Simulation of nonlinear sorption of N-heterocyclic organic contaminates in soil columns.

The transport of organic contaminants in porous media is frequently influenced by nonequilibrium sorption and/or nonlinear sorption. In this study, sorption of coal tar related contaminants with different sorption properties, i.e., toluene, quinoline, quinaldine, and benzotriazole, was studied in column experiments using a European reference soil and compared with batch sorption results in order to quantify the governing sorption features. The breakthrough curves (BTCs) were simulated with a versatile 1-D reactive transport model using a one-site first-order sorption approach. Some differences in fitted parameters from batch and column experiments were found and discussed in terms of different sorption mechanisms in different aqueous concentration ranges, effects of solution properties (e.g., pH) and differences in solid-to-solution ratio and accessible sorption sites. The modeling results show that the fitting results were not sensitive to mass transfer coefficients and that a local equilibrium assumption provides excellent agreement with BTCs in our designed column when Damkohler numbers were greater than 20. Nonequilibrium sorption resulting from intraparticle diffusion thus was negligible in the column experiments. Tailing of BTCs nevertheless occurred and was primarily attributed to nonlinear sorption due to specific interactions in the sorption processes rather than to sorption nonequilibrium. Our study demonstrates how column experiments with different concentrations and flow velocities can be designed to obtain reliable sorption parameters for polar solutes with nonlinear sorption isotherms from modeling.