Acid-enhanced limestone defluoridation in column reactor using oxalic acid

Acid enhanced limestone defluoridation of water has been studied in a crushed limestone column reactor using oxalic acid (OA). The defluoridation has been studied with varying initial fluoride concentrations of 5, 10, 15 and 20 mg/L and acid concentrations of 0.01, 0.05 and 0.1 M. The fluoride removal was found to increase with increase in the concentration of the acid, removing fluoride up to 95% with 0.1 M OA. The observed good fluoride removal has been attributed to a combination of two mechanisms of fluoride removal, viz., precipitation of calcium fluoride and adsorption of fluoride ions on limestone surfaces. While the removal by precipitation remains same on repeated use of the same limestone column, the adsorption is more with the fresh limestone and decreases gradually on repeated use of the same limestone column. The precipitate has been characterized using various analytical tools, viz., X-ray diffraction, IR spectroscopy, thermogravimetric analysis, scanning electron microscopy combined with energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. The Ca2+ ions, formed due to dissolution of limestone by the acid, precipitate calcium fluoride along with precipitation of calcium oxalate. A good fluoride removal ability, low residual oxalate, acceptable final pH, low-cost and simplicity of the process make the present acid-enhanced limestone defluoridation process with OA a potential method for defluoridation of groundwater.

► Oxalic acid has been used for enhancing limestone defluoridation of groundwater.
► The method removes F− from an initial concentration of 10 mg/L to below 1 mg/L.
► The F− removal takes place by both precipitation and adsorption simultaneously.
► The method is safe in terms of pH and residual oxalate and residual heavy metals.
► The method is efficient, low-cost and safe and has potential for application.