Uranium bioavailability in soil pore water: A long-term investigation in a contaminated soil mesocosm

Uranium in soil can exist in both (IV) and (VI) oxidation states, distributed among different soil fractions (exchangeable, carbonate, oxidizable, reducible, and residual). Following its release from these fractions, uranium enters the soil pore water, becoming bioavailable and potentially posing risks due to its radio and chemical toxicity. Given the significant health and environmental risks associated with uranium, it is crucial to understand its behaviour in contaminated soil pore water and how it changes over time, especially in response to seasonal variations. To address this issue, study was designed to investigate the temporal changes in uranium availability in soil pore water, with a special focus on effect of seasonal variations and biogeochemical reactions that govern the bioavailability of uranium in a contaminated soil mesocosm. This field investigation was carried out for two consecutive years, and revealed that, seasonal variation has a significant effect on the bioavailability of the uranium in the upper soil layers (<30 cm). The biogenic NO₃^- induced oxidative dissolution of uranium was found to be the predominant reaction causing the dissolution of uranium into soil pore water, followed by ion-exchange in upper layer, whereas at higher depths (30 cm < d < 70 cm) bioavailability is predominantly controlled by ion-exchange reaction. Furthermore, the study shows that at upper layers bioavailability is high during the summer, which is attributed to higher rate of biogenic denitrification and ion exchange reactions. Fast vertical migration of uranium in the soil column is attributed to formation of stable mobile species such as hydroxo‑carbonato ((UO₂)_xCO₃(OH)_y^-), hydroxo (UO₂)_x(OH)_y and carbonato (UO₂CO₃) complexes, identified by speciation modelling. For the first time, this study reports the process controlling uranium behaviour in soil pore water and the effect of seasonal variation on it in a contaminated soil. The findings are essential for assessing its potential radiological impact and remediation planning.