An arsenic speciation study has been performed in the headwaters of the Tinto River, representing an environment heavily polluted in Acid Mine Drainage originated by the Iberian Pyrite Belt. The variables considered in this study were arsenic species, pH, redox potential, conductivity, temperature, rainfall and concentrations of metals such as Fe, Cu and Zn. The results obtained from the classical statistical treatment confirm the extreme acidity and high concentrations of metals, sulfates and arsenic species (mean values of 2.3 for pH, 1.10 mg L−1 for Cd, 325.4 mg L−1 for Cu, 1241.1 mg L−1 for Fe, 241.2 mg L−1 for Zn, 91.1 mg L−1 for Mn, 0.1 mg L−1 for As(III) and 0.3 mg L−1 for As(V), 5000 mg L−1 of sulfate). Additionally, the speciation of arsenic showed As(V) concentrations always twice or thrice higher than As(III). This distribution of arsenic species was followed along the whole hydrological year, on a daily basis. An increment of the mean concentrations and variability of the arsenic species concentration was also observed in relation to temperature increase during the Spring time.

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