Quantifying 226Ra activity in a complex assemblage of 226Ra-bearing minerals using alpha autoradiography and SEM/EDS.

226Ra is an ultra-trace element with important environmental implications for many industries (including water treatment and oil and mineral extraction). Its extremely low concentrations in natural environments do not allow for direct observation and measurement of the 226Ra-bearing minerals governing 226Ra mobility. To better understand the retention processes for 226Ra in rocks and soil, a synthesized assemblage of 226Ra-doped minerals was made, combining montmorillonite, ferrihydrite and barite. A new methodology was developed using alpha activity maps acquired using alpha autoradiography, and elemental maps by using SEM/EDS. These maps were processed using a global approach, considering the entirety of the signal. The comparison of the alpha activity map and the elemental map enabled a correlation to be established between the 226Ra activity and the chemical composition and identification of the main 226Ra-bearing mineral of the assemblage, from which we were able to estimate the contribution of each mineral to the total activity of the assemblage, and to quantify the 226Ra-activity for each mineral. This methodology makes it possible to link mineralogy and occurrence of 226Ra at the scale of the mineral (tens of µm). It can be applied to natural samples, including fine-grained samples with a complex mineralogy.

Uranium speciation control by uranyl sulfate and phosphate in tailings subject to a Sahelian climate, Cominak, Niger.

Long-term uranium mobility in tailings is an environmental management issue. The present study focuses on two U-enriched layers, surficial and buried 14.5 m, of the tailings pile of Cominak, Niger. The acidic and oxidizing conditions of the tailings pile combined with evapotranspiration cycles related to the Sahelian climate control U speciation. Uraninite, brannerite, and moluranite as well as uranophane are relict U phases. EXAFS spectroscopy, HR-XRD, and SEM/WDS highlight the major role of uranyl sulfate groups in uranium speciation. Uranyl phosphate neoformation in the buried layer (paleolayer) acts as an efficient trap for uranium.

Uranium retention on iron oxyhydroxides in post-mining environmental conditions.

Investigating uranium migration mechanisms related to the weathering of waste rocks is essential for developing strategies that can address the potential environmental issues caused by uranium mining. This work is based on environmental samples containing 2 L ferrihydrite, lepidocrocite and goethite collected in the technosols from granitic waste rock piles, mine drainage conduits and mine waters. The results show the important role of iron oxyhydroxide in U immobilization and re-concentration. EXAFS spectroscopy combined with mineralogical and geochemical studies (Scanning electronic microscopy, Wavelength-dispersive X-ray spectroscopy microprobe, inductively coupled plasma - optical emission spectrometry/mass spectrometry and X-ray diffraction) allowed for the identification of uranyl ternary surface complexes at the ferrihydrite surface that were either composed of phosphate groups or organic matter. Moreover, goethite and lepidocrocite were also identified as a secondary trap for U immobilization. U(VI) is known to be mobile in oxidizing conditions. This study highlights the control of the uranyl mobility by various iron oxyhydroxides in supergene conditions.

Geochemical characterization of uranium mill tailings (Bois Noirs Limouzat, France) highlighting the U and 226Ra retention.

As with other metals, the management of tailings from former uranium (U) mines requires a good knowledge of the geochemical mechanisms governing the retention of radioelements of interest: U and 226Ra. This article presents the results of the study of the bearing phases featuring these two radioelements within the Bois Noirs Limouzat tailings storage facility (Loire), the only site in France where the tailings (a sandy silt facies and a clayey silt facies) are currently stored only under water. The aim is to gain a better understanding of their respective mobility under current storage conditions. For this purpose, a multi-scale approach was adopted combining historical research and airborne image analysis to select the core location, chemical and radiological analyses, mineralogical characterizations supplemented by sequential extractions (two specifically developed protocols). The results show that U and 226Ra are mainly found in the clayey silt facies with an average U concentration of 243.3 ppm (132.3 ppm in the sandy silt facies) and an average 226Ra mass activity of 64.7Bq/g (18.0Bq/g in the sandy silt facies). These results are in accordance with the initial U grade of the ore (2‰), the extraction efficiency of the ore processing plant (95%) and the age of mineralization (305 Ma). The approach adopted made it possible to highlight several mineralogical traps available for each radioelement, regardless of the facies type. Thus, a significant part of the U is still trapped within the primary phases, resistant to treatment and therefore relatively immobile under current storage conditions (49.6%-77.8% for the sandy silt facies and 27.2%-36% for the clayey silt facies). Most of the leached U is mainly associated with weakly crystalised iron oxyhydroxides (8.7%-42.4% for the sandy silt facies and 50.9%-71.8% for the clayey silt facies) and to a lesser extent with clay minerals (5%-12.3% for the sandy silt facies and 0.8%-11.5% for the clayey silt facies). For the 226Ra, irrespective of the facies type, a significant part remains trapped within phosphate phases, resistant to the leaching process and therefore also relatively immobile under storage conditions (24.4%-38.9% for the silty sandy silt facies and 39.9%-98.9% for the clayey silt facies). Sequential extractions revealed a different geochemistry of 226Ra depending on the facies. For the silty sandy silt facies, most of the 226Ra is mainly associated with the clay minerals (6.4%-69.2%) and to a lesser extent with iron oxyhydroxides, barite or aluminum phosphate sulphate minerals (APS) (6.4%-33.9%). For the clayey silt facies, most of the 226Ra is mainly associated with iron oxyhydroxides, barite or APS (6.4%-53.3%) and to lesser extent clay minerals (0.4%-6.8%). The leaching process did not allow the differentiation between the contributions of each of these phases to the retention of 226Ra. At last, all the identified bearing phases demonstrate that the U is relatively immobile under the current storage conditions, irrespective of the facies. For the 226Ra, the bearing phases differ according to the facies. Within the sandy silt facies, the 226Ra is mainly borne by clay minerals and can be mobilised more easily. However, the sandy silt facies represents only one third of the tailings currently.

Uranium speciation in weathered granitic waste rock piles: an XAFS investigation.

Investigation of uranium migration in the waste piles of granite rock in the Limousin region of France is vital for developing strategies which address related environmental issues. Despite the fact that the concentration of uranium is far below the lower end of the cut off level in these piles, the large volume of rocks - which measure in the hundreds of metric tons - and their conditions of repository make this type of waste a source of concern for the international community. In this work, X-ray absorption spectroscopy techniques (XAFS) were employed in order to identify the speciation of uranium in the different categories of samples collected from various regions of the rock piles which had undergone 50 years of weathering. The samples, such as weathered granite, arena and technosoils, were studied in order to probe the transformation of the U bearing complex. XANES indicates U(vi) valence with uranyl species in all samples. Using a linear combination analysis and shell fitting approach, distinct speciation of uranium was observed in the different categories of samples. In the weathered rock and arena samples with relics of magmatic U minerals, uranyl phosphates comparable to autunite are shown to be dominantly linked with monodentate PO4 3-. However, the samples collected from technosoils are found to have a mixture of U-phosphate and U-clay minerals (phyllosilicates and silicates). Irrespective of the collection location, all the samples were found to contain U(vi)-oxo species The equatorial O ligands occur as two shells with an average separation of 0.14-0.21 Å. Moreover, all the samples have an Al/Si/P shell around 3.1 Å. A detailed EXAFS curve fit analysis shows that disorder afflicts the entire range of samples which can be attributed to either inhomogeneous binding sites on the disordered clay minerals or to the presence of a mixture of uranium-bearing minerals. XAFS investigations highlight the uranyl overriding forms of U (as U sorbed on clay minerals and secondary uranyl phosphates or silicates) contribute to the retention of U, even in oxidizing conditions known to enhance the mobility of U.

Mineralizing Filamentous Bacteria from the Prony Bay Hydrothermal Field Give New Insights into the Functioning of Serpentinization-Based Subseafloor Ecosystems.

Despite their potential importance as analogs of primitive microbial metabolisms, the knowledge of the structure and functioning of the deep ecosystems associated with serpentinizing environments is hampered by the lack of accessibility to relevant systems. These hyperalkaline environments are depleted in dissolved inorganic carbon (DIC), making the carbon sources and assimilation pathways in the associated ecosystems highly enigmatic. The Prony Bay Hydrothermal Field (PHF) is an active serpentinization site where, similar to Lost City (Mid-Atlantic Ridge), high-pH fluids rich in H2 and CH4 are discharged from carbonate chimneys at the seafloor, but in a shallower lagoonal environment. This study aimed to characterize the subsurface microbial ecology of this environment by focusing on the earliest stages of chimney construction, dominated by the discharge of hydrothermal fluids of subseafloor origin. By jointly examining the mineralogy and the microbial diversity of the conduits of juvenile edifices at the micrometric scale, we find a central role of uncultivated bacteria belonging to the Firmicutes in the ecology of the PHF. These bacteria, along with members of the phyla Acetothermia and Omnitrophica, are identified as the first chimneys inhabitants before archaeal Methanosarcinales. They are involved in the construction and early consolidation of the carbonate structures via organomineralization processes. Their predominance in the most juvenile and nascent hydrothermal chimneys, and their affiliation with environmental subsurface microorganisms, indicate that they are likely discharged with hydrothermal fluids from the subseafloor. They may thus be representative of endolithic serpentinization-based ecosystems, in an environment where DIC is limited. In contrast, heterotrophic and fermentative microorganisms may consume organic compounds from the abiotic by-products of serpentinization processes and/or from life in the deeper subsurface. We thus propose that the Firmicutes identified at PHF may have a versatile metabolism with the capability to use diverse organic compounds from biological or abiotic origin. From that perspective, this study sheds new light on the structure of deep microbial communities living at the energetic edge in serpentinites and may provide an alternative model of the earliest metabolisms.

Microbial diversity in a submarine carbonate edifice from the serpentinizing hydrothermal system of the Prony Bay (New Caledonia) over a 6-year period.

Active carbonate chimneys from the shallow marine serpentinizing Prony Hydrothermal Field were sampled 3 times over a 6 years period at site ST09. Archaeal and bacterial communities composition was investigated using PCR-based methods (clone libraries, Denaturating Gel Gradient Electrophoresis, quantitative PCR) targeting 16S rRNA genes, methyl coenzyme M reductase A and dissimilatory sulfite reductase subunit B genes. Methanosarcinales (Euryarchaeota) and Thaumarchaea were the main archaeal members. The Methanosarcinales, also observed by epifluorescent microscopy and FISH, consisted of two phylotypes that were previously solely detected in two other serpentinitzing ecosystems (The Cedars and Lost City Hydrothermal Field). Surprisingly, members of the hyperthermophilic order Thermococcales were also found which may indicate the presence of a hot subsurface biosphere. The bacterial community mainly consisted of Firmicutes, Chloroflexi, Alpha-, Gamma-, Beta-, and Delta-proteobacteria and of the candidate division NPL-UPA2. Members of these taxa were consistently found each year and may therefore represent a stable core of the indigenous bacterial community of the PHF chimneys. Firmicutes isolates representing new bacterial taxa were obtained by cultivation under anaerobic conditions. Our study revealed diverse microbial communities in PHF ST09 related to methane and sulfur compounds that share common populations with other terrestrial or submarine serpentinizing ecosystems.

Spatial distribution of microbial communities in the shallow submarine alkaline hydrothermal field of the Prony Bay, New Caledonia.

The shallow submarine hydrothermal field of the Prony Bay (New Caledonia) discharges hydrogen- and methane-rich fluids with low salinity, temperature (< 40°C) and high pH (11) produced by the serpentinization reactions of the ultramafic basement into the lagoon seawater. They are responsible for the formation of carbonate chimneys at the lagoon seafloor. Capillary electrophoresis single-strand conformation polymorphism fingerprinting, quantitative polymerase chain reaction and sequence analysis of 16S rRNA genes revealed changes in microbial community structure, abundance and diversity depending on the location, water depth, and structure of the carbonate chimneys. The low archaeal diversity was dominated by few uncultured Methanosarcinales similar to those found in other serpentinization-driven submarine and subterrestrial ecosystems (e.g. Lost City, The Cedars). The most abundant and diverse bacterial communities were mainly composed of Chloroflexi, Deinococcus-Thermus, Firmicutes and Proteobacteria. Functional gene analysis revealed similar abundance and diversity of both Methanosarcinales methanoarchaea, and Desulfovibrionales and Desulfobacterales sulfate-reducers in the studied sites. Molecular studies suggest that redox reactions involving hydrogen, methane and sulfur compounds (e.g. sulfate) are the energy driving forces of the microbial communities inhabiting the Prony hydrothermal system.