Effects of Halides on Organic Compound Degradation during Plasma Treatment of Brines.

Plasma has been proposed as an alternative strategy to treat organic contaminants in brines. Chemical degradation in these systems is expected to be partially driven by halogen oxidants, which have been detected in halide-containing solutions exposed to plasma. In this study, we characterized specific mechanisms involving the formation and reactions of halogen oxidants during plasma treatment. We first demonstrated that addition of halides accelerated the degradation of a probe compound known to react quickly with halogen oxidants (i.e., para-hydroxybenzoate) but did not affect the degradation of a less reactive probe compound (i.e., benzoate). This effect was attributed to the degradation of para-hydroxybenzoate by hypohalous acids, which were produced via a mechanism involving halogen radicals as intermediates. We applied this mechanistic insight to investigate the impact of constituents in brines on reactions driven by halogen oxidants during plasma treatment. Bromide, which is expected to occur alongside chloride in brines, was required to enable halogen oxidant formation, consistent with the generation of halogen radicals from the oxidation of halides by hydroxyl radical. Other constituents typically present in brines (i.e., carbonates, organic matter) slowed the degradation of organic compounds, consistent with their ability to scavenge species involved during plasma treatment.

Production of Dichloroacetonitrile from Derivatives of Isoxaflutole Herbicide during Water Treatment.

The herbicide isoxaflutole has the potential to contaminate drinking water directly, as well as upon hydrolyzing to its active form diketonitrile. Diketonitrile also may impact water quality by acting as a precursor for dichloroacetonitrile (DCAN), which is an unregulated but highly toxic disinfection byproduct (DBP). In this study, we investigated the reaction of diketonitrile with free chlorine and chloramine to form DCAN. We found that diketonitrile reacts with free chlorine within seconds but reacts with chloramine on the time scale of hours to days. In the presence of both oxidants, DCAN was generated at yields up to 100%. Diketonitrile reacted fastest with chlorine at circumneutral pH, which was consistent with base-catalyzed halogenation involving the enolate form of diketonitrile present at alkaline pH and electrophilic hypochlorous acid, which decreases in abundance above its pKa (7.5). In contrast, we found that diketonitrile reacts faster with chloramine as pH values decreased, consistent with an attack on the enolate by electrophilic protonated monochloramine that increases in abundance at acidic pH approaching its pKa (1.6). Our results indicate that increasing isoxaflutole use, particularly in light of the recent release of genetically modified isoxaflutole-tolerant crops, could result in greater occurrences of a high-yield DCAN precursor during disinfection.

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.

The Overlooked Photochemistry of Iodine in Aqueous Suspensions of Fullerene Derivatives.

Fullerene's low water solubility was a serious challenge to researchers aiming to harness their excellent photochemical properties for aqueous applications. Cationic functionalization of the fullerene cage provided the most effective approach to increase water solubility, but common synthesis practices inadvertently complicated the photochemistry of these systems by introducing iodide as a counterion. This problem was overlooked until recent work noted a potentiation effect which occurred when photosensitizers were used to inactivate microorganisms with added potassium iodide. In this work, several photochemical pathways were explored to determine the extent and underlying mechanisms of iodide's interference in the photosensitization of singlet oxygen by cationic fulleropyrrolidinium ions and rose bengal. Triplet excited state sensitizer lifetimes were measured via laser flash photolysis to probe the role of I- in triplet sensitizer quenching. Singlet oxygen production rates were compared across sensitizers in the presence or absence of I-, SO42-, and other anions. 3,5-Dimethyl-1H-pyrazole was employed as a chemical probe for iodine radical species, such as I·, but none were observed in the photochemical systems. Molecular iodine and triiodide, however, were found in significant quantities when photosensitizers were irradiated in the presence of I- and O2. The formation of I2 in these photochemical systems calls into question the interpretations of prior studies that used I- as a counterion for photosensitizer materials. As an example, MS2 bacteriophages were inactivated here by cationic fullerenes with and without I- present, showing that I- moderately accelerated the MS2 deactivation, likely by producing I2. Production of I2 did not appear to be directly correlated with estimates of 1O2 concentration, suggesting that the relevant photochemical pathways are more complex than direct reactions between 1O2 and I- in the bulk solution. On the basis of the results here, iodine photochemistry may be underappreciated and misunderstood in other environmental systems.

Hematite/selenium disulfide hybrid catalyst for enhanced Fe(III)/Fe(II) redox cycling in advanced oxidation processes.

Regeneration of Fe(II) is a key issue for heterogeneous advanced oxidation processes (AOPs) using iron-based catalysts. Herein, a hybrid catalyst was developed from α-Fe2O3 and SeS2 to enhance the Fe(III)/Fe(II) redox cycling in both hydrogen peroxide (H2O2) system and persulfate (PS) system. The regeneration of Fe(II) was evidenced by the increased Fe(II)/Fe(III) ratio in the used catalyst (205.8% in the H2O2 system or 125.4% in the PS system), compared to 68.4% in the fresh hybrid catalyst Fe/Se-3. Methyl orange was used as a model pollutant to evaluate the degradation performance of the hybrid catalyst. Owing to the promotion of Fe(II) regeneration, Fe/Se-3 achieved a pollutant removal efficiency of 100.0% in 12 min in both systems, significantly higher than that with pure α-Fe2O3 (33.9 ± 3.6% in the H2O2 system or 30.7 ± 2.8% in the PS system). The dominant active species were identified as hydroxyl radicals in the H2O2 system and sulfate radicals in the PS system. In the proposed mechanism, soluble and surface-bound Fe species are provided by α-Fe2O3 to activate H2O2 or PS to radicals, and SeS2 participates in the reactions via Se(IV) reducing Fe(III) to Fe(II) and S atoms being released through protonation to expose more active Se sites.

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.