Cellulose-based wastes can be degraded into short-chain organic acids at the cementitious radioactive waste repository. Isosaccharinic acid (ISA), one of the main degradation products, can form the chelate complex with metals and radionuclides, and these complexes have a potential that can accelerate to move the radionuclides to far-field from the repository. This study characterized the amount of generated ISA from typical cellulosic materials in the repository. Two different degradation experiments were conducted under alkaline conditions (saturated with Ca(OH)2 at pH 12.4): i) cellulosic material mixture under an opened condition (partially aerobic), and ii) cellulosic material under an anaerobic condition in a nitrogen-purged glove box. In the first case, three different types of cellulosic materials–paper, cotton, and wood– were mixed at the same ratio, and the experiments were carried out at three different temperatures (20°C, 40°C, and 60°C). It revealed that both the cellulose degradation rate and generated ISA concentration were high at high reaction temperatures, and various soluble degradation products such as formic acid and lactic acid were generated. The cellulose degradation in this work seems to still stay at a peeling-off process. In the second study, each type of cellulosic material was applied in its own batch experiments, and the amount of generated ISA was in the order of paper > wood > cotton. The above two experiments are supposed to be a long-term study until the generated ISA reaches an equilibrium state.

Technetium (Tc) is a long-lived radioactive isotope, which exists as TcO4 - with high solubility under oxidative condition. The solubility of Tc is fundamental to assess the safety of radioactive waste repository in the case of a leakage of radioactive wastes. Cellulosic materials (paper, wood, cotton, etc.) contaminated by radionuclides are disposed of in low-level and intermediate-level radioactive waste repositories. Cellulose can be decomposed under anaerobic and alkaline conditions when cement pore water is saturated, and then isosaccharinic acid (ISA) is generated as a degradation product of cellulose. ISA forms complexations with radionuclides in solution and affects the solubilities of radionuclides. Therefore, the effect of ISA should be accurately evaluated to predict and assess the mobility of radionuclides in repository environments. In this study, batch tests were conducted to confirm the effect of ISA on the solubility of Rhenium(IV) Oxide. Herein, rhenium was used as a non-radioactive analog of Tc due to their similar chemical properties. Deionized water (DIW) and 0.1 M NaOH solution in pH 12.5 were used as background solutions, and ISA concentration was varied to 1~20 mM using Ca(ISA)2 and NaISA, respectively. The batch tests were conducted under both aerobic and anaerobic conditions. The whole batch tests under anaerobic conditions were performed in the glove box using oxygen purged DIW with a high purity nitrogen gas (99.9%) and low oxygen concentration (< 0.5 ppm). As a result, the rhenium concentration decreases as more ISA is dissolved in the solution, which shows the contrary effect of ISA on the solubility of other metals and radionuclides (e.g., Co, Th, Fe, Ni, etc.). It is assumed that the reducing capacity of ISA decreases the rhenium dissolution in the solution. Additional characterization of the oxidation state of rhenium oxide and the mechanism will be tested and presented.

Organic complexing agents may affect the mobility of radionuclides at low- and intermediate-level radioactive waste repositories. Especially, isosaccharinic acid (ISA) is the main cellulose degradation product under high pH conditions in cement pore water. ISA can combine with radionuclides and form stable complexes that adversely influence adsorption in the concrete phase, resulting in radionuclides to leach to the near- and far-fields of repositories. This study focuses on investigating the sorption of ISA onto engineered barriers such as concrete, thereby studying adsorption isotherms of ISA on concrete and comparing various isotherm models with the experimental data. The adsorption experiment was conducted in three background solutions, groundwater (adjusted to pH 13 using NaOH), State 1 (artificial cement pore water, pH 13.3), and State 2 (artificial cement pore water, pH 12.5), in a batch system at a temperature of 20°C. Concrete was characterized using BET, Zeta-potential analyzer, XRD, XRF, and SEM-EDS. ISA concentrations were detected using HPLC. The experimental data were best fitted to one-site Langmuir isotherm; On the other hand, either two-site isotherm or Freundlich isotherm couldn’t give reasonable fitting to the experimental data. The observed ISA sorption behavior on concrete is crucial for the disposal of radioactive waste because it can significantly lower the concentration of ISA in the pore water. Although one-site Langmuir isotherm might effectively represent the sorption behavior of ISA on concrete, the underlying mechanism is still unknown, and further investigation should be done in the near future.