Abstract
Flushing toilet with seawater is an effective method for preserving freshwater resources, but it introduces iodide and bromide ions into domestic wastewater. During chlorine disinfection, iodide and bromide ions in the saline wastewater effluent lead to the formation of iodinated and brominated aromatic disinfection byproducts (DBPs). Examples of aromatic DBPs include iodophenolic, bromophenolic and chlorophenolic compounds, which generally display substantially higher toxicity than haloaliphatic DBPs. This paper presented for the first time the rates of phototransformation of 21 newly identified halophenolic DBPs in seawater, the receiving waterbody of the wastewater effluent. The phototransformation rate constants (k) were in the range from 7.75 × 10-4 to 4.62 × 10-1 h-1, which gave half-lives of 1.5-895 h. A quantitative structure-activity relationship was established for the phototransformation of halophenolic DBPs as logk=-0.0100×ΔGf0+5.7528×logMW+0.3686×pKa-19.1607, where ΔGf0 is standard Gibbs formation energy, MW is molecular weight, and pKa is dissociation constant. This model well predicted the k values of halophenolic DBPs. Among the tested DBPs, 2,4,6-triiodophenol and 2,6-diiodo-4-nitrophenol were found to exhibit relatively high risks on marine organisms, based on toxicity indices and half-lives. In seawater, the two DBPs underwent photonucleophilic substitutions by bromide, chloride and hydroxide ions, resulting in the conversion to their bromophenolic and chlorophenolic counterparts (which are less toxic than the parent iodophenolic DBPs) and to their hydroxyphenolic counterparts (iodo(hydro)quinones, which are more toxic than the parent iodophenolic DBPs). The formed iodo(hydro)quinones further transformed to hydroxyl-iodo(hydro)quinones, which have lower toxicity than the parent compounds.