Search

The long-term stability of immobilized elements of concern in uranium tailings deposited in the Deilmann Tailings Management Facility (DTMF), northern Saskatchewan, is dependent upon maintenance of highly oxic conditions within the tailings mass. The main objective of this study was to investigate the effect of stimulating microbial activity on the redox potential and state of ferrihydrite, which are considered to be the primary controlling condition and mineral phase, respectively, within the tailings. To determine the potential for biologically mediated decreases in redox potential and ferrihydrite reduction, a series of microcosm assays were performed. Non-sterile material from the tailings–water interface of the DTMF site was inoculated with indigenous flora previously isolated from the tailings material and enriched with a carbon source (50 ppm trypticase soy broth) and incubated under continuous-flow or intermittent-flow conditions, and compared with an uninoculated, no-carbon control that r...

The microbial diversity and biogeochemical potential associated with a northern Saskatchewan uranium mine water-tailings interface was examined using culture-dependent and -independent techniques. Morphologically-distinct colonies from uranium mine water-tailings and a reference lake (MC) obtained using selective and non-selective media were selected for 16S rRNA gene sequencing and identification, revealing that culturable organisms from the uranium tailings interface were dominated by Firmicutes and Betaproteobacteria; whereas, MC organisms mainly consisted of Bacteroidetes and Gammaproteobacteria. Ion Torrent (IT) 16S rRNA metagenomic analysis carried out on extracted DNA from tailings and MC interfaces demonstrated the dominance of Firmicutes in both of the systems. Overall, the tailings-water interface environment harbored a distinct bacterial community relative to the MC, reflective of the ambient conditions (i.e., total dissolved solids, pH, salinity, conductivity, heavy metals) dominating the uranium tailings system. Significant correlations among the physicochemical data and the major bacterial groups present in the tailings and MC were also observed. Presence of sulfate reducing bacteria demonstrated by culture-dependent analyses and the dominance of Desulfosporosinus spp. indicated by Ion Torrent analyses within the tailings-water interface suggests the existence of anaerobic microenvironments along with the potential for reductive metabolic processes.

In northern Saskatchewan, Canada, high-grade U ores and the resulting tailings can contain high levels of As. An environmental concern in the U mining industry is the long-term stability of As within tailings management facilities (TMFs) and its potential transfer to the surrounding groundwater. To mitigate this problem, U mill effluents are neutralized with lime to reduce the aqueous concentration of As. This results in the formation of predominantly Fe 3+ –As 5+ secondary mineral phases, which act as solubility controls on the As in the tailings discharged to the TMF. Because the speciation of As in natural systems is critical for determining its long-term environmental fate, characterization of As-bearing mineral phases and complexes within the deposited tailings is required to evaluate its potential transformation, solubility, and long-term stability within the tailings mass. In this study, synchrotron-based bulk X-ray absorption spectroscopy (XAS) was used to study the speciation of As and Fe in mine tailings samples obtained from the Deilmann TMF at Key Lake, Saskatchewan. Comparisons of K-edge X-ray absorption spectra of tailings samples and reference compounds indicate the dominant oxidation states of As and Fe in the mine tailings samples are +5 and +3, respectively, largely reflecting their generation in a highly oxic mill process, deposition in an oxidized environment, and complexation within stable oxic phases. Linear combination fit analyses of the K-edges for the Fe X-ray absorption near edge spectra (XANES) to reference compounds suggest Fe is predominantly present as ferrihydrite with some amount of the primary minerals pyrite (8–15% in some samples) and chalcopyrite (5–15% in some samples). Extended X-ray absorption fine structure (EXAFS) analysis of As K-edge spectra indicates that As 5+ (arsenate) present in tailings samples is adsorbed to the ferrihydrite though an inner-sphere bidentate linkage.

Uranium (U) ores can contain high concentrations of elements of concern (EOCs), such as arsenic (As) and nickel (Ni) present in sulfide and arsenide minerals. The U in these ores is often solubilized by adding H2SO4 to attain a pH ∼1 under oxic conditions. This process releases some EOCs from the primary minerals into solution. The barren raffinate (solution remaining after U extraction) is subsequently neutralized with Ca(OH)2 to a terminal pH of ∼10.5, resulting in a reduction in the aqueous concentrations of the EOCs. These neutralized raffinates are mixed with the non-reacted primary minerals and discharged as tailing into tailings management facilities (TMFs). To aid in the accurate characterization and quantification of the mineralogical controls on the concentrations of EOCs in the tailings porewater, their spatial distribution and speciation were studied at the micron scale in tailings samples collected from the Deilmann U Tailings Management Facility (DTMF), northern Saskatchewan, Canada. Backscattered electron images of the tailings samples generated using an electron microprobe show the presence of nodules (10–200 μm size) surrounded by bright rims. Wavelength dispersive spectrometric (WDS) and synchrotron-based micro-X-ray fluorescence (μ-XRF) elemental mapping show that the nodules are dominated by Ca and S (as gypsum) and the bright rims are dominated by Fe, As, and Ni. Micro-X-ray absorption near-edge structure (μ-XANES) spectra collected within and near the rims indicate that the Fe and Ni are present mainly in the +3 and +2 oxidation states, respectively; for As, the +5 oxidation state dominates but significant amounts of the +3 oxidation state are present in some areas. Linear combination fit analyses of the K-edges for the Fe, As, and Ni μ-XANES spectra to reference compounds suggest the Fe in the rims is present as ferrihydrite with As and Ni are adsorbed to it. Energy dispersive spectrometric (EDS) data indicate that isolated, highly reflective particles distributed throughout the tailings matrix are primary As-, Cu-, Fe-, and Ni-bearing minerals. Geochemical modeling of the neutralization process shows that the nodules (gypsum) formed at pH ∼1 and acted as a substrate for the precipitation of ferrihydrite at pH ∼3.4. The As and Ni subsequently adsorb to the ferrihydrite. Overall, the microscale data suggest that the As and Ni adsorbed onto the ferrihydrite should remain stable for many years and continue to the control the Fe, As, and Ni concentrations in the tailings porewater.

Uranium ore containing elevated concentrations of arsenic (up to 2 wt %) are processed at the McClean Lake Operation in the Athabasca Basin of northern Saskatchewan (Figure 1). This region of northern Saskatchewan is responsible for 33% of the world production of uranium [1]. A major concern of AREVA Resources Canada Inc. (AREVA) as well as provincial and federal regulators is the potential long-term risk that significant amounts of arsenic may pose to surrounding lakes and waters after their disposal in the JEB Tailings Management Facility (TMF). The regulatory limit is set at 5 mg/L for tailings pore water with an action level set by AREVA of 2 mg/L As.

Sorption and precipitation of Co(II) in simplified model systems related to the Hanford site high-level nuclear waste tank leakage were investigated through solution studies, geochemical modeling, and X-ray absorption fine structure (XAFS) spectroscopy. Studies of Co(II) sorption to pristine Hanford sediments (ERDF and Sub), which consist predominantly of quartz, plagioclase, and alkali feldspar, show an adsorption edge centered at pH ≈ 8.0 for both sediments studied, with sorption >99% above pH ≈ 9.0. Aqueous SiO 2 resulting from dissolution of the sediments increased in concentration with increasing pH, though the systems remained undersaturated with respect to quartz. XAFS studies of Co(II) sorption to both sediment samples reveal the oxidation of Co(II) to Co(III), likely by dissolved O 2 , although this oxidation was incomplete in the Sub sediment samples. The authors propose that Fe(II) species, either in aqueous solution or at mineral surfaces, partially inhibited Co(II) oxidation in the Sub sediment samples, as these sediments contain significantly higher quantities of Fe(II)-bearing minerals which likely partially dissolved under the high-pH solution conditions. In alkaline solutions, Al precipitated as bayerite, gibbsite, or a mixture of the two at pH > 7; an amorphous gel formed at pH values less than 7. Aqueous Co concentrations were well below the solubility of known Co-bearing phases at low pH, suggesting that Co was removed from solution through an adsorption mechanism. At higher pH values, Co concentrations closely matched the solubility of a Co-bearing hydrotalcite-like solid. XAFS spectra of Co(II) sorbed to Al-hydroxide precipitates are similar to previously reported spectra for such hydrotalcite-like phases. The precipitation processes observed in this study can significantly reduce the environmental hazard posed by 60 Co in the environment.

Radioactive core samples containing elevated concentrations of Cr from a high level nuclear waste plume in the Hanford vadose zone were studied to asses the future mobility of Cr. Cr(VI) is an important subsurface contaminant at the Hanford Site. The plume originated in 1969 by leakage of self-boiling supernate from a tank containing REDOX process waste. The supernate contained high concentrations of alkali (NaOH ≈ 5.25 mol/L), salt (NaNO3/NaNO2 >10 mol/L), aluminate [Al(OH)4− = 3.36 mol/L], Cr(VI) (0.413 mol/L), and 137Cs+ (6.51 × 10−5 mol/L). Water and acid extraction of the oxidized subsurface sediments indicated that a significant portion of the total Cr was associated with the solid phase. Mineralogic analyses, Cr valence speciation measurements by X-ray adsorption near edge structure (XANES) spectroscopy, and small column leaching studies were performed to identify the chemical retardation mechanism and leachability of Cr. While X-ray diffraction detected little mineralogic change to the sediments from waste reaction, scanning electron microscopy (SEM) showed that mineral particles within 5 m of the point of tank failure were coated with secondary, sodium aluminosilicate precipitates. The density of these precipitates decreased with distance from the source (e.g., beyond 10 m). The XANES and column studies demonstrated the reduction of 29–75% of the total Cr to insoluble Cr(III), and the apparent precipitation of up to 43% of the Cr(VI) as an unidentified, non-leachable phase. Both Cr(VI) reduction and Cr(VI) precipitation were greater in sediments closer to the leak source where significant mineral alteration was noted by SEM. These and other observations imply that basic mineral hydrolysis driven by large concentrations of OH− in the waste stream liberated Fe(II) from the otherwise oxidizing sediments that served as a reductant for CrO42−. The coarse-textured Hanford sediments contain silt-sized mineral phases (biotite, clinochlore, magnetite, and ilmenite) that are sources of Fe(II). Other dissolution products (e.g., Ba2+) or Al(OH)4− present in the waste stream may have induced Cr(VI) precipitation as pH moderated through mineral reaction. The results demonstrate that a minimum of 42% of the total Cr inventory in all of the samples was immobilized as Cr(III) and Cr(VI) precipitates that are unlikely to dissolve and migrate to groundwater under the low recharge conditions of the Hanford vadose zone.

Aims: To describe microbial diversity, biofilm composition and biogeochemical potential within biofilms in the water overlying uranium tailings characterized by high pH, high metal concentration and low permeability. Methods and Results: To estimate microbial diversity in biofilms formed in water columns overlying uranium mine tailings, culture-dependent and culture-independent methods were employed. High-throughput sequencing revealed the presence of 11 phyla; however, the majority of the sequences were affiliated with four major lineages (Proteobacteria, Bacteroidetes, Actinobacteria and Firmicutes) as confirmed by culture-based methods. Dominant phylotypes were closely related to methylotrophs (Methylobacterium) and bacterial groups able to utilize complex hydrocarbons (Aquabacterium and Dechloromonas). Microbial diversity in biofilms from the 13 m depth was significantly different that in biofilms from 1 to 41 m (P < 0� 05). Phylotypes closely related to ironreducing bacteria were identified at each depth; whereas sulphate-, thiosulphate-, sulphite- and sulphur-reducing bacteria, at low abundance, were only detected at lower depths. Confocal scanning laser microscopy (CSLM) was used to investigate polymer quantity and composition of the biofilm components, and principal component analysis of the CLSM data revealed that the relative abundance of a-L-fucose and N-acetyl-glucosamine/ lipopolysaccharide residues separated tailings–water interface biofilms from those from other depths. Reduced (ferrous) iron was detected within all the biofilm samples examined by scanning X-ray transmission microscopy. Conclusions: Microbial communities within the water column covering a highly alkaline uranium tailings body form biofilms with microenvironments where iron reduction takes place. Significance and Impact of the Study: This study demonstrates the biogeochemical potential of microbial biofilm communities in the water column covering an alkaline uranium tailings body; specifically, the nature of the bacterial groups detected (Aquabacterium, Dechloromonas) and the presence of reduced iron suggest that complex hydrocarbons are available for bacterial growth and geochemical change, such as iron reduction, can occur even though the system bulk phase is predominantly oxic.

We evaluate the hypothesis that the reactivity trend for iodination of natural humic substances (HS) resembles that for the iodination of some substituted phenols. The hypothesis was tested by comparing the rates of reaction of I2(aq) with HS and a series of eight substituted phenolic compounds. Rates of iodination for all of the phenolic compounds, except salicylate, are described with an empirical rate law R = kobs[phenolic compound]1[I3-]1[[H+]-1[I-]-2] with the values of kobs related to the structure of the substituted phenol. The values of kobs, corresponding to iodination of the simple substituted phenols, range from 5.6 × 10-8 to 4.7 × 10-5 M s-1 at 25 °C. These rate coefficients can be predicted over at least three orders-of-magnitude from a modified Hammett relation. The rates of iodination of HS fall within the range measured for substituted phenols, suggesting that iodination of the natural HS proceed by similar pathways. The humic substances differ markedly in their reactivity toward I2(aq) in...

Aims: To describe the diversity and metabolic potential of microbial communities in uranium mine tailings characterized by high pH, high metal concentration and low permeability. Methods and Results: To assess microbial diversity and their potential to influence the geochemistry of uranium mine tailings using aerobic and anaerobic culture-based methods, in conjunction with next generation sequencing and clone library sequencing targeting two universal bacterial markers (the 16S rRNA and cpn60 genes). Growth assays revealed that 69% of the 59 distinct culturable isolates evaluated were multiple-metal resistant, with 15% exhibiting dual-metal hypertolerance. There was a moderately positive correlation coefficient (R = 0·43, P < 0·05) between multiple-metal resistance of the isolates and their enzyme expression profile. Of the isolates tested, 17 reduced amorphous iron, 22 reduced molybdate and seven oxidized arsenite. Based on next generation sequencing, tailings depth was shown to influence bacterial community composition, with the difference in the microbial diversity of the upper (0-20 m) and middle (20-40 m) tailings zones being highly significant (P < 0·01) from the lower zone (40-60 m) and the difference in diversity of the upper and middle tailings zone being significant (P < 0·05). Phylotypes closely related to well-known sulfate-reducing and iron-reducing bacteria were identified with low abundance, yet relatively high diversity. Conclusions: The presence of a population of metabolically-diverse, metal-resistant micro-organisms within the tailings environment, along with their demonstrated capacity for transforming metal elements, suggests that these organisms have the potential to influence the long-term geochemistry of the tailings. Significance and Impact of the study: This study is the first investigation of the diversity and functional potential of micro-organisms present in low permeability, high pH uranium mine tailings.

Reaction of iodide [I−(aq)] with a series of volcanic-ash soils was compared with reaction onto noncrystalline materials that constitute much of the inorganic fraction of these soils, Our hypothesis is that these high-surface-area materials account for iodide retention by providing sites for anion exchange. Iodide sorption onto imogolite and ferrihydrite is rapid (

Uranium mill tailings from northern Saskatchewan, Canada contain elevated levels of As and Ni. The potential mobilization of these elements from the tailings management facilities to regional groundwater systems is an environmental concern for the uranium mining industry. In this study, electron microprobe analysis and synchrotron-based microfocussing X-ray fluorescence mapping and absorption spectroscopy (μ-XRF; μ-XAS) were used to identify and characterize the chemical composition of As-, Ni-, and Fe-bearing mineral phases at the micron scale in mine tailings samples from the Deilmann Tailings Management Facility (DTMF) located at the Key Lake mill of Cameco Corp. in northern Saskatchewan, Canada.

The Department of Energy's Hanford Nuclear Site located in Washington State has accumulated over 2 million curies of radioactive waste from activities related to the production of plutonium (Ahearne, 1997). Sixty-seven of the single-shelled tanks located at the site are thought to have leaked, allowing between 2 and 4 million liters of waste fluids into the underlying vadose zone. The chemical processes employed at the Hanford Site to extract plutonium, as well as the need to minimize corrosion of the high-carbon steel storage tanks, resulted in uncharacterized hyperalkaline waste streams rich in radionuclides as well as other species including significant amounts of sodium and aluminum.

Research Group at Stanford University, we have investigated adsorption processes that could lead to the sequestration of Cr, Co, Sr, and U on minerals representative of the Hanford Vadose Zone sediments and precipitation processes resulting in alkali aluminate solids that form from the highly alkaline and aluminum-rich leachates reacting with these sediments. These elements are among the most important pollutants of concern to the Department of Energy at the Hanford Site in Washington State. The aqueous solutions used in these experiments were simplified surrogates of Tank leachates (i.e., they contained high Na and Al and had pH values of 10-12 in many cases). We have examined the following processes that could lead to sequestration of these pollutant elements: (1) the sorption/coprecipitation of these elements in solids formed from reaction of alkaline aluminate solutions with simple systems of minerals representative of those found in the soils and sediments underlying the Hanford Tank Farm (e.g., quartz, feldspars, clay minerals, iron oxides); (2) the sorption/coprecipitation of these elements in solids formed from reaction of alkaline aluminate solutions with soil and sediment samples obtained from the Hanford site; and (3) the effect of aging on the stability of sorption complexes on Al-oxide and Al-oxyhydroxidemore » surfaces formed from neutralization and homogeneous nucleation of alkaline aluminate solutions. Our investigations have utilized X-ray Absorption Fine Structure (XAFS) spectroscopy, electron and X-ray microprobe analyses, X-ray diffraction and small angle X-ray scattering, and inductively coupled plasma emission spectrometry analysis, as described below.« less

International audience; To Investigate the role played by nickel co-ions in contributing to the stability of arsenic, fluorescence XAFS measurements at both arsenic K-edge and nickel K-edge, respectively, on amorphous arsenical nickel hydroxide, crystalline arsenical nickel hydroxide, and annabergite reference compounds have been carried out. The XAFS results indicate that the arsenic-bearing nickel hydroxides have a well-defined arsenic local structure with multiple coordination shells, suggesting a compound formation mechanism instead of surface adsorption. The degradation of the arsenic local structure in the crystalline arsenical nickel hydroxide is observed. The XAFS of annabergites are compared to that of the arsenical nickel hydroxide and possible structural models are discussed.

Debye-Waller factors for the As-O-O triangular multiple scattering paths within the arsenate in Na2HAsO4·7H2O are evaluated in terms of magnitude ratio with respect to the Debye-Waller factor of the nearest neighbour As-O shell (σ2As−0−0/σ2As-0). The arsenates are studied under two different levels of distortion from an ideal tetrahedron, i.e. a relatively high distortion in the powder form and a nearly ideal tetrahedron in an aqueous solution at pH 14. The Debye-Waller factor ratio σ2As−0−0/σ2As-0) is found to be 2.0 and 1.9 for the powder and liquid sample, respectively, appearing to be insensitive to the distortion of the arsenate tetrahedron.

Review of the mineral chemistry, crystallography, mosaic assemblages, and oriented inclusions of lunar rock sample 76535, and discussion of its depth of formation. Its texture, chemistry, and phase relationships are shown to indicate that it formed deep within the lunar crust. It is the first crystalline lunar rock found to date to contain evidence of a high pressure mineral assemblage formed under static conditions.

Approximately 25 per cent of the glasses in two Apollo 14 soil samples and in the soils at two levels in the Luna 16 core have compositions equivalent to anorthositic gabbro. Reassessment of the non-mare glass components in the Apollo 11 and 12 soils shows that glasses with the composition of anorthositic gabbro are common to both; gabbroic anorthosite glasses are less common, and anorthositic glasses, rare. Anorthositic gabbro glasses have the same major element composition at all four sites, and resemble the Surveyor 7 analysis from a ‘highland’ site. Thus, strong presumptive evidence exists that material with this specific composition is abundant in the lunar highlands.

Extensive microprobe analyses have been made of pyroxenes, plagioclases, olivines, opaque minerals, and glasses in two 0.025 g lunar samples returned from the Luna 16 mission, with the aim to characterize the Mare Fecunditatis regolith. No major differences were found between the near surface soil horizon A and horizon D at approximately 30 cm depth. Resulting characteristics of the mineral examined are presented and discussed.

Ten percent of the 50–150 micron size fraction of Luna 20 soil is glass. A random suite of 270 of these glasses has been analyzed by electron microprobe techniques. The major glass type forms a strong cluster around a mean value corresponding to Highland basalt (anorthositic gabbro) with 70% normative feldspar. Minor glass groups have the compositions of mare basalts and of low-K Fra Mauro type basalts. The glass data indicate that Highland basalt is the major rock type in the highlands north of Mare Fecunditatis.

Approximately 180 glasses in each of three Apollo 15 soils have been analyzed for nine elements. Cluster analysis techniques allow the recognition of preferred glass compositions that are equated with parent rock compositions. Green glass rich in Fe and Mg, poor in Al and Ti may be derived from deep-seated pyroxenitic material now present at the Apennine Front. Fra Mauro basalt (KREEP) is most abundant in the LM soil and is tentatively identified as ray material from the Aristillus-Autolycus area. Highland basalt (anorthositic gabbro), believed to be derived from the lunar highlands, has the same composition as at other landing sites, but is less abundant. The Apennine Front is probably not true highland material but may contain a substantial amount of material with the composition of Fra Mauro basalt, but lacking the high-K content.