Natural Clinoptilolite Modification for Removing Molybdate and Sulfate Ions from Mineral Processing Wastewater

"Wastewater from ores processing is often polluted by molybdate and sulfate (SO42-) ions. Sorption is one of suitable methods for removing those pollutants when presenting in low concentrations. This work reports results on adsorption of sulfate and molybdate ions on metal modified (with barium - Ba and lead - Pb) and organic reagent modified (with Hexadecyl-trimethyl-ammonium bromide - HDTMA) clinoptilolite. Zeolite’s modification with Pb, Ba and HDTMA increases its uptake capacity with respect to Mo(VI) at pH 3, with the uptake capacity decreasing in the order CL-Pb > CL-HDTMA > CL-Ba. Lead-modified clinoptilolite shows high uptake with respect to Mo(VI) in acidic, neutral and slightly alkaline conditions. The presence of SO42- in concentrations twice higher than the amount of Mo(VI) do not interfere with the Mo(VI) removal by CL-Pb. Zeolite’s modification with Ba and Pb renders it able to immobilize SO42- from water in the pH range 3-9. Kinetics of the uptake process is best described by the pseudo-first order kinetic equation. Increasing the initial concentrations of Mo(VI) and SO42- increases the removed amount of pollutants. INTRODUCTION Wastewater from copper-molybdenum ores processing is often polluted by molybdate and sulfate ions. Molybdenum (Mo) migrates easily in water and consequently the Mo polluted areas could extend for hundreds and thousands of meters (Ryzhenko, 2010). Molybdate anion is the only Mo(VI) species in natural water, i.e. at pH > 6.0. Its median freshwater hazardous concentration affecting 5% of the species (HC 5.50%) is 38.2 mg Mo/L (De-Schamphelaere et al., 2010). The marine water chronic toxicity (HC 5.50%) is assessed at 5.74 mg Mo/L (Heijerick et al., 2012). The predicted no-effect concentrations (PNEC) are 12.7 mg Mo/L and 1.92 mg Mo/L correspondingly for freshwater and marine water (Heijerick et al., 2012a). When sulfates present in drinking water in excess of 250 mg/L they cause a cathartic action (especially in children) in the presence of sodium and magnesium, and when the concentration exceeds 600 mg/L, diarrhea. When sulfate-rich effluents are discharged into the environment, they may increase the acidity of water bodies and soils (Guimarães and Leão, 2014). Because of the adverse effects to human health and the environment, limits are set for SO42- concentrations in waters and wastewaters in the range of 250 / 500 mg/L."