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.

Reverse osmosis (RO) is a membrane technology that separates dissolved species from water. RO has been applied for the removal of chemical contaminants from water for potable reuse applications. The presence of a wide variety of influent chemical contaminants and the insufficient rejection of low-molecular-weight neutral organics by RO calls for the need to develop a model that predicts the rejection of various organics. In this study, we develop a group contribution method (GCM) to predict the mass transfer coefficients by fragmenting the structure of low-molecular-weight neutral organics into small parts that interact with the RO membrane. Overall, 54 organics including 26 halogenated and oxygenated alkanes, 8 alkenes, and 20 alkyl and halobenzenes were used to determine 39 parameters to calibrate for 6 different RO membranes, including 4 brackish water and 2 seawater membranes. Through six membranes, approximately 80% of calculated rejection was within an error goal (i.e., ±5%) from the experimental observation. To extend the GCM for a reference RO membrane, ESPA2-LD, 14 additional organics were included from the literature to calibrate nitrogen-containing functional groups of nitrosamine, nitriles, and amide compounds. Overall, 49 organics (72% of 68 compounds) from calibration and 7 compounds (87.5% of 8 compounds) from prediction were within the error goal.