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A comparison of loadings of N-nitrosamines and their precursors from different source water categories is needed to design effective source water blending strategies. Previous research using Formation Potential (FP) chloramination protocols (high dose and prolonged contact times) raised concerns about precursor loadings from various source water categories, but differences in the protocols employed rendered comparisons difficult. In this study, we applied Uniform Formation Condition (UFC) chloramination and ozonation protocols mimicking typical disinfection practice to compare loadings of ambient specific and total N-nitrosamines as well as chloramine-reactive and ozone-reactive precursors in 47 samples, including 6 pristine headwaters, 16 eutrophic waters, 4 agricultural runoff samples, 9 stormwater runoff samples, and 12 municipal wastewater effluents. N-Nitrosodimethylamine (NDMA) formation from UFC and FP chloramination protocols did not correlate, with NDMA FP often being significant in samples where no NDMA formed under UFC conditions. N-Nitrosamines and their precursors were negligible in pristine headwaters. Conventional, and to a lesser degree, nutrient removal wastewater effluents were the dominant source of NDMA and its chloramine- and ozone-reactive precursors. While wastewater effluents were dominant sources of TONO and their precursors, algal blooms, and to a lesser degree agricultural or stormwater runoff, could be important where they affect a major fraction of the water supply.

The excitation of dissolved organic matter (DOM) from sunlight produces a range of reactive intermediates, including triplet-excited state dissolved organic matter ((3)DOM*), hydroxyl radical (HO(•)), and singlet oxygen ((1)O2). These intermediates are important for the inactivation of pathogens and for the degradation of trace organic contaminants (OC) within natural and engineered systems. However, halides found in the background matrix can alter the photoproduction rates by promoting or quenching the formation of these intermediates. Apparent quantum yields (Φ(a)) for (1)O2, HO(•), and steady state (3)DOM* concentrations photoproduced from DOM isolates were determined with varying concentrations of chloride and bromide. Fluorescence quantum yields were measured as well to probe the photophysics of the system. The maximum fluorescence quantum yield (ΦF) decreased with the addition of halides, representing a quenching of the excited singlet state of DOM. In contrast, the steady state concentrations for (3)DOM* were enhanced, suggesting intersystem crossing from the singlet state to the triplet state was increased by the presence of halides. The Φ(a) for (1)O2 was increased with the addition of halides, which was expected following the (3)DOM* results because the mechanism for (1)O2 production occurs through the inactivation of (3)DOM* by dissolved oxygen. Although HO(•) production would be expected to follow (1)O2, the opposite trend was seen, which suggests the formation of HO(•) does not occur through the same precursor. Understanding the impact of specific quenchers on DOM could be a key to understanding the true formation potential for reactive intermediates and is especially important in estuaries and wastewater impacted aquatic systems.

The photochemical formation of hydroxyl radical (HO(•)) from effluent organic matter (EfOM) depends upon the chemical properties of this heterogeneous mixture. In this study, two EfOM samples collected from wastewater treatment plants (WWTP A and B) were fractionated by both hydrophobicity (bulk and non-humic) and apparent molecular weight (AMW). The apparent quantum yield for HO(•) formation (ΦHO(•)) and the maximum fluorescence quantum yield (ΦF) were subsequently measured for each subfraction. The formation rates of HO(•) (considering only the hydrogen-peroxide-independent pathways) for the bulk waters were 4.8 × 10(-10) and 9.6 × 10(-11) M s(-1) for WWTP A and B, respectively. For the AMW fractions, the values of ΦHO(•) increased as the AMW of the material decreased. For the WWTP A sample, the ΦHO(•) increased from 2.54 × 10(-4) (bulk water) to 6.29 × 10(-4) for the <1 kDa fraction, and for the WWTP B sample, the value of ΦHO(•) increased from 6.50 × 10(-5) for bulk water to 3.45 × 10(-4) for the <1 kDa fraction. In the case of fluorescence, the values of ΦF ranged from 2.37 × 10(-4) (bulk water) to 3.48 × 10(-4) (<1 kDa fraction) for WWTP A and 3.19 × 10(-4) (bulk water) to 5.75 × 10(-4) (<1 kDa fraction) for WWTP B. There was a linear correlation between ΦHO(•) and ΦF, suggesting that different photophysical processes occur in the chemical components of the fractions. Understanding the formation of HO(•) from EfOM is essential for understanding wastewater-impacted aquatic systems because these results influence the photochemical degradation and mineralization of trace organic contaminants.