Sorption Properties of Peat for U(VI) and 226Ra in U Mining Areas

AbstractUnderstanding the environmental behavior of U and 226Ra is important for remediation of former mining sites and assessment of their durability. The aim of this study is to determine the sorption properties of an acidic peat for U and 226Ra, located near a former U mine. A 90% retention of U over a pH range of 3 to 10 was observed in Na- conditioned peat samples issued from the mesotelm, with a Rd between 1000 and 12000 mL/g. It seems that U sorption in peat is not only governed by organic matter. The Kd for 226Ra adsorption increases with pH from zero to 4849 mL/g. However in this mining environment, the peat bog proved to be significantly impacted by anthropogenic activities, with the presence of detrital components in the peat material that can also contribute to U and Ra sorption

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 mu M) are also considerably lower than those at the clay-impacted locations (0.21-3.4 mu M) 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

Etude de la migration de l'uranium en milieu naturel : approche expérimentale et modélisation géochimique

The present study deals with characterizing uranium migration in a limited zone of Le Bouchet site, a former uranium ore treatment facility, which is dismantled and the rehabilitation of which is under process. Some wastes are packed in a rehabilitated disposal nearby, called the Itteville site. In the framework of the monitoring of the deposit environment (air, water, sediment) set by prefectorial decrees, a piezometer (PZPK) located downstream to the latter, has shown total dissolved uranium peaks each winter since the 1990's. PZPK collects both the interstitial water of a calcareous peat formation, between the surface and 3 m, and an alluvial aquifer near 6 m of depth. Firstly, a hydrogeochemical characterization of the site has evidenced the uranium source term, which is present in the peat soil near 0.8 m, hence excluding any leaching from the waste disposal. Actually, a few microparticles of uranium oxide and mixed uranium-thorium oxide have been detected, but they do not represent the major part of the source term. Secondly, water chemistry of the peat soil water and PZPK has been monitored every two months from 2004 to 2007 in order to understand the reasons of the seasonal fluctuations of [U]tot.diss.. Completed with geochemical modeling and a bacterial identification by 16S rDNA sequence analysis, water chemistry data showed an important sulfate-reducing bacterial activity in summertime, leading to reducing conditions and therefore, a total dissolved uranium content limited by the low solubility of uraninite UIVO2(s). In wintertime, the latter bacterial activity being minimal and the effective pluviometry more important, conditions are more oxidant, which favors U(VI), more soluble, notably as the Ca2UO2(CO3)3(aq) complex, evidenced by TRLFS. Finally, bacterial activity has been reproduced in laboratory in order to better characterize its impact on uranium solubility in the peat soil. Various parameters were tested (C sources, temperature, nutrients) to recreate conditions close and also different to those in situ. 16S rDNA sequence bacterial identifications, throughout the incubation time, have confirmed an increase of sulfate-reducing bacteria proportion. At the same time, water chemistry, as well as geochemical calculations and SEM observations and XANES analyses, have evidenced an decrease of [U]tot.diss., owing to its reduction as UO2(s) (certainly as nanoparticles). Even though the reaction mechanism could not be determined, that is to say biotic (direct uranium reduction by bacteria) or abiotic (indirect reduction), these experiments have showed that sulfate-reducing bacteria can prevail among a varied indigenous population in conditions close to those in situ. Moreover, the studied calcareous peat contains a significant amount of weddellite (CaC2O4.2H2O(s)), accounting for a permanent input of oxalate ions C2O42- which can be used as C source in the course of sulfate and/or uranium reduction in the summer.Cette étude est consacrée à la caractérisation de la migration de l'uranium dans une zone restreinte du site du Bouchet, ancienne usine de traitement de minerai d'uranium, aujourd'hui démantelé et en cours de réhabilitation. Certains déchets de cette usine ont été stockés dans une déposante réhabilitée à proximité, appelée le site d'Itteville. Dans le cadre de la surveillance de l'environnement autour de la déposante (air, eau, sédiment) imposée par arrêtés préfectoraux, un piézomètre (PZPK) situé à l'aval hydraulique de cette dernière, présente des pics d'uranium dissous total chaque hiver depuis les années 1990. Le PZPK collecte à la fois les eaux d'une formation tourbeuse calcique, saturée en eau, située entre la surface et 3 m, ainsi que l'eau d'une nappe alluviale vers 6 m de profondeur. Dans un premier temps, une caractérisation hydrogéochimique du site a mis en évidence le terme source d'uranium, qui se trouve dans la tourbe vers 0,8 m, écartant ainsi toute fuite provenant de la déposante. En effet, quelques microparticules d'oxyde d'uranium et d'oxyde mixte d'uranium-thorium ont été détectées, mais ne constituent pas la partie majeure du terme source. Dans un second temps, la chimie des eaux de tourbe et du PZPK a fait l'objet d'un suivi bimestriel de 2004 à 2007 permettant de comprendre les raisons des fluctuations saisonnières de [U]tot.diss.. Complétées par des modélisations géochimiques et une identification bactérienne par analyse de l'ADN 16S, les chroniques de chimie de l'eau ont mis en évidence une activité bactérienne sulfato-réductrice importante en été, entraînant des conditions plus réductrices et donc, une teneur en uranium dissous total limitée par la faible solubilité de l'uraninite UIVO2(s). En hiver, cette activité bactérienne étant minime et la pluviométrie efficace plus importante, les conditions sont plus oxydantes favorisant la forme U(VI), plus soluble, notamment sous la forme du complexe Ca2UO2(CO3)3(aq) mis en évidence par SLRT. Enfin, l'activité bactérienne sulfato-réductrice a été reproduite en laboratoire afin de mieux caractériser son impact sur la solubilité de l'uranium dans la tourbe. Divers paramètres ont été étudiés (sources de C, température, nutriments) afin de recréer des conditions à la fois proches et aussi éloignées de celles in situ. Les identifications bactériennes par analyse de l'ADN 16S, en fonction du temps d'incubation, ont confirmé une augmentation de la proportion des bactéries sulfato-réductrices. Parallèlement, la chimie de l'eau, ainsi que des calculs géochimiques et des observations MEB et analyses XANES, ont mis en évidence une diminution de [U]tot.diss., due à sa réduction en UO2(s) (certainement sous forme de nanoparticules). Bien que le mécanisme réactionnel n'ait pu être déterminé, à savoir biotique (réduction directe de U par les bactéries) ou abiotique (réduction indirecte), ces expériences ont montré que les bactéries sulfato-réductrices peuvent prévaloir au sein d'une population autochtone variée dans des conditions proches de celles in situ. De plus, la tourbe calcique étudiée contient un stock important de weddellite (CaC2O4.2H2O(s)), constituant un apport permanent d'ions oxalate C2O42- qui peuvent être utilisés comme source de C lors de la réduction des ions sulfate et/ou uranium en été

Etude de la migration de l'uranium en milieu naturel : approche expérimentale et modélisation géochimique

Cette étude est consacrée à la caractérisation de la migration de l'uranium dans une zone restreinte du site du Bouchet, ancienne usine de traitement de minerai d'uranium, aujourd'hui démantelé et en cours de réhabilitation. Certains déchets de cette usine ont été stockés dans une déposante réhabilitée à proximité, appelée le site d'Itteville. Dans le cadre de la surveillance de l'environnement autour de la déposante (air, eau, sédiment) imposée par arrêtés préfectoraux, un piézomètre (PZPK) situé à l'aval hydraulique de cette dernière, présente des pics d'uranium dissous total chaque hiver depuis les années 1990. Le PZPK collecte à la fois les eaux d'une formation tourbeuse calcique, saturée en eau, située entre la surface et 3 m, ainsi que l'eau d'une nappe alluviale vers 6 m de profondeur. Dans un premier temps, une caractérisation hydrogéochimique du site a mis en évidence le terme source d'uranium, qui se trouve dans la tourbe vers 0,8 m, écartant ainsi toute fuite provenant de la déposante. En effet, quelques microparticules d'oxyde d'uranium et d'oxyde mixte d'uranium-thorium ont été détectées, mais ne constituent pas la partie majeure du terme source. Dans un second temps, la chimie des eaux de tourbe et du PZPK a fait l'objet d'un suivi bimestriel de 2004 à 2007 permettant de comprendre les raisons des fluctuations saisonnières de [U]tot.diss.. Complétées par des modélisations géochimiques et une identification bactérienne par analyse de l'ADN 16S, les chroniques de chimie de l'eau ont mis en évidence une activité bactérienne sulfato-réductrice importante en été, entraînant des conditions plus réductrices et donc, une teneur en uranium dissous total limitée par la faible solubilité de l'uraninite UIVO2(s). En hiver, cette activité bactérienne étant minime et la pluviométrie efficace plus importante, les conditions sont plus oxydantes favorisant la forme U(VI), plus soluble, notamment sous la forme du complexe Ca2UO2(CO3)3(aq) mis en évidence par SLRT. Enfin, l'activité bactérienne sulfato-réductrice a été reproduite en laboratoire afin de mieux caractériser son impact sur la solubilité de l'uranium dans la tourbe. Divers paramètres ont été étudiés (sources de C, température, nutriments) afin de recréer des conditions à la fois proches et aussi éloignées de celles in situ. Les identifications bactériennes par analyse de l'ADN 16S, en fonction du temps d'incubation, ont confirmé une augmentation de la proportion des bactéries sulfato-réductrices. Parallèlement, la chimie de l'eau, ainsi que des calculs géochimiques et des observations MEB et analyses XANES, ont mis en évidence une diminution de [U]tot.diss., due à sa réduction en UO2(s) (certainement sous forme de nanoparticules). Bien que le mécanisme réactionnel n'ait pu être déterminé, à savoir biotique (réduction directe de U par les bactéries) ou abiotique (réduction indirecte), ces expériences ont montré que les bactéries sulfato-réductrices peuvent prévaloir au sein d'une population autochtone variée dans des conditions proches de celles in situ. De plus, la tourbe calcique étudiée contient un stock important de weddellite (CaC2O4.2H2O(s)), constituant un apport permanent d'ions oxalate C2O42- qui peuvent être utilisés comme source de C lors de la réduction des ions sulfate et/ou uranium en été.The present study deals with characterizing uranium migration in a limited zone of Le Bouchet site, a former uranium ore treatment facility, which is dismantled and the rehabilitation of which is under process. Some wastes are packed in a rehabilitated disposal nearby, called the Itteville site. In the framework of the monitoring of the deposit environment (air, water, sediment) set by prefectorial decrees, a piezometer (PZPK) located downstream to the latter, has shown total dissolved uranium peaks each winter since the 1990 s. PZPK collects both the interstitial water of a calcareous peat formation, between the surface and 3 m, and an alluvial aquifer near 6 m of depth. Firstly, a hydrogeochemical characterization of the site has evidenced the uranium source term, which is present in the peat soil near 0.8 m, hence excluding any leaching from the waste disposal. Actually, a few microparticles of uranium oxide and mixed uranium-thorium oxide have been detected, but they do not represent the major part of the source term. Secondly, water chemistry of the peat soil water and PZPK has been monitored every two months from 2004 to 2007 in order to understand the reasons of the seasonal fluctuations of [U]tot.diss.. Completed with geochemical modeling and a bacterial identification by 16S rDNA sequence analysis, water chemistry data showed an important sulfate-reducing bacterial activity in summertime, leading to reducing conditions and therefore, a total dissolved uranium content limited by the low solubility of uraninite UIVO2(s). In wintertime, the latter bacterial activity being minimal and the effective pluviometry more important, conditions are more oxidant, which favors U(VI), more soluble, notably as the Ca2UO2(CO3)3(aq) complex, evidenced by TRLFS. Finally, bacterial activity has been reproduced in laboratory in order to better characterize its impact on uranium solubility in the peat soil. Various parameters were tested (C sources, temperature, nutrients) to recreate conditions close and also different to those in situ. 16S rDNA sequence bacterial identifications, throughout the incubation time, have confirmed an increase of sulfate-reducing bacteria proportion. At the same time, water chemistry, as well as geochemical calculations and SEM observations and XANES analyses, have evidenced an decrease of [U]tot.diss., owing to its reduction as UO2(s) (certainly as nanoparticles). Even though the reaction mechanism could not be determined, that is to say biotic (direct uranium reduction by bacteria) or abiotic (indirect reduction), these experiments have showed that sulfate-reducing bacteria can prevail among a varied indigenous population in conditions close to those in situ. Moreover, the studied calcareous peat contains a significant amount of weddellite (CaC2O4.2H2O(s)), accounting for a permanent input of oxalate ions C2O42- which can be used as C source in the course of sulfate and/or uranium reduction in the summer.GRENOBLE1-BU Sciences (384212103) / SudocSudocFranceF

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

International audienceThe radioactivities of 238U and 226Ra in mill tailings from the U mines of COMINAK and SOMA€IR in Niger were measured and quantified using a portable High-Purity Germanium (HPGe) detector. The 238U and 226Ra 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

Estimating the stabilities of actinide aqueous species. Influence of sulfoxy-anions on uranium(IV) geochemistry and discussion of Pa(V) first hydrolysis

International audienc

A multi-scalar study of the long-term reactivity of uranium mill tailings from Bellezane site (France)

International audienceThe mill tailings from uranium mines constitute very low-level, long-lived, radioactive process waste. Their long-term management therefore requires a good understanding of the geochemical mechanisms regulating the mobility of residual uranium and radium-226. This article presents the results of the detailed characterization of the tailings resulting from the dynamic leaching processes used on the ore of the La Crouzille mining division and stored at the Bellezane site (Haute-Vienne, France) for over 25 years. A multi-scalar and multidisciplinary approach was developed based on a study of the site's history, on the chemical, radiological and mineralogical characterizations of the solid fraction of the tailings, and on porewater analyses. These were complemented by thermodynamic equilibrium models to predict the long-term mobility of U and 226Ra. Weakly acidic (pH = 6.35) and oxidizing (Eh = 138 mV/SHE) porewaters had a sulfated-magnesian facies ([SO4]tot = 43 mmol/L; [Mg]tot = 33 mmol/L) with an accessory calcium bicarbonate component (TIC = 25 mmol/L; [Ca]tot = 13 mmol/L) and dissolved concentrations of uranium and 226Ra of 12 × 10−6 mol/L and 0.58 Bq/L respectively. Ultra-filtration at 10 kDa indicated the absence of colloidal phases. The characterization of the tailings confirmed their homogeneity from a radiological, chemical and mineralogical point of view. The residual U and 226Ra concentrations measured in the solid were 160 ppm and 25 Bq/g respectively, in accordance with the initial ore grades and mill yields, or more than 99% of the total stock. In terms of chemical and mineralogical composition, the tailings were mainly composed of minerals from the granitic ore (quartz, potassium feldspar, plagioclases and micas) in association with their weathering products (smectite and ferric oxyhydroxides) and with neo-formed minerals following rapid diagenesis after neutralization of the tailings before their emplacement (gypsum and barite). All these minerals are effective traps for the retention of U and 226Ra. The uranium is distributed partly in micrometer scale uraninite and coffinite refractory phases embedded in grains of quartz, and partly sorbed to smectite and ferric oxyhydroxides. The 226Ra on the other hand is trapped mainly within the barite. The aqueous concentrations of U and 226Ra could be described using a thermodynamic approach so that their long-term mobility can subsequently be assessed by modeling. The paragenesis of the tailings could be seen to be stable over time with the exception of neo-formed gypsum and calcite, which will gradually dissolve. The presence of retention traps offering surplus capacity, i.e. smectite, ferric oxyhydroxides and barite, will maintain the U and the 226Ra at very low aqueous concentrations, even under oxidizing conditions. Moreover, the low permeability of the mill tailings leads, in the case of 226Ra, to behavior dictated only by the radioactive decay