Carbon-14 release and speciation during corrosion of irradiated steel under radioactive waste disposal conditions.

Carbon-14 is a key radionuclide in the safety assessment of deep geological repositories (DGR) for low- and intermediate-level radioactive waste (L/ILW). Irradiated metallic wastes generated during the decommissioning of nuclear power plants are an important source of 14C after their disposal in a DGR. The chemical form of 14C released from the irradiated metallic wastes determines the pathway of migration from the DGR into the environment. In a long-term corrosion experiment with irradiated steel simulating the hyper-alkaline, anoxic conditions of a cement-based DGR, total inorganic (TI14C2) and organic 14C contents (TO14C) in the liquid and gas phases (TG14C), as well as individual 14C-bearing carbon compounds by compound-specific radiocarbon analysis (CSRA), were quantified using accelerator mass spectrometry (AMS). The AMS-based quantification allows the determination of 14C in the pico- to femtomolar concentration range. An initial increase in TO14C was observed, which could be attributed partially to the release of 14C-bearing oxygenated carbon compounds. In the long term, TO14C and the TI14C remain constant, while TG14C increases over time according to a corrosion rate of steel of 1 nm/yr. In solution, 14C-bearing carboxylic acids (CAs) contribute ~40% to TO14C, and they are the main 14C carriers along with 14C-bearing carbonate (14CO32-). The remaining fraction of TO14C (~ 60%) is likely due to the presence of as yet non-identified polymeric or colloidal organic material. In the gas phase, 14CH4 accounts for more than 80% of the TG14C, while only trace amounts of 14CO, and other small 14C-bearing hydrocarbons have been detected. In a DGR, the release of 14C will be mainly in gaseous form and migrate via the gas pathway from the repository near field to the surrounding host rock and eventually to the environment.