Obtaining the porewater composition of a clay rock by modeling the in- and out-diffusion of anions and cations from an in-situ experiment

A borehole in the Callovo–Oxfordian clay rock in ANDRAʹs underground research facility was sampled during 1 year and chemically analyzed. Diffusion between porewater and the borehole solution resulted in concentration changes which were modeled with PHREEQCʹs multicomponent diffusion module. In the model, the clay rockʹs pore space is divided in free porewater (electrically neutral) and diffuse double layer water (devoid of anions). Diffusion is calculated separately for the two domains, and individually for all the solute species while a zero-charge flux is maintained. We explain how the finite difference formulas for radial diffusion can be translated into mixing factors for solutions. Operator splitting is used to calculate advective flow and chemical reactions such as ion exchange and calcite dissolution and precipitation. The ion exchange reaction is formulated in the form of surface complexation, which allows distributing charge over the fixed sites and the diffuse double layer. The charge distribution affects pH when calcite dissolves, and modeling of the experimental data shows that about 7% of the cation exchange capacity resides in the diffuse double layer. The model calculates the observed concentration changes very well and provides an estimate of the pristine porewater composition in the clay rock.