Review of the kinetics of alkaline degradation of cellulose in view of its relevance for safety assessment of radioactive waste repositories

Abstract

The degradation of cellulose (a substantial component of low- and intermediate-level radioactive waste) under alkaline conditions occurs via two main processes: a peeling-off reaction and a basecatalyzed cleavage of glycosidic bonds (hydrolysis). Both processes show pseudo-first-order kinetics. At ambient temperature, the peeling-off process is the dominant degradation mechanism, resulting in the formation of mainly isosaccharinic acid. The degradation depends strongly on the degree of polymerization (DP) and on the number of reducing end groups present in cellulose. Beyond pH 12.5, the OH^- concentration has only a minor effect on the degradation rate. It was estimated that under repository conditions (alkaline environment, pH 13.3-12.5) about 10% of the cellulosic materials (average DP = 1000-2000) will degrade in the first stage (up to 10⁵ years) by the peeling-off reaction and will cause an ingrowth of isosaccharinic acid in the interstitial cement pore water. In the second stage (10⁵-10⁶ years), alkaline hydrolysis will control the further degradation of the cellulose. The potential role of microorganisms in the degradation of cellulose under alkaline conditions could not be evaluated. Proper assessment of the effect of cellulose degradation on the mobilization of radionuclides basically requires knowing the concentration of isosaccharinic acid in the pore water. This concentration, however, depends on several factors such as the stability of ISA under alkaline conditions, sorption of ISA on cement, formation of sparingly soluble ISA-salts, etc. A discussion of all the relevant processes involved, however, is far beyond the scope of the presented overview.