrological, and biogeochemical controls on the distribution and variability of sediment redox conditions we can develop conceptual and numerical models of contaminant transport within floodplains. The Upper Colorado River Basin (UCRB) is impacted by former uranium and vanadium ore processing, resulting in contamination by V, Cr, Mn, As, Se, Mo and U. Previous authors have suggested that sediment redox activity occurring withinmore » organic carbon-enriched bodies located below the groundwater level may be regionally important to the maintenance and release of contaminant inventories, particularly uranium. To help assess this hypothesis, vertical distributions of Fe and S redox states and sulfide mineralogy were assessed in sediment cores from three floodplain sites spanning a 250 km transect of the central UCRB. Our results support the hypothesis that organic-enriched reduced sediments are important zones of biogeochemical activity within UCRB floodplains. Furthermore, we found that the presence of organic carbon, together with pore saturation, are the key requirements for maintaining reducing conditions, which were dominated by sulfate-reduction products. Sediment texture was found to be of secondary importance and to moderate the response of the system to external forcing, such as oxidant diffusion. Consequently, fine-grain sediments are relatively resistant to oxidation in comparison to coarser-grained sediments. Exposure to oxidants consumes precipitated sulfides, with a disproportionate loss of mackinawite (FeS) as compared to the more stable pyrite. The accompanying loss of redox buffering capacity creates the potential for release of sequestered radionuclides and metals. Because of their redox reactivity and stores of metals, C, and N, organic-enriched sediments are likely to be important to nutrient and contaminant mobility within UCRB floodplain aquifers.« less

Acceptance Test Data for BWXT Coated Particle Batches 93172B and 93173B—Defective IPyC and Pyrocarbon Anisotropy

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

Hunn, John D.; Helmreich, Grant W.; Dyer, John A.

Coated particle batches J52O-16-93172B and J52O-16-93173B were produced by Babcock and Wilcox Technologies (BWXT) as part of the production campaign for the Advanced Gas Reactor Fuel Development and Qualification (AGR) Program’s AGR-5/6/7 irradiation test in the Idaho National Laboratory (INL) Advanced Test Reactor (ATR), but were not used in the final fuel composite. However, these batches may be used as demonstration production-scale coated particle fuel for other experiments. Each batch was coated in a 150-mm-diameter production-scale fluidized-bed chemical vapor deposition (CVD) furnace. Tristructural isotropic (TRISO) coatings were deposited on 425-μm-nominal-diameter spherical kernels from BWXT lot J52R-16-69317 containing a mixture ofmore » 15.5%-enriched uranium carbide and uranium oxide (UCO). The TRISO coatings consisted of four consecutive CVD layers: a ~50% dense carbon buffer layer with 100-μm-nominal thickness, a dense inner pyrolytic carbon (IPyC) layer with 40-μm-nominal thickness, a silicon carbide (SiC) layer with 35-μm-nominal thickness, and a dense outer pyrolytic carbon (OPyC) layer with 40-μm-nominal thickness. The TRISO-coated particle batches were sieved to upgrade the particles by removing over-sized and under-sized material, and the upgraded batches were designated by appending the letter A to the end of the batch number (e.g., 93172A). Secondary upgrading by sieving was performed on the A-designated batches to remove particles with missing or very-thin buffer layers that were identified during previous analysis of the individual batches for defective IPyC, as reported in the acceptance test data report for the AGR-5/6/7 production batches [Hunn et al. 2017b]. The additionally-upgraded batches were designated by appending the letter B to the end of the batch number (e.g., 93172B).« less

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.

Biological reduction of uranium coupled with oxidation of ammonium by Acidimicrobiaceae bacterium A6 under iron reducing conditions.

PubMed

Gilson, Emily R; Huang, Shan; Jaffé, Peter R

2015-11-01

This study investigated the possibility of links between the biological immobilization of uranium (U) and ammonium oxidation under iron (Fe) reducing conditions. The recently-identified Acidimicrobiaceae bacterium A6 (ATCC, PTA-122488) derives energy from ammonium oxidation coupled with Fe reduction. This bacterium has been found in various soil and wetland environments, including U-contaminated wetland sediments. Incubations of Acidimicrobiaceae bacteria A6 with nontronite, an Fe(III)-rich clay, and approximately 10 µM U indicate that these bacteria can use U(VI) in addition to Fe(III) as an electron acceptor in the presence of ammonium. Measurements of Fe(II) production and ammonium oxidation support this interpretation. Concentrations of approximately 100 µM U were found to entirely inhibit Acidimicrobiaceae bacteria A6 activity. These results suggest that natural sites of active ammonium oxidation under Fe reducing conditions by Acidimicrobiaceae bacteria A6 could be hotspots of U immobilization by bioreduction. This is the first report of biological U reduction that is not coupled to carbon oxidation.

Neutronics Analyses of the Minimum Original HEU TREAT Core

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

Kontogeorgakos, D.; Connaway, H.; Yesilyurt, G.

2014-04-01

This work was performed to support the feasibility study on the potential conversion of the Transient Reactor Test Facility (TREAT) at Idaho National Laboratory from the use of high-enriched uranium (HEU) fuel to the use of low-enriched uranium (LEU) fuel. The analyses were performed by the GTRI Reactor Conversion staff at the Argonne National Laboratory (ANL). The objective of this study was to validate the MCNP model of the TREAT reactor with the well-documented measurements which were taken during the start-up and early operation of TREAT. Furthermore, the effect of carbon graphitization was also addressed. The graphitization level was assumedmore » to be 100% (ANL/GTRI/TM-13/4). For this purpose, a set of experiments was chosen to validate the TREAT MCNP model, involving the approach to criticality procedure, in-core neutron flux measurements with foils, and isothermal temperature coefficient and temperature distribution measurements. The results of this study extended the knowledge base for the TREAT MCNP calculations and established the credibility of the MCNP model to be used in the core conversion feasibility analysis.« less