Catherine Cossonnet

Solvent Extraction of U(VI) by Calix[6]arenes

Abstract This paper focuses on the solvent extraction of U(VI) traces by 1,3,5‐OMe‐2,4,6‐OCH2CONHOH‐p‐tert‐butylcalix[6]arene (LH3). The global extraction equation of U(VI) has been established. The complex formed in the organic phase is (UO2)(LH) with an apparent extraction constant equal to 7.1×10−5 M (I=0.04 M). Distribution data show that LH3 efficiently extracts U(VI) from NaNO3 media at pH 5 and that the stripping of U(VI) can be achieved in nitric acid solutions. Finally a comparison with previous results obtained with the 1,3,5‐OMe‐2,4,6‐OCH2COOH‐p‐tert‐butylcalix[6]arene (L′H3) shows that the hydroxamate groups are as efficient as the carboxylate ones for uranyl extraction.

Theoretical Study of the Uranyl Complexation by Hydroxamic and Carboxylic Acid Groups

A theoretical study on the complexation of uranyl cation (UO2(2+)) by three different functional groups of a calix[6]arene cage, that is, two hydroxamic and a carboxylic acid function, has been carried out using density functional theory calculations. In particular, interaction energies between the uranyl and the functional groups have been used to determine their affinity toward uranyl, whereas pKa calculations give some information on the availability of the functional groups in the extraction conditions. On the one hand, calculations of the interaction energies have pointed out clearly a better affinity with the hydroxamic groups. The stabilization of this complex was rationalized in terms of a stronger electrostatic interaction between the uranyl cation and the hydroxamic groups. The presence of a water molecule in the first coordination sphere of uranyl does not destabilize the complex, and the most stable complex is obtained with two functional groups and two water molecules, leading to a coordination number of 8 for the central uranium atom. On the other hand, pKa theoretical evaluation shows that both hydroxamic (deprotonated on the oxygen site) and carboxylic groups are potential extractants in aqueous medium with a preference for carboxylic functions at low pH. Moreover, these data allowed to unambiguously identify the oxygen of the alcohol function as the favored deprotonation site on the hydroxamic function.

Transfer of tritium released into the marine environment by French nuclear facilities bordering the English Channel.

Controlled amounts of liquid tritium are discharged as tritiated water (HTO) by the nuclear industry into the English Channel. Because the isotopic discrimination between 3H and H is small, organically bound tritium (OBT) and HTO should show the same T/H ratio under steady-state conditions. We report data collected from the environment in the English Channel. Tritium concentrations measured in seawater HTO, as well as in biota HTO and OBT, confirm that tritium transfers from HTO to OBT result in conservation of the T/H ratio (ca. 1 × 10(-16)). The kinetics of the turnover of tritium between seawater HTO, biota HTO, and OBT was investigated. HTO in two algae and a mollusk is shown to exchange rapidly with seawater HTO. However, the overall tritium turnover between HTO and the whole-organism OBT is a slow process with a tritium biological half-life on the order of months. Nonsteady-state conditions exist where there are sharp changes in seawater HTO. As a consequence, for kinetic reasons, the T/H ratio in OBT may deviate transiently from that observed in HTO of samples from the marine ecosystem. Dynamic modeling is thus more realistic for predicting tritium transfers to biota OBT under nonsteady-state conditions.

Behaviour of radiocaesium in coastal rivers of the Fukushima Prefecture (Japan) during conditions of low flow and low turbidity--Insight on the possible role of small particles and detrital organic compounds.

To investigate riverine transfers from contaminated soils of the Fukushima Prefecture in Japan to the marine environment, suspended sediments, filtered water, sediments and detrital organic macro debris deposited onto river beds were collected in November 2013 within small coastal rivers during conditions of low flow rates and low turbidity. River waters were directly filtered on the field and high efficiency well-type Ge detectors were used to analyse radiocaesium concentrations in very small quantities of suspended particles and filtered water (a few mg to a few g). For such base-flow conditions, our results show that the watersheds studied present similar hydro-sedimentary behaviours at their outlets and that the exports of dissolved and particulate radiocaesium are comparable. Moreover, the contribution of these rivers to the instantaneous export of radiocaesium to the ocean is similar to that of the Abukuma River. Our preliminary results indicate that, in the estuaries, radiocaesium concentrations in suspended sediments would be reduced by more than 80%, while radiocaesium concentration in filtered waters would be maintained. Significant correlations between radiocaesium concentrations and radiocaesium inventories in the soils of the catchments indicate that there was at that time little intra and inter-watershed variability in the transfer processes of radiocaesium from lands to rivers at this regional scale. The apparent liquid-solid partition coefficient (KD) values acquired for the lowest loads/finest particles complement the values acquired by using sediment traps and highlight the strong capacity of the smallest particles to transfer radiocaesium. Finally, but not least, our observations suggest that there could be a significant transfer of highly contaminated detrital biomass from forest litter to the downstream rivers in a rather conservative way.

The VATO project: An original methodology to study the transfer of tritium as HT and HTO in grassland ecosystem

Tritium (3H) is mainly released into the environment by nuclear power plants, military nuclear facilities and nuclear reprocessing plants. The construction of new nuclear facilities in the world as well as the evolution of nuclear fuel management might lead to an increase of 3H discharges from the nuclear industry. The VATO project was set up by IRSN (Institut de Radioprotection et de Sûreté Nucléaire) and EDF (Electricité de France) to reduce the uncertainties in the knowledge about transfers of 3H from an atmospheric source (currently releasing HT and HTO) to a grassland ecosystem. A fully instrumented technical platform with specifically designed materials was set up downwind of the AREVA NC La Hague reprocessing plant (Northwest of the France). This study, started in 2013, was conducted in four main steps to provide an hourly data set of 3H concentrations in the environment, adequate to develop and/or validate transfer models. It consisted first in characterizing the physico-chemical forms of 3H present in the air around the plant. Then, 3H transfer kinetics to grass were quantified regarding contributions from various compartments of the environment. For this purpose, an original experimental procedure was provided to take account for biases due to rehydration of freeze-dried samples for the determination of OBT activity concentrations in biological samples. In a third step, the 3H concentrations measured in the air and in rainwater were reconstructed at hourly intervals. Finally, a data processing technique was used to determine the biological half-lives of OBT in grass.

Dating of sediment record at two contrasting sites of the Seine River using radioactivity data and hydrological time series

Sediment cores were collected at the outlet of the highly anthropogenized catchment of the Seine River at two contrasting sites: a flood plain of the lower Seine River and a quasi-permanently submerged harbour basin (or wet dock) in the upper tidal estuary. Analyses of artificial radionuclides ((137)Cs and plutonium isotopes), coupled with hydrological and bathymetric data, lead to a precise dating of the sediment cores collected at the two sites. (137)Cs signals originating from global fallout (early 1960s) and from the Chernobyl accident (1986) are identified, but at different levels due to the incomplete nature or variable continuity of the records. Anomalous (238)Pu concentrations found at both sites (1-2 Bq kg(-1)) are attributed to unknown industrial releases originating from upstream. Interpolating (137)Cs sediment activities under the assumption of a constant sediment rate, those releases were dated back to 1975 ± 1, thus providing a local but reliable time-marker. Age models have highlighted a very contrasting sediment filling dynamics in these two sites. This study presents the first sediment record of alpha- and gamma-emitting artificial radionuclides obtained at the outlet of the huge catchment area of the River Seine, over a period covering the last 50 years.

A brief history of origins and contents of Organically Bound Tritium (OBT) and 14C in the sediments of the Rhône watershed

Tritium (3H) and Carbon-14 (14C) are radionuclides of natural (cosmogenic) origin that have also been introduced into the environment by humans since the middle of the last century. They are therefore not compounds that have only recently been released into the environment and they do not pose a recognized health threat due to their low radiotoxicity. However, they hold an important place among current concerns because they are being discharged into the environment by the nuclear industry in large quantities compared to other radionuclides. Those both radionuclides partly integrate organic matter during metabolic processes (i.e., photosynthesis) leading to organically bound forms that can be found in sediments. Organically bound tritium (OBT) analyses carried out on the sediments of the Rhône and its tributaries indicate a significant and historical tritium labelling of sedimentary particles all along the Rhône river, as well as in several northern tributaries, in particular the Ognon and the Tille rivers (tributaries of the Saone), the Doubs River and the Loue River (a tributary of the Doubs) and the Arve river. The recorded levels (10 to over 20,000 Bq/L) are very likely to be related to the presence of synthetic tritiated particles (technogenic tritium), which were used in the past in watchmaking workshops. Although overall contamination levels decrease from north to south in the Rhône watershed and fade over time, particularly due to the radioactive decay of tritium, this contamination source of technogenic tritium in the Rhône watersheds is currently still not negligible. Carbon-14 analyses show that the Rhône sediments generally display 14C levels close to the atmospheric reference values (231 Bq·kg-1 of C in 2015) or even lower in most of cases, and show sporadic and weak labelling near nuclear facilities. The low 14C levels in the Rhône sediments are most likely related to the solid contributions from tributaries draining areas that are rich in fossil organic matter, and therefore devoid of 14C. In the Rhône watershed, the presence in solid particles of tritium in a form organically bound to synthetic compounds and of petrogenic (fossil) organic carbon, can potentially alter the apparent assimilation rates to the food chain of these two radionuclides.