Permanganate preoxidation affects the formation of disinfection byproducts from algal organic matter.

During harmful algal blooms (HABs), permanganate may be used as a preoxidant to improve drinking water quality by removing algal cells and degrading algal toxins. However, permanganate also lyses algal cells, releasing intracellular algal organic matter (AOM). AOM further reacts with permanganate to alter the abundance of disinfection byproduct (DBP) precursors, which in turn affects DBP formation during disinfection. In this study, we evaluated the impacts of preoxidation by permanganate applied at commonly used doses (i.e., 1-5 mg/L) on DBP generation during chlorination and chloramination of AOM. We found that permanganate preoxidation increased trichloronitromethane (TCNM) formation by up to 3-fold and decreased dichloroacetonitrile (DCAN) formation by up to 40% during chlorination, indicating that permanganate oxidized organic amines in AOM to organic nitro compounds rather than organic nitrile compounds. To test this proposed mechanism, we demonstrated that permanganate oxidized organic amines in known DBP precursors (i.e., tyrosine, tryptophan) to favor the production of TCNM over DCAN during chlorination. Compared to the decreased formation of DCAN during chlorination, permanganate increased DCAN formation by 30-50% during chloramination of AOM. This difference likely arose from monochloramine's ability to react with non-nitrogenous precursors (e.g., organic aldehydes) that formed during permanganate preoxidation of AOM to generate nitrogen-containing intermediates that go on to form DCAN. Our results also showed that permanganate preoxidation favored the formation of dichlorobromomethane (DCBM) over trichloromethane (TCM) during chlorination and chloramination. The increased formation of DBPs, especially nitrogenous DBPs that are more toxic than carbonaceous DBPs, may increase the overall toxicity in finished drinking water when permanganate preoxidation is implemented.

Halogen Radicals Contribute to the Halogenation and Degradation of Chemical Additives Used in Hydraulic Fracturing.

In hydraulic fracturing fluids, the oxidant persulfate is used to generate sulfate radical to break down polymer-based gels. However, sulfate radical may be scavenged by high concentrations of halides in hydraulic fracturing fluids, producing halogen radicals (e.g., Cl•, Cl2•-, Br•, Br2•-, and BrCl•-). In this study, we investigated how halogen radicals alter the mechanisms and kinetics of the degradation of organic chemicals in hydraulic fracturing fluids. Using a radical scavenger (i.e., isopropanol), we determined that halogenated products of additives such as cinnamaldehyde (i.e., α-chlorocinnamaldehyde and α-bromocinnamaldehyde) and citrate (i.e., trihalomethanes) were generated via a pathway involving halogen radicals. We next investigated the impact of halogen radicals on cinnamaldehyde degradation rates. The conversion of sulfate radicals to halogen radicals may result in selective degradation of organic compounds. Surprisingly, we found that the addition of halides to convert sulfate radicals to halogen radicals did not result in selective degradation of cinnamaldehyde over other compounds (i.e., benzoate and guar), which may challenge the application of radical selectivity experiments to more complex molecules. Overall, we find that halogen radicals, known to react in advanced oxidative treatment and sunlight photochemistry, also contribute to the unintended degradation and halogenation of additives in hydraulic fracturing fluids.