Selective Extraction of ⁸⁵Sr²⁺ with modified Calix[4]arenes in a liquid-liquid system

⁹⁰Sr is a long-lived radionuclide (T_1/2 = 28.6 a), which is produced as a by-product in nuclear power plants in the decay chain of uranium. In case of release in the biosphere, it can be concentrated in aquatic systems or in soil. It follows the food chain from environment to fauna and human. Due to its chemically similarity to calcium, it can be incorporated in bones. Stable isotopes of strontium might not be harmful, but radioactive analogues can lead to bone disorders and diseases, including leukaemia [1].
Calix[4]arenes represent an important class of supramolecules having various applications, e.g. in the recovery of nuclear fission products of uranium, like cesium or strontium.[2] We synthesised and structurally analysed calix[4]arene-based extractants as shown in Fig. 1 in order to investigate their binding ability towards strontium in liquid-liquid extraction systems.
An aqueous phase was traced using the short-lived radionuclide ⁸⁵Sr (T_1/2 = 64.9 d), which was produced and purified at the in-house 18 MeV-cyclotron [3]. To quantify the extraction behaviour of the calix[4]arenes, the remaining amounts of ⁸⁵Sr in the aqueous phases after the extraction, were recorded using gamma spectrometry. We systematically investigated the influence of various experimental parameters. Figure 1 shows extraction behaviour of various calix[4]arene derivatives depending on the pH of the aqueous strontium phase. Under alkaline conditions of the aqueous strontium phase, extraction yields of >(90±4)% were obtained for calix[4]arenes derivatives having carbonyl binding sites. Furthermore, the competition of inorganic and organic impurities to the extraction performance was studied. The impurities are in naturally occurring concentrations of ions like sodium, calcium, acetate or tartaric acid as groundwater ingredients. By simulating a synthetic groundwater, extraction of strontium was per-formed in yields up to (86±6)%.
In further experiments, the calix[4]arene-strontium complex is going to be analysed spectroscopically with the aim to investigate the complex formation behaviour.

The authors gratefully thank the German Federal Ministry of Education and Research (BMBF) for financial support of this study (project no. 02NUK014).

[1] Wallova, G., N. Kandler, and G. Wallner, Monitoring of radionuclides in soil and bone samples from Austria. Journal of Environmental Radioactivity, 2012. 107: p. 44-50.
[2] Otho, K., Review of the extraction behavior of metal cations with calixarene derivatives. Solvent Extraction Research and Development, 2010. 17: p. 1-18.
[3] Mansel, A., et al., Production of ⁸⁵Sr at a 18 MeV-cyclotron and purification for geochemical investigations, 2012. (submitted)