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The mill tailings from uranium mines constitute very low-level, long-lived, radioactive process waste. Their longterm management therefore requires a good understanding of the geochemical mechanisms regulating the mobility of residual U and 226 Ra. 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 supplemented by thermodynamic equilibrium models to predict the long-term mobility of U and 226 Ra. 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 226 Ra of 12x10-6 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 226 Ra 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 226 Ra. 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 226 Ra on the other hand is trapped mainly within the barite. The aqueous concentrations of U and 226 Ra 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 226 Ra at very low aqueous concentrations, even under oxidizing conditions. Moreover, the low permeability of the mill tailings leads, in the case of 226 Ra, to behavior dictated only by the radioactive decay. Highlights (no more than 85 characters, including spaces)  U mill tailings from Bellezane (France) were studied...

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Barite is ubiquitous and known to incorporate 226Ra through the formation of a solid-solution. In U mining mill tailings, barite is one of the dominant sulfate-binding minerals. In such environments, sequential extractions are generally used to identify the U- and 226Ra-binding phases and their associated reactivity. To better decipher the main processes governing the behavior of 226Ra during such sequential extractions, a geochemical model was developed with PHREEQC mimicking the sequential extraction of U and 226Ra from Bois-Noirs Limouzat U mine tailings, France. The model results were compared with a dataset produced by an experimental sequential extraction from the same mine tailings and including data on the solids and selective extraction results with the major elements, U and 226Ra. The simulations reproduced the results of the experimental chemical extractions accurately, with iron oxyhydroxides being the major U binding phase. However, the modeling indicated rather that barite would be the main 226Ra binding phase, instead of the iron oxyhydroxides identified by the experimental extractions. This is consistent with the 226Ra concentration measured in pore water, but in disagreement with the direct interpretation of the sequential extractions. The direct interpretation disregarded the role of barite in the geochemical behavior of 226Ra because barite was not specifically targeted by any of the extraction steps. However, the modeling showed that the dissolution of 226Ra-binding barite by reactants would lead to a 226Ra redistribution among the clay minerals, resulting in a skew in the experimental results. Similar results were achieved by referring simply to the bulk mineralogy of the tailings. This study highlights the importance of considering the mineralogy, mineral reactivity and retention capacity for more realistic interpretation of sequential extractions. Moreover, this paper provides new perspectives on the long-term consequences of these mill tailings in which barite controls the geochemical behavior of the 226Ra.