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.

Transformation of dissolved organic matter during biological wastewater treatment and relationships with the formation of nitrogenous disinfection byproducts.

Nitrogenous disinfection byproducts (N-DBPs) can be produced from dissolved organic matter (DOM) during the disinfection of secondary wastewater effluent. This study examined the transformation of DOM and the abatement of N-DBP precursors during different types of biological wastewater treatment (e.g., anaerobic/anoxic/oxic activated sludge processes and membrane bioreactor) using high-performance size exclusion chromatography (HPSEC) with dissolved organic carbon, UV, and fluorescence detectors. DOM with molecule weight (MW) larger than 3 kDa and protein-like substances smaller than 0.3 kDa was effectively bio-transformed, whereas DOM fractions with MW in the range of 0.3-3 kDa were the most bio-refractory. Complete nitrification was beneficial to the removal of small amino sugar-like and protein-like molecules (< 0.3 kDa). Haloacetonitrile (HAN) precursors were recalcitrant to biological treatment with a median removal of 17%. Halonitromethane (HNM) and N-nitrosamine (NA) precursors tended to be effectively removed in complete nitrification conditions. The abundance of low-molecular-size protein-like substances (< 0.3 kDa) was significantly correlated with the formation potential of HNM, NA, and total N-nitrosamine (TONO) in post-chloramination (r = 0.81, 0.62, and 0.68, respectively, p < 0.01). This study improved the understanding of DOM transformation and the removal of N-DBPs precursors in wastewater treatment and pointed out the benefit of provision of complete nitrification in removing low-molecular-size protein-like substances and NA and HNM precursors.

Revisiting the protocol for determining submicromolar concentrations of ozone in the water treated by advanced oxidation processes.

Ozone is formed at submicromolar concentrations from photolysis of many oxyanions and oxidants in water and contributes importantly to the degradation of emerging contaminants and inactivation of pathogenic microorganisms in the natural and engineered aquatic systems. In this study, we identified and discussed the critical limitations of the commonly-used protocols using cinnamic acid (CNA) as a probe compound to determine the submicromolar-level ozone and proposed a modified protocol that overcomes those limitations. Our experimental investigation demonstrated that the radicals (e.g., HO•) formed from photolysis of oxyanions and oxidants, other than ozone, could also oxidize CNA and form benzaldehyde, resulting in the overestimation of ozone concentrations by using the commonly-used protocols. Moreover, the benzaldehyde formed from ozone-CNA reactions could be degraded by the radicals, leading to the underestimation of ozone concentrations by using the commonly-used protocols. A new protocol with high accuracy and precision was proposed and the rationales for each operational step of the new protocol were explained in detail and supported with justifications. The new protocol was compared with two commonly-used protocols in determining the concentration of ozone in the same water sample treated by the UV/chlorine process at three different UV wavelengths. The wavelength-dependent overestimation/underestimation of the ozone concentrations by using the two commonly-used protocols was well demonstrated and explained by the overlooked interferences of radicals in the protocols.

Multi-angle comparison of UV/chlorine, UV/monochloramine, and UV/chlorine dioxide processes for water treatment and reuse.

Advanced oxidation processes (AOPs) have been increasingly studied and practiced for micropollutant abatement in drinking water treatment and potable water reuse. This study conducted the multi-angle comparison of the UV/chlorine, UV/monochloramine (UV/NH2Cl), and UV/chlorine dioxide (UV/ClO2) AOPs with respect to reactive species generation, micropollutant degradation, byproduct formation, and toxicity change. The concentrations of radicals (HO·, Cl·, and ClO·) generated in the three AOPs followed the order of UV/chlorine > UV/NH2Cl > UV/ClO2 at an oxidant dose of 70 µM, an irradiation wavelength of 254 nm, and a pH of 7.5. The concentration of ozone generated in the UV/ClO2 AOP was higher than that in the UV/chlorine AOP, while ozone was not generated in the UV/NH2Cl AOP. The effects of pH (pH 6.0, 7.5, and 9.0) and UV wavelength (254 nm, 285 nm, and 300 nm) on the three AOPs were evaluated and compared. Using the radical and ozone concentrations determined in this study, the pseudo-first-order degradation rate constants of 24 micropollutants by the three AOPs were predicted and compared. When the three AOPs were used to treat the water containing the same concentration of natural organic matter, the formation of total organic chlorine (TOCl) and the organic byproduct-associated toxicity followed the same order of UV/chlorine > UV/NH2Cl > UV/ClO2. On the contrary, the inorganic byproduct-associated toxicity followed the order of UV/ClO2 > UV/chlorine > UV/NH2Cl, due to the high concentrations of chlorite and chlorate formed in the UV/ClO2 AOP. Findings in this study offer fundamental information useful for the selection and operation of AOPs for micropollutant abatement in drinking water treatment and potable water reuse.

A Novel UVA/ClO2 Advanced Oxidation Process for the Degradation of Micropollutants in Water.

Ultraviolet (UV)-based advanced oxidation processes (AOPs) are increasingly used for the degradation of micropollutants in water and wastewater. This study reports a novel UVA/chlorine dioxide (ClO2) AOP based on the photolysis of ClO2 using energy-efficient UV radiation sources in the UVA range (e.g., UVA-LEDs). At a ClO2 dosage of 74 µM (5.0 mg L-1 as ClO2) and a UV fluence at 47.5 mJ cm-2, the UVA365/ClO2 AOP generated a spectrum of reactive species, including chlorine oxide radicals (ClO•), chlorine atoms (Cl•), hydroxyl radicals (HO•), and ozone at a concentration of ∼10-13, ∼10-15, ∼10-14, and ∼10-7 M, respectively. A kinetic model to simulate the reactive species generation in the UVA365/ClO2 AOP was established, validated against the experimental results, and used to predict the pseudo-first-order rate constants and relative contributions of different reactive species to the degradation of 19 micropollutants in the UVA365/ClO2 AOP. Compared to the well-documented UVC254/chlorine AOP, the UVA365/ClO2 AOP produced similar levels of reactive species at similar oxidant dosages but was much less pH-dependent and required much lower energy input, with much lower formation of chloro-organic byproducts and marginal formation of chlorite and chlorate.

Simultaneous removal of hydrogen sulfide, phosphate and emerging organic contaminants, and improvement of sludge dewaterability by oxidant dosing in sulfide-iron-laden sludge.

Liquid sludge often contains odorous and toxic hydrogen sulfide and high levels of FeII compounds (e.g., iron sulfides), due to the extensive use of iron salts for hydrogen sulfide control in sewers and for enhanced primary treatment and phosphate removal in wastewater treatment plants. We proposed and verified that dosing appropriate chemical oxidants in the sulfide-iron-laden sludge can be a simple and cost-effective strategy to remove hydrogen sulfide, phosphate, and emerging organic contaminants, and to improve sludge dewaterability simultaneously. Among the seven oxidants investigated, H2O2, ClO2 and NaClO2 were the more cost-effective oxidants than others to control hydrogen sulfide release from the liquid sludge. Dosing these three oxidants also improved sludge dewaterability and removed dissolved phosphate from the liquid sludge, with H2O2 performing the best. Hydrogen sulfide was removed via both direct oxidation by the dosed oxidants and indirect oxidation by the FeIII that was in-situ formed from oxidation of the FeII compounds in the sludge. The in-situ formed FeIII also precipitated/adsorbed the soluble phosphate into the solid form (FePO4). Fenton-like reactions occurred between H2O2 and the FeII compounds in the sludge, and hydroxyl radicals (HO•) were generated. HO• oxidized hydrogen sulfide, destructed refractory organic emerging contaminants and sludge extracellular polymeric compounds (EPSs), and improved the sludge dewaterability. The formation of HO• can be enhanced by hydrogen sulfide and the sludge EPSs present in the sludge through providing more available FeII for the Fenton-like reactions. This study demonstrates the importance of selecting and dosing suitable oxidants to the sulfide-iron-laden sludge with due consideration for the multiple benefits in engineering practices. The same principles may be also used in formulating a dual oxidant-iron strategy to treat sulfide-iron-laden sewage, sludge, and sediments for simultaneous abatement of various pollutants.