Understanding fluoride adsorption from groundwater by alumina modified with alum using PHREEQC surface complexation model

Fluoride is recognized as a vital ion for human and animal growth because of the critical role it plays in preventing skeletal and dental problems. However, when it is ingested at a higher concentration it can cause demineralization of teeth and bones resulting in fluorosis, therefore, the production of high-adsorptive capacity material which is also cost-effective is necessary for the treatment of fluorides. In this study, aluminium foil is valorised into alumina nanoparticles. The as-prepared alumina was modified with alum in two different ratios of 1:0.5 and 1:1 (alumina to alum w/w%) and later used as adsorbents for the removal of fluoride from groundwater. The adsorbents were characterized by Fourier transform infrared spectroscopy, point of zero charge and X-ray diffraction. Different factors that influence the removal efficiency of fluorides such as pH, initial concentrations, contact time and adsorbent dosage were studied and optimized using a simulated fluoride solution. The optimum conditions obtained were used to test real groundwater. The static experiment conditions were used to calibrate a PHREEQC geochemical model which was later used to simulate the fluoride sorption onto the modified alumina at different conditions. PHREEQC was also coupled with parameter estimation software to determine equilibrium constants for the surface reactions between the fluoride species and the adsorbent in a way that the simulations accurately reflect the outcomes of laboratory experiments. Isotherm studies were carried out on the adsorbents. Both Langmuir and Freundlich's non-linear models fitted well for the equilibrium data. However, with a higher coefficient of regression and low chi-square test values, the adsorption process was more of chemisorption on a monolayer surface. Kinetic studies were also carried out by using the non-linear equations from the pseudo-first-order and pseudo-second-order models. The pseudo-second-order model fitted well for the equilibrium data. The mechanism for the fluoride ion adsorption was also studied by the intraparticle (IP) diffusion model and was found that IP was not the rate-determining factor, and therefore the most plausible mechanism for the sorption process was ion exchange or attraction of fluoride ions to the sorbent surface. The findings obtained from this research show that readily available aluminium waste could be valorised into a useful product that could be employed in the removal of fluoride from water samples, including groundwater, that may contain too much fluoride and pose a risk to the general public's health.