U, Th, Eu and colloid mobility in a granite fracture under near-natural flow conditions

Abstract

Summary Laboratory core migration experiments were performed in a granite fracture from the Grimsel Test Site (GTS, central Swiss Alps). The flow velocity was varied (46 m yr-1, 94 m yr-1, 187 m yr-1) and solutions with 10-6 mol L-1 U(VI), 10-8 mol L-1 Th(IV) and 10-8 mol L-1 Eu(III) without (cocktail I) and with addition of 2 mgL-1 bentonite colloids (cocktail II) have been injected. Results are compared with those obtained in a field study at the GTS. Flow field-flow fractionation and ultrafiltration measurements show that U(VI) is not colloid borne, different from Th(IV) and Eu(III) which are associated with colloids in both spiked natural groundwaters with and without bentonite colloid addition. The partly unretarded U(VI) migration observed at short contact times (1-2 h) diminished under near-natural groundwater velocities (∼46 m yr-1) and only a weak retardation (R f=19.5) could be observed. Furthermore, the U(VI) mass recovery decreased with increasing contact time and was as expected unaffected by bentonite colloid addition. A groundwater colloid mediated Th(IV)/Eu(III) migration without bentonite colloid addition could be confirmed in the core experiments but only at fast groundwater flow rates. Experiments at a water flow rate of 94 m yr-1 with cocktail II demonstrated a partially bentonite colloid facilitated transport of Th(IV) and Eu(III) with 27% and 37% mass recovery, respectively. At long tracer residence times in the flow field, no breakthrough of colloidal Th(IV)/Eu(III) could be observed in both runs, indicating the strong dependence of reaction kinetics on their mobility. Reference colloid experiments using fluorescence dye labeled carboxylated polystyrene microspheres (25 nm, 50 nm and 100 nm) revealed in general a higher recovery of smaller colloid size classes increasing with groundwater velocity. Additionally, an earlier peak arrival time of colloids and colloid-associated Th(IV) and Eu(III) was observed with respect to the conservative tracer 3H in all experiments due to pore-size or charge exclusion effects. In general, the colloid recoveries found in the laboratory core experiments are lower than those obtained in the field studies. The decrease of colloid mobility with increasing residence time suggests the occurrence of colloid attachment to the rock surfaces even under the colloid stabilizing groundwater conditions.