A Conservative Darcy-Brinkman-Stokes Formulation for PHREEQC-Coupled Reactive Transport with Cell-Based Surface Complexation

Abstract

We present a mass-conservative Darcy-Brinkman-Stokes (DBS) formulation for reactive transport with cell-based surface complexation in image-based porous media, coupled to PHREEQC and implemented in GeoChemFoam, an OpenFOAM-based toolbox. Dissolved species are transported in the physical mobile-water fraction, adsorbed species are stored as conservative cell-scale surface inventories, and each reactive cell is coupled to PHREEQC. Reactive surface area is prescribed independently as a cell field, so that internal area left unresolved by segmentation of microporous phases can be represented while DBS flow and transport are retained in the resolved pore space. The implementation is verified with a test suite that isolates the coupling of transport and chemistry from the construction of reactive surface area. Aqueous and adsorbed mass balance is evaluated against a one-dimensional analytical retardation benchmark and closed-system batch calculations. The smooth-interface surface-area algorithms are tested on idealised two- and three-dimensional geometries. In a two-scale lithium micromodel, DBS reproduces fully resolved aqueous and sorbed inventories within 0.6% across Pe=0.1-10. The applications comprise Pb2+ retardation by hydrous ferric oxide coatings in a two-dimensional fracture network, competitive Mn2+/Mg2+ exchange in a three-dimensional Kelvin-cell sorbent, and Sr2+/Ca2+ exchange in Estaillades limestone. In the fracture-network and limestone cases, the formulation yields spatially resolved aqueous and adsorbed inventories even where reactive surface area is only partly resolved at the image scale. The framework therefore supports conservative surface-complexation modelling in both resolved and unresolved pore structures, with relevance to contaminant retention, selective ion capture, and radionuclide transport.