Preferential Halogenation of Algal Organic Matter by Iodine over Chlorine and Bromine: Formation of Disinfection Byproducts and Correlation with Toxicity of Disinfected Waters

The increasing occurrence of harmful algal blooms (HABs) in surface waters may increase the input of algal organic matter (AOM) in drinking water. The formation of halogenated disinfection byproducts (DBPs) during combined chlorination and chloramination of AOM and natural organic matter (NOM) in the presence of bromide and iodide and haloform formation during halogenation of model compounds were studied. Results indicated that haloform/halogen consumption ratios of halogens reacting with amino acids (representing proteins present in AOM) follow the order iodine > bromine > chlorine, with ratios for iodine generally 1–2 orders of magnitude greater than those for chlorine (0.19–2.83 vs 0.01–0.16%). This indicates that iodine is a better halogenating agent than chlorine and bromine. In contrast, chlorine or bromine shows higher ratios for phenols (representing the phenolic structure of humic substances present in NOM). Consistent with these observations, chloramination of AOM extracted from Microcystis aeruginosa in the presence of iodide produced 3 times greater iodinated trihalomethanes than those from Suwannee River NOM isolate. Cytotoxicity and genotoxicity of disinfected algal-impacted waters evaluated by Chinese hamster ovary cell bioassays both follow the order chloramination > prechlorination-chloramination > chlorination. This trend is in contrast to additive toxicity calculations based on the concentrations of measured DBPs since some toxic iodinated DBPs were not identified and quantified, suggesting the necessity of experimentally analyzing the toxicity of disinfected waters. During seasonal HAB events, disinfection practices warrant optimization for iodide-enriched waters to reduce the toxicity of finished waters.