Influence of Sulfate on the Kinetics of Uranium(VI) Sorption onto Ferrihydrite/Humic Acid Systems

Since seepage and flood waters of abandoned uranium mines in Saxony and Thuringia (Germany) contain relatively high amounts of sulfate, we studied the influence of sulfate on the kinetics of uranium(VI) adsorption onto ferrihydrite both in the absence and presence of humic acid at pH 6.5 under aerobic conditions. The sequence in which sulfate, uranium and humic acid were added to the ferrihydrite containing solutions was varied in order to obtain indications to sorption mechanisms. Two different sulfate concentrations were applied (0.005 and 0.02 M Na₂SO₄). The ionic strength was held constant at 0.1 M as sum of NaClO₄ and Na₂SO₄. The uranium(VI) concentration was 1·10^-6 M and the humic acid concentration was 5 mg/L.
In the absence of humic acid, the uranium sorption rate and the total uranium sorption in equilibrium decreased with increasing sulfate concentration due to blocking of strong ferrihydrite surface sites by sorbed sulfate. This leads to an increased availability of uranium. Variations of the order of addition of uranium and sulfate primarily affected the initial uranium sorption rate but not its sorption capacity. Direct competition of uranium and sulfate for strong ferrihydrite surface sites predominates electrostatic effects due to changes in net surface charge of ferrihydrite upon sulfate sorption.
In experiments with humic acid, the competitive effect of sulfate on humic acid sorption at pH 6.5 is small. This is attributed to a higher sorption affinity of humic acid for ferrihydrite surface sites compared to that of sulfate. The initial humic acid sorption rate was not affected by sulfate, only the total humic acid sorption was somewhat reduced by sorbed sulfate. Since the total number of potential binding sites for uranyl ions is increased by sorbed humic acid, more uranium is sorbed in the presence than in absence of humic acid. Thus, the influence of sulfate on uranium sorption is smaller when humic acid is present in solution. This effect becomes even more pronounced with increasing amounts of uranyl humate complexes in solution.