Uranyl sorption by smectites: spectroscopic assessment of thermodynamic modeling.
Batch sorption experiments and thermodynamic modeling of the interaction of UO2(2+) and its hydrolysis products with two smectitic clay minerals, the reference material SWy-1 [McKinley et al., Clays Clay Miner. 43 (1995) 586] and the soil isolate LK-1 [Turner et al., Geochim. Cosmochim. Acta 30 (1996) 3399], have established a conceptual framework for uranyl/smectite surface complexation based on general reactions between aqueous uranyl species and the reactive sites on the mineral surfaces. In this report, we have formulated and spectroscopically tested a set of hypotheses based on this conceptual framework using samples prepared under similar or identical conditions to evaluate the agreement between surface complexation/speciation as enumerated by spectroscopic characterization and that elaborated by the surface complexation model. Both steady-state and time-resolved optical emission spectral data are presented for uranyl on both smectite minerals as well as on the analogue phases SiO2 and Al(OH)3 spanning the pH range from approximately 4 to 8 and the background electrolyte concentrations from approximately 0.001 to 0.1 M. The spectral data enable the explicit identification of an outer-sphere exchange-site population of the hydrated cation [UO2(OH2)5(2+) ] in SWy-1. Spectral data also clearly establish the existence of inner-sphere surface complexes on the analogue phases and on the amphoteric clay crystallite edge sites [aluminol (>Al-OH) and silanol (>Si-OH)]. Based on the spectral characteristics of these uranyl edge-site populations, it is possible to readily infer for the SiO2, Al(OH)3, and SWy-1 samples the evolution in surface speciation with increasing pH to more hydrolyzed uranyl-surface complexes consistent with the conceptual model. The spectral domain characteristics of the edge-site populations on LK-1 with increasing pH suggest that there is no change in the hydrolysis of the uranyl-surface species. However, emission lifetime data are interpreted as indicating a shift in the surface speciation of the same uranyl-surface species from aluminol sites to silanol sites with pH increase. This observation is also consistent with the conceptual framework of the model. Data are also reported for Eu3+/smectite samples to provide additional insight into the exchange site populations. The emission spectra for Eu3+ in the basal-plane exchange sites differs significantly between SWy-1 and LK-1 samples reflecting a difference in the basal plane spacing between these two minerals, but the emission lifetime data suggest that the Eu3+ cation remains fully hydrated in both systems. The overall general description of surface speciation of uranyl on these mineral phases as enumerated by spectroscopy is in good accord with that derived from the conceptual thermodynamic model, lending added confidence to our understanding and descriptions of surface complexation behavior in this complex geochemical system.