title: Pore-scale modeling of competitive adsorption in porous media.
abstract: In this paper we present a smoothed particle hydrodynamics (SPH) pore-scale multicomponent reactive transport model with competitive adsorption. SPH is a Lagrangian, particle based modeling method which uses the particles as interpolation points to discretize and solve flow and transport equations. The theory and details of the SPH pore-scale model are presented along with a novel method for handling surface reactions, the continuum surface reaction (CSR) model. The numerical accuracy of the CSR model is validated with analytical and finite difference solutions, and the effects of spatial and temporal resolution on the accuracy of the model are also discussed. The pore-scale model is used to study competitive adsorption for different Damköhler and Peclet numbers in a binary system where a plume of species B is introduced into a system which initially contains species A. The pore-scale model results are compared with a Darcy-scale model to investigate the accuracy of a Darcy-scale reactive transport model for a wide range of Damköhler and Peclet numbers. The comparison shows that the Darcy model over estimates the mass fraction of aqueous and adsorbed species B and underestimates the mass fractions of species A. The Darcy-scale model also predicts faster transport of species A and B through the system than the pore-scale model. The overestimation of the advective velocity and the extent of reactions by the Darcy-scale model are due to incomplete pore-scale mixing. As the degree of the solute mixing decreases with increasing Peclet and Damköhler numbers, so does the accuracy of the Darcy-scale model.
authors.affiliation: Carnegie Mellon University, Department of Mechanical Engineering, Pittsburgh, PA 15213, USA. emily.ryan@pnl.gov
authors.forename: Emily M
authors.initials: EM
authors.lastname: Ryan
authors.forename: Alexandre M
authors.initials: AM
authors.lastname: Tartakovsky
authors.forename: Cristina
authors.initials: C
authors.lastname: Amon
mesh_terms: D000327:Adsorption; D057446:Hydrodynamics; D008962:Models, Theoretical; D016062:Porosity; D012989:Soil Pollutants / Q000032:analysis*; D012996:Solutions; D014874:Water Pollutants, Chemical / Q000032:analysis*
chemical_list: D012989:Soil Pollutants; D012996:Solutions; D014874:Water Pollutants, Chemical