Dissolved Organic Matter-Mediated Photosensitized Activation of Monochloramine for Micropollutant Abatement in Wastewater Effluent.

Utilizing solar light and water matrix components in situ to reduce the chemical and energy demands would make treatment technologies more sustainable for micropollutant abatement in wastewater effluents. We herein propose a new strategy for micropollutant abatement through dissolved organic matter (DOM)-mediated photosensitized activation of monochloramine (NH2Cl). Exposing the chlorinated wastewater effluent with residual NH2Cl to solar irradiation (solar/DOM/NH2Cl process) degrades six structurally diverse micropollutants at rate constants 1.26-34.2 times of those by the solar photolysis of the dechlorinated effluent (solar/DOM process). Notably, among the six micropollutants, the degradation rate constants of estradiol, acetaminophen, bisphenol A, and atenolol by the solar/DOM/NH2Cl process are 1.13-4.32 times the summation of those by the solar/DOM and solar/NH2Cl processes. The synergism in micropollutant degradation is attributed to the generation of reactive nitrogen species (RNS) and hydroxyl radicals (HO·) from the photosensitized activation of NH2Cl. Triplet state-excited DOM (3DOM*) dominates the activation of NH2Cl, leading to the generation of RNS, while HO· is produced from the interactions between RNS and other photochemically produced reactive intermediates (e.g., O2·- and DOM·+/·-). The findings advance the knowledge of DOM-mediated photosensitization and offer a sustainable method for micropollutant abatement in wastewater effluents containing residual NH2Cl.

Advanced oxidation of recalcitrant chromophores in full-scale MBR effluent for non-potable reuse of leachate co-treated municipal wastewater.

Wastewater non-potable reuse involves further processing of secondary effluent to a quality level acceptable for reuse and is a promising solution to combating water scarcity. Recalcitrant chromophores in landfill leachate challenge the water quality for non-potable reuse when leachate is co-treated with municipal wastewater. In this study, we first use multivariate statistical analysis to reveal that leachate is an important source (with a Pearson's coefficient of 0.82) of recalcitrant chromophores in the full-scale membrane bioreactor (MBR) effluent. We then evaluate the removal efficacies of chromophores by chlorination, breakpoint chlorination, and the chlorination-UV/chlorine advanced oxidation treatment. Conventional chlorination and breakpoint chlorination only partially remove chromophores, leaving a colour level exceeding the standards for non-potable reuse (>20 Hazen units). We demonstrate that pre-chlorination (with an initial chlorine dosing of 20 mg/L as Cl2) followed by UV radiation (with a UV fluence of 500 mJ/cm2) effectively degraded recalcitrant chromophores (>90%). By quantifying the electron donating capacity (EDC) and radical scavenging capacity (RSC) of the reclaimed water, we demonstrate that pre-chlorination reduces EDC and RSC by up to 64%, increases UV transmittance by 32%, and increases radical yields from UV photolysis of chlorine by 1.7-2.2 times. The findings advance fundamental understanding of the alteration of dissolved coloured substances by (photo)chlorination treatment and provide implications for applying advanced oxidation processes in treating wastewater effluents towards sustainable non-potable reuse.

Dominant Dissolved Oxygen-Independent Pathway to Form Hydroxyl Radicals and the Generation of Reactive Chlorine and Nitrogen Species in Breakpoint Chlorination.

Due to the complexities of the interactions between ammonia, chlor(am)ine, and intermediate species such as ONOOH, the radical formation in breakpoint chlorination and the consequential removal of micropollutants remain largely unexplored. In this study, the dominant generation pathway of HO•, as a primary radical in breakpoint chlorination, was examined, and the generations of HO•, reactive chlorine species (RCS), and reactive nitrogen species (RNS) were quantitatively evaluated. A dissolved oxygen (DO)-independent pathway was verified by 18O labeling and contributed over 90% to HO• generation. The commonly believed pathway, the decomposition of ONOOH involving DO, contributed only 7% to HO• formation in breakpoint chlorination. The chlorine to nitrogen (Cl/N) ratio and pH greatly affected the generations and speciations of the reactive species. An optimum Cl/N mass ratio for HO•, Cl2•-, and RNS generations occurred at the breakpoint (i.e., Cl/N mass ratio = 9), whereas excessive free chlorine shifted the radical speciation toward ClO• at Cl/N mass ratios above the breakpoint. Basic conditions inhibited the generations of HO• and RNS but significantly promoted that of ClO•. These findings improved the fundamental understanding of the radical chemistry of breakpoint chlorination, which can be extended to estimate the degradations of micropollutants of known rate constants toward the reactive species with influences from the Cl/N ratio and pH in real-world applications.

Degradation of aliphatic halogenated contaminants in water by UVA/Cu-TiO2 and UVA/TiO2 photocatalytic processes: Structure-activity relationship and role of reactive species.

This study investigated the degradation of eight aliphatic halogenated contaminants (one brominated flame retardant and seven disinfection by-products) in synthetic drinking water by the UVA/TiO2 and UVA/Cu-TiO2 processes. The degradation rate constants of 2,2-bis(bromomethyl)-1,3-propanediol and trichloromethane in the UVA/Cu-TiO2 process were 10.1 and 1.29 times, respectively, higher than those in the UVA/TiO2 process. In contrast, the degradation rate constants of dichloroacetaldehyde, monochloroacetonitrile, monobromoacetonitrile and dibromonitromethane in the UVA/Cu-TiO2 process were 8.15, 2.33, 2.84 and 1.80 times, respectively, lower than those in the UVA/TiO2 process. The degradation rate constants of monobromonitromethane and dichloronitromethane were comparable in the two processes. The relationships between the degradation rate constants and the structural characteristics of the selected contaminants were examined to explain the different degradation efficacies of the contaminants in the two processes. As suggested by a quantitative structure-activity relationship (QSAR) model, the UVA/TiO2 process favored the degradation of contaminants with more polar electron-withdrawing moieties and higher degrees of chlorination. While the UVA/Cu-TiO2 process favored the degradation of hydrophilic unsaturated contaminants with multiple bonds. The concentrations of the reactive species (e.g., HO and e-) generated in the two photocatalytic processes were quantified using competition kinetics. The UVA/Cu-TiO2 process generated >10 times higher concentrations of HO than the UVA/TiO2 process, suggesting that the former process was more suitable for the degradation of contaminants that are reactive towards HO, while e- and e--derived superoxide radicals were non-negligible contributors to contaminant degradation in the UVA/TiO2 process.