Investigations within the Silverton caldera, in southwestern Colorado,used a combination of traditional geological mapping, alteration-assemblage mapping, and aqueous geochemical sampling that showed a relationship between geological and hydrologic features that may be used to better understand the provenance and evolution of the water. Veins containing fluorite, huebnerite, and elevated molybdenum concentrations are temporally and perhaps genetically associated with the emplacement of high-silica rhyolite intrusions. Both the rhyolites and the fluorite-bearing veins produce waters containing elevated concentrations of F−, K and Be. The identification of water samples with elevated F/Cl molar ratios (> 10) has also aided in the location of water draining F-rich sources, even after these waters have been diluted substantially. These unique aqueous geochemical signatures can be used to relate water chemistry to key geological features and mineralized source areas. Two examples that illustrate this relationship are: (1) surface-water samples containing elevated F− concentrations (> 1.8 mg/l) that closely bracket the extent of several small high-silica rhyolite intrusions; and (2) water samples containing elevated concentrations of F− (> 1.8 mg/l) that spatially relate to mines or areas that contain late-stage fluorite/huebnerite veins. In two additional cases, the existence of high F− concentrations in water can be used to: (1) infer interaction of the water with mine waste derived from systems known to contain the fluorite/huebnerite association; and (2) relate changes in water quality over time at a high elevation mine tunnel to plugging of a lower elevation mine tunnel and the subsequent rise of the water table into mineralized areas containing fluorite/huebnerite veining. Thus, the unique geochemical signature of the water produced from fluorite veins indicates the location of high-silica rhyolites, mines, and mine waste containing the veins. Existence of high F− concentrations along with K and Be in water in combination with other geological evidence may be used to better understand the provenance of the water.