Leachates from the El Fraile tailings impoundment (Taxco, Mexico) were monitored every 2 months from October 2001 to August 2002 to assess the geochemical characteristics. These leachates are of interest because they are sometimes used as alternative sources of domestic water. Alternatively, they drain into the Cacalotenango creek and may represent a major source of metal contamination of surface water and sediments. Most El Fraile leachates show characteristics of Ca-SO(4), (Ca+Mg)-SO(4), Mg-SO(4 )and Ca-(SO(4)+HCO(3)) water types and are near-neutral (pH=6.3-7.7). Some acid leachates are generated by the interaction of meteoric water with tailings during rainfall events (pH=2.4-2.5). These contain variable levels of SO(4) (2-) (280-29,500 mg l(-1)) and As (<0.01-12.0 mg l(-1)) as well as Fe (0.025-2,352 mg l(-1)), Mn (0.1-732 mg l(-1)), Zn (<0.025-1465 mg l(-1)) and Pb (<0.01-0.351 mg l(-1)). Most samples show the highest metal enrichment during the dry seasons. Leachates used as domestic water typically exceed the Mexican Drinking Water Guidelines for sulfate, hardness, Fe, Mn, Pb and As, while acidic leachates exceed the Mexican Guidelines for Industrial Discharge Waters for pH, Cu, Cd and As. Speciation shows that in near-neutral solutions, metals exist mainly as free ions, sulfates and bicarbonates, while in acidic leachates they are present as sulfates and free ions. Arsenic appears as As((V)) in all samples. Thermodynamic and mineralogical evidence indicates that precipitation of Fe oxides and oxyhydroxides, clay minerals and jarosite as well as sorption by these minerals are the main processes controlling leachate chemistry. These processes occur mainly after neutralization by interaction with bedrock and equilibration with atmospheric oxygen.