Brominated and nitrated byproducts generated from bromide (Br) and nitrite (NO), respectively, by sulfate radical (SO) oxidation have raised increasing concern. However, little is known about the concurrent generation of brominated and nitrated byproducts in the unactivated peroxymonosulfate (PMS) oxidation process. This study revealed that Br can facilitate the transformation of NO to nitrated byproducts during unactivated PMS oxidation of phenol. In the co-existence of 0.1 mM Br and 0.5 mM NO, the total yield of identified nitrated byproducts reached 2.316 μM in 20 min, while none was found with NO alone. Nitryl bromide (BrNO) as the primary nitrating agent was formed via the reaction of NO with free bromine in situ generated through the oxidation of Br by PMS. BrNO rapidly reacted with phenol or bromophenols, generating highly toxic nitrophenols or nitrated bromophenols, respectively. Increasing NO concentration led to more nitrated byproducts but less brominated byproducts. This study advances our understanding of the transformation of Br and NO in the unactivated PMS oxidation process. It also provides important insights into the potentially underestimated environmental risks when PMS is applied to degrade organic contaminants under realistic environments, particularly when Br and NO co-exist.
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