Rate-limited cation exchange in thin bentonitic barrier layers

A three-compartment model was developed for simulating cation transport in bentonitic barrier layers that incorporates diffusion-controlled cation exchange among the mobile intergranular water (bulk pore water), immobile interparticle and interlayer water, and the montmorillonite mineral solid. Exchange on the external surfaces and interlayer region of montmorillonite is included. The model was evaluated for divalent-for-monovalent cation exchange in bentonite with experiments. A parametric study was conducted using the model to investigate factors affecting the time required to establish chemical equilibrium (i.e., completion of cation exchange) between the permeant liquid and thin layers of bentonite simulating geosynthetic clay liners (GCLs). Predictions obtained with the model were in general agreement with the data without calibration, except for Na concentrations in the effluent at very long times. Parametric simulations conducted with the model show that the time required to establish chemical equilibrium in GCLs is affected by the rate at which adsorbing cations are delivered to the pore space (affected by seepage velocity or influent concentration), the rate of mass transfer between the mobile and immobile liquid phases (controlled primarily by granule size of the bentonite), and the number of sites available for sorption (controlled by CEC and the dry density of the bentonite).