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 (O3/BAC)
systems. However, previous research has demonstrated that ozone drastically
increases the formation potential of genotoxic halonitromethanes (HNMs),
including during O3/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.