Simulating Radionuclide Fate And Transport In The Unsaturated Zone PDF Download

The main purpose of this project was to advance the basic scientific understanding of colloid and colloid-facilitated Cs transport of radionuclides in the vadose zone. We focused our research on the hydrological and geochemical conditions beneath the leaking waste tanks at the USDOE Hanford reservation. Specific objectives were (1) to determine the lability and thermodynamic stability of colloidal materials, which form after reacting Hanford sediments with simulated Hanford Tank Waste, (2) to characterize the interactions between colloidal particles and contaminants, i.e., Cs and Eu, (3) to determine the potential of Hanford sediments for \textit{in situ} mobilization of colloids, (4) to evaluate colloid-facilitated radionuclide transport through sediments under unsaturated flow, (5) to implement colloid-facilitated contaminant transport mechanisms into a transport model, and (6) to improve conceptual characterization of colloid-contaminant-soil interactions and colloid-facili\-tated transport for clean-up procedures and long-term risk assessment. We have previously shown that upon contact with simulated waste tank solutions, Hanford sediments change their mineralogical composition. Certain minerals, i.e., quartz, smectite, and kaolinite, are partially dissolved, and new mineral phases, i.e., the feldspathoids cancrinite and sodalite, are formed. We have characterized these mineral transformations and clarified the mineral transformation pathways. The new minerals were mainly in the colloidal size fraction (diameter less than 2 mum), had a negative surface charge, and were microporous, meaning they contained small pores. When Cs was present during the formation of the minerals, contaminants, like Cs, could be trapped inside the mineral structure. Transport experiments under water saturated and unsaturated conditions showed that the colloids were mobile in Hanford sediments. As the water saturation of the sediments decreased, the amount of colloids transported also decreased. The colloids had the ability to enhance the migration of the radionuclide Cs; however, Cs initially sorbed to colloids was desorbed during transport through uncontaminated Hanford sediments. The finding that Cs was stripped off the colloids during the transport through uncontaminated sediments implies that colloids will likely not be an effective carrier for Cs, unless the Cs is incorporated into the mineral structure of the colloids such that the radionuclide cannot desorb from the colloids. Nevertheless, it appears that the amount of Cs that can be transported by mobile colloids beneath Hanford waste tanks is limited. Colloids will not be able to move the bulk mass of Cs through the vadose zone at Hanford. Colloid stability studies indicate that Hanford sediment form stable colloidal suspensions when suspended in Hanford sediment pore waters. Colloid stability was assessed by determination of the critical coagulation concentration, i.e., the chemical electrolyte concentration at which colloidal suspensions flocculate and settle out (become unstable). Although in the stable mode, Hanford colloids will settle out of solution after extended periods of time (months to years). Given the low recharge rates at Hanford range, which from near 0 to more than 100 mm/year, and the long travel times for rainwater to reach the groundwater of more than 40 years, it appears that colloidal transport is unlikely to occur if colloids are initially to be suspended close to the soil surface by infiltrating rainwater. However, if preferential flow or transient flow occurs, then colloidal transport may become more important. The results of this project have also led to improvements of our fundamental understanding of colloid transport and mobilization under unsaturated flow conditions in porous media. We have found that colloid attachment to the liquid-gas interface is not that relevant and that colloids rather attached near the triple phase interface where air, water, and solid phases meet. We have also found that capillary forces are the most dominant forces governing colloid release in unsaturated porous media. These results help to advance our understanding of colloid fate and transport in unsaturated porous media.