Reactivity of nitrate and organic acids at the concrete–bitumen interface of a nuclear waste repository cell

• Interactions of cement paste and organic acid–nitrate solutions were investigated.
• Cement leaching imposed alkaline pH (>10) very rapidly in the liquid media.
• Acetic acid action on cement paste was similar to that of classical leaching.
• Oxalic acid attack formed Ca-oxalate salts; organic matter in solution decreased.
• Nitrate was stable under abiotic conditions and with organic matter.

This study investigates the fate of nitrate and organic acids at the bitumen–concrete interface within repository cell for long-lived, intermediate-level, radioactive wastes. The interface was simulated by a multiphase system in which cementitious matrices (CEM V cement paste specimens) were exposed to bitumen model leachates consisting of nitrates and acetic acid with and without oxalic acid, chemical compounds likely to be released by bitumen. Leaching experiments were conducted with daily renewal of the solutions in order to accelerate reactions. The concentrations of anions (acetate, oxalate, nitrate, and nitrite) and cations (calcium, potassium) and the pH were monitored over time. Mineralogical changes of the cementitious matrices were analysed by XRD. The results confirmed the stability of nitrates in the abiotic conditions of the experiments. The action of acetic acid on the cementitious matrix was similar to that of ordinary leaching in the absence of organic acids (i.e. carried out with water or strong acids); no specific interaction was detected between acetate and cementitious cations. The reaction of oxalic acid with the cementitious phases led to the precipitation of calcium oxalate salts in the outer layer of the matrix. The concentration of oxalate was reduced by 65% inside the leaching medium.