In the past, mining activities have generated major acid drainage sources, which usually carry dissolved metals that flow into the main rivers of the affected basins. The study looks at natural attenuation processes in local, sub-basin and basin areas, in the El Bierzo and Odiel basins of Spain, where coal and metal mining activities were formerly conducted. In this study, sampling and in situ monitoring of pH, Eh, dissolved oxygen, conductivity, temperature, flow, turbidity, acidity, alkalinity, Fe2+, Fe3+ and total Fe were carried out during the hydrological cycle. Chemical analysis was also performed on water samples, following the water quality data of the ICA Network of the Spanish Environment Ministry for a period of 10 years. The results show that the main natural attenuation processes were: dilution by mixing with clean water, oxidation and hydrolysis of dissolved metals, reduction of anaerobic sulphates, and precipitation of secondary minerals.