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 application of advanced oxidation processes (AOPs) for the treatment of wastewater is hindered by scavenging of the hydroxyl radical (HO*) by effluent organic matter (EfOM). This scavenging is directly proportional to the second-order reaction rate constant between EfOM and HO* (kEfOM-HO*). To understand the kinetics of this reaction as a function of the subcomponents of EfOM, four wastewater samples were fractionated by ultrafiltration into distinct apparent molecular weight (AMW) fractions (<1, <3, <5, and <10 kDa), and their kEfOM-HO* values were quantified. In general, the values for k(EfOM-HO*) decreased as the AMW increased. The values of k(EfOM-HO*) for the bulk waters varied between 6.32 and 14.1x10(8) MC(-1)s(-1) (units of per molar carbon concentration per second). In the case of the <1 kDa fraction, the values of kEfOM-HO* varied from 14.3 to 35.0x10(8) MC(-1)s(-1), or approximately 2.31(+/-0.24) times that of the corresponding bulk waters. For the <3 kDa, <5 kDa, and <10 kDa fractions, the k(EfOM-HO*) values were 1.83(+/-0.25), 1.32(+/-0.23), and 1.26(+/-0.35) times that of the bulk waters, respectively. Based on the obtained results, the variability and general magnitude of the kEfOM-HO* values were attributed to the production and reactivity of soluble microbial products (SMP), a major component of EfOM. Two samples collected at a wastewater treatment facility with different treatment variables had different kEfOM-HO* values, indicating that wastewater treatment processes will impact overall HO* scavenging by EfOM and should be considered during the implementation of AOPs.

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The temperature-dependent bimolecular rate constants for the reaction of the hydroxyl radical (HO(•)) with organic matter (OM) (k(OM-HO(•))) have been measured for three natural organic matter (NOM) isolates and three bulk effluent organic matter (EfOM) samples using electron pulse radiolysis and thiocyanate competition kinetics. The range of values for the room temperature k(OM-HO(•)) was 1.21-9.37 × 10(8) M(C)(-1)s(-1), with NOM isolates generally reacting slower than EfOM samples. The NOM isolates had an average apparent activation energy of 19.8 kJ mol(-1), while the EfOM samples had an average value slightly lower (14.3 kJ mol(-1)), although one NOM isolate (Elliot Soil Humic Acid, 29.9 kJ mol(-1)) was a factor of 2 times greater than other samples studied. These apparent activation energies are the first determined for OM and HO(•), and the Arrhenius plots obtained for NOM isolates (lowest R(2) > 0.993) suggest that no significant structural changes are occurring over the temperature range 8-41 °C. In contrast, the greater scatter (lowest R(2) > 0.903) observed for the EfOM samples suggests that some structural changes may be occurring. These results provide a deeper fundamental understanding of the reaction between OM and HO(•) and will be useful in quantifying HO(•) reactions in natural and engineered systems.

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