Transformation of N-Methylamine Drugs during Wastewater Ozonation: Formation of Nitromethane, an Efficient Precursor to Halonitromethanes

Potable reuse of wastewater is expanding, and ozonation for water reuse is becoming more common, either as a preoxidant before membranes or as part of ozone/biological activated carbon (O-3/BAC) systems. However, previous research has demonstrated that ozone drastically increases the formation potential of genotoxic halonitromethanes (HNMs), including during O-3/BAC. Chloropicrin, the most common HNM, is synthesized by chlorinating nitromethane, suggesting that nitromethane may be the immediate precursor of chloropicrin, although nitromethane is unlikely to occur naturally in wastewater. We hypothesized that wastewater ozonation forms nitromethane, which would be the key intermediate toward HNMs. Ozonation of wastewater effluent was shown to form abundant nitromethane, which explained the majority (in one case, all) of subsequent chloropicrin formation. Next, we investigated a suspected category of nitromethane precursor: stimulant drugs, such as ephedrine and methamphetamine, and certain antidepressants. These drugs all feature N-methylamine functional groups, and certain N-alkylamines have been shown to produce primary nitroalkanes upon ozonation. Ozonation of N-methylamine drugs ubiquitously formed nitromethane, typically at >50% yield. Subsequent chlorination converted nitromethane to chloropicrin. The reaction mechanism was investigated to understand the variation in nitromethane yield between different precursors. These results suggest that nitromethane fate during reuse and nitromethane control should be investigated.