[en] The chemistry of groundwaters is one of the most important parameters in determining the mobility of species within a rock formation. A three pronged approach was used to determine the composition of, and geochemical controls, on groundwaters specifically within shale formations: (1) available data were collected from the literature, the US Geological Survey WATSTORE data base, and field sampling, (2) the geochemical modeling code EQ3/6 was used to simulate interaction of various shales and groundwaters, and (3) several types of shale were reacted with synthetic groundwaters in the laboratory. The comparison of model results to field and laboratory data provide a means of validating the models, as well as a means of deconvoluting complex field interactions. Results suggest that groundwaters in shales have a wide range in composition and are primarily of the Na-Cl-HCO₃- type. The constancy of the Na:Cl (molar) ratio at 1:1 and the Ca:Mg ratio from 3:1 to 1:1 suggests the importance of halite and carbonates in controlling groundwater compositions. In agreement with the reaction path modeling, most of the groundwaters are neutral to slightly alkaline at low temperatures. Model and experimental results suggest that reaction (1) at elevated temperatures, or (2) in the presence of oxygen will lead to more acidic conditions. Some acetate was found to be produced in the experiments; depending on the constraints applied, large amounts of acetate were produced in the model results. 13 refs., 1 tab