Geochemical research on natural weathering has often been directed towards explanations of the chemical composition of surface water and ground water resulting from subsurface water-rock interactions. These interactions are often defined as the incongruent dissolution of primary silicates, such as feldspar, producing secondary weathering products, such as clay minerals and oxyhydroxides, and solute fluxes (Meunier and Velde, 1979). The chemical composition of the clay-mineral product is often ignored. However, in earlier investigations, the saprolitic weathering profile at the South Fork Brokenback Run (SFBR) watershed, Shenandoah National Park, Virginia, was characterized extensively in terms of its mineralogical and chemical composition (Piccoli, 1987; Pochatila et al., 2006; Jones et al., 2007) and its basic hydrology. O’Brien et al. (1997) attempted to determine the contribution of primary mineral weathering to observed stream chemistry at SFBR. Mass-balance model results, however, could provide only a rough estimate of the weathering reactions because idealized mineral compositions were utilized in the calculations. Making use of detailed information on the mineral occurrence in the regolith, the objective of the present study was to evaluate the effects of compositional variation on mineral-solute mass-balance modelling and to generate plausible quantitative weathering reactions that support both the chemical evolution of the surface water and ground water in the catchment, as well as the mineralogical evolution of the weathering profile.