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

The 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.

Evaluation of the efficacy of a portable LIBS system for detection of CWA on surfaces.

Laser-induced breakdown spectroscopy (LIBS) is a laser-based optical technique particularly suited for in situ surface analysis. A portable LIBS instrument was tested to detect surface chemical contamination by chemical warfare agents (CWAs). Test of detection of surface contamination was carried out in a toxlab facility with four CWAs, sarin (GB), lewisite (L1), mustard gas (HD), and VX, which were deposited on different substrates, wood, concrete, military green paint, gloves, and ceramic. The CWAs were detected by means of the detection of atomic markers (As, P, F, Cl, and S). The LIBS instrument can give a direct response in terms of detection thanks to an integrated interface for non-expert users or so called end-users. We have evaluated the capability of automatic detection of the selected CWAs. The sensitivity of our portable LIBS instrument was confirmed for the detection of a CWA at surface concentrations above 15 µg/cm(2). The simultaneous detection of two markers may lead to a decrease of the number of false positive.

Laser-induced breakdown spectroscopy (LIBS) for carbon single shot analysis of micrometer-sized particles.

The purpose of this work is to study the ability of the laser-induced breakdown spectroscopy (LIBS) technique to perform in situ (without sample preparation) detection of graphite particles circulating in a gas loop used to simulate the cooling gas circuit of a helium-cooled nuclear reactor. Results obtained with a laboratory scale set up are presented. The experiments were performed in nitrogen with micrometer-sized particles containing carbon (glucose particles and sodium hydrogenocarbonate particles). Statistical shot to shot analysis was used to determine the concentration of the analyte. The variation of LIBS signal as a function of glucose particle diameter showed an underestimation of the signal of particles of diameters larger than 5 microm. This phenomenon is likely to be correlated to an incomplete vaporization in the laser-induced plasma of particles of sizes above 5 microm. Analytical measurements were performed with glucose particles and sodium hydrogenocarbonate particles, and the concentration-based limit of detection of carbon was evaluated to be about 60 microg m(-3).

Mars analysis by laser-induced breakdown spectroscopy (MALIS): influence of mars atmosphere on plasma emission and study of factors influencing plasma emission with the use of doehlert designs.

A project called MALIS (Mars Analysis by Laser-Induced breakdown Spectroscopy) is under progress to perform in situ analysis of Mars soils and rocks. This paper reports on the behavior of plasma in Martian conditions, i.e., in a CO2 atmosphere at pressures between 5 and 12 mbar. Plasma expansion and lifetime have been studied in order to compare plasma evolution under standard conditions (air at atmospheric pressure) and in a Mars atmosphere. We have shown that the Mars environment favors plasma expansion and lifetime. The second part of the study concerns optimization of the emission signal from the plasma. An original approach has been chosen, as we used a Doehlert design for the first time in laser-induced breakdown spectroscopy (LIBS). The best conditions obtained are for a laser wavelength of 1064 nm with the maximum energy available due to space limitations, which is 40 mJ at 15 Hz. The other factors studied are delay, angle of incidence, and CO2 pressure. We have shown that these factors do not have the same influence depending on which spectroscopic line is used, i.e., the atomic line or the ionic line.