Dissolved Organic Matter Composition Determines Its Susceptibility to Complete and Partial Photooxidation within Lakes.

Dissolved organic matter (DOM) plays an important role in carbon cycling within inland surface waters. Under sunlight irradiation, DOM undergoes complete photooxidation to produce carbon dioxide (CO2) and partial photooxidation that alters the molecular composition of DOM. However, a mechanistic understanding of the relationship between DOM composition and its susceptibility to partial and complete photooxidation in surface waters is currently lacking. This work combines light exposure experiments with high-resolution mass spectrometry to investigate DOM photooxidation using two DOM isolates and DOM from 16 lakes that vary in trophic status and size. High ratios of oxygen consumption to dissolved inorganic carbon (DIC) production demonstrate that all samples undergo extensive partial photooxidation. At the molecular level, more oxidized, aromatic DOM formulas are associated with oxygen consumption and DIC production. Bulk level measurements indicate that DOM becomes less aromatic and lower in apparent molecular weight following partial photooxidation, and there is molecular level evidence of oxygen addition and loss of CO2 in all samples. However, formulas most susceptible to photooxidation vary depending on the initial DOM composition. Collectively, this work provides insights into the relationship between DOM composition and photooxidation, which has important implications for carbon cycling in diverse surface waters.

Formation of Targeted and Novel Disinfection Byproducts during Chlorine Photolysis in the Presence of Bromide.

Chlorine photolysis is an advanced oxidation process that relies on the combination of direct chlorination by free available chlorine, direct photolysis, and reactive oxidants to transform contaminants. In waters that contain bromide, free available bromine and reactive bromine species can also form. However, little is known about the underlying mechanisms or formation potential of disinfection byproducts (DBPs) under these conditions. We investigated reactive oxidant generation and DBP formation under dark conditions, chlorine photolysis, and radical-quenched chorine photolysis with variable chlorine (0-10 mg-Cl2/L) and bromide (0-2,000 µg/L) concentrations, as well as with free available bromine. Probe loss rates and ozone concentrations increase with chlorine concentration and are minimally impacted by bromide. Radical-mediated processes partially contribute to the formation targeted DBPs (i.e., trihalomethanes, haloacetic acids, haloacetonitriles, chlorate, and bromate), which increase with increasing chlorine concentration. Chlorinated novel DBPs detected by high-resolution mass spectrometry are attributable to a combination of dark chlorination, direct halogenation by reactive chlorine species, and transformation of precursors, whereas novel brominated DBPs are primarily attributable to dark bromination of electron-rich formulas. The formation of targeted and novel DBPs during chlorine photolysis in waters with elevated bromide may limit treatment applications.

Limitations of conventional approaches to identify photochemically produced reactive intermediates involved in contaminant indirect photodegradation.

Dissolved organic matter (DOM) mediated indirect photodegradation can play an important role in the degradation of aquatic contaminants. Predicting the rate of this process requires knowledge of the photochemically produced reactive intermediates (PPRI) that react with the compound of interest, as well as the ability of individual DOM samples to produce PPRI. Key PPRI are typically identified using quencher studies, yet this approach often leads to results that are difficult to interpret. In this work, we analyze the indirect photodegradation of atorvastatin, carbamazepine, sulfadiazine, and benzotriazole using a diverse set of 48 waters from natural and engineered aquatic systems. We use this large data set to evaluate relationships between PPRI formation and indirect photodegradation rate constants, which are directly compared to results using standard quenching experiments. These data demonstrate that triplet state DOM (3DOM) and singlet oxygen (1O2) are critical PPRI for atorvastatin, carbamazepine, and sulfadiazine, while hydroxyl radical (˙OH) contributes to the indirect photodegradation of benzotriazole. We caution against relying on quenching studies because quenching of 3DOM limits the formation of 1O2 and all studied quenchers react with ˙OH. Furthermore, we show that DOM composition directly influences indirect photodegradation and that low molecular weight, microbial-like DOM is positively correlated with the indirect photodegradation rates of carbamazepine, sulfadiazine, and benzotriazole.

Impact of ozone-biologically active filtration on the breakthrough of Perfluoroalkyl acids during granular activated carbon treatment of municipal wastewater effluent.

The presence of perfluoroalkyl acids (PFAAs) in municipal wastewater has highlighted the need to develop PFAA treatment approaches for wastewater effluent and potable reuse applications. Ozone (O3) and biologically active filtration (BAF) were investigated as standalone and combined pretreatment processes to improve the performance of granular activated carbon (GAC) for PFAA removal from wastewater effluent. As individual processes, ozonation at all three investigated doses (0.35, 0.75, 1.0 mg O3/mg DOC) and BAF at both tested empty bed contact times (EBCT; 15 and 20 min) led to significant improvement in PFAA removal by subsequent GAC treatment. With respect to standalone ozonation, the specific O3 dose of 0.75 mg O3/mg DOC was proven to be the optimum operating condition as further increase of the specific ozone dose to 1.0 mg O3/mg DOC did not provide considerable additional improvement. Extending the EBCT during standalone BAF from 15 to 20 minutes significantly improved the efficacy of GAC for the removal of tested PFAAs. Pretreatment with O3-BAF (0.75 mg O3/mg DOC; 20 min EBCT) in tandem outperformed both standalone ozonation and BAF for the removal of PFAA by GAC. Characterization of effluent organic matter (EfOM) by size exclusion chromatography (SEC) and Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR-MS) before and after pretreatments suggest that among multiple co-occurring phenomena, the shift towards smaller and more polar EfOM may have predominantly alleviated pore constriction/blockage without having adverse impact on direct site competition. This observation is supported by SEC and FT-ICR-MS results indicating reduced EfOM molecular size through O3 and BAF pretreatment as well as transition to more hydrophilic byproducts.

Photochemical degradation of halogenated estrogens under natural solar irradiance.

Halogenated estrogens are thought to be moderately potent endocrine-disrupting compounds that are formed during chlorine-based wastewater disinfection processes and may represent a significant fraction of the total amount of estrogen delivered from wastewater treatment plants to receiving waters. Yet we lack key information about the photochemical degradation of halogenated estrogens, a process that has important implications for UV-based wastewater treatment and environmental fate modeling. To better understand halogenated estrogen degradation in aquatic environments, we studied the direct photolysis of 17ß-estradiol (E2), 2-bromo-17ß-estradiol (monoBrE2), 2,4-dibromo-17ß-estradiol (diBrE2), and 2,4-dichloro-17ß-estradiol (diClE2) as well as the indirect photolysis of diBrE2 under natural solar irradiance. We found that direct photolysis rate constants increased with halogenation as pKa values decreased and molar absorptivity spectra shifted toward higher wavelengths. Compared to E2, quantum yields were threefold larger for monoBrE2, but 15-32% smaller for the dihalogenated forms. The rate of diBrE2 (pKa ∼ 7.5) photolysis was strongly influenced by pH. At pH 7, diBrE2 degraded on minute time scales due to the large red-shifted molar absorptivity values and greater quantum yields of the phenolate form. Degradation rates were only slightly different in the presence of Suwannee River Humic Acid (5 mg L-1), and quenching experiments pointed to excited triplet state dissolved organic matter (3DOM*) as the dominant reactive intermediate responsible for the indirect photolysis of diBrE2. Overall, our data suggest that halogenated estrogens are particularly susceptible to photochemical degradation at environmentally relevant pH values.