This work presents the study of the solubility of selenium under cementitious conditions and its diffusion, as SeO32-, through monolithic cement samples. The solubility studies were carried out under alkaline conditions similar to those anticipated in the near-field of a cement-based repository for low and intermediate-level radioactive waste. Experiments were conducted in NaOH solution, 95%-saturated Ca(OH)(2), water equilibrated with a potential backfill material (Nirex reference vault backfill, NRVB) and in solutions containing cellulose degradation products, with and without reducing agents. The highest selenium concentrations were found in NaOH solution. In the calcium-containing solutions, analysis of the precipitates suggests that the solubility controlling phase is Ca2SeO3(OH)(2)center dot 2H(2)0, which appears as euhedral rhombic crystals. The presence of cellulose degradation products caused an increase in selenium concentration, possibly due to competitive complexation, thereby, limiting the amount of calcium available for precipitation. Iron coupons had a minor effect on selenium solubility in contrast to Na2S2O4, suggesting that effective reduction of Se(IV) occurs only at Eh values below -300 mV. Radial through diffusion experiments on NRVB and in a fly ash cement showed no evidence of selenium breakthrough after one year. However, autoradiography of the exposed surfaces indicated that some migration had occurred and that selenium was more mobile in the higher porosity backfill than in the fly ash cement. (C) 2015 Elsevier B.V. All rights reserved.