Intensive mining and processing of Ag, Sn, Pb and Zn ores have occurred in various locations within and around the city of Potosí, Bolivia since 1545. Surface and subsurface waters, stream sediments and soils are contaminated with various ecotoxic metals in the headwaters of the economically vital, yet highly impacted, upper Rio Pilcomayo watershed. Previous studies have documented downstream trace metal contamination, however, not addressed specific sources. The AMD discharges identified in this study help link downstream pollution to primary origins. The majority of AMD would be considered high-strength due to metal concentrations and acidity orders of magnitude greater than typical AMD. Discharges from both operating and abandoned portals as well as tailings-related deposits displayed a high degree of heterogeneity with total metal concentrations ranging from 0.11 to 7480, \0.022 to 889, \0.0006 to 65.3, \0.001 to 310, 0.12 to 72,100, 0.3 to 402, \0.012 to 34.8, and 0.24 to 19,600 mg/L of Al, As, Cd, Cu, Fe, Mn, Pb and Zn, respectively. Net acidity and pH ranged from -10 to 246,000 mg/L as CaCO 3 equivalent and 0.90-6.94 standard units, respectively. Data were gathered during two sampling events centered around the most extreme periods of the dry and wet seasons of one water-year. Loadings to local streams were marginally greater for most metals in the wet season. If observed loadings are historically representative, Cerro Rico AMD has contributed thousands of tonnes of ecotoxic metals to the upper Rio Pilcomayo over the last five centuries. Metal and hydrogen ion concentrations in the majority of AMD sampled were several orders of magnitude above discharge limits set by the Bolivian government, yet no action has historically or contemporarily been taken.
