Nitrite facilitated transformation of halophenols in ice

This study investigated the expediated transformation of halophenols in the presence of nitrite (NO 2 − ) under slightly acidic conditions in ice, whereas such transformation was negligible in liquid water at 4 °C. We proposed that this phenomenon was attributed to the freeze-concentration effect, incurring a pH drop and the aggregation of NO 2 − and halophenols within the liquid-like grain boundary layer amid ice crystals. Within this micro-environment, NO 2 − underwent protonation to generate reactive nitrous acid (HNO 2 ) and nitrosonium ions (NO + ) that facilitate the nitration and oxidation of halophenols. When 10 μМ halophenol was treated by freezing in the presence of 5 μМ NO 2 − , the total yields of nitrated products reached 2.4 μМ and 1.4 μМ within 12 h for 2-chlorophenol (2CP) and 2-bromophenol (2BP), respectively. NO + drove oxidative coupling reactions, generating hydroxyl polyhalogenated diphenyl ethers (OH-PBDEs) and hydroxyl polyhalogenated diphenyls via C-O or C-C coupling. These two pathways were intricately intertwined. The presence of natural organic matter (NOM) mitigated the formation of nitrated products and completely suppressed the coupling products. This study offers valuable insights into the fate of halophenols in ice and suggests potential pathways for the formation of nitrophenolic compounds and OH-PBDEs in natural cold environments. These findings also open up a new avenue in environmental chemistry research.