Orthophosphate vs. bicarbonate used as a buffering substance for optimizing the bromide-enhanced ozonation process for ammonia nitrogen removal

Bromide-enhanced ozonation (BEO) process can be a fast and effective solution for the complete removal of total nitrogen (TN) from wastewaters containing from moderate to high concentrations of ammonia nitrogen (AN). Like the traditional biological process of AN oxidation, even BEO requires the presence of buffering agents, in order to oppose the progressive acidification induced by the reaction. This study compares the effect of two buffering substances (namely bicarbonate and mixtures of orthophosphates) in hindering the acidification caused by AN oxidation and, consequently, optimizing the overall efficiency of the process. Tests were carried out with on-purpose made solutions containing concentrations of AN of 5–10 mM. The range of [Br−]/[O3] ratio values was from 12 to 18, so as to make ozone the limiting factor in HOBr generation. The results of this study proved that, in the absence of natural buffering agents, mixtures of orthophosphates must be preferred to the more traditionally employed bicarbonate to control the pH evolution of BEO process. In fact, orthophosphates proved to be capable to guarantee an initial pH of the wastewater in the order of 7.5, thus making the zero-order AN removal rates 15% faster than those observed in the presence of bicarbonate. Furthermore, in the presence of mixtures of orthophosphates, the generation of ozonation byproducts in the oxidized form (nitrate, bromate) was reduced by over 70%. Finally, the fine control of pH obtained with orthophosphates in the BEO of AN makes that process an attractive solution for the treatment of effluents containing AN, thus preventing the discharge of residual nitrogen into aquatic environments and avoiding eutrophication of receiving water bodies.