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

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

NASA Astrophysics Data System (ADS)

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

2012-11-01

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

Chemical Equilibrium of the Dissolved Uranium in Groundwaters From a Spanish Uranium-Ore Deposit

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

Garralon, Antonio; Gomez, Paloma; Turrero, Maria Jesus

2007-07-01

The main objectives of this work are to determine the hydrogeochemical evolution of an uranium ore and identify the main water/rock interaction processes that control the dissolved uranium content. The Mina Fe uranium-ore deposit is the most important and biggest mine worked in Spain. Sageras area is located at the north part of the Mina Fe, over the same ore deposit. The uranium deposit was not mined in Sageras and was only perturbed by the exploration activities performed 20 years ago. The studied area is located 10 Km northeast of Ciudad Rodrigo (Salamanca) at an altitude over 650 m.a.s.l. Themore » uranium mineralization is related to faults affecting the metasediments of the Upper Proterozoic to Lower Cambrian schist-graywacke complex (CEG), located in the Centro-Iberian Zone of the Hesperian Massif . The primary uranium minerals are uraninite and coffinite but numerous secondary uranium minerals have been formed as a result of the weathering processes: yellow gummite, autunite, meta-autunite, torbernite, saleeite, uranotile, ianthinite and uranopilite. The water flow at regional scale is controlled by the topography. Recharge takes place mainly in the surrounding mountains (Sierra Pena de Francia) and discharge at fluvial courses, mainly Agueda and Yeltes rivers, boundaries S-NW and NE of the area, respectively. Deep flows (lower than 100 m depth) should be upwards due to the river vicinity, with flow directions towards the W, NW or N. In Sageras-Mina Fe there are more than 100 boreholes drilled to investigate the mineral resources of the deposit. 35 boreholes were selected in order to analyze the chemical composition of groundwaters based on their depth and situation around the uranium ore. Groundwater samples come from 50 to 150 m depth. The waters are classified as calcium-bicarbonate type waters, with a redox potential that indicates they are slightly reduced (values vary between 50 to -350 mV). The TOC varies between <0.1 and 4.0 mgC/L and the dissolved uranium has a maximum value of 7.7 mg/L. According the analytical data of dissolved uranium, the mineral closest to equilibrium seems to be UO{sub 2}(am). The tritium contents in the groundwaters vary between 1.5 and 7.3 T.U. Considering that the mean value of tritium in rainwater from the studied area has a value of 4 T.U., it can be concluded that the residence times of the groundwaters are relatively short, not longer than 50 years in the oldest case. (authors)« less

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

Effects of calcium and phosphate on uranium(IV) oxidation: Comparison between nanoparticulate uraninite and amorphous UIV-phosphate

NASA Astrophysics Data System (ADS)

Latta, Drew E.; Kemner, Kenneth M.; Mishra, Bhoopesh; Boyanov, Maxim I.

2016-02-01

The mobility of uranium in subsurface environments depends strongly on its redox state, with UIV phases being significantly less soluble than UVI minerals. This study compares the oxidation kinetics and mechanisms of two potential products of UVI reduction in natural systems, a nanoparticulate UO2 phase and an amorphous UIV-Ca-PO4 analog to ningyoite (CaUIV(PO4)2·1-2H2O). The valence of U was tracked by X-ray absorption near-edge spectroscopy (XANES), showing similar oxidation rate constants for UIVO2 and UIV-phosphate in solutions equilibrated with atmospheric O2 and CO2 at pH 7.0 (kobs,UO2 = 0.17 ± 0.075 h-1 vs. kobs,UIVPO4 = 0.30 ± 0.25 h-1). Addition of up to 400 μM Ca and PO4 decreased the oxidation rate constant by an order of magnitude for both UO2 and UIV-phosphate. The intermediates and products of oxidation were tracked by electron microscopy, powder X-ray diffraction (pXRD), and extended X-ray absorption fine-structure spectroscopy (EXAFS). In the absence of Ca or PO4, the product of UO2 oxidation is Na-uranyl oxyhydroxide (under environmentally relevant concentrations of sodium, 15 mM NaClO4 and low carbonate concentration), resulting in low concentrations of dissolved UVI (<2.5 × 10-7 M). Oxidation of UIV-phosphate produced a Na-autunite phase (Na2(UO2)PO4·xH2O), resulting in similarly low dissolved U concentrations (<7.3 × 10-8 M). When Ca and PO4 are present in the solution, the EXAFS data and the solubility of the UVI phase resulting from oxidation of UO2 and UIV-phosphate are consistent with the precipitation of Na-autunite. Bicarbonate extractions and Ca K-edge X-ray absorption spectroscopy of oxidized solids indicate the formation of a Ca-UVI-PO4 layer on the UO2 surface and suggest a passivation layer mechanism for the decreased rate of UO2 oxidation in the presence of Ca and PO4. Interestingly, the extractions were unable to remove all of the oxidized U from partially oxidized UO2 solids, suggesting that oxidized U is distributed between the interior of the UO2 nanoparticles and the labile surface layer. Accounting for the entire pool of oxidized U by XANES is the likely reason for the higher UO2 oxidation rate constants determined here relative to prior studies. Our results suggest that the natural presence or addition of Ca and PO4 in groundwater could slow the rates of UIV oxidation, but that the rates are still fast enough to cause complete oxidation of UIV within days under fully oxygenated conditions.

Effects of calcium and phosphate on uranium(IV) oxidation: Comparison between nanoparticulate uraninite and amorphous U IV–phosphate

DOE PAGES

Latta, Drew E.; Kemner, Kenneth M.; Mishra, Bhoopesh; ...

2015-11-17

The mobility of uranium in subsurface environments depends strongly on its redox state, with U IV phases being significantly less soluble than U VI minerals. This study compares the oxidation kinetics and mechanisms of two potential products of U VI reduction in natural systems, a nanoparticulate UO 2 phase and an amorphous U IV–Ca–PO 4 analog to ningyoite (CaU IV(PO 4) 2·1–2H 2O). The valence of U was tracked by X-ray absorption near-edge spectroscopy (XANES), showing similar oxidation rate constants for U IVO 2 and U IV–phosphate in solutions equilibrated with atmospheric O 2 and CO 2 at pH 7.0more » (k obs,UO2 = 0.17 ± 0.075 h -1 vs. k obs,U IV PO4 = 0.30 ± 0.25 h -1). Addition of up to 400 μM Ca and PO 4 decreased the oxidation rate constant by an order of magnitude for both UO 2 and U IV–phosphate. The intermediates and products of oxidation were tracked by electron microscopy, powder X-ray diffraction (pXRD), and extended X-ray absorption fine-structure spectroscopy (EXAFS). In the absence of Ca or PO 4, the product of UO 2 oxidation is Na–uranyl oxyhydroxide (under environmentally relevant concentrations of sodium, 15 mM NaClO 4 and low carbonate concentration), resulting in low concentrations of dissolved U VI (<2.5 × 10 -7 M). Oxidation of U IV–phosphate produced a Na-autunite phase (Na 2(UO 2)PO 4·xH 2O), resulting in similarly low dissolved U concentrations (<7.3 × 10 -8 M). When Ca and PO 4 are present in the solution, the EXAFS data and the solubility of the UVI phase resulting from oxidation of UO 2 and UIV–phosphate are consistent with the precipitation of Na-autunite. Bicarbonate extractions and Ca K-edge X-ray absorption spectroscopy of oxidized solids indicate the formation of a Ca–UVI–PO 4 layer on the UO 2 surface and suggest a passivation layer mechanism for the decreased rate of UO 2 oxidation in the presence of Ca and PO 4. Interestingly, the extractions were unable to remove all of the oxidized U from partially oxidized UO 2 solids, suggesting that oxidized U is distributed between the interior of the UO 2 nanoparticles and the labile surface layer. Accounting for the entire pool of oxidized U by XANES is the likely reason for the higher UO 2 oxidation rate constants determined here relative to prior studies. In conclusion, our results suggest that the natural presence or addition of Ca and PO 4 in groundwater could slow the rates of U IV oxidation, but that the rates are still fast enough to cause complete oxidation of U IV within days under fully oxygenated conditions.« less

The East Slope No. 2 uranium prospect, Piute County, Utah

USGS Publications Warehouse

Wyant, Donald Gray

1954-01-01

The secondary uranium minerals autunite, metatorbernite, uranophane(?), and schroeckingerite occur in altered hornfels at the East Slope No. 9. uranium prospect. The deposit, in sec. 6, T. 9.7 S., R. 3 W., Piute County, Utah, is about 1 mile west of the Bullion Monarch mine which is in the central producing area of the Marysvale uranium district. Hornfels, formed by contact metamorphism of rocks of the Bullion Canyon volcanics borderhug the margin of a quartz monzonite stock, is in fault contact with the later Mount Belknap rhyolite. The hornfels was intensely altered by hydrothermal solutions in pre-Mount Belknap time. Hematite-alunite-quartz-kaolinite rock, the most completely altered hornfels, is surrounded by orange to white argillized hornfels containing beidellite-montmorillonite clay, and secondary uranium minerals. The secondary uranium minerals probably have been derived from pitchblende, the primary ore mineral in other deposits of the Marysvale area. The two uranium-rich zones, 4 feet ad 5 feet thick, have been traced on the surface for 60 feet and 110 feet, respectively. Channel samples from these zones contained as much as 0.047 percent uranium. The deposit is significant because of its position outside the central producing area and because of the association of uranium minerals with alunitic rock in hydrothermally altered hornfels of volcanic rocks of early Tertiary age.

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

The adsorption behavior of U(VI) on granite.

PubMed

Fan, Q H; Hao, L M; Wang, C L; Zheng, Z; Liu, C L; Wu, W S

2014-03-01

The effects of pH, counter ions and temperature on the adsorption of U(VI) on Beishan granite (BsG) were investigated in the presence and absence of fulvic acid (FA) and humic acid (HA). The adsorption edge of U(VI) on BsG suggested that U(VI) adsorption was mainly controlled by ion exchange and outer-sphere complexation at low pH, whereas inner-sphere complex was the dominant adsorption species in the pH range of 4.0-9.0. Above pH 9.0, Na2U2O7 might play an important role in the rise of U(VI) adsorption again. Counter ions such as Cl(-), SO4(2-) and PO4(3-) can provoke U(VI) adsorption on BsG to some extent, which was directly correlated to the complexing ability of U(VI)-ligand. More noticeably, the large enhancement of U(VI) adsorption in the presence of phosphate can be attributed to the ternary complex formation (BsG-PO4-UO2), precipitation ((UO2)3(PO4)2(s)) and secondary phase (Na-autunite). Both FA and HA can slightly increase U(VI) adsorption at low pH, whereas they strongly inhibited U(VI) adsorption at high pH range. Artificial synthesized granite (AsG) prepared in the laboratory is impossible to use as an analogue of natural granite because of the large difference in the adsorption and surface properties.

Occurrence of Uranium Ores in the Schist Formation of the Pre-Ordovician Portugal; OCCURENCE DE MINERAIS D'URANIUM DANS LES FORMATIONS DE SCHISTES ANTE-ORDOVICIENS

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

Lobato, C.P.; Ferrao, C.N.

1959-10-31

The occurrence of uranium ores in concentrations of economical interest in the pre-ordovician schists was noted by the first time, in the region of Pinhel, in November 1958. The occurrence is situated in a zone of graphitic brown-greyish schists which are enclosed in a formation of gneiss with tourmaline near the contact of the latter with the hercinian granite, which constitutes the Beiras' Massif. The uraniferous mineralization is constituted by autunite down to the depth which has been reached by the explorntion work. The radiometric study and the sampling taken nt the depth of about ten meters suggest the continuitymore » of the structure and the persistence of the mineralization associated with it. The structural type and the distribution of the mineralization in the joints and the brecciated zone of the schists suggest that the deposition of uranium ore is not syngenetic, but, rather, that it is attribated to the circulation of mineralized solutions through the breakage produced along the hypothermal veilns, in a posterior reopening connected to the last movements of the alpidic orogenesis. The content obtained in the sampling reveals the existence of an enlarged ore deposit following the directions of the schistosity, wfth an extension of 140 meters and with the medium content of 0.27% U/sub 3/O/ sub 8/. (auth)« less

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.

Mechanisms of uranium interactions with hydroxyapatite: Implications for groundwater remediation

USGS Publications Warehouse

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

2002-01-01

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

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

Uranium deposits in Grant County, New Mexico

USGS Publications Warehouse

Granger, Harry C.; Bauer, Herman L.; Lovering, Tom G.; Gillerman, Elliot

1952-01-01

The known uranium deposits of Grant county, N. Mex., are principally in the White Signal and Black Hawk districts. Both districts are within a northwesterly-trending belt of pre-Cambrian rocks, composed chiefly of granite with included gneisses, schists, and quartzites. Younger dikes and stocks intrude the pre-Cambrian complex. The White Signal district is on the southeast flanks of the Burro Mountains; the Black Hawk district is about 18 miles northwest of the town of White Signal. In the White Signal district the seconday uranium phosphates--autunite and torbernite--occur as fracture coatings and disseminations in oxidized parts of quartz-pyrite veins, and in the adjacent mafic dikes and granites; uraniferous limonite is common locally. Most of the known uraniferous deposits are less that 50 feet in their greatest dimension. The most promising deposits in the district are on the Merry Widow and Blue Jay claims. The richest sample taken from the Merry Widow mine contained more than 2 percent uranium and a sample from the Blue Jay property contained as much as 0.11 percent; samples from the other properties were of lower grade. In the Black Hawk district pitchblende is associated with nickel, silver, and cobalt minerals in fissure veins. The most promising properties in the Black Hawk district are the Black Hawk, Alhambra, and Rose mines. No uranium analyses from this district were available in 1951. There are no known minable reserves of uranium ore in either district, although there is some vein material at the Merry Widow mine of ore grade, if a market were available in the region.

Potential toxic elements in stream sediments, soils and waters in an abandoned radium mine (central Portugal).

PubMed

Antunes, I M H R; Neiva, A M R; Albuquerque, M T D; Carvalho, P C S; Santos, A C T; Cunha, Pedro P

2018-02-01

The Alto da Várzea radium mine (AV) exploited ore and U-bearing minerals, such as autunite and torbernite. The mine was exploited underground from 1911 to 1922, closed in 1946 without restoration, and actually a commercial area is deployed. Stream sediments, soils and water samples were collected between 2008 and 2009. Stream sediments are mainly contaminated in As, Th, U and W, which is related to the AV radium mine. The PTEs, As, Co, Cr, Sr, Th, U, W, Zn, and electrical conductivity reached the highest values in soils collected inside the mine influence. Soils are contaminated with As and U and must not be used for any purpose. Most waters have pH values ranging from 4.3 to 6.8 and are poorly mineralized (EC = 41-186 µS/cm; TDS = 33-172 mg/L). Groundwater contains the highest Cu, Cr and Pb contents. Arsenic occurs predominantly as H 2 (AsO 4 ) - and H(AsO 4 ) 2- . Waters are saturated in goethite, haematite and some of them also in lepidocrocite and ferrihydrite, which adsorbs As (V). Lead is divalent in waters collected during the warm season, being mobile in these waters. Thorium occurs mainly as Th(OH) 3 (CO 3 ) - , Th(OH) 2 (CO 3 ) and Th(OH) 2 (CO 3 ) 2 2- , which increase water Th contents. Uranium occurs predominantly as UO 2 CO 3 , but CaUO 2 (CO 3 ) 3 2- and CaUO 2 (CO 3 ) 3 also occur, decreasing its mobility in water. The waters are contaminated in NO 2 - , Mn, Cu, As, Pb and U and must not be used for human consumption and in agricultural activities. The water contamination is mainly associated with the old radium mine and human activities. A restoration of the mining area with PTE monitoring is necessary to avoid a public hazard.

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

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

PubMed Central

Chandwadkar, Pallavi; Nayak, Chandrani

2017-01-01

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

Geology of the Midnite uranium mine, Stevens County, Washington; a preliminary report

USGS Publications Warehouse

Nash, J. Thomas; Lehrman, Norman J.

1975-01-01

The Midnite mine is one of only two mines in the United States currently producing uranium from discordant deposits in crystalline host rocks. Ore bodies are in metamorphosed steeply dipping Precambrian pelitic and calcareous rocks of a roof pendant adjacent to a Cretaceous(?) porphyritic quartz monzonite pluton. Production during 14 years, of operation has been about 8 million pounds of U3O8 from oxidized and reduced ores averaging 0.23 percent U3O8. Uranium deposits are generally tabular in form and dimensions range up to 380 m long, 210 m wide, and 50 m thick. Deposits are bounded on at least one side by unmineralized intrusive ribs of granitic rock, and thickest mineralized zones invariably occur at depressions in the intrusive contact. Upper limits of some deposits are nearly horizontal, and upper elevations of adjacent mineralized zones separated by ribs of granite are similar. Near surface ore is predominantly autunite, but ore at depth consists of pitchblende and coffinite with abundant pyrite and marcasite. Uranium minerals occur as .disseminations along foliation, replacements, and stockwork fracture-fillings. No stratigraphic controls on ore deposition are recognized. Rather, mineralized zones cut across lithologic boundaries if permeability is adequate. Most ore is in muscovite schist and mica phyllite, but important deposits occur in calc-silicate hornfels. Amphibolite sills and mid-Tertiary dacite dikes locally, carry ore where intensely fractured. High content of iron and sulfur, contained chiefly in FeS2, appear to be an important feature of favorable host rocks. Geometry of deposits, structural, and geochemical features suggest that uranium minerals were deposited over a span of time from late Cretaceous to late Tertiary. Ore occurs in but is not offset by a shear zone that displaces mid-Tertiary rocks.. Economic zones of uranium are interpreted to have been secondarily enriched in late Tertiary time by downward and lateral migration of uranium into permeable zones where deposition was influenced by ground water controls and minerals that could reduce or neutralize uranium-bearing solutions.

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.

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

PubMed

Acharya, Celin; Chandwadkar, Pallavi; Nayak, Chandrani

2017-05-01

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

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

Variations in the uranium isotopic compositions of uranium ores from different types of uranium deposits

NASA Astrophysics Data System (ADS)

Uvarova, Yulia A.; Kyser, T. Kurt; Geagea, Majdi Lahd; Chipley, Don

2014-12-01

Variations in 238U/235U and 234U/238U ratios were measured in uranium minerals from a spectrum of uranium deposit types, as well as diagenetic phosphates in uranium-rich basins and peraluminous rhyolites and associated autunite mineralisation from Macusani Meseta, Peru. Mean δ238U values of uranium minerals relative to NBL CRM 112-A are 0.02‰ for metasomatic deposits, 0.16‰ for intrusive, 0.18‰ for calcrete, 0.18‰ for volcanic, 0.29‰ for quartz-pebble conglomerate, 0.29‰ for sandstone-hosted, 0.44‰ for unconformity-type, and 0.56‰ for vein, with a total range in δ238U values from -0.30‰ to 1.52‰. Uranium mineralisation associated with igneous systems, including low-temperature calcretes that are sourced from U-rich minerals in igneous systems, have low δ238U values of ca. 0.1‰, near those of their igneous sources, whereas uranium minerals in basin-hosted deposits have higher and more variable values. High-grade unconformity-related deposits have δ238U values around 0.2‰, whereas lower grade unconformity-type deposits in the Athabasca, Kombolgie and Otish basins have higher δ238U values. The δ234U values for most samples are around 0‰, in secular equilibrium, but some samples have δ234U values much lower or higher than 0‰ associated with addition or removal of 234U during the past 2.5 Ma. These δ238U and δ234U values suggest that there are at least two different mechanisms responsible for 238U/235U and 234U/238U variations. The 234U/238U disequilibria ratios indicate recent fluid interaction with the uranium minerals and preferential migration of 234U. Fractionation between 235U and 238U is a result of nuclear-field effects with enrichment of 238U in the reduced insoluble species (mostly UO2) and 235U in oxidised mobile species as uranyl ion, UO22+, and its complexes. Therefore, isotopic fractionation effects should be reflected in 238U/235U ratios in uranium ore minerals formed either by reduction of uranium to UO2 or chemical precipitation in the form of U6+ minerals. The δ238U values of uranium ore minerals from a variety of deposits are controlled by the isotopic signature of the uranium source, the efficiency of uranium reduction in the case of UO2 systems, and the degree to which uranium was previously removed from the fluid, with less influence from temperature of ore formation and later alteration of the ore. Uranium isotopes are potentially superb tracers of redox in natural systems.

Radioactive deposits in California

USGS Publications Warehouse

Walker, George W.; Lovering, Tom G.

1954-01-01

Reconnaissance examination by Government geologists of many areas, mine properties, and prospects in California during the period between 1948 and 1953 has confirmed the presence of radioactive materials in place at more than 40 localities. Abnormal radioactivity at these localities is due to concentrations of primary and secondary uranium minerals, to radon gas, radium (?), and to thorium minerals. Of the known occurrences only three were thought to contain uranium oxide (uranitite or pitchblende), 4 contained uranium-bearing columbate, tantalate, or titanate minerals, 12 contained secondary uranium minerals, such as autunite, carnotite, and torbernite, one contained radon gas, 7 contained thorium minerals, and, at the remaining 16 localities, the source of the anomalous radiation was not positively determined. The occurrences in which uranium oxide has been tentatively identified include the Rathgeb mine (Calaveras County), the Yerih group of claims (San Bernardino County), and the Rainbow claim (Madera County). Occurrences of secondary uranium minerals are largely confined to the arid desert regions of south-eastern California including deposits in San Bernardino, Kern, Inyo, and Imperial Counties. Uranium-bearing columbate, tantalate, or titanate minerals have been reported from pegmatite and granitic rock in southeastern and eastern California. Thorium minerals have been found in vein deposits in eastern San Bernardino County and from pegmatites and granitic rocks in various parts of southeastern California; placer concentrations of thorium minerals are known from nearly all areas in the State that are underlain, in part, by plutonic crystalline rocks. The primary uranium minerals occur principally as minute accessory crystals in pegmatite or granitic rock, or with base-metal sulfide minerals in veins. Thorium minerals also occur as accessory crystals in pegmatite or granitic rock, in placer deposits derived from such rock, and, at Mountain Pass, in veins containing rare earths. Secondary uranium minerals have been found as fracture coatings and as disseminations in various types of wall rock, although they are largely confined to areas of Tertiary volcanic rocks. Probably the uranium in the uraniferous deposits in California is related genetically to felsic crystalline rocks and felsic volcanic rocks; the present distribution of the secondary uranium minerals has been controlled, in part, by circulating ground waters and probably, in part, by magmatic waters related to the Tertiary volcanic activity. The thorium minerals are genetically related to the intrusion of pegmatite and plutonic crystalline rocks. None of the known deposits of radioactive minerals in California contain marketable reserves of uranium or thorium ore under economic conditions existing in 1952. With a favorable local market small lots of uranium ore may be available in the following places: the Rosamund prospect, the Rafferty and Chilson properties, the Lucky Star claim, and the Yerih group. The commercial production of thorium minerals will be possible, in the near future, only if these minerals can be recovered cheaply as a byproduct either from the mining of rare earths minerals at Mountain Pass or as a byproduct of placer mining for gold.

Spatial distribution of environmental risk associated to a uranium abandoned mine (Central Portugal)

NASA Astrophysics Data System (ADS)

Antunes, I. M.; Ribeiro, A. F.

2012-04-01

The abandoned uranium mine of Canto do Lagar is located at Arcozelo da Serra, central Portugal. The mine was exploited in an open pit and produced about 12430Kg of uranium oxide (U3O8), between 1987 and 1988. The dominant geological unit is the porphyritic coarse-grained two-mica granite, with biotite>muscovite. The uranium deposit consists of two gaps crushing, parallel to the coarse-grained porphyritic granite, with average direction N30°E, silicified, sericitized and reddish jasperized, with a width of approximately 10 meters. These gaps are accompanied by two thin veins of white quartz, 70°-80° WNW, ferruginous and jasperized with chalcedony, red jasper and opal. These veins are about 6 meters away from each other. They contain secondary U-phosphates phases such as autunite and torbernite. Rejected materials (1000000ton) were deposited on two dumps and a lake was formed in the open pit. To assess the environmental risk of the abandoned uranium mine of Canto do Lagar, were collected and analysed 70 samples on stream sediments, soils and mine tailings materials. The relation between samples composition were tested using the Principal Components Analysis (PCA) (multivariate analysis) and spatial distribution using Kriging Indicator. The spatial distribution of stream sediments shows that the probability of expression for principal component 1 (explaining Y, Zr, Nb, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Hf, Th and U contents), decreases along SE-NW direction. This component is explained by the samples located inside mine influence. The probability of expression for principal component 2 (explaining Be, Na, Al, Si, P, K, Ca, Ti, Mn, Fe, Co, Ni, Cu, As, Rb, Sr, Mo, Cs, Ba, Tl and Bi contents), increases to middle stream line. This component is explained by the samples located outside mine influence. The spatial distribution of soils, shows that the probability of expression for principal component 1 (explaining Mg, P, Ca, Ge, Sr, Y, Zr, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, W, Th and U contents) decreases along SE direction and increases along NE and SW directions. The probability of expression for principal component 2 (explaining pH, K, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr and Pb contents), decreases from central points (inside mine influence) to peripheral points (outside mine influence) and gradually increases along N and SW directions. The spatial distribution of tailing materials did not allowed a consistent spatial distribution. In general, the stream sediments are classified as unpolluted and not polluted or moderately polluted, according to geoaccumulation Müller index with exception of local samples, located inside mine influence. The soils cannot be used for public, private or residential uses according to the Canadian soil legislation. However, almost samples can be used for commercial or industrial occupation. According to the target values and intervention values for soils remediation, these soils need intervention. Tailing materials samples are much polluted in thorium (Th) and uranium (U) and they cannot be used for public, private or residential uses.

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

Beryl-bearing pegmatites in the Ruby Mountains and other areas in Nevada and northwestern Arizona

USGS Publications Warehouse

Olson, Jerry C.; Hinrichs, E. Neal

1960-01-01

Pegmatite occurs widely in Nevada and northwestern Arizona, but little mining has been done for such pegmatite minerals as mica, feldspar, beryl, and lepidolite. Reconnaissance for beryl-bearing pegmatite in Nevada and in part of Mohave County, Ariz., and detailed studies in the Dawley Canyon area, Elko County, Nev., have shown that beryl occurs in at least 11 districts in the region. Muscovite has been prospected or mined in the Ruby and Virgin Mountains, Nev., and in Mohave County, Ariz. Feldspar has been mined in the southern part of the region near Kingman, Ariz., and in Clark County, Nev. The pegmatites in the region range in age from Precambrian to late Mesozoic or Tertiary. Among the pegmatite minerals found or reported in the districts studied are beryl, chrysoberyl, scheelite, wolframite, garnet, tourmaline, fluorite, apatite, sphene, allanite, samarskite, euxenite, gadolinite, monazite, autunite, columbite-tantalite, lepidolite, molybdenite, and pyrite and other sulflde minerals. The principal beryl-bearing pegmatites examined are in the Oreana and Lakeview (Humboldt Canyon) areas, Pershing County; the Dawley Canyon area in the Ruby Mountains, Elko County, Nev.; and on the Hummingbird claims in the Virgin Mountains, Mohave County, Ariz. Beryl has also been reported in the Marietta district, Mineral County; the Sylvania district, Esmeralda County; near Crescent Peak and near Searchlight, Clark County, Nev.; and in the Painted Desert near Hoover Dam, Mohave County, Ariz. Pegmatites are abundant in the Ruby Mountains, chiefly north of the granite stock at Harrison Pass. In the Dawley Canyon area of 2.6 square miles at least 350 pegmatite dikes more than 1 foot thick were mapped, and beryl was found in small quantities in at least 100 of these dikes. Four of these dikes exceed 20 feet in thickness, and 1 is 55 feet thick. A few pegmatites were also examined in the Corral Creek, Gilbert Canyon, and Hankins Canyon areas in the Ruby Mountains.The pegmatite dikes in the Dawley Canyon area intrude granite and metamorphic rocks which consist chiefly of quartzite and schist of probable Early Cambrian age. The granite is of two types: a biotite-muscovite granite that forms the main mass of the stock and albite granite that occurs in the metamorphic rocks near the borders of the stock. The pegmatites were emplaced chiefly along fractures in the granite and along schistosity or bedding planes in the metamorphic rocks.Many of the Dawley Canyon pegmatite dikes are zoned, having several rock units of contrasting mineralogy or grain size formed successively from the walls inward. Aplitic units occur either as zones or in irregular positions in the pegmatite dikes and are a distinctive feature of the Dawley Canyon pegmatites. Some of the aplitic and fine-grained pegmatite units are characterized by thin layers of garnet crystals, forming many parallel bands on outcrop surfaces. The occurrence of aplitic and pegmatitic textures in the same dike presumably indicates abrupt changes in physical-chemical conditions during crystallization, such as changes in viscosity and in content of volatile constituents. Concentrations of 0.1 percent or more beryl, locally more than 1 percent, occur in certain zones in the Dawley Canyon pegmatites. Spectrographic analyses of 23 samples indicate that the BeO content ranges from 0.0017 to 0.003 percent in the albite granite, from ,0.0013 to 0.039 percent in aplitic units in pegmatite, from 0.0005 to 0.10 percent in coarse-grained pegmatite, and from less than 0.0001 to 0.0004 percent in massive quartz veins. The scheelite-beryl deposits at Oreana and in Humboldt Canyon, Pershing County, are rich in beryllium. Twelve samples from the Lakeview (Humboldt Canyon) deposit range from 0.018 to 0.11 percent BeO, but underground crosscuts have failed to intersect similar rock at depth. Beryl locally constitutes as much as 10 percent of the pegmatitic ore at Oreana. The beryl was not recovered during tungsten mining at Oreana and is now in the tailings of the mill at Toulon, Nev. The percentage of beryl is lower than the Oreana ore because of dilution by tailings from other ores milled at Toulon. Beryl has been found in many pegmatite dikes in the Virgin Mountains. Both beryl and chrysoberyl occur in dikes on the Hummingbird claims, north of Virgin Peak, in Mohave County, Ariz. Spectrographic analyses of 5 representative samples of the principal dike on the Hummingbird claims range from 0.055 to 0.11 percent BeO.