Multiport ground‐water sampling systems in five deep core holes near DOE's Y‐12 facility at Oak Ridge, Tennessee provide data on the three‐dimensional distribution of ground‐water types and chemical evolution processes. Interpretation of ground‐water chemistry, coupled with data on the primary and authigenic mineralogy from drill core, indicates the ground water evolves chemically by three main processes: (1) open system dissolution of calcite and dolomite at shallow depths to produce Ca‐Mg‐HCO3 waters; (2) irreversible dissolution of gypsum, which causes dedolomitization and leads to the formation of Ca‐Mg‐SO4 waters at deeper levels; and (3) mixing with deep brines to form saline Na‐Ca‐Cl waters. Evidence for dedolomitization included the precipitation of authigenic calcite in gypsum dissolution cavities, decrease in ground‐water pH, and increases in dissolved Ca, Mg, and SO4. In this study, we document the dedolomitization process along a relatively short (< 2000 ft) flow path in low permeability Paleozoic carbonates. Mixing of the shallower ground water with an Na‐Ca‐Cl brine thought to be present at depth can account for the progressive increase in salinity of ground water with depth and the precipitation of authigenic barite and celestite. The mixing process could be a combination of diffusion from below, diffusion from older matrix water into fractures, or advective mixing.