Formation of halonitromethanes from methylamine in the presence of bromide during UV/Cl2 disinfection

The UV/Cl₂ process is commonly used to achieve a multiple-barrier disinfection and maintain residuals. The study chose methylamine as a precursor to study the formation of high-toxic halonitromethanes (HNMs) in the presence of bromide ions (Br⁻) during UV/Cl₂ disinfection. The maximum yield of HNMs increased first and then decreased with increasing concentration of Br⁻. An excessively high concentration of Br⁻ induced the maximum yield of HNMs in advance. The maximum bromine incorporation factor (BIF) increased, while the maximum bromine utilization factor (BUF) decreased with the increase of Br⁻ concentration. The maximum yield of HNMs decreased as pH value increased from 6.0 to 8.0 due to the deprotonation process. The BUF value remained relatively higher under an acidic condition, while pH value had no evident influence on the BIF value. The maximum yield of HNMs and value of BUF maximized at a Cl₂:Br⁻ ratio of 12.5, whereas the BIF value remained relatively higher at low Cl₂:Br⁻ ratios (2.5 and 5). The amino group in methylamine was first halogenated, and then released into solution as inorganic nitrogen by the rupture of C-N bond or transformed to nitro group by oxidation and elimination pathways. The maximum yield of HNMs in real waters was higher than that in pure water due to the high content of dissolved organic carbon. Two real waters were sampled to verify the law of HNMs formation. This study helps to understand the HNMs formation (especially brominated species) when the UV/Cl₂ process is adopted as a disinfection technique.