Molecular Insights into the Quenching Mechanism of the Triplet Excited State of Rose Bengal through Oxidative and Reductive Organic Compounds.

In oxygenated aquatic environments, the predominant scavenging of the triplet excited state of chromophoric dissolved organic matter (3CDOM*) involves dissolved ground-state oxygen, diverting attention away from the scavenging mechanisms of 3CDOM* mediated through specific organic compounds. Previous studies demonstrated that model 3CDOM* exhibited quantum yields (i.e., 1-56%) in the formation of radical ions, resulting from the competition between physical and chemical quenching through a common exciplex intermediate. Physical quenching was rationalized through the reverse intersystem crossing of the exciplex, followed by back electron transfer, yielding ground-state reactants. Despite this, direct experimental evidence for exciplex involvement has been elusive, owing to detection challenges. Herein, employing density functional theory (DFT) and time-dependent DFT specifically for excited state surrogate CDOM and organic scavengers, we unveil, for the first time, the underlying mechanisms responsible for the quenching of Rose Bengal through oxidative and reductive scavengers. Our computational findings provide evidence for the involvement of exciplexes during the quenching process of the excited triplet state of Rose Bengal, highlighting the impact of electronic coupling between Rose Bengal and quenchers on the quantum yield for radical ion formation.

Role of Carbonyl Compounds for N-Nitrosamine Formation during Nitrosation: Kinetics and Mechanisms.

N-Nitrosamines are potential human carcinogens frequently detected in natural and engineered aquatic systems. This study sheds light on the role of carbonyl compounds in the formation of N-nitrosamines by nitrosation of five secondary amines via different pathways. The results showed that compared to a control system, the presence of formaldehyde enhances the formation of N-nitrosamines by a factor of 5-152 at pH 7, depending on the structure of the secondary amines. Acetaldehyde showed a slight enhancement effect on N-nitrosamine formation, while acetone and benzaldehyde did not promote nitrosation reactions. For neutral and basic conditions, the iminium ion was the dominant intermediate for N-nitrosamine formation, while carbinolamine became the major contributor under acidic conditions. Negative free energy changes (<-19 kcal mol-1) and relatively low activation energies (<18 kcal mol-1) of the reactions of secondary amines with N2O3, iminium ions with nitrite and carbinolamines with N2O3 from quantum chemical computations further support the proposed reaction pathways. This highlights the roles of the iminium ion and carbinolamine in the formation of N-nitrosamines during nitrosation in the presence of carbonyl compounds, especially in the context of industrial wastewater.

Elucidation of the Photochemical Fate of Methionine in the Presence of Surrogate and Standard Dissolved Organic Matter under Sunlight Irradiation.

The abiotic fate of dissolved free amino acids considerably contributes to the cycling of dissolved sulfur and nitrogen in natural aquatic environments. However, the roles of the functional groups of chromophoric dissolved organic matter (CDOM) and the fate of free amino acids under sunlight irradiation in fresh waters are not fully understood. This study aims to elucidate the fate of photolabile methionine in the presence of three CDOM surrogate compounds, i.e., 1,4-naphthoquinone, 2-naphthaldehyde, and umbelliferone, and two standard CDOM by coupling experimental measurement, quantum chemical computations, and kinetic modeling. Results indicate that excited triplet-state CDOM and hydroxyl radicals are able to cleave the C-S bond in methionine, resulting in the formation of smaller amino acids and volatile sulfur-containing compounds. Singlet oxygen forms methionine sulfoxide and methionine sulfone. The distribution of phototransformation products offers an improved understanding of the fate of nitrogen- and sulfur-containing compounds and their uptake by microorganisms in natural aquatic environments.

Reactivity of Bromine Radical with Dissolved Organic Matter Moieties and Monochloramine: Effect on Bromate Formation during Ozonation.

Bromine radical (Br•) has been hypothesized to be a key intermediate of bromate formation during ozonation. Once formed, Br• further reacts with ozone to eventually form bromate. However, this reaction competes with the reaction of Br• with dissolved organic matter (DOM), of which reactivity and reaction mechanisms are less studied to date. To fill this gap, this study determined the second-order rate constant (k) of the reactions of selected organic model compounds, a DOM isolate, and monochloramine (NH2Cl) with Br• using γ-radiolysis. The kBr• of all model compounds were high (kBr• > 108 M-1 s-1) and well correlated with quantum-chemically computed free energies of activation, indicating a selectivity of Br• toward electron-rich compounds, governed by electron transfer. The reaction of phenol (a representative DOM moiety) with Br• yielded p-benzoquinone as a major product with a yield of 59% per consumed phenol, suggesting an electron transfer mechanism. Finally, the potential of NH2Cl to quench Br• was tested based on the fast reaction (kBr•, NH2Cl = 4.4 × 109 M-1 s-1, this study), resulting in reduced bromate formation of up to 77% during ozonation of bromide-containing lake water. Overall, our study demonstrated that Br• quenching by NH2Cl can substantially suppress bromate formation, especially in waters containing low DOC concentrations (1-2 mgC/L).

Mechanistic Insight into the Reactivities of Aqueous-Phase Singlet Oxygen with Organic Compounds.

Singlet oxygen (1O2) is a selective reactive oxygen species that plays a key role for the fate of various organic compounds in the aquatic environment under sunlight irradiation, engineered water oxidation systems, atmospheric water droplets, and biomedical systems. While the initial rate-determining charge-transfer reaction mechanisms and kinetics of 1O2 have been studied extensively, no comprehensive studies have been performed to elucidate the reaction mechanisms with organic compounds that have various functional groups. In this study, we use density functional theory calculations to determine elementary reaction mechanisms with a wide variety of organic compounds. The theoretically calculated aqueous-phase free energies of activation of single electron transfer and 1O2 addition reactions are compared to the experimentally determined rate constants in the literature to determine linear free-energy relationships. The theoretically calculated free energies of activation for the groups of phenolates and phenols show excellent correlations with the Hammett constants that accept electron densities by through-resonance. The dominant elementary reaction mechanism is discussed for each group of compounds. As a practical implication, we demonstrate the fate of environmentally relevant organic compounds induced by photochemically produced intermediate species at different pH and evaluate the impact of predicting rate constants to the half-life.