Separation of Uranium from Aqueous Solution by Textile Bound Calixarenes

The remediation of former uranium mining and milling sites of Saxony and Thuringia requires the purification of uranium contaminated seepage and mine waters. The separation of uranium(VI) from aqueous solution by calixarenes by means of solvent extraction is described in the literature (e.g., [1,2]). Calixarenes are macrocyclic molecules formed by 4, 6 or 8 parasubstituted phenolic units linked by methylene bridges ortho to the OH functions. Thus, molecules of various ring sizes are formed. The substitution of calix[6]arenes on the hydroxyl group by carboxylic and hydroxamic groups, respectively, leads to ligands that are able to bind uranium(VI) selectively.
The present work represents an innovative method for the separation of uranium(VI) from aqueous solution using uranophile calix[6]arenes that are fixed on textile substrates such as polyester fabric. For this, the calix[6]arenes are statistically functionalized by spacer groups (n-alkyl groups) that enable their fixation onto polyester fabric.
The complex formation of the textile bound calixarenes, e.g., carboxymethoxy-p-mono-nonyl-penta-tert-butyl-calix[6]arene, and their selectivity towards uranium(VI) ions is studied as a function of pH value, ionic strength and competing ions by means of batch experiments. Time-resolved laser-induced fluorescence spectroscopy (TRLFS) is used to determine complex formation constants. The reaction mechanisms are discussed. As competing ions, Na⁺, Ca²⁺, Mg²⁺ and Fe³⁺ as well as SO₄ ^2- are studied, that occur typically in mine waters. Furthermore, the reversibility of the uranium binding is evaluated. The results are compared with those obtained for the corresponding non-fixed calixarenes [3].
The new technique for the remediation of uranium contaminated waters is also applicable for lower contamination levels ([UO₂ ²⁺] < 1x10^-6 M) and is especially suitable for smaller remediation objects. The applicability of this separation principle to further actinides is expected.

[1] Shinkai, S., Koreishi, H., Ueda, K., Arimura, T., Manabe, O.: Molecular Design of Calixarene-Based Uranophiles which Exhibit Remarkably High Stability and Selectivity. J. Am. Chem. Soc. 109, 6371 (1987).
[2] Nagasaki, T., Shinkai, S.: Synthesis and Solvent Extraction Studies of Novel Calixarene-based Uranophiles Bearing Hydroxamic Groups. J. Chem. Soc., Perkin Trans. 2 (7), 1063 (1991).
[3] Schmeide, K., Barz, B., Heise, K.H., Bernhard, G., Gloe, K.: Solvent Extraction of Uranium(VI) by Calix[6]arene. In: FZR-318, Annual Report 2000 (Th. Fanghänel, ed.). Forschungszentrum Rossendorf, Institute of Radiochemistry, Rossendorf 2001, p. 17.