Interaction of U(VI) with Äspö diorite: A batch and in situ ATR FT-IR sorption study

Pristine diorite drill cores, obtained from the Äspö Hard Rock Laboratory (HRL, Sweden), were used to study the retention behavior of fresh, anoxic crystalline rock material towards the redox-sensitive uranium. Batch sorption experiments and spectroscopic methods were applied for this study. The impact of various parameters, such as solid-to-liquid ratio (2 to 200 g/L), grain size (0.063 – 0.2 mm, 0.5 – 1 mm, 1 – 2 mm), temperature (room temperature and 10 °C), contact time (5 to 108 days), initial U(VI) concentration (3x10^-9 to 6x10^-5 M), and background electrolyte (synthetic Äspö groundwater and 0.1 M NaClO₄) on the U(VI) sorption onto anoxic diorite was studied under anoxic conditions (N₂). Comparatively, U(VI) sorption onto oxidized diorite material was studied under ambient atmosphere (pCO₂ = 10^-3.5 atm). Conventional distribution coefficients, K_d, and surface area normalized distribution coefficients, K_a, were determined. The K_d value for the U(VI) sorption onto anoxic diorite in Äspö groundwater under anoxic conditions by investigating the sorption isotherm amounts to 3.8 ± 0.6 L/kg which corresponds to K_a = 0.0030 ± 0.0005 cm (grain size 1 – 2 mm). This indicates a weak U sorption onto diorite which can be attributed to the occurrence of the neutral complex Ca₂UO₂(CO₃)₃(aq) in solution. This complex was verified as predominating U species in synthetic Äspö groundwater by time-resolved laser-induced fluorescence spectroscopy (TRLFS). Compared to U sorption at room temperature under anoxic conditions, U sorption is further reduced at decreased temperature (10 °C) and under ambient atmosphere. The U species in aqueous solution as well as sorbed on diorite were studied by in situ time-resolved attenuated total reflection Fourier-transform infrared (ATR FT-IR) spectroscopy. A predominant sorbing species containing a UO₂(CO₃)₃ ^4- moiety was identified. The extent of U sorption onto diorite was found to depend more on the low sorption affinity of the Ca₂UO₂(CO₃)₃(aq) complex than on reduction processes of uranium.