Groundwater in fractured crystalline rocks, the Clara mine, Black Forest (Germany)
The chemical composition of water sampled in a 700 m deep underground barite-fluorite mine in the crystalline basement of the Black Forest area (SW Germany) varies systematically with depth and the length of flow paths trough, the fracture porosity of the gneiss matrix. Calcium and sulfate increase as a result of a combined sulfide oxidation and plagioclase alteration reaction. The gneiss contains andesine–plagioclase (An20–An40) and is rich in primary sulfide. As an effect of Ca and SO4 release by the prime water–rock reaction, dissolved oxygen decreases and the waters become more reduced. The waters have Cl/Br mass ratios of about 50, which is very close to that of experimentally leached gneiss powders indicating that the rock matrix is the source of the halogens. The waters are undersaturated with respect to calcite in the upper parts of the mine. With increasing reaction progress, calcite saturation is reached and carbonate forms as a reaction product of the prime reaction that also controls the partial pressure of CO2 to progressively lower values. The chemical evolution of groundwater in fractured basement of the Clara mine suggests that the partial pressure of CO2 is an internally buffered parameter rather than a controlling external variable.