Multicomponent diffusion of a suite of tracers (HTO, Cl, Br, I, Na, Sr, Cs) in asingle sample of Opalinus Clay

Diffusion experiments with HTO, Cl-36(-), Br-, I-, Na-22(+), Sr-85(2+) and Cs-134(+) at trace concentrations in a single sample of Opalinus Clay are modeled with PHREEQC's multicomponent diffusion module. The model is used first in a classical approach to derive accessible porosities, geometrical factors (the ratio of pore tortuosity and constrictivity) and sorption behavior of the individual tracers assuming that the clay is homogeneous. The accessible porosity for neutral species and cations is obtained from HTO, the anion exclusion volume from Cl-36(-) and Br-, and the cation exchange capacity from 22Na+. The homogeneous model works well for tritium, the anions and Na-22(+). However, the Sr-85(2+) and Cs-134(+) experiments show an early arrival of the tracer and a front-form that Suggest a dual porosity structure. A model with 10% dead-end pores, containing 19% of the total exchange capacity, can satisfactorily calculate all the experimental data. The Cs+ diffusion model builds on a 3-site exchange model, constructed from batch sorption data. The excellent agreement of modeled and measured data contradicts earlier reports that the exchange capacity for Cs+ would be smaller in diffusion than in batch experiments. The geometrical factors for the anions are 1.5 times larger than for HTO, and for the cations 2-4 times smaller than for HTO. The different behavior is explained by a tripartite division of the porespace in free porewater, diffuse double layer (DDL) water, and interlayer water in montmorillonite. Differences between estimated and observed geometrical factors for cations are attributed to increased ion-pairing of the divalent cations in DDL water as a result of the low relative dielectric permittivity. Interlayer and/or surface diffusion contributes significantly to the diffusive flux of Cs+ but is negligible for the other solutes. The geometrical factors for anions are higher than estimated, because pore constrictions with overlapping double layers force the anions to take longer routes than HTO and the cations. Small differences among the anions can also be attributed to different ion-pairing in DDL water. (C) 2009 Elsevier Ltd. All rights reserved.