Remediation of ¹³⁷Cs-contaminated concrete rubble by supercritical CO₂ extraction

The removal of cesium contamination is a critical issue for the recycling of concrete rubble in most decommissioning operations. The high solvent strength and diffusivity of supercritical CO₂ make it an attractive choice as vector for extractant system in this context. Experimental extraction runs have been carried out in a radioactive environment on rubble contaminated with ¹³⁷Cs. The best extraction system was found to be CalixOctyl (25,27-Bis(1-octyloxy)calix[4]arene-crown-6, 1,3-alternate) with pentadecafluorooctanoic acid as a modifier. The effects of various operating parameters were investigated, namely the coarseness of rubble, the temperature of supercritical CO₂, the residual water and initial cesium concentrations, and the amounts of extractant and modifier used. The yields from direct extraction were low (<30%), because of the virtually irreversible sorption of Cs in concrete. The best extraction yield of ∼55% was achieved by leaching concrete rubble with nitric acid prior to supercritical CO₂ extraction.