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.
99Tc is a long-lived radioactive fission product whose mobility in the subsurface is largely governed by its oxidation state. Migration of Tc from a waste repository may be prevented by immobilizing Tc(IV) in durable glass forms. Thus, efficient incorporation and high retention of Tc by glasses is very important for radioactive waste management and environmental remediation. Tc(IV) oxidation to higly volatile Tc(VII) (TcO4 −) at glass vitrification temperatures results in poor Tc retention in the final waste glass. Retention of Tc in the glass is generally improved by reducing conditions since Tc(IV) is not volatile. However, experiments with Tc-magnetite under high temperature and oxic conditions showed re-oxidation of Tc(IV) to volatile pertechnetate. To understand this phenomenon, we employed ab initio molecular dynamics simulations to study structural and electronic properties of Tc-incorporation in magnetite. The study provides the ramification of high temperature on Tc mobilization and changes of Tc retention in magnetite. Theory predictions also indicated enhanced Tc retention in the presence of 1st row transition metal dopants in Tc-incorporated magnetite that was confirmed by experiments. Furthermore, the overwhelming concentration of Cr(VI) co-mingled with Tc(VII) within the secondary waste form where Cr(VI) is more readily reduced than Tc(VII) by reduction potential metrics. Experiments with Tc-magnetite under high temperature and oxic conditions showed re-oxidation of Tc(IV) to volatile pertechnetate. Experiments also showed that magnetite transforms to maghematite resulting in disproportionation and re-oxidation of Tc. This transformation can be suppressed through incorporation of trace elements such as Co, Ni, Zn into magnetite forming spinel. In this talk, I will present results from ab initio molecular dynamics simulations and experiments on the structural and electronic properties of Tc and/or Cr incorporation in magnetite. I will also discuss the temperature effect on Tc/Cr mobilization and changes of Tc/Cr retention in magnetite. In addition, I will discuss the effect of Tc/Cr concentration and 1st row transition metal dopants on their incorporation in magnetite.