A combined DGT - DET approach for an in situ investigation of uranium resupply from large soil profiles in a wetland impacted by former mining activities.

An in situ methodology combining DET and DGT probes was applied in a wetland soil, downstream of a former uranium mine (Rophin), to evaluate metal resupply by calculating the R ratio (R = [U]DGT/[U]pore water) from a high resolution and large (75 cm) soil profile. Our study confirms its applicability in soil layers with varying properties; only soil layers with low water content or coarse texture appear to be limiting factors. For soil profiles, DET provides new insights of the distribution of Uranium as soluble species (free ions, small inorganic complexes, …) along the pore water profile, whereas DGT highlights the presence of other "DGT labile" species. The pairing of DET and DGT, plus the calculation of the R, highlights two U behaviors in combining results from red-ox sensitive elements (Mn, Fe). First, in the organic topsoil layer, an increase in [U]DET and [U]DGT at 3-4 cm reflects the desorption of U probably trapped onto Fe- and Mn-oxohydroxides in a DGT-labile form. However, the resupply from soil to pore water is close to a diffusion only case (R < 0.2) meaning that a portion of U is certainly tightly bound by OM in soil as non-labile species. Second, a peak in [U]DGT perfectly corresponding to the former mine deposit layer signifies the presence of U under DGT-labile species. Moreover, a maximum R value of 0.87 demonstrates the near complete resupply of U from a labile fraction in this layer, as opposed to other elements like Pb.

Flow period influence on uranium and trace elements release in water from the waste rock pile of the former La Commanderie uranium mine (France).

Uranium mining activities expose uranium ore and mine tailings to the surface environment, where the release of radionuclides is facilitated by weathering at rates exceeding those typically found in nature. Therefore, close to former uranium mining sites, radionuclides and especially uranium concentrations in water may surpass local background levels. The methodology proposed herein, entails coupling, gamma-ray mapping, water sampling and chemical analyses including DGT (Diffusive Gradient in Thin Film) measurements, provides new insights into describing the environment of the La Commanderie site (France). Gamma-ray mapping allows identifying water seepage, output from a waste rock pile, as a potential pathway for radionuclides into the environment. Water seepage monitoring has shown: a low pH value (4.2), high sulfate content (179 mg.L-1) and high uranium concentrations of up to 436 µg.L-1. These recordings indicate that an acid mining drainage (AMD) process is occurring inside or under the oxidized parts of the waste rock pile. Monitoring data over three flow periods revealed the release of the highest uranium concentrations during a high-flow period downstream of the site, which is compliant with local regulations. The AMD process is also responsible for the release of significant amounts of Fe, Mn and As within the immediate environment in both dissolved and particulate forms. Changes in dissolved oxygen concentration and redox potential during low flow periods, modify the speciation of Fe (in AMD waters) which acts as a scavenger for other elements such as As, Mn and U. The use of DGT under environmental conditions, and specifically AMD waters, seems to be relevant in comparison to filtered spot water sampling strategies. Moreover, based on DGT measurements, the dissolved part of the released uranium is considered as labile with concentrations above the environmental standards for freshwater organisms.

Towards speciation of organically bound tritium and deuterium: Quantification of non-exchangeable forms in carbohydrate molecules.

An original methodology to quantitatively explore exchangeability of hydrogen isotopes in carbohydrate molecules is proposed. To access the speciation of organically bound hydrogen isotopes, isotopic exchanges were carried out under a soft path regime in the vapor phase at 20 °C with set (D,T/H) vapor pressure ratios. When steady states were reached, the fraction of exchangeable hydrogen of microcrystalline cellulose, alpha-cellulose and wheat grains were obtained and ranged from 13 to 31% (versus a theoretical value of 30%). In cellulose, and more specifically in microcrystalline cellulose, the molecular hydrogen bonds as well as the different conformations of the network seemed to decrease the hydroxyl groups of glucose units available for isotopic exchange. On the contrary, the assumed enzymatic hydrolysis of the constitutive molecules of wheat starch into low-molecular weight carbohydrate molecules enhanced the exchangeable pool. An average value of the activity between non-exchangeable organically bound tritium (NE-OBT) and non-exchangeable organically bound hydrogen was calculated for wheat grains, (TH)NE  = 0.55 ±â€¯0.03 Bq.g-1 of hydrogen atoms.

Alteration of vitrified intermediate level nuclear waste in alkaline media: effects of cementitious materials, pH and temperature.

Alteration experiments involving intermediate level nuclear waste (ILW) glass in contact with hardened cement paste (HCP) were performed to assess its behavior under simulated repository conditions. Batch experiments were conducted at 20 °C and 50 °C in several artificial cement pore water (ACW) samples (pH from 10 to 13), in the presence of HCP (CEM-I, CEM-V and low pH), with a ratio of glass surface to volume of solution of 8000 m-1 and a ratio of mass of HCP to volume of solution of 10 g L-1. Glass alteration rates increase up to ∼4 × 10-2 g m-2 d-1 with pH in contact with HCP, notably with CEM-I. This value decreases by 2 orders of magnitude in low pH cement solution and also for residual alteration rates. The effect of calcium on glass alteration was observed, mainly in Ca(OH)2 saturated solution, with an incubation effect on the release of Si in solution. Experimental data were successfully modeled with the PhreeqC geochemical code. Glass and HCP samples were characterized via SEM/EDX and micro-Raman studies. This work showed that vitrified glass exhibits good performance in terms of low alteration rates (∼10-4 g m-2 d-1), the absence of secondary phases, and the formation of a gel layer at the surface, when in contact with low pH conditions (in the presence or absence of low pH HCP).

Strontium binding by calcium silicate hydrates.

In the present study the binding of strontium with pure calcium silicate hydrates (C-S-H) has been investigated using batch-type experiments. Synthetic C-S-H phases with varying CaO:SiO(2) (C:S) mol ratios, relevant to non-degraded and degraded hardened cement paste, were prepared in the absence of alkalis (Na(I), K(I)) and in an alkali-rich artificial cement pore water (ACW). Two types of experimental approaches have been employed, investigating sorption and co-precipitation processes, respectively. The Sr(II) sorption kinetics were determined as well as sorption isotherms, the effect of the solid to liquid ratio and the composition (C:S ratio) of the C-S-H phases. In addition, the reversibility of the Sr(II) sorption was tested. It was shown that both the sorption and co-precipitation tests resulted in Sr(II) distribution ratios which were similar in value, indicating that the same sites are involved in Sr(II) binding. In alkali-free solutions, the Sr(II) uptake by C-S-H phases was described in terms of a Sr(2+)-Ca(2+) ion exchange model. The selectivity coefficient for the Sr(2+)-Ca(2+) exchange was determined to be 1.2+/-0.3.

Subcellular and intranuclear localization of neptunium-237 (V) in rat liver.

The present investigation was aimed at establishing the distribution of 237Np within the different structures of hepatocytes. Rats were contaminated experimentally by intravenous injection of 237Np (V) and the subcellular structures of the liver were separated by ultracentrifugation. Twenty-four hours after contamination, the nuclear and cytosolic fractions bound 54 and 32%, respectively, of the total radionuclide. Purification of the nuclei followed by dissociation of the protein components in medium of increasing ionic strength showed a specific binding of neptunium to the structural proteins of the nuclear matrix.