Radiolytic gas formation in high-level liquid waste solutions

Abstract

High-level fission product waste solutions originating from the first-cycle raffinate stream of spent fast breeder reactor fuel reprocessing have been investigated gas chromatographically for their radiolytic and chemical gas production. The solutions showed considerable formation of hydrogen, carbon dioxide and dinitrogen oxide, whereas atmospheric oxygen was consumed completely within a short time. In particular, carbon dioxide resulted from the radiolytic degradation of entrained organic solvent. After nearly complete degradation of the organic solvent, the influence of hydrazine and nitrogen dioxide on hydrogen formation was investigated. Hydrazinium hydroxide led to the formation of dinitrogen oxide and nitrogen. After 60 d, the concentration of dinitrogen oxide had reduced to zero, whereas the amount of nitrogen formed had reached a maximum. This may be explained by simultaneous chemical and radiolytic reactions leading to the formation of dinitrogen oxide and nitrogen and photolytic fission of dinitrogen oxide. Addition of sodium nitrite resulted in the rapid formation of dinitrogen oxide. The rate of hydrogen production was not changed significantly after the addition of hydrazine or nitrite. The results indicate that under normal operating conditions no dangerous hydrogen radiolysis yields should develop in the course of reprocessing and high-level liquid waste tank storage. Organic entrainment may lead to enhanced radiolytic decomposition and thus to considerable hydrogen production rates and pressure build-up in closed systems.