The Panasqueira hydrothermal mineralization, located in central Portugal, is the biggest Sn–W deposit of the Western Europe. The main evidences of the mining exploitation and ore treatment operations are testified with huge tailings, mainly, in the Rio and Barroca Grande areas. The mining and beneficiation processes, at the site, produces metal rich mine wastes. Oxidation of sulfides tailings and flow from open impoundments are responsible for the mobilization and migration of metals from the mine wastes into the environment. Acid mine drainage (AMD) discharged from Rio tailing has a pH around 3 and high metal concentrations. In Zêzere river, Fe and As are the most rapidly depleted downstream from AMD once As adsorbs, coprecipitate and form compounds with iron oxyhydroxides. The Zêzere river waters are oversaturated with respect to kaolinite and goethite and ferrihydrite can precipitate on stream with a near-neutral pH. At sites having low pH the dissolved Fe species in the water, mainly, occur as sulfate complexes due to a high SO4 concentration. Melanterite (Fe2+(SO4)·7(H2O)) and minor amounts of rozenite (Fe2+(SO4)·4(H2O)) and szomolnokite (Fe2+(SO4)·(H2O)) were observed on Rio tailing basement.