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.

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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.

Perfluoroalkyl and polyfluoroalkyl substances (PFASs) are a group of persistent contaminants that have been identified throughout the aquatic environment. In this study, ten targeted perfluoroalkyl acids (PFAAs), three targeted PFAA precursors, and non-targeted PFAA precursors were monitored in four full- and pilot-scale potable reuse plants at each stage of advanced treatment. Non-targeted PFAA precursors were quantified by applying a total oxidizable precursor assay in which PFAA precursors are oxidized by hydroxyl radicals to targeted PFAAs. Two of the potable reuse systems had membrane-based treatments with reverse osmosis and UV-advanced oxidation (RO-UV/AOP) and two used ozone, biological activated carbon filtration and granular activated carbon adsorption (O-BAC-GAC). The total targeted PFAAs in the four tertiary effluents, the influent sources for the potable reuse systems, ranged from 52 to 227 ng/L with non-targeted PFAA precursors accounting for 30-67% of total PFASs on a molar basis. The RO-UV/AOP treatment trains reduced PFAAs and PFAA precursors to below their method reporting limits through the barrier provided by RO. The O-BAC-GAC based treatment trains reduced, but did not completely remove PFAAs or PFAA precursors and the PFASs present in the product water were primarily shorter-chain PFAAs, some of which lack human health guidance values for drinking water. The relative fraction of targeted shorter-chain PFAAs increased after each treatment step indicating that there was preferential removal of the PFAA precursors and longer-chain PFAAs. This study provides new insight on the concentrations and treatment of PFAA precursors through potable reuse treatment systems.

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Algicides, like hydrogen peroxide and copper sulfate, are commonly applied to recreational waters and drinking water sources to mitigate cyanobacterial blooms. In this work, the effects of hydrogen peroxide and copper sulfate were evaluated in two natural bloom samples (collected from Canadian and American waterbodies) and one lab-cultured Microcystis aeruginosa suspended in Colorado River water. Five algicide to dissolved organic carbon (DOC) dose ratios were evaluated during an initial exposure period of 24 h. One dose ratio (0.4 H2O2:DOC or 0.25 CuSO4:DOC) was then evaluated during stagnation after quenching (hydrogen peroxide) or extended exposure (copper sulfate) for up to 96 or 168 h. During the initial hydrogen peroxide exposure, the CA bloom had no release of intracellular microcystins (MCs) and the USA bloom only released MC at 4 H2O2:DOC. The reverse occurred with copper sulfate, where the CA bloom released MCs at 0.6 CuSO4:DOC but the USA bloom had no detectable extracellular MCs. Extracellular MC was released from the lab-cultured Microcystis at the lowest hydrogen peroxide and copper sulfate doses. In the hydrogen peroxide stagnation experiment, intracellular MC decreased in the USA bloom after 168 h despite the low dose applied. Similarly, the extended copper sulfate exposure led to intracellular MC decreases in both bloom samples after 168 h, despite showing no impact during the initial 24 h monitoring period. The lab-cultured Microcystis was again less resistant to both algicides, with releases observed after less than 2 h of stagnation or exposure. The damage to cells as measured by pigments during these experiments did not match the MC data, indicating that blooms with depressed pigment levels can still be a risk to nearby drinking water sources or recreational activities. These results provide insight on the timeline (up to one week) required for monitoring the potential release of MCs after algicide application.