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.
The immobilization of hazardous wastes in ordinary Portland cement (OPC)-based materials has been widely studied and implemented. OPC-based materials have a high carbon footprint associated with their production and geopolymer materials are a sustainable and eco-friendly alternative. Therefore, this work aimed to immobilize two hazardous industrial wastes: copper wastewater sludge and phosphogypsum in one-part geopolymer materials. For that purpose, the precursor was partially substituted by these wastes (5, 10 and 20 wt.%) in the formulations. The geopolymer fresh and hardened state properties were evaluated, and the immobilisation of pollutants was determined through leaching tests. In phosphogypsum pastes (PG5, PG10 and PG20) it was observed that the compressive strength decreased with the increase in its amount, varying between 67 MPa and 19 MPa. In copper sludge pastes, the compressive strength of the specimens (CWS5 and CWS10) reached ~50 MPa. The mortars, MPG10 and MCWSs10, had compressive strengths of 13 MPa and 21 MPa, respectively. Leaching tests showed that pastes and mortars immobilise the hazardous species of the wastes, except for As from copper sludge, whose the best result was found in the compact paste (CWSs10) that leached 2 mg/kg of As. Results suggest that optimized compositions are suitable for the construction sector.
Four industrial wastes, namely, tionite (T), iron grit (IG), electroplating sludge (ES), and mill scale (MS), are typically disposed of in controlled hazardous landfills because of their toxic content, posing potential harm to human health and to the environment. At the same time, the chemical composition of these wastes, specifically the nature and content of transition metals, makes them potentially attractive for reuse in pigments manufacturing. This work details the study of these residues for producing coloured perovskites to be tested as inorganic pigments. The residues were mixed, in different proportions, and subsequently calcined to produce the required structures. The colouring potential was then assessed in a ceramic paste and in a transparent glaze. Leaching tests were carried out to verify the effective immobilisation of the hazardous species. Dark pigments were successfully obtained from the mixtures of T: ES: Co3O4, T: MS and T: IG. The crystalline phases present in T: ES: Co3O4 are nickel–chromium iron oxide spinel–Fe1.5Cr0.5NiO4 (without Co) or trevorite–Fe2NiO4 (with Co), titanium nickel oxide–TiNiO3 and titanite–CaTiSiO5. The mixtures T: MS and T: IG presented hematite (Fe2O3) and pseudobrookite (Fe2TiO5). Leaching tests confirmed the non-hazardous or inert character of the synthesized pigments. Products showed brownish or greyish hues, depending on the pigment added. T:75ES_1100, T:73ES:2Co_1100, T:75MS_1000, T:75MS_1100 and T:75IG_1000 pigments can effectively and safely be used to colour ceramic paste replacing partially or totally the commercial pigments.