A low- and intermediate-level radioactive waste repository contains different types of radionuclides and organic complexing agents. Their chemical interaction in the repository can result in the formation of radionuclide-ligand complexes, leading to their high transport behaviors in the engineered and natural rock barriers. Furthermore, the release of radionuclides from the repository can pose a significant risk to both human health and the environment. This study explores the impact of different experimental conditions on the transport behaviors of 99Tc, 137Cs, and 238U through three types of barrier samples: concrete, sedimentary rock, and granite. To assess the transport behavior of the samples, the geochemical characteristics were determined using X-ray diffraction (XRD), X-ray fluorescence (XRF), Fouriertransform infrared spectroscopy (FTIR), scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDS), and Brunauer-Emmett-Teller (BET) analysis. The adsorption distribution coefficient (Kd) was used as an indicator of transport behavior, and it was determined in batch systems under different conditions such as solution pH (ranging from 7 to 13), temperature (ranging from 10 to 40°C), and with the presence of organic complexing agents such as ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), and isosaccharinic acid (ISA). A support vector machine (SVM) was used to develop a prediction model for the Kd values. It was found that, regardless of the experimental parameters, 99Tc may migrate easily due to its anionic property. Conversely, 137Cs showed low transport behaviors under all tested conditions. The transport behaviors of 238U were impacted by the order of EDTA > NTA> ISA, particularly with the concrete sample. The SVM models can also be used to predict the Kd values of the radionuclides in the event of an accidental release from the repository.

The organic complexing agents such as ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), and isosaccharinic acid (ISA) can enhance the radionuclides’ solubility and have the potential to induce the acceleration of radionuclides’ mobility to a far-field from the radioactive waste repository. Hence, it is essential to evaluate the effect of organic complexing agents on radionuclide solubility through experimental analysis under similar conditions to those at the radioactive waste disposal site. In this study, five radionuclides (cesium, cobalt, strontium, iodine, and uranium) and three organic complexing agents (EDTA, NTA, and ISA) were selected as model substances. To simulate environmental conditions, the groundwater was collected near the repository and applied for solubility experiments. The solubility experiments were carried out under various ranges of pHs (7, 9, 11, and 13), temperatures (10°C, 20°C, and 40°C), and concentrations of organic complexing agents (0, 10-5, 10-4, 10-3, and 10-2 M). Experimental results showed that the presence of organic complexing agents significantly increased the solubility of the radionuclides. Cobalt and strontium had high solubility enhancement factors, even at low concentrations of organic complexing agents. We also developed a support vector machine (SVM) model using some of the experimental data and validated it using the rest of the solubility data. The root mean square error (RMSE) in the training and validation sets was 0.012 and 0.016, respectively. The SVM model allowed us to estimate the solubility value under untested conditions (e.g., pH 12, temperature 30°C, ISA 5×10-4 M). Therefore, our experimental solubility data and the SVM model can be used to predict radionuclide solubility and solubility enhancement by organic complexing agents under various conditions.

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.

Low- and intermediate-level radioactive wastes have been disposed of in the first-phase deep underground silo disposal at Gyeongju in South Korea. These radioactive wastes contain harmful radionuclides such as Uranium-238 (238U), which can pose long-term and deleterious effects on humans and the natural environment. Ethylenediaminetetraacetic acid and isosaccharinic acid, which can be formed via cellulosic waste degradation under high alkaline conditions might considerably enhance the transport behavior of 238U with the intrusion of rainwater and groundwater. In this study, the engineered barriers (concrete and grout) and natural barriers (sedimentary rock and granite) were used to investigate the 238U transport behavior in artificial cementitious porewater of State I (pH 13.3) and State II (pH 12.5) based on groundwater or rainwater. The surface properties and geochemical compositions of barrier samples were characterized using XRD, XRF, SEM-EDX, and BET. The transport behaviors of 238U in various solution conditions were observed by sorption distribution coefficient (Kd) at a range of initial chelating agents concentration (10-5-10-2 M). The sorption behavior of 238U was retarded more in the engineered rock barriers than in the natural rock barriers. The mobility enhancement of 238U was more significant in State I than in State II. In comparison with the absence of chelating agents, negligible changes in the Kd values of 238U were observed at less than initial chelating agent concentrations of 10-4 M. However, the Kd values of 238U were significantly reduced at initial chelating agent concentrations higher than 10-3 M. Therefore, these experimental findings show that the transport behavior of 238U into the geo- and bio-sphere could be accelerated by the presence of chelating agents and the type of cement degradation states.

Engineered barriers (concrete and grout) in Low- and Intermediate-Level Waste (L/ILW) disposal facilities tend to degrade by groundwater or rainfall water over a long period of time. During the degradation process, radionuclides stored in the disposal facility might be released into the pore water, which can pass through the natural rock barriers (granite and sedimentary rock) and may reach the near-field and far-field. In this transportation, radionuclide might be sorbed onto the engineered and natural rock barriers. In addition, the organic complexing agent such as ethylenediaminetetraacetic acid (EDTA) and α-isosaccharinic acid (ISA), is also present in pore water, which may affect the sorption and mobility of radionuclide. In this study, the sorption and mobility of 90Sr under different conditions such as two pHs (7 and 13), different initial concentrations of organic complexing agents (from 10-5 M to 10-2 M), and solutions (groundwater, pore water, and rainfall water) were investigated in a batch system. The groundwater was collected at the L/ILW disposal facility located at Gyeongju in South Korea. The pore water and rainfall water were artificially made in the laboratory. The concrete, grout, granite, and sedimentary rock samples were collected from the same study sites from where the groundwater was collected. The rock samples were crushed to 53-150 micrometers and were characterized by XRD, XRF, SEM-EDS, BET, and zeta potential analyzer. 90Sr concentration was determined using liquid scintillation counting. The sorption of 90Sr was described by distribution coefficients (Kd) and sorption reduction factor (SRF). In the case of EDTA, the Kd values of 90Sr remained constant from 10-5 M to 10-3 M and tended to decrease at 10-2 M, while in case of ISA the Kd values decreased steadily as the concentration of ISA was increased from 10-5 M to 10-3 M; However, a sudden reduction in the Kd values were observed above 10-2 M. In comparison to EDTA, ISA gave a higher SRF of 90Sr. Therefore, from the above results, it can be concluded that the presence of ISA has a greater effect on the sorption and mobility of radionuclide in the solutions than EDTA, and the radionuclide may reach near- and far-field of the L/ILW disposal facility.

Radionuclides stored in a radioactive waste repository over a long period of time might be leached through the barriers such as engineered rock (cement) and natural rock (granite). Organic complexing agents such as ethylenediaminetetraacetic acid (EDTA) and isosaccharinic acid (ISA) may also influence the mobility of radionuclides. In this study, a continuous fixed-column reactor packed with engineered and natural rocks was designed to investigate the effect of organic complexing agents on cesium mobility through cement and granite under anaerobic conditions. The influent flow rate of the mixed solution (organic complexing agent and cesium) at the column bottom was 0.1 mL/min, while that of groundwater was 0.2 mL/min, which was introduced between cement and granite layers in the middle of the column. The hydraulic properties such as diffusion coefficient and retardation factor were derived by a bromide tracer test. The effects of different operating parameters, such as initial cesium concentrations, initial EDTA or ISA concentrations, and bed size, on the cesium adsorption were investigated. The Thomas, Adams-Bohart, and Yoon-Nelson models were applied to the experimental data to predict the breakthrough curves using non-linear regression. These results suggest that organic complexing agents such as EDTA and ISA significantly influence the mobility of cesium in the barriers, indicating that the presence of complexing agents enhances the migration of cesium to the geosphere.

Radionuclides can be leached into groundwater or soil over a long period of time due to unexpected situations even after being permanently disposed of in a repository. Therefore, it is necessary to investigate the mobility of radionuclides for the safety assessment of radioactive waste disposal. In this study, the effects of organic complexing agents such as ethylenediaminetetraacetic acid (EDTA) and isosaccharinic acid (ISA) on the sorption behavior of 239Pu and 99Tc over cementitious (concrete and grout) and natural rock samples (granite and sedimentary rock) were investigated in batch sorption experiments. For characterization of rock samples, XRD, XRF, FT-IR, FE-SEM, BET, and Zeta-potential analyses were performed. For the evaluation of mobility, the distribution coefficient (Kd) was selected and compared. The adsorption experiment was carried out at two pHs (7 and 13), a temperature of 20°C, and a range of organic complexing agents concentrations (10-7~10-2 M and 10- 5~10-2 M for 239Pu and 99Tc, respectively). The radionuclides concentrations in adsorption samples were analyzed using ICP-MS. The Kd values for 239Pu in all rock samples reduced significantly due to the presence of EDTA, even at low concentrations such as 10-5 M. In the case of ISA, the limiting noeffect concentration was much higher than that of EDTA. On the other hand, 99Tc showed relatively lower Kd values than 239Pu, and the sorption behavior of 99Tc was almost unaffected by the organic complexing agents for all rock samples. Therefore, it is possible to assume that the increased mobility of radionuclides, especially, 239Pu, in groundwater caused by the lowering of sorption at even low concentrations of organic complexing agents may result in the transport of radionuclides to the nearand far-field location of the repository.

Organic complexing agents which are contained in the radioactive waste can form the complex with radionuclides and enhance the solubility of radionuclides. The mobility of radionuclides to the far-field from the repository will be increased by radionuclide-ligand complex formation. Therefore, the assessment of the radionuclides’ solubility should be performed in the presence of organic complexing agents. In this study, five radionuclides (cobalt, strontium, iodine, cesium, and uranium) and three organic complexing agents (ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), and isosaccharinic acid (ISA)) were selected as model radionuclides and organic complexing agents, respectively. For simulating the in-situ condition, the groundwater near the repository was collected and applied in solubility experiments and the solubility was measured in various environmental conditions such as different pHs (7, 9, 11, and 13), temperatures (10°C, 20°C, and 40°C), and a range of organic complexing agent concentrations (10-5, 10-4, 10-3, and 10-2 M). In cases of cesium and iodine, they were very soluble in all conditions, and the effect on their solubilities was not observed. However, at high pHs, cobalt and strontium showed lower solubilities than at neutral pH and the solubility enhancement by the organic complexing agents was significant. Moreover, the effects of each organic ligand showed obvious differences and were in the order of EDTA > NTA > ISA. The solubility of uranium was increased with increasing the organic ligand concentration at lower pHs, but the organic complexing agents did not cause a remarkable difference at high pHs. According to these results, the presence of complexing agents could enhance the radionuclides’ solubility and increase the potential to release the radionuclides to the far-field from the repository. Solubility experiments of other major radionuclides in the repository are in progress.