Retardation of nonlinearly sorbed solutes in porous media

The impact of the assumption of linear sorption on retardation of nonlinearly sorbed solutes in porous media is numerically explored in this paper. Breakthrough data of nonlinearly sorbed solutes are generated using the BIO1D simulation code along with the Freundlich-type nonlinear sorption model. Retardation coefficients (R) from generated breakthrough curves are estimated using first-moment analysis. Variations of R with experimental conditions revealed that R of a nonlinearly sorbed solute is a function of the input concentration, the injection period and the pore-water velocity but is independent of the length scale. This study also showed that it is appropriate to estimate R of a nonlinearly sorbed solute using a linearized isotherm if all soil particles experience sorption with liquid concentration equal to the induced concentration. Otherwise, the estimated linearized R will be either under- or overestimated depending on the applied experimental conditions and Freundlich parameters. The study further revealed that inability to account for sorption nonlinearity may in some cases erroneously be interpreted as evidence of the presence of transport nonequilibrium. A method is suggested to determine nonlinear sorption parameters from miscible displacement experiments.