Study of leaching mechanisms of caesium ions incorporated in Ordinary Portland Cement.

In this work, a study of the leaching kinetics of Cs(+) ions from cement paste solids, containing inactive Cs(2)SO(4), is presented, involving (i) the parallel performance of leaching experiments at two temperatures (30 degrees C and 70 degrees C); (ii) the performance of leaching tests with intermediate changes in temperature between 30 degrees C and 70 degrees C; (iii) the use of specimens of two different thicknesses and (iv) the determination of the distribution of Cs(+) in the cement specimen at various stages of the leaching test. The results of leaching studies at 30 degrees C with cement solids simulating the composition of real radioactive wastes, containing NaNO(3), small amounts of inactive CsNO(3) and traces of (137)Cs(+) are also reported. Concentration profiles of Cs(+) in inactive specimens showed that part of the Cs(+) (20-30%) tends to be immobilized in the matrix, while elution of the readily leachable portion follows Fick's law reasonably well. No immobilized Cs(+) was detected in the samples containing considerable amounts of NaNO(3). Long-term leaching experiments (up to 8 years) revealed acceleration of the elution process (not detectable in short-term tests), attributable to increase in porosity caused by erosion of the cement matrix. Sorption experiments of Cs(+) ions by cement granules indicated that adsorption on cement pore surfaces is not significant. On the other hand, the leaching tests at two different temperatures or with intermediate changes in temperature between 30 degrees C and 70 degrees C, yielded activation energies that indicated a more complicated kinetic behavior.