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

NASA Astrophysics Data System (ADS)

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

2013-06-01

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

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

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

None, None

2009-03-09

Previous work had suggested that Acholeplasma palmae has a higher capacity for uranium sorption than other bacteria studied. Sorption studies were performed with cells in suspension in various solutions containing uranium and results were used to generate uranium-biosorption isotherms.

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

Catalano, Jeffrey G.; Giammar, Daniel E.; Wang, Zheming

Phosphate addition is an in situ remediation approach that may enhance the sequestration of uranium without requiring sustained reducing conditions. However, the geochemical factors that determine the dominant immobilization mechanisms upon phosphate addition are insufficiently understood to design efficient remediation strategies or accurately predict U(VI) transport. The overall objective of our project is to determine the dominant mechanisms of U(VI)-phosphate reactions in subsurface environments. Our research approach seeks to determine the U(VI)-phosphate solid that form in the presence of different groundwater cations, characterize the effects of phosphate on U(VI) adsorption and precipitation on smectite and iron oxide minerals, examples ofmore » two major reactive mineral phases in contaminated sediments, and investigate how phosphate affects U(VI) speciation and fate during water flow through sediments from contaminated sites. The research activities conducted for this project have generated a series of major findings. U(VI) phosphate solids from the autunite mineral family are the sole phases to form during precipitation, with uranyl orthophosphate not occurring despite its predicted greater stability. Calcium phosphates may take up substantial quantities of U(VI) through three different removal processes (adsorption, coprecipitation, and precipitation) but the dominance of each process varies with the pathway of reaction. Phosphate co-adsorbs with U(VI) onto smectite mineral surfaces, forming a mixed uranium-phosphate surface complex over a wide range of conditions. However, this molecular-scale association of uranium and phosphate has not effect on the overall extent of uptake. In contrast, phosphate enhanced U(VI) adsorption to iron oxide minerals at acidic pH conditions but suppresses such adsorption at neutral and alkaline pH, despite forming mixed uranium-phosphate surface complexes during adsorption. Nucleation barriers exist that inhibit U(VI) phosphate solids from precipitating in the presence of smectite and iron oxide minerals as well as sediments from contaminated sites. Phosphate addition enhances retention of U(VI) by sediments from the Rifle, CO and Hanford, WA field research sites, areas containing substantial uranium contamination of groundwater. This enhanced retention is through adsorption processes. Both fast and slow uptake and release behavior is observed, indicating that diffusion of uranium between sediment grains has a substantial effect of U(VI) fate in flowing groundwater systems. This project has revealed the complexity of U(VI)-phosphate reactions in subsurface systems. Distinct chemical processes occur in acidic and alkaline groundwater systems. For the latter, calcium phosphate formation, solution complexation, and competition between phosphate and uranium for adsorption sites may serve to either enhance or inhibit U(VI) removal from groundwater. Under the groundwater conditions present at many contaminated sites in the U.S., phosphate appears to general enhance U(VI) retention and limit transport. However, formation of low-solubility uranium phosphate solids does not occur under field-relevant conditions, despite this being the desired product of phosphate-based remediation approaches. In addition, simple equilibrium approaches fail to well-predict uranium fate in contaminated sediments amended with phosphate, with reactive transport models that include reaction rates and mass transport through occluded domains needed to properly describe the system. Phosphate addition faces challenges to being effective as a stand-alone groundwater treatment approach but would prove beneficial as an add-on to other treatment methods that will further limit uranium migration in the subsurface.« less

Characterization of the biochemical-pathway of uranium (VI) reduction in facultative anaerobic bacteria.

PubMed

Mtimunye, Phalazane J; Chirwa, Evans M N

2014-10-01

Cultures of U(VI) reducing bacteria sourced from abandoned uranium mine tailing dam were evaluated for their ability to reduce U(VI) to U(IV). The species in the cultures reduced U(VI) in solutions with initial U(VI) concentration up to 400mgL(-)(1) under a near neutral pH of 6.5. The electron flow pathway and fate of reduced species was also analysed in the individual species in order to evaluate the potential for control and optimisation of the reduction potential at the biochemical level. The results showed that U(VI) reduction in live cells was completely blocked by the NADH-dehydrogenase inhibitor, rotenone (C23H22O6), and thioredoxin inhibitor, cadmium chloride (CdCl2), showing that U(VI) reduction involves the electron flow through NADH-dehydrogenase, a primary electron donor to the electron transport respiratory (ETR) system. Mass balance analysis of uranium species aided by visual and electron microscopy suggest that most U(VI) reduction occurred on the cell surface of the isolated species. This finding indicates the possibility of easy uranium recovery for beneficial use through biological remediation. Should the U(VI) be reduced inside the cell, recovery would require complete disruption of the cells and therefore would be difficult. The study contributes new knowledge on the underlying mechanisms in the U(VI) reduction in facultative anaerobes. Copyright © 2014 Elsevier Ltd. All rights reserved.

Anaerobic bioremediation of hexavalent uranium in groundwater by reductive precipitation with methanogenic granular sludge.

PubMed

Tapia-Rodriguez, Aida; Luna-Velasco, Antonia; Field, Jim A; Sierra-Alvarez, Reyes

2010-04-01

Uranium has been responsible for extensive contamination of groundwater due to releases from mill tailings and other uranium processing waste. Past evidence has confirmed that certain bacteria can enzymatically reduce soluble hexavalent uranium (U(VI)) to insoluble tetravalent uranium (U(IV)) under anaerobic conditions in the presence of appropriate electron donors. This paper focuses on the evaluation of anaerobic granular sludge as a source of inoculum for the bioremediation of uranium in water. Batch experiments were performed with several methanogenic anaerobic granular sludge samples and different electron donors. Abiotic controls consisting of heat-killed inoculum and non-inoculated treatments confirmed the biological removal process. In this study, unadapted anaerobic granular sludge immediately reduced U(VI), suggesting an intrinsic capacity of the sludge to support this process. The high biodiversity of anaerobic granular sludge most likely accounts for the presence of specific microorganisms capable of reducing U(VI). Oxidation by O(2) was shown to resolubilize the uranium. This observation combined with X-ray diffraction evidence of uraninite confirmed that the removal during anaerobic treatment was due to reductive precipitation. The anaerobic removal activity could be sustained after several respikes of U(VI). The U(VI) removal was feasible without addition of electron donors, indicating that the decay of endogenous biomass substrates was contributing electron equivalents to the process. Addition of electron donors, such as H(2) stimulated the removal of U(VI) to varying degrees. The stimulation was greater in sludge samples with lower endogenous substrate levels. The present work reveals the potential application of anaerobic granular sludge for continuous bioremediation schemes to treat uranium-contaminated water. Copyright (c) 2009 Elsevier Ltd. All rights reserved.

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.

Hydrothermal synthesis of (C6N2H14)2(UVI2UIVO4F12), a mixed-valent one-dimensional uranium oxyfluoride.

PubMed

Allen, S; Barlow, S; Halasyamani, P S; Mosselmans, J F; O'Hare, D; Walker, S M; Walton, R I

2000-08-21

A new hybrid organic-inorganic mixed-valent uranium oxyfluoride, (C6N2H14)2(U3O4F12), UFO-17, has been synthesized under hydrothermal conditions using uranium dioxide as the uranium source, hydrofluoric acid as mineralizer, and 1,4-diazabicyclo[2.2.2]octane as template. The single-crystal X-ray structure was determined. Crystals of UFO-17 belonged to the orthorhombic space group Cmcm (no. 63), with a = 14.2660(15) A, b = 24.5130(10) A, c = 7.201(2) A, and Z = 4. The structure reveals parallel uranium-containing chains of two types: one type is composed of edge-sharing UO2F5 units; the other has a backbone of edge-sharing UF8 units, each sharing an edge with a pendant UO2F5 unit. Bond-valence calculations suggest the UF8 groups contain UIV, while the UO2F5 groups contain UVI. EXAFS data give results consistent with the single-crystal X-ray structure determination, while comparison of the uranium LIII-edge XANES of UFO-17 with that of related UIV and UVI compounds supports the oxidation-state assignment. Variable-temperature magnetic susceptibility measurements on UFO-17 and a range of related hybrid organic-inorganic uranium(IV) and uranium(VI) fluorides and oxyfluorides further support the formulation of UFO-17 as a mixed-valent UIV/UVI compound.

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.

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

PubMed

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

2012-07-03

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

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

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

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

1973-07-01

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

Non-enzymatic U(VI) interactions with biogenic mackinawite

NASA Astrophysics Data System (ADS)

Veeramani, H.; Qafoku, N. P.; Kukkadapu, R. K.; Murayama, M.; Hochella, M. F.

2011-12-01

Reductive immobilization of hexavalent uranium [U(VI)] by stimulation of dissimilatory metal and/or sulfate reducing bacteria (DMRB or DSRB) has been extensively researched as a remediation strategy for subsurface U(VI) contamination. These bacteria derive energy by reducing oxidized metals as terminal electron acceptors, often utilizing organic substrates as electron donors. Thus, when evaluating the potential for in-situ uranium remediation in heterogeneous subsurface media, it is important to understand how the presence of alternative electron acceptors such as Fe(III) and sulfate affect U(VI) remediation and the long term behavior and reactivity of reduced uranium. Iron, an abundant subsurface element, represents a substantial sink for electrons from DMRB, and the reduction of Fe(III) leads to the formation of dissolved Fe(II) or to reactive biogenic Fe(II)- and mixed Fe(II)/Fe(III)- mineral phases. Consequently, abiotic U(VI) reduction by reactive forms of biogenic Fe(II) minerals could be a potentially important process for uranium immobilization. In our study, the DMRB Shewanella putrefaciens CN32 was used to synthesize a biogenic Fe(II)-bearing sulfide mineral: mackinawite, that has been characterized by XRD, SEM, HRTEM and Mössbauer spectroscopy. Batch experiments involving treated biogenic mackinawite and uranium (50:1 molar ratio) were carried out at room temperature under strict anoxic conditions. Following complete removal of uranium from solution, the biogenic mackinawite was analyzed by a suite of analytical techniques including XAS, HRTEM and Mössbauer spectroscopy to determine the speciation of uranium and investigate concomitant Fe(II)-phase transformation. Determining the speciation of uranium is critical to success of a remediation strategy. The present work elucidates non-enzymatic/abiotic molecular scale redox interactions between biogenic mackinawite and uranium.

Microbial reduction of uranium (VI) by Bacillus sp. dwc-2: A macroscopic and spectroscopic study.

PubMed

Li, Xiaolong; Ding, Congcong; Liao, Jiali; Du, Liang; Sun, Qun; Yang, Jijun; Yang, Yuanyou; Zhang, Dong; Tang, Jun; Liu, Ning

2017-03-01

The microbial reduction of U(VI) by Bacillus sp. dwc-2, isolated from soil in Southwest China, was explored using transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and X-ray absorption near edge spectroscopy (XANES). Our studies indicated that approximately 16.0% of U(VI) at an initial concentration of 100mg/L uranium nitrate could be reduced by Bacillus sp. dwc-2 at pH8.2 under anaerobic conditions at room temperature. Additionally, natural organic matter (NOM) played an important role in enhancing the bioreduction of U(VI) by Bacillus sp. dwc-2. XPS results demonstrated that the uranium presented mixed valence states (U(VI) and U(IV)) after bioreduction, which was subsequently confirmed by XANES. Furthermore, the TEM and high resolution transmission electron microscopy (HRTEM) analysis suggested that the reduced uranium was bioaccumulated mainly within the cell and as a crystalline structure on the cell wall. These observations implied that the reduction of uranium may have a significant effect on its fate in the soil environment in which these bacterial strains occur. Copyright © 2016. Published by Elsevier B.V.

In-situ evidence for uranium immobilization and remobilization

USGS Publications Warehouse

Senko, John M.; Istok, Jonathan D.; Suflita, Joseph M.; Krumholz, Lee R.

2002-01-01

The in-situ microbial reduction and immobilization of uranium was assessed as a means of preventing the migration of this element in the terrestrial subsurface. Uranium immobilization (putatively identified as reduction) and microbial respiratory activities were evaluated in the presence of exogenous electron donors and acceptors with field push−pull tests using wells installed in an anoxic aquifer contaminated with landfill leachate. Uranium(VI) amended at 1.5 μM was reduced to less than 1 nM in groundwater in less than 8 d during all field experiments. Amendments of 0.5 mM sulfate or 5 mM nitrate slowed U(VI) immobilization and allowed for the recovery of 10% and 54% of the injected element, respectively, as compared to 4% in the unamended treatment. Laboratory incubations confirmed the field tests and showed that the majority of the U(VI) immobilized was due to microbial reduction. In these tests, nitrate treatment (7.5 mM) inhibited U(VI) reduction, and nitrite was transiently produced. Further push−pull tests were performed in which either 1 or 5 mM nitrate was added with 1.0 μM U(VI) to sediments that already contained immobilized uranium. After an initial loss of the amendments, the concentration of soluble U(VI) increased and eventually exceeded the injected concentration, indicating that previously immobilized uranium was remobilized as nitrate was reduced. Laboratory experiments using heat-inactivated sediment slurries suggested that the intermediates of dissimilatory nitrate reduction (denitrification or dissimilatory nitrate reduction to ammonia), nitrite, nitrous oxide, and nitric oxide were all capable of oxidizing and mobilizing U(IV). These findings indicate that in-situ subsurface U(VI) immobilization can be expected to take place under anaerobic conditions, but the permanence of the approach can be impaired by disimilatory nitrate reduction intermediates that can mobilize previously reduced uranium.

Biomineralization of U(VI) phosphate promoted by microbially-mediated phytate hydrolysis in contaminated soils

NASA Astrophysics Data System (ADS)

Salome, Kathleen R.; Beazley, Melanie J.; Webb, Samuel M.; Sobecky, Patricia A.; Taillefert, Martial

2017-01-01

The bioreduction of uranium may immobilize a significant fraction of this toxic contaminant in reduced environments at circumneutral pH. In oxic and low pH environments, however, the low solubility of U(VI)-phosphate minerals also makes them good candidates for the immobilization of U(VI) in the solid phase. As inorganic phosphate is generally scarce in soils, the biomineralization of U(VI)-phosphate minerals via microbially-mediated organophosphate hydrolysis may represent the main immobilization process of uranium in these environments. In this study, contaminated sediments were incubated aerobically in two pH conditions to examine whether phytate, a naturally-occurring and abundant organophosphate in soils, could represent a potential phosphorous source to promote U(VI)-phosphate biomineralization by natural microbial communities. While phytate hydrolysis was not evident at pH 7.0, nearly complete hydrolysis was observed both with and without electron donor at pH 5.5, suggesting indigenous microorganisms express acidic phytases in these sediments. While the rate of hydrolysis of phytate generally increased in the presence of uranium, the net rate of inorganic phosphate production in solution was decreased and inositol phosphate intermediates were generated in contrast to similar incubations conducted without uranium. These findings suggest uranium stress enhanced the phytate-metabolism of the microbial community, while simultaneously inhibiting phosphatase production and/or activity by the indigenous population. Finally, phytate hydrolysis drastically decreased uranium solubility, likely due to formation of ternary sorption complexes, U(VI)-phytate precipitates, and U(VI)-phosphate minerals. Overall, the results of this study provide evidence for the ability of natural microbial communities to liberate phosphate from phytate in acidic sediments, possibly as a detoxification mechanism, and demonstrate the potential utility of phytate-promoted uranium immobilization in subsurface environments. These processes should be investigated in more detail with pure cultures isolated from these sediments.

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.

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

PubMed

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

2015-01-01

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

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

PubMed Central

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

2015-01-01

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

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.

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

The absorption spectra of the complexes of uranium (VI) with some β-diketones

USGS Publications Warehouse

Feinstein, H.I.

1956-01-01

The absorption spectra of the complexes of uranium (VI) with four β-dike tones were determined under various conditions of pH, concentration of uranium, and alcohol concentration. Under optimum conditions, the maximum molar absorptivity (31,200) is obtained using 2-furoyltrifluoroacetone. This compares with about 4,000 and 19,000 for the thiocyanate and dibenzoylmethane complexes, respectively.

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

DOE PAGES

Bader, Miriam; Müller, Katharina; Foerstendorf, Harald; ...

2016-12-27

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

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

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

Bader, Miriam; Müller, Katharina; Foerstendorf, Harald

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

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

PubMed

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

2017-04-05

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

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.

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.

Mechanism of uranium (VI) removal by two anaerobic bacterial communities.

PubMed

Martins, Mónica; Faleiro, Maria Leonor; da Costa, Ana M Rosa; Chaves, Sandra; Tenreiro, Rogério; Matos, António Pedro; Costa, Maria Clara

2010-12-15

The mechanism of uranium (VI) removal by two anaerobic bacterial consortia, recovered from an uncontaminated site (consortium A) and other from an uranium mine (consortium U), was investigated. The highest efficiency of U (VI) removal by both consortia (97%) occurred at room temperature and at pH 7.2. Furthermore, it was found that U (VI) removal by consortium A occurred by enzymatic reduction and bioaccumulation, while the enzymatic process was the only mechanism involved in metal removal by consortium U. FTIR analysis suggested that after U (VI) reduction, U (IV) could be bound to carboxyl, phosphate and amide groups of bacterial cells. Phylogenetic analysis of 16S rRNA showed that community A was mainly composed by bacteria closely related to Sporotalea genus and Rhodocyclaceae family, while community U was mainly composed by bacteria related to Clostridium genus and Rhodocyclaceae family. Copyright © 2010 Elsevier B.V. All rights reserved.

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

PubMed

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

2017-12-19

A new strategy combining iron-electrocoagulation and organic ligands (OGLs) cooperative chelation was proposed to screen and precipitate low concentrations (0-18.52 μmol/L) of uranium contaminant in aqueous solution. We hypothesized that OGLs with amino, hydroxyl, and carboxyl groups hydrophobically/hydrophilically would realize precuring of uranyl ion at pH < 3.0, and the following iron-electrocoagulation would achieve faster and more efficient uranium precipitation. Experimentally, the strategy demonstrated highly efficient uranium(VI) precipitation efficiency, especially with hydrophilic macromolecular OGLs. The uranium removal efficiency at optimized experimental condition reached 99.65%. The decrease of zeta potential and the lattice enwrapping between U-OGLs chelates and flocculation precursor were ascribed to the enhanced uranium precipitation activity. Uranium was precipitated as oxides of U(VI) or higher valences that were easily captured in aggregated micelles under low operation current potential. The actual uranium tailing wastewater was treated, and a satisfied uranium removal efficiency of 99.02% was discovered. After elution of the precipitated flocs, a concentrated uranium solution (up to 106.52 μmol/L) with very few other metallic impurities was obtained. Therefore, the proposed strategy could remove uranium and concentrate it concurrently. This work could provide new insights into the purification and recovery of uranium from aqueous solutions in a cost-effective and environmentally friendly process.

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

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

PubMed

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

2011-12-15

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

Sustained removal of uranium from contaminated groundwater following stimulation of dissimilatory metal reduction.

PubMed

N'Guessan, A Lucie; Vrionis, Helen A; Resch, Charles T; Long, Philip E; Lovley, Derek R

2008-04-15

Previous field studies on in situ bioremediation of uranium-contaminated groundwater in an aquifer in Rifle, Colorado identified two distinct phases following the addition of acetate to stimulate microbial respiration. In phase I, Geobacter species are the predominant organisms, Fe(III) is reduced, and microbial reduction of soluble U(VI) to insoluble U(IV) removes uranium from the groundwater. In phase II, Fe(III) is depleted, sulfate is reduced, and sulfate-reducing bacteria predominate. Long-term monitoring revealed an unexpected third phase during which U(VI) removal continues even after acetate additions are stopped. All three of these phases were successfully reproduced in flow-through sediment columns. When sediments from the third phase were heat sterilized, the capacity for U(VI) removal was lost. In the live sediments U(VI) removed from the groundwater was recovered as U(VI) in the sediments. This contrasts to the recovery of U(IV) in sediments resulting from the reduction of U(VI) to U(IV) during the Fe(III) reduction phase in acetate-amended sediments. Analysis of 16S rRNA gene sequences in the sediments in which U(VI) was being adsorbed indicated that members of the Firmicutes were the predominant organisms whereas no Firmicutes sequences were detected in background sediments which did not have the capacity to sorb U(VI), suggesting that the U(VI) adsorption might be due to the presence of these living organisms or at least their intact cell components. This unexpected enhanced adsorption of U(VI) onto sediments following the stimulation of microbial growth in the subsurface may potentially enhance the cost effectiveness of in situ uranium bioremediation.

Spectroscopic confirmation of uranium(VI)-carbonato adsorption complexes on hematite

USGS Publications Warehouse

Bargar, John R.; Reitmeyer, Rebecca; Davis, James A.

1999-01-01

Evaluating societal risks posed by uranium contamination from waste management facilities, mining sites, and heavy industry requires knowledge about uranium transport in groundwater, often the most significant pathway of exposure to humans. It has been proposed that uranium mobility in aquifers may be controlled by adsorption of U(VI)−carbonato complexes on oxide minerals. The existence of such complexes has not been demonstrated, and little is known about their compositions and reaction stoichiometries. We have used attenuated total reflectance Fourier transform infrared (ATR-FTIR) and extended X-ray absorption fine structure (EXAFS) spectroscopies to probe the existence, structures, and compositions of ≡FeOsurface−U(VI)−carbonato complexes on hematite throughout the pH range of uranyl uptake under conditions relevant to aquifers. U(VI)−carbonato complexes were found to be the predominant adsorbed U(VI) species at all pH values examined, a much wider pH range than previously postulated based on analogy to aqueous U(VI)−carbonato complexes, which are trace constituents at pH < 6. This result indicates the inadequacy of the common modeling assumption that the compositions and predominance of adsorbed species can be inferred from aqueous species. By extension, adsorbed carbonato complexes may be of major importance to the groundwater transport of similar actinide contaminants such as neptunium and plutonium.

Reduction of uranium by Desulfovibrio desulfuricans

USGS Publications Warehouse

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

1992-01-01

The possibility that sulfate-reducing microorganisms contribute to U(VI) reduction in sedimentary environments was investigated. U(VI) was reduced to U(IV) when washed cells of sulfate-grown Desulfovibrio desulfuricans were suspended in a bicarbonate buffer with lactate or H2 as the electron donor. There was no U(VI) reduction in the absence of an electron donor or when the cells were killed by heat prior to the incubation. The rates of U(VI) reduction were comparable to those in respiratory Fe(III)-reducing microorganisms. Azide or prior exposure of the cells to air did not affect the ability of D. desulfuricans to reduce U(VI). Attempts to grow D. desulfuricans with U(VI) as the electron acceptor were unsuccessful. U(VI) reduction resulted in the extracellular precipitation of the U(IV) mineral uraninite. The presence of sulfate had no effect on the rate of U(VI) reduction. Sulfate and U(VI) were reduced simultaneously. Enzymatic reduction of U(VI) by D. desulfuricans was much faster than nonenzymatic reduction of U(VI) by sulfide, even when cells of D. desulfuricans were added to provide a potential catalytic surface for the nonenzymatic reaction. The results indicate that enzymatic U(VI) reduction by sulfate-reducing microorganisms may be responsible for the accumulation of U(IV) in sulfidogenic environments. Furthermore, since the reduction of U(VI) to U(IV) precipitates uranium from solution, D. desulfuricans might be a useful organisms for recovering uranium from contaminated waters and waste streams.

Incorporation of Uranium into Hematite during Crystallization from Ferrihydrite

PubMed Central

2014-01-01

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

Uranium(VI) Binding Forms in Selected Human Body Fluids: Thermodynamic Calculations versus Spectroscopic Measurements.

PubMed

Osman, Alfatih A A; Geipel, Gerhard; Barkleit, Astrid; Bernhard, Gert

2015-02-16

Human exposure to uranium increasingly becomes a subject of interest in many scientific disciplines such as environmental medicine, toxicology, and radiation protection. Knowledge about uranium chemical binding forms(speciation) in human body fluids can be of great importance to understand not only its biokinetics but also its relevance in risk assessment and in designing decorporation therapy in the case of accidental overexposure. In this study, thermodynamic calculations of uranium speciation in relevant simulated and original body fluids were compared with spectroscopic data after ex-situ uranium addition. For the first time, experimental data on U(VI) speciation in body fluids (saliva, sweat, urine) was obtained by means of cryogenic time-resolved laser-induced fluorescence spectroscopy (cryo-TRLFS) at 153 K. By using the time dependency of fluorescence decay and the band positions of the emission spectra, various uranyl complexes were demonstrated in the studied samples. The variations of the body fluids in terms of chemical composition, pH, and ionic strength resulted in different binding forms of U(VI). The speciation of U(VI) in saliva and in urine was affected by the presence of bioorganic ligands, whereas in sweat, the distribution depends mainly on inorganic ligands. We also elucidated the role of biological buffers, i.e., phosphate (H(2)PO(4−)/HPO(4)(2−)) on U(VI) distribution, and the system Ca(2+)/UO(2)(2+)/PO(4)(3−) was discussed in detail in both saliva and urine. The theoretical speciation calculations of the main U(VI) species in the investigated body fluids were significantly consistent with the spectroscopic data. Laser fluorescence spectroscopy showed success and reliability for direct determination of U(VI) in such biological matrices with the possibility for further improvement.

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

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

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

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

2010-03-15

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

Biosorption and biomineralization of uranium(VI) by Saccharomyces cerevisiae-Crystal formation of chernikovite.

PubMed

Zheng, Xin-Yan; Wang, Xiao-Yu; Shen, Yang-Hao; Lu, Xia; Wang, Tie-Shan

2017-05-01

Biosorption of heavy metal elements including radionuclides by microorganisms is a promising and effective method for the remediation of the contaminated places. The responses of live Saccharomyces cerevisiae in the toxic uranium solutions during the biosorption process and the mechanism of uranium biomineralization by cells were investigated in the present study. A novel experimental phenomenon that uranium concentrations have negative correlation with pH values and positive correlation with phosphate concentrations in the supernatant was observed, indicating that hydrogen ions, phosphate ions and uranyl ions were involved in the chernikovite precipitation actively. During the biosorption process, live cells desorb deposited uranium within the equilibrium state of biosorption system was reached and the phosphorus concentration increased gradually in the supernatant. These metabolic detoxification behaviours could significantly alleviate uranium toxicity and protect the survival of the cells better in the environment. The results of microscopic and spectroscopic analysis demonstrated that the precipitate on the cell surface was a type of uranium-phosphate compound in the form of a scale-like substance, and S. cerevisiae could transform the uranium precipitate into crystalline state-tetragonal chernikovite [H 2 (UO 2 ) 2 (PO 4 ) 2 ·8H 2 O]. Copyright © 2017 Elsevier Ltd. All rights reserved.

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.

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

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

Katsenovich, Yelena; Gonzalez, Nathan; Moreno-Pastor, Carol

2012-07-01

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

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

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

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

B.D. Wood

2007-01-01

Subsurface contamination by metals and radionuclides represent some of the most challenging remediation problems confronting the Department of Energy (DOE) complex. In situ remediation of these contaminants by dissimilatory metal reducing bacteria (DMRB) has been proposed as a potential cost effective remediation strategy. The primary focus of this research is to determine the mechanisms by which the fluxes of electron acceptors, electron donors, and other species can be controlled to maximize the transfer of reductive equivalents to the aqueous and solid phases. The proposed research is unique in the NABIR portfolio in that it focuses on (i) the role ofmore » flow and transport in the initiation of biostimulation and the successful sequestration of metals and radionuclides [specifically U(VI)], (ii) the subsequent reductive capacity and stability of the reduced sediments produced by the biostimulation process, and (iii) the potential for altering the growth of biomass in the subsurface by the addition of specific metabolic uncoupling compounds. A scientifically-based understanding of these phenomena are critical to the ability to design successful bioremediation schemes. The laboratory research will employ Shewanella putrefaciens (CN32), a facultative DMRB that can use Fe(III) oxides as a terminal electron acceptor. Sediment-packed columns will be inoculated with this organism, and the reduction of U(VI) by the DMRB will be stimulated by the addition of a carbon and energy source in the presence of Fe(III). Separate column experiments will be conducted to independently examine: (1) the importance of the abiotic reduction of U(VI) by biogenic Fe(II); (2) the influence of the transport process on Fe(III) reduction and U(VI) immobilization, with emphasis on methods for controlling the fluxes of aqueous species to maximize uranium reduction; (3) the reductive capacity of biologically-reduced sediments (with respect to re-oxidation by convective fluxes of O2 and NO3-) and the long-term stability of immobilized uranium mineral phases after bioremediation processes are complete, and (4) the ability for metabolic uncoupling compounds to maintain microbial growth while limiting biomass production. The results of the laboratory experiments will be used to develop mathematical descriptive models for the coupled transport and reduction processes.« less

Electrochemical and Spectroscopic Evidence on the One-Electron Reduction of U(VI) to U(V) on Magnetite

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

Yuan, Ke; Ilton, Eugene S.; Antonio, Mark R.

2015-05-19

Reduction of U(VI) to U(VI) on mineral surfaces is often considered a one-step two-electron process. However, stabilized U(V), with no evidence of U(IV), found in recent studies Indicates U(VI) can undergo a one-electron reduction to U(V) without further progression to U(VI),. We investigated reduction pathways of uranium by reducing U(VI) electrochemically on a, magnetite electrode at,pH 3.4. Cyclic voltammetry confirms the one-electron reduction of U(VI) . Formation of nanosize uranium precipitates on the magnetite surface at reducing potentials and dissolution of the solids at oxidizing potentials are observed by in situ electrochemical atomic force microscopy. XPS, analysis Of the magnetitemore » electrodes polarized in uranium solutions at voltages - from -0.1 to -0.9 V (E-U(VI)/U(V)(0)= -0.135 V vs Ag/AgCl) show the presence of, only U(V) and U(VI). The sample with the highest U(V)/U(VI) ratio was prepared at -0.7 V, where the longest average U-O-axial distance of 2.05 + 0.01 A was evident in the same sample revealed by extended X-ray absorption fine structure analysis. The results demonstrate that the electrochemical reduction of U(VI) On magnetite only yields,U(V), even at a potential of -0.9 V, which favors the one-electron reduction mechanism, U(V) does not disproportionate but stabilizes on magnetite through precipitation Of mixed-valence state -U(V)/U(VI) solids.« less

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

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

Khalifa, M.E.

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

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

PubMed Central

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

2012-01-01

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

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.

In situ Bioreduction of Uranium (VI) in Groundwater and Sediments with Edible Oil as the Electron Donor

NASA Astrophysics Data System (ADS)

Wu, W.; Watson, D. B.; Mehlhorn, T.; Zhang, G.; Earles, J.; Lowe, K.; Phillips, J.; Boyanov, M.; Kemner, K. M.; Schadt, C. W.; Brooks, S. C.; Criddle, C.; Jardine, P.

2009-12-01

In situ bioremediation of a uranium-contaminated aquifer was conducted at the US DOE Environmental Remediation Sciences Program (ERSP) Integrated Field Research Challenge (IFRC) site, in Oak Ridge, TN. Edible oil was tested as a slow-release electron donor for microbially mediated U (VI) reduction. Uranium contaminated sediments from the site were used in laboratory microcosm tests to study the feasibility of using this electron donor under anaerobic, ambient temperature conditions. Parallel microcosms were established using ethanol as electron donor for comparison. The tests also examined the impact of sulfate concentrations on U (VI) reduction. The oil was degraded by indigenous microorganisms with acetate as a major product but at a much slower rate than ethanol. The rapid removal of U (VI) from the aqueous phase occurred concurrently with acetate production and sulfate reduction. Initial U(VI) concentration in the aqueous phase increased with increased sulfate concentration (1 vs. 5 mM), likely due to U(VI) desorption from the solid phase, but more U(VI) was reduced with higher initial sulfate level. Finally, the bioreaction in microcosms progressed to methanogenesis. Subsequently, a field test with the edible oil was conducted in a highly permeable gravelly layer (hydraulic conductivity 0.076 cm/sec). Groundwater at the site contained 5-6 μM U; 1.0-1.2 mM sulfate; 3-4 mM Ca; pH 6.8. Diluted emulsified oil (20% solution) was injected into three injection wells within 2 hrs. Geochemical analysis of site groundwater demonstrated the sequential reduction of nitrate, Mn, Fe(III) and sulfate. Transient accumulation of acetate was observed as an intermediate in the oil degradation. Reduction and removal of uranium from groundwater was observed in all wells connected to the injection wells after 2-4 weeks. Uranium concentrations in groundwater were reduced to below 0.126 μM (EPA drinking water standard), at some well locations. Rebound of U in groundwater was observed together with the rebound of sulfate concentrations as the oil was consumed. Uranium (VI) reduction to U (IV) in the microcosm and in situ field tests was confirmed by X-ray near-edge absorption spectroscopy analysis. Bacterial populations in microcosms and field samples were analyzed using 16S rRNA gene libraries and Geochip analysis.

Sorption characteristic of uranium(VI) ion onto K-feldspar.

PubMed

Gao, Xiaoqing; Bi, Mingliang; Shi, Keliang; Chai, Zhifang; Wu, Wangsuo

2017-10-01

The effect of pH, contact time, temperature, ionic strength and initial U(VI) concentration on U(VI) sorption onto K-feldspar was investigated using batch techniques. The sorption kinetics was evaluated and the activation energy was obtained based on the rate constants at different temperature. Graphical correlations of sorption isotherm models have been evaluated and applied for U(VI) uptake by K-feldspar. Various thermodynamic parameters, such as, Gibb's free energy, entropy and enthalpy of the on-going sorption process have been calculated and the possible sorption mechanism of U(VI) was deduced. The results are expected to help better understand the migration of uranium in the host materials of granite. Copyright © 2017 Elsevier Ltd. All rights reserved.

Visualizing different uranium oxidation states during the surface alteration of uraninite and uranium tetrachloride.

PubMed

Grossmann, Kay; Arnold, Thuro; Steudtner, Robin; Weiss, Stefan; Bernhard, Gert

2009-08-01

Low-temperature alteration reactions on uranium phases may lead to the mobilization of uranium and thereby poses a potential threat to humans living close to uranium-contaminated sites. In this study, the surface alteration of uraninite (UO(2)) and uranium tetrachloride (UCl(4)) in air atmosphere was studied by confocal laser scanning microscopy (CLSM) and laser-induced fluorescence spectroscopy using an excitation wavelength of 408 nm. It was found that within minutes the oxidation state on the surface of the uraninite and the uranium tetrachloride changed. During the surface alteration process U(IV) atoms on the uraninite and uranium tetrachloride surface became stepwise oxidized by a one-electron step at first to U(V) and then further to U(VI). These observed changes in the oxidation states of the uraninite surface were microscopically visualized and spectroscopically identified on the basis of their fluorescence emission signal. A fluorescence signal in the wavelength range of 415-475 nm was indicative for metastable uranium(V), and a fluorescence signal in the range of 480-560 nm was identified as uranium(VI). In addition, the oxidation process of tetravalent uranium in aqueous solution at pH 0.3 was visualized by CLSM and U(V) was fluorescence spectroscopically identified. The combination of microscopy and fluorescence spectroscopy provided a very convincing visualization of the brief presence of U(V) as a metastable reaction intermediate and of the simultaneous coexistence of the three states U(IV), U(V), and U(VI). These results have a significant importance for fundamental uranium redox chemistry and should contribute to a better understanding of the geochemical behavior of uranium in nature.

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

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

PubMed

Lysandrou, M; Pashalidis, I

2008-02-01

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

Electrochemical and spectroscopic evidence on the one-electron reduction of U(VI) to U(V) on magnetite

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

Yuan, Ke; Ilton, Eugene S.; Antonio, Mark R.

2015-05-19

Reduction of U(VI) to U(IV) on mineral surfaces has been considered as a one-step two electron process. However, stabilized U(V), with no evidence of U(IV), found in recent studies indicates U(VI) can undergo a one electron reduction to U(V) without further progression to U(IV). We investigated the mechanisms of uranium reduction by reducing U(VI) electrochemically on a magnetite electrode at pH 3.4 . The one electron reduction of U(VI) was first confirmed using the cyclic voltammetry method. Formation of nano-size uranium precipitates on the surface of magnetite at reducing potentials and dissolution of the solids at oxidizing potentials were observedmore » by in situ electrochemical AFM. XPS analysis of the magnetite electrodes polarized in uranium solutions at voltages from 0.1 ~ 0.9 V (vs. Ag/AgCl) showed the presence of only U(V) and U(VI). The highest amount of U(V) relative to U(VI) was prepared at 0.7 V, where the longest average U–Oaxial distance of 2.05 ± 0.01 Å was evident in the same sample revealed by EXAFS analysis. The results demonstrate that the electrochemical reduction of U(VI) on magnetite only yields U(V), even at a potential of 0.9 V, which favors the one-electron reduction mechanism. U(V) did not disproportionate but stabilized on magnetite through precipitation of mixed-valence state U(VI)/U(V) solids.« less

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

PubMed

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

2017-04-01

Natural uranium (U), which is present in our environment, exerts a chemical toxicity, particularly in bone where it accumulates. Generally, U is found at oxidation state +VI in its oxocationic form [Formula: see text] in aqueous media. Although U(VI) has been reported to induce cell death in osteoblasts, the cells in charge of bone formation, the molecular mechanism for U(VI) effects in these cells remains poorly understood. The objective of our study was to explore U(VI) effect at doses ranging from 5 to 600 µM, on mineralization and autophagy induction in the UMR-106 model osteoblastic cell line and to determine U(VI) speciation after cellular uptake. Our results indicate that U(VI) affects mineralization function, even at subtoxic concentrations (<100 µM). The combination of thermodynamic modeling of U with EXAFS data in the culture medium and in the cells clearly indicates the biotransformation of U(VI) carbonate species into a meta-autunite phase upon uptake by osteoblasts. We next assessed U(VI) effect at 100 and 300 µM on autophagy, a survival process triggered by various stresses such as metal exposure. We observed that U(VI) was able to rapidly activate autophagy but an inhibition of the autophagic flux was observed after 24 h. Thus, our results indicate that U(VI) perturbs osteoblastic functions by reducing mineralization capacity. Our study identifies for the first time U(VI) in the form of meta-autunite in mammalian cells. In addition, U(VI)-mediated inhibition of the autophagic flux may be one of the underlying mechanisms leading to the decreased mineralization and the toxicity observed in osteoblasts.

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

Role of U(VI) Reduction by Geobacter species

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

Lovely, Derrick

2008-12-23

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

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

Sorption and bioreduction of hexavalent uranium at a military facility by the Chesapeake Bay.

PubMed

Dong, Wenming; Xie, Guibo; Miller, Todd R; Franklin, Mark P; Oxenberg, Tanya Palmateer; Bouwer, Edward J; Ball, William P; Halden, Rolf U

2006-07-01

Directly adjacent to the Chesapeake Bay lies the Aberdeen Proving Ground, a U.S. Army facility where testing of armor-piercing ammunitions has resulted in the deposition of >70,000 kg of depleted uranium (DU) to local soils and sediments. Results of previous environmental monitoring suggested limited mobilization in the impact area and no transport of DU into the nation's largest estuary. To determine if physical and biological reactions constitute mechanisms involved in limiting contaminant transport, the sorption and biotransformation behavior of the radionuclide was studied using geochemical modeling and laboratory microcosms (500 ppb U(VI) initially). An immediate decline in dissolved U(VI) concentrations was observed under both sterile and non-sterile conditions due to rapid association of U(VI) with natural organic matter in the sediment. Reduction of U(VI) to U(IV) occurred only in non-sterile microcosms. In the non-sterile samples, intrinsic bioreduction of uranium involved bacteria of the order Clostridiales and was only moderately enhanced by the addition of acetate (41% vs. 56% in 121 days). Overall, this study demonstrates that the migration of depleted uranium from the APG site into the Chesapeake Bay may be limited by a combination of processes that include rapid sorption of U(VI) species to natural organic matter, followed by slow, intrinsic bioreduction to U(IV).

The effect of calcium on aqueous uranium(VI) speciation and adsorption to ferrihydrite and quartz

USGS Publications Warehouse

Fox, P.M.; Davis, J.A.; Zachara, J.M.

2006-01-01

Recent studies of uranium(VI) geochemistry have focused on the potentially important role of the aqueous species, CaUO2 (CO3)32- and Ca2 UO2(CO3)30(aq), on inhibition of microbial reduction and uranium(VI) aqueous speciation in contaminated groundwater. However, to our knowledge, there have been no direct studies of the effects of these species on U(VI) adsorption by mineral phases. The sorption of U(VI) on quartz and ferrihydrite was investigated in NaNO3 solutions equilibrated with either ambient air (430 ppm CO2) or 2% CO2 in the presence of 0, 1.8, or 8.9 mM Ca2+. Under conditions where the Ca2UO2(CO3)30 (aq) species predominates U(VI) aqueous speciation, the presence of Ca in solution lowered U(VI) adsorption on quartz from 77% in the absence of Ca to 42% and 10% at Ca concentrations of 1.8 and 8.9 mM, respectively. U(VI) adsorption to ferrihydrite decreased from 83% in the absence of Ca to 57% in the presence of 1.8 mM Ca. Surface complexation model predictions that included the formation constant for aqueous Ca2UO2(CO3)30(aq) accurately simulated the effect of Ca2+ on U(VI) sorption onto quartz and ferrihydrite within the thermodynamic uncertainty of the stability constant value. This study confirms that Ca2+ can have a significant impact on the aqueous speciation of U(VI), and consequently, on the sorption and mobility of U(VI) in aquifers. ?? 2005 Elsevier Inc. All rights reserved.

Réduction des nitrates et de l'uranium par les bactéries indigènes

NASA Astrophysics Data System (ADS)

Abdelouas, Abdesselam; Lutze, Werner; Nuttall, Eric

1998-07-01

A bioremediation concept has been developed to clean up ground water contaminated with nitrate (1200 mg·L -1) and uranium (0.25 mg·L -1). We studied the Tuba City mill tailings site, Arizona, USA. Indigenous bacteria capable of catalyzing the reduction of NO 3- and U(VI) were identified in the ground water and in the host rock, the Navajo sandstone. After complete reduction of O 2 and NO 3- within one week, U(VI) was reduced and precipitated as uraninite. Final uranium concentrations < 15 μg·L -1 were reached after a few weeks at 24 °C. Iron sulfide also precipitated as a result of reduction of Fe(III) on the sand surface and sulfate in the ground water. U(VI) was not reduced by sulfide. It was found that enzymatic reduction of U(VI) is faster than abiotic reduction under the conditions given by the composition of the ground water.

Thermal expansion of the nuclear fuel-sodium reaction product Na3(U0.84(2),Na0.16(2))O4 - Structural mechanism and comparison with related sodium-metal ternary oxides

NASA Astrophysics Data System (ADS)

Illy, Marie-Claire; Smith, Anna L.; Wallez, Gilles; Raison, Philippe E.; Caciuffo, Roberto; Konings, Rudy J. M.

2017-07-01

Na3.16(2)UV,VI0.84(2)O4 is obtained from the reaction of sodium with uranium dioxide under oxygen potential conditions typical of a sodium-cooled fast nuclear reactor. In the event of a breach of the steel cladding, it would be the dominant reaction product forming at the rim of the mixed (U,Pu)O2 fuel pellets. High-temperature X-ray diffraction measurements show that a distortion of the uranium environment in Na3.16(2)UV,VI0.84(2)O4 results in a strongly anisotropic thermal expansion. A comparison with several related sodium metallates Nan-2Mn+On-1 - including Na3SbO4 and Na3TaO4, whose crystal structures are reported for the first time - has allowed us to assess the role played in the lattice expansion by the Mn+ cation radius and the Na/M ratio. On this basis, the thermomechanical behavior of the title compound is discussed, along with those of several related double oxides of sodium and actinide elements, surrogate elements, or fission products.

Different biosorption mechanisms of Uranium(VI) by live and heat-killed Saccharomyces cerevisiae under environmentally relevant conditions.

PubMed

Wang, Tieshan; Zheng, Xinyan; Wang, Xiaoyu; Lu, Xia; Shen, Yanghao

2017-02-01

Uranium adsorption mechanisms of live and heat-killed Saccharomyces cerevisiae in different pH values and biomass concentrations were studied under environmentally relevant conditions. Compared with live cells, the adsorption capacity of heat-killed cells is almost one order of magnitude higher in low biomass concentration and highly acidic pH conditions. To explore the mesoscopic surface interactions between uranium and cells, the characteristic of uranium deposition was investigated by SEM-EDX, XPS and FTIR. Biosorption process of live cells was considered to be metabolism-dependent. Under stimulation by uranyl ions, live cells could gradually release phosphorus and reduce uranium from U(VI) to U(IV) to alleviate uranium toxicity. The uranyl-phosphate complexes were formed in scale-like shapes on cell surface. The metabolic detoxification mechanisms such as reduction and "self-protection" are of significance to the migration of radionuclides. In the metabolism-independent biosorption process of heat-killed cells: the cells cytomembrane was damaged by autoclaving which led to the free diffusion of phosphorous from intracellular, and the rough surface and nano-holes indicated that the dead cells provided larger contact area to precipitate U(VI) as spherical nano-particles. The high biosorption capacity of heat-killed cells makes it become a suitable biological adsorbent for uranium removal. Copyright © 2016 Elsevier Ltd. All rights reserved.

Rare-earth element fractionation in uranium ore and its U(VI) alteration minerals

DOE PAGES

Balboni, Enrica; Spano, T; Cook, N; ...

2017-10-20

We developed a cation exchange chromatography method employing sulfonated polysterene cation resin (DOWEX AG50-X8) in order to separate rare-earth elements (REEs) from uranium-rich materials. The chemical separation scheme is designed to reduce matrix effects and consequently yield enhanced ionization efficiencies for concentration determinations of REEs without significant fractionation using solution mode-inductively coupled plasma mass spectrometry (ICP-MS) analysis. This method was then applied to determine REE abundances in four uraninite (ideally UO 2) samples and their associated U(VI) alteration minerals. In three of the samples analyzed, the concentration of REEs for primary uraninite are higher than those for their corresponding secondarymore » uranium alteration phases. The results for U(VI) alteration minerals of two samples indicate enrichment of the light REEs (LREEs) over the heavy REEs (HREEs). This differential mobilization is attributed to differences in the mineralogical composition of the U(VI) alteration. There is a lack of fractionation of the LREEs in the uraninite alteration rind that is composed of U(VI) minerals containing Ca 2+ as the interlayer cation (uranophane and bequerelite); contrarily, U(VI) alteration minerals containing K + and Pb 2+ as interlayer cations (fourmarierite, dumontite) indicate fractionation (enrichment) of the LREEs. Our results have implications for nuclear forensic analyses since a comparison is reported between the REE abundances for the CUP-2 (processed uranium ore) certified reference material and previously determined values for uranium ore concentrate (UOC) produced from the same U deposit (Blind River/Elliott Lake, Canada). UOCs represent the most common form of interdicted nuclear material and consequently is material frequently targeted for forensic analysis. The comparison reveals similar chondrite normalized REE signatures but variable absolute abundances. Based on the results reported here, the latter may be attributed to the differing REE abundances between primary ore and associated alteration phases, and/or is related to varying fabrication processes adopted during production of UOC.« less

Rare-earth element fractionation in uranium ore and its U(VI) alteration minerals

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

Balboni, Enrica; Spano, T; Cook, N

We developed a cation exchange chromatography method employing sulfonated polysterene cation resin (DOWEX AG50-X8) in order to separate rare-earth elements (REEs) from uranium-rich materials. The chemical separation scheme is designed to reduce matrix effects and consequently yield enhanced ionization efficiencies for concentration determinations of REEs without significant fractionation using solution mode-inductively coupled plasma mass spectrometry (ICP-MS) analysis. This method was then applied to determine REE abundances in four uraninite (ideally UO 2) samples and their associated U(VI) alteration minerals. In three of the samples analyzed, the concentration of REEs for primary uraninite are higher than those for their corresponding secondarymore » uranium alteration phases. The results for U(VI) alteration minerals of two samples indicate enrichment of the light REEs (LREEs) over the heavy REEs (HREEs). This differential mobilization is attributed to differences in the mineralogical composition of the U(VI) alteration. There is a lack of fractionation of the LREEs in the uraninite alteration rind that is composed of U(VI) minerals containing Ca 2+ as the interlayer cation (uranophane and bequerelite); contrarily, U(VI) alteration minerals containing K + and Pb 2+ as interlayer cations (fourmarierite, dumontite) indicate fractionation (enrichment) of the LREEs. Our results have implications for nuclear forensic analyses since a comparison is reported between the REE abundances for the CUP-2 (processed uranium ore) certified reference material and previously determined values for uranium ore concentrate (UOC) produced from the same U deposit (Blind River/Elliott Lake, Canada). UOCs represent the most common form of interdicted nuclear material and consequently is material frequently targeted for forensic analysis. The comparison reveals similar chondrite normalized REE signatures but variable absolute abundances. Based on the results reported here, the latter may be attributed to the differing REE abundances between primary ore and associated alteration phases, and/or is related to varying fabrication processes adopted during production of UOC.« less

Simultaneous reduction of arsenic(V) and uranium(VI) by mackinawite: role of uranyl arsenate precipitate formation.

PubMed

Troyer, Lyndsay D; Tang, Yuanzhi; Borch, Thomas

2014-12-16

Uranium (U) and arsenic (As) often occur together naturally and, as a result, can be co-contaminants at sites of uranium mining and processing, yet few studies have examined the simultaneous redox dynamics of U and As. This study examines the influence of arsenate (As(V)) on the reduction of uranyl (U(VI)) by the redox-active mineral mackinawite (FeS). As(V) was added to systems containing 47 or 470 μM U(VI) at concentrations ranging from 0 to 640 μM. In the absence of As(V), U was completely removed from solution and fully reduced to nano-uraninite (nano-UO2). While the addition of As(V) did not reduce U uptake, at As(V) concentrations above 320 μM, the reduction of U(VI) was limited due to the formation of a trögerite-like uranyl arsenate precipitate. The presence of U also significantly inhibited As(V) reduction. While less U(VI) reduction to nano-UO2 may take place in systems with high As(V) concentrations, formation of trögerite-like mineral phases may be an acceptable reclamation end point due to their high stability under oxic conditions.

Bis(hydroxylamino)triazines: High Selectivity and Hydrolytic Stability of Hydroxylamine-Based Ligands for Uranyl Compared to Vanadium(V) and Iron(III).

PubMed

Hadjithoma, Sofia; Papanikolaou, Michael G; Leontidis, Epameinondas; Kabanos, Themistoklis A; Keramidas, Anastasios D

2018-06-08

The development of ligands with high selectivity and affinity for uranium is critical in the extraction of uranium from human body, radioactive waste, and seawater. A scientific challenge is the improvement of the selectivity of chelators for uranium over other heavy metals, including iron and vanadium. Flat ligands with hard donor atoms that satisfy the geometric and electronic requirements of the U VI O 2 2+ exhibit high selectivity for the uranyl moiety. The bis(hydroxylamino)(triazine) ligand, 2,6-bis[hydroxy(methyl)amino]-4-morpholino-1,3,5-triazine (H 2 bihyat), a strong binder for hard metal ions (Fe III , Ti IV , V V , and Mo VI ), reacted with [U VI O 2 (NO 3 ) 2 (H 2 O) 2 ]·4H 2 O in aqueous solution and resulted in the isolation of the complexes [U VI O 2 (bihyat)(H 2 O)], [U VI O 2 (bihyat) 2 ] 2- , and {[U VI O 2 (bihyat)(μ-OH)]} 2 2- . These three species are in equilibrium in aqueous solution, and their abundance varies with the concentration of H 2 bihyat and the pH. Reaction of H 2 bihyat with [U VI O 2 (NO 3 ) 2 (H 2 O) 2 ]·4H 2 O in CH 3 CN gave the trinuclear complex [U VI 3 O 6 (bihyat) 2 (μ-bihyat) 2 ] 2- , which is the major species in organic solvents. The dynamics between the U VI O 2 2+ and the free ligand H 2 bihyat in aqueous and dimethyl sulfoxide solutions; the metal binding ability of the H 2 bihyat over pyridine-2,6-dicarboxylic acid (H 2 dipic) or glutarimidedioxime for U VI O 2 2+ , and the selectivity of the H 2 bihyat to bind U VI O 2 2+ in comparison to V V O 4 3- and Fe III in either U VI O 2 2+ /V V O 4 3- or U VI O 2 2+ /Fe III solutions were examined by NMR and UV-vis spectroscopies. The results revealed that H 2 bihyat is a superior ligand for U VI O 2 2+ with high selectivity compared to Fe III and V V O 4 3- , which increases at higher pHs. Thus, this type of ligand might find applications in the extraction of uranium from the sea and its removal from the environment and the human body.

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

PubMed

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

2009-11-15

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

Uranium(VI) Scavenging by Amorphous Iron Phosphate Encrusting Sphaerotilus natans Filaments.

PubMed

Seder-Colomina, Marina; Morin, Guillaume; Brest, Jessica; Ona-Nguema, Georges; Gordien, Nilka; Pernelle, Jean-Jacques; Banerjee, Dipanjan; Mathon, Olivier; Esposito, Giovanni; van Hullebusch, Eric D

2015-12-15

U(VI) sorption to iron oxyhydroxides, precipitation of phosphate minerals, as well as biosorption on bacterial biomass are among the most reported processes able to scavenge U(VI) under oxidizing conditions. Although phosphates significantly influence bacterially mediated as well as iron oxyhydroxide mediated scavenging of uranium, the sorption or coprecipitation of U(VI) with poorly crystalline nanosized iron phosphates has been scarcely documented, especially in the presence of microorganisms. Here we show that dissolved U(VI) can be bound to amorphous iron phosphate during their deposition on Sphaerotilus natans filamentous bacteria. Uranium LIII-edge EXAFS analysis reveals that the adsorbed uranyl ions share an equatorial oxygen atom with a phosphate tetrahedron of the amorphous iron phosphate, with a characteristic U-P distance of 3.6 Å. In addition, the uranyl ions are connected to FeO6 octahedra with U-Fe distances at ~3.4 Å and at ~4.0 Å. The shortest U-Fe distance corresponds to a bidentate edge-sharing complex often reported for uranyl adsorption onto iron oxyhydroxides, whereas the longest U-Fe and U-P distances can be interpreted as a bidentate corner-sharing complex, in which two adjacent equatorial oxygen atoms are shared with the vertices of a FeO6 octahedron and of a phosphate tetrahedron. Furthermore, based on these sorption reactions, we demonstrate the ability of an attached S. natans biofilm to remove uranium from solution without any filtration step.

Model-based Analysis of Mixed Uranium(VI) Reduction by Biotic and Abiotic Pathways During in Situ Bioremediation

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

Zhao, Jiao; Scheibe, Timothy D.; Mahadevan, Radhakrishnan

2013-10-24

Uranium bioremediation has emerged as a potential strategy of cleanup of radionuclear contamination worldwide. An integrated geochemical & microbial community model is a promising approach to predict and provide insights into the bioremediation of a complicated natural subsurface. In this study, an integrated column-scale model of uranium bioremediation was developed, taking into account long-term interactions between biotic and abiotic processes. It is also combined with a comprehensive thermodynamic analysis to track the fate and cycling of biogenic species. As compared with other bioremediation models, the model increases the resolution of the connection of microbial community to geochemistry and establishes directmore » quantitative correlation between overall community evolution and geochemical variation, thereby accurately predicting the community dynamics under different sedimentary conditions. The thermodynamic analysis examined a recently identified homogeneous reduction of U(VI) by Fe(II) under dynamic sedimentary conditions across time and space. It shows that the biogenic Fe(II) from Geobacter metabolism can be removed rapidly by the biogenic sulphide from sulfate reducer metabolism, hence constituting one of the reasons that make the abiotic U(VI) reduction thermodynamically infeasible in the subsurface. Further analysis indicates that much higher influent concentrations of both Fe(II) and U(VI) than normal are required to for abiotic U(VI) reduction to be thermodynamically feasible, suggesting that the abiotic reduction cannot be an alternative to the biotic reduction in the remediation of uranium contaminated groundwater.« less

Uranium Redox Transformations after U(VI) Coprecipitation with Magnetite Nanoparticles.

PubMed

Pidchenko, Ivan; Kvashnina, Kristina O; Yokosawa, Tadahiro; Finck, Nicolas; Bahl, Sebastian; Schild, Dieter; Polly, Robert; Bohnert, Elke; Rossberg, André; Göttlicher, Jörg; Dardenne, Kathy; Rothe, Jörg; Schäfer, Thorsten; Geckeis, Horst; Vitova, Tonya

2017-02-21

Uranium redox states and speciation in magnetite nanoparticles coprecipitated with U(VI) for uranium loadings varying from 1000 to 10 000 ppm are investigated by X-ray absorption spectroscopy (XAS). It is demonstrated that the U M 4 high energy resolution X-ray absorption near edge structure (HR-XANES) method is capable to clearly characterize U(IV), U(V), and U(VI) existing simultaneously in the same sample. The contributions of the three different uranium redox states are quantified with the iterative transformation factor analysis (ITFA) method. U L 3 XAS and transmission electron microscopy (TEM) reveal that initially sorbed U(VI) species recrystallize to nonstoichiometric UO 2+x nanoparticles within 147 days when stored under anoxic conditions. These U(IV) species oxidize again when exposed to air. U M 4 HR-XANES data demonstrate strong contribution of U(V) at day 10 and that U(V) remains stable over 142 days under ambient conditions as shown for magnetite nanoparticles containing 1000 ppm U. U L 3 XAS indicates that this U(V) species is protected from oxidation likely incorporated into octahedral magnetite sites. XAS results are supported by density functional theory (DFT) calculations. Further characterization of the samples include powder X-ray diffraction (pXRD), scanning electron microscopy (SEM) and Fe 2p X-ray photoelectron spectroscopy (XPS).

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

PubMed

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

2008-09-01

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

Biosorption characteristics of Uranium (VI) from aqueous solution by pollen pini.

PubMed

Wang, Feihong; Tan, Lichao; Liu, Qi; Li, Rumin; Li, Zhanshuang; Zhang, Hongsen; Hu, Songxia; Liu, Lianhe; Wang, Jun

2015-12-01

Uranium biosorption from aqueous solutions by pollen pini (Pinus massoniana pollen) was studied in a bath system. The biosorbent was characterized by Fourier-transform infrared spectroscopy and scanning electron microscope. The influences of pH, contact time and initial uranium concentration at room temperature were investigated and the experimental curves were obtained. The pollen pini exhibited the highest uranium sorption capacity at pH 5.0 after 2 h contact. At pH 2.5 pollen pini also exhibited a good uranium loading capacity (>15%). Therefore biosorption characteristics of uranium from aqueous solution onto pollen pini were examined at pH 2.5 as well. The kinetics followed a pseudo-second-order rate equation and adsorption process was well fitted with the Freundlich isotherm at both pH. The adsorption of uranium by the biosorbent was confirmed by energy dispersive spectroscopy. The present study suggested that pollen pini could be a suitable biosorbent for biosorption uranium (VI) from aqueous solution in a fast, low cost and convenient approach. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

PubMed

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

2017-12-01

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

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

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

Luo, Wensui; Zhou, Jizhong; Wu, Weimin

2007-01-01

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

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

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

Long, Philip E.; Williams, Kenneth H.; Davis, James A.

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

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

NASA Astrophysics Data System (ADS)

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

2015-02-01

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

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

PubMed

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

2009-10-01

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

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

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

Bao, Yizhong; Wang, Dan; Li, Zhiming

2013-05-15

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

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

EPA Science Inventory

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

Bioreduction of U(VI) and stability of immobilized uranium under suboxic conditions.

PubMed

Hu, Nan; Ding, De-xin; Li, Shi-mi; Tan, Xiang; Li, Guang-yue; Wang, Yong-dong; Xu, Fei

2016-04-01

In order to study the bioreduction of U(VI) and stability of immobilized uranium under suboxic conditions, microcosm were amended with ethanol, lactate and glucose, and incubated under suboxic conditions. During the incubation, total dissolved U in amended microcosms decreased from 0.95 mg/L to 0.03 mg/L. Pyrosequencing results showed that, the proportion of anaerobic microorganisms capable of reducing U(VI) under suboxic conditions was small compared with that under anoxic conditions; the proportion of aerobic and facultative anaerobic microorganisms capable of consuming the dissolved oxygen was large; and some of the facultative anaerobic microorganisms could reduce U(VI). These results indicated that different microbial communities were responsible for the bioreduction of U(VI) under suboxic and anoxic conditions. After the electron donors were exhausted, total dissolved U in the amended microcosms remained unchanged, while the U(VI)/U(IV) ratio in the solid phase of sediments increased obviously. This implied that the performance of bioreduction of the U(VI) can be maintained under suboxic condition. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

PubMed

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

2016-04-01

Reoxidation and mobilization of previously reduced and immobilized uranium by dissolved-phase oxidants poses a significant challenge for remediating uranium-contaminated groundwater. Preferential oxidation of reduced sulfur-bearing species, as opposed to reduced uranium-bearing species, has been demonstrated to limit the mobility of uranium at the laboratory scale yet field-scale investigations are lacking. In this study, the mobility of uranium in the presence of nitrate oxidant was investigated in a shallow groundwater system after establishing conditions conducive to uranium reduction and the formation of reduced sulfur-bearing species. A series of three injections of groundwater (200 L) containing U(VI) (5 μM) and amended with ethanol (40 mM) and sulfate (20 mM) were conducted in ten test wells in order to stimulate microbial-mediated reduction of uranium and the formation of reduced sulfur-bearing species. Simultaneous push-pull tests were then conducted in triplicate well clusters to investigate the mobility of U(VI) under three conditions: 1) high nitrate (120 mM), 2) high nitrate (120 mM) with ethanol (30 mM), and 3) low nitrate (2 mM) with ethanol (30 mM). Dilution-adjusted breakthrough curves of ethanol, nitrate, nitrite, sulfate, and U(VI) suggested that nitrate reduction was predominantly coupled to the oxidation of reduced-sulfur bearing species, as opposed to the reoxidation of U(IV), under all three conditions for the duration of the 36-day tests. The amount of sulfate, but not U(VI), recovered during the push-pull tests was substantially more than injected, relative to bromide tracer, under all three conditions and further suggested that reduced sulfur-bearing species were preferentially oxidized under nitrate-reducing conditions. However, some reoxidation of U(IV) was observed under nitrate-reducing conditions and in the absence of detectable nitrate and/or nitrite. This suggested that reduced sulfur-bearing species may not be fully effective at limiting the mobility of uranium in the presence of dissolved and/or solid-phase oxidants. The results of this field study confirmed those of previous laboratory studies which suggested that reoxidation of uranium under nitrate-reducing conditions can be substantially limited by preferential oxidation of reduced sulfur-bearing species. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

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

DOE PAGES

Paradis, Charles J.; Jagadamma, Sindhu; Watson, David B.; ...

2016-02-11

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

Sorption of uranium (VI) on homoionic sodium smectite experimental study and surface complexation modeling.

PubMed

Korichi, Smain; Bensmaili, Aicha

2009-09-30

This paper is an extension of a previous paper where the natural and purified clay in the homoionic Na form were physico-chemically characterized (doi:10.1016/j.clay.2008.04.014). In this study, the adsorption behavior of U (VI) on a purified Na-smectite suspension is studied using batch adsorption experiments and surface complexation modeling (double layer model). The sorption of uranium was investigated as a function of pH, uranium concentration, solid to liquid ratio, effect of natural organic matter (NOM) and NaNO(3) background electrolyte concentration. Using the MINTEQA2 program, the speciation of uranium was calculated as a function of pH and uranium concentration. Model predicted U (VI) aqueous speciation suggests that important aqueous species in the [U (VI)]=1mg/L and pH range 3-7 including UO(2)(2+), UO(2)OH(+), and (UO(2))(3)(OH)(5)(+). The concentration of UO(2)(2+) decreased and that of (UO(2))(3)(OH)(5)(+) increased with increasing pH. The potentiometric titration values and uptake of uranium in the sodium smectite suspension were simulated by FITEQL 4.0 program using a two sites model, which is composed of silicate and aluminum reaction sites. We compare the acidity constants values obtained by potentiometric titration from the purified sodium smectite with those obtained from single oxides (quartz and alpha-alumina), taking into account the surface heterogeneity and the complex nature of natural colloids. We investigate the uranium sorption onto purified Na-smectite assuming low, intermediate and high edge site surfaces which are estimated from specific surface area percentage. The sorption data is interpreted and modeled as a function of edge site surfaces. A relationship between uranium sorption and total site concentration was confirmed and explained through variation in estimated edge site surface value. The modeling study shows that, the convergence during DLM modeling is related to the best estimation of the edge site surface from the N(2)-BET specific surface area, SSA(BET) (thus, total edge site concentrations). The specific surface area should be at least 80-100m(2)/g for smectite clays in order to reach convergence during the modeling. The range of 10-20% SSA(BET) was used to estimate the values of edge site surfaces that led to the convergence during modeling. An agreement between the experimental data and model predictions is found reasonable when 15% SSA(BET) was used as edge site surface. However, the predicted U (VI) adsorption underestimated and overestimated the experimental observations at the 10 and 20% of the measured SSA(BET), respectively. The dependence of uranium sorption modeling results on specific surface area and edge site surface is useful to describe and predict U (VI) retardation as a function of chemical conditions in the field-scale reactive transport simulations. Therefore this approach can be used in the environmental quality assessment.

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.

Post Audit of a Field Scale Reactive Transport Model of Uranium at a Former Mill Site

NASA Astrophysics Data System (ADS)

Curtis, G. P.

2015-12-01

Reactive transport of hexavalent uranium (U(VI)) in a shallow alluvial aquifer at a former uranium mill tailings site near Naturita CO has been monitored for nearly 30 years by the US Department of Energy and the US Geological Survey. Groundwater at the site has high concentrations of chloride, alkalinity and U(VI) as a owing to ore processing at the site from 1941 to 1974. We previously calibrated a multicomponent reactive transport model to data collected at the site from 1986 to 2001. A two dimensional nonreactive transport model used a uniform hydraulic conductivity which was estimated from observed chloride concentrations and tritium helium age dates. A reactive transport model for the 2km long site was developed by including an equilibrium U(VI) surface complexation model calibrated to laboratory data and calcite equilibrium. The calibrated model reproduced both nonreactive tracers as well as the observed U(VI), pH and alkalinity. Forward simulations for the period 2002-2015 conducted with the calibrated model predict significantly faster natural attenuation of U(VI) concentrations than has been observed by the persistent high U(VI) concentrations at the site. Alternative modeling approaches are being evaluating evaluated using recent data to determine if the persistence can be explained by multirate mass transfer models developed from experimental observations at the column scale(~0.2m), the laboratory tank scale (~2m), the field tracer test scale (~1-4m) or geophysical observation scale (~1-5m). Results of this comparison should provide insight into the persistence of U(VI) plumes and improved management options.

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

PubMed

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

2012-04-01

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

Synthesis and structural features of U VI and V IV chelate complexes with (hhmmbH)Cl·H 2O [hhmmb = {3-hydroxyl-5-(hydroxymethyl)-2-methylpyridine-4-yl-methylene}benzohydrazide], a new Schiff base ligand derived from vitamin B6

NASA Astrophysics Data System (ADS)

Back, Davi Fernando; Ballin, Marco Aurélio; de Oliveira, Gelson Manzoni

2009-10-01

The Schiff base ligand {3-hydroxyl-5-(hydroxymethyl)-2-methylpyridine-4-yl-methylene}benzohydrazide hydrochloride monohydrated {(hhmmbH)Cl·H 2O} ( 1) was prepared by reaction of pyridoxine hydrochloride with benzoic acid hydrazide. The reaction of 1 with [VO(acac) 2] and triethylamine yields the neutral vanadium IV complex [VO 2(hhmmb)]·Py ( 2), with a distorted quadratic pyramidal configuration. The Schiff base 1 reacts also with UO 2(NO 3) 2·6H 2O and triethylamine under deprotonation giving the uranium VI cationic complexes [UO 2(hhmmb)(H 2O)Cl] + ( 3) and [UO 2(hhmmb)(CH 3OH)Cl] + ( 4), both showing the classical pentagonal bipyrimidal geometry of UO22+ complexes. The structural features of all compounds are discussed.

PRECIPITATION OF ZIRCONIUM AND FLUORIDE IONS FROM SOLUTIONS

DOEpatents

Newby, B.J.

1963-06-11

A process is given for removing zirconium and fluorine ions from aqueous solutions also containing uranium(VI). The precipitation is carried out with sodium formate, and the uranium remains in solution. (AEC)

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.

Effect of Reaction Pathway on the Extent and Mechanism of Uranium(VI) Immobilization with Calcium and Phosphate

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

Mehta, Vrajesh S.; Maillot, Fabien; Wang, Zheming

Phosphate addition to subsurface environments contaminated with uranium can be used as an in situ remediation approach. Batch experiments were conducted to evaluate the dependence of the extent and mechanism of uranium uptake on the pathway for reaction with calcium phosphates. At pH 4.0 and 6.0 uranium uptake occurred via autunite (Ca(UO2)(PO4)3) precipitation irrespective of the starting forms of calcium and phosphate. At pH 7.5, the uptake mechanism depended on the nature of the calcium and phosphate. When dissolved uranium, calcium, and phosphate were added simultaneously, uranium was structurally incorporated into a newly formed amorphous calcium phosphate solid. Adsorption wasmore » the dominant removal mechanism for uranium contacted with pre-formed amorphous calcium phosphate solids,. When U(VI) was added to a suspension containing amorphous calcium phosphate solids as well as dissolved calcium and phosphate, then removal occurred through precipitation (57±4 %) of autunite and adsorption (43±4 %) onto calcium phosphate. The solid phase speciation of the uranium was determined using X-ray absorption spectroscopy and laser induced fluorescence spectroscopy. Dissolved uranium, calcium, and phosphate concentrations with saturation index calculations helped identify removal mechanisms and determine thermodynamically favorable solid phases.« less

Reactivity of Uranium and Ferrous Iron with Natural Iron Oxyhydroxides.

PubMed

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

2015-09-01

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

XANES and EXAFS investigation of uranium incorporation on nZVI in the presence of phosphate.

PubMed

Qiu, Muqing; Wang, Min; Zhao, Qingzhou; Hu, Baowei; Zhu, Yuling

2018-06-01

Effect of phosphate on the reduction of U(VI) on nZVI was determined by batch, XPS, XANES and EXAFS techniques. The batch experiments showed that nZVI was quite effective for the removal of uranium under the anaerobic conditions, whereas the addition of phosphate enhanced uranium removal over wide pH range. At low pH, the reduction of U(VI) to U(IV) significantly decreased with increasing phosphate concentration by XPS and XANES analysis. According to EXAFS analysis, the occurrence of UU shell at 10 mg/L phosphate and pH 4.0 was similar to that of U (IV) O 2 (s), whereas the UP and UFe shells were observed at 50 mg/L phosphate, revealing that reductive co-precipitate (U (IV) O 2 (s)) and precipitation of uranyl-phosphate were observed at low and high phosphate, respectively. The findings are crucial for the prediction of the effect of phosphate on the speciation and binding of uranium by nZVI at low pH, which is significant in controlling the mobility of U(VI) in contaminated environments. Copyright © 2018 Elsevier Ltd. All rights reserved.

Incorporation of oxidized uranium into Fe (hydr)oxides during Fe(II) catalyzed remineralization

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

Nico, Peter S.; Stewart, Brandy D.; Fendorf, Scott

2009-07-01

The form of solid phase U after Fe(II) induced anaerobic remineralization of ferrihydrite in the presence of aqueous and absorbed U(VI) was investigated under both abiotic batch and biotic flow conditions. Experiments were conducted with synthetic ground waters containing 0.168 mM U(VI), 3.8 mM carbonate, and 3.0 mM Ca{sup 2+}. In spite of the high solubility of U(VI) under these conditions, appreciable removal of U(VI) from solution was observed in both the abiotic and biotic systems. The majority of the removed U was determined to be substituted as oxidized U (U(VI) or U(V)) into the octahedral position of the goethitemore » and magnetite formed during ferrihydrite remineralization. It is estimated that between 3% and 6% of octahedral Fe(III) centers in the new Fe minerals were occupied by U(VI). This site specific substitution is distinct from the non-specific U co-precipitation processes in which uranyl compounds, e.g. uranyl hydroxide or carbonate, are entrapped with newly formed Fe oxides. The prevalence of site specific U incorporation under both abiotic and biotic conditions and the fact that the produced solids were shown to be resistant to both extraction (30 mM KHCO{sub 3}) and oxidation (air for 5 days) suggest the potential importance of sequestration in Fe oxides as a stable and immobile form of U in the environment.« less

Study on kinetics of adsorption of humic acid modified by ferric chloride on U(VI)

NASA Astrophysics Data System (ADS)

Zhang, Y. Y.; Lv, J. W.; Song, Y.; Dong, X. J.; Fang, Q.

2017-11-01

In order to reveal the adsorption mechanism of the ferric chloride modified humic acid on uranium, the influence of pH value and contact time of adsorption on uranium was studied through a series of batch experiments. Meanwhile, the adsorption kinetics was analyzed with pseudo-first order kinetic model and pseudo-second order kinetic model. The results show that adsorption is affected by the pH value of the solution and by contract time, and the best condition for adsorption on uranium is at pH=5 and the adsorption equilibrium time is about 80 min. Kinetics of HA-Fe adsorption on uranium accords with pseudo-second order kinetic model. The adsorption is mainly chemical adsorption, and complexes were produced by the reaction between uranium ions and the functional groups on the surface of HA-Fe, which can provide reference for further study of humic acid effecting on the migration of U(VI) in soil.

Uranium Reduction by Fe(II) in the Presence of Montmorillonite and Nontronite.

PubMed

Tsarev, Sergey; Waite, T David; Collins, Richard N

2016-08-02

Uranium(VI) interactions with three smectites (one montmorillonite and two nontronites - NAu1 and NAu2) were examined with 0, 1, and 2 mM aqueous concentrations of Fe(II) over the pH range of 3-9.5 in a background electrolyte of 100 mM NaCl and 1 mM CaCl2 in equilibration with 400 ppmv CO2(g) ([U(VI)] = 4 μM and 0.5 g smectite/L). In the absence of Fe(II), no differences were observed in the U(VI) sorption curves for the three clay minerals. In the presence of 1 or 2 mM Fe(II), under anoxic conditions, U(VI) uptake by the smectites changed slightly between ∼pH 3 and 6; however, uranium uptake increased significantly above ∼pH 6 and was proportional to the concentration of Fe(II) added to the system, particularly at pH values >8. The uptake of Fe(II) showed a sharp edge starting from ∼pH 6.5 with 95%-100% uptake occurring at pH values >7.5, with no difference observed between the iron-rich nontronites and montmorillonite. After 3 days of reaction at pH 7.6 (i.e., above the Fe(II) "sorption" edge), U(VI) was transformed to a mixture of U(IV) and U(VI) sorption complexes, and after 14 days of reaction, 100% of the U was found to be reduced to U(IV) in the form of nanocrystalline uraninite. In contrast, U remained as sorbed species until 14 days of reaction at pH 6.5. Ferrihydrite (NAu1), lepidocrocite, and magnetite (NAu2) were detected as secondary mineralization products upon reaction of the nontronites with Fe(II) but appeared to have no effect on the partitioning or speciation of uranium.

Microbial reduction of U(VI) under alkaline conditions: implications for radioactive waste geodisposal.

PubMed

Williamson, Adam J; Morris, Katherine; Law, Gareth T W; Rizoulis, Athanasios; Charnock, John M; Lloyd, Jonathan R

2014-11-18

Although there is consensus that microorganisms significantly influence uranium speciation and mobility in the subsurface under circumneutral conditions, microbiologically mediated U(VI) redox cycling under alkaline conditions relevant to the geological disposal of cementitious intermediate level radioactive waste, remains unexplored. Here, we describe microcosm experiments that investigate the biogeochemical fate of U(VI) at pH 10-10.5, using sediments from a legacy lime working site, stimulated with an added electron donor, and incubated in the presence and absence of added Fe(III) as ferrihydrite. In systems without added Fe(III), partial U(VI) reduction occurred, forming a U(IV)-bearing non-uraninite phase which underwent reoxidation in the presence of air (O2) and to some extent nitrate. By contrast, in the presence of added Fe(III), U(VI) was first removed from solution by sorption to the Fe(III) mineral, followed by bioreduction and (bio)magnetite formation coupled to formation of a complex U(IV)-bearing phase with uraninite present, which also underwent air (O2) and partial nitrate reoxidation. 16S rRNA gene pyrosequencing showed that Gram-positive bacteria affiliated with the Firmicutes and Bacteroidetes dominated in the post-reduction sediments. These data provide the first insights into uranium biogeochemistry at high pH and have significant implications for the long-term fate of uranium in geological disposal in both engineered barrier systems and the alkaline, chemically disturbed geosphere.

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

PubMed

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

2015-11-01

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

Optimization of a bioremediation system of soluble uranium based on the biostimulation of an indigenous bacterial community.

PubMed

Maleke, Maleke; Williams, Peter; Castillo, Julio; Botes, Elsabe; Ojo, Abidemi; DeFlaun, Mary; van Heerden, Esta

2015-06-01

High concentrations of uranium(VI) in the Witwatersrand Basin, South Africa from mining leachate is a serious environmental concern. Treatment systems are often ineffective. Therefore, optimization of a bioremediation system that facilitates the bioreduction of U(VI) based on biostimulation of indigenous bacterial communities can be a viable alternative. Tolerance of the indigenous bacteria to high concentrations of U and the amount of citric acid required for U removal was optimized. Two bioreactor studies which showed effective U(VI) removal more than 99 % from low (0.0037 mg L(-1)) and high (10 mg L(-1)) concentrations of U to below the limit allowed by South African National Standards for drinking water (0.0015 mg L(-1)). The second bioreactor was able to successfully adapt even with increasing levels of U(VI) feed water up to 10 mg L(-1), provided that enough electron donor was available. Molecular biology analyses identified Desulfovibrio sp. and Geobacter sp. among known species, which are known to reduce U(VI). The mineralogical analysis determined that part of the uranium precipitated intracellularly, which meant that the remaining U(VI) was precipitated as U(IV) oxides and TEM-EDS also confirmed this analysis. This was predicted with the geochemical model from the chemical data, which demonstrated that the treated drainage was supersaturated with respect to uraninite > U4O9 > U3O8 > UO2(am). Therefore, the tolerance of the indigenous bacterial community could be optimized to remediate up to 10 mg L(-1), and the system can thus be upscaled and employed for remediation of U(VI) impacted sites.

Sequestration of U(VI) from Acidic, Alkaline, and High Ionic-Strength Aqueous Media by Functionalized Magnetic Mesoporous Silica Nanoparticles: Capacity and Binding Mechanisms

EPA Science Inventory

Uranium (VI) exhibits little adsorption onto sediment minerals in acidic, alkaline or high ionic-strength aqueous media that often occur in U mining or contaminated sites, which makes U(VI) very mobile and difficult to sequester. In this work, magnetic mesoporous silica nanoparti...

Total electron acceptor loading and composition affect hexavalent uranium reduction and microbial community structure in a membrane biofilm reactor.

PubMed

Ontiveros-Valencia, Aura; Zhou, Chen; Ilhan, Zehra Esra; de Saint Cyr, Louis Cornette; Krajmalnik-Brown, Rosa; Rittmann, Bruce E

2017-11-15

Molecular microbiology tools (i.e., 16S rDNA gene sequencing) were employed to elucidate changes in the microbial community structure according to the total electron acceptor loading (controlled by influent flow rate and/or medium composition) in a H 2 -based membrane biofilm reactor evaluated for removal of hexavalent uranium. Once nitrate, sulfate, and dissolved oxygen were replaced by U(VI) and bicarbonate and the total acceptor loading was lowered, slow-growing bacteria capable of reducing U(VI) to U(IV) dominated in the biofilm community: Replacing denitrifying bacteria Rhodocyclales and Burkholderiales were spore-producing Clostridiales and Natranaerobiales. Though potentially competing for electrons with U(VI) reducers, homo-acetogens helped attain steady U(VI) reduction, while methanogenesis inhibited U(VI) reduction. U(VI) reduction was reinstated through suppression of methanogenesis by addition of bromoethanesulfonate or by competition from SRB when sulfate was re-introduced. Predictive metagenome analysis further points out community changes in response to alterations in the electron-acceptor loading: Sporulation and homo-acetogenesis were critical factors for strengthening stable microbial U(VI) reduction. This study documents that sporulation was important to long-term U(VI) reduction, whether or not microorganisms that carry out U(VI) reduction mediated by cytochrome c 3 , such as SRB and ferric-iron-reducers, were inhibited. Copyright © 2017 Elsevier Ltd. All rights reserved.

The effect of humic acid on uranyl sorption onto bentonite at trace uranium levels.

PubMed

Ivanov, Peter; Griffiths, Tamara; Bryan, Nick D; Bozhikov, Gospodin; Dmitriev, Serguei

2012-11-01

The effect of humic acid (HA) on U(VI) sorption on bentonite was studied in batch experiments at room temperature and ambient atmosphere at a (237)U(VI) concentration of 8.4 × 10(-11) M and HA concentration of 100 mg L(-1). The distribution of U(VI) between the liquid and solid phases was studied as a function of pH and ionic strength both in the absence and presence of HA. It was shown that the uranyl sorption on bentonite is strongly dependent on pH and the presence of humics, and the effect of the addition order was negligible. In the absence of HA an enhancement in the uptake with increasing pH was observed and a sharp sorption edge was found to take place between pH 3.2 and 4.2. The presence of HA slightly increases uranium(VI) sorption at low pH and curtails it at moderate pH, compared to the absence of HA. In the basic pH range for both the presence and absence of HA the sorption of uranium is significantly reduced, which could be attributed to the formation of soluble uranyl carbonate complexes. The influence of ionic strength on U(VI) and HA uptake by bentonite were investigated in the range of 0.01-1.0 M, and while there was an enhancement in the sorption of humic acid with increasing ionic strength, no significant effect of the ionic strength on the U(VI) sorption was observed in both the absence and presence of HA.

Modulation of Medium pH by Caulobacter crescentus Facilitates Recovery from Uranium-Induced Growth Arrest

PubMed Central

Park, Dan M.

2014-01-01

The oxidized form of uranium [U(VI)] predominates in oxic environments and poses a major threat to ecosystems. Due to its ability to mineralize U(VI), the oligotroph Caulobacter crescentus is an attractive candidate for U(VI) bioremediation. However, the physiological basis for U(VI) tolerance is unclear. Here we demonstrated that U(VI) caused a temporary growth arrest in C. crescentus and three other bacterial species, although the duration of growth arrest was significantly shorter for C. crescentus. During the majority of the growth arrest period, cell morphology was unaltered and DNA replication initiation was inhibited. However, during the transition from growth arrest to exponential phase, cells with shorter stalks were observed, suggesting a decoupling between stalk development and the cell cycle. Upon recovery from growth arrest, C. crescentus proliferated with a growth rate comparable to that of a control without U(VI), although a fraction of these cells appeared filamentous with multiple replication start sites. Normal cell morphology was restored by the end of exponential phase. Cells did not accumulate U(VI) resistance mutations during the prolonged growth arrest, but rather, a reduction in U(VI) toxicity occurred concomitantly with an increase in medium pH. Together, these data suggest that C. crescentus recovers from U(VI)-induced growth arrest by reducing U(VI) toxicity through pH modulation. Our finding represents a unique U(VI) detoxification strategy and provides insight into how microbes cope with U(VI) under nongrowing conditions, a metabolic state that is prevalent in natural environments. PMID:25002429

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.

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

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

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

The apparent enthalpy and entropy of the complexation of uranium (VI) and vanadium (V) with amidoxime ligands grafted onto polyethylene fiber was determined using time series measurements of adsorption capacities in natural seawater at three different temperatures. The complexation of uranium was highly endothermic, while the complexation of vanadium showed minimal temperature sensitivity. Amidoxime-based polymeric adsorbents exhibit significantly increased uranium adsorption capacities and selectivity in warmer waters.

In situ ligand synthesis with the UO{sub 2}{sup 2+} cation under hydrothermal conditions

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

Frisch, Mark; Cahill, Christopher L.; Geophysical Laboratory, Carnegie Institution of Washington, Washington, DC

A novel uranium (VI) coordination polymer, (UO{sub 2}){sub 2}(C{sub 2}O{sub 4})(C{sub 5}H{sub 6}NO{sub 3}){sub 2} (1), has been prepared under the hydrothermal reaction of uranium nitrate hexahydrate and L-pyroglutamic acid. Compound 1 (monoclinic, C2/c, a=22.541(6) A, b=5.7428(15) A, c=15.815(4) A, {beta}=119.112(4){sup o}, Z=4, R{sub 1}=0.0237, wR{sub 2}=0.0367) consists of uranium pentagonal bipyramids linked via L-pyroglutamate and oxalate anions to form an overall two-dimensional (2D) structure. With the absence of oxalic acid within the starting materials, the oxalate anions are hypothesized to form in situ whereby decarboxylation of L-pyroglutamic acid occurs followed by coupling of CO{sub 2} to form the oxalatemore » linkages as observed in the crystal structure. Addition of copper (II) to this system appears to promote oxalate formation in that synthetic moolooite (Cu(C{sub 2}O{sub 4}).nH{sub 2}O; 0{<=}n{<=}1) and a known uranyl oxalate [(UO{sub 2}){sub 2}(C{sub 2}O{sub 4})(OH){sub 2}(H{sub 2}O){sub 2}.H{sub 2}O], co-crystallize in significant quantity. Compound 1 exhibits the characteristic uranyl emission spectrum upon either direct uranyl excitation or ligand excitation, the latter of which shows an increase in relative intensity. This subsequent increase in the intensity indicates an energy transfer from the ligand to the uranyl cations thus illustrating an example of the antenna effect in the solid state. - Graphical abstract: A novel homometallic coordination polymer (UO{sub 2}){sub 2}(C{sub 2}O{sub 4})(C{sub 5}H{sub 6}NO{sub 3}){sub 2}, in the uranium-L-pyroglutamic acid system has been synthesized under hydrothermal conditions. The title compound consists of uranium pentagonal bipyramids bridged through both L-pyroglutamate and oxalate linkages to produce a 3D crystal structure. The oxalate anions are theorized to result from decarboxylation of L-pyroglutamic acid followed by subsequent coupling of CO{sub 2}.« less

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.

Understanding Uranium Behavior in a Reduced Aquifer

NASA Astrophysics Data System (ADS)

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

2012-12-01

Uranium contamination of groundwater is a concern at several US Department of Energy sites, such Old Rifle, CO. Uranium transport in the environment is mainly controlled by its oxidation state, since oxidized U(VI) is relatively mobile, whereas U(IV) is relatively insoluble. Bio-remediation of contaminated aquifers aims at immobilizing uranium in a reduced form. Previous laboratory and field studies have shown that adding electron donor (lactate, acetate, ethanol) to groundwater stimulates the activity of metal- and sulfate-reducing bacteria, which promotes U(VI) reduction in contaminated aquifers. However, obtaining information on chemical and physical forms of U, Fe and S species for sediments biostimulated in the field, as well as kinetic parameters such as U(VI) reduction rate, is challenging due to the low concentration of uranium in the aquifers (typically < 10 ppm) and the expense of collecting large number of cores. An in-situ technique has been developed for studying uranium, iron and sulfur reduction dynamics during such bioremediation episodes. This technique uses in-well columns to obtain direct access to chemical and physical forms of U(IV) produced in the aquifer, evolving microbial communities, and trace and major ion groundwater constituents. While several studies have explored bioreduction of uranium under sulfate-reducing conditions, less attention has been paid to the initial iron-reducing phase, noted as being of particular importance to uranium removal. The aim of this work was to assess the formation of U(IV) during the early stages of a bio-remediation experiment at the Old Rifle site, CO, from early iron-reducing conditions to the transition to sulfate-reducing conditions. Several in-well chromatographic columns packed with sediment were deployed and were sampled at different days after the start of bio-reduction. X-ray absorption spectroscopy and X-ray microscopy were used to obtain information on Fe, S and U speciation and distribution. Chemical extractions of the reduced sediments have also been performed, to determine the rate of Fe(II) and U(IV) accumulation.

Sorption behavior of uranium(VI) on a biotite mineral

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

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

1995-12-31

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

Using High Performance Computing to Understand Roles of Labile and Nonlabile U(VI) on Hanford 300 Area Plume Longevity

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

Lichtner, Peter C.; Hammond, Glenn E.

Evolution of a hexavalent uranium [U(VI)] plume at the Hanford 300 Area bordering the Columbia River is investigated to evaluate the roles of labile and nonlabile forms of U(VI) on the longevity of the plume. A high fidelity, three-dimensional, field-scale, reactive flow and transport model is used to represent the system. Richards equation coupled to multicomponent reactive transport equations are solved for times up to 100 years taking into account rapid fluctuations in the Columbia River stage resulting in pulse releases of U(VI) into the river. The peta-scale computer code PFLOTRAN developed under a DOE SciDAC-2 project is employed inmore » the simulations and executed on ORNL's Cray XT5 supercomputer Jaguar. Labile U(VI) is represented in the model through surface complexation reactions and its nonlabile form through dissolution of metatorbernite used as a surrogate mineral. Initial conditions are constructed corresponding to the U(VI) plume already in place to avoid uncertainties associated with the lack of historical data for the waste stream. The cumulative U(VI) flux into the river is compared for cases of equilibrium and multirate sorption models and for no sorption. The sensitivity of the U(VI) flux into the river on the initial plume configuration is investigated. The presence of nonlabile U(VI) was found to be essential in explaining the longevity of the U(VI) plume and the prolonged high U(VI) concentrations at the site exceeding the EPA MCL for uranium.« less

Direct observation of pure pentavalent uranium in U2O5 thin films by high resolution photoemission spectroscopy.

PubMed

Gouder, T; Eloirdi, R; Caciuffo, R

2018-05-29

Thin films of the elusive intermediate uranium oxide U 2 O 5 have been prepared by exposing UO 3 precursor multilayers to atomic hydrogen. Electron photoemission spectra measured about the uranium 4f core-level doublet contain sharp satellites separated by 7.9(1) eV from the 4f main lines, whilst satellites characteristics of the U(IV) and U(VI) oxidation states, expected respectively at 6.9(1) and 9.7(1) eV from the main 4f lines, are absent. This shows that uranium ions in the films are in a pure pentavalent oxidation state, in contrast to previous investigations of binary oxides claiming that U(V) occurs only as a metastable intermediate state coexisting with U(IV) and U(VI) species. The ratio between the 5f valence band and 4f core-level uranium photoemission intensities decreases by about 50% from UO 2 to U 2 O 5 , which is consistent with the 5f  2 (UO 2 ) and 5f  1 (U 2 O 5 ) electronic configurations of the initial state. Our studies conclusively establish the stability of uranium pentoxide.

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.

Decrease of U(VI) Immobilization Capability of the Facultative Anaerobic Strain Paenibacillus sp. JG-TB8 under Anoxic Conditions Due to Strongly Reduced Phosphatase Activity

PubMed Central

Reitz, Thomas; Rossberg, Andre; Barkleit, Astrid; Selenska-Pobell, Sonja; Merroun, Mohamed L.

2014-01-01

Interactions of a facultative anaerobic bacterial isolate named Paenibacillus sp. JG-TB8 with U(VI) were studied under oxic and anoxic conditions in order to assess the influence of the oxygen-dependent cell metabolism on microbial uranium mobilization and immobilization. We demonstrated that aerobically and anaerobically grown cells of Paenibacillus sp. JG-TB8 accumulate uranium from aqueous solutions under acidic conditions (pH 2 to 6), under oxic and anoxic conditions. A combination of spectroscopic and microscopic methods revealed that the speciation of U(VI) associated with the cells of the strain depend on the pH as well as on the aeration conditions. At pH 2 and pH 3, uranium was exclusively bound by organic phosphate groups provided by cellular components, independently on the aeration conditions. At higher pH values, a part (pH 4.5) or the total amount (pH 6) of the dissolved uranium was precipitated under oxic conditions in a meta-autunite-like uranyl phosphate mineral phase without supplying an additional organic phosphate substrate. In contrast to that, under anoxic conditions no mineral formation was observed at pH 4.5 and pH 6, which was clearly assigned to decreased orthophosphate release by the cells. This in turn was caused by a suppression of the indigenous phosphatase activity of the strain. The results demonstrate that changes in the metabolism of facultative anaerobic microorganisms caused by the presence or absence of oxygen can decisively influence U(VI) biomineralization. PMID:25157416

Characteristics of uranium biosorption from aqueous solutions on fungus Pleurotus ostreatus.

PubMed

Zhao, Changsong; Liu, Jun; Tu, Hong; Li, Feize; Li, Xiyang; Yang, Jijun; Liao, Jiali; Yang, Yuanyou; Liu, Ning; Sun, Qun

2016-12-01

Uranium(VI) biosorption from aqueous solutions was investigated in batch studies by using fungus Pleurotus ostreatus biomass. The optimal biosorption conditions were examined by investigating the reaction time, biomass dosage, pH, temperature, and uranium initial concentration. The interaction between fungus biomass and uranium was confirmed using Fourier transformed infrared (FT-IR), scanning electronic microscopy energy dispersive X-ray (SEM-EDX), and X-ray photoelectron spectroscopy (XPS) analysis. Results exhibited that the maximum biosorption capacity of uranium on P. ostreatus was 19.95 ± 1.17 mg/g at pH 4.0. Carboxylic, amine, as well as hydroxyl groups were involved in uranium biosorption according to FT-IR analysis. The pseudo-second-order model properly evaluated the U(VI) biosorption on fungus P. ostreatus biomass. The Langmuir equation provided better fitting in comparison with Freundlich isotherm models. The obtained thermodynamic parameters suggested that biosorption is feasible, endothermic, and spontaneous. SEM-EDX and XPS were additionally conducted to comprehend the biosorption process that could be described as a complex process involving several mechanisms of physical adsorption, chemisorptions, and ion exchange. Results obtained from this work indicated that fungus P. ostreatus biomass can be used as potential biosorbent to eliminate uranium or other radionuclides from aqueous solutions.

In situ ligand synthesis with the UO22+ cation under hydrothermal conditions

NASA Astrophysics Data System (ADS)

Frisch, Mark; Cahill, Christopher L.

2007-09-01

A novel uranium (VI) coordination polymer, (UO 2) 2(C 2O 4)(C 5H 6NO 3) 2 ( 1), has been prepared under the hydrothermal reaction of uranium nitrate hexahydrate and L-pyroglutamic acid. Compound 1 (monoclinic, C2/ c, a=22.541(6) Å, b=5.7428(15) Å, c=15.815(4) Å, β=119.112(4)°, Z=4, R1=0.0237, w R2=0.0367) consists of uranium pentagonal bipyramids linked via L-pyroglutamate and oxalate anions to form an overall two-dimensional (2D) structure. With the absence of oxalic acid within the starting materials, the oxalate anions are hypothesized to form in situ whereby decarboxylation of L-pyroglutamic acid occurs followed by coupling of CO 2 to form the oxalate linkages as observed in the crystal structure. Addition of copper (II) to this system appears to promote oxalate formation in that synthetic moolooite (Cu(C 2O 4)· nH 2O; 0⩽ n⩽1) and a known uranyl oxalate [(UO 2) 2(C 2O 4)(OH) 2(H 2O) 2·H 2O], co-crystallize in significant quantity. Compound 1 exhibits the characteristic uranyl emission spectrum upon either direct uranyl excitation or ligand excitation, the latter of which shows an increase in relative intensity. This subsequent increase in the intensity indicates an energy transfer from the ligand to the uranyl cations thus illustrating an example of the antenna effect in the solid state.

Predicting equilibrium uranium isotope fractionation in crystals and solution

NASA Astrophysics Data System (ADS)

Schauble, E. A.

2015-12-01

Despite the rapidly growing interest in using 238U/235U measurements as a proxy for changes in oxygen abundance in surface and near-surface environments, the present theoretical understanding of uranium isotope fractionation is limited to a few simple gas-phase molecules and analogues of dissolved species (e.g., 1,2,3). Understanding uranium isotope fractionation behavior in more complicated species, such as crystals and adsorption complexes, will help in the design and interpretation of experiments and field studies, and may suggest other uses for 38U/235U measurements. In this study, a recently developed first-principles method for estimating the nuclear volume component of field shift fractionation in crystals and complex molecular species (4) is combined with mass-dependent fractionation theory to predict equilibrium 38U/235U fractionations in aqueous and crystalline uranium compounds, including uraninite (UO2). The nuclear field shift effect, caused by the interaction of electrons with the finite volume of the positive charge distribution in uranium nuclei, is estimated using Density Functional Theory and the Projector Augmented Wave method (DFT-PAW). Tests against relativistic electronic structure calculations and Mössbauer isomer shift data indicate that the DFT-PAW method is reasonably accurate, while being much better suited to models of complex and crystalline species. Initial results confirm previous predictions that the nuclear volume effect overwhelms mass depdendent fractionation in U(VI)-U(IV) exchange reactions, leading to higher 238U/235U in U(IV) species (i.e., for UO2 xtal vs. UO22+aq, ln αNV ≈ +1.8‰ , ln αMD ≈ -0.8‰, ln αTotal ≈ +1.0‰ at 25ºC). UO2 and U(H2O)94+, are within ~0.4‰ of each other, while U(VI) species appear to be more variable. This suggests that speciation is likely to significantly affect natural uranium isotope fractionations, in addition to oxidation state. Tentatively, it appears that uranyl-type (UO22+-bearing) structures will tend to have higher 238U/235U than uranate-type structures that lack strong U=O bonds. References: 1. Bigeleisen (1996) JACS 118:3676; 2. Schauble (2006) Eos 87:V21B-0570; 3. Abe et al. (2008) J Chem Phys 128:144309, 129:164309, & Abe et al. (2010) J Chem Phys 133:044309; 4. Schauble (2013) PNAS 110:17714.

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

Chemistry of uranium in aluminophosphate glasses

NASA Technical Reports Server (NTRS)

Schreiber, H. D.; Balazs, G. B.; Williams, B. J.

1982-01-01

The U(VI)-U(V)-U(IV) redox equilibria are investigated in two sodium aluminophosphate base compositions at a variety of melt temperatures, imposed oxygen fugacities, and uranium contents. Results show that the higher redox states of uranium are quite soluble in the phosphate glasses, although U(IV) readily precipitates from the melts as UO2. In addition, comparisons of the uranium redox equilibria established in phosphate melts versus those in silicate melts shows that the coordination sites of the individual uranium species are generally the same in both solvent systems although they differ in detail.

Uranium redox transition pathways in acetate-amended sediments

USGS Publications Warehouse

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

2013-01-01

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

Diffusive parameters of tritiated water and uranium in chalk

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

Descostes, M.; UMR 8587 CEA, Universite d'Evry, CNRS,; Pili, E.

2012-07-15

The Cretaceous Chalk of North-western Europe exhibits a double porosity (matrix and fracture) providing pathways for both slow and rapid flow of water. The present study aims at understanding and predicting the contaminant transfer properties through a significant section of this formation, with a particular emphasis on diffusion. This requires to study the nature of porosity and to perform diffusion experiments in representative samples using uranium and tritiated water (HTO), respectively taken as a reactive tracer and an inert one. The diffusive parameters, i.e. the accessible porosity and the effective diffusion coefficient were determined. Additional information was obtained with mercurymore » porosimetry, gravimetric water content, textural and mineralogical characterization. The diffusion tests performed with HTO appear to be the best method to measure the total accessible porosity in any type of porous media, especially those having large pore size distributions. Our study demonstrates that classical gravimetric water content measurements are not sensitive to the reduction in pore size as opposed to HTO diffusion tests because capillary water is not extracted by conventional gravimetric method but can still be probed by diffusion experiments. We found effective diffusion coefficients D{sub e}(U(VI)) near 4 x 10{sup -10} m{sup 2}s{sup -1}). The slower migration of U(VI) compared to HTO indicates sorption, with R{sub d}(U(VI)) from 100 to 360 mL g{sup -1}. These values are one order of magnitude larger than other determinations of the U(VI) sorption coefficient because only the matrix porosity is concerned here. The migration of U(VI) in chalk is only limited by sorption on ancillary Fe-Pb-bearing minerals. Transport of HTO and U(VI) is independent of the porosity distribution. Uranium diffusion in the chalk matrix porosity is fast enough to allow the total invasion of the pore space within characteristic time scales of the order of 1000 years. This results in a partitioning of uranium velocities in fracture flow and matrix flow proportionally to the respective fracture and matrix porosities. (authors)« less

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

PubMed Central

Yung, Mimi C.

2014-01-01

Caulobacter crescentus is known to tolerate high levels of uranium [U(VI)], but its detoxification mechanism is poorly understood. Here we show that C. crescentus is able to facilitate U(VI) biomineralization through the formation of U-Pi precipitates via its native alkaline phosphatase activity. The U-Pi precipitates, deposited on the cell surface in the form of meta-autunite structures, have a lower U/Pi ratio than do chemically produced precipitates. The enzyme that is responsible for the phosphatase activity and thus the biomineralization process is identified as PhoY, a periplasmic alkaline phosphatase with broad substrate specificity. Furthermore, PhoY is shown to confer a survival advantage on C. crescentus toward U(VI) under both growth and nongrowth conditions. Results obtained in this study thus highlight U(VI) biomineralization as a resistance mechanism in microbes, which not only improves our understanding of bacterium-mineral interactions but also aids in defining potential ecological niches for metal-resistant bacteria. PMID:24878600

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

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

Yung, M C; Jiao, Y

2014-07-22

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

The measurement of U(VI) and Np(IV) mass transfer in a single stage centrifugal contactor

NASA Astrophysics Data System (ADS)

May, I.; Birkett, E. J.; Denniss, I. S.; Gaubert, E. T.; Jobson, M.

2000-07-01

BNFL currently operates two reprocessing plants for the conversion of spent nuclear fuel into uranium and plutonium products for fabrication into uranium oxide and mixed uranium and plutonium oxide (MOX) fuels. To safeguard the future commercial viability of this process, BNFL is developing novel single cycle flowsheets that can be operated in conjunction with intensified centrifugal contactors.

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.

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

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

Sepulveda, Paola; Katsenovich, Yelena; Lagos, Leonel

2013-07-01

Precipitating autunite minerals by polyphosphate injection was identified as a feasible remediation strategy for sequestering uranium in contaminated groundwater and soil in situ at the Hanford Site. Autunite stability under vadose and saturated zone environmental conditions can help to determine the long-term effectiveness of this remediation strategy. The Arthrobacter bacteria are one of the most common groups in soils and are found in large numbers in Hanford soil as well as other subsurface environments contaminated with radionuclides. Ubiquitous in subsurface microbial communities, these bacteria can play a significant role in the dissolution of minerals and the formation of secondary minerals.more » The main objective of this investigation was to study the bacterial interactions under oxidizing conditions with uranium (VI); study the potential role of bicarbonate, which is an integral complexing ligand for U(VI) and a major ion in groundwater compositions; and present data from autunite dissolution experiments using Arthrobacter strain G968, a less U(VI)-tolerant strain. Sterile 100 mL glass mixed reactors served as the major bioreactor for initial experimentation. These autunite-containing bioreactors were injected with bacterial cells after the autunite equilibrated with the media solution amended with 0 mM, 3 mM 5 mM and 10 mM concentrations of bicarbonate. G968 Arthrobacter cells in the amount of 10{sup 6} cells/mL were injected into the reactors after 27 days, giving time for the autunite to reach steady state. Abiotic non-carbonate controls were kept without bacterial inoculation to provide a control for the biotic samples. Samples of the solution were analyzed for dissolved U(VI) by means of kinetic phosphorescence analyzer KPA-11 (Chemcheck Instruments, Richland, WA). Analysis showed that as [HCO{sub 3}{sup -}] increases, a diminishing trend on the effect of bacteria on autunite leaching is observed. Viability of cells was conducted after 24 hours of cell incubation with the appropriate uranium and bicarbonate concentration treatment. As expected, the cells started to reduce after day 41 due to the nutritional exhaustion of the media. Moreover, viable bacteria accounted for more than 94% in the presence of 10 mM bicarbonate. Experiments showed that despite differences between the G975 and the G968 bacterial strains resistance to U(VI), in the presence of bicarbonate ions they are able to dissolute uranium from autunite mineral at the same capacity. The effect of both bacterial strains on autunite dissolution is reduced as the concentration of bicarbonate increases while the increase in soluble U(VI) concentration induced by G968 and G975 is dwarfed, for larger [HCO{sub 3}{sup -}]. (authors)« less

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

PubMed

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

2013-08-20

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

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

USGS Publications Warehouse

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

2013-01-01

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

Uranium bioreduction rates across scales: biogeochemical hot moments and hot spots during a biostimulation experiment at Rifle, Colorado.

PubMed

Bao, Chen; Wu, Hongfei; Li, Li; Newcomer, Darrell; Long, Philip E; Williams, Kenneth H

2014-09-02

We aim to understand the scale-dependent evolution of uranium bioreduction during a field experiment at a former uranium mill site near Rifle, Colorado. Acetate was injected to stimulate Fe-reducing bacteria (FeRB) and to immobilize aqueous U(VI) to insoluble U(IV). Bicarbonate was coinjected in half of the domain to mobilize sorbed U(VI). We used reactive transport modeling to integrate hydraulic and geochemical data and to quantify rates at the grid block (0.25 m) and experimental field scale (tens of meters). Although local rates varied by orders of magnitude in conjunction with biostimulation fronts propagating downstream, field-scale rates were dominated by those orders of magnitude higher rates at a few selected hot spots where Fe(III), U(VI), and FeRB were at their maxima in the vicinity of the injection wells. At particular locations, the hot moments with maximum rates negatively corresponded to their distance from the injection wells. Although bicarbonate injection enhanced local rates near the injection wells by a maximum of 39.4%, its effect at the field scale was limited to a maximum of 10.0%. We propose a rate-versus-measurement-length relationship (log R' = -0.63 log L - 2.20, with R' in μmol/mg cell protein/day and L in meters) for orders-of-magnitude estimation of uranium bioreduction rates across scales.

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

PubMed

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

2015-01-01

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

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

PubMed Central

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

2010-01-01

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

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

PubMed

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

2010-10-01

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

Uranium Biomineralization by Natural Microbial Phosphatase Activities in the Subsurface

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

Sobecky, Patricia A.

2015-04-06

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

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.

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

NASA Astrophysics Data System (ADS)

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

2012-12-01

The aquifer below the 300-Area of the Hanford site (Richland, WA, USA) is plagued by a persistent plume of dissolved uranium (U(VI)) in excess of the Environmental Protection Agency drinking water maximum contamination level even after the removal of highly contaminated sediments. The aquifer sediments in the seasonally saturated lower vadose zone act as both a source and sink for uranium during stage changes in the nearby Columbia River. Diffusion limitation of uranium mass-transfer within these sediments has been cited as a potential cause of the plume's persistence. Equilibrium U(VI) sorption is a strong function of variable chemical conditions, especially carbonate, hydrogen, and uranyl ion activities. Field-contaminated sediments from the site require up to 1,000 hours to reach equilibrium in static batch reactors. Increases in U(VI) concentrations over longer time-scales result from changes in chemical conditions, which drive reactions with sediments that favor U(VI) desorption. Grain-scale U(VI) sorption/desorption rates are slow, likely owing to diffusion of U(VI) and other solutes through intra-granular pore domains. In order to improve understanding of the impact of intra-granular diffusion and chemical reactions controlling grain-scale U(VI) release, experiments were conducted on individual particle size fractions of a <8 mm composite of field-contaminated, lower vadose zone sediments. For each size fraction, equilibrium U(VI) sorption/desorption in static batch reactors was well-described by surface complexation models over a range of chemical conditions applicable to the field site. Desorption rates from individual size fractions in flow-through batch reactors, examined under a single set of constant chemical conditions with multiple stop-flow events, were similar for all size fractions <2 mm. Kinetic U(VI) desorption in flow-through batch reactors was modeled using a multi-rate surface complexation approach, where sorption/desorption rates were assumed to be proportional to the displacement from equilibrium and multiple diffusion domains were described with a two-parameter lognormal distribution of mass-transfer rate coefficients. Parameters describing mass transfer were the same for all size fractions <2 mm but differed for the largest (2-8 mm) size fraction. The evolution of pH, along with dissolved cation and carbonate concentrations, was modeled using equilibrium cation exchange, rate-limited calcite dissolution, aerobic respiration, and silica dissolution. Desorption and chemical reaction models calibrated with individual size fractions predicted U(VI) and chemical composition as a function of time for the bulk sediment sample. Volumes of pores less than 2.4 nm, quantified using nitrogen adsorption-desorption isotherms, were the same for all size fractions < 2 mm, nearly double that of the 2-8 mm size fraction. Similarity in the observed pore volumes and multi-rate mass-transfer parameters across all size fractions <2 mm suggest the importance of pores in this size class in controlling slow grain-scale U(VI) desorption rates. Models like these provide a means for testing the influence of grain-scale mass-transfer on the persistence of U(VI) plume at the site.

The Model VI transmission fluorimeter for the determination of uranium

USGS Publications Warehouse

Kinser, Charles Alvin

1954-01-01

An improved transmission fluorimeter (Model VI) for use in the determination of uranium consists of a line-operated, low-voltage d-c supply, powering a small 3-watt ultraviolet lamp as a source of long wavelength ultraviolet radiation; a Model V phototube housing and. fluorimeter head containing the sample holder, shutter, and primary and secondary filters; an end-window multiplier phototube powered by a stable, commercially available high-voltage supply; and an electronic microammeter for measuring the output current from the photomultiplier tube. The instrument has excellent electrical stability and operates over a wide range of sensitivity. Its versatility makes it useful for both routine and research work.

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

Technical Basis for Assessing Uranium Bioremediation Performance

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

PE Long; SB Yabusaki; PD Meyer

2008-04-01

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

Bioremediation of uranium-contaminated groundwater: a systems approach to subsurface biogeochemistry.

PubMed

Williams, Kenneth H; Bargar, John R; Lloyd, Jonathan R; Lovley, Derek R

2013-06-01

Adding organic electron donors to stimulate microbial reduction of highly soluble U(VI) to less soluble U(IV) is a promising strategy for immobilizing uranium in contaminated subsurface environments. Studies suggest that diagnosing the in situ physiological status of the subsurface community during uranium bioremediation with environmental transcriptomic and proteomic techniques can identify factors potentially limiting U(VI) reduction activity. Models which couple genome-scale in silico representations of the metabolism of key microbial populations with geochemical and hydrological models may be able to predict the outcome of bioremediation strategies and aid in the development of new approaches. Concerns remain about the long-term stability of sequestered U(IV) minerals and the release of co-contaminants associated with Fe(III) oxides, which might be overcome through targeted delivery of electrons to select microorganisms using in situ electrodes. Copyright © 2012 Elsevier Ltd. All rights reserved.

Preparation of uranium compounds

DOEpatents

Kiplinger, Jaqueline L; Montreal, Marisa J; Thomson, Robert K; Cantat, Thibault; Travia, Nicholas E

2013-02-19

UI.sub.3(1,4-dioxane).sub.1.5 and UI.sub.4(1,4-dioxane).sub.2, were synthesized in high yield by reacting turnings of elemental uranium with iodine dissolved in 1,4-dioxane under mild conditions. These molecular compounds of uranium are thermally stable and excellent precursor materials for synthesizing other molecular compounds of uranium including alkoxide, amide, organometallic, and halide compounds.

Cation–cation interactions and cation exchange in a series of isostructural framework uranyl tungstates

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

Balboni, Enrica; Burns, Peter C., E-mail: pburns@nd.edu; Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556

2014-05-01

The isotypical compounds (UO{sub 2}){sub 3}(WO{sub 6})(H{sub 2}O){sub 5} (1), Ag(UO{sub 2}){sub 3}(WO{sub 6})(OH)(H{sub 2}O){sub 3} (2), K(UO{sub 2}){sub 3}(WO{sub 6})OH(H{sub 2}O){sub 4} (3), Rb(UO{sub 2}){sub 3}(WO{sub 6})(OH)(H{sub 2}O){sub 3.5} (4), and Cs(UO{sub 2}){sub 3}(WO{sub 6})OH(H{sub 2}O){sub 3} (5) were synthesized, characterized, and their structures determined. Each crystallizes in space group Cc. (1): a=12.979 (3), b=10.238 (2), c=11.302 (2), β=102.044 (2); (2): a=13.148 (2), b=9.520 (1), c=11.083 (2), β=101.568 (2); (3): a=13.111 (8), b=9.930 (6), c=11.242 (7), β=101.024 (7); (4): a=12.940 (2), b=10.231 (2), c=11.259(2), β=102.205 (2); (5): a=12.983 (3), b=10.191 (3), c=11.263 (4), β=101.661 (4). Compounds 1–5 are amore » framework of uranyl and tungsten polyhedra containing cation–cation interactions. The framework has three symmetrically distinct U(VI) cations, one tungsten, sixteen to eighteen oxygen atoms, and in 2–5, one monovalent cation. Each atom occupies a general position. Each U(VI) cation is present as a typical (UO{sub 2}){sup 2+} uranyl ion in an overall pentagonal bipyramidal coordination environment. Each pentagonal bipyramid shares two equatorial edges with two other pentagonal bipyramids, forming a trimer. Trimers are connected into chains by edge-sharing with WO{sub 6} octahedra. Chains are linked through cation–cation interactions between two symmetrically independent uranyl ions. This yields a remarkably complex system of intersecting channels that extend along [0 0 1] and [−1 1 0]. The cation exchange properties of 2 and 3 were characterized at room temperature and at 140 °C. - Graphical abstract: Chains of uranium and tungsten polyhedra are connected into a three dimensional framework by cation–cation interactions occurring between two symmetrically independent uranyl pentagonal bipyramids. Monovalent cations present in channels within the structure can be exchanged by room temperature or mild hydrothermal treatments. The framework of these compounds is robust to cation exchange and heat. (yellow polyhedra=uranium pentagonal bipyramids; blue polyhedra=tungsten octahedral, purple balls=K; yellow balls=Na; grey balls=Tl). - Highlights: • Five isostructural uranyl tungstates compounds were synthesized hydrothermally. • The structures consist of a chains of uranium and tungstate polyhedral. • Chains are connected into a framework by cation–cation interactions. • Cation exchange does not alter the structural integrity of the compounds. • Cation exchange was successful at room temperature and mild hydrothermal conditions.« less

A procedure for quantitation of total oxidized uranium for bioremediation studies

USGS Publications Warehouse

Elias, Dwayne A.; Senko, John M.; Krumholz, Lee R.

2003-01-01

A procedure was developed for the quantitation of complexed U(VI) during studies on U(VI) bioremediation. These studies typically involve conversion of soluble or complexed U(VI) (oxidized) to U(IV) (the reduced form which is much less soluble). Since U(VI) freely exchanges between material adsorbed to the solid phase and the dissolved phase, uranium bioremediation experiments require a mass balance of U in both its soluble and adsorbed forms as well as in the reduced sediment bound phase. We set out to optimize a procedure for extraction and quantitation of sediment bound U(VI). Various extractant volumes to sediment ratios were tested and it was found that between 1:1 to 8:1 ratios (v/w) there was a steady increase in U(VI) recovered, but no change with further increases in v/w ratio.Various strengths of NaHCO3, Na-EDTA, and Na-citrate were used to evaluate complexed U(VI) recovery, while the efficiency of a single versus repeated extraction steps was compared with synthesized uranyl-phosphate and uranyl-hydroxide. Total recovery with 1 M NaHCO3 was 95.7% and 97.9% from uranyl-phosphate and uranyl-hydroxide, respectively, compared to 80.7% and 89.9% using 450 mM NaHCO3. Performing the procedure once yielded an efficiency of 81.1% and 92.3% for uranyl-phosphate and uranyl-hydroxide, respectively, as compared to three times. All other extractants yielded 7.9–82.0% in both experiments.

Comparative analysis of uranium bioassociation with halophilic bacteria and archaea

PubMed Central

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

2018-01-01

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

In Situ Immobilization of Uranium in Structured Porous Media (Invited)

NASA Astrophysics Data System (ADS)

Brooks, S. C.; Gu, B.; Wu, W.; Spalding, B. P.; Watson, D. B.; Jardine, P.

2009-12-01

Defense related activities have resulted in broad areas of uranium contaminated groundwater across the U. S. Department of Energy complex. For example, past waste disposal practices at the DOE’s Y-12 site generated a plume of uranium and nitrate contamination in the underlying vadose and saturated zones which extends more than 120 meters deep and thousands of meters along geologic strike. Several DOE sponsored research programs have enabled the study of multiple biotic and abiotic methods of immobilizing uranium in situ at the site. These include biostimulation of metal reducing bacteria to promote reduction of the more soluble U(VI) to the sparingly soluble U(IV) and pH manipulation to immobilize U(VI) through its interactions (e.g., sorption, coprecipitation) with incipient aluminum oxyhydroxide minerals. The application of laboratory based results to the field site must also account for (i) the structured media which can impose incomplete mixing conditions and (ii) steep geochemical gradients or transition zones which differ significantly from the typically well mixed laboratory conditions. In this presentation results of several of these studies will be reviewed and lessons learned summarized.

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.

High loading uranium fuel plate

DOEpatents

Wiencek, Thomas C.; Domagala, Robert F.; Thresh, Henry R.

1990-01-01

Two embodiments of a high uranium fuel plate are disclosed which contain a meat comprising structured uranium compound confined between a pair of diffusion bonded ductile metal cladding plates uniformly covering the meat, the meat having a uniform high fuel loading comprising a content of uranium compound greater than about 45 Vol. % at a porosity not greater than about 10 Vol. %. In a first embodiment, the meat is a plurality of parallel wires of uranium compound. In a second embodiment, the meat is a dispersion compact containing uranium compound. The fuel plates are fabricated by a hot isostatic pressing process.

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.

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.

Biosorption and Biomineralization of U(VI) by the Marine Bacterium Idiomarina loihiensis MAH1: Effect of Background Electrolyte and pH

PubMed Central

Morcillo, Fernando; González-Muñoz, María T.; Reitz, Thomas; Romero-González, María E.; Arias, José M.; Merroun, Mohamed L.

2014-01-01

The main goal of this study is to compare the effects of pH, uranium concentration, and background electrolyte (seawater and NaClO4 solution) on the speciation of uranium(VI) associated with the marine bacterium Idiomarina loihiensis MAH1. This was done at the molecular level using a multidisciplinary approach combining X-ray Absorption Spectroscopy (XAS), Time-Resolved Laser-Induced Fluorescence Spectroscopy (TRLFS), and High Resolution Transmission Electron Microscopy (HRTEM). We showed that the U(VI)/bacterium interaction mechanism is highly dependent upon pH but also the nature of the used background electrolyte played a role. At neutral conditions and a U concentration ranging from 5·10−4 to 10−5 M (environmentally relevant concentrations), XAS analysis revealed that uranyl phosphate mineral phases, structurally resembling meta-autunite [Ca(UO2)2(PO4)2 2–6H2O] are precipitated at the cell surfaces of the strain MAH1. The formation of this mineral phase is independent of the background solution but U(VI) luminescence lifetime analyses demonstrated that the U(VI) speciation in seawater samples is more intricate, i.e., different complexes were formed under natural conditions. At acidic conditions, pH 2, 3 and 4.3 ([U] = 5·10−4 M, background electrolyte  = 0.1 M NaClO4), the removal of U from solution was due to biosorption to Extracellular Polysaccharides (EPS) and cell wall components as evident from TEM analysis. The L III-edge XAS and TRLFS studies showed that the biosorption process observed is dependent of pH. The bacterial cell forms a complex with U through organic phosphate groups at pH 2 and via phosphate and carboxyl groups at pH 3 and 4.3, respectively. The differences in the complexes formed between uranium and bacteria on seawater compared to NaClO4 solution demonstrates that the actinide/microbe interactions are influenced by the three studied factors, i.e., the pH, the uranium concentration and the chemical composition of the solution. PMID:24618567

Method of manufacturing semiconductor having group II-group VI compounds doped with nitrogen

DOEpatents

Compaan, Alvin D.; Price, Kent J.; Ma, Xianda; Makhratchev, Konstantin

2005-02-08

A method of making a semiconductor comprises depositing a group II-group VI compound onto a substrate in the presence of nitrogen using sputtering to produce a nitrogen-doped semiconductor. This method can be used for making a photovoltaic cell using sputtering to apply a back contact layer of group II-group VI compound to a substrate in the presence of nitrogen, the back coating layer being doped with nitrogen. A semiconductor comprising a group II-group VI compound doped with nitrogen, and a photovoltaic cell comprising a substrate on which is deposited a layer of a group II-group VI compound doped with nitrogen, are also included.

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.

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Use of spectroscopic techniques for uranium(VI)/montmorillonite interaction modeling.

PubMed

Kowal-Fouchard, A; Drot, R; Simoni, E; Ehrhardt, J J

2004-03-01

To experimentally identify both clay sorption sites and sorption equilibria and to understand the retention mechanisms at a molecular level, we have characterized the structure of hexavalent uranium surface complexes resulting from the interaction between the uranyl ions and the surface retention groups of a montmorillonite clay. We have performed laser-induced fluorescence spectroscopy (LIFS) and X-ray photoelectron spectroscopy (XPS) on uranyl ion loaded montmorillonite. These structural results were then compared to those obtained from the study of uranyl ions sorbed onto an alumina and also from U(VI) sorbed on an amorphous silica. This experimental approach allowed for a clear determination of the reactive surface sites of montmorillonite for U(VI) sorption. The lifetime values and the U4f XPS spectra of uranium(VI) sorbed on montmorillonite have shown that this ion is sorbed on both exchange and edge sites. The comparison of U(VI)/clay and U(VI)/oxide systems has determined that the interaction between uranyl ions and montmorillonite edge sites occurs via both [triple bond]AlOH and [triple bond]SiOH surface groups and involves three distinct surface complexes. The surface complexation modeling of the U(VI)/montmorillonite sorption edges was determined using the constant capacitance model and the above experimental constraints. The following equilibria were found to account for the uranyl sorption mechanisms onto montmorillonite for metal concentrations ranged from 10(-6) to 10(-3) M and two ionic strengths (0.1 and 0.5 M): 2[triple bond]XNa + UO2(2+) <==> ([triple bond]X)2UO2 + 2Na+, log K0(exch) = 3.0; [triple bond]Al(OH)2 + UO2(2+) <==> [triple bond]Al(OH)2UO2(2+), log K0(Al) = 14.9; [triple bond]Si(OH)2 + UO2(2+) <==> [triple bond]SiO2UO2 + 2H+, log K0(Si1) = -3.8; and [triple bond]Si(OH)2 + 3UO2(2+) + 5H2O <==> [triple bond]SiO2(UO2)3(OH)5- + 7H+, log K0(Si2) = -20.0.

Synthesis, analgesic, anti-inflammatory and anti-ulcerogenic activities of certain novel Schiff's bases as fenamate isosteres.

PubMed

Alafeefy, Ahmed M; Bakht, Mohammed A; Ganaie, Majid A; Ansarie, Mohd N; El-Sayed, Nahed N; Awaad, Amani S

2015-01-15

A series of certain novel Schiff bases as fenamate isosteres (VI:a-k) were synthesized to locate analgesic, anti-inflammatory agent with minimal ulcerogenic potential. The structures of the newly synthesized compounds were elucidated on the basis of their elemental analysis as well as IR, and NMR and mass spectroscopic data. All the compounds were evaluated for their anti-inflammatory activity by carrageenan induced paw oedema method. The compounds possessing good anti-inflammatory activity were further tested for analgesic, ulcerogenic, lipid peroxidation potentials and liver toxicity. Compounds (VI-c), (VI-f), (VI-h) and (VI-i) showed the best anti-inflammatory and significant analgesic activities at doses comparable to that of the standard drug Indomethacin. However, compounds (VI-c) and (VI-f) could be considered the most potent anti-inflammatory and analgesic molecules with maximum reduction in gastro-intestinal ulceration with no hepatocyte necrosis or liver degeneration. Copyright © 2014 Elsevier Ltd. All rights reserved.

A modified model for calculating lattice thermal expansion of I{sub 2}-IV-VI{sub 3} and I{sub 3}-V-VI{sub 4} tetrahedral compounds

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

Omar, M.S.

2007-05-03

A general empirical formula was found for calculating lattice thermal expansion for compounds having their properties extended for compound groups having different mean ionicity as well as more than one type of cation atoms with that of different numbers of them such as I{sub 2}-IV-VI{sub 3} and I{sub 3}-V-VI{sub 4}. The difference in the valence electrons for cations and anions in the compound was used to correlate the deviations caused by the compound ionicity. The ionicity effects, which are due to their different numbers for their types, were also added to the correlation equation. In general, the lattice thermal expansionmore » for a compound semiconductor can be calculated from a relation containing melting point, mean atomic distance and number of valence electrons for the atoms forming the compound. The mean ionicity for the group compounds forming I{sub 2}-IV-VI{sub 3} was found to be 0.323 and 0.785 for the ternary group compounds of I{sub 3}-V-VI{sub 4}.« less

Uranium Bioreduction Rates across Scales: Biogeochemical Hot Moments and Hot Spots during a Biostimulation Experiment at Rifle, Colorado

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

Bao, Chen; Wu, Hongfei; Li, Li

2014-09-02

We aim to understand the scale-dependent evolution of uranium bioreduction during a field experiment at a former uranium mill site near Rifle, Colorado. Acetate was injected to stimulate Fe-reducing bacteria (FeRB) and to immobilize aqueous U(VI) to insoluble U(IV). Bicarbonate was coinjected in half of the domain to mobilize sorbed U(VI). We used reactive transport modeling to integrate hydraulic and geochemical data and to quantify rates at the grid block (0.25 m) and experimental field scale (tens of meters). Although local rates varied by orders of magnitude in conjunction with biostimulation fronts propagating downstream, field-scale rates were dominated by thosemore » orders of magnitude higher rates at a few selected hot spots where Fe(III), U(VI), and FeRB were at their maxima in the vicinity of the injection wells. At particular locations, the hot moments with maximum rates negatively corresponded to their distance from the injection wells. Although bicarbonate injection enhanced local rates near the injection wells by a maximum of 39.4%, its effect at the field scale was limited to a maximum of 10.0%. We propose a rate-versus-measurement-length relationship (log R' = -0.63« less

Method for producing uranium atomic beam source

DOEpatents

Krikorian, Oscar H.

1976-06-15

A method for producing a beam of neutral uranium atoms is obtained by vaporizing uranium from a compound UM.sub.x heated to produce U vapor from an M boat or from some other suitable refractory container such as a tungsten boat, where M is a metal whose vapor pressure is negligible compared to that of uranium at the vaporization temperature. The compound, for example, may be the uranium-rhenium compound, URe.sub.2. An evaporation rate in excess of about 10 times that of conventional uranium beam sources is produced.

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

USGS Publications Warehouse

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

2009-01-01

A study of U(VI) adsorption by aquifer sediment samples from a former uranium mill tailings site at Rifle, Colorado, was conducted under oxic conditions as a function of pH, U(VI), Ca, and dissolved carbonate concentration. Batch adsorption experiments were performed using <2mm size sediment fractions, a sand-sized fraction, and artificial groundwater solutions prepared to simulate the field groundwater composition. To encompass the geochemical conditions of the alluvial aquifer at the site, the experimental conditions ranged from 6.8 ?? 10-8 to 10-5 M in [U(VI)]tot, 7.2 to 8.0 in pH, 3.0 ?? 10-3 to 6.0 ?? 10 -3 M in [Ca2+], and 0.05 to 2.6% in partial pressure of carbon dioxide. Surface area normalized U(VI) adsorption Kd values for the sand and <2 mm sediment fraction were similar, suggesting a similar reactive surface coating on both fractions. A two-site two-reaction, nonelectrostatic generalized composite surface complexation model was developed and successfully simulated the U(VI) adsorption data. The model successfully predicted U(VI) adsorption observed from a multilevel sampling well installed at the site. A comparison of the model with the one developed previously for a uranium mill tailings site at Naturita, Colorado, indicated that possible calcite nonequilibrium of dissolved calcium concentration should be evaluated. The modeling results also illustrate the importance of the range of data used in deriving the best fit model parameters. ?? 2009 American Chemical Society.

A series of uranium (IV, V, VI) tritylimido complexes, their molecular and electronic structures and reactivity with CO2.

PubMed

Schmidt, Anna-Corina; Heinemann, Frank W; Maron, Laurent; Meyer, Karsten

2014-12-15

A series of uranium tritylimido complexes with structural continuity across complexes in different oxidation states, namely U(IV), U(V), and U(VI), is reported. This series was successfully synthesized by employing the trivalent uranium precursor, [(((nP,Me)ArO)3tacn)U(III)] (1) (where ((nP,Me)ArO)3tacn(3-) = trianion of 1,4,7-tris(2-hydroxy-5-methyl-3-neopentylbenzyl)-1,4,7-triazacyclononane), with the organic azides Me3SiN3, Me3SnN3, and Ph3CN3 (tritylazide). While the reaction with Me3SiN3 yields an inseparable mixture of both the azido and imido uranium complexes, applying the heavier Sn homologue yields the bis-μ-azido complex [{(((nP,Me)ArO)3tacn)U(IV)}2(μ-N3)2] (2) exclusively. In contrast to this one-electron redox chemistry, the reaction of precursor 1 with tritylazide solely leads to the two-electron oxidized U(V) imido [(((nP,Me)ArO)3tacn)U(V)(N-CPh3)] (3). Oxidation and reduction of 3 yield the corresponding U(VI) and U(IV) complexes [(((nP,Me)ArO)3tacn)U(VI)(N-CPh3)][B(C6F5)4] (4) and K[(((nP,Me)ArO)3tacn)U(IV)(N-CPh3)] (5), respectively. In addition, the U(V) imido 3 engages in a H atom abstraction reaction with toluene to yield the closely related amido complex [(((nP,Me)ArO)3tacn)U(IV)(N(H)-CPh3)] (6). Complex 6 and the three tritylimido complexes 3, 4, and 5, with oxidation states ranging from +IV to +VI and homologous core structures, were investigated by X-ray diffraction analyses and magnetochemical and spectroscopic studies as well as density functional theory (DFT) computational analysis. The series of structurally very similar imido complexes provides a unique opportunity to study electronic properties and to probe the uranium imido reactivity solely as a function of electron count of the metal-imido entity. Evidence for the U-N bond covalency and f-orbital participation in complexes 3-6 was drawn from the in-depth and comparative DFT study. The reactivity of the imido and amido complexes with CO2 was probed, and conclusions about the influence of the formal oxidation state are reported.

Solid state speciation of uranium and its local structure in Sr2CeO4 using photoluminescence spectroscopy.

PubMed

Sahu, M; Gupta, Santosh K; Jain, D; Saxena, M K; Kadam, R M

2018-04-15

An effort was taken to carry our speciation study of uranium ion in technologically important cerate host Sr 2 CeO 4 using time resolved photoluminescence spectroscopy. Such studies are not relevant only to nuclear industry but can give rich insight into fundamentals of 5f electron chemistry in solid state systems. In this work both undoped and varied amount of uranium doped Sr 2 CeO 4 compound is synthesized using complex polymerization method and is characterized systematically using X-ray diffraction (XRD), Raman spectroscopy, impedance spectroscopy and scanning electron microscopy (SEM). Both XRD and Raman spectroscopy confirmed the formation of pure Sr 2 CeO 4 which has tendency to decompose peritectically to SrCeO 3 and SrO at higher temperature. Uranium doping is confirmed by XRD. Uranium exhibits a rich chemistry owing to its variable oxidation state from +3 to +6. Each of them exhibits distinct luminescence properties either due to f-f transitions or ligand to metal charge transfer (LMCT). We have taken Sr 2 CeO 4 as a model host lattice to understand the photophysical characteristics of uranium ion in it. Emission spectroscopy revealed the stabilization of uranium as U (VI) in the form of UO 6 6- (octahedral uranate) in Sr 2 CeO 4 . Emission kinetics study reflects that uranate ions are not homogeneously distributed in Sr 2 CeO 4 and it has two different environments due to its stabilization at both Sr 2+ as well as Ce 4+ site. The lifetime population analysis interestingly pinpointed that majority of uranate ion resided at Ce 4+ site. The critical energy-transfer distance between the uranate ion was determined based on which the concentration quenching mechanism was attributed to electric multipolar interaction. These studies are very important in designing Sr 2 CeO 4 based optoelectronic material as well exploring it for actinides studies. Copyright © 2018 Elsevier B.V. All rights reserved.

Solid state speciation of uranium and its local structure in Sr2CeO4 using photoluminescence spectroscopy

NASA Astrophysics Data System (ADS)

Sahu, M.; Gupta, Santosh K.; Jain, D.; Saxena, M. K.; Kadam, R. M.

2018-04-01

An effort was taken to carry our speciation study of uranium ion in technologically important cerate host Sr2CeO4 using time resolved photoluminescence spectroscopy. Such studies are not relevant only to nuclear industry but can give rich insight into fundamentals of 5f electron chemistry in solid state systems. In this work both undoped and varied amount of uranium doped Sr2CeO4 compound is synthesized using complex polymerization method and is characterized systematically using X-ray diffraction (XRD), Raman spectroscopy, photoluminescence spectroscopy and scanning electron microscopy (SEM). Both XRD and Raman spectroscopy confirmed the formation of pure Sr2CeO4 which has tendency to decompose peritectically to SrCeO3 and SrO at higher temperature. Uranium doping is confirmed by XRD. Uranium exhibits a rich chemistry owing to its variable oxidation state from +3 to +6. Each of them exhibits distinct luminescence properties either due to f-f transitions or ligand to metal charge transfer (LMCT). We have taken Sr2CeO4 as a model host lattice to understand the photophysical characteristics of uranium ion in it. Emission spectroscopy revealed the stabilization of uranium as U (VI) in the form of UO66- (octahedral uranate) in Sr2CeO4. Emission kinetics study reflects that uranate ions are not homogeneously distributed in Sr2CeO4 and it has two different environments due to its stabilization at both Sr2+ as well as Ce4+ site. The lifetime population analysis interestingly pinpointed that majority of uranate ion resided at Ce4+ site. The critical energy-transfer distance between the uranate ion was determined based on which the concentration quenching mechanism was attributed to electric multipolar interaction. These studies are very important in designing Sr2CeO4 based optoelectronic material as well exploring it for actinides studies.

Characterization of U(VI) reduction in contaminated sediments with slow-degrading electron donor source

NASA Astrophysics Data System (ADS)

Wu, W.; Watson, D. B.; Zhang, G.; Mehlhorn, T.; Lowe, K.; Earles, J.; Phillips, J.; Kelly, S. D.; Boyanov, M.; Kemner, K. M.; Schadt, C.; Criddle, C. S.; Jardine, P. M.; Brooks, S. C.

2011-12-01

In order to select sustainable, high efficiency and cost effective electron donor source, oleate and emulsified vegetable oil (EVO) were tested uranium (VI) reduction in comparison with ethanol in microcosms using uranium contaminated sediments and groundwater from the US DOE Oak Ridge Integrated Field Research Challenge (ORIFRC) site. The effect of initial sulfate concentration on U(VI) reduction was also tested. Both oleate and EVO were effective electron donor sources for U(VI) reduction. Accumulation of acetate as a major product and the removal of aqueous U(VI) were observed and were associated with sulfate reduction. Both oleate and EVO supported U(VI) reduction but at slower rates with a comparable but slightly lower extent of reduction than ethanol. X-ray absorption near-edge spectroscopy (XANES) analysis confirmed reduction of U(VI) to U(IV). The extent of U(VI) reduction in solid phase was negatively influenced by aqueous calcium concentration. The majority of electrons of the three substrates were consumed by sulfate reduction, Fe(III) reduction, and methanogenesis. Initial U(VI) concentration in the aqueous phase increased with increased sulfate concentration (1 versus 5 mM), likely due to U(VI) desorption from the solid phase. At the higher initial sulfate concentration more U(VI) was reduced and fewer electrons were used in methanogenesis. Analysis of bacterial and archeal populations using 16S rRNA gene libraries showed a significant increase in Deltaproteobacteria after biostimulation. The microbial community structures developed with oleate and EVO were significantly distinct from those developed with ethanol. Bacteria similar to Desulforegula spp. was predominant for oleate and EVO degradation but were not observed in ethanol-amended microcosms. Known U(VI)-reducing bacteria in the microcosms amended with the three electron donor sources included iron(III) reducing Geobacter spp. but in lower abundances than sulfate-reducing Desulfovibrio spp. The test results were used for the design a field test by one-time injection of EVO to the subsurface for U(VI) reduction in Area 2 of the ORIFRC site.

Model-Based Analysis of the Role of Biological, Hydrological and Geochemical Factors Affecting Uranium Bioremediation

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

Zhao, Jiao; Scheibe, Timothy D.; Mahadevan, Radhakrishnan

2011-01-24

Uranium contamination is a serious concern at several sites motivating the development of novel treatment strategies such as the Geobacter-mediated reductive immobilization of uranium. However, this bioremediation strategy has not yet been optimized for the sustained uranium removal. While several reactive-transport models have been developed to represent Geobacter-mediated bioremediation of uranium, these models often lack the detailed quantitative description of the microbial process (e.g., biomass build-up in both groundwater and sediments, electron transport system, etc.) and the interaction between biogeochemical and hydrological process. In this study, a novel multi-scale model was developed by integrating our recent model on electron capacitancemore » of Geobacter (Zhao et al., 2010) with a comprehensive simulator of coupled fluid flow, hydrologic transport, heat transfer, and biogeochemical reactions. This mechanistic reactive-transport model accurately reproduces the experimental data for the bioremediation of uranium with acetate amendment. We subsequently performed global sensitivity analysis with the reactive-transport model in order to identify the main sources of prediction uncertainty caused by synergistic effects of biological, geochemical, and hydrological processes. The proposed approach successfully captured significant contributing factors across time and space, thereby improving the structure and parameterization of the comprehensive reactive-transport model. The global sensitivity analysis also provides a potentially useful tool to evaluate uranium bioremediation strategy. The simulations suggest that under difficult environments (e.g., highly contaminated with U(VI) at a high migration rate of solutes), the efficiency of uranium removal can be improved by adding Geobacter species to the contaminated site (bioaugmentation) in conjunction with the addition of electron donor (biostimulation). The simulations also highlight the interactive effect of initial cell concentration and flow rate on U(VI) reduction.« less

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

PubMed

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

2018-07-15

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

Evaluation of sequential extraction procedures for soluble and insoluble hexavalent chromium compounds in workplace air samples.

PubMed

Ashley, Kevin; Applegate, Gregory T; Marcy, A Dale; Drake, Pamela L; Pierce, Paul A; Carabin, Nathalie; Demange, Martine

2009-02-01

Because toxicities may differ for Cr(VI) compounds of varying solubility, some countries and organizations have promulgated different occupational exposure limits (OELs) for soluble and insoluble hexavalent chromium (Cr(VI)) compounds, and analytical methods are needed to determine these species in workplace air samples. To address this need, international standard methods ASTM D6832 and ISO 16740 have been published that describe sequential extraction techniques for soluble and insoluble Cr(VI) in samples collected from occupational settings. However, no published performance data were previously available for these Cr(VI) sequential extraction procedures. In this work, the sequential extraction methods outlined in the relevant international standards were investigated. The procedures tested involved the use of either deionized water or an ammonium sulfate/ammonium hydroxide buffer solution to target soluble Cr(VI) species. This was followed by extraction in a sodium carbonate/sodium hydroxide buffer solution to dissolve insoluble Cr(VI) compounds. Three-step sequential extraction with (1) water, (2) sulfate buffer and (3) carbonate buffer was also investigated. Sequential extractions were carried out on spiked samples of soluble, sparingly soluble and insoluble Cr(VI) compounds, and analyses were then generally carried out by using the diphenylcarbazide method. Similar experiments were performed on paint pigment samples and on airborne particulate filter samples collected from stainless steel welding. Potential interferences from soluble and insoluble Cr(III) compounds, as well as from Fe(II), were investigated. Interferences from Cr(III) species were generally absent, while the presence of Fe(II) resulted in low Cr(VI) recoveries. Two-step sequential extraction of spiked samples with (first) either water or sulfate buffer, and then carbonate buffer, yielded quantitative recoveries of soluble Cr(VI) and insoluble Cr(VI), respectively. Three-step sequential extraction gave excessively high recoveries of soluble Cr(VI), low recoveries of sparingly soluble Cr(VI), and quantitative recoveries of insoluble Cr(VI). Experiments on paint pigment samples using two-step extraction with water and carbonate buffer yielded varying percentages of relative fractions of soluble and insoluble Cr(VI). Sequential extractions of stainless steel welding fume air filter samples demonstrated the predominance of soluble Cr(VI) compounds in such samples. The performance data obtained in this work support the Cr(VI) sequential extraction procedures described in the international standards.

Cytotoxic and clastogenic effects of soluble and insoluble compounds containing hexavalent and trivalent chromium.

PubMed Central

Levis, A. G.; Majone, F.

1981-01-01

Cr(III) and Cr(VI) compounds of varying solubilities have been tested in vitro for their ability to inhibit cell growth and nucleic acid and protein syntheses in BHK cells, to induce alterations in the mitotic cycle in HEp cells, and to increase the frequency of chromosomal aberrations and sister chromatid exchanges (SCE) in CHO cells. All Cr(VI) compounds, and particularly those containing soluble Cr(VI), such as potassium dichromate and zinc yellow, differentially inhibit macromolecular syntheses in BKH cells, that of DNA being always the most affected. Among Cr(III) compounds, which generally have very low cytotoxicity, chromite is particularly active, and inhibits cell growth and DNA synthesis even more than the poorly soluble Cr(VI) compounds. Preincubation in growth medium, with or without metabolizing cell cultures, solubilizes considerable amounts of Cr(VI) from zinc yellow and chromite, but significant amounts are also obtained from the most insoluble Cr(VI) pigments. When BHK cells are treated with such preincubated solutions, reduction of soluble Cr(VI) to Cr(III) by cell metabolites is seen with all Cr(VI) compounds, accompanied by decreased cytotoxicity. The same differences between Cr(VI) and Cr(III) compounds apply to the cytotoxic effects on mitosis of HEp cells and the clastogenic effects on CHO cells. The activity of chromite, the only Cr(III) pigment capable of significantly increasing the frequency of SCE, is due to contamination with soluble Cr(VI). In contrast to the very low cytotoxicity of Cr(III), much higher chromium levels are detected in the cells incubated with soluble Cr(III) than with the same concentrations of soluble Cr(VI). 50% and 75% of chromium accumulated in the cells during treatments with Cr(VI) and Cr(III) respectively remains firmly bound to the cells, even when they are incubated for up to 48 h in normal growth medium. Chromium accumulated in the cells after treatment with Cr(III) is most probably bound to the cell membrane, whereas some of the Cr(VI) is transported through the cell membrane and reduced in the cell nucleus. The results of the present investigation are in agreement with those obtained with the same Cr(VI) and Cr(III) compounds in mutagenicity assays in bacteria and carcinogenicity tests in rodents. A re-evaluation of the mechanisms of chromium carcinogenisis is proposed. PMID:7272188

Preparation of UO2, ThO2 and (Th,U)O2 pellets from photochemically-prepared nano-powders

NASA Astrophysics Data System (ADS)

Pavelková, Tereza; Čuba, Václav; de Visser-Týnová, Eva; Ekberg, Christian; Persson, Ingmar

2016-02-01

Photochemically-induced preparation of nano-powders of crystalline uranium and/or thorium oxides and their subsequent pelletizing has been investigated. The preparative method was based on the photochemically induced formation of amorphous solid precursors in aqueous solution containing uranyl and/or thorium nitrate and ammonium formate. The EXAFS analyses of the precursors shown that photon irradiation of thorium containing solutions yields a compound with little long-range order but likely "ThO2 like" and the irradiation of uranium containing solutions yields the mixture of U(IV) and U(VI) compounds. The U-containing precursors were carbon free, thus allowing direct heat treatment in reducing atmosphere without pre-treatment in the air. Subsequent heat treatment of amorphous solid precursors at 300-550 °C yielded nano-crystalline UO2, ThO2 or solid (Th,U)O2 solutions with high purity, well-developed crystals with linear crystallite size <15 nm. The prepared nano-powders of crystalline oxides were pelletized without any binder (pressure 500 MPa), the green pellets were subsequently sintered at 1300 °C under an Ar:H2 (20:1) mixture (UO2 and (Th,U)O2 pellets) or at 1600 °C in ambient air (ThO2 pellets). The theoretical density of the sintered pellets varied from 91 to 97%.

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

Simultaneous spectrophotometric determination of trace amounts of uranium, thorium, and zirconium using the partial least squares method after their preconcentration by alpha-benzoin oxime modified Amberlite XAD-2000 resin.

PubMed

Ghasemi, Jahan B; Zolfonoun, E

2010-01-15

A new solid phase extraction method for separation and preconcentration of trace amounts of uranium, thorium, and zirconium in water samples is proposed. The procedure is based on the adsorption of U(VI), Th(IV) and Zr(IV) ions on a column of Amberlite XAD-2000 resin loaded with alpha-benzoin oxime prior to their simultaneous spectrophotometric determination with Arsenazo III using orthogonal signal correction partial least squares method. The enrichment factor for preconcentration of uranium, thorium, and zirconium was found to be 100. The detection limits for U(VI), Th(IV) and Zr(IV) were 0.50, 0.54, and 0.48microgL(-1), respectively. The precision of the method, evaluated as the relative standard deviation obtained by analyzing a series of 10 replicates, was below 4% for all elements. The practical applicability of the developed sorbent was examined using synthetic seawater, natural waters and ceramic samples.

Effect of pH on uranium(VI) biosorption and biomineralization by Saccharomyces cerevisiae.

PubMed

Zheng, X Y; Shen, Y H; Wang, X Y; Wang, T S

2018-07-01

Biosorption of radionuclides by microorganisms is a promising and effective method for the remediation of contaminated areas. pH is the most important factor during uranium biosorption by Saccharomyces cerevisiae because the pH value not only affects the biosorption rate but also affects the precipitation structure. This study investigated the effect of pH on uranium (VI) biosorption and biomineralization by S. cerevisiae. Cells have the ability to buffer the solution to neutral, allowing the biosorption system to reach an optimal level regardless of the initial pH value. This occurs because there is a release of phosphate and ammonium ions during the interaction between cells and uranium. The uranyl and phosphate ions formed nano-particles, which is chernikovite H 2 (UO 2 ) 2 (PO 4 ) 2 ·8H 2 O (PDF #08-0296), on cell surface under the initial acidic conditions. However, under the initial alkaline conditions, the uranyl, phosphate and ammonium ions formed a large amount of scale-like precipitation, which is uramphite (NH 4 )(UO 2 )PO 4 ·3H 2 O (PDF #42-0384), evenly over on cell surface. Copyright © 2018 Elsevier Ltd. All rights reserved.

Trigonal Cu2-II-Sn-VI4 (II = Ba, Sr and VI = S, Se) quaternary compounds for earth-abundant photovoltaics.

PubMed

Hong, Feng; Lin, Wenjun; Meng, Weiwei; Yan, Yanfa

2016-02-14

We propose trigonal Cu2-II-Sn-VI4 (II = Ba, Sr and VI = S, Se) quaternary compounds for earth-abundant solar cell applications. Through density functional theory calculations, we show that these compounds exhibit similar electronic and optical properties to kesterite Cu2ZnSnS4 (CZTS): high optical absorption with band gaps suitable for efficient single-junction solar cell applications. However, the trigonal Cu2-II-Sn-VI4 compounds exhibit defect properties more suitable for photovoltaic applications than those of CZTS. In CZTS, the dominant defects are the deep acceptors, Cu substitutions on Zn sites, which cause non-radiative recombination and limit the open-circuit voltages of CZTS solar cells. On the contrary, the dominant defects in trigonal Cu2-II-Sn-VI4 are the shallow acceptors, Cu vacancies, similar to those in CuInSe2. Our results suggest that the trigonal Cu2-II-Sn-VI4 quaternary compounds could be promising candidates for efficient earth-abundant thin-film solar cell and photoeletrochemical water-splitting applications.

Molecular analysis of phosphate limitation in Geobacteraceae during the bioremediation of a uranium-contaminated aquifer

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

N'Guessan, L.A.; Elifantz, H.; Nevin, K.P.

2009-09-01

Nutrient limitation is an environmental stress that may reduce the effectiveness of bioremediation strategies, especially when the contaminants are organic compounds or when organic compounds are added to promote microbial activities such as metal reduction. Genes indicative of phosphate-limitation were identified via microarray analysis of chemostat cultures of Geobacter sulfureducens. This analysis revealed that genes in the pst-pho operon, which is associated with a high affinity phosphate uptake system in other microorganisms, had significantly higher transcript abundance under phosphate-limiting conditions, with the genes pstB and phoU the most up-regulated. Quantitative PCR analysis of pstB and phoU transcript levels in G.more » sulfurreducens grown in chemostats demonstrated that the expression of these genes increased when phosphate was removed from the culture medium. Transcripts of pstB and phoU within the subsurface Geobacter species predominating during an in situ uranium bioremediation field experiment were more abundant than in chemostat cultures of G. sulfurreducens that were not limited for phosphate. Addition of phosphate to incubations of subsurface sediments did not stimulate dissimilatory metal reduction. The added phosphate was rapidly adsorbed onto the sediments. The results demonstrate that Geobacter species can effectively reduce U(VI) even when experiencing suboptimal phosphate concentrations and that increasing phosphate availability with phosphate additions is difficult to achieve due to the high reactivity of this compound. This transcript-based approach developed for diagnosing phosphate limitation should be applicable to assessing the potential need for additional phosphate in other bioremediation processes.« less

Molecular Analysis of Phosphate Limitation in Geobacteraceae During the Bioremediation of a Uranium-Contaminated Aquifer

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

N'Guessan, A. Lucie; Elifantz, H.; Nevin, Kelly P.

2010-02-01

Nutrient limitation is an environmental stress that may reduce the effectiveness of bioremediation strategies, especially when the contaminants are organic compounds or when organic compounds are added to promote microbial activities such as metal reduction. Genes indicative of phosphate-limitation were identified via microarray analysis of chemostat cultures of Geobacter sulfureducens. This analysis revealed that genes in the pst-pho operon, which is associated with a high affinity phosphate uptake system in other microorganisms, had significantly higher transcript abundance under phosphate-limiting conditions, with the genes pstB and phoU the most up-regulated. Quantitative PCR analysis of pstB and phoU transcript levels in G.more » sulfurreducens grown in chemostats demonstrated that the expression of these genes increased when phosphate was removed from the culture medium. Transcripts of pstB and phoU within the subsurface Geobacter species predominating during an in situ uranium bioremediation field experiment were more abundant than in chemostat cultures of G. sulfurreducens that were not limited for phosphate. Addition of phosphate to incubations of subsurface sediments did not stimulate dissimilatory metal reduction. The added phosphate was rapidly adsorbed onto the sediments. The results demonstrate that Geobacter species can effectively reduce U(VI) even when experiencing suboptimal phosphate concentrations and that increasing phosphate availability with phosphate additions is difficult to achieve due to the high reactivity of this compound. This transcript-based approach developed for diagnosing phosphate limitation should be applicable to assessing the potential need for additional phosphate in other bioremediation processes.« less

Molecular analysis of phosphate limitation in Geobacteraceae during the bioremediation of a uranium-contaminated aquifer

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

N'Guessan, A. Lucie; Elifantz, H.; Nevin, Kelly P.

2010-01-10

Nutrient limitation is an environmental stress that may reduce the effectiveness of bioremediation strategies, especially when the contaminants are organic compounds or when organic compounds are added to promote microbial activities such as metal reduction. Genes indicative of phosphatelimitation were identified by microarray analysis of chemostat cultures of Geobacter sulfureducens. This analysis revealed that genes in the pst-pho operon, which is associated with a high-affinity phosphate uptake system in other microorganisms, had significantly higher transcript abundance under phosphate-limiting conditions, with the genes pstB and phoU upregulated the most. Quantitative PCR analysis of pstB and phoU transcript levels in G. sulfurreducensmore » grown in chemostats demonstrated that the expression of these genes increased when phosphate was removed from the culture medium. Transcripts of pstB and phoU within the subsurface Geobacter species predominating during an in situ uranium-bioremediation field experiment were more abundant than in chemostat cultures of G. sulfurreducens that were not limited for phosphate. Addition of phosphate to incubations of subsurface sediments did not stimulate dissimilatory metal reduction. The added phosphate was rapidly adsorbed onto the sediments. The results demonstrate that Geobacter species can effectively reduce U(VI) even when experiencing suboptimal phosphate concentrations and that increasing phosphate availability with phosphate additions is difficult to achieve because of the high reactivity of this compound. This transcript-based approach developed for diagnosing phosphate limitation should be applicable to assessing the potential need for additional phosphate in other bioremediation processes.« 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

Uranium Isotope Ratios in Modern and Precambrian Soils

NASA Astrophysics Data System (ADS)

DeCorte, B.; Planavsky, N.; Wang, X.; Auerbach, D. J.; Knudsen, A. C.

2015-12-01

Uranium isotopes (δ238U values) are an emerging paleoredox proxy that can help to better understand the redox evolution of Earth's surface environment. Recently, uranium isotopes have been used to reconstruct ocean and atmospheric redox conditions (Montoya-Pino et al., 2010; Brennecka et al., 2011; Kendall et al., 2013; Dahl et al., 2014). However, to date, there have not been studies on paleosols, despite that paleosols are, arguably better suited to directly tracking the redox conditions of the atmosphere. Sedimentary δ238U variability requires the formation of the soluble, oxidized form of U, U(VI). The formation of U(VI) is generally thought to require oxygen levels orders of magnitude higher than prebiotic levels. Without significant U mobility, it would have been impossible to develop isotopically distinct pools of uranium in ancient Earth environments. Conversely, an active U redox cycle leads to significant variability in δ238U values. Here we present a temporally and geographically expansive uranium isotope record from paleosols and modern soils to better constrain atmospheric oxygen levels during the Precambrian. Preliminary U isotope measurements of paleosols are unfractionated (relative to igneous rocks), possibly because of limited fractionation during oxidation (e.g., {Wang, 2015 #478}) or insufficient atmospheric oxygen levels to oxidize U(IV)-bearing minerals in the bedrock. Further U isotope measurements of paleosols with comparison to modern soils will resolve this issue.

Adsorption isotherm studies of chromium (VI) from aqueous solutions using sol-gel hydrotalcite-like compounds.

PubMed

Ramos-Ramírez, Esthela; Ortega, Norma L Gutiérrez; Soto, Cesar A Contreras; Gutiérrez, Maria T Olguín

2009-12-30

In under-developed countries, industries such as paint and pigment manufacturing, leather tanning, chrome plating and textile processing, usually discharge effluents containing Cr(VI) and Cr(III) into municipal sanitary sewers. It has been reported that Cr(VI) acts as a powerful epithelial irritant and as a human carcinogen. In the present work, hydrotalcite-like compounds with a Mg/Al ratio=2 were synthesized by the sol-gel method. The hydrotalcite-like compounds and their corresponding thermally treated products were characterized by powder X-ray diffraction, infrared spectroscopy and N(2) adsorption. The hydrotalcite-like compounds and the heated solids were used as adsorbents for Cr(VI) in aqueous solutions. Adsorption isotherm studies of Cr(VI) from aqueous solution are described. The adsorbent capacity was determined using the Langmuir, Freundlich and Dubinin-Radushkevich adsorption isotherm models. The Cr(VI) adsorption isotherm data fit best to the Langmuir isotherm model. The maximum Cr(VI) uptake by hydrotalcite and the heated solids was determined using the Langmuir equation and was found to range between 26 and 29 mg Cr(VI)/g adsorbent.

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

NASA Astrophysics Data System (ADS)

Davis, James A.; Meece, David E.; Kohler, Matthias; Curtis, Gary P.

2004-09-01

Uranium(VI) adsorption onto aquifer sediments was studied in batch experiments as a function of pH and U(VI) and dissolved carbonate concentrations in artificial groundwater solutions. The sediments were collected from an alluvial aquifer at a location upgradient of contamination from a former uranium mill operation at Naturita, Colorado (USA). The ranges of aqueous chemical conditions used in the U(VI) adsorption experiments (pH 6.9 to 7.9; U(VI) concentration 2.5 · 10 -8 to 1 · 10 -5 M; partial pressure of carbon dioxide gas 0.05 to 6.8%) were based on the spatial variation in chemical conditions observed in 1999-2000 in the Naturita alluvial aquifer. The major minerals in the sediments were quartz, feldspars, and calcite, with minor amounts of magnetite and clay minerals. Quartz grains commonly exhibited coatings that were greater than 10 nm in thickness and composed of an illite-smectite clay with occluded ferrihydrite and goethite nanoparticles. Chemical extractions of quartz grains removed from the sediments were used to estimate the masses of iron and aluminum present in the coatings. Various surface complexation modeling approaches were compared in terms of the ability to describe the U(VI) experimental data and the data requirements for model application to the sediments. Published models for U(VI) adsorption on reference minerals were applied to predict U(VI) adsorption based on assumptions about the sediment surface composition and physical properties (e.g., surface area and electrical double layer). Predictions from these models were highly variable, with results overpredicting or underpredicting the experimental data, depending on the assumptions used to apply the model. Although the models for reference minerals are supported by detailed experimental studies (and in ideal cases, surface spectroscopy), the results suggest that errors are caused in applying the models directly to the sediments by uncertain knowledge of: 1) the proportion and types of surface functional groups available for adsorption in the surface coatings; 2) the electric field at the mineral-water interface; and 3) surface reactions of major ions in the aqueous phase, such as Ca 2+, Mg 2+, HCO 3-, SO 42-, H 4SiO 4, and organic acids. In contrast, a semi-empirical surface complexation modeling approach can be used to describe the U(VI) experimental data more precisely as a function of aqueous chemical conditions. This approach is useful as a tool to describe the variation in U(VI) retardation as a function of chemical conditions in field-scale reactive transport simulations, and the approach can be used at other field sites. However, the semi-empirical approach is limited by the site-specific nature of the model parameters.

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

USGS Publications Warehouse

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

2004-01-01

Uranium(VI) adsorption onto aquifer sediments was studied in batch experiments as a function of pH and U(VI) and dissolved carbonate concentrations in artificial groundwater solutions. The sediments were collected from an alluvial aquifer at a location upgradient of contamination from a former uranium mill operation at Naturita, Colorado (USA). The ranges of aqueous chemical conditions used in the U(VI) adsorption experiments (pH 6.9 to 7.9; U(VI) concentration 2.5 ?? 10-8 to 1 ?? 10-5 M; partial pressure of carbon dioxide gas 0.05 to 6.8%) were based on the spatial variation in chemical conditions observed in 1999-2000 in the Naturita alluvial aquifer. The major minerals in the sediments were quartz, feldspars, and calcite, with minor amounts of magnetite and clay minerals. Quartz grains commonly exhibited coatings that were greater than 10 nm in thickness and composed of an illite-smectite clay with occluded ferrihydrite and goethite nanoparticles. Chemical extractions of quartz grains removed from the sediments were used to estimate the masses of iron and aluminum present in the coatings. Various surface complexation modeling approaches were compared in terms of the ability to describe the U(VI) experimental data and the data requirements for model application to the sediments. Published models for U(VI) adsorption on reference minerals were applied to predict U(VI) adsorption based on assumptions about the sediment surface composition and physical properties (e.g., surface area and electrical double layer). Predictions from these models were highly variable, with results overpredicting or underpredicting the experimental data, depending on the assumptions used to apply the model. Although the models for reference minerals are supported by detailed experimental studies (and in ideal cases, surface spectroscopy), the results suggest that errors are caused in applying the models directly to the sediments by uncertain knowledge of: 1) the proportion and types of surface functional groups available for adsorption in the surface coatings; 2) the electric field at the mineral-water interface; and 3) surface reactions of major ions in the aqueous phase, such as Ca2+, Mg2+, HCO3-, SO42-, H4SiO4, and organic acids. In contrast, a semi-empirical surface complexation modeling approach can be used to describe the U(VI) experimental data more precisely as a function of aqueous chemical conditions. This approach is useful as a tool to describe the variation in U(VI) retardation as a function of chemical conditions in field-scale reactive transport simulations, and the approach can be used at other field sites. However, the semi-empirical approach is limited by the site-specific nature of the model parameters. ?? 2004 Elsevier Ltd.

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

PubMed

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

2014-12-09

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

Enzymatic iron and uranium reduction by sulfate-reducing bacteria

USGS Publications Warehouse

Lovley, D.R.; Roden, E.E.; Phillips, E.J.P.; Woodward, J.C.

1993-01-01

The potential for sulfate-reducing bacteria (SRB) to enzymatically reduce Fe(III) and U(VI) was investigated. Five species of Desulfovibrio as well as Desulfobacterium autotrophicum and Desulfobulbus propionicus reduced Fe(III) chelated with nitrilotriacetic acid as well as insoluble Fe(III) oxide. Fe(III) oxide reduction resulted in the accumulation of magnetite and siderite. Desulfobacter postgatei reduced the chelated Fe(III) but not Fe(III) oxide. Desulfobacter curvatus, Desulfomonile tiedjei, and Desulfotomaculum acetoxidans did not reduce Fe(III). Only Desulfovibrio species reduced U(VI). U(VI) reduction resulted in the precipitation of uraninite. None of the SRB that reduced Fe(III) or U(VI) appeared to conserve enough energy to support growth from this reaction. However, Desulfovibrio desulfuricans metabolized H2 down to lower concentrations with Fe(III) or U(VI) as the electron acceptor than with sulfate, suggesting that these metals may be preferred electron acceptors at the low H2 concentrations present in most marine sediments. Molybdate did not inhibit Fe(III) reduction by D. desulfuricans. This indicates that the inability of molybdate to inhibit Fe(III) reduction in marine sediments does not rule out the possibility that SRB are important catalysts for Fe(III) reduction. The results demonstrate that although SRB were previously considered to reduce Fe(III) and U(VI) indirectly through the production of sulfide, they may also directly reduce Fe(III) and U(VI) through enzymatic mechanisms. These findings, as well as our recent discovery that the So-reducing microorganism Desulfuromonas acetoxidans can reduce Fe(III), demonstrate that there are close links between the microbial sulfur, iron, and uranium cycles in anaerobic marine sediments. ?? 1993.

PRODUCTION OF PURIFIED URANIUM

DOEpatents

Burris, L. Jr.; Knighton, J.B.; Feder, H.M.

1960-01-26

A pyrometallurgical method for processing nuclear reactor fuel elements containing uranium and fission products and for reducing uranium compound; to metallic uranium is reported. If the material proccssed is essentially metallic uranium, it is dissolved in zinc, the sulution is cooled to crystallize UZn/sub 9/ , and the UZn/sub 9/ is distilled to obtain uranium free of fission products. If the material processed is a uranium compound, the sollvent is an alloy of zinc and magnesium and the remaining steps are the same.

URANIUM LEACHING AND RECOVERY PROCESS

DOEpatents

McClaine, L.A.

1959-08-18

A process is described for recovering uranium from carbonate leach solutions by precipitating uranium as a mixed oxidation state compound. Uranium is recovered by adding a quadrivalent uranium carbon;te solution to the carbonate solution, adjusting the pH to 13 or greater, and precipitating the uranium as a filterable mixed oxidation state compound. In the event vanadium occurs with the uranium, the vanadium is unaffected by the uranium precipitation step and remains in the carbonate solution. The uranium-free solution is electrolyzed in the cathode compartment of a mercury cathode diaphragm cell to reduce and precipitate the vanadium.

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

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

Jaffe, Peter R.; Kaplan, Daniel I.

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

HPLC separation post-column reaction, UV-visible and fluorescence detection of trace UO/sub 2//sup 2 +//U/sup 4 +/ species in aqueous solutions

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

Karimi, A.R.

In this study a method for the measurement of uranium in natural waters at sub-ppB concentration levels by the separation and determination of U/sup 4 +/ and UO/sub 2//sup 2 +/ species is proposed. Reversed phase high performance liquid chromatography, followed by a post-column reaction and a sensitive UV-visible detection system was the method of choice to determine qualitatively and quantitatively the two uranium species. Also a cation-exchange and fluorescence detection system was studied for separation and determination of UO/sub 2//sup 2 +/ ions. Uranyl ion was selectively complexed with L-phenylalanine moetie in the sample solution containing U/sup 4 +/more » ions. Uranium (IV)/U(VI)-ligand was separated on a C/sub 18/ column with acetate buffer. Hexanesulfonate was found to be the choice for ion-pair reagent. The separation was best done with the acetate buffer at .01 M concentration and pH of 3.5. Absorption of the two species were measured after a post-column reaction with Arsenazo-III. Chromatographic parameters were calculated and a calibration curves were constructed. The detection limit for the procedure was 0.7 ..mu..g/mo and 1.2..mu..g/ml for U(IV) and U(VI) respectively. When U(VI) was separated on the cation-exchange column the limit of detection was calculated to be 1 ..mu..g/ml. The direct fluorometric method for U(VI) measurement results in a detection limit of 2 ppB and upper concentration limit of 2 ppM. The effect of interfering ions in the direct method of determination could be eliminated by dilution of sample solution.« less

A Uranium Bioremediation Reactive Transport Benchmark

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

Yabusaki, Steven B.; Sengor, Sevinc; Fang, Yilin

A reactive transport benchmark problem set has been developed based on in situ uranium bio-immobilization experiments that have been performed at a former uranium mill tailings site in Rifle, Colorado, USA. Acetate-amended groundwater stimulates indigenous microorganisms to catalyze the reduction of U(VI) to a sparingly soluble U(IV) mineral. The interplay between the flow, acetate loading periods and rates, microbially-mediated and geochemical reactions leads to dynamic behavior in metal- and sulfate-reducing bacteria, pH, alkalinity, and reactive mineral surfaces. The benchmark is based on an 8.5 m long one-dimensional model domain with constant saturated flow and uniform porosity. The 159-day simulation introducesmore » acetate and bromide through the upgradient boundary in 14-day and 85-day pulses separated by a 10 day interruption. Acetate loading is tripled during the second pulse, which is followed by a 50 day recovery period. Terminal electron accepting processes for goethite, phyllosilicate Fe(III), U(VI), and sulfate are modeled using Monod-type rate laws. Major ion geochemistry modeled includes mineral reactions, as well as aqueous and surface complexation reactions for UO2++, Fe++, and H+. In addition to the dynamics imparted by the transport of the acetate pulses, U(VI) behavior involves the interplay between bioreduction, which is dependent on acetate availability, and speciation-controlled surface complexation, which is dependent on pH, alkalinity and available surface complexation sites. The general difficulty of this benchmark is the large number of reactions (74), multiple rate law formulations, a multisite uranium surface complexation model, and the strong interdependency and sensitivity of the reaction processes. Results are presented for three simulators: HYDROGEOCHEM, PHT3D, and PHREEQC.« less

Quantitative Analysis of Uranium Accumulation on Sediments during Field-scale Biostimulation under Variable Bicarbonate Concentrations at the Rifle IFRC Site

NASA Astrophysics Data System (ADS)

Fox, P. M.; Davis, J. A.; Bargar, J.; Williams, K. H.; Singer, D. M.; Long, P.

2011-12-01

Bioremediation of uranium in subsurface environments is an approach that has been used at numerous field sites throughout the U.S in an attempt to lower dissolved U(VI) concentrations in groundwater. At the Rifle IFRC research site in Colorado, biostimulation of the native microbial population through acetate amendment for various periods of time has been tested in order to immobilize uranium through reduction U(VI) to U(IV). While this approach has successfully decreased U(VI) concentrations in the dissolved phase, often to levels below the EPA's maximum contaminant level of 0.13 μM, little work has examined the solid-phase accumulation of U during field-scale biostimulation. The lack of information on solid-phase U accumulation is due in large part to the difficulty of obtaining comparable pre- and post-biostimulation field sediment samples. In addition, the relatively low (<10 ppm) U concentrations present in most sediments preclude the use of spectroscopic techniques such as XAS for examining solid-phase U speciation. However, a recently developed technique of performing column experiments in situ has allowed us to overcome both of these problems, obtaining sediment samples which were exposed to the same biogeochemical conditions as subsurface sediments during the course of biostimulation. During the 2010 Rifle IFRC field experiment (dubbed "Super 8"), a number of in situ columns were deployed in various wells representing regions of the aquifer affected by acetate amendment (ambient bicarbonate) and concomitant acetate and bicarbonate amendment (elevated bicarbonate). Elevated levels of bicarbonate have been shown to cause desorption of U(VI) from the solid phase at the Rifle site under non-stimulated conditions, resulting in higher dissolved U(VI) concentrations in the aquifer. The Super 8 field experiment was designed in part to test the effect of elevated bicarbonate concentrations on U sequestration during biostimulation. Results from this experiment provide a comparison of temporal aqueous and solid-phase U concentrations under ambient and elevated bicarbonate conditions during field-scale biostimulation. Additionally, a subset of in situ columns amended with 20 μM U(VI) were analyzed by XANES in order to determine the relative importance of U(VI) and U(IV) in the solid phase. While the elevated bicarbonate concentrations did not impede reduction and sequestration of U, differences in the behavior of dissolved U(VI) after acetate amendment was stopped demonstrate the importance of U adsorption-desorption reactions in controlling dissolved U concentrations post-biostimulation.

Thermogravimetric Control of Intermediate Products in the Metallurgy of Uranium; CONTROL TERMOGRAVIMETRICO DE PRODUCTOS INTERMEDIOS DE LA METALURGIA DEL URANIO

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

Sanchez, L.G.; Cellini, R.F.

1959-01-01

The thermal decomposition of some intermediate compounds in the metallurgy of uranium such as uranium peroxide, ammonium uranate, ammonium uranium pentafluoride, uranium tetrafluoride, and UO/sub 2/, were studied using Chevenard's thermobalance. Some data on the pyrolysis of synthetic mixtures of intermediate compounds which may appear during the industrial processing are given. Thermogravimetric methods of control are suggested for use in uranium metallurgy. (tr-auth)

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.

Uranium XAFS analysis of kidney from rats exposed to uranium

PubMed Central

Kitahara, Keisuke; Numako, Chiya; Terada, Yasuko; Nitta, Kiyohumi; Homma-Takeda, Shino

2017-01-01

The kidney is the critical target of uranium exposure because uranium accumulates in the proximal tubules and causes tubular damage, but the chemical nature of uranium in kidney, such as its chemical status in the toxic target site, is poorly understood. Micro-X-ray absorption fine-structure (µXAFS) analysis was used to examine renal thin sections of rats exposed to uranyl acetate. The U L III-edge X-ray absorption near-edge structure spectra of bulk renal specimens obtained at various toxicological phases were similar to that of uranyl acetate: their edge position did not shift compared with that of uranyl acetate (17.175 keV) although the peak widths for some kidney specimens were slightly narrowed. µXAFS measurements of spots of concentrated uranium in the micro-regions of the proximal tubules showed that the edge jump slightly shifted to lower energy. The results suggest that most uranium accumulated in kidney was uranium (VI) but a portion might have been biotransformed in rats exposed to uranyl acetate. PMID:28244440

Uranium XAFS analysis of kidney from rats exposed to uranium.

PubMed

Kitahara, Keisuke; Numako, Chiya; Terada, Yasuko; Nitta, Kiyohumi; Shimada, Yoshiya; Homma-Takeda, Shino

2017-03-01

The kidney is the critical target of uranium exposure because uranium accumulates in the proximal tubules and causes tubular damage, but the chemical nature of uranium in kidney, such as its chemical status in the toxic target site, is poorly understood. Micro-X-ray absorption fine-structure (µXAFS) analysis was used to examine renal thin sections of rats exposed to uranyl acetate. The U L III -edge X-ray absorption near-edge structure spectra of bulk renal specimens obtained at various toxicological phases were similar to that of uranyl acetate: their edge position did not shift compared with that of uranyl acetate (17.175 keV) although the peak widths for some kidney specimens were slightly narrowed. µXAFS measurements of spots of concentrated uranium in the micro-regions of the proximal tubules showed that the edge jump slightly shifted to lower energy. The results suggest that most uranium accumulated in kidney was uranium (VI) but a portion might have been biotransformed in rats exposed to uranyl acetate.

Volumetric determination of uranium titanous sulfate as reductant before oxidimetric titration

USGS Publications Warehouse

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

1957-01-01

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

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.

Identifying anthropogenic uranium compounds using soft X-ray near-edge absorption spectroscopy

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

Ward, Jesse D.; Bowden, Mark; Tom Resch, C.

2017-01-01

Uranium ores mined for industrial use are typically acid-leached to produce yellowcake and then converted into uranium halides for enrichment and purification. These anthropogenic chemical forms of uranium are distinct from their mineral counterparts. The purpose of this study is to use soft X-ray absorption spectroscopy to characterize several common anthropogenic uranium compounds important to the nuclear fuel cycle. Non-destructive chemical analyses of these compounds is important for process and environmental monitoring and X-ray absorption techniques have several advantages in this regard, including element-specificity, chemical sensitivity, and high spectral resolution. Oxygen K-edge spectra were collected for uranyl nitrate, uranyl fluoride,more » and uranyl chloride, and fluorine K-edge spectra were collected for uranyl fluoride and uranium tetrafluoride. Interpretation of the data is aided by comparisons to calculated spectra. These compounds have unique spectral signatures that can be used to identify unknown samples.« less

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

40 CFR Appendix Vi to Part 265 - Compounds With Henry's Law Constant Less Than 0.1 Y/X

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 27 2013-07-01 2013-07-01 false Compounds With Henry's Law Constant Less Than 0.1 Y/X VI Appendix VI to Part 265 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Law Constant Less Than 0.1 Y/X Compound name CAS No. Acetaldol 107-89-1 Acetamide 60-35-5 2...

40 CFR Appendix Vi to Part 265 - Compounds With Henry's Law Constant Less Than 0.1 Y/X

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 26 2014-07-01 2014-07-01 false Compounds With Henry's Law Constant Less Than 0.1 Y/X VI Appendix VI to Part 265 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Law Constant Less Than 0.1 Y/X Compound name CAS No. Acetaldol 107-89-1 Acetamide 60-35-5 2...

40 CFR Appendix Vi to Part 265 - Compounds With Henry's Law Constant Less Than 0.1 Y/X

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 25 2010-07-01 2010-07-01 false Compounds With Henry's Law Constant Less Than 0.1 Y/X VI Appendix VI to Part 265 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Law Constant Less Than 0.1 Y/X Compound name CAS No. Acetaldol 107-89-1 Acetamide 60-35-5 2...

40 CFR Appendix Vi to Part 265 - Compounds With Henry's Law Constant Less Than 0.1 Y/X

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 27 2012-07-01 2012-07-01 false Compounds With Henry's Law Constant Less Than 0.1 Y/X VI Appendix VI to Part 265 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Law Constant Less Than 0.1 Y/X Compound name CAS No. Acetaldol 107-89-1 Acetamide 60-35-5 2...

40 CFR Appendix Vi to Part 265 - Compounds With Henry's Law Constant Less Than 0.1 Y/X

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 26 2011-07-01 2011-07-01 false Compounds With Henry's Law Constant Less Than 0.1 Y/X VI Appendix VI to Part 265 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Law Constant Less Than 0.1 Y/X Compound name CAS No. Acetaldol 107-89-1 Acetamide 60-35-5 2...

Bioprospecting of gum kondagogu (Cochlospermum gossypium) for bioremediation of uranium (VI) from aqueous solution and synthetic nuclear power reactor effluents.

PubMed

Sashidhar, R B; Selvi, S Kalaignana; Vinod, V T P; Kosuri, Tanuja; Raju, D; Karuna, R

2015-10-01

An ecofriendly green chemistry method using a natural biopolymer, Gum Kondagogu (GK) for the removal of U (VI) from aqueous, simulated nuclear effluents was studied. The adsorption characteristic of GK towards U (VI) from aqueous solution was studied at varied pH, contact time, adsorbent dose, initial U (VI) concentration and temperature using UV-Visible spectroscopy and ICP-MS. Maximum adsorption was seen at pH 4, 0.1% GK with 60 min contact time at room temperature. The GK- U (VI) composite was characterized by FT-IR, zeta potential, TEM and SEM-EDAX. The Langmuir isotherm was found to be 487 mg of U (VI) g(-1) of GK. The adsorption capacity and (%) of U (VI) was found to be 490 ± 5.4 mg g(-1) and 98.5%. Moreover adsorption of U (VI) by GK was not influenced by other cations present in the simulated effluents. The adsorbed U (VI) was efficiently stripped from composite using 1 M HCl. Copyright © 2015 Elsevier Ltd. All rights reserved.

[Studies on the chemical constituents of Ficus microcarpa].

PubMed

Li, Yan-Wen; Sun, Zhi-Rong; Li, Zhi-Yong; Jin, Jia-Xing; Wang, Wen-Quan; Yan, Yu-Ning

2010-06-01

To study the chemical constituents of the Ficus microcarpa. Isolation and identification were carried out by using various chromatography techniques and spectral methods. Eight compounds were isolated. Their structures were identified as beta-amyrone (I), lupeol (II), lupeol acetate (III), maslinic acid (IV), epifriedelinol (V), stearic acid (VI), beta-sitosterol (VI), daucosterol (VI). Compounds I, II, VI are isolated from this plant for the first time.

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

PubMed

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

2010-03-01

An Fe(III)- and uranium(VI)-reducing bacterium, designated strain FRC-32(T), was isolated from a contaminated subsurface of the USA Department of Energy Oak Ridge Field Research Center (ORFRC) in Oak Ridge, Tennessee, where the sediments are exposed to mixed waste contamination of radionuclides and hydrocarbons. Analyses of both 16S rRNA gene and the Geobacteraceae-specific citrate synthase (gltA) mRNA gene sequences retrieved from ORFRC sediments indicated that this strain was abundant and active in ORFRC subsurface sediments undergoing uranium(VI) bioremediation. The organism belonged to the subsurface clade of the genus Geobacter and shared 92-98 % 16S rRNA gene and 75-81 % rpoB gene sequence similarities with other recognized species of the genus. In comparison to its closest relative, Geobacter uraniireducens Rf4(T), according to 16S rRNA gene sequence similarity, strain FRC-32(T) showed a DNA-DNA relatedness value of 21 %. Cells of strain FRC-32(T) were Gram-negative, non-spore-forming, curved rods, 1.0-1.5 microm long and 0.3-0.5 microm in diameter; the cells formed pink colonies in a semisolid cultivation medium, a characteristic feature of the genus Geobacter. The isolate was an obligate anaerobe, had temperature and pH optima for growth at 30 degrees C and pH 6.7-7.3, respectively, and could tolerate up to 0.7 % NaCl although growth was better in the absence of NaCl. Similar to other members of the Geobacter group, strain FRC-32(T) conserved energy for growth from the respiration of Fe(III)-oxyhydroxide coupled with the oxidation of acetate. Strain FRC-32(T) was metabolically versatile and, unlike its closest relative, G. uraniireducens, was capable of utilizing formate, butyrate and butanol as electron donors and soluble ferric iron (as ferric citrate) and elemental sulfur as electron acceptors. Growth on aromatic compounds including benzoate and toluene was predicted from preliminary genomic analyses and was confirmed through successive transfer with fumarate as the electron acceptor. Thus, based on genotypic, phylogenetic and phenotypic differences, strain FRC-32(T) is considered to represent a novel species of the genus Geobacter, for which the name Geobacter daltonii sp. nov. is proposed. The type strain is FRC-32(T) (=DSM 22248(T)=JCM 15807(T)).

Defense Technical Information Center Thesaurus

DTIC Science & Technology

2000-10-01

acquisition radar 4 + Indicates existence of further generic levels of the term DTIC Thesaurus Actuators Acridines Actinide series (cont.) Activated sintering...BT Heterocyclic compounds+ Uranium+ BT Sintering Acrilan Actinide series compounds Activated sludge process use Acrylonitrile polymers RT Actinide...Waste treatment+ Protactinium compounds Acronyms Thorium compounds+ Activation use Abbreviations Transuranium compounds+ UF Energizing Uranium compounds

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

USGS Publications Warehouse

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

2015-01-01

A proposed approach for groundwater remediation of uranium contamination is to generate reducing conditions by stimulating the growth of microbial populations through injection of electron donor compounds into the subsurface. Sufficiently reducing conditions will result in reduction of soluble hexavalent uranium, U(VI), and precipitation of the less soluble +4 oxidation state uranium, U(IV). This process is termed biostimulated reduction. A key issue in the remediation of uranium (U) contamination in aquifers by biostimulated reduction is the long term stability of the sequestered uranium. Three flow-through column experiments using aquifer sediment were used to evaluate the remobilization of bioreduced U sequestered under conditions in which biostimulation extended well into sulfate reduction to enhance precipitation of reduced sulfur phases such as iron sulfides. One column received added ferrous iron, Fe(II), increasing production of iron sulfides, to test their effect on remobilization of the sequestered uranium, either by serving as a redox buffer by competing for dissolved oxygen, or by armoring the reduced uranium. During biostimulation of the ambient microbial population with acetate, dissolved uranium was lowered by a factor of 2.5 or more with continued removal for over 110 days of biostimulation, well after the onset of sulfate reduction at ~30 days. Sequestered uranium was essentially all U(IV) resulting from the formation of nano-particulate uraninite that coated sediment grains to a thickness of a few 10’s of microns, sometimes in association with S and Fe. A multicomponent biogeochemical reactive transport model simulation of column effluents during biostimulation was generally able to describe the acetate oxidation, iron, sulfate, and uranium reduction for all three columns using parameters derived from simulations of field scale biostimulation experiments. Columns were eluted with artificial groundwater at equilibrium with atmospheric oxygen to simulate the upper limit of dissolved oxygen in recharge water. Overall about 9% of total uranium removed from solution during biostimulation was remobilized. Release of U during oxic elution was a continuous process over 140 days with dissolved uranium concentrations about 0.2 and 0.8 aM for columns with and without ferrous iron addition, respectively. Uranium remaining on the sediment was in the reduced form. The prolonged period of biostimulation and concomitant sulfate reduction appears to limit the rate of U(IV) oxidative remobilization in contrast to a large release observed for columns in previous studies that did not undergo sulfate reduction. Although continued sulfate reduction may cause decreased permeability from precipitation of iron sulfide, the greater apparent stability of the sequestered U(IV) provided by the sustained biostimulation should be considered in design of field scale remediation efforts. Remobilization of uranium following biostimulated reduction should be tested further at the field scale.

A Laboratory Procedure for the Reduction of Chromium(VI) to Chromium(III).

ERIC Educational Resources Information Center

Lunn, George; Sansone, Eric B.

1989-01-01

Chromium(VI) compounds are classified as oxidizers and must be specially packaged and transported for disposal while Cr(III) compounds are considered nonoxidizers. A process which reduces Cr(VI) to Cr(III) by adding sodium metabisulfite followed by neutralization with magnesium hydroxide is explored. (MVL)

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

PubMed Central

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

2016-01-01

ABSTRACT Cell suspensions of Pelosinus sp. strain UFO1 were previously shown, using spectroscopic analysis, to sequester uranium as U(IV) complexed with carboxyl and phosphoryl group ligands on proteins. The goal of our present study was to characterize the proteins involved in uranium binding. Virtually all of the uranium in UFO1 cells was associated with a heterodimeric protein, which was termed the uranium-binding complex (UBC). The UBC was composed of two S-layer domain proteins encoded by UFO1_4202 and UFO1_4203. Samples of UBC purified from the membrane fraction contained 3.3 U atoms/heterodimer, but significant amounts of phosphate were not detected. The UBC had an estimated molecular mass by gel filtration chromatography of 15 MDa, and it was proposed to contain 150 heterodimers (UFO1_4203 and UFO1_4202) and about 500 uranium atoms. The UBC was also the dominant extracellular protein, but when purified from the growth medium, it contained only 0.3 U atoms/heterodimer. The two genes encoding the UBC were among the most highly expressed genes within the UFO1 genome, and their expressions were unchanged by the presence or absence of uranium. Therefore, the UBC appears to be constitutively expressed and is the first line of defense against uranium, including by secretion into the extracellular medium. Although S-layer proteins were previously shown to bind U(VI), here we showed that U(IV) binds to S-layer proteins, we identified the proteins involved, and we quantitated the amount of uranium bound. IMPORTANCE Widespread uranium contamination from industrial sources poses hazards to human health and to the environment. Herein, we identified a highly abundant uranium-binding complex (UBC) from Pelosinus sp. strain UFO1. The complex makes up the primary protein component of the S-layer of strain UFO1 and binds 3.3 atoms of U(IV) per heterodimer. While other bacteria have been shown to bind U(VI) on their S-layer, we demonstrate here an example of U(IV) bound by an S-layer complex. The UBC provides a potential tool for the microbiological sequestration of uranium for the cleaning of contaminated environments. PMID:27913415

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

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

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

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

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

PubMed

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

2017-02-15

Cell suspensions of Pelosinus sp. strain UFO1 were previously shown, using spectroscopic analysis, to sequester uranium as U(IV) complexed with carboxyl and phosphoryl group ligands on proteins. The goal of our present study was to characterize the proteins involved in uranium binding. Virtually all of the uranium in UFO1 cells was associated with a heterodimeric protein, which was termed the uranium-binding complex (UBC). The UBC was composed of two S-layer domain proteins encoded by UFO1_4202 and UFO1_4203. Samples of UBC purified from the membrane fraction contained 3.3 U atoms/heterodimer, but significant amounts of phosphate were not detected. The UBC had an estimated molecular mass by gel filtration chromatography of 15 MDa, and it was proposed to contain 150 heterodimers (UFO1_4203 and UFO1_4202) and about 500 uranium atoms. The UBC was also the dominant extracellular protein, but when purified from the growth medium, it contained only 0.3 U atoms/heterodimer. The two genes encoding the UBC were among the most highly expressed genes within the UFO1 genome, and their expressions were unchanged by the presence or absence of uranium. Therefore, the UBC appears to be constitutively expressed and is the first line of defense against uranium, including by secretion into the extracellular medium. Although S-layer proteins were previously shown to bind U(VI), here we showed that U(IV) binds to S-layer proteins, we identified the proteins involved, and we quantitated the amount of uranium bound. Widespread uranium contamination from industrial sources poses hazards to human health and to the environment. Herein, we identified a highly abundant uranium-binding complex (UBC) from Pelosinus sp. strain UFO1. The complex makes up the primary protein component of the S-layer of strain UFO1 and binds 3.3 atoms of U(IV) per heterodimer. While other bacteria have been shown to bind U(VI) on their S-layer, we demonstrate here an example of U(IV) bound by an S-layer complex. The UBC provides a potential tool for the microbiological sequestration of uranium for the cleaning of contaminated environments. Copyright © 2017 American Society for Microbiology.

Microbiological, Geochemical and Hydrologic Processes Controlling Uranium Mobility: An Integrated Field-Scale Subsurface Research Challenge Site at Rifle, Colorado, Quality Assurance Project Plan

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

Fix, N. J.

The U.S. Department of Energy (DOE) is cleaning up and/or monitoring large, dilute plumes contaminated by metals, such as uranium and chromium, whose mobility and solubility change with redox status. Field-scale experiments with acetate as the electron donor have stimulated metal-reducing bacteria to effectively remove uranium [U(VI)] from groundwater at the Uranium Mill Tailings Site in Rifle, Colorado. The Pacific Northwest National Laboratory and a multidisciplinary team of national laboratory and academic collaborators has embarked on a research proposed for the Rifle site, the object of which is to gain a comprehensive and mechanistic understanding of the microbial factors andmore » associated geochemistry controlling uranium mobility so that DOE can confidently remediate uranium plumes as well as support stewardship of uranium-contaminated sites. This Quality Assurance Project Plan provides the quality assurance requirements and processes that will be followed by the Rifle Integrated Field-Scale Subsurface Research Challenge Project.« less

Extractive separation of uranium and zirconium sulfates by amines

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

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

1992-04-01

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

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

Zhang, Yingjie, E-mail: yzx@ansto.gov.au; Karatchevtseva, Inna; Bhadbhade, Mohan

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

METHOD OF RECOVERING URANIUM COMPOUNDS

DOEpatents

Poirier, R.H.

1957-10-29

S>The recovery of uranium compounds which have been adsorbed on anion exchange resins is discussed. The uranium and thorium-containing residues from monazite processed by alkali hydroxide are separated from solution, and leached with an alkali metal carbonate solution, whereby the uranium and thorium hydrorides are dissolved. The carbonate solution is then passed over an anion exchange resin causing the uranium to be adsorbed while the thorium remains in solution. The uranium may be recovered by contacting the uranium-holding resin with an aqueous ammonium carbonate solution whereby the uranium values are eluted from the resin and then heating the eluate whereby carbon dioxide and ammonia are given off, the pH value of the solution is lowered, and the uranium is precipitated.

Fate and transport of uranium (VI) in weathered saprolite

DOE PAGES

Kim, Young-Jin; Brooks, Scott C.; Zhang, Fan; ...

2014-11-09

We conducted batch and column experiments to investigate sorption and transport of uranium (U) in the presence of saprolite derived from interbedded shale, limestone, and sandstone sequences. Sorption kinetics were measured at two initial concentrations (C0; 1, 10 mM) and three soil:solution ratios (Rs/w; 0.005, 0.25, 2 kg/L) at pH 4.5 (pH of the saprolite). The rate of U loss from solution (mmole/L/h) increased with increasing Rs/w. Uranium sorption exhibited a fast phase with 80% sorption in the first eight hours for all C0 and Rs/w values and a slow phase during which the reaction slowly approached (pseudo) equilibrium overmore » the next seven days. The pH-dependency of U sorption was apparent in pH sorption edges. U(VI) sorption increased over the pH range 4e6, then decreased sharply at pH > 7.5. U(VI) sorption edges were well described by a surface complexation model using calibrated parameters and the reaction network proposed by Waite et al. (1994). Sorption isotherms measured using the same Rs/w and pH values showed a solids concentration effect where U(VI) sorption capacity and affinity decreased with increasing solids concentration. Moreover, this effect may have been due to either particle aggregation or competition between U(VI) and exchangeable cations for sorption sites. The surface complexation model with calibrated parameters was able to predict the general sorption behavior relatively well, but failed to reproduce solid concentration effects, implying the importance of appropriate design if batch experiments are to be utilized for dynamic systems. Transport of U(VI) through the packed column was significantly retarded. We also conducted transport simulations using the reactive transport model HydroGeoChem (HGC) v5.0 that incorporated the surface complexation reaction network used to model the batch data. Model parameters reported by Waite et al. (1994) provided a better prediction of U transport than optimized parameters derived from our sorption edges. The results presented in this study highlight the challenges in defining appropriate conditions for batch-type experiments used to extrapolate parameters for transport models, and also underline a gap in our ability to transfer batch results to transport simulations.« less

Identifying anthropogenic uranium compounds using soft X-ray near-edge absorption spectroscopy

NASA Astrophysics Data System (ADS)

Ward, Jesse D.; Bowden, Mark; Tom Resch, C.; Eiden, Gregory C.; Pemmaraju, C. D.; Prendergast, David; Duffin, Andrew M.

2017-01-01

Uranium ores mined for industrial use are typically acid-leached to produce yellowcake and then converted into uranium halides for enrichment and purification. These anthropogenic chemical forms of uranium are distinct from their mineral counterparts. The purpose of this study is to use soft X-ray absorption spectroscopy to characterize several common anthropogenic uranium compounds important to the nuclear fuel cycle. Chemical analyses of these compounds are important for process and environmental monitoring. X-ray absorption techniques have several advantages in this regard, including element-specificity, chemical sensitivity, and high spectral resolution. Oxygen K-edge spectra were collected for uranyl nitrate, uranyl fluoride, and uranyl chloride, and fluorine K-edge spectra were collected for uranyl fluoride and uranium tetrafluoride. Interpretation of the data is aided by comparisons to calculated spectra. The effect of hydration state on the sample, a potential complication in interpreting oxygen K-edge spectra, is discussed. These compounds have unique spectral signatures that can be used to identify unknown samples.

Analysis of benchmark critical experiments with ENDF/B-VI data sets

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

Hardy, J. Jr.; Kahler, A.C.

1991-12-31

Several clean critical experiments were analyzed with ENDF/B-VI data to assess the adequacy of the data for U{sup 235}, U{sup 238} and oxygen. These experiments were (1) a set of homogeneous U{sup 235}-H{sub 2}O assemblies spanning a wide range of hydrogen/uranium ratio, and (2) TRX-1, a simple, H{sub 2}O-moderated Bettis lattice of slightly-enriched uranium metal rods. The analyses used the Monte Carlo program RCP01, with explicit three-dimensional geometry and detailed representation of cross sections. For the homogeneous criticals, calculated k{sub crit} values for large, thermal assemblies show good agreement with experiment. This supports the evaluated thermal criticality parameters for U{supmore » 235}. However, for assemblies with smaller H/U ratios, k{sub crit} values increase significantly with increasing leakage and flux-spectrum hardness. These trends suggest that leakage is underpredicted and that the resonance eta of the ENDF/B-VI U{sup 235} is too large. For TRX-1, reasonably good agreement is found with measured lattice parameters (reaction-rate ratios). Of primary interest is rho28, the ratio of above-thermal to thermal U{sup 238} capture. Calculated rho28 is 2.3 ({+-} 1.7) % above measurement, suggesting that U{sup 238} resonance capture remains slightly overpredicted with ENDF/B-VI. However, agreement is better than observed with earlier versions of ENDF/B.« less

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

NASA Astrophysics Data System (ADS)

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

2014-10-01

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

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.

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

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

Massey, Michael S.; Lezama Pacheco, Juan S.; Jones, Morris

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

Refining and Mutual Separation of Rare Earths Using Biomass Wastes

NASA Astrophysics Data System (ADS)

Inoue, Katsutoshi; Alam, Shafiq

2013-10-01

Two different types of adsorption gels were prepared from biomass wastes. The first gel was produced from astringent persimmon peel rich in persimmon tannin, a polyphenol compound, which was prepared by means of simple dehydration condensation reaction using concentrated sulfuric acid for crosslinking. This adsorption gel was intended to be employed for the removal of radioactive elements, uranium (U(VI)) and thorium (Th(IV)), from rare earths. The second gel was prepared from chitosan, a basic polysaccharide, produced from shells of crustaceans such as crabs, shrimps, prawns, and other biomass wastes generated in marine product industry, by immobilizing functional groups of complexanes such as ethylendiaminetetraacetic acid and diethylentriaminepentaacetic acid (DTPA). This gel was developed for the mutual separation of rare earths. Of the two adsorption gels evaluated, the DTPA immobilized chitosan exhibited the most effective mutual separation among light rare earths.

Microbacterium lemovicicum sp. nov., a bacterium isolated from a natural uranium-rich soil.

PubMed

Mondani, Laure; Piette, Laurie; Christen, Richard; Bachar, Dipankar; Berthomieu, Catherine; Chapon, Virginie

2013-07-01

An actinobacterial strain, designated ViU22(T), was isolated from a natural uranium-rich soil and was studied using a polyphasic approach. Cells formed orange-pigmented colonies, were rod-shaped, Gram-positive (non-staining method), non-motile and non-spore-forming. This organism grew in 0-4.5 % (w/v) NaCl and at 15-37 °C, with optimal growth occurring in 0.5 % (w/v) NaCl and at 30 °C. Comparative 16S rRNA gene sequence analysis revealed that the strain ViU22(T) belonged to the genus Microbacterium. It exhibited highest 16S rRNA gene sequence similarity with the type strains of Microbacterium testaceum (98.14 %) and Microbacterium binotii (98.02 %). The DNA-DNA relatedness of strains ViU22(T) with the most closely related type strains Microbacterium testaceum and Microbacterium binotii DSM 19164(T) was 20.10 % (± 0.70) and 28.05 % (± 0.35), respectively. Strain ViU22(T) possessed a type B2β peptidoglycan with partial substitution of glutamic acid by 3-hydroxy glutamic acid. The major menaquinones were MK-11 and MK-12. Major polar lipids detected in the strain ViU22(T) were diphosphatidylglycerol, phosphatidylglycerol, an unknown phospholipid and unknown glycolipids. The predominant fatty acids were anteiso-C15 : 0, anteiso-C17 : 0 and iso-C16 : 0, a pattern reported for other Microbacterium species. The major cell-wall sugars were galactose, xylose and mannose and the DNA G+C content was 71 mol%. Together, the DNA-DNA hybridization results and the differentiating phenotypic characteristics, showed that strain ViU22(T) should be classified as the type strain of a novel species within the genus Microbacterium, for which the name Microbacterium lemovicicum sp. nov. is proposed. The type strain is ViU22(T) ( = ATCC BAA-2396(T) = CCUG 62198(T) = DSM 25044(T)).

Comparative Genotoxicity and Cytotoxicity of Four Hexavalent Chromium Compounds in Human Bronchial Cells

PubMed Central

Wise, Sandra S.; Holmes, Amie L.; Qin, Qin; Xie, Hong; Katsifis, Spiros P.; Thompson, W. Douglas; Wise, John Pierce

2010-01-01

Hexavalent chromium (Cr(VI)) compounds are well-established human lung carcinogens. Solubility plays an important role in their carcinogenicity with the particulate Cr(VI) compounds being the most carcinogenic. Epidemiology and animal studies suggest that zinc chromate is the most potent particulate Cr(VI) compound, however, there are few comparative data to support these observations. The purpose of this study was to compare the genotoxicity of zinc chromate with two other particulate Cr(VI) compounds, barium chromate and lead chromate, and one soluble Cr(VI) compound, sodium chromate. The clastogenic effects of barium chromate and zinc chromate were similar but lead chromate induced significantly less damage. The levels of DNA damage measured by gamma-H2A.X foci formation were similar for the three particulate chromium compounds. Corrected for chromium uptake differences, we found that zinc chromate and barium chromate were the most cytotoxic and lead chromate and sodium chromate were less cytotoxic. Zinc chromate was more clastogenic than all other chromium compounds and lead chromate was the least clastogenic. There was no significant difference between any of the compounds for the induction of DNA double strand breaks. All together, these data suggest that the difference in the carcinogenic potency of zinc chromate over the other chromium compounds is not due solely to a difference in chromium ion uptake and the zinc cation may in fact have an important role in its carcinogenicity. PMID:20000473

Linking Specific Heterotrophic Bacterial Populations to Bioreduction of Uranium and Nitrate in Contaminated Subsurface Sediments by Using Stable Isotope Probing▿†

PubMed Central

Akob, Denise M.; Kerkhof, Lee; Küsel, Kirsten; Watson, David B.; Palumbo, Anthony V.; Kostka, Joel E.

2011-01-01

Shifts in terminal electron-accepting processes during biostimulation of uranium-contaminated sediments were linked to the composition of stimulated microbial populations using DNA-based stable isotope probing. Nitrate reduction preceded U(VI) and Fe(III) reduction in [13C]ethanol-amended microcosms. The predominant, active denitrifying microbial groups were identified as members of the Betaproteobacteria, whereas Actinobacteria dominated under metal-reducing conditions. PMID:21948831

High-Quality Draft Genome Sequence of Desulfovibrio carbinoliphilus FW-101-2B, an Organic Acid-Oxidizing Sulfate-Reducing Bacterium Isolated from Uranium(VI)-Contaminated Groundwater

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

Ramsay, Bradley D.; Hwang, Chiachi; Woo, Hannah L.

2015-03-12

Desulfovibrio carbinoliphilus subsp. oakridgensis FW-101-2B is an anaerobic, organic acid/alcohol-oxidizing, sulfate-reducing δ-proteobacterium. FW-101-2B was isolated from contaminated groundwater at The Field Research Center at Oak Ridge National Lab after in situ stimulation for heavy metal-reducing conditions. The genome will help elucidate the metabolic potential of sulfate-reducing bacteria during uranium reduction.

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

Bacterial population dynamics during uranium reduction andre-oxidation: Application of a novel high density oligonucleotidemicroarray approach

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

Brodie, Eoin L.; DeSantis, Todd Z.; Joyner, Dominique C.

2006-01-30

Reduction of soluble uranium U(VI) to less-soluble uraniumU(IV) is a promising approach to minimize migration from contaminatedaquifers. It is generally assumed that, under constant reducingconditions, U(IV) is stable and immobile; however, in a previous study,we documented reoxidation of U(IV) under continuous reducing conditions(Wan et al., Environ. Sci. Technol. 2005, 39:6162 6169). To determine ifchanges in microbial community composition were a factor in U(IV)reoxidation, we employed a high-density phylogenetic DNA microarray (16Smicroarray) containing 500,000 probes to monitor changes in bacterialpopulations during this remediation process. Comparison of the 16Smicroarray with clone libraries demonstrated successful detection andclassification of most clone groups. Analysis ofmore » the most dynamic groupsof 16S rRNA gene amplicons detected by the 16S microarray identified fiveclusters of bacterial subfamilies responding in a similar manner. Thisapproach demonstrated that amplicons of known metal-reducing bacteriasuch as Geothrix fermentans (confirmed by quantitative PCR) and thosewithin the Geobacteraceae were abundant during U(VI) reduction and didnot decline during the U(IV) reoxidation phase. Significantly, it appearsthat the observed reoxidation of uranium under reducing conditionsoccurred despite elevated microbial activity and the consistent presenceof metal-reducing bacteria. High-density phylogenetic microarraysconstitute a powerful tool, enabling the detection and monitoring of asubstantial portion of the microbial population in a routine, accurate,and reproducible manner.« less

Upscaling of U (VI) desorption and transport from decimeter‐scale heterogeneity to plume‐scale modeling

USGS Publications Warehouse

Curtis, Gary P.; Kohler, Matthias; Kannappan, Ramakrishnan; Briggs, Martin A.; Day-Lewis, Frederick D.

2015-01-01

Scientifically defensible predictions of field scale U(VI) transport in groundwater requires an understanding of key processes at multiple scales. These scales range from smaller than the sediment grain scale (less than 10 μm) to as large as the field scale which can extend over several kilometers. The key processes that need to be considered include both geochemical reactions in solution and at sediment surfaces as well as physical transport processes including advection, dispersion, and pore-scale diffusion. The research summarized in this report includes both experimental and modeling results in batch, column and tracer tests. The objectives of this research were to: (1) quantify the rates of U(VI) desorption from sediments acquired from a uranium contaminated aquifer in batch experiments;(2) quantify rates of U(VI) desorption in column experiments with variable chemical conditions, and(3) quantify nonreactive tracer and U(VI) transport in field tests.

Characterization of U(VI)-carbonato ternary complexes on hematite: EXAFS and electrophoretic mobility measurements

USGS Publications Warehouse

Bargar, John R.; Reitmeyer, Rebecca; Lenhart, John J.; Davis, James A.

2000-01-01

We have measured U(VI) adsorption on hematite using EXAFS spectroscopy and electrophoresis under conditions relevant to surface waters and aquifers (0.01 to 10 μM dissolved uranium concentrations, in equilibrium with air, pH 4.5 to 8.5). Both techniques suggest the existence of anionic U(VI)-carbonato ternary complexes. Fits to EXAFS spectra indicate that U(VI) is simultaneously coordinated to surface FeO6 octahedra and carbonate (or bicarbonate) ligands in bidentate fashions, leading to the conclusion that the ternary complexes have an inner-sphere metal bridging (hematite-U(VI)-carbonato) structure. Greater than or equal to 50% of adsorbed U(VI) was comprised of monomeric hematite-U(VI)-carbonato ternary complexes, even at pH 4.5. Multimeric U(VI) species were observed at pH ≥ 6.5 and aqueous U(VI) concentrations approximately an order of magnitude more dilute than the solubility of crystalline β-UO2(OH)2. Based on structural constraints, these complexes were interpreted as dimeric hematite-U(VI)-carbonato ternary complexes. These results suggest that Fe-oxide-U(VI)-carbonato complexes are likely to be important transport-limiting species in oxic aquifers throughout a wide range of pH values.

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

NASA Astrophysics Data System (ADS)

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

2017-07-01

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

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.

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

NASA Astrophysics Data System (ADS)

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

2017-09-01

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

238U and 235U isotope fractionation upon oxidation of uranium-bearing rocks by fracture waters

NASA Astrophysics Data System (ADS)

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

2016-10-01

The variations in 238U/235U values accompanying mobilization of U by fracture waters from uranium-bearing rocks, in which U occurs as a fine impregnation of oxides and silicates, were studied by the high-precision (±0.07‰) MC-ICP-MS method. Transition of U into the aqueous phase in the oxidized state U(VI) is accompanied by its isotope fractionation with enrichment of dissolved U(VI) in the heavy isotope 238U up to 0.32‰ in relation to the composition of the solid phases. According to the sign, this effect is consistent with the tendency of the behavior of 238U and 235U upon interaction of river waters with rocks of the catchment areas [11] and with the effect observed during oxidation of uraninite by the oxygen-bearing NaHCO3 solution [12].

Nano-Scale Hydroxyapatite: Synthesis, Two-Dimensional Transport Experiments, and Application for Uranium Remediation

DOE PAGES

Kanel, S. R.; Clement, T. P.; Barnett, M. O.; ...

2011-01-01

Synthetic nano-scale hydroxyapatite (NHA) was prepared and characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM) methods. The XRD data confirmed that the crystalline structure and chemical composition of NHA correspond to Ca 5 OH(PO 4 ) 3 . The SEM data confirmed the size of NHA to be less than 50 nm. A two-dimensional physical model packed with saturated porous media was used to study the transport characteristics of NHA under constant flow conditions. The data show that the transport patterns of NHA were almost identical to tracer transport patterns. This result indicates that the NHA material can movemore » with water like a tracer, and its movement was neither retarded nor influenced by any physicochemical interactions and/or density effects. We have also tested the reactivity of NHA with 1 mg/L hexavalent uranium (U(VI)) and found that complete removal of U(VI) is possible using 0.5 g/L NHA at pH 5 to 6. Our results demonstrate that NHA has the potential to be injected as a dilute slurry for in situ treatment of U(VI)-contaminated groundwater systems.« less

Comparison of heavy metals and uranium removal using adsorbent in soil

NASA Astrophysics Data System (ADS)

Choi, Jaeyoung; Yun, Hunsik

2017-04-01

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

Mortality (1968-2008) in a French cohort of uranium enrichment workers potentially exposed to rapidly soluble uranium compounds.

PubMed

Zhivin, Sergey; Guseva Canu, Irina; Samson, Eric; Laurent, Olivier; Grellier, James; Collomb, Philippe; Zablotska, Lydia B; Laurier, Dominique

2016-03-01

Until recently, enrichment of uranium for civil and military purposes in France was carried out by gaseous diffusion using rapidly soluble uranium compounds. We analysed the relationship between exposure to soluble uranium compounds and exposure to external γ-radiation and mortality in a cohort of 4688 French uranium enrichment workers who were employed between 1964 and 2006. Data on individual annual exposure to radiological and non-radiological hazards were collected for workers of the AREVA NC, CEA and Eurodif uranium enrichment plants from job-exposure matrixes and external dosimetry records, differentiating between natural, enriched and depleted uranium. Cause-specific mortality was compared with the French general population via standardised mortality ratios (SMR), and was analysed via Poisson regression using log-linear and linear excess relative risk models. Over the period of follow-up, 131 161 person-years at risk were accrued and 21% of the subjects had died. A strong healthy worker effect was observed: all causes SMR=0.69, 95% CI 0.65 to 0.74. SMR for pleural cancer was significantly increased (2.3, 95% CI 1.06 to 4.4), but was only based on nine cases. Internal uranium and external γ-radiation exposures were not significantly associated with any cause of mortality. This is the first study of French uranium enrichment workers. Although limited in statistical power, further follow-up of this cohort, estimation of internal uranium doses and pooling with similar cohorts should elucidate potential risks associated with exposure to soluble uranium compounds. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://www.bmj.com/company/products-services/rights-and-licensing/

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

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

Taillefert, Martial; Van Cappellen, Philippe

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

Oxidative dissolution of biogenic uraninite in groundwater at Old Rifle, CO

USGS Publications Warehouse

Campbell, Kate M.; Veeramani, Harish; Ulrich, Kai-Uwe; Blue, Lisa Y.; Giammar, Dianiel E.; Bernier-Latmani, Rizlan; Stubbs, Joanne E.; Suvorova, Elena; Yabusaki, Steve; Lezama-Pacheco, Juan S.; Mehta, Apurva; Long, Philip E.; Bargar, John R.

2011-01-01

Reductive bioremediation is currently being explored as a possible strategy for uranium-contaminated aquifers such as the Old Rifle site (Colorado). The stability of U(IV) phases under oxidizing conditions is key to the performance of this procedure. An in situ method was developed to study oxidative dissolution of biogenic uraninite (UO2), a desirable U(VI) bioreduction product, in the Old Rifle, CO, aquifer under different variable oxygen conditions. Overall uranium loss rates were 50–100 times slower than laboratory rates. After accounting for molecular diffusion through the sample holders, a reactive transport model using laboratory dissolution rates was able to predict overall uranium loss. The presence of biomass further retarded diffusion and oxidation rates. These results confirm the importance of diffusion in controlling in-aquifer U(IV) oxidation rates. Upon retrieval, uraninite was found to be free of U(VI), indicating dissolution occurred via oxidation and removal of surface atoms. Interaction of groundwater solutes such as Ca2+ or silicate with uraninite surfaces also may retard in-aquifer U loss rates. These results indicate that the prolonged stability of U(IV) species in aquifers is strongly influenced by permeability, the presence of bacterial cells and cell exudates, and groundwater geochemistry.

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

PubMed

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

2016-10-04

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

Modeling Reduction of Uranium U(VI) under Variable Sulfate Concentrations by Sulfate-Reducing Bacteria

PubMed Central

Spear, John R.; Figueroa, Linda A.; Honeyman, Bruce D.

2000-01-01

The kinetics for the reduction of sulfate alone and for concurrent uranium [U(VI)] and sulfate reduction, by mixed and pure cultures of sulfate-reducing bacteria (SRB) at 21 ± 3°C were studied. The mixed culture contained the SRB Desulfovibrio vulgaris along with a Clostridium sp. determined via 16S ribosomal DNA analysis. The pure culture was Desulfovibrio desulfuricans (ATCC 7757). A zero-order model best fit the data for the reduction of sulfate from 0.1 to 10 mM. A lag time occurred below cell concentrations of 0.1 mg (dry weight) of cells/ml. For the mixed culture, average values for the maximum specific reaction rate, Vmax, ranged from 2.4 ± 0.2 μmol of sulfate/mg (dry weight) of SRB · h−1) at 0.25 mM sulfate to 5.0 ± 1.1 μmol of sulfate/mg (dry weight) of SRB · h−1 at 10 mM sulfate (average cell concentration, 0.52 mg [dry weight]/ml). For the pure culture, Vmax was 1.6 ± 0.2 μmol of sulfate/mg (dry weight) of SRB · h−1 at 1 mM sulfate (0.29 mg [dry weight] of cells/ml). When both electron acceptors were present, sulfate reduction remained zero order for both cultures, while uranium reduction was first order, with rate constants of 0.071 ± 0.003 mg (dry weight) of cells/ml · min−1 for the mixed culture and 0.137 ± 0.016 mg (dry weight) of cells/ml · min−1 (U0 = 1 mM) for the D. desulfuricans culture. Both cultures exhibited a faster rate of uranium reduction in the presence of sulfate and no lag time until the onset of U reduction in contrast to U alone. This kinetics information can be used to design an SRB-dominated biotreatment scheme for the removal of U(VI) from an aqueous source. PMID:10966381

HNO3 modified biochars for uranium (VI) removal from aqueous solution.

PubMed

Jin, Jie; Li, Shiwei; Peng, Xianqiang; Liu, Wei; Zhang, Chenlu; Yang, Yan; Han, Lanfang; Du, Ziwen; Sun, Ke; Wang, Xiangke

2018-05-01

The HNO 3 treatment was used to chemically modify the biochars produced from wheat straw (WH) and cow manure for U(VI) removal from aqueous solution. Macroscopic experiments proved that the enrichment of U(VI) on the biochars was regulated by surface complexation and electrostatic interactions. FTIR and XPS analyses confirmed that the highly efficient adsorption of U(VI) was due to the carboxyl groups on the biochar surfaces. The reducing agents of the R-CH 2 OH groups facilitated U(VI) adsorption on the untreated biochars. Owing to the higher contents of surface COO groups and more negative surface charge, the modified biochars showed enhanced U(VI) adsorption ability than the untreated ones. The maximum adsorption capacity of U(VI) by the oxidized WH was calculated to be 355.6 mg/g at pH 4.5 and 298 K, which was an improvement of 40 times relative to the untreated WH and was higher than that of most carbon-based adsorbents. Copyright © 2018 Elsevier Ltd. All rights reserved.

Removal of uranium (VI) from aqueous systems by nanoscale zero-valent iron particles suspended in carboxy-methyl cellulose

NASA Astrophysics Data System (ADS)

Popescu (Hoştuc), Ioana-Carmen; Filip, Petru; Humelnicu, Doina; Humelnicu, Ionel; Scott, Thomas Bligh; Crane, Richard Andrew

2013-11-01

Carboxy-methyl-cellulose (CMC), a common "delivery vehicle" for the subsurface deployment of iron nanoparticles (INP) has been tested in the current work for the removal of aqueous uranium from synthetic water samples. A comparison of the removal of aqueous uranium from solutions using carboxy-methyl-cellulose with and without iron nanoparticles (CMC-INP and CMC, respectively) was tested over a 48 h reaction period. Analysis of liquid samples using spectrophotometry determined a maximum sorption capacity of uranium, Qmax, of 185.18 mg/g and 322.58 mg/g for CMC and CMC-INP respectively, providing strong evidence of an independent aqueous uranium removal ability exhibited by CMC. The results point out that CMC provides an additional capacity for aqueous uranium removal. Further tests are required to determine whether similar behaviour will be observed for other aqueous contaminant species and if the presence of CMC within a INP slurry inhibits or aids the reactivity, reductive capacity and affinity of INP for aqueous contaminant removal.

Influence of uranium on bacterial communities: a comparison of natural uranium-rich soils with controls.

PubMed

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

2011-01-01

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

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

PubMed Central

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

2011-01-01

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

Study of uranium oxidation states in geological material.

PubMed

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

2013-10-01

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

Immobilization of uranium into magnetite from aqueous solution by electrodepositing approach.

PubMed

Lu, Bing-Qing; Li, Mi; Zhang, Xiao-Wen; Huang, Chun-Mei; Wu, Xiao-Yan; Fang, Qi

2018-02-05

Immobilization of uranium into magnetite (Fe 3 O 4 ), which was generated from metallic iron by electrochemical method, was proposed to rapidly remove uranium from aqueous solution. The effects of electrochemical parameters such as electrode materials, voltage, electrode gap, reaction time and pH value on the crystallization of Fe 3 O 4 and uranium removal efficiencies were investigated. More than 90% uranium in the solution was precipitated with Fe 3 O 4 under laboratory conditions when uranium concentration range from 0.5mg/L to 10mg/L. The Fe 3 O 4 crystallization mechanism and immobilization of uranium was proved by XPS, XRD, TEM, FTIR and VSM methods. The results indicated that the cationic (including Fe 2+ , Fe 3+ and U(VI)) migrate to cathode side under the electric field and the uranium was incorporated or adsorbed by Fe 3 O 4 which was generated at cathode while the pH ranges between 2-7. The uranium-containing precipitate of Fe 3 O 4 can exist stably at the acid concentration below 60g/L. Furthermore, the precipitate may be used as valuable resources for uranium or iron recycling, which resulted in no secondary pollution in the removal of uranium from aqueous solution. Copyright © 2017. Published by Elsevier B.V.

Measurement of the Auger parameter and Wagner plot for uranium compounds

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

Holliday, Kiel S.; Siekhaus, Wigbert; Nelson, Art J.

2013-05-15

In this study, the photoemission from the U 4f{sub 7/2} and 4d{sub 5/2} states and the U N{sub 6}O{sub 45}O{sub 45} and N{sub 67}O{sub 45}V x-ray excited Auger transitions were measured for a range of uranium compounds. The data are presented in Wagner plots and the Auger parameter is calculated to determine the utility of this technique in the analysis of uranium materials. It was demonstrated that the equal core-level shift assumption holds for uranium. It was therefore possible to quantify the relative relaxation energies, and uranium was found to have localized core-hole shielding. The position of compounds within themore » Wagner plot made it possible to infer information on bonding character and local electron density. The relative ionicity of the uranium compounds studied follows the trend UF{sub 4} > UO{sub 3} > U{sub 3}O{sub 8} > U{sub 4}O{sub 9}/U{sub 3}O{sub 7} Almost-Equal-To UO{sub 2} > URu{sub 2}Si{sub 2}.« less

Recovery of tritium from tritiated molecules

DOEpatents

Swansiger, William A.

1987-01-01

A method of recovering tritium from tritiated compounds comprises the steps of heating tritiated water and other co-injected tritiated compounds in a preheater to temperatures of about 600.degree. C. The mixture is injected into a reactor charged with a mixture of uranium and uranium dioxide. The injected mixture undergoes highly exothermic reactions with the uranium causing reaction temperatures to occur in excess of the melting point of uranium, and complete decomposition of the tritiated compounds to remove tritium therefrom. The uranium dioxide functions as an insulating material and heat sink preventing the reactor side walls from attaining reaction temperatures to thereby minimize tritium permeation rates. The uranium dioxide also functions as a diluent to allow for volumetric expansion of the uranium as it is converted to uranium dioxide. The reactor vessel is preferably stainless steel of sufficient mass so as to function as a heat sink preventing the reactor side walls from approaching high temperatures. A disposable copper liner extends between the reaction chamber and stainless steel outer vessel to prevent alloying of the uranium with the outer vessel. Apparatus used to carry out the method of the invention is also disclosed.

Influence of Calcium on Microbial Reduction of Solid Phase Uranium (VI)

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

Liu, Chongxuan; Jeon, Byong-Hun; Zachara, John M.

2007-06-27

The effect of calcium on microbial reduction of a solid phase U(VI), sodium boltwoodite (NaUO2SiO3OH ∙1.5H2O), was evaluated in a culture of a dissimilatory metal-reducing bacterium (DMRB), Shewanella oneidensis strain MR-1. Batch experiments were performed in a non-growth bicarbonate medium with lactate as electron donor at pH 7 buffered with PIPES. Calcium increased both the rate and extent of Na-boltwoodite dissolution by increasing its solubility through the formation of a ternary aqueous calcium-uranyl-carbonate species. The ternary species, however, decreased the rates of microbial reduction of aqueous U(VI). Laser-induced fluorescence spectroscopy (LIFS) and transmission electron microscopy (TEM) revealed that microbial reductionmore » of solid phase U(VI) is a sequentially coupled process of Na-boltwoodite dissolution, U(VI) aqueous speciation, and microbial reduction of dissolved U(VI) to U(IV) that accumulated on bacterial surfaces/periplasm. The overall rates of microbial reduction of solid phase U(VI) can be described by the coupled rates of dissolution and microbial reduction that were both influenced by calcium. The results demonstrated that dissolved U(VI) concentration during microbial reduction was a complex function of solid phase U(VI) dissolution kinetics, aqueous U(VI) speciation, and microbial activity.« less

LIQUID METAL COMPOSITIONS CONTAINING URANIUM

DOEpatents

Teitel, R.J.

1959-04-21

Liquid metal compositions containing a solid uranium compound dispersed therein is described. Uranium combines with tin to form the intermetallic compound USn/sub 3/. It has been found that this compound may be incorporated into a liquid bath containing bismuth and lead-bismuth components, if a relatively small percentage of tin is also included in the bath. The composition has a low thermal neutron cross section which makes it suitable for use in a liquid metal fueled nuclear reactor.

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

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

Not Available

2011-06-22

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

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 bacteria synthesizing ribosomal RNA in response to uranium addition during biostimulation at the Rifle, CO Integrated Field Research site

DOE PAGES

McGuinness, Lora R.; Wilkins, Michael J.; Williams, Kenneth H.; ...

2015-09-18

Understanding which organisms are capable of reducing uranium at historically contaminated sites provides crucial information needed to evaluate treatment options and outcomes. One approach is determination of the bacteria which directly respond to uranium addition. In this research, uranium amendments were made to groundwater samples from a site of ongoing biostimulation with acetate. The active microbes in the planktonic phase were deduced by monitoring ribosomes production via RT-PCR. The results indicated several microorganisms were synthesizing ribosomes in proportion with uranium amendment up to 2 μM. Concentrations of U (VI) >2 μM were generally found to inhibit ribosome synthesis. Two activemore » bacteria responding to uranium addition in the field were close relatives of Desulfobacter postgateii and Geobacter bemidjiensis. Since RNA content often increases with growth rate, our findings suggest it is possible to rapidly elucidate active bacteria responding to the addition of uranium in field samples and provides a more targeted approach to stimulate specific populations to enhance radionuclide reduction in contaminated sites.« less

Identification of Bacteria Synthesizing Ribosomal RNA in Response to Uranium Addition During Biostimulation at the Rifle, CO Integrated Field Research Site

PubMed Central

McGuinness, Lora R.; Wilkins, Michael J.; Williams, Kenneth H.; Long, Philip E.; Kerkhof, Lee J.

2015-01-01

Understanding which organisms are capable of reducing uranium at historically contaminated sites provides crucial information needed to evaluate treatment options and outcomes. One approach is determination of the bacteria which directly respond to uranium addition. In this study, uranium amendments were made to groundwater samples from a site of ongoing biostimulation with acetate. The active microbes in the planktonic phase were deduced by monitoring ribosomes production via RT-PCR. The results indicated several microorganisms were synthesizing ribosomes in proportion with uranium amendment up to 2 μM. Concentrations of U (VI) >2 μM were generally found to inhibit ribosome synthesis. Two active bacteria responding to uranium addition in the field were close relatives of Desulfobacter postgateii and Geobacter bemidjiensis. Since RNA content often increases with growth rate, our findings suggest it is possible to rapidly elucidate active bacteria responding to the addition of uranium in field samples and provides a more targeted approach to stimulate specific populations to enhance radionuclide reduction in contaminated sites. PMID:26382047

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.

Bulk semiconducting scintillator device for radiation detection

DOEpatents

Stowe, Ashley C.; Burger, Arnold; Groza, Michael

2016-08-30

A bulk semiconducting scintillator device, including: a Li-containing semiconductor compound of general composition Li-III-VI.sub.2, wherein III is a Group III element and VI is a Group VI element; wherein the Li-containing semiconductor compound is used in one or more of a first mode and a second mode, wherein: in the first mode, the Li-containing semiconductor compound is coupled to an electrical circuit under bias operable for measuring electron-hole pairs in the Li-containing semiconductor compound in the presence of neutrons and the Li-containing semiconductor compound is also coupled to current detection electronics operable for detecting a corresponding current in the Li-containing semiconductor compound; and, in the second mode, the Li-containing semiconductor compound is coupled to a photodetector operable for detecting photons generated in the Li-containing semiconductor compound in the presence of the neutrons.

Electrochemical alkaline Fe(VI) water purification and remediation.

PubMed

Licht, Stuart; Yu, Xingwen

2005-10-15

Fe(VI) is an unusual and strongly oxidizing form of iron, which provides a potentially less hazardous water-purifying agent than chlorine. A novel on-line electrochemical Fe(VI) water purification methodology is introduced. Fe(VI) addition had been a barrier to its effective use in water remediation, because solid Fe(VI) salts require complex (costly) syntheses steps and solutions of Fe(VI) decompose. Online electrochemical Fe(VI) water purification avoids these limitations, in which Fe(VI) is directly prepared in solution from an iron anode as the FeO42- ion, and is added to the contaminant stream. Added FeO42- decomposes, by oxidizing a wide range of water contaminants including sulfides (demonstrated in this study) and other sulfur-containing compounds, cyanides (demonstrated in this study), arsenic (demonstrated in this study), ammonia and other nitrogen-containing compounds (previously demonstrated), a wide range of organics (phenol demonstrated in this study), algae, and viruses (each previously demonstrated).

Uranium induces oxidative stress in lung epithelial cells

PubMed Central

Periyakaruppan, Adaikkappan; Kumar, Felix; Sarkar, Shubhashish; Sharma, Chidananda S.

2009-01-01

Uranium compounds are widely used in the nuclear fuel cycle, antitank weapons, tank armor, and also as a pigment to color ceramics and glass. Effective management of waste uranium compounds is necessary to prevent exposure to avoid adverse health effects on the population. Health risks associated with uranium exposure includes kidney disease and respiratory disorders. In addition, several published results have shown uranium or depleted uranium causes DNA damage, mutagenicity, cancer and neurological defects. In the current study, uranium toxicity was evaluated in rat lung epithelial cells. The study shows uranium induces significant oxidative stress in rat lung epithelial cells followed by concomitant decrease in the antioxidant potential of the cells. Treatment with uranium to rat lung epithelial cells also decreased cell proliferation after 72 h in culture. The decrease in cell proliferation was attributed to loss of total glutathione and superoxide dismutase in the presence of uranium. Thus the results indicate the ineffectiveness of antioxidant system’s response to the oxidative stress induced by uranium in the cells. PMID:17124605

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

EPA Pesticide Factsheets

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

Aqueous solubility of Cr(VI) compounds in ferrochrome bag filter dust and the implications thereof

DOE PAGES

Du Preez, S. P.; Beukes, J. P.; Van Dalen, W. P. J.; ...

2017-04-21

The production of ferrochrome (FeCr) is a reducing process. However, it is impossible to completely exclude oxygen from all of the high-temperature production process steps, which may lead to unintentional formation of small amounts of Cr(VI). The majority of Cr(VI) is associated with particles found in the off-gas of the high-temperature processes, which are cleaned by means of venturi scrubbers or bag filter dust (BFD) systems. BFD contains the highest concentration of Cr(VI) of all FeCr wastes. In this study, the solubility of Cr(VI) present in BFD was determined by evaluating four different BFD samples. The results indicate that themore » currently applied Cr(VI) treatment strategies of the FeCr producer (with process water pH ≤ 9) only effectively extract and treat the water-soluble Cr(VI) compounds, which merely represented approximately 31% of the total Cr(VI) present in the BFD samples evaluated. Extended extraction time, within the afore-mentioned pH range, proved futile in extracting sparingly-soluble and water-insoluble Cr(VI) species, which represented approximately 34% and 35% of the total Cr(VI), respectively. Due to the deficiencies of the current treatment strategies, it is highly likely that sparingly water-soluble Cr(VI) compounds will leach from waste storage facilities (e.g. slimes dams) over time. Therefore, it is critical that improved Cr(VI) treatment strategies be formulated, which should be an important future perspective for FeCr producers and researchers alike.« less

The effect of bicarbonate on the microbial dissolution of autunite mineral in the presence of gram-positive bacteria.

PubMed

Sepulveda-Medina, Paola M; Katsenovich, Yelena P; Wellman, Dawn M; Lagos, Leonel E

2015-06-01

Bacteria are key players in the processes that govern fate and transport of contaminants. The uranium release from Na and Ca-autunite by Arthrobacter oxydans strain G968 was evaluated in the presence of bicarbonate ions. This bacterium was previously isolated from Hanford Site soil and in earlier prescreening tests demonstrated low tolerance to U(VI) toxicity compared to other A. oxydans isolates. Experiments were conducted using glass serum bottles as mixed bioreactors and sterile 6-well cell culture plates with inserts separating bacteria cells from mineral solids. Reactors containing phosphorus-limiting media were amended with bicarbonate ranging between 0 and 10 mM and meta-autunite solids to provide a U(VI) concentration of 4.4 mmol/L. Results showed that in the presence of bicarbonate, A. oxydans G968 was able to enhance the release of U(VI) from Na and Ca autunite at the same capacity as other A. oxydans isolates with relatively high tolerance to U(VI). The effect of bacterial strains on autunite dissolution decreases as the concentration of bicarbonate increases. The results illustrate that direct interaction between the bacteria and the mineral is not necessary to result in U(VI) biorelease from autunite. The formation of secondary calcium-phosphate mineral phases on the surface of the mineral during the dissolution can ultimately reduce the natural autunite mineral contact area, which bacterial cells can access. This thereby reduces the concentration of uranium released into the solution. This study provides a better understanding of the interactions between meta-autunite and microbes in conditions mimicking arid and semiarid subsurface environments of western U.S. Copyright © 2015 Elsevier Ltd. All rights reserved.

The Effect of Bicarbonate on the Microbial Dissolution of Autunite Mineral in the Presence of Gram-Positive Bacteria

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

Sepulveda-Medina, Paola; Katsenovich, Yelena; Wellman, Dawn M.

Bacteria are key players in the processes that govern fate and transport of contaminants. The uranium release from Na and Ca-autunite by Arthrobacter oxydans strain G968 was evaluated in the presence of bicarbonate ions. This bacterium was previously isolated from Hanford Site soil and in earlier prescreening tests demonstrated low tolerance to U(VI) toxicity compared to other A.oxydans isolates. Experiments were conducted using glass serum bottles as mixed bioreactors and sterile 6-well cell culture plates with inserts separating bacteria cells from mineral solids. Reactors containing phosphorus-limiting media were amended with bicarbonate ranging between 0-10 mM and metaautunite solids to providemore » a U(VI) concentration of 4.4 mmol/L. Results showed that in the presence of bicarbonate, A.oxydans G968 was able to enhance the release of U(VI) from Na and Ca autunite at the same capacity as other A.oxydans isolates with relatively high tolerance to U(VI). The effect of bacterial strains on autunite dissolution decreases as the concentration of bicarbonate increases. The results illustrate that direct interaction between the bacteria and the mineral is not necessary to result in U (VI) biorelease from autunite. The formation of secondary calcium-phosphate mineral phases on the surface of the mineral during the dissolution can ultimately reduce the natural autunite mineral contact area, which bacterial cells can access. This thereby reduces the concentration of uranium released into the solution. This study provides a better understanding of the interactions between meta-autunite and microbes in conditions mimicking arid and semiarid subsurface environments of western U.S.« less

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

Raoultella sp. SM1, a novel iron-reducing and uranium-precipitating strain.

PubMed

Sklodowska, Aleksandra; Mielnicki, Sebastian; Drewniak, Lukasz

2018-03-01

The main aim of this study was the characterisation of novel Raoutella isolate, an iron-reducing and uranium-precipitating strain, originating from microbial mats occurring in the sediments of a closed down uranium mine in Kowary (SW Poland). Characterisation was done in the context of its potential role in the functioning of these mats and the possibility to use them in uranium removal/recovery processes. In our experiment, we observed the biological precipitation of iron and uranium's secondary minerals containing oxygen, potassium, sodium and phosphor, which were identified as ningyoite-like minerals. The isolated strain, Raoultella sp. SM1, was also able to dissimilatory reduce iron (III) and uranium (VI) in the presence of citrate as an electron donor. Our studies allowed us to characterise a new strain which may be used as a model microorganism in the study of Fe and U respiratory processes and which may be useful in the bioremediation of uranium-contaminated waters and sediments. During this process, uranium may be immobilised in ningyoite-like minerals and can then be recovered in nano/micro-particle form, which may be easily transformed to uraninite. Copyright © 2017 Elsevier Ltd. All rights reserved.

Semi-automatic version of the potentiometric titration method for characterization of uranium compounds.

PubMed

Cristiano, Bárbara F G; Delgado, José Ubiratan; da Silva, José Wanderley S; de Barros, Pedro D; de Araújo, Radier M S; Dias, Fábio C; Lopes, Ricardo T

2012-09-01

The potentiometric titration method was used for characterization of uranium compounds to be applied in intercomparison programs. The method is applied with traceability assured using a potassium dichromate primary standard. A semi-automatic version was developed to reduce the analysis time and the operator variation. The standard uncertainty in determining the total concentration of uranium was around 0.01%, which is suitable for uranium characterization and compatible with those obtained by manual techniques. Copyright © 2012 Elsevier Ltd. All rights reserved.

Efficient sorption and reduction of U(VI) on zero-valent iron-polyaniline-graphene aerogel ternary composite.

PubMed

Chen, Lili; Feng, Shaojie; Zhao, Donglin; Chen, Shaohua; Li, Feifei; Chen, Changlun

2017-03-15

In this work, zero-valent iron-polyaniline-graphene aerogel composite (Fe-PANI-GA) was prepared and applied in the removal of U(VI) from aqueous solutions by batch sorption experiments. The experimental results showed that the Fe-PANI-GA composite had an excellent removal capacity for the removal of U(VI) in acidic solutions. The results also showed that the maximum removal capacity of the Fe-PANI-GA toward U(VI) was 350.47mg/g at pH 5.5. The sorption kinetics data were well-described by pseudo-second-order. The sorption isotherms of U(VI) fitted well with Langmuir isotherm and exhibited better removal efficiency with the increase of temperature. The thermodynamic parameters (ΔG, ΔS, ΔH) indicated that the sorption of U(VI) on the Fe-PANI-GA was an endothermic and spontaneous process. Moreover, removal mechanisms were studied based on the results of XRD, FTIR and XPS. Both U(VI) sorption and partially reductive precipitation of U(VI) to U(IV) contributed to the removal of U(VI) on Fe-PANI-GA. Therefore, Fe-PANI-GA was an economic and effective material for the removal of uranium from nuclear waste in practical application. Copyright © 2016 Elsevier Inc. All rights reserved.

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.

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

Cubic and Rhombohedral Heterobimetallic Networks Constructed from Uranium, Transition Metals, and Phosphonoacetate. New Methods for Constructing Porous Materials

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

Alsobrook, Andera N.; Hauser, B. G.; Hupp, Joseph T.

2010-11-01

Four heterobimetallic U(VI)/M(II) (M = Mn, Co, Cd) carboxyphosphonates have been synthesized. M 2[(UO 2) 6(PO 3CH 2CO 2) 3O 3(OH)(H 2O) 2]·16H 2O (M = Mn(II), Co(II), and Cd(II)) adopt cubic three-dimensional network structures with large cavities approximately 16 Å in diameter that are filled with co-crystallized water molecules. [Cd 3(UO 2) 6(PO 3CH 2CO 2) 6(H 2O) 13]·6H 2 O forms a rhombohedral channel structure with hydrated Cd(II) within the channels. The cubic compound (Co) displays differential gas absorption with a surface area for CO 2 uptake of 40 m 2 g -1 at 273 K, and nomore » uptake of N 2 at 77 K.« less

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

USGS Publications Warehouse

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

2011-01-01

Field biostimulation experiments at the U.S. Department of Energy's Integrated Field Research Challenge (IFRC) site in Rifle, Colorado, have demonstrated that uranium concentrations in groundwater can be decreased to levels below the U.S. Environmental Protection Agency's (EPA) drinking water standard (0.126??M).During successive summer experiments - referred to as "Winchester" (2007) and "Big Rusty" (2008) - acetate was added to the aquifer to stimulate the activity of indigenous dissimilatory metal reducing bacteria capable of reductively immobilizing uranium. The two experiments differed in the length of injection (31 vs. 110 days), the maximum concentration of acetate (5 vs. 30 mM),and the extent to which iron reduction ("Winchester") or sulfate reduction("Big Rusty") was the predominant metabolic process. In both cases, rapid removal of U(VI) from groundwater occurred at calcium concentrations (6 mM) and carbonate alkalinities (8 meq/L) where Ca-UO2-CO3 ternary complexes constitute >90% of uranyl species in groundwater. Complete consumption of acetate and increased alkalinity (>30 meq/L) accompanying the onset of sulfate reduction corresponded to temporary increases in U(VI);however, by increasing acetate concentrations in excess of available sulfate (10 mM), low U(VI) concentrations (0.1-0.05 ??M) were achieved for extended periods of time (>140 days). Uniform delivery of acetate during "Big Rusty" was impeded due to decreases in injection well permeability, likely resulting from biomass accumulation and carbonate and sulfide mineral precipitation. Such decreases were not observed during the short-duration "Winchester" experiment. Terminal restriction fragment length polymorphism (TRFLP) analysis of 16S rRNA genes demonstrated that Geobacter sp. and Geobacter-like strains dominated the groundwater community profile during iron reduction, with 13C stable isotope probing (SIP) results confirming these strains were actively utilizing acetate to replicate their genome during the period of optimal U(VI) removal. Gene transcript levels during "Big Rusty" were quantified for Geobacter-specific citrate synthase (gltA), with ongoing transcription during sulfate reduction indicating that members of the Geobacteraceae were still active and likely contributing to U(VI) removal. The persistence of reducible Fe(III) in sediments recovered from an area of prolonged (110-day) sulfate reduction is consistent with this conclusion. These results indicate that acetate availability and its ability to sustain the activity of iron- and uranyl-respiring Geobacter strains during sulfate reduction exerts a primary control on optimized U(VI) removal from groundwater at the Rifle IFRC site over extended time scales (>50 days). ?? Taylor & Francis Group, LLC.

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

PRODUCTION OF URANIUM AND THORIUM COMPOUNDS

DOEpatents

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

1955-12-27

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

Conversion of depleted uranium hexafluoride to a solid uranium compound

DOEpatents

Rothman, Alan B.; Graczyk, Donald G.; Essling, Alice M.; Horwitz, E. Philip

2001-01-01

A process for converting UF.sub.6 to a solid uranium compound such as UO.sub.2 and CaF. The UF.sub.6 vapor form is contacted with an aqueous solution of NH.sub.4 OH at a pH greater than 7 to precipitate at least some solid uranium values as a solid leaving an aqueous solution containing NH.sub.4 OH and NH.sub.4 F and remaining uranium values. The solid uranium values are separated from the aqueous solution of NH.sub.4 OH and NH.sub.4 F and remaining uranium values which is then diluted with additional water precipitating more uranium values as a solid leaving trace quantities of uranium in a dilute aqueous solution. The dilute aqueous solution is contacted with an ion-exchange resin to remove substantially all the uranium values from the dilute aqueous solution. The dilute solution being contacted with Ca(OH).sub.2 to precipitate CaF.sub.2 leaving dilute NH.sub.4 OH.

Subsurface Conditions Controlling Uranium Incorporation in Iron Oxides: A Redox Stable Sink

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

Fendorf, Scott

2016-04-05

Toxic metals and radionuclides throughout the U.S. Department of Energy Complex pose a serious threat to ecosystems and to human health. Of particular concern is the redox-sensitive radionuclide uranium, which is classified as a priority pollutant in soils and groundwaters at most DOE sites owing to its large inventory, its health risks, and its mobility with respect to primary waste sources. The goal of this research was to contribute to the long-term mission of the Subsurface Biogeochemistry Program by determining reactions of uranium with iron (hydr)oxides that lead to long-term stabilization of this pervasive contaminant. The research objectives of thismore » project were thus to (1) identify the (bio)geochemical conditions, including those of the solid-phase, promoting uranium incorporation in Fe (hydr)oxides, (2) determine the magnitude of uranium incorporation under a variety of relevant subsurface conditions in order to quantify the importance of this pathway when in competition with reduction or adsorption; (3) identify the mechanism(s) of U(VI/V) incorporation in Fe (hydr)oxides; and (4) determine the stability of these phases under different biogeochemical (inclusive of redox) conditions. Our research demonstrates that redox transformations are capable of achieving U incorporation into goethite at ambient temperatures, and that this transformation occurs within days at U and Fe(II) concentrations that are common in subsurface geochemical environments with natural ferrihydrites—inclusive of those with natural impurities. Increasing Fe(II) or U concentration, or initial pH, made U(VI) reduction to U(IV) a more competitive sequestration pathway in this system, presumably by increasing the relative rate of U reduction. Uranium concentrations commonly found in contaminated subsurface environments are often on the order of 1-10 μM, and groundwater Fe(II) concentrations can reach exceed 1 mM in reduced zones of the subsurface. The redox-driven U(V) incorporation mechanism may help to explain U retention in some geologic materials, improving our understanding of U-based geochronology and the redox status of ancient geochemical environments. Additionally, U(VI) may be incorporated within silicate minerals though encapsulation of U-bearing iron oxides, leading to a redox stable solid. Our research detailing previously unrecognized mechanism of U incorporation within sediment minerals may even lead to new approaches for in situ contamination remediation techniques, and will help refine models of U fate and transport in reduced subsurface zones.« less

Harnessing redox activity for the formation of uranium tris(imido) compounds

NASA Astrophysics Data System (ADS)

Anderson, Nickolas H.; Odoh, Samuel O.; Yao, Yiyi; Williams, Ursula J.; Schaefer, Brian A.; Kiernicki, John J.; Lewis, Andrew J.; Goshert, Mitchell D.; Fanwick, Phillip E.; Schelter, Eric J.; Walensky, Justin R.; Gagliardi, Laura; Bart, Suzanne C.

2014-10-01

Classically, late transition-metal organometallic compounds promote multielectron processes solely through the change in oxidation state of the metal centre. In contrast, uranium typically undergoes single-electron chemistry. However, using redox-active ligands can engage multielectron reactivity at this metal in analogy to transition metals. Here we show that a redox-flexible pyridine(diimine) ligand can stabilize a series of highly reduced uranium coordination complexes by storing one, two or three electrons in the ligand. These species reduce organoazides easily to form uranium-nitrogen multiple bonds with the release of dinitrogen. The extent of ligand reduction dictates the formation of uranium mono-, bis- and tris(imido) products. Spectroscopic and structural characterization of these compounds supports the idea that electrons are stored in the ligand framework and used in subsequent reactivity. Computational analyses of the uranium imido products probed their molecular and electronic structures, which facilitated a comparison between the bonding in the tris(imido) structure and its tris(oxo) analogue.

Stochastic simulation of uranium migration at the Hanford 300 Area.

PubMed

Hammond, Glenn E; Lichtner, Peter C; Rockhold, Mark L

2011-03-01

This work focuses on the quantification of groundwater flow and subsequent U(VI) transport uncertainty due to heterogeneity in the sediment permeability at the Hanford 300 Area. U(VI) migration at the site is simulated with multiple realizations of stochastically-generated high resolution permeability fields and comparisons are made of cumulative water and U(VI) flux to the Columbia River. The massively parallel reactive flow and transport code PFLOTRAN is employed utilizing 40,960 processor cores on DOE's petascale Jaguar supercomputer to simultaneously execute 10 transient, variably-saturated groundwater flow and U(VI) transport simulations within 3D heterogeneous permeability fields using the code's multi-realization simulation capability. Simulation results demonstrate that the cumulative U(VI) flux to the Columbia River is less responsive to fine scale heterogeneity in permeability and more sensitive to the distribution of permeability within the river hyporheic zone and mean permeability of larger-scale geologic structures at the site. Copyright © 2010 Elsevier B.V. All rights reserved.

Upscaling of U(VI) Desorption and Transport from Decimeter-Scale Heterogeneity to Plume-Scale Modeling

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

Curtis, Gary P.; Kohler, Matthias; Kannappan, Ramakrishnan

2015-02-24

Scientifically defensible predictions of field scale U(VI) transport in groundwater requires an understanding of key processes at multiple scales. These scales range from smaller than the sediment grain scale (less than 10 μm) to as large as the field scale which can extend over several kilometers. The key processes that need to be considered include both geochemical reactions in solution and at sediment surfaces as well as physical transport processes including advection, dispersion, and pore-scale diffusion. The research summarized in this report includes both experimental and modeling results in batch, column and tracer tests. The objectives of this research weremore » to: (1) quantify the rates of U(VI) desorption from sediments acquired from a uranium contaminated aquifer in batch experiments;(2) quantify rates of U(VI) desorption in column experiments with variable chemical conditions, and(3) quantify nonreactive tracer and U(VI) transport in field tests.« less

Innovative Approach to Prevent Acid Drainage from Uranium Mill Tailings Based on the Application of Na-Ferrate (VI)

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

Fernandes, H.M.; Reinhart, D.; Lettie, L.

2006-07-01

The operation of uranium mining and milling plants gives rise to huge amounts of wastes from both mining and milling operations. When pyrite is present in these materials, the generation of acid drainage can take place and result in the contamination of underground and surface waters through the leaching of heavy metals and radionuclides. To solve this problem, many studies have been conducted to find cost-effective solutions to manage acid mine drainage; however, no adequate strategy to deal with sulfide-ric h wastes is currently available. Ferrate (VI) is a powerful oxidizing agent in aqueous media. Under acidic conditions, the redoxmore » potential of the Ferrate (VI) ion is the highest of any other oxidant used in wastewater treatment processes. The standard half cell reduction potential of ferrate (VI) has been determined as +2.20 V to + 0.72 V in acidic and basic solutions, respectively. Ferrate (VI) exhibits a multitude of advantageous properties, including higher reactivity and selectivity than traditional oxidant alternatives, as well as disinfectant, flocculating, and coagulant properties. Despite numerous beneficial properties in environmental applications, ferrate (VI) has remained commercially unavailable. Starting in 1953, different methods for producing a high purity, powdered ferrate (VI) product were developed. However, producing this dry, stabilized ferrate (VI) product required numerous process steps which led to excessive synthesis costs (over $20/lb) thereby preventing bulk industrial use. Recently a novel synthesis method for the production of a liquid ferrate (VI) based on hypochlorite oxidation of ferric ion in strongly alkaline solutions has been discovered (USPTO 6,790,428; September 14, 2004). This on-site synthesis process dramatically reduces manufacturing cost for the production of ferrate (VI) by utilizing common commodity feedstocks. This breakthrough means that for the first time ferrate (VI) can be an economical alternative to treating acid mining drainage generating materials. The objective of the present study was to investigate a methodology of preventing the generation of acid drainage by applying ferrate (VI) to acid generating materials prior to the disposal in impoundments or piles. Oxidizing the pyritic material in mining waste could diminish the potential for acid generation and its related environmental risks and long-term costs at disposal sites. The effectiveness of toxic metals removal from acid mine drainage by applying ferrate (VI) is also examined. Preliminary results presented in this paper show that the oxidation of pyrite by ferrate is a first-order rate reaction in Fe(VI) with a half-life of about six hours. The stability of Fe(VI) in water solutions will not influence the reaction rate in a significant manner. New low-cost production methods for making liquid ferrate on-site makes this technology a very attractive option to mitigate one of the most pressing environmental problems in the mining industry. (authors)« less

Methods for determining soluble and insoluble Cr III and Cr VI compounds in welding fumes.

PubMed

Matczak, W; Chmielnicka, J

1989-01-01

An analytical procedure for simultaneous determination of soluble and insoluble Cr III and Cr VI compounds in welding fumes has been proposed. In the welding fume samples collected on a membrane filter, total chromium was determined with atomic absorption spectrophotometry (AAS). Glass filters with collected samples were divided into two parts. In one part of the sample, soluble and insoluble chromium was determined by means of AAS. The separation of soluble chromium III and VI was carried out on diphenylcarbazide resin. In the second part of the sample total chromium VI was determined by means of the colorimetric method with s-diphenylcarbazide. The difference in the results of these determinations allowed the calculation of the content of total Cr III, Cr III insolub. and Cr VI insolub. The results of determining chromium compounds in welding fumes samples collected in the welder's breathing zone and in experimental chambers are also presented in this paper. The content of total chromium in the fumes determined by AAS (from a membrane filtr) and that calculated from the sum of soluble and insoluble chromium (from a glass filter) were concordant and within the limits of the admissible error for the method. Total chromium content in welding fume samples collected individually was found to range from 2.4-4.2%. The percentage of particular chromium compounds as compared to total chromium (100%) amounted: total Cr III--34%, total Cr VI--66%, soluble chromium--66% and in this Cr III--20% and Cr VI--43%, insoluble chromium--34% and in this: Cr III--14% and Cr VI--20%.

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

NASA Astrophysics Data System (ADS)

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

2011-12-01

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

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

Zhang, Yingjie, E-mail: yzx@ansto.gov.au; Bhadbhade, Mohan; Karatchevtseva, Inna

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

Deviation between the chemistry of Ce(IV) and Pu(IV) and routes to ordered and disordered heterobimetallic 4f/5f and 5f/5f phosphonates

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

Diwu, Juan; Wang, Shuao; Good, Justin J.

2011-06-06

The heterobimetallic actinide compound UO₂Ce(H₂O)[C₆H₄(PO₃H)₂]₂·H₂O was prepared via the hydrothermal reaction of U(VI) and Ce(IV) in the presence of 1,2-phenylenediphosphonic acid. We demonstrate that this is a kinetic product that is not stable with respect to decomposition to the monometallic compounds. Similar reactions have been explored with U(VI) and Ce(III), resulting in the oxidation of Ce(III) to Ce(IV) and the formation of the Ce(IV) phosphonate, Ce[C₆H₄(PO₃H)(PO₃H₂)][C₆H₄(PO₃H)(PO₃)]·2H₂O, UO₂Ce(H₂O)[C₆H₄(PO₃H)₂]₂·H₂O, and UO₂[C₆H₄(PO₃H)₂](H₂O)·H₂O. In comparison, the reaction of U(VI) with Np(VI) only yields Np[C₆H₄(PO₃H)₂]₂·2H₂O and aqueous U(VI), whereas the reaction of U(VI) with Pu(VI) yields the disordered U(VI)/Pu(VI) compound, (U 0.9Pu 0.1)O₂[C₆H₄(PO₃H)₂](H₂O)·H₂O, and themore » Pu(IV) phosphonate, Pu[C₆H₄(PO₃H)(PO₃H₂)][C₆H₄(PO₃H)(PO₃)]·2H₂O. The reactions of Ce(IV) with Np(VI) yield disordered heterobimetallic phosphonates with both M[C₆H₄(PO₃H)(PO₃H₂)][C₆H₄(PO₃H)(PO₃)]·2H₂O (M = Ce, Np) and M[C₆H₄(PO₃H)₂]₂·2H₂O (M = Ce, Np) structures, as well as the Ce(IV) phosphonate Ce[C₆H₄(PO₃H)(PO₃H₂)][C₆H₄(PO₃H)(PO₃)]·2H₂O. Ce(IV) reacts with Pu(IV) to yield the Pu(VI) compound, PuO₂[C₆H₄(PO₃H)₂](H₂O)·3H₂O, and a disordered heterobimetallic Pu(IV)/Ce(IV) compound with the M[C₆H₄(PO₃H)(PO₃H₂)][C₆H₄(PO₃H)(PO₃)]·2H₂O (M = Ce, Pu) structure. Mixtures of Np(VI) and Pu(VI) yield disordered heterobimetallic Np(IV)/Pu(IV) phosphonates with both the An[C₆H₄(PO₃H)(PO₃H₂)][C₆H₄(PO₃H)(PO₃)]·2H₂O (M = Np, Pu) and An[C₆H₄(PO₃H)₂]₂·2H₂O (M = Np, Pu) formulas.« less

Uranium(VI) reduction by nanoscale zero-valent iron in anoxic batch systems: the role of Fe(II) and Fe(III).

PubMed

Yan, Sen; Chen, Yongheng; Xiang, Wu; Bao, Zhengyu; Liu, Chongxuan; Deng, Baolin

2014-12-01

The role of Fe(II) and Fe(III) in U(VI) reduction by nanoscale zerovalent iron (nanoFe0) was investigated using two iron chelators 1,10-phenanthroline and triethanolamine (TEA) under a CO2-free anoxic condition. The results showed that U(VI) reduction was strongly inhibited by 1,10-phenanthroline and TEA in a pH range from 6.9 to 9.0. For instance, at pH 6.9 the observed U(VI) reduction rates decreased by 81% and 82% in the presence of 1,10-phenanthroline and TEA, respectively. The inhibition was attributed to the formation of stable complexes between 1,10-phenanthroline and Fe(II) or TEA and Fe(III). In the absence of iron chelators, U(VI) reduction can be enhanced by surface-bound Fe(II) on nanoFe0. Our results suggested that Fe(III) and Fe(II) possibly acted as an electron shuttle to ferry the electrons from nanoFe0 to U(VI), therefore a combined system with Fe(II), Fe(III) and nanoFe0 could facilitate U(VI) reductive immobilization in the contaminated groundwater.

Uranium(VI) reduction by nanoscale zero-valent iron in anoxic batch systems: The role of Fe(II) and Fe(III)

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

Yan, Sen; Chen, Yongheng; Xiang, Wu

2014-12-01

The role of Fe(II) and Fe(III) on U(VI) reduction by nanoscale zerovalent iron (nanoFe0) was investigated using two iron chelators 1,10-phenanthroline and triethanolamine (TEA) under a CO2-free anoxic condition. The results showed U(VI) reduction was strongly inhibited by 1,10-phenanthroline and TEA in a pH range from 6.92 to 9.03. For instance, at pH 6.92 the observed U(VI) reduction rates decreased by 80.7% and 82.3% in the presence of 1,10-phenanthroline and TEA, respectively. The inhibition was attributed to the formation of stable complexes between 1,10-phenanthroline and Fe(II) or TEA and Fe(III). In the absence of iron chelators, U(VI) reduction can bemore » enhanced by surface-bound Fe(II) on nanoFe0. Our results suggested that Fe(III) and Fe(II) probably acted as an electron shuttle to mediate the transfer of electrons from nanoFe0 to U(VI), therefore a combined system with Fe(II), Fe(III) and nanoFe0 can facilitate the U(VI) reductive immobilization in the contaminated groundwater.« less

Influence of calcium on microbial reduction of solid phase uranium(VI).

PubMed

Liu, Chongxuan; Jeon, Byong-Hun; Zachara, John M; Wang, Zheming

2007-08-15

The effect of calcium on the dissolution and microbial reduction of a representative solid phase uranyl [U(VI)], sodium boltwoodite (NaUO(2)SiO(3)OH . 1.5H(2)O), was investigated to evaluate the rate-limiting step of microbial reduction of the solid phase U(VI). Microbial reduction experiments were performed in a culture of a dissimilatory metal-reducing bacterium (DMRB), Shewanella oneidensis strain MR-1, in a bicarbonate medium with lactate as electron donor at pH 6.8 buffered with PIPES. Calcium increased the rate of Na-boltwoodite dissolution and U(VI) bioavailability by increasing its solubility through the formation of a ternary aqueous calcium-uranyl-carbonate species. The ternary species, however, decreased the rates of microbial reduction of aqueous U(VI). Laser-induced fluorescence spectroscopy (LIFS) and transmission electron microscopy (TEM) collectively revealed that microbial reduction of solid phase U(VI) was a sequentially coupled process of Na-boltwoodite dissolution, U(VI) aqueous speciation, and microbial reduction of dissolved U(VI) to U(IV) that accumulated on bacterial surfaces/periplasm. Under studied experimental conditions, the overall rate of microbial reduction of solid phase U(VI) was limited by U(VI) dissolution reactions in solutions without calcium and limited by microbial reduction in solutions with calcium. Generally, the overall rate of microbial reduction of solid phase U(VI) was determined by the coupling of solid phase U(VI) dissolution, U(VI) aqueous speciation, and microbial reduction of dissolved U(VI) that were all affected by calcium. (c) 2007 Wiley Periodicals, Inc.

Speciation and reactivity of uranium products formed during in situ bioremediation in a shallow alluvial aquifer.

PubMed

Alessi, Daniel S; Lezama-Pacheco, Juan S; Janot, Noémie; Suvorova, Elena I; Cerrato, José M; Giammar, Daniel E; Davis, James A; Fox, Patricia M; Williams, Kenneth H; Long, Philip E; Handley, Kim M; Bernier-Latmani, Rizlan; Bargar, John R

2014-11-04

In this study, we report the results of in situ U(VI) bioreduction experiments at the Integrated Field Research Challenge site in Rifle, Colorado, USA. Columns filled with sediments were deployed into a groundwater well at the site and, after a period of conditioning with groundwater, were amended with a mixture of groundwater, soluble U(VI), and acetate to stimulate the growth of indigenous microorganisms. Individual reactors were collected as various redox regimes in the column sediments were achieved: (i) during iron reduction, (ii) just after the onset of sulfate reduction, and (iii) later into sulfate reduction. The speciation of U retained in the sediments was studied using X-ray absorption spectroscopy, electron microscopy, and chemical extractions. Circa 90% of the total uranium was reduced to U(IV) in each reactor. Noncrystalline U(IV) comprised about two-thirds of the U(IV) pool, across large changes in microbial community structure, redox regime, total uranium accumulation, and reaction time. A significant body of recent research has demonstrated that noncrystalline U(IV) species are more suceptible to remobilization and reoxidation than crystalline U(IV) phases such as uraninite. Our results highlight the importance of considering noncrystalline U(IV) formation across a wide range of aquifer parameters when designing in situ remediation plans.

Speciation and Reactivity of Uranium Products Formed during in Situ Bioremediation in a Shallow Alluvial Aquifer

PubMed Central

2015-01-01

In this study, we report the results of in situ U(VI) bioreduction experiments at the Integrated Field Research Challenge site in Rifle, Colorado, USA. Columns filled with sediments were deployed into a groundwater well at the site and, after a period of conditioning with groundwater, were amended with a mixture of groundwater, soluble U(VI), and acetate to stimulate the growth of indigenous microorganisms. Individual reactors were collected as various redox regimes in the column sediments were achieved: (i) during iron reduction, (ii) just after the onset of sulfate reduction, and (iii) later into sulfate reduction. The speciation of U retained in the sediments was studied using X-ray absorption spectroscopy, electron microscopy, and chemical extractions. Circa 90% of the total uranium was reduced to U(IV) in each reactor. Noncrystalline U(IV) comprised about two-thirds of the U(IV) pool, across large changes in microbial community structure, redox regime, total uranium accumulation, and reaction time. A significant body of recent research has demonstrated that noncrystalline U(IV) species are more suceptible to remobilization and reoxidation than crystalline U(IV) phases such as uraninite. Our results highlight the importance of considering noncrystalline U(IV) formation across a wide range of aquifer parameters when designing in situ remediation plans. PMID:25265543

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

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

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

Tournassat, C.; Tinnacher, R. M.; Grangeon, S.

The prediction of U(VI) adsorption onto montmorillonite clay is confounded by the complexities of: (1) the montmorillonite structure in terms of adsorption sites on basal and edge surfaces, and the complex interactions between the electrical double layers at these surfaces, and (2) U(VI) solution speciation, which can include cationic, anionic and neutral species. Previous U(VI)-montmorillonite adsorption and modeling studies have typically expanded classical surface complexation modeling approaches, initially developed for simple oxides, to include both cation exchange and surface complexation reactions. However, previous models have not taken into account the unique characteristics of electrostatic surface potentials that occur at montmorillonitemore » edge sites, where the electrostatic surface potential of basal plane cation exchange sites influences the surface potential of neighboring edge sites (‘spillover’ effect).« less

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

DOE PAGES

Tournassat, C.; Tinnacher, R. M.; Grangeon, S.; ...

2017-10-06

The prediction of U(VI) adsorption onto montmorillonite clay is confounded by the complexities of: (1) the montmorillonite structure in terms of adsorption sites on basal and edge surfaces, and the complex interactions between the electrical double layers at these surfaces, and (2) U(VI) solution speciation, which can include cationic, anionic and neutral species. Previous U(VI)-montmorillonite adsorption and modeling studies have typically expanded classical surface complexation modeling approaches, initially developed for simple oxides, to include both cation exchange and surface complexation reactions. However, previous models have not taken into account the unique characteristics of electrostatic surface potentials that occur at montmorillonitemore » edge sites, where the electrostatic surface potential of basal plane cation exchange sites influences the surface potential of neighboring edge sites (‘spillover’ effect).« less

Recovery of uranium from seawater by immobilized tannin

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

Sakaguchi, T.; Nakajima, A.

1987-06-01

Tannin compounds having multiple adjacent hydroxy groups have an extremely high affinity for uranium. To prevent the leaching of tannins into water and to improve the adsorbing characteristics of these compounds, the authors tried to immobilize tannins. The immobilized tannin has the most favorable features for uranium recovery; high selective adsorption ability to uranium, rapid adsorption rate, and applicability in both column and batch systems. The immobilized tannin can recover uranium from natural seawater with high efficiency. About 2530 ..mu..g uranium is adsorbed per gram of this adsorbent within 22 h. Depending on the concentration in seawater, an enrichment ofmore » up to 766,000-fold within the adsorbent is possible. Almost all uranium adsorbed is easily desorbed with a very dilute acid. Thus, the immobilized tannin can be used repeatedly in the adsorption-desorption process.« less

[Two new glycosides from Erigeron breviscapus (Vant.) Hand.-Mazz].

PubMed

Zhang, W D; Chen, W S; Wang, Y H; Liu, W Y; Kong, D Y; Li, H T

2001-10-01

To study the chemical constituents from the upground part of Erigeron breviscapus. The compounds were separated and purified by column chromatography with silica gel, and identified by IR, MS, NMR and 2D-NMR. Two new compounds were isolated and identified as 5,4'-dihydroxy flavonod-7-O-beta-D-pyranglycuronate buthyl ester(VI) and 3,5-dimethoxy benzene carbonic acid-4-O-beta-D-pyranglucose(VII). Compounds VI and VII were new compounds.

Variably Saturated Flow and Multicomponent Biogeochemical Reactive Transport Modeling of a Uranium Bioremediation Field Experiment

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

Yabusaki, Steven B.; Fang, Yilin; Williams, Kenneth H.

2011-11-01

Field experiments at a former uranium mill tailings site have identified the potential for stimulating indigenous bacteria to catalyze the conversion of aqueous uranium in the +6 oxidation state to immobile solid-associated uranium in the +4 oxidation state. This effectively removes uranium from solution resulting in groundwater concentrations below actionable standards. Three-dimensional, coupled variably-saturated flow and biogeochemical reactive transport modeling of a 2008 in situ uranium bioremediation field experiment is used to better understand the interplay of transport rates and biogeochemical reaction rates that determine the location and magnitude of key reaction products. A comprehensive reaction network, developed largely throughmore » previous 1-D modeling studies, was used to simulate the impacts on uranium behavior of pulsed acetate amendment, seasonal water table variation, spatially-variable physical (hydraulic conductivity, porosity) and geochemical (reactive surface area) material properties. A principal challenge is the mechanistic representation of biologically-mediated terminal electron acceptor process (TEAP) reactions whose products significantly alter geochemical controls on uranium mobility through increases in pH, alkalinity, exchangeable cations, and highly reactive reduction products. In general, these simulations of the 2008 Big Rusty acetate biostimulation field experiment in Rifle, Colorado confirmed previously identified behaviors including (1) initial dominance by iron reducing bacteria that concomitantly reduce aqueous U(VI), (2) sulfate reducing bacteria that become dominant after {approx}30 days and outcompete iron reducers for the acetate electron donor, (3) continuing iron-reducer activity and U(VI) bioreduction during dominantly sulfate reducing conditions, and (4) lower apparent U(VI) removal from groundwater during dominantly sulfate reducing conditions. New knowledge on simultaneously active metal and sulfate reducers has been incorporated into the modeling. In this case, an initially small population of slow growing sulfate reducers is active from the initiation of biostimulation. Three-dimensional, variably saturated flow modeling was used to address impacts of a falling water table during acetate injection. These impacts included a significant reduction in aquifer saturated thickness and isolation of residual reactants and products, as well as unmitigated uranium, in the newly unsaturated vadose zone. High permeability sandy gravel structures resulted in locally high flow rates in the vicinity of injection wells that increased acetate dilution. In downgradient locations, these structures created preferential flow paths for acetate delivery that enhanced local zones of TEAP reactivity and subsidiary reactions. Conversely, smaller transport rates associated with the lower permeability lithofacies (e.g., fine) and vadose zone were shown to limit acetate access and reaction. Once accessed by acetate, however, these same zones limited subsequent acetate dilution and provided longer residence times that resulted in higher concentrations of TEAP products when terminal electron donors and acceptors were not limiting. Finally, facies-based porosity and reactive surface area variations were shown to affect aqueous uranium concentration distributions; however, the ranges were sufficiently small to preserve general trends. Large computer memory and high computational performance were required to simulate the detailed coupled process models for multiple biogeochemical components in highly resolved heterogeneous materials for the 110-day field experiment and 50 days of post-biostimulation behavior. In this case, a highly-scalable subsurface simulator operating on 128 processor cores for 12 hours was used to simulate each realization. An equivalent simulation without parallel processing would have taken 60 days, assuming sufficient memory was available.« less

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

Bioreduction of U(VI)-Phthalate to a Polymeric U(IV)-Phthalate Colloid

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

Vazquez, G.; Dodge, C; Francis, A

2009-01-01

Phthalic acid, a ubiquitous organic ligand, formed soluble mono- and biligand complexes with a uranyl ion that was then reduced to a U(IV)-phthalate by a Clostridium species under anaerobic conditions. We confirmed the reduction of the hexavalent uranium to the tetravalent oxidation state by UV-vis absorption and X-ray absorption near edge structure spectroscopy. Sequential micro- and ultrafiltration of the solution revealed that the bioreduced uranium was present as a colloid with particles between 0.03 and 0.45 {mu}m. Analysis with extended X-ray absorption fine structure revealed the association of the reduced uranium with the phthalic acid as a repeating biligand 1:2more » U(IV):phthalic acid polymer. This is the first report of the formation of a U(IV) complexed to two phthalic acid molecules in the form of a polymeric colloid. Although it was proposed that the bioreduction and the precipitation of uranium might be an invaluable strategy to immobilize uranium in contaminated environments, our results suggest that the organic ligands present there might hinder the precipitation of the bioreduced uranium under anaerobic conditions and, thereby, enhance its environmental mobility as uranium organic complexes or colloids.« less

Biogenic formation and growth of uraninite (UO₂).

PubMed

Lee, Seung Yeop; Baik, Min Hoon; Choi, Jong Won

2010-11-15

Biogenic UO₂ (uraninite) nanocrystals may be formed as a product of a microbial reduction process in uranium-enriched environments near the Earth's surface. We investigated the size, nanometer-scale structure, and aggregation state of UO₂ formed by iron-reducing bacterium, Shewanella putrefaciens CN32, from a uranium-rich solution. Characterization of biogenic UO₂ precipitates by high-resolution transmission electron microscopy (HRTEM) revealed that the UO₂ nanoparticles formed were highly aggregated by organic polymers. Nearly all of the nanocrystals were networked in more or less 100 nm diameter spherical aggregates that displayed some concentric UO₂ accumulation with heterogeneity. Interestingly, pure UO₂ nanocrystals were piled on one another at several positions via UO₂-UO₂ interactions, which seem to be intimately related to a specific step in the process of growing large single crystals. In the process, calcium that was easily complexed with aqueous uranium(VI) appeared not to be combined with bioreduced uranium(IV), probably due to its lower binding energy. However, when phosphate was added to the system, calcium was found to be easily associated with uranium(IV), forming a new uranium phase, ningyoite. These results will extend the limited knowledge of microbial uraniferous mineralization and may provide new insights into the fate of aqueous uranium complexes.

The effect of uranium on bacterial viability and cell surface morphology using atomic force microscopy in the presence of bicarbonate ions

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

Sepulveda-Medina, Paola; Katsenovich, Yelena; Musaramthota, Vishal

Nuclear production facilities during the Cold War have caused liquid waste to leak and soak into the ground creating multiple radionuclide plumes. The Arthrobacter bacteria are one of the most common groups in soils and are found in large numbers in subsurface environments contaminated with radionuclides. This study experimentally analyzed changes on the bacteria surface after uranium exposure and evaluated the effect of bicarbonate ions on U(VI) toxicity of a less uranium tolerant Arthrobacter strain, G968, by investigating changes in adhesion forces and cells dimensions via atomic force microscopy (AFM). AFM and viability studies showed that samples containing bicarbonate aremore » able to acclimate and withstand uranium toxicity. Samples containing no bicarbonate exhibited deformed surfaces and a low height profile, which might be an indication that the cells are not alive.« less

High density dispersion fuel

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

Hofman, G.L.

1996-09-01

A fuel development campaign that results in an aluminum plate-type fuel of unlimited LEU burnup capability with an uranium loading of 9 grams per cm{sup 3} of meat should be considered an unqualified success. The current worldwide approved and accepted highest loading is 4.8 g cm{sup {minus}3} with U{sub 3}Si{sub 2} as fuel. High-density uranium compounds offer no real density advantage over U{sub 3}Si{sub 2} and have less desirable fabrication and performance characteristics as well. Of the higher-density compounds, U{sub 3}Si has approximately a 30% higher uranium density but the density of the U{sub 6}X compounds would yield the factormore » 1.5 needed to achieve 9 g cm{sup {minus}3} uranium loading. Unfortunately, irradiation tests proved these peritectic compounds have poor swelling behavior. It is for this reason that the authors are turning to uranium alloys. The reason pure uranium was not seriously considered as a dispersion fuel is mainly due to its high rate of growth and swelling at low temperatures. This problem was solved at least for relatively low burnup application in non-dispersion fuel elements with small additions of Si, Fe, and Al. This so called adjusted uranium has nearly the same density as pure {alpha}-uranium and it seems prudent to reconsider this alloy as a dispersant. Further modifications of uranium metal to achieve higher burnup swelling stability involve stabilization of the cubic {gamma} phase at low temperatures where normally {alpha} phase exists. Several low neutron capture cross section elements such as Zr, Nb, Ti and Mo accomplish this in various degrees. The challenge is to produce a suitable form of fuel powder and develop a plate fabrication procedure, as well as obtain high burnup capability through irradiation testing.« less

Thiocyanate complexes of uranium in multiple oxidation states: a combined structural, magnetic, spectroscopic, spectroelectrochemical, and theoretical study.

PubMed

Hashem, Emtithal; Platts, James A; Hartl, František; Lorusso, Giulia; Evangelisti, Marco; Schulzke, Carola; Baker, Robert J

2014-08-18

A comprehensive study of the complexes A4[U(NCS)8] (A = Cs, Et4N, (n)Bu4N) and A3[UO2(NCS)5] (A = Cs, Et4N) is described, with the crystal structures of [(n)Bu4N]4[U(NCS)8]·2MeCN and Cs3[UO2(NCS)5]·O0.5 reported. The magnetic properties of square antiprismatic Cs4[U(NCS)8] and cubic [Et4N]4[U(NCS)8] have been probed by SQUID magnetometry. The geometry has an important impact on the low-temperature magnetic moments: at 2 K, μeff = 1.21 μB and 0.53 μB, respectively. Electronic absorption and photoluminescence spectra of the uranium(IV) compounds have been measured. The redox chemistry of [Et4N]4[U(NCS)8] has been explored using IR and UV-vis spectroelectrochemical methods. Reversible 1-electron oxidation of one of the coordinated thiocyanate ligands occurs at +0.22 V vs Fc/Fc(+), followed by an irreversible oxidation to form dithiocyanogen (NCS)2 which upon back reduction regenerates thiocyanate anions coordinating to UO2(2+). NBO calculations agree with the experimental spectra, suggesting that the initial electron loss of [U(NCS)8](4-) is delocalized over all NCS(-) ligands. Reduction of the uranyl(VI) complex [Et4N]3[UO2(NCS)5] to uranyl(V) is accompanied by immediate disproportionation and has only been studied by DFT methods. The bonding in [An(NCS)8](4-) (An = Th, U) and [UO2(NCS)5](3-) has been explored by a combination of DFT and QTAIM analysis, and the U-N bonds are predominantly ionic, with the uranyl(V) species more ionic that the uranyl(VI) ion. Additionally, the U(IV)-NCS ion is more ionic than what was found for U(IV)-Cl complexes.

URANIUM EXTRACTION PROCESS USING SYNERGISTIC REAGENTS

DOEpatents

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

1958-11-01

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

Methods for synthesizing semiconductor quality chalcopyrite crystals for nonlinear optical and radiation detection applications and the like

DOEpatents

Stowe, Ashley; Burger, Arnold

2016-05-10

A method for synthesizing I-III-VI.sub.2 compounds, including: melting a Group III element; adding a Group I element to the melted Group III element at a rate that allows the Group I and Group III elements to react thereby providing a single phase I-III compound; and adding a Group VI element to the single phase I-III compound under heat, with mixing, and/or via vapor transport. The Group III element is melted at a temperature of between about 200 degrees C. and about 700 degrees C. Preferably, the Group I element consists of a neutron absorber and the group III element consists of In or Ga. The Group VI element and the single phase I-III compound are heated to a temperature of between about 700 degrees C. and about 1000 degrees C. Preferably, the Group VI element consists of S, Se, or Te. Optionally, the method also includes doping with a Group IV element activator.

The role of uranium-arene bonding in H2O reduction catalysis

NASA Astrophysics Data System (ADS)

Halter, Dominik P.; Heinemann, Frank W.; Maron, Laurent; Meyer, Karsten

2018-03-01

The reactivity of uranium compounds towards small molecules typically occurs through stoichiometric rather than catalytic processes. Examples of uranium catalysts reacting with water are particularly scarce, because stable uranyl groups form that preclude the recovery of the uranium compound. Recently, however, an arene-anchored, electron-rich uranium complex has been shown to facilitate the electrocatalytic formation of H2 from H2O. Here, we present the precise role of uranium-arene δ bonding in intermediates of the catalytic cycle, as well as details of the atypical two-electron oxidative addition of H2O to the trivalent uranium catalyst. Both aspects were explored by synthesizing mid- and high-valent uranium-oxo intermediates and by performing comparative studies with a structurally related complex that cannot engage in δ bonding. The redox activity of the arene anchor and a covalent δ-bonding interaction with the uranium ion during H2 formation were supported by density functional theory analysis. Detailed insight into this catalytic system may inspire the design of ligands for new uranium catalysts.

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

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

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

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

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

DOE PAGES

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

2016-09-16

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

Apparatus to recover tritium from tritiated molecules

DOEpatents

Swansiger, William A.

1988-01-01

An apparatus for recovering tritium from tritiated compounds is provided, including a preheater for heating tritiated water and other co-injected tritiated compounds to temperatures of about 600.degree. C. and a reactor charged with a mixture of uranium and uranium dioxide for receiving the preheated mixture. The reactor vessel is preferably stainless steel of sufficient mass so as to function as a heat sink preventing the reactor side walls from approaching high temperatures. A disposable copper liner extends between the reaction chamber and stainless steel outer vessel to prevent alloying of the uranium with the outer vessel. The uranium dioxide functions as an insulating material and heat sink preventing the reactor side walls from attaining reaction temperatures to thereby minimize tritium permeation rates. The uranium dioxide also functions as a diluent to allow for volumetric expansion of the uranium as it is converted to uranium dioxide.

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

PubMed

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

2016-12-01

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

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.

Floquet Topological Insulators in Uranium Compounds

NASA Astrophysics Data System (ADS)

Pi, Shu-Ting; Savrasov, Sergey

2014-03-01

A major issue regarding the Uranium based nuclear fuels is to conduct the heat from the core area to its outer area. Unfortunately, those materials are notorious for their extremely low thermal conductivity due to the phonon-dominated-heat-transport properties in insulating states. Although metallic Uranium compounds are helpful in increasing the thermal conductivity, their low melting point still make those efforts in vain. In this report, we will figure out potential Uranium based Floquet topological insulators where the insulating bulk states accompanied with metallic surface states is achieved by applying periodic electrical fields which makes the coexistence of both benefits possible.

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

NASA Astrophysics Data System (ADS)

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

2018-02-01

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

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.

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.

Analysis of a Uranium Oxide Sample Interdicted in Slovakia (FSC 12-3-1)

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

Borg, Lars E.; Dai, Zurong; Eppich, Gary R.

2014-01-17

We provide a concise summary of analyses of a natural uranium sample seized in Slovakia in November 2007. Results are presented for compound identification, water content, U assay, trace element abundances, trace organic compounds, isotope compositions for U, Pb, Sr and O, and age determination using the 234U – 230Th and 235U – 231Pa chronometers. The sample is a mixture of two common uranium compounds - schoepite and uraninite. The uranium isotope composition is indistinguishable from natural; 236U was not detected. The O, Sr and Pb isotope compositions and trace element abundances are unremarkable. The 234U – 230Th chronometer givesmore » an age of 15.5 years relative to the date of analysis, indicating the sample was produced in January 1997. A comparison of the data for this sample with data in the Uranium Sourcing database failed to find a match, indicating the sample was not produced at a facility represented in the database.« less

Radiation shielding materials and containers incorporating same

DOEpatents

Mirsky, Steven M.; Krill, Stephen J.; Murray, Alexander P.

2005-11-01

An improved radiation shielding material and storage systems for radioactive materials incorporating the same. The PYRolytic Uranium Compound ("PYRUC") shielding material is preferably formed by heat and/or pressure treatment of a precursor material comprising microspheres of a uranium compound, such as uranium dioxide or uranium carbide, and a suitable binder. The PYRUC shielding material provides improved radiation shielding, thermal characteristic, cost and ease of use in comparison with other shielding materials. The shielding material can be used to form containment systems, container vessels, shielding structures, and containment storage areas, all of which can be used to house radioactive waste. The preferred shielding system is in the form of a container for storage, transportation, and disposal of radioactive waste. In addition, improved methods for preparing uranium dioxide and uranium carbide microspheres for use in the radiation shielding materials are also provided.

PROCESSES OF RECOVERING URANIUM FROM A CALUTRON

DOEpatents

Baird, D.O.; Zumwalt, L.R.

1958-07-15

An improved process is described for recovering the residue of a uranium compound which has been subjected to treatment in a calutron, from the parts of the calutron disposed in the source region upon which the residue is deposited. The process may be utilized when the uranium compound adheres to a surface containing metals of the group consisting of copper, iron, chromium, and nickel. The steps comprise washing the surface with an aqueous acidic oxidizing solvent for the uranium whereby there is obtained an acidic aqueous Solution containing uranium as uranyl ions and metals of said group as impurities, treating the acidic solution with sodium acetate in the presenee of added sodium nitrate to precipitate the uranium as sodium uranyl acetate away from the impurities in the solution, and separating the sodium uranyl acetate from the solution.

Radiation Shielding Materials and Containers Incorporating Same

DOEpatents

Mirsky, Steven M.; Krill, Stephen J.; and Murray, Alexander P.

2005-11-01

An improved radiation shielding material and storage systems for radioactive materials incorporating the same. The PYRolytic Uranium Compound (''PYRUC'') shielding material is preferably formed by heat and/or pressure treatment of a precursor material comprising microspheres of a uranium compound, such as uranium dioxide or uranium carbide, and a suitable binder. The PYRUC shielding material provides improved radiation shielding, thermal characteristic, cost and ease of use in comparison with other shielding materials. The shielding material can be used to form containment systems, container vessels, shielding structures, and containment storage areas, all of which can be used to house radioactive waste. The preferred shielding system is in the form of a container for storage, transportation, and disposal of radioactive waste. In addition, improved methods for preparing uranium dioxide and uranium carbide microspheres for use in the radiation shielding materials are also provided.

Novel Sensor for the In Situ Measurement of Uranium Fluxes

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

Hatfield, Kirk

2015-02-10

The goal of this project was to develop a sensor that incorporates the field-tested concepts of the passive flux meter to provide direct in situ measures of flux for uranium and groundwater in porous media. Measurable contaminant fluxes [J] are essentially the product of concentration [C] and groundwater flux or specific discharge [q ]. The sensor measures [J] and [q] by changes in contaminant and tracer amounts respectively on a sorbent. By using measurement rather than inference from static parameters, the sensor can directly advance conceptual and computational models for field scale simulations. The sensor was deployed in conjunction withmore » DOE in obtaining field-scale quantification of subsurface processes affecting uranium transport (e.g., advection) and transformation (e.g., uranium attenuation) at the Rifle IFRC Site in Rifle, Colorado. Project results have expanded our current understanding of how field-scale spatial variations in fluxes of uranium, groundwater and salient electron donor/acceptors are coupled to spatial variations in measured microbial biomass/community composition, effective field-scale uranium mass balances, attenuation, and stability. The coupling between uranium, various nutrients and micro flora can be used to estimate field-scale rates of uranium attenuation and field-scale transitions in microbial communities. This research focuses on uranium (VI), but the sensor principles and design are applicable to field-scale fate and transport of other radionuclides. Laboratory studies focused on sorbent selection and calibration, along with sensor development and validation under controlled conditions. Field studies were conducted at the Rifle IFRC Site in Rifle, Colorado. These studies were closely coordinated with existing SBR (formerly ERSP) projects to complement data collection. Small field tests were conducted during the first two years that focused on evaluating field-scale deployment procedures and validating sensor performance under controlled field conditions. In the third and fourth year a suite of larger field studies were conducted. For these studies, the uranium flux sensor was used with uranium speciation measurements and molecular-biological tools to characterize microbial community and active biomass at synonymous wells distributed in a large grid. These field efforts quantified spatial changes in uranium flux and field-scale rates of uranium attenuation (ambient and stimulated), uranium stability, and quantitatively assessed how fluxes and effective reaction rates were coupled to spatial variations in microbial community and active biomass. Analyses of data from these field experiments were used to generate estimates of Monod kinetic parameters that are ‘effective’ in nature and optimal for modeling uranium fate and transport at the field-scale. This project provided the opportunity to develop the first sensor that provides direct measures of both uranium (VI) and groundwater flux. A multidisciplinary team was assembled to include two geochemists, a microbiologist, and two quantitative contaminant hydrologists. Now that the project is complete, the sensor can be deployed at DOE sites to evaluate field-scale uranium attenuation, source behavior, the efficacy of remediation, and off-site risk. Because the sensor requires no power, it can be deployed at remote sites for periods of days to months. The fundamental science derived from this project can be used to advance the development of predictive models for various transport and attenuation processes in aquifers. Proper development of these models is critical for long-term stewardship of contaminated sites in the context of predicting uranium source behavior, remediation performance, and off-site risk.« less

Plasma-induced grafting of acrylic acid on bentonite for the removal of U(VI) from aqueous solution

NASA Astrophysics Data System (ADS)

Hongshan, ZHU; Shengxia, DUAN; Lei, CHEN; Ahmed, ALSAEDI; Tasawar, HAYAT; Jiaxing, LI

2017-11-01

Fabrication of reusable adsorbents with satisfactory adsorption capacity and using environment-friendly preparation processes is required for the environment-related applications. In this study, acrylic acid (AA) was grafted onto bentonite (BT) to generate an AA-graft-BT (AA-g-BT) composite using a plasma-induced grafting technique considered to be an environment-friendly method. The as-prepared composite was characterized by scanning electron microscopy, x-ray powder diffraction, thermal gravity analysis, Fourier transform infrared spectroscopy and Barrett-Emmett-Teller analysis, demonstrating the successful grafting of AA onto BT. In addition, the removal of uranium(VI) (U(VI)) from contaminated aqueous solutions was examined using the as-prepared composite. The influencing factors, including contact time, pH value, ionic strength, temperature, and initial concentration, for the removal of U(VI) were investigated by batch experiments. The experimental process fitted best with the pseudo-second-order kinetic and the Langmuir models. Moreover, thermodynamic investigation revealed a spontaneous and endothermic process. Compared with previous adsorbents, AA-g-BT has potential practical applications in treating U(VI)-contaminated solutions.

PEROXIDE PROCESS FOR SEPARATION OF RADIOACTIVE MATERIALS

DOEpatents

Seaborg, G.T.; Perlman, I.

1958-09-16

reduced state, from hexavalent uranium. It consists in treating an aqueous solution containing such uranium and plutonium ions with sulfate ions in order to form a soluble uranium sulfate complex and then treating the solution with a soluble thorium compound and a soluble peroxide compound in order to ferm a thorium peroxide carrier precipitate which carries down with it the plutonium peroxide present. During this treatment the pH of the solution must be maintained between 2 and 3.

An Ultrastable Heterobimetallic Uranium(IV)/Vanadium(III) Solid Compound Protected by a Redox-Active Phosphite Ligand: Crystal Structure, Oxidative Dissolution, and First-Principles Simulation.

PubMed

Gui, Daxiang; Dai, Xing; Zheng, Tao; Wang, Xiangxiang; Silver, Mark A; Chen, Lanhua; Zhang, Chao; Diwu, Juan; Zhou, Ruhong; Chai, Zhifang; Wang, Shuao

2018-02-05

The first heterobimetallic uranium(IV)/vanadium(III) phosphite compound, Na 2 UV 2 (HPO 3 ) 6 (denoted as UVP), was synthesized via an in situ redox-active hydrothermal reaction. It exhibits superior hydrolytic and antioxidant stability compared to the majority of structures containing low-valent uranium or vanadium, further elucidated by first-principles simulations, and therefore shows potential applications in nuclear waste management.

Communication: Relativistic Fock-space coupled cluster study of small building blocks of larger uranium complexes.

PubMed

Tecmer, Paweł; Gomes, André Severo Pereira; Knecht, Stefan; Visscher, Lucas

2014-07-28

We present a study of the electronic structure of the [UO2](+), [UO2](2 +), [UO2](3 +), NUO, [NUO](+), [NUO](2 +), [NUN](-), NUN, and [NUN](+) molecules with the intermediate Hamiltonian Fock-space coupled cluster method. The accuracy of mean-field approaches based on the eXact-2-Component Hamiltonian to incorporate spin-orbit coupling and Gaunt interactions are compared to results obtained with the Dirac-Coulomb Hamiltonian. Furthermore, we assess the reliability of calculations employing approximate density functionals in describing electronic spectra and quantities useful in rationalizing Uranium (VI) species reactivity (hardness, electronegativity, and electrophilicity).

Communication: Relativistic Fock-space coupled cluster study of small building blocks of larger uranium complexes

NASA Astrophysics Data System (ADS)

Tecmer, Paweł; Severo Pereira Gomes, André; Knecht, Stefan; Visscher, Lucas

2014-07-01

We present a study of the electronic structure of the [UO2]+, [UO2]2 +, [UO2]3 +, NUO, [NUO]+, [NUO]2 +, [NUN]-, NUN, and [NUN]+ molecules with the intermediate Hamiltonian Fock-space coupled cluster method. The accuracy of mean-field approaches based on the eXact-2-Component Hamiltonian to incorporate spin-orbit coupling and Gaunt interactions are compared to results obtained with the Dirac-Coulomb Hamiltonian. Furthermore, we assess the reliability of calculations employing approximate density functionals in describing electronic spectra and quantities useful in rationalizing Uranium (VI) species reactivity (hardness, electronegativity, and electrophilicity).

Influence of calcite and dissolved calcium on uranium(VI) sorption to a hanford subsurface sediment.

PubMed

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

2005-10-15

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

Phosphate-Induced Immobilization of Uranium in Hanford Sediments.

PubMed

Pan, Zezhen; Giammar, Daniel E; Mehta, Vrajesh; Troyer, Lyndsay D; Catalano, Jeffrey G; Wang, Zheming

2016-12-20

Phosphate can be added to subsurface environments to immobilize U(VI) contamination. The efficacy of immobilization depends on the site-specific groundwater chemistry and aquifer sediment properties. Batch and column experiments were performed with sediments from the Hanford 300 Area in Washington State and artificial groundwater prepared to emulate the conditions at the site. Batch experiments revealed enhanced U(VI) sorption with increasing phosphate addition. X-ray absorption spectroscopy measurements of samples from the batch experiments found that U(VI) was predominantly adsorbed at conditions relevant to the column experiments and most field sites (low U(VI) loadings, <25 μM), and U(VI) phosphate precipitation occurred only at high initial U(VI) (>25 μM) and phosphate loadings. While batch experiments showed the transition of U(VI) uptake from adsorption to precipitation, the column study was more directly relevant to the subsurface environment because of the high solid:water ratio in the column and the advective flow of water. In column experiments, nearly six times more U(VI) was retained in sediments when phosphate-containing groundwater was introduced to U(VI)-loaded sediments than when the groundwater did not contain phosphate. This enhanced retention persisted for at least one month after cessation of phosphate addition to the influent fluid. Sequential extractions and laser-induced fluorescence spectroscopy of sediments from the columns suggested that the retained U(VI) was primarily in adsorbed forms. These results indicate that in situ remediation of groundwater by phosphate addition provides lasting benefit beyond the treatment period via enhanced U(VI) adsorption to sediments.

Phosphate-Induced Immobilization of Uranium in Hanford Sediments

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

Pan, Zezhen; Giammar, Daniel E.; Mehta, Vrajesh

2016-12-20

Phosphate can be added to subsurface environments to immobilize U(VI) contamination. The efficacy of immobilization depends on the site-specific groundwater chemistry and aquifer sediment properties. Batch and column experiments were performed with sediments from the Hanford 300 Area in Washington State and artificial groundwater prepared to emulate the conditions at the site. Batch experiments revealed enhanced U(VI) sorption with increasing phosphate addition. X-ray absorption spectroscopy measurements of samples from the batch experiments found that U(VI) was predominantly adsorbed at conditions relevant to the column experiments and most field sites (low U(VI) loadings, <25 μM), and U(VI) phosphate precipitation occurred onlymore » at high initial U(VI) (>25 μM) and phosphate loadings. While batch experiments showed the transition of U(VI) uptake from adsorption to precipitation, the column study was more directly relevant to the subsurface environment because of the high solid:water ratio in the column and the advective flow of water. In column experiments, nearly six times more U(VI) was retained in sediments when phosphate-containing groundwater was introduced to U(VI)-loaded sediments than when the groundwater did not contain phosphate. This enhanced retention persisted for at least one month after cessation of phosphate addition to the influent fluid. Sequential extractions and laser-induced fluorescence spectroscopy of sediments from the columns suggested that the retained U(VI) was primarily in adsorbed forms. These results indicate that in situ remediation of groundwater by phosphate addition provides lasting benefit beyond the treatment period via enhanced U(VI) adsorption to sediments.« less

Phosphate-Induced Immobilization of Uranium in Hanford Sediments

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

Pan, Zezhen; Giammar, Daniel E.; Mehta, Vrajesh

2016-12-20

Phosphate can be added to subsurface environments to immobilize U(VI) contamination. The efficacy of immobilization depends on the site-specific groundwater chemistry and aquifer sediment properties. Batch and column experiments were performed with sediments from the Hanford 300 Area in Washington State and artificial groundwater prepared to emulate the conditions at the site. Batch experiments revealed enhanced U(VI) sorption with increasing phosphate addition. X-ray absorption spectroscopy measurements of samples from the batch experiments found that U(VI) was predominantly adsorbed at conditions relevant to the column experiments and most field sites (low U(VI) loadings, <25 μM), and U(VI) phosphate precipitation occurred onlymore » at high initial U(VI) (>25μM) and phosphate loadings. While batch experiments showed the transition of U(VI) uptake from adsorption to precipitation, the column study was more directly relevant to the subsurface environment because of the high solid:water ratio in the column and the advective flow of water. In column experiments, nearly six times more U(VI) was retained in sediments when phosphate-containing groundwater was introduced to U(VI)-loaded sediments than when the groundwater did not contain phosphate. This enhanced retention persisted for at least one month after cessation of phosphate addition to the influent fluid. Sequential extractions and laser-induced fluorescence spectroscopy of sediments from the columns suggested that the retained U(VI) was primarily in adsorbed forms. These results indicate that in situ remediation of groundwater by phosphate addition provides lasting benefit beyond the treatment period via enhanced U(VI) adsorption to sediments.« less

Chromium oxidation state mapping in human cells

NASA Astrophysics Data System (ADS)

Ortega, R.; Fayard, B.; Salomé, M.; Devès, G.; Susini, J.

2003-03-01

The widespread use of chromium in industrial applications such as chemical production of pigments, refractory brick production, tanning, metallurgy, electroplating, and combustion of fuels has lead to human occupational exposure and to its increased introduction into the environment. Hexavalent chromium compounds are established carcinogens but their mechanism of cell transformation is not known. Up to now, no microanalytical technique was sensitive enough to allow the observation of chromium distribution, and oxidation state identification, within isolated cells at carcinogenic concentrations. In this experiment, we used successfully the ID-21 X-ray microscope to map Cr(VI) and total Cr distributions in cells exposed in vitro to soluble, and insoluble, Cr(VI) compounds. Exposure to soluble compounds, weak carcinogens, resulted in a homogeneous intracellular distribution of Cr, confirming by in situ measurement that Cr is present in the cell nucleus. Cr(VI) was never detected in cells which suggests a mechanism of rapid intracellular reducticn. On the other hand, exposure to insoluble compounds, strong carcinogens, also resulted in a homogeneous distribution of reduced forms of Cr in cells, and their nucleus. However, in this case, Cr(VI)-rich structures were observed into the cells suggesting that carcinogenicity is enhanced when oxidation reactions due to Cr(VI) chronic exposure are associated to Cr-DNA alterations.

Bacterial community succession during in situ uranium bioremediation: spatial similarities along controlled flow paths.

PubMed

Hwang, Chiachi; Wu, Weimin; Gentry, Terry J; Carley, Jack; Corbin, Gail A; Carroll, Sue L; Watson, David B; Jardine, Phil M; Zhou, Jizhong; Criddle, Craig S; Fields, Matthew W

2009-01-01

Bacterial community succession was investigated in a field-scale subsurface reactor formed by a series of wells that received weekly ethanol additions to re-circulating groundwater. Ethanol additions stimulated denitrification, metal reduction, sulfate reduction and U(VI) reduction to sparingly soluble U(IV). Clone libraries of SSU rRNA gene sequences from groundwater samples enabled tracking of spatial and temporal changes over a 1.5-year period. Analyses showed that the communities changed in a manner consistent with geochemical variations that occurred along temporal and spatial scales. Canonical correspondence analysis revealed that the levels of nitrate, uranium, sulfide, sulfate and ethanol were strongly correlated with particular bacterial populations. As sulfate and U(VI) levels declined, sequences representative of sulfate reducers and metal reducers were detected at high levels. Ultimately, sequences associated with sulfate-reducing populations predominated, and sulfate levels declined as U(VI) remained at low levels. When engineering controls were compared with the population variation through canonical ordination, changes could be related to dissolved oxygen control and ethanol addition. The data also indicated that the indigenous populations responded differently to stimulation for bioreduction; however, the two biostimulated communities became more similar after different transitions in an idiosyncratic manner. The strong associations between particular environmental variables and certain populations provide insight into the establishment of practical and successful remediation strategies in radionuclide-contaminated environments with respect to engineering controls and microbial ecology.

Experimental and modeling study of the uranium (VI) sorption on goethite.

PubMed

Missana, Tiziana; García-Gutiérrez, Miguel; Maffiotte, Cesar

2003-04-15

Acicular goethite was synthesized in the laboratory and its main physicochemical properties (composition, microstructure, surface area, and surface charge) were analyzed as a previous step to sorption experiments. The stability of the oxide, under the conditions used in sorption studies, was also investigated. The sorption of U(VI) onto goethite was studied under O(2)- and CO(2)-free atmosphere and in a wide range of experimental conditions (pH, ionic strength, radionuclide, and solid concentration), in order to assess the validity of different surface complexation models available for the interpretation of sorption data. Three different models were used to fit the experimental data. The first two models were based on the diffuse double layer concept. The first one (Model 1) considered two different monodentate complexes with the goethite surface and the second (Model 2) a single binuclear bidentate complex. A nonelectrostatic (NE) approach was used as a third model and, in that case, the same species considered in Model 1 were used. The results showed that all the models are able to describe the sorption behavior fairly well as a function of pH, electrolyte concentration, and U(VI) concentration. However, Model 2 fails in the description of the uranium sorption behavior as a function of the sorbent concentration. This demonstrates the importance of checking the validity of any surface complexation model under the widest possible range of experimental conditions.

Removal of uranium from aqueous solution by a low cost and high-efficient adsorbent

NASA Astrophysics Data System (ADS)

Liu, Yun-Hai; Wang, You-Qun; Zhang, Zhi-Bin; Cao, Xiao-Hong; Nie, Wen-Bin; Li, Qin; Hua, Rong

2013-05-01

In this study, a low-cost and high-efficient carbonaceous adsorbent (HTC-COOH) with carboxylic groups was developed for U(VI) removal from aqueous solution compared with the pristine hydrothermal carbon (HTC). The structure and chemical properties of resultant adsorbents were characterized by Scanning electron microscope (SEM), N2 adsorption-desorption, Fourier transform-infrared spectra (FT-IR) and acid-base titration. The key factors (solution pH, contact time, initial U(VI) concentrations and temperature) affected the adsorption of U(VI) on adsorbents were investigated using batch experiments. The adsorption of U(VI) on HTC and HTC-COOH was pH-dependent, and increased with temperature and initial ion concentration. The adsorption equilibrium of U(VI) on adsorbents was well defined by the Langmuir isothermal equation, and the monolayer adsorption capacity of HTC-COOH was found to be 205.8 mg/g. The kinetics of adsorption was very in accordance with the pseudo-second-order rate model. The adsorption processes of U(VI) on HTC and HTC-COOH were endothermic and spontaneous in nature according to the thermodynamics of adsorption. Furthermore, HTC-COOH could selectively adsorption of U(VI) in aqueous solution containing co-existing ions (Mg2+, Co2+, Ni2+, Zn2+ and Mn2+). From the results of the experiments, it is found that the HTC-COOH is a potential adsorbent for effective removal of U(VI) from polluted water.

Preparation of graphene oxide-manganese dioxide for highly efficient adsorption and separation of Th(IV)/U(VI).

PubMed

Pan, Ning; Li, Long; Ding, Jie; Li, Shengke; Wang, Ruibing; Jin, Yongdong; Wang, Xiangke; Xia, Chuanqin

2016-05-15

Manganese dioxide decorated graphene oxide (GOM) was prepared via fixation of crystallographic MnO2 (α, γ) on the surface of graphene oxide (GO) and was explored as an adsorbent material for simultaneous removal of thorium/uranium ions from aqueous solutions. In single component systems (Th(IV) or U(VI)), the α-GOM2 (the weight ratio of GO/α-MnO2 of 2) exhibited higher maximum adsorption capacities toward both Th(IV) (497.5mg/g) and U(VI) (185.2 mg/g) than those of GO. In the binary component system (Th(IV)/U(VI)), the saturated adsorption capacity of Th(IV) (408.8 mg/g)/U(VI) (66.8 mg/g) on α-GOM2 was also higher than those on GO. Based on the analysis of various data, it was proposed that the adsorption process may involve four types of molecular interactions including coordination, electrostatic interaction, cation-pi interaction, and Lewis acid-base interaction between Th(IV)/U(VI) and α-GOM2. Finally, the Th(IV)/U(VI) ions on α-GOM2 can be separated by a two-stage desorption process with Na2CO3/EDTA. Those results displayed that the α-GOM2 may be utilized as an potential adsorbent for removing and separating Th(IV)/U(VI) ions from aqueous solutions. Copyright © 2016 Elsevier B.V. All rights reserved.

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

Li, Na; Huang, Rudan, E-mail: huangrd@bit.edu.cn

Six new inorganic–organic hybrids based on rigid triangular N-containing ligands, NaCu{sup I}{sub 2}(tib){sub 4}(H{sub 2}O){sub 4}[H{sub 2}PW{sup V}W{sup VI}{sub 11}O{sub 40}][H{sub 2}PW{sup VI}{sub 12}O{sub 40}]·6H{sub 2}O (1), Cu{sup II}{sub 3}(tib){sub 4}Cl{sub 4}[H{sub 2}PW{sup VI}{sub 12}O{sub 40}]{sub 2}·4H{sub 2}O (2), Co(tib){sub 2}[PW{sup V}{sub 3}W{sup VI}{sub 9}O{sub 38}]·5H{sub 2}O (3), Cu{sup II}{sub 3}(tib){sub 2}[P{sub 2}Mo{sup VI}{sub 5}O{sub 22}(O{sub 2})]·4H{sub 2}O (4), Mn(pytpy){sub 2}Mo{sup VI}{sub 4}O{sub 13} (5) and Co(pytpy){sub 2}Mo{sup VI}{sub 4}O{sub 13} (6) (tib=1,3,5-tris(1-imidazolyl)benzene, pytpy=4’-(4”-pyridyl)2,4’:6’,4”-terpyridine), have been hydrothermally synthesized. Single crystal X-ray diffraction studies revealed that compounds 1–4 display two-dimensional (2D) layered structures, and in compounds 1–3, the adjacent Keggin anionsmore » link with each other by W–O–W covalent interactions to form 1D inorganic chains. Compounds 5–6 are 3D “pillar-layer” frameworks based on bimetal–oxide layers pillared by the pytpy ligands. The compounds have been characterized by elemental analysis, powder X−ray diffraction, X-ray photoelectron spectroscopy and thermo gravimetric analyses. Moreover, the electrochemical and catalytic properties of compound 1 have been investigated as well. - Graphical abstract: Six new inorganic–organic hybrids based on rigid triangular N-containing ligands have been obtained under hydrothermal conditions and characterized by single-crystal X-ray diffraction analyses, elemental analyses, IR spectra, and thermogravimetric (TG) analyses. Compounds 1–4 display two-dimensional (2D) layers structure, and in compounds 1–3, the adjacent Keggin anions link with each other by W–O–W covalent interactions to form 1D inorganic Keggin anions chains. Compounds 5–6 are 3D “pillar-layer” frameworks based on bimetal–oxide layers pillared by the pytpy ligands. - Highlights: • MOFs based on POMs have been prepared. • Six new compounds based on rigid triangular N-containing ligands. • The adjacent POMs only share the oxygen atom to form a 1D inorganic Keggin chains.« less

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

EPA Pesticide Factsheets

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

Investigations on the nephrotoxicity and hepatotoxicity of trivalent and hexavalent chromium compounds.

PubMed

Dartsch, P C; Hildenbrand, S; Kimmel, R; Schmahl, F W

1998-09-01

In contrast to trivalent chromium (Cr(III)) compounds, hexavalent chromium ((Cr(VI)) compounds are oxidizing agents capable of directly inducing tissue damage and possessing carcinogenic, mutagenic and teratogenic potency. After oral or dermal absorption of Cr(VI), the kidney is the main target organ for chromium accumulation, which might result in acute tubular necrosis in humans. In contrast, an acute toxic effect of Cr(VI) on the liver has not yet been described. Therefore, we used two established epithelial cell lines from the kidney (Opossum kidney cells) and the liver (Hep G2 cells) to design an in vitro-assay which is able to examine acute toxic effects of chromium compounds. Cells of both cell lines were treated with various concentrations of Cr(III) and Cr(VI) ranging from 0.01 micromol/l to 1 mmol/l for 24 h. Thereafter, cell morphology, organization of the intracellular cytoskeleton, number of viable cells and mean cell volume were examined. The results show that Cr(VI), but not Cr(III), has an acute cytotoxic effect and causes a dose-dependent loss in cell viability. The effective dose that caused 50% of cell death was 5 micromol/l for kidney epithelial cells and 50 micromol/l for liver epithelial cells. This means that kidney epithelial cells are 10 times more sensitive towards Cr(VI) treatment than liver epithelial cells and this might explain the known nephrotoxicity in vivo. The loss in cell viability was accompanied by a rounding and detachment of the cells and a marked reduction of intracellular F-actin-containing stress fibers. Microtubules and intermediate-sized filaments were observed to be unaffected. Only in the case of kidney epithelial cells, a dose-dependent cell volume increase was observed after Cr(VI) treatment at concentrations up to 50 micromol/l. At higher concentrations, the cell volume decreased due to the high number of cells undergoing lysis and the appearance of cellular fragments. Various chloride channel blockers with different specificities, molecular structures and inhibitory potentials were tested for their ability to prevent Cr(VI)-induced cell damage. None of the channel blockers was able to inhibit cell damage, suggesting that the uptake of Cr(VI) through the general anion transport system of the cell membrane might be only one facet of cellular uptake and toxification. The data presented here not only confirm the different organ-specific effects of Cr(III) and Cr(VI), but also provide a basis for future experiments on the understanding of acute toxicity of Cr(VI) compounds. Moreover, the results demonstrate that the designed in vitro-assay might be a useful tool to prove whether non-toxic Cr(III) can be oxidized to Cr(VI) under specific industrial conditions (for example, in the leather or chrome industry).

Studies on supercritical hydrothermal syntheses of uranium and lanthanide oxide particles and their reaction mechanisms

NASA Astrophysics Data System (ADS)

Hwang, DongKi; Tsukahara, Takehiko; Tanaka, Kosuke; Osaka, Masahiko; Ikeda, Yasuhisa

2015-11-01

In order to develop preparation method of raw metal oxide particles for low decontaminated MOX fuels by supercritical hydrothermal (SH) treatments, we have investigated behavior of aqueous solutions dissolving U(VI), Ln(III) (Ln: lanthanide = Ce, Pr, Nd, Sm, Tb), Cs(I), and Sr(II) nitrate or chloride compounds under SH conditions (temperature = 400-500 °C, pressure = 30-40 MPa). As a result, it was found that Ln(NO3)3 (Ln = Ce, Pr, Tb) compounds produce LnO2, that Ln(NO3)3 (Ln = Nd, Sm) compounds are hardly converted to their oxides, and that LnCl3 (Ln = Ce, Pr, Nd, Sm, Tb), CsNO3, and Sr(NO3)2 do not form their oxide compounds. Furthermore, HNO2 species were detected in the liquid phase obtained after treating HNO3 aqueous solutions containing Ln(NO3)3 (Ln = Ce, Pr, Tb) under SH conditions, and also NO2 and NO compounds were found to be produced by decomposition of HNO3. From these results, it was proposed that the Ln oxide (LnO2) particles are directly formed with oxidation of Ln(III) to Ln(IV) by HNO3 and HNO2 species in the SH systems. Moreover, the uranyl ions were found to form U3O8 and UO3 depending on the concentration of HNO3. From these results, it is expected that the raw metal oxide particles for low decontaminated MOX fuels are efficiently prepared by the SH method.

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.

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

PubMed

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

2009-01-01

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

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

NASA Astrophysics Data System (ADS)

Nie, Xiaoqin; Dong, Faqin; Liu, Ning; Liu, Mingxue; Zhang, Dong; Kang, Wu; Sun, Shiyong; Zhang, Wei; Yang, Jie

2015-08-01

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

Bioreduction and immobilization of uranium in situ: a case study at a USA Department of Energy radioactive waste site, Oak Ridge, Tennessee

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

Wu, Weimin; Carley, Jack M; Watson, David B

Bioremediation of uranium contaminated groundwater was tested by delivery of ethanol as an electron donor source to stimulate indigenous microbial bioactivity for reduction and immobilization of uranium in situ, followed by tests of stability of uranium sequestration in the bioreduced area via delivery of dissolved oxygen or nitrate at the US Department of energy's Integrated Field Research Challenge site located at Oak Ridge, Tennessee, USA. After long term treatment that spanned years, uranium in groundwater was reduced from 40-60 mg {center_dot} L{sup -1} to <0.03 mg {center_dot} L{sup -1}, below the USA EPA standard for drinking water. The bioreduced uraniummore » was stable under anaerobic or anoxic conditions, but addition of DO and nitrate to the bioreduced zone caused U remobilization. The change in the microbial community and functional microorganisms related to uranium reduction and oxidation were characterized. The delivery of ethanol as electron donor stimulated the activities of indigenous microorganisms for reduction of U(VI) to U(IV). Results indicated that the immobilized U could be partially remobilized by D0 and nitrate via microbial activity. An anoxic environmental condition without nitrate is essential to maintain the stability of bioreduced uranium.« less

Use of Compound-Specific Stable Isotope Analysis to Distinguish between Vapor Intrusion and Indoor Sources of VOC

DTIC Science & Technology

2013-12-01

trichloroethylene USEPA U.S. Environmental Protection Agency UST underground storage tank V-PDB Vienna - Pee Dee Belemnite ACRONYMS AND...compound (e.g., trichloroethylene [TCE]) can vary as a result of differences in their source material or compound synthesis or due to transformation... trichloroethylene [TCE], and benzene) that commonly drive VI investigations; 2) development of a protocol for application of CSIA in VI investigations; and 3

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.

Chemical state of fission products in irradiated uranium carbide fuel

NASA Astrophysics Data System (ADS)

Arai, Yasuo; Iwai, Takashi; Ohmichi, Toshihiko

1987-12-01

The chemical state of fission products in irradiated uranium carbide fuel has been estimated by equilibrium calculation using the SOLGASMIX-PV program. Solid state fission products are distributed to the fuel matrix, ternary compounds, carbides of fission products and intermetallic compounds among the condensed phases appearing in the irradiated uranium carbide fuel. The chemical forms are influenced by burnup as well as stoichiometry of the fuel. The results of the present study almost agree with the experimental ones reported for burnup simulated carbides.

Method of passivating semiconductor surfaces

DOEpatents

Wanlass, M.W.

1990-06-19

A method is described for passivating Group III-V or II-VI semiconductor compound surfaces. The method includes selecting a passivating material having a lattice constant substantially mismatched to the lattice constant of the semiconductor compound. The passivating material is then grown as an ultrathin layer of passivating material on the surface of the Group III-V or II-VI semiconductor compound. The passivating material is grown to a thickness sufficient to maintain a coherent interface between the ultrathin passivating material and the semiconductor compound. In addition, a device formed from such method is also disclosed.

Method of passivating semiconductor surfaces

DOEpatents

Wanlass, Mark W.

1990-01-01

A method of passivating Group III-V or II-VI semiconductor compound surfaces. The method includes selecting a passivating material having a lattice constant substantially mismatched to the lattice constant of the semiconductor compound. The passivating material is then grown as an ultrathin layer of passivating material on the surface of the Group III-V or II-VI semiconductor compound. The passivating material is grown to a thickness sufficient to maintain a coherent interface between the ultrathin passivating material and the semiconductor compound. In addition, a device formed from such method is also disclosed.

Simulation of uranium and plutonium oxides compounds obtained in plasma

NASA Astrophysics Data System (ADS)

Novoselov, Ivan Yu.; Karengin, Alexander G.; Babaev, Renat G.

2018-03-01

The aim of this paper is to carry out thermodynamic simulation of mixed plutonium and uranium oxides compounds obtained after plasma treatment of plutonium and uranium nitrates and to determine optimal water-salt-organic mixture composition as well as conditions for their plasma treatment (temperature, air mass fraction). Authors conclude that it needs to complete the treatment of nitric solutions in form of water-salt-organic mixtures to guarantee energy saving obtainment of oxide compounds for mixed-oxide fuel and explain the choice of chemical composition of water-salt-organic mixture. It has been confirmed that temperature of 1200 °C is optimal to practice the process. Authors have demonstrated that condensed products after plasma treatment of water-salt-organic mixture contains targeted products (uranium and plutonium oxides) and gaseous products are environmental friendly. In conclusion basic operational modes for practicing the process are showed.

Reaction-Based Reactive Transport Modeling of Iron Reduction and Uranium Immobilization at Area 2 of the NABIR Field Research Center

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

Burgos, W.D.

2009-09-02

This report summarizes research conducted in conjunction with a project entitled “Reaction-Based Reactive Transport Modeling of Iron Reduction and Uranium Immobilization at Area 2 of the NABIR Field Research Center”, which was funded through the Integrative Studies Element of the former NABIR Program (now the Environmental Remediation Sciences Program) within the Office of Biological and Environmental Research. Dr. William Burgos (The Pennsylvania State University) was the overall PI/PD for the project, which included Brian Dempsey (Penn State), Gour-Tsyh (George) Yeh (Central Florida University), and Eric Roden (formerly at The University of Alabama, now at the University of Wisconsin) as separately-fundedmore » co-PIs. The project focused on development of a mechanistic understanding and quantitative models of coupled Fe(III)/U(VI) reduction in FRC Area 2 sediments. The work builds on our previous studies of microbial Fe(III) and U(VI) reduction, and was directly aligned with the Scheibe et al. ORNL FRC Field Project at Area 2.« less

Emergence of Uranium as a Distinct Metal Center for Building Intrinsic X-ray Scintillators.

PubMed

Wang, Yaxing; Yin, Xuemiao; Liu, Wei; Xie, Jian; Chen, Junfeng; Silver, Mark A; Sheng, Daopeng; Chen, Lanhua; Diwu, Juan; Liu, Ning; Chai, Zhifang; Albrecht-Schmitt, Thomas E; Wang, Shuao

2018-06-25

The combination of high atomic number and high oxidation state in U VI materials gives rise to both high X-ray attenuation efficiency and intense green luminescence originating from ligand-to-metal charge transfer. These two features suggest that U VI materials might act as superior X-ray scintillators, but this postulate has remained substantially untested. Now the first observation of intense X-ray scintillation in a uranyl-organic framework (SCU-9) that is observable by the naked eye is reported. Combining the advantage in minimizing the non-radiative relaxation during the X-ray excitation process over those of inorganic salts of uranium, SCU-9 exhibits a very efficient X-ray to green light luminescence conversion. The luminescence intensity shows an essentially linear correlation with the received X-ray intensity, and is comparable with that of commercially available CsI:Tl. SCU-9 possesses an improved X-ray attenuation efficiency (E>20 keV) as well as enhanced radiation resistance and decreased hygroscopy compared to CsI:Tl. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Izbicki, John A.; Wright, Michael T.; Seymour, Whitney A.

Hexavalent chromium, Cr(VI), in 918 wells sampled throughout California between 2004 and 2012 by the Groundwater Ambient Monitoring and Assessment Program—Priority Basin Project (GAMA—PBP) ranged from less than the study reporting limit (SRL) of 1 microgram per liter (μg/L) to 32 μg/L. Statewide, Cr(VI) was reported in 31 percent of sampled wells and equaled or exceeded the recently established (2014) California Maximum Contaminant Level (MCL) for Cr(VI) of 10 μg/L in 4 percent of sampled wells. Cr(VI) data collected for regulatory purposes overestimate Cr(VI) occurrence. Ninety percent of chromium was present as Cr(VI), which was detected more frequently and atmore » higher concentrations in alkaline (pH > 8), oxic water, and more frequently in agricultural and urban land uses compared to native land uses. Chemical, isotopic (tritium and carbon-14), and noble-gas data show high Cr(VI) in water from wells in alluvial aquifers in the southern California deserts result from long groundwater-residence times and geochemical reactions such as silicate weathering that increase pH, while oxic conditions persist. High Cr(VI) in water from wells in alluvial aquifers along the west-side of the Central Valley results from high-chromium abundance in source rock eroded to form those aquifers, and areal recharge processes (including irrigation return) that mobilize chromium from the unsaturated zone. Cr(VI) co-occurred with oxyanions having similar chemistry, including vanadium, selenium, and uranium. Cr(VI) was positively correlated with nitrate, consistent with increased concentrations in areas of agricultural land use and mobilization of chromium from the unsaturated zone by irrigation return.« less

Determination of Cr(III) solids formed by reduction of Cr(VI) in a contaminated fractured bedrock aquifer: evidence for natural attenuation of Cr(VI)

EPA Science Inventory

Hexavalent chromium Cr(VI) is toxic and can be highly mobile in many aquifer systems. Redox reactions with naturally occurring minerals and organic compounds can reduce Cr(VI) to Cr(III), forming labile Cr(III) oxyhydroxide precipitates, which is a natural attenuation process. In...

Extraction of hexavalent chromium from chromated copper arsenate treated wood under alkaline conditions.

PubMed

Radivojevic, Suzana; Cooper, Paul A

2008-05-15

Information on chromium (Cr) oxidation states is essential for the assessment of environmental and health risks associated with the overall life-cycle of chromated copper arsenate (CCA) treated wood products because of differences in toxicity between trivalent [Cr(III)] and hexavalent [Cr(VI)] chromium compounds. Hypothetical Cr(VI) fixation products were investigated in CCA type C treated sawdust of aspen and red pine during or following preservative fixation by extraction with Cr(VI)-specific extractants. Cr(VI) was found only in alkaline extracts of treated wood. A major source of Cr(VI) was method-induced oxidation of fixed Cr(III) during alkaline extraction, as confirmed by demonstrated oxidation of Cr(III) from CrCl3 treated wood. Oxidation of nontoxic and immobile Cr(III) to toxic and mobile Cr(VI) was facilitated by the presence of wood at pH > 8.5. Thermodynamic equilibrium between Cr(III) and Cr(VI) is affected by pH, temperature, rates of dissolution of CrIII) compounds, and oxygen availability. Results of this study recommend against alkaline extraction protocols for determination of Cr(VI) in treated wood. This Cr oxidation mechanism can act as a previously unrecognized route for generation of hazardous Cr(VI) if CCA treated wood is exposed to alkaline conditions during its production, use, or waste management.

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

Wang, Yan; Pan, Cheng-Ling; Xiao, Li-Na

Three new supramolecular compounds based on triethylenediamine and different polyoxometalates [W{sup VI}{sub 3}V{sup V}{sub 3}O{sub 19}H]{l_brace}[Cu(HDABCO)]{sub 2}(H{sub 2}O){r_brace} (1), [P{sub 2}Mo{sup VI}{sub 18}O{sub 62}][HDABCO]{sub 2}[H{sub 2}DABCO]{sub 2}.12 H{sub 2}O (2) and [Mo{sup VI}{sub 7.5}W{sup VI}{sub 0.5}O{sub 27}][Cu(HDABCO)]{sub 2}.2 H{sub 3}O.2 H{sub 2}O (3) (DABCO=triethylenediamine) have been synthesized hydrothermally and characterized by IR, TG, XPS and X-ray diffraction analyses. Crystal structure analyses reveal that compound 1 exhibits a face-centered cubic packing motif, compound 2 displays a supramolecular structure constructed form the 'chains' arranged hexagonally, compound 3 contains [Mo{sub 7.5}W{sub 0.5}O{sub 27}]{sub {infinity}} chain decorated by [Cu(HDABCO)]{sup 2+} cations, which was thenmore » packed into a layer structure. These results show that the same organonitrogen combining with the different POMs will yield different supramolecular networks. -- Graphical abstract: Three new supramolecular compounds based on triethylenediamine and different polyoxometalates have been hydrothermally synthesized and characterized by IR, XPS, TG, elemental analysis and X-ray diffraction analysis.« less

Inhibition of bone resorption by Tanshinone VI isolated from Salvia miltiorrhiza Bunge.

PubMed

Nicolin, V; Dal Piaz, F; Nori, S L; Narducci, P; De Tommasi, N

2010-05-10

During the last decade, a more detailed knowledge of molecular mechanisms involved in osteoclastogenesis has driven research efforts in the development and screening of compound libraries of several small molecules that specifically inhibit the pathway involved in the commitment of the osteoclast precursor cells. Natural compounds that suppress osteoclast differentiation may have therapeutic value in treating osteoporosis and other bone erosive diseases such as rheumatoid arthritis or metastasis associated with bone loss. In ongoing investigation into anti-osteoporotic compounds from natural products we have analyzed the effect of Tanshinone VI on osteoclasts differentiation, using a physiologic three-dimensional osteoblast/bone marrow model of cell co-culture. Tanshinone VI is an abietane diterpene extracted from the root of Salvia miltiorrhiza Bunge (Labiatae), a Chinese traditional crude drug, "Tan-Shen". Tashinone has been widely used in clinical practice for the prevention of cardiac diseases, arthritis and other inflammation-related disorders based on its pharmacological actions in multiple tissues. Although Tanshinone VI A has been used as a medicinal agent in the treatment of many diseases, its role in osteoclast-related bone diseases remains unknown. We showed previously that Tanshinone VI greatly inhibits osteoclast differentiation and suppresses bone resorption through disruption of the actin ring; subsequently, we intended to examine the precise inhibitory mechanism of Tanshinone VI on osteoclast differentiating factor. This study shows, for the first time, that Tanshinone VI prevents osteoclast differentiation by inhibiting RANKL expression and NFkB induction.

Cr(VI) Occurrence and Geochemistry in Water From Public-Supply Wells in California

DOE PAGES

Izbicki, John A.; Wright, Michael T.; Seymour, Whitney A.; ...

2015-08-18

Hexavalent chromium, Cr(VI), in 918 wells sampled throughout California between 2004 and 2012 by the Groundwater Ambient Monitoring and Assessment Program—Priority Basin Project (GAMA—PBP) ranged from less than the study reporting limit (SRL) of 1 microgram per liter (μg/L) to 32 μg/L. Statewide, Cr(VI) was reported in 31 percent of sampled wells and equaled or exceeded the recently established (2014) California Maximum Contaminant Level (MCL) for Cr(VI) of 10 μg/L in 4 percent of sampled wells. Cr(VI) data collected for regulatory purposes overestimate Cr(VI) occurrence. Ninety percent of chromium was present as Cr(VI), which was detected more frequently and atmore » higher concentrations in alkaline (pH > 8), oxic water, and more frequently in agricultural and urban land uses compared to native land uses. Chemical, isotopic (tritium and carbon-14), and noble-gas data show high Cr(VI) in water from wells in alluvial aquifers in the southern California deserts result from long groundwater-residence times and geochemical reactions such as silicate weathering that increase pH, while oxic conditions persist. High Cr(VI) in water from wells in alluvial aquifers along the west-side of the Central Valley results from high-chromium abundance in source rock eroded to form those aquifers, and areal recharge processes (including irrigation return) that mobilize chromium from the unsaturated zone. Cr(VI) co-occurred with oxyanions having similar chemistry, including vanadium, selenium, and uranium. Cr(VI) was positively correlated with nitrate, consistent with increased concentrations in areas of agricultural land use and mobilization of chromium from the unsaturated zone by irrigation return.« less

Cr(VI) occurrence and geochemistry in water from public-supply wells in California

USGS Publications Warehouse

Izbicki, John; Wright, Michael; Seymour, Whitney A.; McCleskey, R. Blaine; Fram, Miranda S.; Belitz, Kenneth; Esser, Bradley K.

2015-01-01

Hexavalent chromium, Cr(VI), in 918 wells sampled throughout California between 2004 and 2012 by the Groundwater Ambient Monitoring and Assessment-Priority Basin Project (GAMA-PBP) ranged from less than the study reporting limit of 1 microgram per liter (μg/L) to 32 μg/L. Statewide, Cr(VI) was reported in 31 percent of wells and equaled or exceeded the recently established (2014) California Maximum Contaminant Level (MCL) for Cr(VI) of 10 μg/L in 4 percent of wells. Cr(VI) data collected for regulatory purposes overestimated Cr(VI) occurrence compared to spatially-distributed GAMA-PBP data. Ninety percent of chromium was present as Cr(VI), which was detected more frequently and at higher concentrations in alkaline (pH ≥ 8), oxic water; and more frequently in agricultural and urban land uses compared to native land uses. Chemical, isotopic (tritium and carbon-14), and noble-gas data show high Cr(VI) in water from wells in alluvial aquifers in the southern California deserts result from long groundwater-residence times and geochemical reactions such as silicate weathering that increase pH, while oxic conditions persist. High Cr(VI) in water from wells in alluvial aquifers along the west-side of the Central Valley results from high-chromium in source rock eroded to form those aquifers, and areal recharge processes (including irrigation return) that can mobilize chromium from the unsaturated zone. Cr(VI) co-occurred with oxyanions having similar chemistry, including vanadium, selenium, and uranium. Cr(VI) was positively correlated with nitrate, consistent with increased concentrations in areas of agricultural land use and mobilization of chromium from the unsaturated zone by irrigation return.

Antibacterial and DNA cleavage activity of carbonyl functionalized N-heterocyclic carbene-silver(I) and selenium compounds

NASA Astrophysics Data System (ADS)

Haque, Rosenani A.; Iqbal, Muhammad Adnan; Mohamad, Faisal; Razali, Mohd R.

2018-03-01

The article describes syntheses and characterizations of carbonyl functionalized benzimidazolium salts, I-IV. While salts I-III are unstable at room temperature, salt IV remained stable and was further utilised to form N-heterocyclic carbene (NHC) compounds of silver(I), V and VI, and selenium compound, VII respectively. Compounds IV-VII were tested for their antibacterial potential against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). Salt IV shows a very low inhibition potential (minimum inhibitory concentration, MIC 500 μg/mL) compared to the respective silver(I)-NHC, V and VI (MIC 31.25 μg/mL against both, E. coli and S. aureus) and selenium compound, VII (MIC 125 μg/mL against E. coli and 62.50 μg/mL against S. aureus). In DNA cleavage abilities, all the test compounds cleave DNA in which the VII cleaves the DNA at the faster rate. Meanwhile, the silver(I)-NHC complexes V and VI act at the same mode and pattern of DNA cleavage while VII is similar to IV.

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

Du Preez, S. P.; Beukes, J. P.; Van Dalen, W. P. J.

The production of ferrochrome (FeCr) is a reducing process. However, it is impossible to completely exclude oxygen from all of the high-temperature production process steps, which may lead to unintentional formation of small amounts of Cr(VI). The majority of Cr(VI) is associated with particles found in the off-gas of the high-temperature processes, which are cleaned by means of venturi scrubbers or bag filter dust (BFD) systems. BFD contains the highest concentration of Cr(VI) of all FeCr wastes. In this study, the solubility of Cr(VI) present in BFD was determined by evaluating four different BFD samples. The results indicate that themore » currently applied Cr(VI) treatment strategies of the FeCr producer (with process water pH ≤ 9) only effectively extract and treat the water-soluble Cr(VI) compounds, which merely represented approximately 31% of the total Cr(VI) present in the BFD samples evaluated. Extended extraction time, within the afore-mentioned pH range, proved futile in extracting sparingly-soluble and water-insoluble Cr(VI) species, which represented approximately 34% and 35% of the total Cr(VI), respectively. Due to the deficiencies of the current treatment strategies, it is highly likely that sparingly water-soluble Cr(VI) compounds will leach from waste storage facilities (e.g. slimes dams) over time. Therefore, it is critical that improved Cr(VI) treatment strategies be formulated, which should be an important future perspective for FeCr producers and researchers alike.« less

[Study on the chemical constituents from Melicope ptelefolia].

PubMed

Xie, Yu-Feng; Liang, Yue; Du, Qing-Tao; Guo, Li-Bing

2011-03-01

To study the chemical constituents from Melicope ptelefolia. Several chromatographic methods were applied to isolate and purify compounds. Their structures were identified on the basis of physicochemical properties and spectroscopic data. Seven compounds were isolated and elucidated as n-octadecanyl palmitate (I), beta-sitosterol (II), palmitic acid (III), 3, 5,3'-trihydroxy-8,4'-dimethoxy-7-(3-methylbut-2-enyloxy) flavone (IV), daucosterol (V), salylic acid (VI), kaempferol-3-O-alpha-D-arabinpyranoside (VII). Compound VII is isolated from the genus for the first time, Compounds V and VI are isolated from Melicope ptelefolia for the first time.

[A new secoiridoid from the flowers of Jasminum officinale L. var. grandiflorum].

PubMed

Zhao, Gui-Qin; Yin, Zhi-Feng; Dong, Jun-Xing

2008-05-01

To study the chemical constituents of the flowers of Jasminum officinale L. var. grandiflorum, the compounds were isolated and purified by HPLC, recrystallization and chromatography on silica gel and Sephadex LH-20 column. Their structures were elucidated on the basis of physicochemical properties and spectral analysis. Six secoiridoids were identified as jasgranoside (I), jaspolyoside (II), 8-epi-kingiside (III), 10-hydroxy-oleuropein (IV), 10-hydroxy-ligstroside (V), oleoside-7, 11-dimethyl ester (VI). Compound I is a new compound. Compounds II, III, IV, V and VI were isolated from Jasminum officinale L. var. grandiflorum for the first time.

URANIUM BISMUTHIDE DISPERSION IN MOLTEN METAL

DOEpatents

Teitel, R.J.

1959-10-27

The formation of intermetallic bismuth compounds of thorium or uranium dispersed in a liquid media containing bismuth and lead is described. A bismuthide of uranium dispersed in a liquid metal medium is formed by dissolving uranium in composition of lead and bismuth containing less than 80% lead and lowering the temperature of the composition to a temperature below the point at which the solubility of uranium is exceeded and above the melting point of the composition.

Methods for Estimating Adsorbed Uranium(VI) and Distribution Coefficients of Contaminated Sediments

USGS Publications Warehouse

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

2004-01-01

Assessing the quantity of U(VI) that participates in sorption/desorption processes in a contaminated aquifer is an important task when investigating U migration behavior. U-contaminated aquifer sediments were obtained from 16 different locations at a former U mill tailings site at Naturita, CO (U.S.A.) and were extracted with an artificial groundwater, a high pH sodium bicarbonate solution, hydroxylamine hydrochloride solution, and concentrated nitric acid. With an isotopic exchange method, both a KD value for the specific experimental conditions as well as the total exchangeable mass of U(VI) was determined. Except for one sample, KD values determined by isotopic exchange with U-contaminated sediments that were in equilibrium with atmospheric CO2 agreed within a factor of 2 with KD values predicted from a nonelectrostatic surface complexation model (NEM) developed from U(VI) adsorption experiments with uncontaminated sediments. The labile fraction of U(VI) and U extracted by the bicarbonate solution were highly correlated (r2 = 0.997), with a slope of 0.96 ?? 0.01. The proximity of the slope to one suggests that both methods likely access the same reservoir of U(VI) associated with the sediments. The results indicate that the bicarbonate extraction method is useful for estimating the mass of labile U(VI) in sediments that do not contain U(IV). In-situ KD values calculated from the measured labile U(VI) and the dissolved U(VI) in the Naturita alluvial aquifer agreed within a factor of 3 with in-situ K D values predicted with the NEM and groundwater chemistry at each well.

Anaerobic U(IV) Bio-oxidation and the Resultant Remobilization of Uranium in Contaminated Sediments

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

Coates, John D.

2005-06-01

A proposed strategy for the remediation of uranium (U) contaminated sites is based on immobilizing U by reducing the oxidized soluble U, U(VI), to form a reduced insoluble end product, U(IV). Due to the use of nitric acid in the processing of nuclear fuels, nitrate is often a co-contaminant found in many of the environments contaminated with uranium. Recent studies indicate that nitrate inhibits U(VI) reduction in sediment slurries. However, the mechanism responsible for the apparent inhibition of U(VI) reduction is unknown, i.e. preferential utilization of nitrate as an electron acceptor, direct biological oxidation of U(IV) coupled to nitrate reduction,more » and/or abiotic oxidation by intermediates of nitrate reduction. Recent studies indicates that direct biological oxidation of U(IV) coupled to nitrate reduction may exist in situ, however, to date no organisms have been identified that can grow by this metabolism. In an effort to evaluate the potential for nitrate-dependent bio-oxidation of U(IV) in anaerobic sedimentary environments, we have initiated the enumeration of nitrate-dependent U(IV) oxidizing bacteria. Sediments, soils, and groundwater from uranium (U) contaminated sites, including subsurface sediments from the NABIR Field Research Center (FRC), as well as uncontaminated sites, including subsurface sediments from the NABIR FRC and Longhorn Army Ammunition Plant, Texas, lake sediments, and agricultural field soil, sites served as the inoculum source. Enumeration of the nitrate-dependent U(IV) oxidizing microbial population in sedimentary environments by most probable number technique have revealed sedimentary microbial populations ranging from 9.3 x 101 - 2.4 x 103 cells (g sediment)-1 in both contaminated and uncontaminated sites. Interestingly uncontaminated subsurface sediments (NABIR FRC Background core FB618 and Longhorn Texas Core BH2-18) both harbored the most numerous nitrate-dependent U(IV) oxidizing population 2.4 x 103 cells (g sediment)-1. The nitrate-dependent U(IV) oxidizing microbial population in groundwaters is less numerous ranging from 0 cells mL-1 (Well FW300, Uncontaminated Background NABIR FRC) to 4.3 x 102 cells mL-1 (Well TPB16, Contaminated Area 2 NABIR FRC). The presence of nitrate-dependent U(IV) oxidizing bacteria supports our hypothesis that bacteria capable of anaerobic U(IV) oxidation are ubiquitous and indigenous to sedimentary and groundwater environments.« less

Changes of Metabolomic Profile in Helianthus annuus under Exposure to Chromium(VI) Studied by capHPLC-ESI-QTOF-MS and MS/MS

PubMed Central

Gonzalez Ibarra, Alan Alexander; Wrobel, Kazimierz; Yanez Barrientos, Eunice; Corrales Escobosa, Alma Rosa; Gutierrez Corona, J. Felix; Enciso Donis, Israel

2017-01-01

The application of capHPLC-ESI-QTOF-MS and MS/MS to study the impact of Cr(VI) on metabolites profile in Helianthus annuus is reported. Germinated seeds were grown hydroponically in the presence of Cr(VI) (25 mgCr/L) and root extracts of the exposed and control plants were analyzed by untargeted metabolomic approach. The main goal was to detect which metabolite groups were mostly affected by Cr(VI) stress; two data analysis tools (ProfileAnalysis, Bruker, and online XCMS) were used under criteria of intensity threshold 5 · 104 cps, fold change ≥ 5, and p ≤ 0.01, yielding precursor ions. Molecular formulas were assigned based on data processing with two computational tools (SIRIUS and MS-Finder); annotation of candidate structures was performed by database search using CSI:FingerID and MS-Finder. Even though ultimate identification has not been achieved, it was demonstrated that secondary metabolism became activated under Cr(VI) stress. Among 42 candidate compounds returned from database search for seven molecular formulas, ten structures corresponded to isocoumarin derivatives and eleven were sesquiterpenes or sesquiterpene lactones; three benzofurans and four glycoside or pyrane derivatives of phenolic compounds were also suggested. To gain further insight on the effect of Cr(VI) in sunflower, isocoumarins and sesquiterpenes were selected as the target compounds for future study. PMID:29359067

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

Mouser, Paula J.; N'Guessan, A. Lucie; Qafoku, Nikolla

The capacity for subsurface sediments to sequester metal contaminants, such as uranium (U), and retain them after bioremediation efforts are completed is critical to site stewardship. Sediments enriched in natural organic matter are capable of sequestering significant quantities of U, but may also serve as sources to the aquifer, contributing to plume persistence. Two types of sediments were compared to better understand the mechanisms contributing to the sequestration and release of U in the presence of organic matter. Artificially bioreduced sediments were retrieved from a field experimental plot previously stimulated with acetate while naturally bioreduced sediments were collected from amore » location enriched in organic matter but never subject to acetate amendment. Batch incubations demonstrated that the artificially bioreduced sediments were primed to rapidly remove uranium from the groundwater whereas naturally bioreduced sediments initially released a sizeable portion of sediment U before U(VI)-removal commenced. Column experiments confirmed that U release persisted for 65 pore volumes in naturally bioreduced sediments, demonstrating the sink-source behavior of this sediment. Acetate addition to artificially bioreduced sediments shifted the microbial community from one dominated by sulfate-reducing bacteria within Desulfobacteraceae to the iron-reducing family Geobacteraceae and Firmicutes during U(VI) reduction. In contrast, initial Geobacteraceae communities innaturally reduced sediments were replaced by clone sequences with similarity to opportunistic Pseudomonas spp. during U release, while U(VI) removal occurred concurrent with enrichment of Firmicutes. These investigations stress the importance of characterizing zones with heterogeneous carbon pools at U contaminated sites prior to the determination of a remedial strategy.« less

Bacterial Community Succession During in situ Uranium Bioremediation: Spatial Similarities Along Controlled Flow Paths

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

Hwang, Chiachi; Wu, Weimin; Gentry, Terry J.

2009-05-22

Bacterial community succession was investigated in a field-scale subsurface reactor formed by a series of wells that received weekly ethanol additions to re-circulating groundwater. Ethanol additions stimulated denitrification, metal reduction, sulfate reduction, and U(VI) reduction to sparingly soluble U(IV). Clone libraries of SSU rRNA gene sequences from groundwater samples enabled tracking of spatial and temporal changes over a 1.5 y period. Analyses showed that the communities changed in a manner consistent with geochemical variations that occurred along temporal and spatial scales. Canonical correspondence analysis revealed that the levels of nitrate, uranium, sulfide, sulfate, and ethanol strongly correlated with particular bacterialmore » populations. As sulfate and U(VI) levels declined, sequences representative of sulfate-reducers and metal-reducers were detected at high levels. Ultimately, sequences associated with sulfate-reducing populations predominated, and sulfate levels declined as U(VI) remained at low levels. When engineering controls were compared to the population variation via canonical ordination, changes could be related to dissolved oxygen control and ethanol addition. The data also indicated that the indigenous populations responded differently to stimulation for bio-reduction; however, the two bio-stimulated communities became more similar after different transitions in an idiosyncratic manner. The strong associations between particular environmental variables and certain populations provide insight into the establishment of practical and successful remediation strategies in radionuclide-contaminated environments with respect to engineering controls and microbial ecology.« less

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.

49 CFR 176.84 - Other requirements for stowage and segregation for cargo vessels and passenger vessels.

Code of Federal Regulations, 2014 CFR

2014-10-01

...” flammable liquids. 29 Stow “away from” ammonium compounds. 30 Stow “away from” animal or vegetable oils. 31... vegetable oils. 55 Stow “separated from” ammonia. 56 Stow “separated from” ammonium compounds. 57 Stow... hexahydrate solution, uranium metal hexahydrate solution, uranium metal pyrophoric and thorium metal...

49 CFR 176.84 - Other requirements for stowage and segregation for cargo vessels and passenger vessels.

Code of Federal Regulations, 2013 CFR

2013-10-01

...” flammable liquids. 29 Stow “away from” ammonium compounds. 30 Stow “away from” animal or vegetable oils. 31... vegetable oils. 55 Stow “separated from” ammonia. 56 Stow “separated from” ammonium compounds. 57 Stow... hexahydrate solution, uranium metal hexahydrate solution, uranium metal pyrophoric and thorium metal...

Fluorination process using catalyst

DOEpatents

Hochel, Robert C.; Saturday, Kathy A.

1985-01-01

A process for converting an actinide compound selected from the group consisting of uranium oxides, plutonium oxides, uranium tetrafluorides, plutonium tetrafluorides and mixtures of said oxides and tetrafluorides, to the corresponding volatile actinide hexafluoride by fluorination with a stoichiometric excess of fluorine gas. The improvement involves conducting the fluorination of the plutonium compounds in the presence of a fluoride catalyst selected from the group consisting of CoF.sub.3, AgF.sub.2 and NiF.sub.2, whereby the fluorination is significantly enhanced. The improvement also involves conducting the fluorination of one of the uranium compounds in the presence of a fluoride catalyst selected from the group consisting of CoF.sub.3 and AgF.sub.2, whereby the fluorination is significantly enhanced.

Fluorination process using catalysts

DOEpatents

Hochel, R.C.; Saturday, K.A.

1983-08-25

A process is given for converting an actinide compound selected from the group consisting of uranium oxides, plutonium oxides, uranium tetrafluorides, plutonium tetrafluorides and mixtures of said oxides and tetrafluorides, to the corresponding volatile actinide hexafluoride by fluorination with a stoichiometric excess of fluorine gas. The improvement involves conducting the fluorination of the plutonium compounds in the presence of a fluoride catalyst selected from the group consisting of CoF/sub 3/, AgF/sub 2/ and NiF/sub 2/, whereby the fluorination is significantly enhanced. The improvement also involves conducting the fluorination of one of the uranium compounds in the presence of a fluoride catalyst selected from the group consisting of CoF/sub 3/ and AgF/sub 2/, whereby the fluorination is significantly enhanced.

Retardation of uranium and thorium by a cementitious backfill developed for radioactive waste disposal.

PubMed

Felipe-Sotelo, M; Hinchliff, J; Field, L P; Milodowski, A E; Preedy, O; Read, D

2017-07-01

The solubility of uranium and thorium has been measured under the conditions anticipated in a cementitious, geological disposal facility for low and intermediate level radioactive waste. Similar solubilities were obtained for thorium in all media, comprising NaOH, Ca(OH) 2 and water equilibrated with a cement designed as repository backfill (NRVB, Nirex Reference Vault Backfill). In contrast, the solubility of U(VI) was one order of magnitude higher in NaOH than in the remaining solutions. The presence of cellulose degradation products (CDP) results in a comparable solubility increase for both elements. Extended X-ray Absorption Fine Structure (EXAFS) data suggest that the solubility-limiting phase for uranium corresponds to a becquerelite-type solid whereas thermodynamic modelling predicts a poorly crystalline, hydrated calcium uranate phase. The solubility-limiting phase for thorium was ThO 2 of intermediate crystallinity. No breakthrough of either uranium or thorium was observed in diffusion experiments involving NRVB after three years. Nevertheless, backscattering electron microscopy and microfocus X-ray fluorescence confirmed that uranium had penetrated about 40 μm into the cement, implying active diffusion governed by slow dissolution-precipitation kinetics. Precise identification of the uranium solid proved difficult, displaying characteristics of both calcium uranate and becquerelite. Copyright © 2017 Elsevier Ltd. All rights reserved.

Spatial Distribution of an Uranium-Respiring Betaproteobacterium at the Rifle, CO Field Research Site

PubMed Central

Koribanics, Nicole M.; Tuorto, Steven J.; Lopez-Chiaffarelli, Nora; McGuinness, Lora R.; Häggblom, Max M.; Williams, Kenneth H.; Long, Philip E.; Kerkhof, Lee J.

2015-01-01

The Department of Energy’s Integrated Field-Scale Subsurface Research Challenge Site (IFRC) at Rifle, Colorado was created to address the gaps in knowledge on the mechanisms and rates of U(VI) bioreduction in alluvial sediments. Previous studies at the Rifle IFRC have linked microbial processes to uranium immobilization during acetate amendment. Several key bacteria believed to be involved in radionuclide containment have been described; however, most of the evidence implicating uranium reduction with specific microbiota has been indirect. Here, we report on the cultivation of a microorganism from the Rifle IFRC that reduces uranium and appears to utilize it as a terminal electron acceptor for respiration with acetate as electron donor. Furthermore, this bacterium constitutes a significant proportion of the subsurface sediment community prior to biostimulation based on TRFLP profiling of 16S rRNA genes. 16S rRNA gene sequence analysis indicates that the microorganism is a betaproteobacterium with a high similarity to Burkholderia fungorum. This is, to our knowledge, the first report of a betaproteobacterium capable of uranium respiration. Our results indicate that this microorganism occurs commonly in alluvial sediments located between 3-6 m below ground surface at Rifle and may play a role in the initial reduction of uranium at the site. PMID:25874721

Rapid and efficient uranium(VI) capture by phytic acid/polyaniline/FeOOH composites.

PubMed

Wei, Xintao; Liu, Qi; Zhang, Hongsen; Liu, Jingyuan; Chen, Rongrong; Li, Rumin; Li, Zhangshuang; Liu, Peili; Wang, Jun

2018-02-01

Uranium plays an indispensable role in nuclear energy, but there are limited land resources to meet the ever growing demand; therefore, a need exists to develop efficient materials for capturing uranium from water. Herein, we synthesize a promising adsorbent of phytic acid/polyaniline/FeOOH composites (PA/PANI/FeOOH) by oxidative polymerization. Phytic acid, acting asa gelator and dopant, plays an important role in the formation of polyaniline (PANI). The PA/PANI/FeOOH exhibites high adsorption capacity (q m =555.8mgg -1 , T=298K), rapid adsorption rate (within 5min), excellent selectivity and cyclic stability. In addition, the results show that the adsorption isotherm is well fitted to the Langmuir isotherm model, and the adsorption kinetics agree with a pseudo-second order model. XPS analysis indicates that the removal of uranium is mainly attributed to abundant amine and imine groups on the surface of PA/PANI/FeOOH. Importantly, the removal of uranium from low concentrations of simulated seawater is highly efficient with a removal rate exceeding 92%. From our study, superior adsorption capacities, along with a low-cost, environmentally friendly and facile synthesis, reveal PA/PANI/FeOOH asa promising material for uranium capture. Copyright © 2017. Published by Elsevier Inc.

Complexation of Uranium by Cells and S-Layer Sheets of Bacillus sphaericus JG-A12

PubMed Central

Merroun, Mohamed L.; Raff, Johannes; Rossberg, André; Hennig, Christoph; Reich, Tobias; Selenska-Pobell, Sonja

2005-01-01

Bacillus sphaericus JG-A12 is a natural isolate recovered from a uranium mining waste pile near the town of Johanngeorgenstadt in Saxony, Germany. The cells of this strain are enveloped by a highly ordered crystalline proteinaceous surface layer (S-layer) possessing an ability to bind uranium and other heavy metals. Purified and recrystallized S-layer proteins were shown to be phosphorylated by phosphoprotein-specific staining, inductive coupled plasma mass spectrometry analysis, and a colorimetric method. We used extended X-ray absorption fine-structure (EXAFS) spectroscopy to determine the structural parameters of the uranium complexes formed by purified and recrystallized S-layer sheets of B. sphaericus JG-A12. In addition, we investigated the complexation of uranium by the vegetative bacterial cells. The EXAFS analysis demonstrated that in all samples studied, the U(VI) is coordinated to carboxyl groups in a bidentate fashion with an average distance between the U atom and the C atom of 2.88 ± 0.02 Å and to phosphate groups in a monodentate fashion with an average distance between the U atom and the P atom of 3.62 ± 0.02 Å. Transmission electron microscopy showed that the uranium accumulated by the cells of this strain is located in dense deposits at the cell surface. PMID:16151146

Spatial distribution of an uranium-respiring betaproteobacterium at the Rifle, CO field research site

DOE PAGES

Koribanics, Nicole M.; Tuorto, Steven J.; Lopez-Chiaffarelli, Nora; ...

2015-04-13

The Department of Energy’s Integrated Field-Scale Subsurface Research Challenge Site (IFRC) at Rifle, Colorado was created to address the gaps in knowledge on the mechanisms and rates of U(VI) bioreduction in alluvial sediments. Previous studies at the Rifle IFRC have linked microbial processes to uranium immobilization during acetate amendment. Several key bacteria believed to be involved in radionuclide containment have been described; however, most of the evidence implicating uranium reduction with specific microbiota has been indirect. Here, we report on the cultivation of a microorganism from the Rifle IFRC that reduces uranium and appears to utilize it as a terminalmore » electron acceptor for respiration with acetate as electron donor. Furthermore, this bacterium constitutes a significant proportion of the subsurface sediment community prior to biostimulation based on TRFLP profiling of 16S rRNA genes. 16S rRNA gene sequence analysis indicates that the microorganism is a betaproteobacterium with a high similarity to Burkholderia fungorum. This is, to our knowledge, the first report of a betaproteobacterium capable of uranium respiration. Our results indicate that this microorganism occurs commonly in alluvial sediments located between 3-6 m below ground surface at Rifle and may play a role in the initial reduction of uranium at the site.« less

Deviation between the chemistry of Ce(IV) and Pu(IV) and routes to ordered and disordered heterobimetallic 4f/5f and 5f/5f phosphonates.

PubMed

Diwu, Juan; Wang, Shuao; Good, Justin J; DiStefano, Victoria H; Albrecht-Schmitt, Thomas E

2011-06-06

The heterobimetallic actinide compound UO(2)Ce(H(2)O)[C(6)H(4)(PO(3)H)(2)](2)·H(2)O was prepared via the hydrothermal reaction of U(VI) and Ce(IV) in the presence of 1,2-phenylenediphosphonic acid. We demonstrate that this is a kinetic product that is not stable with respect to decomposition to the monometallic compounds. Similar reactions have been explored with U(VI) and Ce(III), resulting in the oxidation of Ce(III) to Ce(IV) and the formation of the Ce(IV) phosphonate, Ce[C(6)H(4)(PO(3)H)(PO(3)H(2))][C(6)H(4)(PO(3)H)(PO(3))]·2H(2)O, UO(2)Ce(H(2)O)[C(6)H(4)(PO(3)H)(2)](2)·H(2)O, and UO(2)[C(6)H(4)(PO(3)H)(2)](H(2)O)·H(2)O. In comparison, the reaction of U(VI) with Np(VI) only yields Np[C(6)H(4)(PO(3)H)(2)](2)·2H(2)O and aqueous U(VI), whereas the reaction of U(VI) with Pu(VI) yields the disordered U(VI)/Pu(VI) compound, (U(0.9)Pu(0.1))O(2)[C(6)H(4)(PO(3)H)(2)](H(2)O)·H(2)O, and the Pu(IV) phosphonate, Pu[C(6)H(4)(PO(3)H)(PO(3)H(2))][C(6)H(4)(PO(3)H)(PO(3))]·2H(2)O. The reactions of Ce(IV) with Np(VI) yield disordered heterobimetallic phosphonates with both M[C(6)H(4)(PO(3)H)(PO(3)H(2))][C(6)H(4)(PO(3)H)(PO(3))]·2H(2)O (M = Ce, Np) and M[C(6)H(4)(PO(3)H)(2)](2)·2H(2)O (M = Ce, Np) structures, as well as the Ce(IV) phosphonate Ce[C(6)H(4)(PO(3)H)(PO(3)H(2))][C(6)H(4)(PO(3)H)(PO(3))]·2H(2)O. Ce(IV) reacts with Pu(IV) to yield the Pu(VI) compound, PuO(2)[C(6)H(4)(PO(3)H)(2)](H(2)O)·3H(2)O, and a disordered heterobimetallic Pu(IV)/Ce(IV) compound with the M[C(6)H(4)(PO(3)H)(PO(3)H(2))][C(6)H(4)(PO(3)H)(PO(3))]·2H(2)O (M = Ce, Pu) structure. Mixtures of Np(VI) and Pu(VI) yield disordered heterobimetallic Np(IV)/Pu(IV) phosphonates with both the An[C(6)H(4)(PO(3)H)(PO(3)H(2))][C(6)H(4)(PO(3)H)(PO(3))]·2H(2)O (M = Np, Pu) and An[C(6)H(4)(PO(3)H)(2)](2)·2H(2)O (M = Np, Pu) formulas. © 2011 American Chemical Society

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.

Synthesis and characterization of UO(2)(2+)-ion imprinted polymer for selective extraction of UO(2)(2+).

PubMed

Singh, Dhruv K; Mishra, Shraddha

2009-06-30

Ion-imprinted polymers (IIPs) were prepared for uranyl ion (imprint ion) by formation of binary (salicylaldoxime (SALO) or 4-vinylpyridine (VP)) or ternary (salicylaldoxime and 4-vinylpyridine) complex in 2-methoxy ethanol (porogen) following copolymerization with methacrylic acid (MAA) as a functional monomer and ethylene glycol dimethacrylate (EGDMA) as crosslinking monomer using 2,2'-azobisisobutyronitrile as initiator. Control polymers (CPs) were also prepared under identical experimental conditions without using imprint ion. The above synthesized polymers were characterized by surface area measurement, microanalysis and FT-IR analysis techniques. The imprinted polymer formed with ternary complex of UO(2)(2+)-SALO-VP (1:2:2, IIP3) showed quantitative enrichment of uranyl ion from dilute aqueous solution and hence was chosen for detailed studies. The optimal pH for quantitative enrichment is 3.5-6.5. The adsorbed UO(2)(2+) was completely eluted with 10 mL of 1.0 M HCl. The retention capacity of IIP3 was found to be 0.559 mmol g(-1). Further, the distribution ratio and selectivity coefficients of uranium and other selected inorganic ions were also evaluated. Five replicate determinations of 25 microg L(-1) of uranium(VI) gave a mean absorbance of 0.032 with a relative standard deviation of 2.20%. The detection limit corresponding to three times the standard deviation of the blank was found to be 5 microg L(-1). IIP3 was tested for preconcentration of uranium(VI) from ground, river and sea water samples.

Advective removal of intraparticle uranium from contaminated vadose zone sediments, Hanford, U.S.

PubMed

Ilton, Eugene S; Qafoku, Nikolla P; Liu, Chongxuan; Moore, Dean A; Zachara, John M

2008-03-01

A column study on U(VI)-contaminated vadose zone sediments from the Hanford Site, WA, was performed to investigate U(VI) release kinetics with water advection and variable geochemical conditions. The sediments were collected from an area adjacent to and below tank BX-102 that was contaminated as a result of a radioactive tank waste overfill event. The primary reservoir for U(VI) in the sediments are micrometer-size precipitates composed of nanocrystallite aggregates of a Na-U-Silicate phase, most likely Na-boltwoodite, that nucleated and grew within microfractures of the plagioclase component of sand-sized granitic clasts. Two sediment samples, with different U(VI) concentrations and intraparticle mass transfer properties, were leached with advective flows of three different solutions. The influent solutions were all calcite-saturated and in equilibrium with atmospheric CO2. One solution was prepared from DI water, the second was a synthetic groundwater (SGW) with elevated Na that mimicked groundwater at the Hanford site, and the third was the same SGW but with both elevated Na and Si. The latter two solutions were employed, in part, to test the effect of saturation state on U(VI) release. For both sediments, and all three electrolytes, there was an initial rapid release of U(VI) to the advecting solution followed by slower near steady-state release. U(VI)aq concentrations increased during subsequent stop-flow events. The electrolytes with elevated Na and Si depressed U(VL)aq concentrations in effluent solutions. Effluent U(VI)aq concentrations for both sediments and all three electrolytes were simulated reasonably well by a three domain model (the advecting fluid, fractures, and matrix) that coupled U(VI) dissolution, intraparticle U(VI)aq diffusion, and interparticle advection, where diffusion and dissolution properties were parameterized in a previous batch study.

Long-term diffusion of U(VI) in bentonite: Dependence on density

DOE PAGES

Joseph, Claudia; Mibus, Jens; Trepte, Paul; ...

2016-10-12

As a contribution to the safety assessment of nuclear waste repositories, U(VI) diffusion through the potential buffer material MX-80 bentonite was investigated at three clay dry densities over six years. Synthetic MX-80 model pore water was used as background electrolyte. Speciation calculations showed that Ca 2UO 2(CO 3) 3(aq) was the main U(VI) species. The in- and out-diffusion of U(VI) was investigated separately. U(VI) diffused about 3 mm, 1.5 mm, and 1 mm into the clay plug at ρ = 1.3, 1.6, and 1.9 g/cm 3, respectively. No through-diffusion of the U(VI) tracer was observed. However, leaching of natural uraniummore » contained in the clay occurred and uranium was detected in all receiving reservoirs. As expected, the effective and apparent diffusion coefficients, D e and D a, decreased with increasing dry density. The D a values for the out-diffusion of natural U(VI) were in good agreement with previously determined values. Surprisingly, D a values for the in-diffusion of U(VI) were about two orders of magnitude lower than values obtained in short-term in-diffusion experiments reported in the literature. Some potential reasons for this behavior that were evaluated are changes of the U(VI) speciation within the clay (precipitation, reduction) or changes of the clay porosity and pore connectivity with time. By applying Archie's law and the extended Archie's law, it was estimated that a significantly smaller effective porosity must be present for the long-term in-diffusion of U(VI). Finally, the results suggest that long-term studies of key transport phenomena may reveal additional processes that can directly impact long-term repository safety assessments.« less

Neutron imaging systems utilizing lithium-containing semiconductor crystals

DOEpatents

Stowe, Ashley C.; Burger, Arnold

2017-04-25

A neutron imaging system, including: a plurality of Li-III-VI.sub.2 semiconductor crystals arranged in an array, wherein III represents a Group III element and VI represents a Group VI element; and electronics operable for detecting and a charge in each of the plurality of crystals in the presence of neutrons and for imaging the neutrons. Each of the crystals is formed by: melting the Group III element; adding the Li to the melted Group III element at a rate that allows the Li and Group III element to react, thereby providing a single phase Li-III compound; and adding the Group VI element to the single phase Li-III compound and heating. Optionally, each of the crystals is also formed by doping with a Group IV element activator.

Genotoxicity of Tri- and Hexavalent Chromium Compounds In Vivo and Their Modes of Action on DNA Damage In Vitro

PubMed Central

Fang, Zhijia; Zhao, Min; Zhen, Hong; Chen, Lifeng; Shi, Ping; Huang, Zhiwei

2014-01-01

Chromium occurs mostly in tri- and hexavalent states in the environment. Hexavalent chromium [Cr(VI)] compounds are extensively used in diverse industries, and trivalent chromium [Cr(III)] salts are used as micronutrients and dietary supplements. In the present work, we report that they both induce genetic mutations in yeast cells. They both also cause DNA damage in both yeast and Jurkat cells and the effect of Cr(III) is greater than that of Cr(VI). We further show that Cr(III) and Cr(VI) cause DNA damage through different mechanisms. Cr(VI) intercalates DNA and Cr(III) interferes base pair stacking. Based on our results, we conclude that Cr(III) can directly cause genotoxicity in vivo. PMID:25111056

Fractionation of 238U/235U by reduction during low temperature uranium mineralisation processes

NASA Astrophysics Data System (ADS)

Murphy, Melissa J.; Stirling, Claudine H.; Kaltenbach, Angela; Turner, Simon P.; Schaefer, Bruce F.

2014-02-01

Investigations of ‘stable’ uranium isotope fractionation during low temperature, redox transformations may provide new insights into the usefulness of the 238U/235U isotope system as a tracer of palaeoredox processes. Sandstone-hosted uranium deposits accumulate at an oxidation/reduction interface within an aquifer from the low temperature reduction of soluble U(VI) complexes in groundwaters, forming insoluble U(IV) minerals. This setting provides an ideal environment in which to investigate the effects of redox transformations on 238U/235U fractionation. Here we present the first coupled measurements of 238U/235U isotopic compositions and U concentrations for groundwaters and mineralised sediment samples from the same redox system in the vicinity of the high-grade Pepegoona sandstone-hosted uranium deposit, Australia. The mineralised sediment samples display extremely variable 238U/235U ratios (herein expressed as δUCRM145238, the per-mil deviation from the international NBL standard CRM145). The majority of mineralised sediment samples have δUCRM145238 values between -1.30±0.05 and 0.55±0.12‰, spanning a ca. 2‰ range. However, one sample has an unusually light isotopic composition of -4.13±0.05‰, which suggests a total range of U isotopic variability of up to ca. 5‰, the largest variation found thus far in a single natural redox system. The 238U/235U isotopic signature of the mineralised sediments becomes progressively heavier (enriched in 238U) along the groundwater flow path. The groundwaters show a greater than 2‰ variation in their 238U/235U ratios, ranging from δUCRM145238 values of -2.39±0.07 to -0.71±0.05‰. The majority of the groundwater data exhibit a clear systematic relationship between 238U/235U isotopic composition and U concentration; samples with the lowest U concentrations have the lowest 238U/235U ratios. The preferential incorporation of 238U during reduction of U(VI) to U(IV) and precipitation of uranium minerals leaves the groundwaters enriched in 235U, resulting in a progressive shift in 238U/235U towards lighter values in the aqueous phase as U is removed. These data can be modelled by a closed system Rayleigh fractionation model, with a fractionation factor (α, representing the 238U/235U composition of the groundwater relative to the solid uranium minerals) ranging from ∼0.9996 to 1.0000, with the majority of datapoints ranging from α values of 0.9998 to 0.9999. The sense and magnitude of the results of this study imply that 238U/235U fractionation is likely to be controlled by volume-dependent nuclear field shift effects during the reduction of U(VI) to U(IV) during mineralisation processes. These findings support the use of the 238U/235U isotopic system as a tracer to constrain the nature and timing of palaeoredox conditions.

Ferrate(VI) oxidation of polychlorinated diphenyl sulfides: Kinetics, degradation, and oxidized products.

PubMed

Chen, Jing; Xu, Xinxin; Zeng, Xiaolan; Feng, Mingbao; Qu, Ruijuan; Wang, Zunyao; Nesnas, Nasri; Sharma, Virender K

2018-06-13

This paper presents oxidation of polychlorinated diphenyl sulfides (PCDPSs), dioxin-like compounds, by ferrate(VI) (Fe VI O 4 2- , Fe(VI)). Kinetics of the reactions of Fe(VI) with seventeen PCDPSs, differ in number and positions of chlorine atoms (from 2 to 7), were investigated at pH 8.0. The second-order rate constants (k, M -1 s -1 ) of the reactions varied with the numbers and positions of chlorine atoms and appeared to be related with standard Gibbs free energy of formation (Δ f G 0 ) of PCDPSs. Degradation experiments in the presence of ions and humic acid demonstrated complete removal of PeCDPS by Fe(VI) in minutes. Pathways of the reaction were investigated by identifying oxidized products (OPs) of the reaction between Fe(VI) and 2,2',3',4,5-pentachlorodiphenyl sulfide (PeCDPS) at pH 8.0. Pathways of oxidation involved major pathway of attack on sulfur(II) by Fe(VI) in steps to yield sulfoxide type products, and subsequent breakage of C-S bond with the formation of sulfonic acid-containing trichloro compound. Minor pathways were hydroxylation of benzene ring and substitution of chlorine atom with hydroxyl group. Estimation of toxicity of OPs of the oxidation of PeCDPS by Fe(VI) suggested the decreased toxicity from the parent contaminant. Copyright © 2018. Published by Elsevier Ltd.

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

Joel E. Kostka

This project represented a joint effort between Oak Ridge National Laboratory (ORNL), the University of Tennessee (UT), and Florida State University (FSU). ORNL served as the lead in-stitution with Dr. A.V. Palumbo responsible for project coordination, integration, and deliver-ables. In situ uranium bioremediation is focused on biostimulating indigenous microorganisms through a combination of pH neutralization and the addition of large amounts of electron donor. Successful biostimulation of U(VI) reduction has been demonstrated in the field and in the laboratory. However, little data is available on the dynamics of microbial populations capable of U(VI) reduction, and the differences in the microbialmore » community dynamics between proposed electron donors have not been explored. In order to elucidate the potential mechanisms of U(VI) reduction for optimization of bioremediation strategies, structure-function relationships of microbial populations were investigated in microcosms of subsurface materials cocontaminated with radionuclides and nitrate from the Oak Ridge Field Research Center (ORFRC), Oak Ridge, Tennessee.« less

Effect of phosphate on U(VI) sorption to montmorillonite: Ternary complexation and precipitation barriers

NASA Astrophysics Data System (ADS)

Troyer, Lyndsay D.; Maillot, Fabien; Wang, Zheming; Wang, Zimeng; Mehta, Vrajesh S.; Giammar, Daniel E.; Catalano, Jeffrey G.

2016-02-01

Phosphate addition is a potential treatment method to lower the solubility of U(VI) in soil and groundwater systems by causing U(VI) phosphate precipitation as well as enhancing adsorption. Previous work has shown that iron oxide surfaces may facilitate the nucleation of U(VI) phosphate minerals and, that under weakly acidic conditions, phosphate also enhances U(VI) adsorption to such phases. Like iron oxides, clays are important reactive phases in the subsurface but little is known about the interaction of U(VI) and phosphate with these minerals. The effect of aqueous phosphate on U(VI) binding to Wyoming montmorillonite (SWy-2) in air-equilibrated systems was investigated. Equilibrium U(VI) uptake to montmorillonite was determined at pH 4, 6 and 8 at discrete initial phosphate concentrations between 0 and 100 μM. The observed behavior of U(VI) indicates a transition from adsorption to precipitation with increasing total uranium and phosphate concentrations at all pH values. At the highest phosphate concentration examined at each pH value, a barrier to U(VI) phosphate nucleation is observed. At lower concentrations, phosphate has no effect on macroscopic U(VI) adsorption. To assess the mechanisms of U(VI)-phosphate interactions on smectite surfaces, U(VI) speciation was investigated under selected conditions using laser-induced fluorescence spectroscopy (LIFS) and extended X-ray absorption fine-structure (EXAFS) spectroscopy. Samples above the precipitation threshold display EXAFS and LIFS spectral signatures consistent with the autunite family of U(VI) phosphate minerals. However, at lower U(VI) concentrations, changes in LIFS spectra upon phosphate addition suggest that U(VI)-phosphate ternary surface complexes form on the montmorillonite surface at pH 4 and 6 despite the lack of a macroscopic effect on adsorption. The speciation of solid-associated U(VI) below the precipitation threshold at pH 8 is dominated by U(VI)-carbonate surface complexes. This work reveals that ternary complexation may occur without a macroscopic signature, which is attributed to phosphate not appreciably binding to smectite in the absence of U(VI), with U(VI) surface complexes serving as the sole reactive surface sites for phosphate. This study shows that phosphate does not enhance U(VI) adsorption to smectite clay minerals, unlike oxide phases, and that a barrier to homogeneous nucleation of U(VI) phosphates was not affected by the presence of the smectite surface.

XAS and TRLIF spectroscopy of uranium and neptunium in seawater.

PubMed

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

2015-03-28

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

Industrial Production of Uranium; PRODUCCION INDUSTRIAL DE URANIO

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

Pedregal, J.D.

1956-01-01

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

Uranium carbide fission target R&D for RIA - an update

NASA Astrophysics Data System (ADS)

Greene, J. P.; Levand, A.; Nolen, J.; Burtseva, T.

2004-12-01

For the Rare Isotope Accelerator (RIA) facility, ISOL targets employing refractory compounds of uranium are being developed to produce radioactive ions for post-acceleration. The availability of refractory uranium compounds in forms that have good thermal conductivity, relatively high density, and adequate release properties for short-lived isotopes remains an important issue. Investigations using commercially obtained uranium carbide material and prepared into targets involving various binder materials have been carried out at ANL. Thin sample pellets have been produced for measurements of thermal conductivity using a new method based on electron bombardment with the thermal radiation observed using a two-color optical pyrometer and performed on samples as a function of grain size, pressing pressure and sintering temperature. Manufacture of uranium carbide powder has now been achieved at ANL. Simulations have been carried out on the thermal behavior of the secondary target assembly incorporating various heat shield configurations.

On the mechanism of Cr (VI)-induced carcinogenesis: dose dependence of uptake and cellular responses.

PubMed

Liu, K; Husler, J; Ye, J; Leonard, S S; Cutler, D; Chen, F; Wang, S; Zhang, Z; Ding, M; Wang, L; Shi, X

2001-06-01

Cr (VI) compounds are widely used industrial chemicals and are recognized human carcinogens. The mechanisms of carcinogenesis associated with these compounds remain to be investigated. The present study focused on dose-dependence of Cr (VI)-induced uptake and cellular responses. The results show that Cr (VI) is able to enter the cells (human lung epithelial cell line A549) at low concentration (< 10 microM) and that the Cr (VI) uptake appears to be a combination of saturable transport and passive diffusion. Electron spin resonance (ESR) trapping measurements showed that upon stimulation with Cr (VI), A549 cells were able to generate reactive oxygen species (ROS). The amount of ROS generated depended on the Cr (VI) concentration. ROS generation involved NADPH-dependent flavoenzymes. Cr (VI) affected the following cellular parameters in a dose-dependent manner, (a) activation of nuclear transcription factors NF-kappaB, and p53, (b) DNA damage, (c) induction of cell apoptosis, and (d) inhibition of cell proliferation. The activation of transcription factors was assessed by electrophoretic mobility shift assay and western blot analysis, DNA damage by single cell gel electrophoresis assay, cell apoptosis by DNA fragmentation assay, and cell proliferation by a non-radioactive ELISA kit. At the concentration range used in the present study, no thresholds were found in all of these cell responses to Cr (VI). The results may guide further research to better understand and evaluate the risk of Cr (VI)-induced carcinogenesis at low levels of exposure.

Treatment of selected pharmaceuticals by ferrate(VI): performance, kinetic studies and identification of oxidation products.

PubMed

Zhou, Zhengwei; Jiang, Jia-Qian

2015-03-15

The performance of ferrate(VI) in treating sulfamethoxazole (SMX), diclofenac (DCF), carbamazepine (CBZ) and bezafibrate (BZF) in test solutions containing the four compounds was investigated. A series of jar-test experiments was performed on a bench-scale at pH 6-9 and at a ferrate(VI) dose of 1-5 mg Fe/L. The results suggested that ferrate(VI) can effectively remove SMX, DCF and CBZ from the test solutions, with greater than 80% removal under optimum conditions. However, the removal efficiency of BZF was very low, less than 25% under the studied conditions. Increasing the dose of ferrate(VI) improved the treatment performance, while the influence of solution pH on ferrate(VI) performance varied among the different target compounds. Ferrate(VI) demonstrated the highest reactivity with SMX at pH 8 and pH 9 (20 °C), with apparent second-order rate constants of 360±17 M(-1) s(-1) and 1.26±0.02 M(-1) s(-1), respectively. However, BZF showed the lowest removal by ferrate(VI) with the smallest rate constants (less than 0.5 M(-1) s(-1)) at pH 8 and pH 9. Furthermore, a number of oxidation products (OPs) of SMX, DCF and CBZ during ferrate(VI) oxidation were detected by liquid chromatography and mass spectrometry (LC-MS), and their degradation pathways were tentatively proposed. No OPs of BZF were detected during ferrate(VI) oxidation. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

Effects of nitrate on the stability of uranium in a bioreduced region of the subsurface.

PubMed

Wu, Wei-Min; Carley, Jack; Green, Stefan J; Luo, Jian; Kelly, Shelly D; Van Nostrand, Joy; Lowe, Kenneth; Mehlhorn, Tonia; Carroll, Sue; Boonchayanant, Benjaporn; Löfller, Frank E; Watson, David; Kemner, Kenneth M; Zhou, Jizhong; Kitanidis, Peter K; Kostka, Joel E; Jardine, Philip M; Criddle, Craig S

2010-07-01

The effects of nitrate on the stability of reduced, immobilized uranium were evaluated in field experiments at a U.S. Department of Energy site in Oak Ridge, TN. Nitrate (2.0 mM) was injected into a reduced region of the subsurface containing high levels of previously immobilized U(IV). The nitrate was reduced to nitrite, ammonium, and nitrogen gas; sulfide levels decreased; and Fe(II) levels increased then deceased. Uranium remobilization occurred concomitant with nitrite formation, suggesting nitrate-dependent, iron-accelerated oxidation of U(IV). Bromide tracer results indicated changes in subsurface flowpaths likely due to gas formation and/or precipitate. Desorption-adsorption of uranium by the iron-rich sediment impacted uranium mobilization and sequestration. After rereduction of the subsurface through ethanol additions, background groundwater containing high levels of nitrate was allowed to enter the reduced test zone. Aqueous uranium concentrations increased then decreased. Clone library analyses of sediment samples revealed the presence of denitrifying bacteria that can oxidize elemental sulfur, H(2)S, Fe(II), and U(IV) (e.g., Thiobacillus spp.), and a decrease in relative abundance of bacteria that can reduce Fe(III) and sulfate. XANES analyses of sediment samples confirmed changes in uranium oxidation state. Addition of ethanol restored reduced conditions and triggered a short-term increase in Fe(II) and aqueous uranium, likely due to reductive dissolution of Fe(III) oxides and release of sorbed U(VI). After two months of intermittent ethanol addition, sulfide levels increased, and aqueous uranium concentrations gradually decreased to <0.1 microM.

PROCESS FOR THE PRODUCTION OF AMMONIUM URANIUM FLUORIDE

DOEpatents

Ellis, A.S.; Mooney, R.B.

1953-08-25

This patent relates to the preparation of ammonium uranium fluoride. The process comprises adding a water soluble fluoride to an aqueous solution of a uranous compound containing an ammonium salt, and isolating the resulting precipitate. This patent relates to the manufacture of uranium tetnafluoride from ammonium uranium fluoride, NH/sub 4/UF/sub 5/. Uranium tetrafluoride is prepared by heating the ammonium uranium fluoride to a temperature at which dissociation occurs with liberation of ammonium fluoride. Preferably the process is carried out under reduced pressure, or in a current of an inert gas.

Purification of Hydrogen

DOEpatents

Newton, A S

1950-12-05

Disclosed is a process for purifying hydrogen containing various gaseous impurities by passing the hydrogen over a large surface of uranium metal at a temperature above the decomposition temperature of uranium hydride, and below the decomposition temperature of the compounds formed by the combination of the uranium with the impurities in the hydrogen.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Uranium 5f shell in UPd2Al3 and URu2Si2 studied by x-ray magnetic circular dichroism

NASA Astrophysics Data System (ADS)

Yaouanc, A.; Dalmas de Réotier, P.; van der Laan, G.; Hiess, A.; Goulon, J.; Neumann, C.; Lejay, P.; Sato, N.

1998-10-01

We report x-ray magnetic circular dichroism (XMCD) measurements performed at the uranium M4,5 edges in the paramagnetic phase of the heavy fermion superconductors UPd2Al3 and URu2Si2. The analysis of the spectra with the first sum rule yields the orbital moment of the 5f shell for both compounds. The shape of the dichroic spectrum at the M5 edge for the two compounds is qualitatively different: a single lobe is observed for URu2Si2 and two lobes are detected for UPd2Al3. This two lobe structure reflects the strong effect of the interaction of the uranium 5f electrons with their environment in the latter compound.

Identification of simultaneous U(VI) sorption complexes and U(IV) nanoprecipitates on the magnetite (111) surface.

PubMed

Singer, David M; Chatman, Shawn M; Ilton, Eugene S; Rosso, Kevin M; Banfield, Jillian F; Waychunas, Glenn A

2012-04-03

Sequestration of uranium (U) by magnetite is a potentially important sink for U in natural and contaminated environments. However, molecular-scale controls that favor U(VI) uptake including both adsorption of U(VI) and reduction to U(IV) by magnetite remain poorly understood, in particular, the role of U(VI)-CO(3)-Ca complexes in inhibiting U(VI) reduction. To investigate U uptake pathways on magnetite as a function of U(VI) aqueous speciation, we performed batch sorption experiments on (111) surfaces of natural single crystals under a range of solution conditions (pH 5 and 10; 0.1 mM U(VI); 1 mM NaNO(3); and with or without 0.5 mM CO(3) and 0.1 mM Ca) and characterized surface-associated U using grazing incidence extended X-ray absorption fine structure spectroscopy (GI-EXAFS), grazing incidence X-ray diffraction (GI-XRD), and scanning electron microscopy (SEM). In the absence of both carbonate ([CO(3)](T), denoted here as CO(3)) and calcium (Ca), or in the presence of CO(3) only, coexisting adsorption of U(VI) surface species and reduction to U(IV) occurs at both pH 5 and 10. In the presence of both Ca and CO(3), only U(VI) adsorption (VI) occurs. When U reduction occurs, nanoparticulate UO(2) forms only within and adjacent to surface microtopographic features such as crystal boundaries and cracks. This result suggests that U reduction is limited to defect-rich surface regions. Further, at both pH 5 and 10 in the presence of both CO(3) and Ca, U(VI)-CO(3)-Ca ternary surface species develop and U reduction is inhibited. These findings extend the range of conditions under which U(VI)-CO(3)-Ca complexes inhibit U reduction.

THERMAL DECOMPOSITION OF URANIUM COMPOUNDS

DOEpatents

Magel, T.T.; Brewer, L.

1959-02-10

A method is presented of preparing uranium metal of high purity consisting contacting impure U metal with halogen vapor at between 450 and 550 C to form uranium halide vapor, contacting the uranium halide vapor in the presence of H/sub 2/ with a refractory surface at about 1400 C to thermally decompose the uranium halides and deposit molten U on the refractory surface and collecting the molten U dripping from the surface. The entire operation is carried on at a sub-atmospheric pressure of below 1 mm mercury.

COATING URANIUM FROM CARBONYLS

DOEpatents

Gurinsky, D.H.; Storrs, S.S.

1959-07-14

Methods are described for making adherent corrosion resistant coatings on uranium metal. According to the invention, the uranium metal is heated in the presence of an organometallic compound such as the carbonyls of nickel, molybdenum, chromium, niobium, and tungsten at a temperature sufficient to decompose the metal carbonyl and dry plate the resultant free metal on the surface of the uranium metal body. The metal coated body is then further heated at a higher temperature to thermally diffuse the coating metal within the uranium bcdy.

Structure and thermodynamic stability of UTa 3 O 10 , a U( v )-bearing compound

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

Guo, Xiaofeng; Lipp, Christian; Tiferet, Eitan

Heating a mixture of uranyl(VI) nitrate and tantalum(V) oxide in the molar ratio of 2 : 3 to 1400 °C resulted in the formation of a new compound, UTa 3O 10. The honey colored to yellow brown crystals of UTa 3O 10 crystallize in an orthorhombic structure with the space group Fddd (no. 70), lattice parameters a = 7.3947(1), b = 12.7599(2), c = 15.8156(2) Å, and Z = 8. Vertex sharing [TaO 6] 7- octahedra of two crystallographically distinct Ta cations form a three dimensional tantalate framework. Within this framework, six membered rings of [TaO 6] 7- octahedra aremore » formed within the (001) plane. The center of these rings is occupied by the uranyl cations [UO 2] +, with an oxidation state of +5 for uranium. The pentavalence of U and Ta was confirmed by X-ray photoelectron spectroscopy and X-ray adsorption spectroscopy. The enthalpy of formation of UTa 3O 10 from Ta 2O 5, β-U 3O 7, and U 3O 8 has been determined to be 13.1 ± 18.1 kJ mol -1 using high temperature oxide melt solution calorimetry with sodium molybdate as the solvent at 700 °C. The close to zero enthalpy of formation of UTa 3O 10 can be explained by closely balanced structural stabilizing and destabilizing factors, which may also apply to other UM 3O 10 compounds.« less

Dynamics of microbial community composition and function during in-situ bioremediation of a uranium-contaminated aquifer

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

Nostrand, J.D. Van; Wu, L.; Wu, W.M.

2010-08-15

A pilot-scale system was established to examine the feasibility of in situ U(VI) immobilization at a highly contaminated aquifer (U.S. DOE Integrated Field Research Challenge site, Oak Ridge, TN). Ethanol was injected intermittently as an electron donor to stimulate microbial U(VI) reduction, and U(VI) concentrations fell to below the Environmental Protection Agency drinking water standard (0.03 mg liter{sup -1}). Microbial communities from three monitoring wells were examined during active U(VI) reduction and maintenance phases with GeoChip, a high-density, comprehensive functional gene array. The overall microbial community structure exhibited a considerable shift over the remediation phases examined. GeoChip-based analysis revealed thatmore » Fe(III)-reducing bacterial (FeRB), nitrate-reducing bacterial (NRB), and sulfate-reducing bacterial (SRB) functional populations reached their highest levels during the active U(VI) reduction phase (days 137 to 370), in which denitrification and Fe(III) and sulfate reduction occurred sequentially. A gradual decrease in these functional populations occurred when reduction reactions stabilized, suggesting that these functional populations could play an important role in both active U(VI) reduction and maintenance of the stability of reduced U(IV). These results suggest that addition of electron donors stimulated the microbial community to create biogeochemical conditions favorable to U(VI) reduction and prevent the reduced U(IV) from reoxidation and that functional FeRB, SRB, and NRB populations within this system played key roles in this process.« less

Dynamics of Microbial Community Composition and Function during In Situ Bioremediation of a Uranium-Contaminated Aquifer▿‡

PubMed Central

Van Nostrand, Joy D.; Wu, Liyou; Wu, Wei-Min; Huang, Zhijian; Gentry, Terry J.; Deng, Ye; Carley, Jack; Carroll, Sue; He, Zhili; Gu, Baohua; Luo, Jian; Criddle, Craig S.; Watson, David B.; Jardine, Philip M.; Marsh, Terence L.; Tiedje, James M.; Hazen, Terry C.; Zhou, Jizhong

2011-01-01

A pilot-scale system was established to examine the feasibility of in situ U(VI) immobilization at a highly contaminated aquifer (U.S. DOE Integrated Field Research Challenge site, Oak Ridge, TN). Ethanol was injected intermittently as an electron donor to stimulate microbial U(VI) reduction, and U(VI) concentrations fell to below the Environmental Protection Agency drinking water standard (0.03 mg liter−1). Microbial communities from three monitoring wells were examined during active U(VI) reduction and maintenance phases with GeoChip, a high-density, comprehensive functional gene array. The overall microbial community structure exhibited a considerable shift over the remediation phases examined. GeoChip-based analysis revealed that Fe(III)-reducing bacterial (FeRB), nitrate-reducing bacterial (NRB), and sulfate-reducing bacterial (SRB) functional populations reached their highest levels during the active U(VI) reduction phase (days 137 to 370), in which denitrification and Fe(III) and sulfate reduction occurred sequentially. A gradual decrease in these functional populations occurred when reduction reactions stabilized, suggesting that these functional populations could play an important role in both active U(VI) reduction and maintenance of the stability of reduced U(IV). These results suggest that addition of electron donors stimulated the microbial community to create biogeochemical conditions favorable to U(VI) reduction and prevent the reduced U(IV) from reoxidation and that functional FeRB, SRB, and NRB populations within this system played key roles in this process. PMID:21498771

Uranium and Cesium sorption to bentonite colloids in high salinity and carbonate-rich environments: Implications for radionuclide transport

NASA Astrophysics Data System (ADS)

Tran, E. L.; Teutsch, N.; Klein-BenDavid, O.; Weisbrod, N.

2017-12-01

When radionuclides are leaked into the subsurface due to engineered waste disposal container failure, the ultimate barrier to migration of radionuclides into local aquifers is sorption to the surrounding rock matrix and sediments, which often includes a bentonite backfill. The extent of this sorption is dependent on pH, ionic strength, surface area availability, radionuclide concentration, surface mineral composition, and solution chemistry. Colloidal-sized bentonite particles eroded from the backfill have been shown to facilitate the transport of radionuclides sorbed to them away from their source. Thus, sorption of radionuclides such as uranium and cesium to bentonite surfaces can be both a mobilization or retardation factor. Though numerous studies have been conducted to-date on sorption of radionuclides under low ionic strength and carbonate-poor conditions, there has been little research conducted on the behavior of radionuclides in high salinities and carbonate rich conditions typical of aquifers in the vicinity of some potential nuclear repositories. This study attempts to characterize the sorption properties of U(VI) and Cs to bentonite colloids under these conditions using controlled batch experiments. Results indicated that U(VI) undergoes little to no sorption to bentonite colloids in a high-salinity (TDS= 9000 mg/L) artificial groundwater. This lack of sorption was attributed to the formation of CaUO2(CO3)22- and Ca2UO2(CO3)3 aqueous ions which stabilize the UO22+ ions in solution. In contrast, Cs exhibited greater sorption, the extent to which was influenced greatly by the matrix water's ionic strength and the colloid concentration used. Surprisingly, when both U and Cs were together, the presence of U(VI) in solution decreased Cs sorption, possibly due to the formation of stabilizing CaUO2(CO3)22- anions. The implications of this research are that rather than undergoing colloid-facilitated transport, U(VI) is expected to migrate similarly to a conservative dissolved species under these conditions, and little retardation through sorption onto the surrounding rock matrix is predicted. Cs is expected to undergo more sorption, though U(VI) presence may have a mobilizing effect.

Uranium fate in wetland mesocosms: Effects of plants at two iron loadings with different pH values.

PubMed

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

2016-11-01

Small-scale continuous flow wetland mesocosms (∼0.8 L) were used to evaluate how plant roots under different iron loadings affect uranium (U) mobility. When significant concentrations of ferrous iron (Fe) were present at circumneutral pH values, U concentrations in root exposed sediments were an order of magnitude greater than concentrations in root excluded sediments. Micro X-ray absorption near-edge structure (μ-XANES) spectroscopy indicated that U was associated with the plant roots primarily as U(VI) or U(V), with limited evidence of U(IV). Micro X-ray fluorescence (μ-XRF) of plant roots suggested that for high iron loading at circumneutral pH, U was co-located with Fe, perhaps co-precipitated with root Fe plaques, while for low iron loading at a pH of ∼4 the correlation between U and Fe was not significant, consistent with previous observations of U associated with organic matter. Quantitative PCR analyses indicated that the root exposed sediments also contained elevated numbers of Geobacter spp., which are likely associated with enhanced iron cycling, but may also reduce mobile U(VI) to less mobile U(IV) species. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

Joseph, Claudia; Mibus, Jens; Trepte, Paul

As a contribution to the safety assessment of nuclear waste repositories, U(VI) diffusion through the potential buffer material MX-80 bentonite was investigated at three clay dry densities over six years. Synthetic MX-80 model pore water was used as background electrolyte. Speciation calculations showed that Ca 2UO 2(CO 3) 3(aq) was the main U(VI) species. The in- and out-diffusion of U(VI) was investigated separately. U(VI) diffused about 3 mm, 1.5 mm, and 1 mm into the clay plug at ρ = 1.3, 1.6, and 1.9 g/cm 3, respectively. No through-diffusion of the U(VI) tracer was observed. However, leaching of natural uraniummore » contained in the clay occurred and uranium was detected in all receiving reservoirs. As expected, the effective and apparent diffusion coefficients, D e and D a, decreased with increasing dry density. The D a values for the out-diffusion of natural U(VI) were in good agreement with previously determined values. Surprisingly, D a values for the in-diffusion of U(VI) were about two orders of magnitude lower than values obtained in short-term in-diffusion experiments reported in the literature. Some potential reasons for this behavior that were evaluated are changes of the U(VI) speciation within the clay (precipitation, reduction) or changes of the clay porosity and pore connectivity with time. By applying Archie's law and the extended Archie's law, it was estimated that a significantly smaller effective porosity must be present for the long-term in-diffusion of U(VI). Finally, the results suggest that long-term studies of key transport phenomena may reveal additional processes that can directly impact long-term repository safety assessments.« less

METHOD FOR THE REDUCTION OF URANIUM COMPOUNDS

DOEpatents

Cooke, W.H.; Crawford, J.W.C.

1959-05-12

An improved technique of preparing massive metallic uranium by the reaction at elevated temperature between an excess of alkali in alkaline earth metal and a uranium halide, such ss uranium tetrafluoride is presented. The improvement comprises employing a reducing atmosphere of hydrogen or the like, such as coal gas, in the vessel during the reduction stage and then replacing the reducing atmosphere with argon gas prior to cooling to ambient temperature.

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.

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

PubMed

Lingamdinne, Lakshmi Prasanna; Choi, Yu-Lim; Kim, Im-Soon; Yang, Jae-Kyu; Koduru, Janardhan Reddy; Chang, Yoon-Young

2017-03-15

For the removal of uranium(VI) (U(VI)) and thorium(IV) (Th(IV)), graphene oxide based inverse spinel nickel ferrite (GONF) nanocomposite and reduced graphene oxide based inverse spinel nickel ferrite (rGONF) nanocomposite were prepared by co-precipitation of GO with nickel and iron salts in one pot. The spectral characterization analyses revealed that GONF and rGONF have a porous surface morphology with an average particle size of 41.41nm and 32.16nm, respectively. The magnetic property measurement system (MPMS) studies confirmed the formation of ferromagnetic GONF and superparamagnetic rGONF. The adsorption kinetics studies found that the pseudo-second-order kinetics was well tune to the U(VI) and Th(IV) adsorption. The results of adsorption isotherms showed that the adsorption of U(VI) and Th(IV) were due to the monolayer on homogeneous surface of the GONF and rGONF. The adsorptions of both U(VI) and Th(IV) were increased with increasing system temperature from 293 to 333±2K. The thermodynamic studies reveal that the U(VI) and Th(IV) adsorption onto GONF and rGONF was endothermic. GONF and rGONF, which could be separated by external magnetic field, were recycled and re-used for up to five cycles without any significant loss of adsorption capacity. Copyright © 2016 Elsevier B.V. All rights reserved.

Determination of chromium (VI) in primary and secondary fertilizer and their respective precursors.

PubMed

Krüger, Oliver; Fiedler, Francesca; Adam, Christian; Vogel, Christian; Senz, Rainer

2017-09-01

Hexavalent chromium species (Cr(VI)) are often carcinogenic, of high acute toxicity, highly mobile, and thus pose a severe risk to health and environment. Fertilizers usually contain significant amounts of chromium. Therefore, a reliable analysis of chromium and the fraction of Cr(VI) are crucial for safe use of fertilizers. This problem is expected to increase in the future, since more and more recycled fertilizers emerge due to increasing fertilizer demand and respective supply risks. However, existing analytical methods have been developed for conventional fertilizers and have to be tested whether they are suitable for the new materials. Thus, we performed a wet-chemical extraction for Cr(VI) on several matrices as well as respective quality control experiments including spiking with Cr(III) and Cr(VI) compounds. We found the Cr(VI) amounts to be below 2 mg/kg except for a thermally post-treated sewage sludge ash (SSA) that showed 12.3 mg/kg. The presence of organic matter e.g. in sludge or precipitated struvite caused a reduction of spiked Cr(VI) and thus no satisfying recovery for quality control. Cr(VI) reduction was also observed for SSA, presumably due to the presence of Fe(II) compounds. Even though the tested procedure can be hampered in some recycled fertilizer matrices, it might be adapted to be applicable also for these complex samples. Copyright © 2017 Elsevier Ltd. All rights reserved.

A Green Microbial Fuel Cell-Based Biosensor for In Situ Chromium (VI) Measurement in Electroplating Wastewater.

PubMed

Wu, Li-Chun; Tsai, Teh-Hua; Liu, Man-Hai; Kuo, Jui-Ling; Chang, Yung-Chu; Chung, Ying-Chien

2017-10-27

The extensive use of Cr(VI) in many industries and the disposal of Cr(VI)-containing wastes have resulted in Cr(VI)-induced environmental contamination. Cr(VI) compounds are associated with increased cancer risks; hence, the detection of toxic Cr(VI) compounds is crucial. Various methods have been developed for Cr(VI) measurement, but they are often conducted offsite and cannot provide real-time toxicity monitoring. A microbial fuel cell (MFC) is an eco-friendly and self-sustaining device that has great potential as a biosensor for in situ Cr(VI) measurement, especially for wastewater generated from different electroplating units. In this study, Exiguobacterium aestuarii YC211, a facultatively anaerobic, Cr(VI)-reducing, salt-tolerant, and exoelectrogenic bacterium, was isolated and inoculated into an MFC to evaluate its feasibility as a Cr(VI) biosensor. The Cr(VI) removal efficiency of E. aestuarii YC211 was not affected by the surrounding environment (pH 5-9, 20-35 °C, coexisting ions, and salinity of 0-15 g/L). The maximum power density of the MFC biosensor was 98.3 ± 1.5 mW/m² at 1500 Ω. A good linear relationship ( r ² = 0.997) was observed between the Cr(VI) concentration (2.5-60 mg/L) and the voltage output. The developed MFC biosensor is a simple device that can accurately measure Cr(VI) concentrations in the actual electroplating wastewater that is generated from different electroplating units within 30 min with low deviations (-6.1% to 2.2%). After treating the actual electroplating wastewater with the MFC, the predominant family in the biofilm was found to be Bacillaceae (95.3%) and was further identified as the originally inoculated E. aestuarii YC211 by next generation sequencing (NGS). Thus, the MFC biosensor can measure Cr(VI) concentrations in situ in the effluents from different electroplating units, and it can potentially help in preventing the violation of effluent regulations.

A Green Microbial Fuel Cell-Based Biosensor for In Situ Chromium (VI) Measurement in Electroplating Wastewater

PubMed Central

Wu, Li-Chun; Tsai, Teh-Hua; Liu, Man-Hai; Kuo, Jui-Ling; Chang, Yung-Chu

2017-01-01

The extensive use of Cr(VI) in many industries and the disposal of Cr(VI)-containing wastes have resulted in Cr(VI)-induced environmental contamination. Cr(VI) compounds are associated with increased cancer risks; hence, the detection of toxic Cr(VI) compounds is crucial. Various methods have been developed for Cr(VI) measurement, but they are often conducted offsite and cannot provide real-time toxicity monitoring. A microbial fuel cell (MFC) is an eco-friendly and self-sustaining device that has great potential as a biosensor for in situ Cr(VI) measurement, especially for wastewater generated from different electroplating units. In this study, Exiguobacterium aestuarii YC211, a facultatively anaerobic, Cr(VI)-reducing, salt-tolerant, and exoelectrogenic bacterium, was isolated and inoculated into an MFC to evaluate its feasibility as a Cr(VI) biosensor. The Cr(VI) removal efficiency of E. aestuarii YC211 was not affected by the surrounding environment (pH 5–9, 20–35 °C, coexisting ions, and salinity of 0–15 g/L). The maximum power density of the MFC biosensor was 98.3 ± 1.5 mW/m2 at 1500 Ω. A good linear relationship (r2 = 0.997) was observed between the Cr(VI) concentration (2.5–60 mg/L) and the voltage output. The developed MFC biosensor is a simple device that can accurately measure Cr(VI) concentrations in the actual electroplating wastewater that is generated from different electroplating units within 30 min with low deviations (−6.1% to 2.2%). After treating the actual electroplating wastewater with the MFC, the predominant family in the biofilm was found to be Bacillaceae (95.3%) and was further identified as the originally inoculated E. aestuarii YC211 by next generation sequencing (NGS). Thus, the MFC biosensor can measure Cr(VI) concentrations in situ in the effluents from different electroplating units, and it can potentially help in preventing the violation of effluent regulations. PMID:29076985

Studies on the chemical constituents from the stem and leaves of Tagetes erecta.

PubMed

Zhang, Yu; Zhang, Ting-Ting

2010-09-01

To investigate the chemical constituents of the stem and leaves of Tagetes erecta. The materials extracted with ethanol were first purified with D101 resin and then separated by repeated silica gel column chromatography as well as recrystallization to get single compounds. The chemical structures of the compounds were elucidated on the basis of physicochemical properties, spectroscopic analysis and comparing with standard sample and literatures. Six compounds were identified as 4'-methoxy-eupatolitin-3-O-glucoside (I), kaempferitrin (II), rutin (III), beta-sitosterol (IV), daucosterol (V) and gallic acid (VI). Compounds I, II, III are isolated from the plant for the first time; the compounds IV, V, VI are isolated from the stem and leaves of the plant for the first time.

Relation between various chromium compounds and some other elements in fumes from manual metal arc stainless steel welding.

PubMed

Matczak, W; Chmielnicka, J

1993-03-01

For the years 1987-1990 160 individual samples of manual metal arc stainless steel (MMA/SS) welding fumes from the breathing zone of welders in four industrial plants were collected. Concentrations of soluble and insoluble chromium (Cr) III and Cr VI compounds as well as of some other welding fume elements (Fe, Mn, Ni, F) were determined. Concentration of welding fumes in the breathing zone ranged from 0.2 to 23.4 mg/m3. Total Cr amounted to 0.005-0.991 mg/m3 (including 0.005-0.842 mg/m3 Cr VI). Total Cr content of fumes varied from 0.1 to 7.4%. The distribution of particular Cr compounds was: 52.6% soluble Cr (including 50.7% Cr VI), 65.5% total Cr VI, and 11.4% insoluble Cr VI. The results obtained indicate that MMA/SS welding is a process that could be highly hazardous to human health. Evaluation of occupational exposure has shown that MMA/SS welders may exceed the admissible concentrations of soluble and insoluble Cr VI forms as well as of Mn and Ni. In the plants investigated the sum of the ratios of concentrations of particular welding fumes in the breathing zone of welders exceeded corresponding maximum allowable concentration values by 24 times (including 17 times for total Cr VI). Due to the variety and changeability of particular parameters occurring in the working environment, the composition of MMA/SS welding fumes (in the welder's breathing zone) is so variable that it is not possible to assess the exposure by means of one universal exposure indicator (maximum additive hygienic limit value). The evaluation should be based on the results of measurements of concentrations of particular elements in welding fumes.

Relation between various chromium compounds and some other elements in fumes from manual metal arc stainless steel welding.

PubMed Central

Matczak, W; Chmielnicka, J

1993-01-01

For the years 1987-1990 160 individual samples of manual metal arc stainless steel (MMA/SS) welding fumes from the breathing zone of welders in four industrial plants were collected. Concentrations of soluble and insoluble chromium (Cr) III and Cr VI compounds as well as of some other welding fume elements (Fe, Mn, Ni, F) were determined. Concentration of welding fumes in the breathing zone ranged from 0.2 to 23.4 mg/m3. Total Cr amounted to 0.005-0.991 mg/m3 (including 0.005-0.842 mg/m3 Cr VI). Total Cr content of fumes varied from 0.1 to 7.4%. The distribution of particular Cr compounds was: 52.6% soluble Cr (including 50.7% Cr VI), 65.5% total Cr VI, and 11.4% insoluble Cr VI. The results obtained indicate that MMA/SS welding is a process that could be highly hazardous to human health. Evaluation of occupational exposure has shown that MMA/SS welders may exceed the admissible concentrations of soluble and insoluble Cr VI forms as well as of Mn and Ni. In the plants investigated the sum of the ratios of concentrations of particular welding fumes in the breathing zone of welders exceeded corresponding maximum allowable concentration values by 24 times (including 17 times for total Cr VI). Due to the variety and changeability of particular parameters occurring in the working environment, the composition of MMA/SS welding fumes (in the welder's breathing zone) is so variable that it is not possible to assess the exposure by means of one universal exposure indicator (maximum additive hygienic limit value). The evaluation should be based on the results of measurements of concentrations of particular elements in welding fumes. PMID:8457491

Variations of uranium concentrations in a multi-aquifer system under the impact of surface water-groundwater interaction

NASA Astrophysics Data System (ADS)

Wu, Ya; Li, Junxia; Wang, Yanxin; Xie, Xianjun

2018-04-01

Understanding uranium (U) mobility is vital to minimizing its concentrations in potential drinking water sources. In this study, we report spatial-seasonal variations in U speciation and concentrations in a multi-aquifer system under the impact of Sanggan River in Datong basin, northern China. Hydrochemical and H, O, Sr isotopic data, thermodynamic calculations, and geochemical modeling are used to investigate the mechanisms of surface water-groundwater mixing-induced mobilization and natural attenuation of U. In the study site, groundwater U concentrations are up to 30.2 μg/L, and exhibit strong spatial-seasonal variations that are related to pH and Eh values, as well as dissolved Ca2+, HCO3-, and Fe(III) concentrations. For the alkaline aquifers of this site (pH 7.02-8.44), U mobilization is due to the formation and desorption of Ca2UO2(CO3)30 and CaUO2(CO3)32- caused by groundwater Ca2+ elevation via mineral weathering and Na-Ca exchange, incorporated U(VI) release from calcite, and U(IV) oxidation by Fe(OH)3. U immobilization is linked to the adsorption of CaUO2(CO3)32- and UO2(CO3)34- shifted from Ca2UO2(CO3)30 because of HCO3- elevation and Ca2+ depletion, U(VI) co-precipitation with calcite, and U(VI) reduction by adsorbed Fe2+ and FeS. Those results are of great significance for the groundwater resource management of this and similar other surface water-groundwater interaction zones.

Responses of microbial community functional structures to pilot-scale uranium in situ bioremediation

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

Xu, M.; Wu, W.-M.; Wu, L.

2010-02-15

A pilot-scale field test system with an inner loop nested within an outer loop was constructed for in situ U(VI) bioremediation at a US Department of Energy site, Oak Ridge, TN. The outer loop was used for hydrological protection of the inner loop where ethanol was injected for biostimulation of microorganisms for U(VI) reduction/immobilization. After 2 years of biostimulation with ethanol, U(VI) levels were reduced to below drinking water standard (<30 {micro}gl{sup -1}) in the inner loop monitoring wells. To elucidate the microbial community structure and functions under in situ uranium bioremediation conditions, we used a comprehensive functional gene arraymore » (GeoChip) to examine the microbial functional gene composition of the sediment samples collected from both inner and outer loop wells. Our study results showed that distinct microbial communities were established in the inner loop wells. Also, higher microbial functional gene number, diversity and abundance were observed in the inner loop wells than the outer loop wells. In addition, metal-reducing bacteria, such as Desulfovibrio, Geobacter, Anaeromyxobacter and Shewanella, and other bacteria, for example, Rhodopseudomonas and Pseudomonas, are highly abundant in the inner loop wells. Finally, the richness and abundance of microbial functional genes were highly correlated with the mean travel time of groundwater from the inner loop injection well, pH and sulfate concentration in groundwater. These results suggest that the indigenous microbial communities can be successfully stimulated for U bioremediation in the groundwater ecosystem, and their structure and performance can be manipulated or optimized by adjusting geochemical and hydrological conditions.« less

Imaging, photophysical properties and DFT calculations of manganese blue (barium manganate(VI) sulphate)--a modern pigment.

PubMed

Accorsi, Gianluca; Verri, Giovanni; Acocella, Angela; Zerbetto, Francesco; Lerario, Giovanni; Gigli, Giuseppe; Saunders, David; Billinge, Rachel

2014-12-18

Manganese blue is a synthetic barium manganate(VI) sulphate compound that was produced from 1935 to the 1990s and was used both as a blue pigment in works of art and by conservators in the restoration of paintings. The photophysical properties of the compound are described as well as the setup needed to record the spatial distribution of the pigment in works of art.

Standardization of Protocol for the Sampling, Testing and abatement of Asbestos Containing Joint Compound

DTIC Science & Technology

1994-09-01

vi A b stract...5-2 Proposed Decision Tree for ACJC Abatement Activities 5-10 Vi AFIT/GEE/ENV/94S-23 ABSTRACT This study investigated the differing regulatory...specific amount. According to 29 CFR 1910.58(k)(2)( vi )(B), labeling provisions do not apply unless asbestos is present in a product in concentrations

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

PubMed Central

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

2008-01-01

Microbial enumeration, 16S rRNA gene clone libraries, and chemical analysis were used to evaluate the in situ biological reduction and immobilization of uranium(VI) in a long-term experiment (more than 2 years) conducted at a highly uranium-contaminated site (up to 60 mg/liter and 800 mg/kg solids) of the U.S. Department of Energy in Oak Ridge, TN. Bioreduction was achieved by conditioning groundwater above ground and then stimulating growth of denitrifying, Fe(III)-reducing, and sulfate-reducing bacteria in situ through weekly injection of ethanol into the subsurface. After nearly 2 years of intermittent injection of ethanol, aqueous U levels fell below the U.S. Environmental Protection Agency maximum contaminant level for drinking water and groundwater (<30 μg/liter or 0.126 μM). Sediment microbial communities from the treatment zone were compared with those from a control well without biostimulation. Most-probable-number estimations indicated that microorganisms implicated in bioremediation accumulated in the sediments of the treatment zone but were either absent or in very low numbers in an untreated control area. Organisms belonging to genera known to include U(VI) reducers were detected, including Desulfovibrio, Geobacter, Anaeromyxobacter, Desulfosporosinus, and Acidovorax spp. The predominant sulfate-reducing bacterial species were Desulfovibrio spp., while the iron reducers were represented by Ferribacterium spp. and Geothrix spp. Diversity-based clustering revealed differences between treated and untreated zones and also within samples of the treated area. Spatial differences in community structure within the treatment zone were likely related to the hydraulic pathway and to electron donor metabolism during biostimulation. PMID:18456853

Effect of Phosphate on U(VI) Sorption to Montmorillonite: Ternary Complexation and Precipitation Barriers

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

Troyer, Lyndsay D.; Maillot, Fabien; Wang, Zheming

Phosphate addition is a potential treatment method to lower the solubility of U(VI) in soil and groundwater systems by causing U(VI) phosphate precipitation as well as enhancing adsorption. Previous work has shown that iron oxide surfaces may facilitate the nucleation of U(VI) phosphate minerals and, that under weakly acidic conditions, phosphate also enhances U(VI) adsorption to such phases. Like iron oxides, clays are important reactive phases in the subsurface but little is known about the interaction of U(VI) and phosphate with these minerals. The effect of aqueous phosphate on U(VI) binding to Wyoming montmorillonite (SWy-2) in air-equilibrated systems was investigated.more » Equilibrium U(VI) uptake to montmorillonite was determined at pH 4, 6 and 8 at discrete initial phosphate concentrations between 0 and 100 μM. The observed behavior of U(VI) indicates a transition from adsorption to precipitation with increasing total uranium and phosphate concentrations at all pH values. At the highest phosphate concentration examined at each pH value, a barrier to U(VI) phosphate nucleation is observed. At lower concentrations, phosphate has no effect on macroscopic U(VI) adsorption. To assess the mechanisms of U(VI)-phosphate interactions on smectite surfaces, U(VI) speciation was investigated under selected conditions using laser-induced fluorescence spectroscopy (LIFS) and extended X-ray absorption fine-structure (EXAFS) spectroscopy. Samples above the precipitation threshold display EXAFS and LIFS spectral signatures consistent with the autunite family of U(VI) phosphate minerals. However, at lower U(VI) concentrations, changes in LIFS spectra upon phosphate addition suggest that U(VI)-phosphate ternary surface complexes form on the montmorillonite surface at pH 4 and 6 despite the lack of a macroscopic effect on adsorption. The speciation of solid-associated U(VI) below the precipitation threshold at pH 8 is dominated by U(VI)-carbonate surface complexes. This work reveals that ternary complexation may occur without a macroscopic signature, which is attributed to phosphate not appreciably binding to smectite in the absence of U(VI), with U(VI) surface complexes serving as the sole reactive surface sites for phosphate. This study shows that phosphate does not enhance U(VI) adsorption to smectite clay minerals, unlike oxide phases, and that a barrier to homogeneous nucleation of U(VI) phosphates was not affected by the presence of the smectite surface« less

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.

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.

Galvanic cell for processing of used nuclear fuel

DOEpatents

Garcia-Diaz, Brenda L.; Martinez-Rodriguez, Michael J.; Gray, Joshua R.; Olson, Luke C.

2017-02-07

A galvanic cell and methods of using the galvanic cell is described for the recovery of uranium from used nuclear fuel according to an electrofluorination process. The galvanic cell requires no input energy and can utilize relatively benign gaseous fluorinating agents. Uranium can be recovered from used nuclear fuel in the form of gaseous uranium compound such as uranium hexafluoride, which can then be converted to metallic uranium or UO.sub.2 and processed according to known methodology to form a useful product, e.g., fuel pellets for use in a commercial energy production system.

Electrochemical fluorination for processing of used nuclear fuel

DOEpatents

Garcia-Diaz, Brenda L.; Martinez-Rodriguez, Michael J.; Gray, Joshua R.; Olson, Luke C.

2016-07-05

A galvanic cell and methods of using the galvanic cell is described for the recovery of uranium from used nuclear fuel according to an electrofluorination process. The galvanic cell requires no input energy and can utilize relatively benign gaseous fluorinating agents. Uranium can be recovered from used nuclear fuel in the form of gaseous uranium compound such as uranium hexafluoride, which can then be converted to metallic uranium or UO.sub.2 and processed according to known methodology to form a useful product, e.g., fuel pellets for use in a commercial energy production system.

Synthesis of actinide nitrides, phosphides, sulfides and oxides

DOEpatents

Van Der Sluys, William G.; Burns, Carol J.; Smith, David C.

1992-01-01

A process of preparing an actinide compound of the formula An.sub.x Z.sub.y wherein An is an actinide metal atom selected from the group consisting of thorium, uranium, plutonium, neptunium, and americium, x is selected from the group consisting of one, two or three, Z is a main group element atom selected from the group consisting of nitrogen, phosphorus, oxygen and sulfur and y is selected from the group consisting of one, two, three or four, by admixing an actinide organometallic precursor wherein said actinide is selected from the group consisting of thorium, uranium, plutonium, neptunium, and americium, a suitable solvent and a protic Lewis base selected from the group consisting of ammonia, phosphine, hydrogen sulfide and water, at temperatures and for time sufficient to form an intermediate actinide complex, heating said intermediate actinide complex at temperatures and for time sufficient to form the actinide compound, and a process of depositing a thin film of such an actinide compound, e.g., uranium mononitride, by subliming an actinide organometallic precursor, e.g., a uranium amide precursor, in the presence of an effectgive amount of a protic Lewis base, e.g., ammonia, within a reactor at temperatures and for time sufficient to form a thin film of the actinide compound, are disclosed.

Exploratory Solid-State Synthesis of Uranium Chalcogenides and Mixed Anion Uranium Chalcogenides

NASA Astrophysics Data System (ADS)

Ward, Matthew David

Several uranium chalcogenides and mixed anion uranium chalcogenides have been synthesized by solid-state synthetic methods. Structural determinations were carried out via single-crystal X-ray diffraction. Some of these compounds have been further characterized by magnetic measurements, optical properties measurements, Raman spectroscopy, resistivity measurements, XANES and XPS. Eight compounds of the composition MU8Q17 were synthesized and characterized by single-crystal X-ray diffraction. All of these compounds crystallize in the CrU8S17 structure type. XANES measurements indicate that ScU8S17 contains Sc3+ and must be charge balanced with some amount of U 3+. Two compounds of the composition ATiU3Te9 crystallize as black rectangular plates. From single-crystal magnetic measurements, CsTiU 3Te9 is consistent with antiferromagnetic coupling between magnetic U atoms. The uranium chalcogenide compounds NiUS3 and Cr4US 8 were synthesized from reaction of the elements in various fluxes. NiUS3 crystallizes in the GdFeO3 structure type. Cr 4US8 crystallizes in the orthorhombic space group D - Pnma and its structure is related to that of Li4UF 8. The compounds Rh2U6S15, Cs 2Ti2U6Se15, and Cs2Cr 2U6Se15 crystallize as black prisms in the cubic space group O-Im3m. Magnetic measurements on Cs 2Cr2U6Se15 give a value for the Weiss temperature, θWeiss, of 57.59 K, indicative of ferromagnetic coupling. Black plates of CsScU(Se2)Se3 were synthesized from the reaction of the elements in a CsCl flux. CsScU(Se2)Se 3 crystallizes in the orthorhombic space group D- Cmcm . Magnetic susceptibility measurements on CsScU(Se2)Se 3 indicate three regions of magnetic response. The uranium double salt Cs5[U2(μ-S 2)2Cl8]I crystallizes as red plates. Cs 5[U2(μ-S2)2Cl 8]I displays optical anisotropy with band gap energies of 1.99 eV and 2.08 eV along the [001] and [100] polarizations. The uranium oxychalcogenides U7O2Se12 and Na2Ba2(UO2)S4 were synthesized by intentional oxygen contamination. The structure of U7O 2Se12 is related to the previously reported U7Q 12. Na2Ba2(UO2)S4 contains isolated uranyl polyhedra in which each uranium atom may be assigned an oxidation state of +6. The four uranium(IV) chlorophosphates, UCl4(POCl3), [U2Cl9][PCl4], UCl3(PO2Cl 2), and U2Cl8(POCl3) were synthesized in an effort to synthesize new novel uranyl sulfides. All are unstable, but UCl4(POCl3) is the thermodynamically favorable phase.

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.

The effect of uranium on bacterial viability and cell surface morphology using atomic force microscopy in the presence of bicarbonate ions.

PubMed

Sepulveda-Medina, Paola; Katsenovich, Yelena; Musaramthota, Vishal; Lee, Michelle; Lee, Brady; Dua, Rupak; Lagos, Leonel

2015-06-01

Past disposal practices at nuclear production facilities have led to the release of liquid waste into the environment creating multiple radionuclide plumes. Microorganisms are known for the ability to interact with radionuclides and impact their mobility in soils and sediments. Gram-positive Arthrobacter sp. are one of the most common bacterial groups in soils and are found in large numbers in subsurface environments contaminated with radionuclides. This study experimentally analyzed changes on the bacteria surface at the nanoscale level after uranium exposure and evaluated the effect of aqueous bicarbonate ions on U(VI) toxicity of a low uranium-tolerant Arthrobacter oxydans strain G968 by investigating changes in adhesion forces and cell dimensions via atomic force microscopy (AFM). Experiments were extended to assess cell viability by the Live/Dead BacLight Bacterial Viability Kit (Molecular Probes) and quantitatively illustrate the effect of uranium exposure in the presence of varying concentrations of bicarbonate ions. AFM and viability studies showed that samples containing bicarbonate were able to withstand uranium toxicity and remained viable. Samples containing no bicarbonate exhibited deformed surfaces and a low height profile, which, in conjunction with viability studies, indicated that the cells were not viable. Copyright © 2015 Institut Pasteur. All rights reserved.

[Glycosides from flowers of Jasminum officinale L. var. grandiflorum].

PubMed

Zhao, Gui-qin; Xia, Jing-jing; Dong, Jun-xing

2007-10-01

To study the chemical constituents of the flower of Jasminum officinale L. var. grandiflorum. The compounds were isolated and purified by re-crystallization and chromatography on silica gel and Sephadex LH-20 column. Their structures were elucidated on the physicochemical properties and spectral analysis. Seven glycosides were identified as kaempferol-3-O-alpha-L-rhamnopyranosyl (1-->3)-[alpha-L-rhamnopyranosyl (1-->6)]-beta-D-galactopyranoside (I), kaempferol-3-O-rutinoside (II), 7-ketologanin (III), oleoside-11-methyl ester (IV), 7-glucosyl-l1-methyl oleoside (V), ligstroside (VI), oleuropein (VII). Compound I is a new compound. Compounds III and V were isolated from the family of Jasminum for the first time and compounds II, IV and VI were isolated from Jasminum officinale L. var. grandiflorum for the first time.

A Multireference Density Functional Approach to the Calculation of the Excited States of Uranium Ions

DTIC Science & Technology

2007-03-01

approach. xiv A MULTIREFERENCE DENSITY FUNCTIONAL APPROACH TO THE CALCULATION OF THE EXCITED STATES OF URANIUM IONS I. Introduction Actinide chemistry, in...oxidation state of the uranium atom. Uranium, like most early actinides , can possess a wide range of oxidation states, ranging from +3 to +6, due in part...in predicting the electronic spectra for heavy element compounds. The first difficulty is that relativistic effects for actinides are significant

RECOVERY OF URANIUM FROM PITCHBLENDE

DOEpatents

Ruehle, A.E.

1958-06-24

The decontamination of uranium from molybdenum is described. When acid solutions containing uranyl nitrate are contacted with ether for the purpose of extracting the uranium values, complex molybdenum compounds are coextracted with the uranium and also again back-extracted from the ether with the uranium. This invention provides a process for extracting uranium in which coextraction of molybdenum is avoided. It has been found that polyhydric alcohols form complexes with molybdenum which are preferentially water-soluble are taken up by the ether extractant to only a very minor degree. The preferred embodiment of the process uses mannitol, sorbitol or a mixture of the two as the complexing agent.

Effects of sulfate ligand on uranyl carbonato surface species on ferrihydrite surfaces

USGS Publications Warehouse

Arai, Yuji; Fuller, C.C.

2012-01-01

Understanding uranium (U) sorption processes in permeable reactive barriers (PRB) are critical in modeling reactive transport for evaluating PRB performance at the Fry Canyon demonstration site in Utah, USA. To gain insight into the U sequestration mechanism in the amorphous ferric oxyhydroxide (AFO)-coated gravel PRB, U(VI) sorption processes on ferrihydrite surfaces were studied in 0.01 M Na2SO4 solutions to simulate the major chemical composition of U-contaminatedgroundwater (i.e., [SO42-]~13 mM L-1) at the site. Uranyl sorption was greater at pH 7.5 than that at pH 4 in both air- and 2% pCO2-equilibrated systems. While there were negligible effects of sulfate ligands on the pH-dependent U(VI) sorption (<24 h) in both systems, X-ray absorption spectroscopy (XAS) analysis showed sulfate ligand associated U(VI) surface species at the ferrihydrite–water interface. In air-equilibrated systems, binary and mono-sulfate U(VI) ternary surface species co-existed at pH 5.43. At pH 6.55–7.83, a mixture of mono-sulfate and bis-carbonato U(VI) ternary surface species became more important. At 2% pCO2, there was no contribution of sulfate ligands on the U(VI) ternary surface species. Instead, a mixture of bis-carbonato inner-sphere (38%) and tris-carbonato outer-sphere U(VI) ternary surface species (62%) was found at pH 7.62. The study suggests that the competitive ligand (bicarbonate and sulfate) coordination on U(VI) surface species might be important in evaluating the U solid-state speciation in the AFO PRB at the study site where pCO2 fluctuates between 1 and 2 pCO2%.

Effects of sulfate ligand on uranyl carbonato surface species on ferrihydrite surfaces.

PubMed

Arai, Yuji; Fuller, C C

2012-01-01

Understanding uranium (U) sorption processes in permeable reactive barriers (PRB) are critical in modeling reactive transport for evaluating PRB performance at the Fry Canyon demonstration site in Utah, USA. To gain insight into the U sequestration mechanism in the amorphous ferric oxyhydroxide (AFO)-coated gravel PRB, U(VI) sorption processes on ferrihydrite surfaces were studied in 0.01 M Na(2)SO(4) solutions to simulate the major chemical composition of U-contaminated groundwater (i.e., [SO(4)(2-)] ~13 mM L(-1)) at the site. Uranyl sorption was greater at pH 7.5 than that at pH 4 in both air- and 2% pCO(2)-equilibrated systems. While there were negligible effects of sulfate ligands on the pH-dependent U(VI) sorption (<24 h) in both systems, X-ray absorption spectroscopy (XAS) analysis showed sulfate ligand associated U(VI) surface species at the ferrihydrite-water interface. In air-equilibrated systems, binary and mono-sulfate U(VI) ternary surface species co-existed at pH 5.43. At pH 6.55-7.83, a mixture of mono-sulfate and bis-carbonato U(VI) ternary surface species became more important. At 2% pCO(2), there was no contribution of sulfate ligands on the U(VI) ternary surface species. Instead, a mixture of bis-carbonato inner-sphere (38%) and tris-carbonato outer-sphere U(VI) ternary surface species (62%) was found at pH 7.62. The study suggests that the competitive ligand (bicarbonate and sulfate) coordination on U(VI) surface species might be important in evaluating the U solid-state speciation in the AFO PRB at the study site where pCO(2) fluctuates between 1 and 2 pCO(2)%. Copyright © 2011 Elsevier Inc. All rights reserved.

Chemical and mineralogical composition of the Mongolian rural soils and their uranium sorption behavior.

PubMed

Tserenpil, Sh; Maslov, O D; Norov, N; Liu, Q C; Fillipov, M F; Theng, Benny K G; Belov, A G

2013-04-01

Distribution of uranium (VI) between soil solids and solutions is a key parameter in assessing the risk to the biosphere of disposing uranium-rich waste products from nuclear plants as well as uranium (U) ore mining. Both of these topics have recently been brought to public attention in Mongolia. Regional background levels of soil elements are an important dataset for accessing the actual environmental situation and monitoring pollution levels. Little information, however, is available on background concentrations of various elements in Mongolian soils. Thirteen rural soils were sampled from six provinces in Mongolia, and the concentrations of macro-, micro- and trace elements were measured. The values obtained served as a reference (baseline) for uncontaminated soils. The soils were characterized with slightly acidic to strongly alkaline pH values. With the exception of the sample from a western province, all the soils investigated contained little organic matter. The content of soil elements did not vary widely among geographical regions. The concentration of most micro elements was within the range of worldwide soil values but the value for Zn tended to be moderately higher. The U (VI) sorption into the soils was investigated using the batch technique and the (237)U radionuclide tracer, produced by the photo fission reaction (238)U(γ, n) (237)U at an electron accelerator. The (237)U distribution coefficient (K(d)), derived from the sorption isotherms, was related to solution pH and varying from 9 to 2547 mL g(-1) when the pH ranged between 3 and 7.7. The sorption process was interpreted in terms of the formation of different U (VI) species at given concentrations, calculated using the Speciation program with and without carbonate in the system. The U sorption isotherm displayed two general patterns: one where sorption decreased as solution pH increased, showing a maximum at pH 3, and another pattern revealed an adsorption maximum at pH 5 and then decreased up to pH 7.7 (the final solution pH). The observed decrease in K(d) when solution pH increased from 6 to 8 was consistent with the increased formation of soluble UO(2)(OH)(2) species. A linear negative correlation between lgK(d) and the solution pH was observed similarly to that reported for the soils with a pH ≥ 6. Copyright © 2012 Elsevier Ltd. All rights reserved.

Kinetic study of the thermal decomposition of uranium metaphosphate, U(PO3)4, into uranium pyrophosphate, UP2O7

NASA Astrophysics Data System (ADS)

Yang, Hee-Chul; Kim, Hyung-Ju; Lee, Si-Young; Yang, In-Hwan; Chung, Dong-Yong

2017-06-01

The thermochemical properties of uranium compounds have attracted much interest in relation to thermochemical treatments and the safe disposal of radioactive waste bearing uranium compounds. The characteristics of the thermal decomposition of uranium metaphosphate, U(PO3)4, into uranium pyrophosphate, UP2O7, have been studied from the view point of reaction kinetics and acting mechanisms. A mixture of U(PO3)4 and UP2O7 was prepared from the pyrolysis residue of uranium-bearing spent TBP. A kinetic analysis of the reaction of U(PO3)4 into UP2O7 was conducted using an isoconversional method and a master plot method on the basis of data from a non-isothermal thermogravimetric analysis. The thermal decomposition of U(PO3)4 into UP2O7 followed a single-step reaction with an activation energy of 175.29 ± 1.58 kJ mol-1. The most probable kinetic model was determined as a type of nucleation and nuclei-growth models, the Avrami-Erofeev model (A3), which describes that there are certain restrictions on nuclei growth of UP2O7 during the solid-state decomposition of U(PO3)4.

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

Li, Na; Mu, Bao; Lv, Lei

Four new polyoxometalate(POM)–templated metal–organic frameworks based on flexible ligands, namely, [Cu{sub 6}(bip){sub 12}(PMo{sup VI}{sub 12}O{sub 40}){sub 2}(PMo{sup V}Mo{sup VI}{sub 11}O{sub 40}O{sub 2})]·8H{sub 2}O(1), [Cu{sup I}{sub 3}Cu{sup II}{sub 3}(bip){sub 12}(PMo{sup VI}{sub 12}O{sub 40}){sub 2}(PMo{sup V}{sub 12}O{sub 34})]·8H{sub 2}O(2), [Ni{sub 6}(bip){sub 12}(PMo{sup VI}{sub 12}O{sub 40})(PMo{sup VI}{sub 11}Mo{sup V}O{sub 40}){sub 2}]Cl·6H{sub 2}O(3), [Co{sup II}{sub 3}Co{sup III}{sub 2}(H{sub 2}bib){sub 2}(Hbib){sub 2}(PW{sub 9}O{sub 34}){sub 2}(H{sub 2}O){sub 6}]·6H{sub 2}O(4) (bip=1,3-bis(imidazolyl)propane, bib=1,4-bis(imidazolyl)butane) have been obtained under hydrothermal condition and characterized by single-crystal X-ray diffraction analyses, elemental analyses, and thermogravimetric (TG) analyses. The studies of single crystal X-ray indicate that compounds 1–3 crystallize in the trigonal space groupmore » P-3, and compound 4 crystallizes in the triclinic space group P-1. Compounds 1 and 3 represent 3D frameworks, and POMs as the guest molecules are incorporated into the cages which are composed of the ligands and metals, while compounds 2 and 4 show 3D frameworks by hydrogen bonds. This compounds provide new examples of host–guest compounds based on flexible bis(imidazole) ligands. In addition, the electrochemical property and the catalytic property of compound 1 have also been investigated. - Graphical abstract: Four inorganic–organic hybrid compounds based polyoxometalates (POMs) and flexible ligands, namely, have been obtained under hydrothermal conditions and characterized by single-crystal X-ray diffraction analyses, elemental analyses, IR spectra, and thermogravimetric (TG) analyses. Compounds 1–3 are new examples of host–guest compounds based on flexible bis(imidazole) ligands and POMs as the guest molecules are incorporated into the cages which are composed of the ligands and metals. - Highlights: • Polyoxometalate–templated metal–organic frameworks have been prepared. • POMs as the guest molecules are incorporated into the cages. • The cages are flexibility based on flexible bis(imidazole) ligands.« less

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

Reactivity of nitrido complexes of ruthenium(VI), osmium(VI), and manganese(V) bearing Schiff base and simple anionic ligands.

PubMed

Man, Wai-Lun; Lam, William W Y; Lau, Tai-Chu

2014-02-18

Nitrido complexes (M≡N) may be key intermediates in chemical and biological nitrogen fixation and serve as useful reagents for nitrogenation of organic compounds. Osmium(VI) nitrido complexes bearing 2,2':6',2″-terpyridine (terpy), 2,2'-bipyridine (bpy), or hydrotris(1-pyrazolyl)borate anion (Tp) ligands are highly electrophilic: they can react with a variety of nucleophiles to generate novel osmium(IV)/(V) complexes. This Account describes our recent results studying the reactivity of nitridocomplexes of ruthenium(VI), osmium(VI), and manganese(V) that bear Schiff bases and other simple anionic ligands. We demonstrate that these nitrido complexes exhibit rich chemical reactivity. They react with various nucleophiles, activate C-H bonds, undergo N···N coupling, catalyze the oxidation of organic compounds, and show anticancer activities. Ruthenium(VI) nitrido complexes bearing Schiff base ligands, such as [Ru(VI)(N)(salchda)(CH3OH)](+) (salchda = N,N'-bis(salicylidene)o-cyclohexyldiamine dianion), are highly electrophilic. This complex reacts readily at ambient conditions with a variety of nucleophiles at rates that are much faster than similar reactions using Os(VI)≡N. This complex also carries out unique reactions, including the direct aziridination of alkenes, C-H bond activation of alkanes and C-N bond cleavage of anilines. The addition of ligands such as pyridine can enhance the reactivity of [Ru(VI)(N)(salchda)(CH3OH)](+). Therefore researchers can tune the reactivity of Ru≡N by adding a ligand L trans to nitride: L-Ru≡N. Moreover, the addition of various nucleophiles (Nu) to Ru(VI)≡N initially generate the ruthenium(IV) imido species Ru(IV)-N(Nu), a new class of hydrogen-atom transfer (HAT) reagents. Nucleophiles also readily add to coordinated Schiff base ligands in Os(VI)≡N and Ru(VI)≡N complexes. These additions are often stereospecific, suggesting that the nitrido ligand has a directing effect on the incoming nucleophile. M≡N is also a potential platform for the design of new oxidation catalysts. For example, [Os(VI)(N)Cl4](-) catalyzes the oxidation of alkanes by a variety of oxidants, and the addition of Lewis acids greatly accelerates these reactions. [Mn(V)(N)(CN)4]2(-) is another highly efficient oxidation catalyst, which facilitates the epoxidation of alkenes and the oxidation of alcohols to carbonyl compounds using H2O2. Finally, M≡N can potentially bind to and exert various effects on biomolecules. For example, a number of Os(VI)≡N complexes exhibit novel anticancer properties, which may be related to their ability to bind to DNA or other biomolecules.

[Effect of the chelator BPCBG on the decorporation of uranium in vivo and uranium-induced damage of human renal tubular epithelial cells in vitro].

PubMed

Bao, Yi-zhong; Wang, Dan; Hu, Yu-xing; Xu, Ai-hong; Sun, Mei-zhen; Chen, Hong-hong

2011-11-01

This study is to assess the efficacy of BPCBG on the decorporation of uranium (VI) and protecting human renal proximal tubular epithelial cells (HK-2) against uranium-induced damage. BPCBG at different doses was injected intramuscularly to male SD rats immediately after a single intraperitoneal injection of UO2(CH3COO)2. Twenty-four hours later uranium contents in urine, kidneys and femurs were measured by ICP-MS. After HK-2 cells were exposed to UO2(CH3COO)2 immediately or for 24 h followed by BPCBG treatment at different doses for another 24 or 48 h, the uranium contents in HK-2 cells were measured by ICP-MS, the cell survival was assayed by cell counting kit-8 assay, formation of micronuclei was determined by the cytokinesis-block (CB) micronucleus assay and the production of intracellular reactive oxygen species (ROS) was detected by 2',7'-dichlorofluorescin diacetate (DCFH-DA) oxidation. DTPA-CaNa3 was used as control. It was found that BPCBG at dosages of 60, 120, and 600 micromol kg(-1) resulted in 37%-61% increase in 24 h-urinary uranium excretion, and significantly decreased the amount of uranium retention in kidney and bone to 41%-31% and 86%-42% of uranium-treated group, respectively. After HK-2 cells that had been pre-treated with UO2(CH3COO)2 for 24 h were treated with the chelators for another 24 h, 55%-60% of the intracellular uranium was removed by 10-250 micromol L(-1) of BPCBG. Treatment of uranium-treated HK-2 cells with BPCBG significantly enhanced the cell survival, decreased the formation of micronuclei and inhibited the production of intracellular ROS. Although DTPA-CaNa3 markedly reduced the uranium retention in kidney of rats and HK-2 cells, its efficacy of uranium removal from body was significantly lower than that of BPCBG and it could not protect uranium-induced cell damage. It can be concluded that BPCBG effectively decorporated the uranium from UO2(CH3COO)2-treated rats and HK-2 cells, which was better than DTPA-CaNa3. It could also scavenge the uranium-induced intracellular ROS and protect against the uranium-induced cell damage. BPCBG is worth further investigation.

GeoChip-based analysis of functional microbial communities in a bioreduced uranium-contaminated aquifer during reoxidation by oxygen

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

Van Nostrand, J.D.; Wu, W.-M.; Wu, L.

2009-07-15

A pilot-scale system was established for in situ biostimulation of U(VI) reduction by ethanol addition at the US Department of Energy's (DOE's) Field Research Center (Oak Ridge, TN). After achieving U(VI) reduction, stability of the bioreduced U(IV) was evaluated under conditions of (i) resting (no ethanol injection), (ii) reoxidation by introducing dissolved oxygen (DO), and (iii) reinjection of ethanol. GeoChip, a functional gene array with probes for N, S and C cycling, metal resistance and contaminant degradation genes, was used for monitoring groundwater microbial communities. High diversity of all major functional groups was observed during all experimental phases. The microbialmore » community was extremely responsive to ethanol, showing a substantial change in community structure with increased gene number and diversity after ethanol injections resumed. While gene numbers showed considerable variations, the relative abundance (i.e. percentage of each gene category) of most gene groups changed little. During the reoxidation period, U(VI) increased, suggesting reoxidation of reduced U(IV). However, when introduction of DO was stopped, U(VI) reduction resumed and returned to pre-reoxidation levels. These findings suggest that the community in this system can be stimulated and that the ability to reduce U(VI) can be maintained by the addition of electron donors. This biostimulation approach may potentially offer an effective means for the bioremediation of U(VI)-contaminated sites.« less

METHOD OF PROCESSING MONAZITE SAND

DOEpatents

Calkins, G.D.

1957-10-29

A method is given for the pretreatment of monazite sand with sodium hydroxide. When momazite sand is reacted with sodium hydroxide, the thorium, uranium, and rare earths are converted to water-insoluble hydrous oxides; but in the case of uranium, the precipitate compound may at least partly consist of a slightly soluble uranate. According to the patent, monazite sand is treated with an excess of aqueous sodium hydroxide solution, and the insoluble compounds of thorium, uranium, and the rare earths are separated from the aqueous solution. This solution is then concentrated causing sodium phosphate to crystallize out. The crystals are removed from the remaining solution, and the solution is recycled for reaction with a mew supply of momazite sand.

Optimizing Metalloporphyrin-Catalyzed Reduction Reactions for In Situ Remediation of DOE Contaminants

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

Schlautman, Mark A.

2013-07-14

Past activities have resulted in a legacy of contaminated soil and groundwater at Department of Energy facilities nationwide. Uranium and chromium are among the most frequently encountered and highest-priority metal and radionuclide contaminants at DOE installations. Abiotic chemical reduction of uranium and chromium at contaminated DOE sites can be beneficial because the reduced metal species are less soluble in water, less mobile in the environment, and less toxic to humans and ecosystems. Although direct biological reduction has been reported for U(VI) and Cr(VI) in laboratory studies and at some field sites, the reactions can sometimes be slow or even inhibitedmore » due to unfavorable environmental conditions. One promising approach for the in-situ remediation of DOE contaminants is to develop electron shuttle catalysts that can be delivered precisely to the specific subsurface locations where contaminants reside. Previous research has shown that reduction of oxidized organic and inorganic contaminants often can be catalyzed by electron shuttle systems. Metalloporphyrins and their derivatives are well known electron shuttles for many biogeochemical systems, and thus were selected to study their catalytic capabilities for the reduction of chromium and uranium in the presence of reducing agents. Zero valent iron (ZVI) was chosen as the primary electron donor in most experimental systems. Research proceeded in three phases and the key findings of each phase are reported here. Phase I examined Cr(VI) reduction and utilized micro- and nano-sized ZVI as the electron donors. Electron shuttle catalysts tested were cobalt- and iron-containing metalloporphyrins and Vitamin B12. To aid in the recycle and reuse of the nano-sized ZVI and soluble catalysts, sol-gels and calcium-alginate gel beads were tested as immobilization/support matrices. Although the nano-sized ZVI could be incorporated within the alginate gel beads, preliminary attempts to trap it in sol-gels were not successful. Conversely, the water-soluble catalysts could be trapped within sol-gel matrices but they tended to leach out of the alginate gel beads during use. In general, immobilization of the nano-sized ZVI in gel beads and of the catalysts in sol-gels tended to result in slower rates of Cr(VI) reduction, but these effects could be overcome to some extent by using higher reactant/catalyst concentrations. In addition, the lowering of their effectiveness would likely be offset by the benefits obtained when recycling and reusing the materials because they were immobilized. Addition of the catalytic electron shuttles will be most useful when the micro-sized or nano-sized ZVI becomes less reactive with reaction time. Continued work in Phase II in the area of nano-sized ZVI immobilization led to procedures that were successful in incorporating the iron particles in sol-gel matrices. The water-soluble reductants sodium dithionite and L-ascorbic acid were also tested, but their use appeared to lead to formation of complexes with the uranyl cation which limited their effectiveness. Also, although the sol-gel supported nano-sized ZVI showed some promise at reducing uranium, the fluoride used in the sol-gel synthesis protocol appeared to lead to formation of uranyl-fluoride complexes that were less reactive. Because hexavalent chromium is an anion which does not form complexes with fluoride, it was used to demonstrate the intrinsic reactivity of the sol-gel immobilized nano-sized ZVI. Consistent with our observations in Phase I, the sol-gel matrix once again slowed down the reduction reaction but the expected benefits of recycle/reuse should outweigh this adverse effect. The major emphasis in Phase III of this study was to simultaneously incorporate nano-sized ZVI and water-soluble catalysts in the same sol-gel matrix. The catalysts utilized were cobalt complexes of uroporphyrin and protoporphyrin and Cr(VI) reduction was used to test the efficacy of the combined "catalyst + reductant" sol-gel matrix. When enough catalyst was added to the sol-gels, enhancement of the Cr(VI) reduction reaction was observed. At the lowest levels of catalyst addition, however, the rates of Cr(VI) reduction were similar to those systems which only used sol-gel immobilized nano-sized ZVI without any catalyst present. These findings suggest future areas of research that should be pursued to further optimize abiotic reduction reactions of metals with combined "catalyst + reductant" matrices.« less

NUCLEAR REACTOR FUEL ELEMENT AND METHOD OF MANUFACTURE

DOEpatents

Brooks, H.

1960-04-26

A description is given for a fuel element comprising a body of uranium metal or an uranium compound dispersed in a matrix material made from magnesium, calcium, or barium and a stainless steel jacket enclosing the body.

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.

Diversity and Characterization of Sulfate-Reducing Bacteria in Groundwater at a Uranium Mill Tailings Site

PubMed Central

Chang, Yun-Juan; Peacock, Aaron D.; Long, Philip E.; Stephen, John R.; McKinley, James P.; Macnaughton, Sarah J.; Hussain, A. K. M. Anwar; Saxton, Arnold M.; White, David C.

2001-01-01

Microbially mediated reduction and immobilization of U(VI) to U(IV) plays a role in both natural attenuation and accelerated bioremediation of uranium-contaminated sites. To realize bioremediation potential and accurately predict natural attenuation, it is important to first understand the microbial diversity of such sites. In this paper, the distribution of sulfate-reducing bacteria (SRB) in contaminated groundwater associated with a uranium mill tailings disposal site at Shiprock, N.Mex., was investigated. Two culture-independent analyses were employed: sequencing of clone libraries of PCR-amplified dissimilatory sulfite reductase (DSR) gene fragments and phospholipid fatty acid (PLFA) biomarker analysis. A remarkable diversity among the DSR sequences was revealed, including sequences from δ-Proteobacteria, gram-positive organisms, and the Nitrospira division. PLFA analysis detected at least 52 different mid-chain-branched saturate PLFA and included a high proportion of 10me16:0. Desulfotomaculum and Desulfotomaculum-like sequences were the most dominant DSR genes detected. Those belonging to SRB within δ-Proteobacteria were mainly recovered from low-uranium (≤302 ppb) samples. One Desulfotomaculum-like sequence cluster overwhelmingly dominated high-U (>1,500 ppb) sites. Logistic regression showed a significant influence of uranium concentration over the dominance of this cluster of sequences (P = 0.0001). This strong association indicates that Desulfotomaculum has remarkable tolerance and adaptation to high levels of uranium and suggests the organism's possible involvement in natural attenuation of uranium. The in situ activity level of Desulfotomaculum in uranium-contaminated environments and its comparison to the activities of other SRB and other functional groups should be an important area for future research. PMID:11425735

Uranium speciation in Fernald soils. Progress report, January 1--May 31, 1992

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

Morris, D.E.; Conradson, S.D.; Tait, C.D.

1992-05-31

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

LIQUID PHASE SINTERING OF METALLIC CARBIDES

DOEpatents

Hammond, J.; Sease, J.D.

1964-01-21

An improved method is given for fabricating uranium carbide composites, The method comprises forming a homogeneous mixture of powdered uranium carbide, a uranium intermetallic compound which wets and forms a eutectic with said carbide and has a non-uranium component which has a relatively high vapor pressure at a temperature in the range 1200 to 1500 deg C, and an organic binder, pressing said mixture to a composite of desired green strength, and then vacuum sintering said composite at the eutectic forming temperature for a period sufficient to remove at least a portion of the non-uranium containing component of said eutectic. (AEC)

Development studies for a novel wet oxidation process

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

Dhooge, P.M.; Hakim, L.B.

1994-01-01

A catalytic wet oxidation process (DETOX), which uses an acidic iron solution to oxidize organic compounds to carbon dioxide, water, and other simple products, was investigated as a potential method for the treatment of multicomponent hazardous and mixed wastes. The organic compounds picric acid, poly(vinyl chloride), tetrachlorothiophene, pentachloropyridine, Aroclor 1260 (a polychlorinated biphenyl), and hexachlorobenzene were oxidized in 125 ml reaction vessels. The metals arsenic, barium, beryllium, cadmium, cerium (as a surrogate for plutonium), chromium, lead, mercury, neodymium (as a surrogate for uranium), nickel, and vanadium were tested in the DETOX solution. Barium, beryllium, cerium, chromium, mercury, neodymium, nickel, andmore » vanadium were all found to be very soluble (>100 g/l) in the DETOX chloride-based solution. Arsenic, barium, cadmium, and lead solubilities were lower. Lead could be selectively precipitated from the DETOX solution. Chromium(VI) was reduced to relatively non-toxic chromium(III) by the solution. Six soils were contaminated with arsenic, barium, beryllium, chromium, lead, and neodymium oxides at approximately 0.1% by weight, and benzene, trichloroethene, mineral oil, and Aroclor 1260 at approximately 5% by weight total, and 5.g amounts treated with the DETOX solution in unstirred 125. ml reaction bombs. It is felt that soil treatment in a properly designed system is entirely possible despite incomplete oxidation of the less volatile organic materials in these unstirred tests.« less

Donor exciton of cobalt and its interaction with lattice vibrations in the semiconductor crystal ZnO:Co

NASA Astrophysics Data System (ADS)

Gruzdev, N. B.; Sokolov, V. I.; Yemelchenko, G. A.

2009-01-01

Vibrational states interacting with a donor exciton in the compound ZnO:Co are revealed by the sensitive method of field exciton-vibrational spectroscopy. The vibrational modes of the electroabsorption spectrum of the compound ZnO:Co in the region of the donor exciton are given an interpretation based on the existing data on the symmetrized local density of states of the compounds ZnO and ZnO :Ni3+. The results are compared with the known data for II-VI:Ni compounds in the case of an acceptor exciton. The position of the donor level of the Co2+ ion relative to the bottom of the conduction band in the given compound is determined and found to conform well to the universal trend for donor levels of 3d ions in II-VI compounds.

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

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

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

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

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

DOE PAGES

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

2018-01-16

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

[Studies on the phenolic acids from Sarcopyramis bodinieri var. delicata].

PubMed

Yang, Jia-Yong; Wan, Chun-Peng; Qiu, Yan

2010-04-01

To study the chemical constituents from Sarcopyramis bodinieri var. delicata. These compounds were isolated and purified by chromatography with silica gel column combined with Sephadex LH-20 column from high polar extracts. The structures were identified on the basis of extensive spectroscopic data analysis, and by comparison of their spectral data with those reported. Seven compounds were isolated as 3, 3'-di-O-methylellagic acid-4'-O-alpha-L-rhamnopyranoside (I), ellagic acid (II), ferulic acid (III), isoferulic acid (IV), caffeic acid (V), 3, 4-di-hydroxybenzoic acid (VI), p-hydroxycinnamic acid (VII). Compound I, III, VI, VII are isolated from the genus for the first time.

High-Pressure Viewports for Infrared Systems. Phase 2. Chalcogenide Glass

DTIC Science & Technology

1982-01-28

radiation. the permanent microcopic dipole domain undergoes spontaneous polarization, which results in the buildup of charge on the opposite surface of the...are quantified in table 3. Materials that have been useful in the 8-12 prm region are all II-VI compounds , ie prepared from elements of group II and...Polycrystalline II-VI compounds . 18 ’T 6" ý4 04 MELT-FORMED GLASS The properties of the melt-formed glasses are quantified in table 4. Only glasses that have been

Biospectroscopy for studying the influences of anti-diabetic metals (V, Cr, Mo, and W) to the insulin signaling pathway

NASA Astrophysics Data System (ADS)

Safitri, Anna; Levina, Aviva; Lee, Joonsup; Carter, Elizabeth A.; Lay, Peter A.

2017-03-01

The prevalence of diabetes, particularly with respect to type 2 diabetes, has reached epidemic proportions and continues to grow worldwide. One of the potential therapeutic targets in the treatment of type 2 diabetes involves the role of protein tyrosine phosphatases in the negative regulation of insulin signaling. The complexes of V(V/IV), Cr(III), W(VI), and Mo(VI), have all been proposed as possible drugs in the treatment of diabetes mellitus. Anti-diabetic activities of V(V/IV), Cr(III), Mo(VI), and W(VI) compounds are likely to be based on similar mechanisms, which involve phosphorylation/dephosphorylation reactions in the glucose uptake and metabolism. In order to clearly understand biological activities and phosphorylation/dephosphorylation reactions involved in anti-diabetic actions of Cr(III), V(V/IV), Mo(VI), and W(VI) complexes, the current research involves the use of cultured insulin-sensitive cells treated with these compounds. These reactions were investigated through vibrational spectroscopy. Protein phosphorylation/dephosphorylation induced conformational changes in secondary protein structure from α-helix to β-sheet, and these changes were detected by the IR spectra, which showed changes in the wavenumber and intensities of signals within the composite protein amide I band.

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

USGS Publications Warehouse

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

2011-01-01

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

Draft Genome Sequences for Two Metal-Reducing Pelosinus fermentans Strains Isolated from a Cr(VI)-Contaminated Site and for Type Strain R7

PubMed Central

Brown, Steven D.; Podar, Mircea; Klingeman, Dawn M.; Johnson, Courtney M.; Yang, Zamin K.; Utturkar, Sagar M.; Land, Miriam L.; Mosher, Jennifer J.; Hurt, Richard A.; Phelps, Tommy J.; Palumbo, Anthony V.; Arkin, Adam P.; Hazen, Terry C.

2012-01-01

Pelosinus fermentans 16S rRNA gene sequences have been reported from diverse geographical sites since the recent isolation of the type strain. We present the genome sequence of the P. fermentans type strain R7 (DSM 17108) and genome sequences for two new strains with different abilities to reduce iron, chromate, and uranium. PMID:22933770

Pore-scale characterization of biogeochemical controls on iron and uranium speciation under flow conditions.

PubMed

Pearce, Carolyn I; Wilkins, Michael J; Zhang, Changyong; Heald, Steve M; Fredrickson, Jim K; Zachara, John M

2012-08-07

Etched silicon microfluidic pore network models (micromodels) with controlled chemical and redox gradients, mineralogy, and microbiology under continuous flow conditions are used for the incremental development of complex microenvironments that simulate subsurface conditions. We demonstrate the colonization of micromodel pore spaces by an anaerobic Fe(III)-reducing bacterial species (Geobacter sulfurreducens) and the enzymatic reduction of a bioavailable Fe(III) phase within this environment. Using both X-ray microprobe and X-ray absorption spectroscopy, we investigate the combined effects of the precipitated Fe(III) phases and the microbial population on uranium biogeochemistry under flow conditions. Precipitated Fe(III) phases within the micromodel were most effectively reduced in the presence of an electron shuttle (AQDS), and Fe(II) ions adsorbed onto the precipitated mineral surface without inducing any structural change. In the absence of Fe(III), U(VI) was effectively reduced by the microbial population to insoluble U(IV), which was precipitated in discrete regions associated with biomass. In the presence of Fe(III) phases, however, both U(IV) and U(VI) could be detected associated with biomass, suggesting reoxidation of U(IV) by localized Fe(III) phases. These results demonstrate the importance of the spatial localization of biomass and redox active metals, and illustrate the key effects of pore-scale processes on contaminant fate and reactive transport.

Uranium (VI) transport in saturated heterogeneous media: Influence of kaolinite and humic acid.

PubMed

Chen, Chong; Zhao, Kang; Shang, Jianying; Liu, Chongxuan; Wang, Jin; Yan, Zhifeng; Liu, Kesi; Wu, Wenliang

2018-05-07

Natural aquifers typically exhibit a variety of structural heterogeneities. However, the effect of mineral colloids and natural organic matter on the transport behavior of uranium (U) in saturated heterogeneous media are not totally understood. In this study, heterogeneous column experiments were conducted, and the constructed columns contained a fast-flow domain (FFD) and a slow-flow domain (SFD). The effect of kaolinite, humic acid (HA), and kaolinite/HA mixture on U(VI) retention and release in saturated heterogeneous media was examined. Media heterogeneity significantly influenced U fate and transport behavior in saturated subsurface environment. The presence of kaolinite, HA, and kaolinite/HA enhanced the mobility of U in heterogeneous media, and the mobility of U was the highest in the presence of kaolinite/HA and the lowest in the presence of kaolinite. In the presence of kaolinite, there was no difference in the amount of U released from the FFD and SFD. However, in the presence of HA and kaolinite/HA, a higher amount of U was released from the FFD. The findings in this study showed that medium structure and mineral colloids, as well as natural organic matter in the aqueous phase had significant effects on U transport and fate in subsurface environment. Copyright © 2018 Elsevier Ltd. All rights reserved.

Physicochemical heterogeneity controls on uranium bioreduction rates at the field scale.

PubMed

Li, Li; Gawande, Nitin; Kowalsky, Michael B; Steefel, Carl I; Hubbard, Susan S

2011-12-01

It has been demonstrated in laboratory systems that U(VI) can be reduced to immobile U(IV) by bacteria in natural environments. The ultimate efficacy of bioreduction at the field scale, however, is often challenging to quantify and depends on site characteristics. In this work, uranium bioreduction rates at the field scale are quantified, for the first time, using an integrated approach. The approach combines field data, inverse and forward hydrological and reactive transport modeling, and quantification of reduction rates at different spatial scales. The approach is used to explore the impact of local scale (tens of centimeters) parameters and processes on field scale (tens of meters) system responses to biostimulation treatments and the controls of physicochemical heterogeneity on bioreduction rates. Using the biostimulation experiments at the Department of Energy Old Rifle site, our results show that the spatial distribution of hydraulic conductivity and solid phase mineral (Fe(III)) play a critical role in determining the field-scale bioreduction rates. Due to the dependence on Fe-reducing bacteria, field-scale U(VI) bioreduction rates were found to be largely controlled by the abundance of Fe(III) minerals at the vicinity of the injection wells and by the presence of preferential flow paths connecting injection wells to down gradient Fe(III) abundant areas.

Uranium isotopes fingerprint biotic reduction.

PubMed

Stylo, Malgorzata; Neubert, Nadja; Wang, Yuheng; Monga, Nikhil; Romaniello, Stephen J; Weyer, Stefan; Bernier-Latmani, Rizlan

2015-05-05

Knowledge of paleo-redox conditions in the Earth's history provides a window into events that shaped the evolution of life on our planet. The role of microbial activity in paleo-redox processes remains unexplored due to the inability to discriminate biotic from abiotic redox transformations in the rock record. The ability to deconvolute these two processes would provide a means to identify environmental niches in which microbial activity was prevalent at a specific time in paleo-history and to correlate specific biogeochemical events with the corresponding microbial metabolism. Here, we demonstrate that the isotopic signature associated with microbial reduction of hexavalent uranium (U), i.e., the accumulation of the heavy isotope in the U(IV) phase, is readily distinguishable from that generated by abiotic uranium reduction in laboratory experiments. Thus, isotope signatures preserved in the geologic record through the reductive precipitation of uranium may provide the sought-after tool to probe for biotic processes. Because uranium is a common element in the Earth's crust and a wide variety of metabolic groups of microorganisms catalyze the biological reduction of U(VI), this tool is applicable to a multiplicity of geological epochs and terrestrial environments. The findings of this study indicate that biological activity contributed to the formation of many authigenic U deposits, including sandstone U deposits of various ages, as well as modern, Cretaceous, and Archean black shales. Additionally, engineered bioremediation activities also exhibit a biotic signature, suggesting that, although multiple pathways may be involved in the reduction, direct enzymatic reduction contributes substantially to the immobilization of uranium.

Process for producing an aggregate suitable for inclusion into a radiation shielding product

DOEpatents

Lessing, Paul A.; Kong, Peter C.

2000-01-01

The present invention is directed to methods for converting depleted uranium hexafluoride to a stable depleted uranium silicide in a one-step reaction. Uranium silicide provides a stable aggregate material that can be added to concrete to increase the density of the concrete and, consequently, shield gamma radiation. As used herein, the term "uranium silicide" is defined as a compound generically having the formula U.sub.x Si.sub.y, wherein the x represents the molecules of uranium and the y represent the molecules of silicon. In accordance with the present invention, uranium hexafluoride is converted to a uranium silicide by contacting the uranium hexafluoride with a silicon-containing material at a temperature in a range between about 1450.degree. C. and about 1750.degree. C. The stable depleted uranium silicide is included as an aggregate in a radiation shielding product, such as a concrete product.

Structure and thermodynamic stability of UTa 3O 10, aU(v)-bearing compound

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

Guo, Xiaofeng; Lipp, Christian; Tiferet, Eitan

Heating a mixture of uranyl (VI) nitrate and tantalum (V) oxide in the molar ratio of 2 : 3 to 1400 °C resulted in the formation of a new compound, UTa 3O 10. The honey colored to yellow brown crystals of UTa 3O 10 crystallize in an orthorhombic structure with the space group Fddd (no. 70), lattice parameters a = 7.3947(1), b = 12.7599(2), c = 15.8156(2) Å, and Z = 8. Vertex sharing [TaO 6] 7– octahedra of two crystallographically distinct Ta cations form a three dimensional tantalate framework. Within this framework, six membered rings of [TaO 6] 7–more » octahedra are formed within the (001) plane. The center of these rings is occupied by the uranyl cations [UO 2]+, with an oxidation state of +5 for uranium. The pentavalence of U and Ta was confirmed by X-ray photoelectron spectroscopy and X-ray adsorption spectroscopy. The enthalpy of formation of UTa 3O 10 from Ta 2O 5, β-U 3O 7, and U3O8 has been determined to be 13.1 ± 18.1 kJ mol–1 using high temperature oxide melt solution calorimetry with sodium molybdate as the solvent at 700 °C. As a result, the close to zero enthalpy of formation of UTa 3O 10 can be explained by closely balanced structural stabilizing and destabilizing factors, which may also apply to other UM 3O 10 compounds.« less

Structure and thermodynamic stability of UTa 3O 10, aU(v)-bearing compound

DOE PAGES

Guo, Xiaofeng; Lipp, Christian; Tiferet, Eitan; ...

2016-09-09

Heating a mixture of uranyl (VI) nitrate and tantalum (V) oxide in the molar ratio of 2 : 3 to 1400 °C resulted in the formation of a new compound, UTa 3O 10. The honey colored to yellow brown crystals of UTa 3O 10 crystallize in an orthorhombic structure with the space group Fddd (no. 70), lattice parameters a = 7.3947(1), b = 12.7599(2), c = 15.8156(2) Å, and Z = 8. Vertex sharing [TaO 6] 7– octahedra of two crystallographically distinct Ta cations form a three dimensional tantalate framework. Within this framework, six membered rings of [TaO 6] 7–more » octahedra are formed within the (001) plane. The center of these rings is occupied by the uranyl cations [UO 2]+, with an oxidation state of +5 for uranium. The pentavalence of U and Ta was confirmed by X-ray photoelectron spectroscopy and X-ray adsorption spectroscopy. The enthalpy of formation of UTa 3O 10 from Ta 2O 5, β-U 3O 7, and U3O8 has been determined to be 13.1 ± 18.1 kJ mol–1 using high temperature oxide melt solution calorimetry with sodium molybdate as the solvent at 700 °C. As a result, the close to zero enthalpy of formation of UTa 3O 10 can be explained by closely balanced structural stabilizing and destabilizing factors, which may also apply to other UM 3O 10 compounds.« less

Argon/UF6 plasma exhaust gas reconstitution experiments using preheated fluorine and on-line diagnostics. [fissioning uranium plasma core reactor design

NASA Technical Reports Server (NTRS)

Roman, W. C.

1979-01-01

The feasibility of employing a flowing, high-temperature, pure fluorine/UF6 regeneration system to efficiently convert a large fraction of the effluent plasma exhaust back to pure UF6 was demonstrated. The custom built T.O.F. mass spectrometer sampling system permitted on-line measurements of the UF6 concentration at different locations in the exhaust system. Negligible amounts ( 100 ppm) of UF6 were detected in the axial bypass exhaust duct and the exhaust ducts downstream of the cryogenic trap system used to collect the UF6, thus verifying the overall system efficiency over a range of operating conditions. Use of a porous Monel duct as part of the exhaust duct system, including provision for injection of pure fluorine, provided a viable technique to eliminate uranium compound residue on the inside surface of the exhaust ducts. Typical uranium compound mass deposition per unit area of duct was 2 micron g/sq cm. This porous duct technique is directly applicable to future uranium compound transfer exhaust systems. Throughout these experiments, additional basic data on the corrosion aspects of hot, pressurized UF6/fluorine were also accumulated.

United States-Gulf Cooperation Council Security Cooperation in a Multipolar World

DTIC Science & Technology

2014-10-01

including plu- tonium separation experiments, uranium enrichment and conversion experiments, and importing various uranium compounds.28 Subsequent...against political protest, a status shared with the two other remaining Arab monarchies, Morocco and Jordan . Geopolitically, the GCC as a region has...commitments, the UAE will not enrich uranium itself, relying instead on imported, enriched fuel. “Abu Dhabi Moves Ahead With Nuclear Program,” Middle

Decontamination of TCE- and U-rich waters by granular iron: Role of sorbed Fe(II)

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

Charlet, L.; Liger, E.; Gerasimo, P.

1998-01-01

Uranium (UO{sub 2}{sup 2+}) and chlorinated aliphatics [tetrachloroethane (PCE) and trichloroethane (TCE)] can be reduced and thus immobilized or degraded, respectively, by the same abiotic mechanism. In this mechanism the reduction reaction is coupled to the oxidation of Fe(II) sorbed on iron corrosion products such as hematite. This is indicated by the equilibrium E{sub h} values measured during uranium immobilization and PCE degradation reactions of zerovalent iron. These values fit closely with those measured in the Fe(II)-{alpha}Fe{sub 2}O{sub 3}-H{sub 2}O system (in the absence of U or PCE), not those of the Fe(o)/Fe(II) or H{sub 2}(g)/H{sub 2}O couples. Because ironmore » (II) is very unstable in environments that are not strictly anaerobic, Fe(o) serves as a source of Fe(II). The reduction kinetic rate, analyzed in detail for the reduction of U(VI), is found to be a function of the concentration of OH{sup {minus}}, Fe{sup 2+} and reactive surface sites, and is given in terms of sorbed species concentrations by {l_brace}d[U(VI)]{sub ads}{r_brace}/dt = {l_brace}{minus}k{prime}[{triple_bond}FeOFeOH{sup 0}][U(VI)]{sub ads}{r_brace}. This rate law applies to organic pollutants as well, as long as they can be reduced by surface Fe(II): {l_brace}d[Pollutant]{r_brace}/dt = {l_brace}{minus}k{prime}[{triple_bond}FeOFeOH{sup 0}][Pollutant]{r_brace}. This mechanism suggests new possibilities for the improvement of low-cost decontamination techniques for U- and chlorinated aliphatic-rich waters.« less

Precipitation and Dissolution of Uranyl Phosphates in a Microfluidic Pore Structure

NASA Astrophysics Data System (ADS)

Werth, C. J.; Fanizza, M.; Strathmann, T.; Finneran, K.; Oostrom, M.; Zhang, C.; Wietsma, T. W.; Hess, N. J.

2011-12-01

The abiotic precipitation of uranium (U(VI)) was evaluated in a microfluidic pore structure (i.e. micromodel) to assess the efficacy of using a phosphate amendment to immobilize uranium in groundwater and mitigate the risk of this contaminant to potential down-gradient receptor sites. U(VI) was mixed transverse to the direction of flow with hydrogen phosphate (HPO42-), in the presence or absence of calcium (Ca2+) or sulfate (SO42-), in order to identify precipitation rates, the morphology and types of minerals formed, and the stability of these minerals to dissolution with and without bicarbonate (HCO3-) present. Raman backscattering spectroscopy and micro X-ray diffraction (μ-XRD) results both showed that the only mineral precipitated was chernikovite (also known as hydrogen uranyl phosphate; UO2HPO4), even though the formation of other minerals were thermodynamically favored depending on the experimental conditions. Precipitation and dissolution rates varied with influent conditions. Relative to when only U(VI) and HPO42- were present, precipitation rates were 2.3 times slower when SO42- was present, and 1.4 times faster when Ca2+ was present. These rates were inversely related to the size of crystals formed during precipitation. Dissolution rates for chernikovite increased with increasing HCO3- concentrations, consistent with formation of uranyl carbonate complexes in aqueous solution, and they were the fastest for chernikovite formed in the presence of SO42-, and slowest for the chernikovite formed in the presence of Ca2+. These rates are related to the ratios of mineral-water interfacial area to mineral volume. Fluorescent tracer studies and laser confocal microscopy images showed that densely aggregated precipitates blocked pores and reduced permeability. The results suggest that changes in the solute conditions evaluated affect precipitation rates, crystal morphology, and crystal stability, but not mineral type.

Microscale geochemical gradients in Hanford 300 Area sediment biofilms and influence of uranium

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

Nguyen, Hung D.; Cao, Bin; Mishra, Bhoopesh

2012-01-01

The presence and importance of microenvironments in the subsurface at contaminated sites were suggested by previous geochemical studies. However, no direct quantitative characterization of the geochemical microenvironments had been reported. We quantitatively characterized microscale geochemical gradients (dissolved oxygen (DO), H(2), pH, and redox potential) in Hanford 300A subsurface sediment biofilms. Our results revealed significant differences in geochemical parameters across the sediment biofilm/water interface in the presence and absence of U(VI) under oxic and anoxic conditions. While the pH was relatively constant within the sediment biofilm, the redox potential and the DO and H(2) concentrations were heterogeneous at the microscale (<500-1000more » μm). We found microenvironments with high DO levels (DO hotspots) when the sediment biofilm was exposed to U(VI). On the other hand, we found hotspots (high concentrations) of H(2) under anoxic conditions both in the presence and in the absence of U(VI). The presence of anoxic microenvironments inside the sediment biofilms suggests that U(VI) reduction proceeds under bulk oxic conditions. To test this, we operated our biofilm reactor under air-saturated conditions in the presence of U(VI) and characterized U speciation in the sediment biofilm. U L(III)-edge X-ray absorption spectroscopy (XANES and EXAFS) showed that 80-85% of the U was in the U(IV) valence state.« less

Microscale geochemical gradients in Hanford 300 Area sediment biofilms and influence of uranium.

PubMed

Nguyen, Hung Duc; Cao, Bin; Mishra, Bhoopesh; Boyanov, Maxim I; Kemner, Kenneth M; Fredrickson, Jim K; Beyenal, Haluk

2012-01-01

The presence and importance of microenvironments in the subsurface at contaminated sites were suggested by previous geochemical studies. However, no direct quantitative characterization of the geochemical microenvironments had been reported. We quantitatively characterized microscale geochemical gradients (dissolved oxygen (DO), H(2), pH, and redox potential) in Hanford 300A subsurface sediment biofilms. Our results revealed significant differences in geochemical parameters across the sediment biofilm/water interface in the presence and absence of U(VI) under oxic and anoxic conditions. While the pH was relatively constant within the sediment biofilm, the redox potential and the DO and H(2) concentrations were heterogeneous at the microscale (<500-1000 μm). We found microenvironments with high DO levels (DO hotspots) when the sediment biofilm was exposed to U(VI). On the other hand, we found hotspots (high concentrations) of H(2) under anoxic conditions both in the presence and in the absence of U(VI). The presence of anoxic microenvironments inside the sediment biofilms suggests that U(VI) reduction proceeds under bulk oxic conditions. To test this, we operated our biofilm reactor under air-saturated conditions in the presence of U(VI) and characterized U speciation in the sediment biofilm. U L(III)-edge X-ray absorption spectroscopy (XANES and EXAFS) showed that 80-85% of the U was in the U(IV) valence state. Copyright © 2011 Elsevier Ltd. All rights reserved.

Se Isotopes as groundwater redox indicators: Detecting natural attenuation of Se at an in situ recovery U mine

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

Anirban, Basu; Schilling, Kathrin; Brown, Shaun T.

One of the major ecological concerns associated with the in situ recovery (ISR) of uranium (U) is the environmental release of soluble, toxic selenium (Se) oxyanions generated by mining. Post-mining natural attenuation by the residual reductants in the ore body and reduced down-gradient sediments should mitigate the risk of Se contamination in groundwater. Here in this work, we investigate the Se concentrations and Se isotope systematics of groundwater and of U ore bearing sediments from an ISR site at Rosita, TX, USA. Our results show that selenate (Se(VI)) is the dominant Se species in Rosita groundwater, and while several up-gradientmore » wells have elevated Se(VI), the majority of the ore zone and down-gradient wells have little or no Se oxyanions. In addition, the δ 82SeVI of Rosita groundwater is generally elevated relative to the U ore up to +6.14‰, with the most enriched values observed in the ore-zone wells. Increasing δ 82Se with decreasing Se(VI) conforms to a Rayleigh type distillation model with an ε of $-$2.25‰ ± 0.61‰, suggesting natural Se(VI) reduction occurring along the hydraulic gradient at the Rosita ISR site. Moreover, our results show that Se isotopes are excellent sensors for detecting and monitoring post-mining natural attenuation of Se oxyanions at ISR sites.« less

Se Isotopes as groundwater redox indicators: Detecting natural attenuation of Se at an in situ recovery U mine

DOE PAGES

Anirban, Basu; Schilling, Kathrin; Brown, Shaun T.; ...

2016-08-22

One of the major ecological concerns associated with the in situ recovery (ISR) of uranium (U) is the environmental release of soluble, toxic selenium (Se) oxyanions generated by mining. Post-mining natural attenuation by the residual reductants in the ore body and reduced down-gradient sediments should mitigate the risk of Se contamination in groundwater. Here in this work, we investigate the Se concentrations and Se isotope systematics of groundwater and of U ore bearing sediments from an ISR site at Rosita, TX, USA. Our results show that selenate (Se(VI)) is the dominant Se species in Rosita groundwater, and while several up-gradientmore » wells have elevated Se(VI), the majority of the ore zone and down-gradient wells have little or no Se oxyanions. In addition, the δ 82SeVI of Rosita groundwater is generally elevated relative to the U ore up to +6.14‰, with the most enriched values observed in the ore-zone wells. Increasing δ 82Se with decreasing Se(VI) conforms to a Rayleigh type distillation model with an ε of $-$2.25‰ ± 0.61‰, suggesting natural Se(VI) reduction occurring along the hydraulic gradient at the Rosita ISR site. Moreover, our results show that Se isotopes are excellent sensors for detecting and monitoring post-mining natural attenuation of Se oxyanions at ISR sites.« less

Growth of Wide Band Gap II-VI Compound Semiconductors by Physical Vapor Transport

NASA Technical Reports Server (NTRS)

Su, Ching-Hua; Sha, Yi-Gao

1995-01-01

The studies on the crystal growth and characterization of II-VI wide band gap compound semiconductors, such as ZnTe, CdS, ZnSe and ZnS, have been conducted over the past three decades. The research was not quite as extensive as that on Si, III-V, or even narrow band gap II-VI semiconductors because of the high melting temperatures as well as the specialized applications associated with these wide band gap semiconductors. In the past several years, major advances in the thin film technology such as Molecular Beam Epitaxy (MBE) and Metal Organic Chemical Vapor Deposition (MOCVD) have demonstrated the applications of these materials for the important devices such as light-emitting diode, laser and ultraviolet detectors and the tunability of energy band gap by employing ternary or even quaternary systems of these compounds. At the same time, the development in the crystal growth of bulk materials has not advanced far enough to provide low price, high quality substrates needed for the thin film growth technology.

Mechanisms of chromium (VI)-induced apoptosis in anterior pituitary cells.

PubMed

Quinteros, Fernanda A; Machiavelli, Leticia I; Miler, Eliana A; Cabilla, Jimena P; Duvilanski, Beatriz H

2008-07-30

Hexavalent chromium (Cr (VI)) is a highly toxic metal. Exposure to Cr (VI) compounds may affect reproductive functions. Due to the importance of anterior pituitary hormones on reproductive physiology we have studied the effects of Cr (VI) on anterior pituitary. We previously demonstrated that, after in vivo Cr (VI) administration, Cr accumulates in the pituitary gland and affects prolactin secretion. In vitro, Cr (VI) causes apoptosis in anterior pituitary cells due to oxidative stress generation. To better understand the mechanisms involved in Cr (VI)-induced apoptosis we studied: (a) whether Cr (VI) affects the intracellular antioxidant response and (b) which of the apoptotic factors participates in Cr (VI) effect. Our results show that Cr (VI) treatment induces a decrease in catalase and glutathione peroxidase (GPx) activity but does not modify glutathione reductase (GR) activity. Cr (VI) exposure causes an increase of GSH levels. p53 and Bax mRNA are also upregulated by the metal. Pifithrin alpha, a p53 transcriptional inhibitor, increases Cr (VI) cytotoxicity, suggesting a role of p53 as a survival molecule. The antioxidant N-acetyl-cysteine (NAC) could prevent Bax mRNA increase and caspase 3 activation, confirming that Cr (VI)-induced apoptosis involves oxidative stress generation.

Exposure to Particulate Hexavalent Chromium Exacerbates Allergic Asthma Pathology

PubMed Central

Schneider, Brent C.; Constant, Stephanie L.; Patierno, Steven R.; Jurjus, Rosalyn A.; Ceryak, Susan M.

2011-01-01

Airborne hexavalent chromate, Cr(VI), has been identified by the Environmental Protection Agency as a possible health threat in urban areas, due to the carcinogenic potential of some of its forms. Particulate chromates are produced in many different industrial settings, with high levels of aerosolized forms historically documented. Along with an increased risk of lung cancer, a high incidence of allergic asthma has been reported in workers exposed to certain inhaled particulate Cr(VI) compounds. However, a direct causal association between Cr(VI) and allergic asthma has not been established. We recently showed that inhaled particulate Cr(VI) induces an innate neutrophilic inflammatory response in BALB/c mice. In the current studies we investigated how the inflammation induced by inhaled particulate Cr(VI) might alter the pathology of an allergic asthmatic response. We used a well-established mouse model of allergic asthma. Groups of ovalbumin protein (OVA)-primed mice were challenged either with OVA alone, or with a combination of OVA and particulate zinc chromate, and various parameters associated with asthmatic responses were measured. Co-exposure to particulate Cr(VI) and OVA mediated a mixed form of asthma in which both eosinophils and neutrophils are present in airways, tissue pathology is markedly exacerbated, and airway hyperresponsiveness is significantly increased. Taken together these findings suggest that inhalation of particulate forms of Cr(VI) may augment the severity of ongoing allergic asthma, as well as alter its phenotype. Such findings may have implications for asthmatics in settings in which airborne particulate Cr(VI) compounds are present at high levels. PMID:22178736

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

PubMed

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

2017-07-01

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

Miniaturizing and automation of free acidity measurements for uranium (VI)-HNO3 solutions: Development of a new sequential injection analysis for a sustainable radio-analytical chemistry.

PubMed

Néri-Quiroz, José; Canto, Fabrice; Guillerme, Laurent; Couston, Laurent; Magnaldo, Alastair; Dugas, Vincent

2016-10-01

A miniaturized and automated approach for the determination of free acidity in solutions containing uranium (VI) is presented. The measurement technique is based on the concept of sequential injection analysis with on-line spectroscopic detection. The proposed methodology relies on the complexation and alkalimetric titration of nitric acid using a pH 5.6 sodium oxalate solution. The titration process is followed by UV/VIS detection at 650nm thanks to addition of Congo red as universal pH indicator. Mixing sequence as well as method validity was investigated by numerical simulation. This new analytical design allows fast (2.3min), reliable and accurate free acidity determination of low volume samples (10µL) containing uranium/[H(+)] moles ratio of 1:3 with relative standard deviation of <7.0% (n=11). The linearity range of the free nitric acid measurement is excellent up to 2.77molL(-1) with a correlation coefficient (R(2)) of 0.995. The method is specific, presence of actinide ions up to 0.54molL(-1) does not interfere on the determination of free nitric acid. In addition to automation, the developed sequential injection analysis method greatly improves the standard off-line oxalate complexation and alkalimetric titration method by reducing thousand fold the required sample volume, forty times the nuclear waste per analysis as well as the analysis time by eight fold. These analytical parameters are important especially in nuclear-related applications to improve laboratory safety, personnel exposure to radioactive samples and to drastically reduce environmental impacts or analytical radioactive waste. Copyright © 2016 Elsevier B.V. All rights reserved.