Vannapha Phrommavanh

Mobile uranium(IV)-bearing colloids in a mining-impacted wetland.

Tetravalent uranium is commonly assumed to form insoluble species, resulting in the immobilization of uranium under reducing conditions. Here we present the first report of mobile U(IV)-bearing colloids in the environment, bringing into question this common assumption. We investigate the mobility of uranium in a mining-impacted wetland in France harbouring uranium concentrations of up to 14,000 p.p.m. As an apparent release of uranium into the stream passing through the wetland was observable, we examine soil and porewater composition as a function of depth to assess the geochemical conditions leading to this release. The analyses show the presence of U(IV) in soil as a non-crystalline species bound to amorphous Al-P-Fe-Si aggregates, and in porewater, as a distinct species associated with Fe and organic matter colloids. These results demonstrate the lability of U(IV) in these soils and its association with mobile porewater colloids that are ultimately released into surface water.

Geochemical control on uranium(IV) mobility in a mining-impacted wetland

Wetlands often act as sinks for uranium and other trace elements. Our previous work at a mining-impacted wetland in France showed that a labile noncrystalline U(IV) species consisting of U(IV) bound to Al-P-Fe-Si aggregates was predominant in the soil at locations exhibiting a U-containing clay-rich layer within the top 30 cm. Additionally, in the porewater, the association of U(IV) with Fe(II) and organic matter colloids significantly increased U(IV) mobility in the wetland. In the present study, within the same wetland, we further demonstrate that the speciation of U at a location not impacted by the clay-rich layer is a different noncrystalline U(IV) species, consisting of U(IV) bound to organic matter in soil. We also show that the clay-poor location includes an abundant sulfate supply and active microbial sulfate reduction that induce substantial pyrite (FeS2) precipitation. As a result, Fe(II) concentrations in the porewater are much lower than those at clay-impacted zones. U porewater concentrations (0.02-0.26 μM) are also considerably lower than those at the clay-impacted locations (0.21-3.4 μM) resulting in minimal U mobility. In both cases, soil-associated U represents more than 99% of U in the wetland. We conclude that the low U mobility reported at clay-poor locations is due to the limited association of Fe(II) with organic matter colloids in porewater and/or higher stability of the noncrystalline U(IV) species in soil at those locations.

Field analyses of (238)U and (226)Ra in two uranium mill tailings piles from Niger using portable HPGe detector.

The radioactivities of (238)U and (226)Ra in mill tailings from the U mines of COMINAK and SOMAÏR in Niger were measured and quantified using a portable High-Purity Germanium (HPGe) detector. The (238)U and (226)Ra activities were measured under field conditions on drilling cores with 600s measurements and without any sample preparation. Field results were compared with those obtained by Inductive Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) and emanometry techniques. This comparison indicates that gamma-ray absorption by such geological samples does not cause significant deviations. This work shows the feasibility of using portable HPGe detector in the field as a preliminary method to observe variations of radionuclides concentration with the aim of identifying samples of interest. The HPGe is particularly useful for samples with strong secular disequilibrium such as mill tailings.

Evolution of uranium distribution and speciation in mill tailings, COMINAK Mine, Niger.

This study investigated the evolution of uranium distribution and speciation in mill tailings from the COMINAK mine (Niger), in production since 1978. A multi-scale approach was used, which combined high resolution remote sensing imagery, ICP-MS bulk rock analyses, powder X-ray diffraction, Scanning Electron Microscopy, Focused Ion Beam--Transmission Electron Microscopy and X-ray Absorption Near Edge Spectroscopy. Mineralogical analyses showed that some ore minerals, including residual uraninite and coffinite, undergo alteration and dissolution during tailings storage. The migration of uranium and other contaminants depends on (i) the chemical stability of secondary phases and sorbed species (dissolution and desorption processes), and (ii) the mechanical transport of fine particles bearing these elements. Uranium is stabilized after formation of secondary uranyl sulfates and phosphates, and adsorbed complexes on mineral surfaces (e.g. clay minerals). In particular, the stock of insoluble uranyl phosphates increases with time, thus contributing to the long-term stabilization of uranium. At the surface, a sulfate-cemented duricrust is formed after evaporation of pore water. This duricrust limits water infiltration and dust aerial dispersion, though it is enriched in uranium and many other elements, because of pore water rising from underlying levels by capillary action. Satellite images provided a detailed description of the tailings pile over time and allow monitoring of the chronology of successive tailings deposits. Satellite images suggest that uranium anomalies that occur at deep levels in the pile are most likely former surface duricrusts that have been buried under more recent tailings.

Evaluation and application of Diffusive Gradients in Thin Films (DGT) technique using Chelex®-100, Metsorb™ and Diphonix® binding phases in uranium mining environments.

A new resin- Diphonix(®) in Diffusive Gradients in Thin Films (DGT) technique for the determination of uranium was investigated and compared with previously used binding phases for uranium, Chelex(®)-100 and Metsorb™. The DGT gel preparation and the elution procedure were optimized for the new resin. The U uptake on Diphonix(®) resin gel was 97.4 ± 1.5% (batch method; [U] = 20 μg L(-1); 0.01 M NaNO3; pH = 7.0 ± 0.2). The optimal eluent was found to be 1 M 1-hydroxyethane-1, 1-diphosphonic acid (HEDPA) with an elution efficiency of 80 ± 4.2%. Laboratory DGT study on U accumulation using a DGT samplers with Diphonix(®) resin showed a very good performance across a wide range of pH (3-9) and ionic strength (0.001-0.7 M NaNO3). Diffusion coefficients of uranium at different pH were determined using both, a diffusion cell and the DGT time-series, demonstrating the necessity of the implementation of the effective diffusion coefficients into U-DGT calculations. Diphonix(®) resin gel exhibits greater U capacity than Chelex(®)-100 and Metsorb™ binding phase gels (a Diphonix(®) gel disc is not saturated, even with loading of 10.5 μmol U). Possible interferences with Ca(2+) (up to 1.33 × 10(-2) M), PO4(3-) (up to 1.72 × 10(-4) M), SO4(2-) (up to 4.44 × 10(-3) M) and HCO3(-) (up to 8.20 × 10(-3) M) on U-DGT uptake ([U] = 20 μg L(-1)) were investigated. No effect or minor effect of Ca(2+), PO4(3-), SO4(2-), and HCO3(-) on the quantitative measurement of U by Diphonix(®)-DGT was observed. The results of this study demonstrated the DGT technique with Diphonix(®) resin is a reliable and robust method for the measurement of labile uranium species under laboratory conditions.

Screening of bacterial strains isolated from uranium mill tailings porewaters for bioremediation purposes

The present work characterizes at different levels a number of bacterial strains isolated from porewaters sampled in the vicinity of two French uranium tailing repositories. The 16S rRNA gene from 33 bacterial isolates, corresponding to the different morphotypes recovered, was almost fully sequenced. The resulting sequences belonged to 13 bacterial genera comprised in the phyla Firmicutes, Actinobacteria and Proteobacteria. Further characterization at physiological level and metals/metalloid tolerance provided evidences for an appropriate selection of bacterial strains potentially useful for immobilization of uranium and other common contaminants. By using High Resolution Transmission Electron Microscope (HRTEM), this potential ability to immobilize uranium as U phosphate mineral phases was confirmed for the bacterial strains Br3 and Br5 corresponding to Arthrobacter sp. and Microbacterium oxydans, respectively. Scanning Transmission Electron Microscope- High-Angle Annular Dark-Field (STEM-HAADF) analysis showed U accumulates on the surface and within bacterial cytoplasm, in addition to the extracellular space. Energy Dispersive X-ray (EDX) element-distribution maps demonstrated the presence of U and P within these accumulates. These results indicate the potential of certain bacterial strains isolated from porewaters of U mill tailings for immobilizing uranium, likely as uranium phosphates. Some of these bacterial isolates might be considered as promising candidates in the design of uranium bioremediation strategies.

Determination of Uranium source term in a Polluted Site: a multitechnique study

This study aims at understanding a potential migration of uranium in a polluted calcareous peat-land. Aqueous uranium monitoring indicates a seasonal variation of uranium content. During winter, aqueous uranium was found to be mostly under the +VI oxidation state, which is potentially mobile, while it was reduced into less soluble U(IV) species in summer. These observations were correlated with changes of the redox potential due to the activity of sulphate-reducing bacteria. A companion study (Phrommavanh et al., 2008 in this congress) focuses on the determination of the uranium aqueous speciation. Concurrently, one has to know the origin of the source term which is a part of the understanding of the uranium mobility. Several techniques were used in order to discriminate the chemical form of uranium: gamma spectrometry and aqua regia extractions on soil samples, porous PTFE quartz cells in order to sample the aqueous fraction, SEM observations with automatic U particles detection and XANES to assess the U redox state. The association of these different techniques gave consistent results with an increasing U content at a depth of 0.8 m. Such a localisation is explained by a redox front where anoxic and reducing conditions prevail.

Speciation of Uranium in a Polluted Site: a TRLFS study

The uranium speciation in a polluted soil was investigated to assess the possible impact on geo- and biosphere. During winter, uranium was found to be mostly under the +VI oxidation state, which is potentially mobile, while it was reduced into less soluble U(IV) species in summer. These observations were correlated with changes of the redox potential due to the activity of sulphate-reducing bacteria. The potential migration of uranium is also highly dependent on its aqueous speciation, particularly concerning U(VI). In this work, the speciation of U(VI) was investigated in real samples by using time-resolved laser-induced fluorescence spectroscopy (TRLFS) and speciation calculations. We show that U(VI) speciation can be determined in carbonate-rich solutions and at ambient temperature by using TRLFS on chemically-treated samples, to remove U(VI)-fluorescence-quenching molecules such as organics.

Chemical reactivity of natural peat towards U and Ra

Peat is a complex material with several organic constituents that contribute to its high capacity to retain metals. In the context of uranium mining, peat can accumulate high concentrations of uranium and its decay products such as radium. Hence, interaction with peat appears to be a key factor in the understanding of the geochemical mechanisms controlling the fate of these products. This study aims to determine the sorption properties of two trace elements, U(VI) and 226Ra, on natural organic matter from peat. The presented method was applied to both natural peat samples originating from a mining context, with various contents of organic matter (from 40 to 70%) and detrital loads, and wetland peat with a more than 98% composition of organic matter. In the present study, considering peat material as a sorbent, its reactivity towards metals and other contaminants can be described as that of an ion-exchanger. A relatively simple model of ion-exchange based on the sorption properties of carboxylic sites has been applied with success to describe the sorption of uranium and radium. In the general overview of the different mechanisms able to control the mobility of these radionuclides in a uranium mining context, organic matter is likely one of the main contributors to radionuclide scavenging even under oxic conditions.