In underground repository environments, various types of engineered barriers are installed to hinder the mobility of radionuclides. Cement admixtures, especially used to improve workability for concrete, are composed of fairly high organic molecules and have a dispersing effect through bonding with the C-S-H of the concrete. Previous studies have shown that complex-forming organics like EDTA, NTA, and ISA have a significant effect on the mobility of radionuclides, but the studies on the behavior and stability of combined complexes in hydrated cement are lacking. So, we selected a commonly used polycarboxylic-ester (PCE) type cement admixture and stable Co as a surrogate of Co-60 to perform desorption experiments from hydrated cement containing the admixture. Radioactive Co is known to be a common contaminant in nuclear fission and medical facilities and considered to exist as a relatively stable phase in repositories. In addition, the evaluation of cobalt can be a standard of safety issue for other radionuclides with the presence of cement admixture in repository. In this study, cement samples were prepared at water/cement ratio of 0.55 and cured for 28 days at 23-25°C and at least 80% of humidity with varying cement admixtures of 0.0, 0.1, and 2.0wt%. To evaluate the stability of cobalt in the weathered cement, a 0.001 M HCl solution was used to simulate cement weathering conditions on a hot plate at 60°C for 1 day using a solid/liquid ratio of 1:100. Degree of weathering was confirmed using XRD analysis. The adsorption experiments were performed by adding 0.0042 mmol of cobalt (CoCl2, Sigma-Aldrich, anhydrous ≥ 98.0%) to the weathered cement for 3 days using a platform shaker at 200 rpm, and the supernatant was separated using a syringe filter (<0.20 um) before ICP-MS analysis to determine the amount of Co adsorption. Cobalt desorption was tested for the Co-adsorbed cement using 0.019 mmol of calcium (Ca(NO3)2·4H2O, Sigma-Aldrich, 99%) for 3 hours to 14 days. The results showed that adsorbed cobalt with and without cement admixture was stably bound to cement, and did not increase any noticeable Co release by 2.0wt% PCE admixture. However, additional experiments using varying contents of PCE and other admixtures should be conducted to provide a standard for assessing the safety of cement admixtures in repositories.

Polycarboxylic ether-based high-range water reducer (PCE) has been proposed to use due to the operational advantages of reduced water content and increased fluidity of cementitious mixtures. But the concern about using PCE can increase the mobility of radionuclides as well. Nuclear Decommissioning Authority (NDA) showed that the PCE formulations increased radionuclide solubility in free solution. Solubility of U(VI), 239Pu, 241Am with the cementitious materials tested with 3:1 pulverized fuel Ash/Ordinary Portland Cement (PFA:OPC) and 9:1 Ground Granulated Blast Furnace Slag/OPC (GGBS:OPC) with PCE that increased at least one and, in some cases, more than three orders of magnitude (between 10-9 and 10-4 mol dm-3) for these radionuclides in the cement-equilibrated solution. It is possible that the relatively low molecular weight substances present in the PCE cement mixture increase the solubility of radionuclides. In addition, the organic substances that are easily miscible with water can contribute to increase the solubility. In this study, several radionuclides (Nb, Ni, Pd, Zr, and Sn) that may be present in intermediate and low-level waste (LIW) repositories were selected based on the half-life and the estimated dose accordingly, and the solubility tests were conducted with and without PCE in solution. To simulate the field condition of the underground repository, synthetic groundwater was prepared based on the recipe by the KAERI Underground Research Tunnel (KURT) DB-3 GW and used as a solvent. The solubility limiting solid phase (SLSP) of each radionuclide was determined using Geochemist’s WorkBench (GWB) model. The selected solid phases are Ni(OH)2, ZrSiO4, Nb2O5, Pd(metal), and SnO2, respectively, and the solubility experiments were conducted with 1.0wt% of PCE per total weight and 0.5 g / 250 ml of selected radionuclide’s SLSP for 90 days at room temperature (25°C). Compared with and without PCE presence in solution, the selected radionuclides also showed an increased solubility with the presence of water reducing agent like PCE. This results can be used to correctly estimate the mobility of target radionuclides with the presence of PCE in repository environments.