Groundwater transport modeling with nonlinear sorption and intraparticle diffusion

• We present split-operator models for solute transport with nonideal sorption.
• Numerical experiments address transport with “dual mode” and nonlinear isotherms.
• Numerical experiments address intraparticle diffusion for multi-particle systems.

Despite recent advances in the mechanistic understanding of sorption in groundwater systems, most contaminant transport models provide limited support for nonideal sorption processes such as nonlinear isotherms and/or diffusion-limited sorption. However, recent developments in the conceptualization of “dual mode” sorption for hydrophobic organic contaminants have provided more realistic and mechanistically sound alternatives to the commonly used Langmuir and Freundlich models. To support the inclusion of both nonlinear and diffusion-limited sorption processes in groundwater transport models, this paper presents two numerical algorithms based on the split operator approach. For the nonlinear equilibrium scenario, the commonly used two-step split operator algorithm has been modified to provide a more robust treatment of complex multi-parameter isotherms such as the Polanyi-partitioning model. For diffusion-limited sorption, a flexible three step split-operator procedure is presented to simulate intraparticle diffusion in multiple spherical particles with different sizes and nonlinear isotherms. Numerical experiments confirmed the accuracy of both algorithms for several candidate isotherms. However, the primary advantages of the algorithms are: (1) flexibility to accommodate any isotherm equation including “dual mode” and similar expressions, and (2) ease of adapting existing grid-based transport models of any dimensionality to include nonlinear sorption and/or intraparticle diffusion. Comparisons are developed for one-dimensional transport scenarios with different isotherms and particle configurations. Illustrative results highlight (1) the potential influence of isotherm model selection on solute transport predictions, and (2) the combined effects of intraparticle diffusion and nonlinear sorption on the plume transport and flushing for both single-particle and multi-particle scenarios.