Surface charge and UO 22+ adsorption were measured on a clay-sized, subsurface mineral isolate whose mineralogy was dominated by a ferrogenous beidellite. Experiments were performed in batch at 25°C with N 2(g) atmosphere and sorbent suspensions (9.46 g clay/kg suspension) that had been adjusted in pH between 4 and 9. Surface charge was defined by measurements of adsorbed Na by isotopic exchange and of proton adsorption by potentiometric titration in NaClO 4 ( I = 0.1, 0.01, 0.001). Extraction of the clay with La(NO 3) 3 and aqueous-phase analyses were necessary to establish the contributions of Al and Si dissolution to the proton balance and the total adsorbed cation charge (i.e., Na ads+ + 3Al ads3+). The adsorption of UO 22+ (7.5 × 10 -6 mol L -1) was determined in Na + (0.1, 0.01, 0.001 mol L -1) and Ca 2+ (0.05 and 0.005 mol L -1) electrolytes. Adsorption of UO 22+ showed contributions of ion exchange and edge complexation reactions in Na + electrolyte, but by only edge complexation reactions in Ca 2+ electrolyte. A multiple-site surface-complexation model containing fixed- X- and variable-charge sites (SiOH, AlOH) was fit to adsorbed cation charge data between pH 4 and 10, with the concentrations of AlOH, SiOH, and X- as the adjustable parameters. Surface acidity and ion-pair formation constants for gibbsite and silica were used to describe the ionization and electrolyte binding of the AlOH and SiOH sites. The model provided an excellent description of the surface-charge characteristics of the clay as measured by sodium isotopic exchange and potentiometric titration. A composite model was formulated to predict UO 22+ adsorption by incorporating UO 22+ aqueous speciation, competitive ion exchange with background electrolyte cations, and UO 22+ complexation with AlOH and SiOH sites. UO 22+ complexation with AlOH and SiOH was parameterized by UO 22+ sorption on α-Al(OH) 3(s) and α-SiO 2(s), respectively. The composite model overpredicted UO 22+ sorption across the entire pH range in both electrolytes. Acceptable predictions could be obtained if the UO 22+ affinity for edge AlOH sites were adjusted 2.03 log units below that of gibbsite. Changes in chemical affinity arising from lattice substitutions and edge site morphology are, therefore, concluded to contribute significantly to adsorption, although the potential competitive effects of dissolved Al 3+ and H 4SiO 4 could not be discounted. The adsorption of UO 22+ on the subsurface smectite was similar to that of the reference montmorillonite, SWy-1, with the exception that Al dissolution contributed significantly to adsorbed cation charge.