This study was focused on the historical evolution of the waste management policy carried out by the Spanish industry devoted to titanium dioxide pigments manufacturing for minimising its environmental impact. This challenge was achieved by modifying the original chemical process and converting the originally dissolved sulphate and sulphuric acid present in the final streams of the factory into sulphate minerals (melanterite FeSO4·7H2O, szomolnokite FeSO4·H2O, and gypsum CaSO4·2H2O). These by-products were physicochemically, mineralogically and radiologically characterised in order to gain basic information for its subsequent commercial use. Some of the uses summarised in this study for both ferrous sulphates are as a supplier of iron to prevent chlorosis, animal food, manufacture of cement (to reduce Cr VI), primary flocculants for ferrous sulphates, magnetite nanoparticle and nano-Fe2O3 formation, production of magnetite concentrate, remediation of polluted soils with metals, and treatment of wastewaters. Red gypsum was analysed as a substitute for natural gypsum in the manufacture of cement, construction materials, inhibitor in soil erosion, and the immobilisation of heavy metals in agricultural soils and carbonation processes.
The spatiotemporal evolution of both U and Th isotopes in a mine effluent highly polluted by acid mine drainage (AMD) was evaluated. The acidic tributary, which born from the outflows of an abandoned sulfide mine, flows into the Odiel River. AMD comprises an important source of natural radionuclides, presenting concentrations of 238U and 232Th, two and four orders of magnitude higher, respectively, than the background values of surface continental waters. These natural radionuclides behave conservatively along the mine effluent (pH < 2.5) throughout the hydrological year. Under AMD conditions uranium is in the hexavalent state U(VI) and the main dissolved species are uranyl sulfate complexes. The polluted tributary has a significant impact on the Odiel River acidifying its waters during the low flow season and increasing up to one order of magnitude the activity concentrations of U and Th isotopes. U presented a conservative behavior in the Odiel River during the low flow season (pH ≈ 3), however it is removed from the liquid phase in the wet season (pH ≈ 6), probably due its coprecipitation/adsorption onto Al-phases. Th shows a high sensitivity to small increases of pH, and it is strongly coprecipitated/adsorbed with or onto Fe-oxyhydroxydizes in the river.