The use of laboratory-determined ion exchange parameters in the predictive modelling of field-scale major cation migration in groundwater over a 40-year period.

An attempt has been made to estimate quantitatively cation concentration changes as estuary water invades a Triassic Sandstone aquifer in northwest England. Cation exchange capacities and selectivity coefficients for Na(+), K(+), Ca(2+), and Mg(2+) were measured in the laboratory using standard techniques. Selectivity coefficients were also determined using a method involving optimized back-calculation from flushing experiments, thus permitting better representation of field conditions; in all cases, the Gaines-Thomas/constant cation exchange capacity (CEC) model was found to be a reasonable, though not perfect, first description. The exchange parameters interpreted from the laboratory experiments were used in a one-dimensional reactive transport mixing cell model, and predictions compared with field pumping well data (Cl and hardness spanning a period of around 40 years, and full major ion analyses in approximately 1980). The concentration patterns predicted using Gaines-Thomas exchange with calcite equilibrium were similar to the observed patterns, but the concentrations of the divalent ions were significantly overestimated, as were 1980 sulphate concentrations, and 1980 alkalinity concentrations were underestimated. Including representation of sulphate reduction in the estuarine alluvium failed to replicate 1980 HCO(3) and pH values. However, by including partial CO(2) degassing following sulphate reduction, a process for which there is 34S and 18O evidence from a previous study, a good match for SO(4), HCO(3), and pH was attained. Using this modified estuary water and averaged values from the laboratory ion exchange parameter determinations, good predictions for the field cation data were obtained. It is concluded that the Gaines-Thomas/constant exchange capacity model with averaged parameter values can be used successfully in ion exchange predictions in this aquifer at a regional scale and over extended time scales, despite the numerous assumptions inherent in the approach; this has also been found to be the case in the few other published studies of regional ion exchanging flow.