Mineralogy and geochemistry of alluvium contaminated by metal mining in the Rio Tinto area, southwest Spain

The Rio Tinto in SW Spain drains Cu and pyrite mines which have been in operation since at least the Bronze Age. Extensive metal mining, especially from 1873 to 1954, has resulted in contamination of the Rio Tinto alluvium with As, Cu, Pb, Ag and Zn. X-ray diffraction (XRD), wavelength-dispersive X-ray mapping, scanning electron microscope petrography and X-ray energy-dispersive (EDX) analysis has revealed that 4 major groups of contaminant metal and As-bearing minerals, including sulphides, Fe-As oxides, Fe oxides/hydroxides/oxyhydroxides, and Fe oxyhydroxysulphates, occur in the alluvium. Sulphide minerals, including pyrite, chalcopyrite, arsenopyrite and sphalerite, occur in alluvium near the mining areas. Iron hydroxides and oxyhydroxides such as goethite and possibly ferrihydrite occur in cements in both the mining areas and alluvium downstream, and carry minor amounts of As, Cu and Zn. Iron oxyhydroxysulphates; including jarosite, plumbojarosite and possibly schwertmannite, are the most common minerals in alluvium downstream of the mining areas, and are major hosts of Cu, Pb, Zn and of As, next to the Fe-As minerals. This work, and other field observations, suggest that (1) the extreme acidity and elevated metal concentrations of the river water will probably be maintained for some time due to oxidation of pyrite and other sulphides in the alluvium and mine-waste tips, and from formation of secondary oxide and oxyhydroxysulphates; (2) soluble Fe oxyhydroxysulphates such as copiapite, which form on the alluvium, are a temporary store of contaminant metals, but are dissolved during periods Of high rainfall or flooding, releasing contaminants to the aqueous system; (3) relatively insoluble Fe oxyhydroxysulphates and hydroxides such as jarosite and goethite may be the major long-term store of alluvial contaminant metals; and (4) raising river pH will probably cause precipitation of Fe oxyhydroxides and oxides/hydroxides/oxyhydroxides and thus have a positive effect on water quality, but this action may destabilise some of these contaminant metal-bearing minerals, releasing metals back to the aqueous system