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Water utilities must control microbial regrowth in the distribution system to protect public health. In this study, an adenosine triphosphate (ATP)-based biomass production potential test using indigenous bacterial communities were used to evaluate regrowth potential following ozonation with either biofiltration (BF) or sustained chlorination (SCl 2 ). Two full-scale water treatment plants with different upstream processes (i.e., WTP-BF: ozonation, coagulation/flocculation, biofiltration, UV irradiation, chlorination; and WTP-SCl 2 : ozonation, chlorination, coagulation/flocculation, filtration, chlorination) were compared. Characterization of indigenous bacteria using 16S rRNA gene sequencing, qPCR, and cellular ATP (cATP) showed microbial diversity changes across treatment, biomass sloughing from biofilters (effluent cATP = 30 ± 1 ng/L), and disinfection by chlorine (cATP < 1 ng/L). For both WTPs, 14-day cumulative biomass production (CBP t  =  ∑t=0tATP(t)×Δt) was highest for ozonated water samples (CBP 14  = 1.2 × 10 3 -3.0 × 10 3  d ngATP/L). CBP further increased with increasing ozone dose due to production of more biodegradable carbon. Growth promotion by carbon was confirmed from the consumption of ozonation byproducts (carboxylic acids, aldehydes) and the increase in CBP (9.5 × 10 2 -2.9 × 10 3  d ngATP/L) after addition of 50-300 μgC/L acetate. Ozone followed by sustained chlorination (WTP-SCl 2 ) effectively controlled biomass growth across the treatment process (CBP 14 <10 d ngATP/L). In contrast, ozone followed by biofiltration (WTP-BF) reduced regrowth potential by 30% (biofilter influent CBP 14  = 1.3 × 10 3  d ngATP/L; biofilter effluent CBP 14  = 9.3 × 10 2  d ngATP/L). After adding chlorine to the biofilter effluent, CBP 14 was reduced to <10 d ngATP/L. Lastly, online ATP measurements confirmed the discrete measurements and improved identification of the cATP peak and growth phases of indigenous bacteria., (Copyright © 2019 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

The combination of biological growth and particle loading can adversely affect hydraulic performance in drinking water biofilters. In this study, upstream oxidant addition was used to distribute biologically-derived filter clogging in granular activated carbon (GAC) biofilters. Oxidant penetration was assessed during pilot-scale operation and backwashing of dual media (GAC/sand) and multimedia (GAC/anthracite/sand) biofilters. Influent chlorine (HOCl), monochloramine (NH 2 Cl), and hydrogen peroxide (H 2 O 2 ) residuals were optimized to react with the GAC surface in the upper portion of the filter media bed (depth < 0.5 m) to attenuate biomass development. As the oxidant residual was quenched by surface-mediated reaction with the filter media, biomass growth was promoted deeper in the filter bed (depth > 0.5 m). The oxidant-induced effects on biomass and hydraulic performance were monitored through measurements of adenosine triphosphate (ATP) and head loss accumulation at different media depths. Addition of oxidants (e.g., 0.6 mg Cl 2 /L HOCl) could decrease terminal head loss by 20% in dual media filters and 40% in multimedia filters. These hydraulic benefits were achieved without significantly affecting removal of assimilable organic carbon (AOC), total organic carbon (TOC), turbidity, and particle counts. Oxidant type, residual concentration, media type, media age, and media depth influenced the passage of oxidant residuals and distribution of filter biomass. When oxidants were added during backwashing, oxidant residual was quenched through the bed depth from a combination of reactions with GAC media and biofilm degradation. This attenuation of residual oxidant may prevent the oxidant residual from penetrating the entire bed depth, potentially compromising backwashing objectives., (Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Chlorine demand of a water sample depends on the characteristics of dissolved organic matter (DOM). It is an important parameter for water utilities used to assess oxidant and/or disinfectant consumption of source waters during treatment and distribution. In this study, model compounds namely resorcinol, tannic acid, vanillin, cysteine, tyrosine, and tryptophan were used to represent the reactive moieties of complex DOM mixtures. The reactivity of these compounds was evaluated in terms of Cl 2 demand and electron donating capacity (EDC). The EDC was determined by mediated electrochemical oxidation (MEO) which involves the use of 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) as an electron shuttle. The Cl 2 demand of readily oxidizable compounds (resorcinol, tannic acid, vanillin, and cysteine) was found to correlate well with EDC (R 2  = 0.98). The EDC values (mol e - /mol C) of the model compounds are as follows: 1.18 (cysteine) > 0.77 (resorcinol) > 0.59 (vanillin) > 0.52 (tannic acid) > 0.36 (tryptophan) > 0.19 (tyrosine). To determine the effect of pre-oxidation on EDC, ozone was added (0.1 mol O 3 /mol C) into each model compound solution. Ozonation caused a general decrease in EDC (10-40%), chlorine demand (10-30%), and UV absorbance (10-40%), except for tyrosine which showed both increased UV 275 and EDC. Before and after ozonation, 24 h disinfection byproduct (DBP) formation potential tests (Cl 2 residual = 1.5 mg/L) were conducted to evaluate the use of EDC for DBP formation prediction. The results indicate that there was no significant correlation between the EDC of the model compounds and the formation potentials of adsorbable organic chlorine, trichloromethane, and trichloroacetic acid. This suggests that while EDC correlates with Cl 2 demand, chlorine consumption may not directly translate to DBP formation because oxidation reactions may dominate over substitution reactions. Overall, this study provides useful insights on the reactions of ABTS + and HOCl with model DOM compounds, and highlights the potential application of MEO for rapid determination of Cl 2 demand of a water sample., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Dissolved organic nitrogen (DON) is an emerging concern in oxidative water treatment because it exerts oxidant demand and may form nitrogenous oxidation/disinfection by-products. In this study, we investigated the reactions of ozone with DON with a special emphasis on the formation of nitrate (NO 3 - ) and ammonium (NH 4 + ). In batch ozonation experiments, the formation of NO 3 - and NH 4 + was investigated for natural organic matter standards, surface water, and wastewater effluent samples. A good correlation was found between NO 3 - formation and the O 3 exposure (R 2  > 0.82) during ozonation of both model DON solutions and real water samples. To determine the main precursor of NO 3 - , solutions composed of tannic acid and model compounds with amine functional groups were ozonated. The NO 3 - yield during ozonation was significantly higher for glycine than for trimethylamine and dimethylamine. Experiments with glycine also showed that NO 3 - was formed via an intermediate with a second-order rate constant of 7.7 ± 0.1 M -1 s -1 while NH 4 + was formed by an electron-transfer mechanism with O 3 as confirmed from a hydroxyl radical (OH) yield of 24.7 ± 1.9%. The NH 4 + concentrations, however, were lower than the OH yield (0.03 mol NH 4 + /mol OH) suggesting other OH-producing reactions that compete with NH 4 + formation. This study concludes that NO 3 - formation during ozonation of DON is induced by an oxygen-transfer to nitrogen forming hydroxylamine and oxime, while NH 4 + formation is induced by electron-transfer reactions involving C-centered radicals and imine intermediates., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Ozonation is known to generate biodegradable organic matter, which is typically reduced by biological filtration to avoid bacterial regrowth in distribution systems. Post-chlorination generates halogenated disinfection byproducts (DBPs) but little is known about the biodegradability of their precursors. This study determined the effect of ozonation and biofiltration conditions, specifically ozone exposure and empty bed contact time (EBCT), on the control of DBP formation potentials in drinking water. Ozone exposure was varied through addition of H 2 O 2 during ozonation at 1 mgO 3 /mgDOC followed by biological filtration using either activated carbon (BAC) or anthracite. Ozonation led to a 10% decrease in dissolved organic carbon (DOC), without further improvement from H 2 O 2 addition. Raising H 2 O 2 concentrations from 0 to 2 mmol/mmolO 3 resulted in increased DBP formation potentials during post-chlorination of the ozonated water (target Cl 2 residual after 24 h = 1-2 mg/L) as follows: 4 trihalomethanes (THM4, 37%), 8 haloacetic acids (HAA8, 44%), chloral hydrate (CH, 107%), 2 haloketones (HK2, 97%), 4 haloacetonitriles (HAN4, 33%), trichloroacetamide (TCAM, 43%), and adsorbable organic halogen (AOX, 27%), but a decrease in the concentrations of 2 trihalonitromethanes (THNM2, 43%). Coupling ozonation with biofiltration prior to chlorination effectively lowered the formation potentials of all DBPs including CH, HK2, and THNM2, all of which increased after ozonation. The dynamics of DBP formation potentials during BAC filtration at different EBCTs followed first-order reaction kinetics. Minimum steady-state concentrations were attained at an EBCT of about 10-20 min, depending on the DBP species. The rate of reduction in DBP formation potentials varied among individual species before reaching their minimum concentrations. CH, HK2, and THNM2 had the highest rate constants of between 0.5 and 0.6 min -1 followed by HAN4 (0.4 min -1 ), THM4 (0.3 min -1 ), HAA8 (0.2 min -1 ), and AOX (0.1 min -1 ). At an EBCT of 15 min, the reduction in formation potential for most DBPs was less than 50% but was higher than 70% for CH, HK2, and THNM2. The formation of bromine-containing DBPs increased with increasing EBCT, most likely due to an increase in Br - /DOC ratio. Overall, this study demonstrated that the combination of ozonation and biofiltration is an effective approach to mitigate DBP formation during drinking water treatment., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

When ozonation is employed in advanced water treatment plants to produce drinking water, dissolved organic matter reacts with ozone (O3) and/or hydroxyl radicals (OH) affecting disinfection byproduct (DBP) formation with subsequently used chlorine-based disinfectants. This study presents the effects of varying exposures of O3 and •OH on DBP concentrations and their associated toxicity generated after subsequent chlorination. DBP formation potential tests and in vitro bioassays were conducted after batch ozonation experiments of coagulated surface water with and without addition of tertiary butanol (t-BuOH, 10 mM) and hydrogen peroxide (H2O2, 1 mg/mg O3), and at different pH (6-8) and transferred ozone doses (0-1 mg/mg TOC). Although ozonation led to a 24-37% decrease in formation of total trihalomethanes, haloacetic acids, haloacetonitriles, and trihaloacetamides, an increase in formation of total trihalonitromethanes, chloral hydrate, and haloketones was observed. This effect however was less pronounced for samples ozonated at conditions favoring molecular ozone (e.g., pH 6 and in the presence of t-BuOH) over •OH reactions (e.g., pH 8 and in the presence of H2O2). Compared to ozonation only, addition of H2O2 consistently enhanced formation of all DBP groups (20-61%) except trihalonitromethanes. This proves that •OH-transformed organic matter is more susceptible to halogen incorporation. Analogously, adsorbable organic halogen (AOX) concentrations increased under conditions that favor •OH reactions. The ratio of unknown to known AOX, however, was greater at conditions that promote direct O3 reactions. Although significant correlation was found between AOX and genotoxicity with the p53 bioassay, toxicity tests using 4 in vitro bioassays showed relatively low absolute differences between various ozonation conditions., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Oxidation of β-lactam antibiotics by aqueous ferrate(VI) was investigated to determine reaction kinetics, reaction sites, antibacterial activity changes, and transformation products. Apparent second-order rate constants (kapp) were determined in the pH range 6.0-9.5 for the reaction of ferrate(VI) with penicillins (amoxicillin, ampicillin, cloxacillin, and penicillin G), a cephalosporin (cephalexin), and several model compounds. Ferrate(VI) shows an appreciable reactivity toward the selected β-lactams (kapp for pH 7 = 110-770 M(-1) s(-1)). The pH-dependent kapp could be well explained by considering species-specific reactions between ferrate(VI) and the β-lactams (with reactions occurring at thioether, amine, and/or phenol groups). On the basis of the kinetic results, the thioether is the main reaction site for cloxacillin and penicillin G. In addition to the thioether, the amine is a reaction site for ampicillin and cephalexin, and amine and phenol are reaction sites for amoxicillin. HPLC/MS analysis showed that the thioether of β-lactams was transformed to stereoisomeric (R)- and (S)-sulfoxides and then to a sulfone. Quantitative microbiological assay of ferrate(VI)-treated β-lactam solutions indicated that transformation products resulting from the oxidation of cephalexin exhibited diminished, but non-negligible residual activity (i.e., ∼24% as potent as the parent compound). For the other β-lactams, the transformation products showed much lower (<5%) antibacterial potencies compared to the parent compounds. Overall, ferrate(VI) oxidation appears to be effective as a means of lowering the antibacterial activities of β-lactams, although alternative approaches may be necessary to achieve complete elimination of cephalosporin activities.