Mechanism of fluoride removal by AlCl3 and Al13: The role of aluminum speciation

Coagulation is an important defluorination process. However, because of the poor sedimentation properties, conventional coagulants often result in limited defluorination performance and excessive residual aluminum. In this study, AlCl3 and the highly-positively-charged molecule [AlO4Al12(OH)24(H2O)12]7+ (Al13) was utilized to treat fluoride-containing water. By comparison, the role of aluminum speciation in fluoride removal was elucidated. Under initial pH of 6.0, 7.0 and 8.0, the highest defluorination efficiencies of high-fluoride water ([F−]0 = 8.0 mg/L) were 78.2%, 71.6% and 83.2% at Al13 dosage of 20 mg/L, 40 mg/L and 50 mg/L. Combined with detailed investigations of the chemical compositions of flocs, along with electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS) analysis of residual aluminum, the defluorination mechanisms of both coagulants were discussed. In acidic conditions, both coagulants hydrolyzed and formed various Al clusters, among which transient Al (Alts) was the intermediate of the other clusters. The coprecipitation of high-polymerized Al and F− contributed most of the defluorination rate. While under neutral and alkaline conditions, hydrogen bonding and ion exchange together with coprecipitation were the main roles for Al13. The effects of AlCl3 were merely physical actions, and were affected by the decreased pH. This work provides new insights into the coagulation and defluorination process.