Modelling cation exchange in columns of disturbed and undisturbed subsoil

Cation exchange is often studied with disturbed and dried soils, but the applicability of the results to undisturbed soils is not straightforward. We investigated the value of exchange coefficients obtained from standard procedures for predicting cation exchange in soil. Columns of undisturbed and disturbed subsoil of a Luvisol (SBt horizon) were leached under saturated conditions with 0.4, 4, 20, 41, 102 and 205 mm BaCl₂ at a Darcy velocity of 1400 mm day^?1. The model PHREEQC was used to calculate one‐dimensional transport, inorganic complexation and multiple cation exchange. Two model variants were tested: m1 (exchangeable cations obtained by percolation with NH₄Cl) and m2 (exchangeable cations obtained by shaking the soil with BaCl₂). The exchange coefficients (Gaines–Thomas formalism) were calculated from the ion activities in solution and exchangeable cations obtained by NH₄Cl percolation (m1) or shaking with BaCl₂ (m2). Variant m1 predicted cation exchange of the disturbed (homogenized) soil for the entire BaCl₂ concentration range, whereas variant m2 resulted in a two‐fold overestimation of desorbed K for all experiments, which was related to large amounts of K released from the soil by shaking with BaCl₂. In experiments with undisturbed soil, variant m1 predicted the concentrations of Mg, Ca, K, and Na in the solution phase and the sum of cations released from exchange sites. However, variant m2 predicted changes in ion concentrations and exchangeable cations somewhat less well. This study suggests that the amounts of exchangeable cations and exchange coefficients obtained from experiments with homogenized soil by percolation are useful to predict cation concentrations in column experiments with undisturbed soils.