Hydrogeochemical characteristics of the Tinto and Odiel Rivers (SW Spain). Factors controlling metal contents

The Tinto and Odiel Rivers are strongly affected by acid mine drainage (AMD) due to the intense sulphide mining developed in their basins over the past 5000 years. In this study the results obtained from a weekly sampling in both rivers, before their mouth in the Ría of Huelva, over three and a half years of control are analysed. In the Tinto River, the concentrations of sulphates, Al, Cd, Co, Li and Zn are double to those of the Odiel as a consequence of lower dilution. However, the concentration of Fe in the Odiel River is 20 times lower, since the precipitation of Fe oxyhydroxysulphates caused by neutralisation processes is more intense. Lower As, Cr, Cu and Pb concentrations are also found in the Odiel River as, to a greater or lesser extent, they are sorbed and/or coprecipitated with Fe. Other elements such as Be, Mn, Ni and Mg show similar values in both systems, which is ascribed to lithological factors. The seasonal evolution of contaminants is typical of rivers affected by AMD, reaching a maximum in autumn due to the dissolution of evaporitic salts precipitated during the summer. Nevertheless, in the Tinto River, Ca, Na and Sr show a strong increase during the summer, probably due to a greater water interaction with marly materials, through which the last reach of the river flows. Barium has a different behaviour from the rest of the metals and its concentration seems to be controlled by the solubility of barite. Iron, As and Pb show different behaviours in both rivers, those for Fe and As possibly linked to the prevalence of different dissolved species of Fe. The different Pb pattern is probably due to the control of Pb solubility by anglesite or other minerals rich in Pb in the Tinto River.