Copahue volcano erupted altered rock debris, siliceous dust, pyroclastic sulfur, and rare juvenile fragments between 1992 and 1995, and magmatic eruptions occurred in July– October 2000. Prior to 2000, the Copahue crater lake, acid hot springs, and rivers carried acid brines with compositions that reflected close to congruent rock dissolution. The ratio between rock-forming elements and chloride in the central zone of the volcano-hydrothermal system has diminished over the past few years, reflecting increased water/rock ratios as a result of progressive rock dissolution. Magmatic activity in 2000 provided fresh rocks for the acid fluids, resulting in higher ratios between rock-forming elements and chloride in the fluids and enhanced Mg fluxes. The higher Mg fluxes started several weeks prior to the eruption. Model data on the crater lake and river element flux determinations indicate that Copahue volcano was hollowed out at a rate of about 20 000–25 000 m3/yr, but that void space was filled with about equal amounts of silica and liquid elemental sulfur. The extensive rock dissolution has weakened the internal volcanic structure, making flank collapse a volcanic hazard at Copahue.