In performance assessments for nuclear wastes repositories, Kd values are often used to describe sorption of radionuclides on fracture surfaces. The weakness of the Kd concept is that values determined under certain conditions can only be used when the chemistry is similar to those. Alternatives include surface complexation models. The problem with such models is that the parameters required are not easily determined, and thus are missing for several systems.

Another alternative is to use surface phase thermodynamics. Such a theory has been developed, in which the surface of a solid phase and the species adsorbed upon it are treated as a separate phase of variable composition. The composition is described in terms of pure end members. For each end member, the free enthalpy is described by a series expansion. To calculate coefficients, the theory makes use of the fact that at equilibrium, the chemical potential of a component has the same value in all phases. Thus, speciation of the bulk aqueous phase can be used. Making use of only the linear term in the expansion, one measured Kd value is enough to determine the corresponding coefficient.

The theory has been applied to sorption of U(VI) on alumina with the aid of data from the literature. The coefficient was determined from the measured Kd values in the interval pH = 4 – 12. The resulting model curve was found to agree reasonably well with observed values, although the Kd varies by a factor of 200.