Singlet oxygen ((1)O2) plays an important role in the inactivation of pathogens and the degradation of organic contaminants. The present study looks at the surface steady-state concentration of (1)O2 and quantum yields (ΦSO) for organic matter present in or derived from wastewater (WWOM), including those that are partially treated and after undergoing oxidation. The surface steady state concentrations of (1)O2 ranged from 1.23 to 1.43 × 10(-13) M for bulk wastewaters under simulated sunlight. The ΦSO values for these samples varied from 2.8% to 4.7% which was higher than the values observed for the natural organic matter isolates evaluated (1.6-2.1%). Size fractionation of WWOM resulted in ΦSO increases, with a value of up to 8.6% for one of the <1 kDa fractions. Furthermore, oxidation of WWOM by hypochlorous acid (HOCl) and molecular ozone also resulted in an increase in ΦSO, with the highest measured value being 9.3%. This research further explores the correlations between the photosensitizing properties of WWOM and optical characteristics (e.g., absorbance, E2:E3 ratio). Making use of easily measurable absorbance values, a model for the prediction of (1)O2 steady-state concentrations is proposed.

The photochemical properties of dissolved organic matter (DOM) have been of interest to scientists and engineers since the 1970s. Upon light absorption, chromophoric DOM (CDOM) can sensitize the formation of different short-lived reactive intermediates (RIs), including hydroxyl radical (OH), singlet oxygen (O) and superoxide radical anion (O). In addition, a fraction of the excited singlet states in CDOM decays into excited triplet states (CDOM*), which are also important photochemical transients in environmental systems. These RIs have a significant impact on different processes in sunlit waters, including degradation of organic contaminants and the inactivation of pathogens. Due to their transient nature and low steady-state concentrations, the use of common analytical techniques for the direct measurement of these species is impractical. Therefore, specific probe compounds (PCs) are used. PCs include furfuryl alcohol for O, and terephthalic acid for OH. In this publication, we present a critical review of the use of PCs for the assessment of the formation of photochemically generated RIs. We first introduce the concept of a PC, including the kinetic treatment and necessary assumptions needed to conduct a specific measurement. Afterward, we present short overviews of the most studied RIs and review relevant issues regarding the use of specific PCs for their measurement. We finalize by offering recommendations regarding the use of PCs in environmental photochemistry.

The photochemical formation of hydroxyl radical (HO•) from effluent organic matter (EfOM) was evaluated using three bulk wastewater samples collected at different treatment facilities under simulated sunlight. For the samples studied, the formation rates of HO•(R(HO•)) were obtained from the formation rate of phenol following the hydroxylation of benzene. The values of R(HO•) ranged from 2.3 to 3.8 × 10(-10) M s(-1) for the samples studied. The formation rate of HO• from nitrate photolysis (R(NO3)(HO•)) was determined to be 3.0 × 10(-7) M(HO)• M(NO3)(-1) s(-1). The HO• production rate from EfOM (R(EfOM)(HO•)) ranged from 0.76 to 1.3 × 10(-10) M s(-1). For the wastewater samples studied, R(EfOM)(HO•) varied from 1.5 to 2.4 × 10(-7) M(HO)• M(C)(-1) (s-1) on molarcarbon basis, which was close to HO• production from nitrate photolysis. The apparent quantum yield for the formation of HO• from nitrate (Φ(NO3-HO•)(a)) was determined as 0.010 ± 0.001 for the wavelength range 290-400 nm in ultrapure water. The apparent quantum yield for HO• formation in EfOM (Φ(EfOM-HO•)(a)) ranged from 6.1 to 9.8 × 10(-5), compared to 2.99 to 4.56 × 10(-5) for organic matter (OM) isolates. The results indicate that wastewater effluents could produce significant concentrations of HO•, as shown by potential higher nitrate levels and relatively higher quantum yields of HO• formation from EfOM.

The antioxidant capacity and formation of photochemically produced reactive intermediates (RI) was studied for water samples collected from the Florida Everglades with different spatial (marsh versus estuarine) and temporal (wet versus dry season) characteristics. Measured RI included triplet excited states of dissolved organic matter (DOM*), singlet oxygen (O), and the hydroxyl radical (OH). Single and multiple linear regression modeling were performed using a broad range of extrinsic (to predict RI formation rates, R) and intrinsic (to predict RI quantum yields, Φ) parameters. Multiple linear regression models consistently led to better predictions of R and Φ for our data set but poor prediction of Φ for a previously published data set,1 probably because the predictors are intercorrelated (Pearson's r > 0.5). Single linear regression models were built with data compiled from previously published studies (n ≈ 120) in which E2:E3, S, and Φ values were measured, which revealed a high degree of similarity between RI-optical property relationships across DOM samples of diverse sources. This study reveals that OH formation is, in general, decoupled fromDOM* and O formation, providing supporting evidence that DOM* is not aOH precursor. Finally, Φ for O and DOM* correlated negatively with antioxidant activity (a surrogate for electron donating capacity) for the collected samples, which is consistent with intramolecular oxidation of DOM moieties byDOM*.