Analytical and conceptual deficiencies in understanding compositional variability in the smectite clays are expected to generate uncertainty in models used to simulate the chemical environment in bentonite backfill. Equilibrium models accounting for nonstoichiometry in smectite can nevertheless bound ranges in aqueous solution compositions that are an explicit function of the uncertainty in smectite compositions. In one approach, we quantify uncertainty in terms of ranges in concentrations of octahedral and tetrahedral Al, and exchange-site cations and vacancies. Heterogeneous mass transfer in bentonite-water systems is modeled using conventional mass-action relations and standard Gibbs energies for stoichiometric minerals, and the site-occupancy constraints combined with site-mixing relations for smectite. The resultant bounding conditions in groundwater compositions may be large or small depending on which aqueous species are of interest in a given situation, but they are valid irrespective of whether equilibrium in smectite-water reactions is attained or is inhibited by slow intracrystalline reaction rates.