During drinking water treatment, advanced oxidation process (AOP) with O3 and H2O2 may result in by-products, residual H2O2 and BrO3−. The water containing H2O2 and BrO3− often flows into subsequent granular activated carbon (GAC) filters. A concentrated H2O2 solution can be used as GAC modification reagent at 60 °C to improve its adsorption ability. However, whether low concentrations of H2O2 residuals from AOP can modify GAC, and the impact of H2O2 residuals on BrO3− removal by the subsequent GAC filter at ambient temperature, is unknown. This study evaluated the modification of GAC surface functional groups by residual H2O2 and its effect on BrO3− removal by GAC. Results showed that both H2O2 and BrO3− were effectively removed by virgin GAC, while pre-loaded and regenerated GACs removed H2O2 but not BrO3− anymore. At the ambient temperature 150 µmol/L H2O2 residuals consumed large amounts of functional groups, which resulted in the decrease of BrO3− removal by virgin GAC in the presence of H2O2 residuals. Redox reactions between BrO3− and surface functional groups played a dominant role in BrO3− removal by GAC, and only a small amount of BrO3− was removed by GAC adsorption. The higher the pH, the less BrO3− removal and the more H2O2 removal was observed.@en

Riverbank filtration (RBF) as a barrier of pathogenic microorganisms and organic micropollutants recently has been proven capable of removing sulfonamides. However, the study about the effect of redox conditions on biodegradation of common and persistent sulfonamides in RBF is limited and the response of microbial communities to sulfonamides stress during RBF is unknown. In this study, two column set-ups (with residence time 5 days and 11 days respectively), simulating different redox conditions of riverbank filtration systems, were operated for seven months to investigate 1) the long-term effect of redox conditions on ng∙L−1 level sulfonamides (sulfapyridine, sulfadiazine, sulfamethoxazole, sulfamethazine, sulfaquinoxaline) removal, and 2) the microbial community evolution represented by the phylogenetic and metabolic function shift under non-lethal selective pressures of sulfonamides. The results showed that sulfonamides were more degradable under anoxic conditions than oxic and suboxic conditions. In the sulfonamides stressed community, the phylogenetic diversity increased slightly. Relative abundance of an intrinsic sulfonamides resistant bacteria Bacillus spp. increased, suggesting that sulfonamide resistance developed in specific bacteria under sulfonamides contamination pressure in RBF systems. At the same time, an activated transport function in the stressed microbial community was noticed. The predicted relative abundance of gene folP, which encodes dihydropteroate synthase, also increased significantly, indicating a detoxification mechanism and sulfonamides resistance potential under non-lethal selective pressures of sulfonamides in RBF systems.@en

Previous studies have examined the effects of peptide bond and unsaturated bond on the formation of disinfection by-products (DBPs). However, limited information has been available for the impact of reduced sulfur group on the formation of DBPs. This study investigated the formation of carbonaceous and nitrogenous DBPs (C-DBPs and N-DBPs) with a similar structure of ‘’CX3R” (X = H, Cl, Br or I, R = functional group), including trihalomethanes, haloacetaldehydes, haloketones, haloacetonitriles, haloacetamides and halonitromethanes, during chlor(am)ination of three reduced sulfur compounds (RSCs), such as N-acetylcysteine, glutathione and glutathiol. Results showed that all DBPs except dichloroacetonitrile (DCAN) continuously increased with increasing Cl2 or NH2Cl doses in this study. The chlor(am)ination of three RSCs with lower disinfectant doses (the molar ratio of disinfectant to precursor ≤5) generated low DBPs compare to non-RSCs. More chloroform was observed in alkaline condition, while weak acidic condition was in favor of DCAN and dichloroacetamide formation. The results of frontier electron density calculation reported that the much higher reactivity for Cl2 and NH2Cl toward reduced sulfur group in RSCs protects other groups, which account for the formation of CX3R-type DBPs. This phenomenon has important environmental implications. When RSCs are present in the water, Cl2 or NH2Cl will reacts preferably with them rather than non-RSCs to form RSO3H as the major products. Hence, the trade-offs of between the products generated upon S-chlorination, which account for the formation RSO3H, and alkyl halogenation and N-chlorination, which account for the formation of CX3R-type DBPs, influence the formation of CX3R-type DBPs.@en

Chloroacetamides (CAMs) as a class of highly toxic nitrogenous disinfection by-products (N-DBPs) have been widely detected in drinking water. It has been reported that weak magnetic field (WMF) could improve the removal ability of zero-valent iron (ZVI) to some pollutants, but CAMs removal by ZVI coupled with WMF has never been studied. This study through oxic batch experiments was executed to investigate the effect of WMF on trichloroacetamide (TCAM) removal by different doses of ZVI under different pH levels and to explore how WMF works on TCAM removal for the first time. The results showed that the WMF improved TCAM removal by ZVI and the strengthening effect of WMF was more significant at lower ZVI dose or higher pH conditions. The formation of trichloroacetic acid indicated the occurrence of TCAM hydrolysis. Chlorine mass balance was observed in TCAM and its potential products, dichloroacetamide, monochloroacetamide, and chloride, indicating these were all the products and a dechlorination process occurred when TCAM contacted with ZVI. By calculating the yields of hydrolytic products and dechlorinated products, it was determined that dechlorination of TCAM was the dominant reaction for TCAM removal by ZVI with and without WMF, while hydrolysis reaction played a minor role. Mechanism analysis showed that the WMF promoted TCAM hydrolysis through impacting the electromigration within the oxide scale and improving the migration of paramagnetic oxygen to the surface of magnetized ZVI. Taken together, ZVI coupled with WMF is a potential effective technology for TCAM removal in effluent of chlorination.

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The removal of bromate (BrO3 -) as a byproduct of ozonation in subsequent managed aquifer recharge (MAR) systems has so far gained little attention. This preliminary study with anoxic batch experiments was executed to explore the feasibility of chemical BrO3 - reduction in Fe-reducing zones of MAR systems and to estimate potential inhibition by NO3 -. Results show that the reaction rate was affected by initial Fe2+/BrO3 - ratios and by pH. The pH dropped significantly due to the hydrolysis of Fe3+ to hydrous ferric oxide (HFO) flocs. These HFO flocs were found to adsorb Fe2+, especially at high Fe2+/BrO3 - ratios, whereas at low Fe2+/BrO3 - ratios, the mass sum loss of BrO3 - and Br- indicated intermediate species formation. Under MAR conditions with relatively low BrO3 - and Fe2+ concentrations, BrO3 - can be reduced by naturally occurring Fe2+, as the extensive retention time in MAR systems will compensate for the slow reaction kinetics of low BrO3 - and Fe2+ concentrations. Under specific flow conditions, Fe2+ and NO3 - may co-occur during MAR, but NO3 - hardly competes with BrO3 -, since Fe2+ prefers BrO3 - over NO3 -. However, it was found that when NO3 - concentration exceeds BrO3 - concentration by multiple orders of magnitude, NO3 - may slightly inhibit BrO3 - reduction by Fe2+.@en

The effective removal of haloacetamides (HAMs) as a group of emerging disinfection by-products is essential for drinking water safety. This study investigated the degradation of 10 HAMs, including chlorinated, brominated, and iodinated analogues, by sodium sulfite (S(IV)) and the mechanism behind it. The results indicated that all HAMs, excluding chlorinated HAMs, decomposed immediately when exposed to S(IV). The reductive dehalogenation kinetics were well described by a second-order kinetics model, first-order in S(IV) and first-order in HAMs. The degradation rates of HAMs increased with the increase of pH and they were positively correlated with sulfite concentration, indicating that the reaction of S(IV) with HAMs mainly depends on sulfite. The rank order and relative activity of the reaction of sulfite with HAMs depends on bimolecular nucleophilic substitution reaction reactivity. The order of the reductive dehalogenation rates of HAMs versus the substitution of halogen atoms was iodo- > bromo- >> chloro-. During reductive dehalogenation of HAMs by sulfite, the α-carbon bound to the amide group underwent nucleophilic attack at 180° to the leaving group (halide). As a consequence, the halide was pushed off the opposite side, generating a transition state pentacoordinate. The breaking of the C-X bond and the formation of the new C-S bond occurred simultaneously and HAM sulfonate formed as the immediate product. Results suggest that S(IV) can be used to degrade brominated and iodinated HAMs in drinking water and therefore should not be added as a quenching agent before HAM analysis to accurately determine the HAM concentrations produced during water disinfection.

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Managed Aquifer Recharge (MAR) is a technology that relies on soil passage - after pond infiltration - for water treatment. MAR is a proven technology for the removal of pathogenic micro-organisms, turbidity and a selection of specific organic micro-pollutions (OMPs). Nevertheless, removal of the wide variety of OMPs found in surface waters requires additional treatment. The application of O3-based advanced oxidation processes (AOPs) before MAR has been proposed as a smart solution, because previous studies have documented complementary and synergetic benefits for the removal of OMPs. However, the effect of the installation of O3-based AOP as a chemical process on the subsequent MAR as a biological process is not known yet. Especially the behaviour and fate of O3-based AOP by-products and residuals on MAR raise many questions. This thesis focused on the behaviour and fate of BrO3 - as an O3-based AOP by-product and H2O2 as an AOP residual during MAR.@en

Atmospheric particulate matter (PM) can be scavenged by rainfall and contribute dissolved organic matter (DOM) to rainwater. Rainwater may serve as a part or the whole of drinking water sources, leading to the introduction of PM-derived DOM into drinking water. However, little information is available on the role of PM-derived DOM as a remarkable precursor of CX₃R-type disinfection by-products (DBPs) in rainwater. In this study, samples were collected from ten occurrences of rainfall in Shanghai and batch experiments were executed to explore the contribution of PM-derived DOM to CX₃R-type DBP formation in rainwater and to further understand some of unknowns regarding its characteristics. Results revealed that a part of PM was scavenged by rainfall and the scavenge performance was better for smaller PM. The formation potentials (FPs) of individual CX₃R-type DBP were similar among size-isolated PM. TCM was predominant (around 0.5–4.5 μg-C/mg-C) and TCAA was the secondary (around 0.6–3.2 μg-C/mg-C) among all detectable CX₃R-type DBPs. Based on the PM removal data and DBP FP results, the contribution of PM-derived DOM to CX₃R-type DBP formation in rainwater was modeled. Furthermore, aromatic proteins and soluble microbial product-like compounds were found to be significant compositions, which were reported to be DBP precursors. And low molecular weight (< 10 kDa) DOM derived from total PM and rainwater exhibited higher CX₃R-type DBP FPs. DOM fractions with higher SUVA₂₅₄ and SUVA₂₈₅ values gave relatively higher yields of CX₃R-type DBPs, indicating that aromatic compounds played an important role in DBP formation.

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H2O2 residuals from advanced oxidation processes (AOPs) may have critical impacts on the microbial ecology and performance of subsequent biological treatment processes, but little is known. The objective of this study was to evaluate how H2O2 residuals influence sand systems with an emphasis on dissolved organic carbon (DOC) removal, microbial activity change and bacterial community evolution. The results from laboratory batch studies showed that 0.25 mg/L H2O2 lowered DOC removal by 10% while higher H2O2 concentrations at 3 and 5 mg/L promoted DOC removal by 8% and 28%. A H2O2 dosage of 0.25 mg/L did not impact microbial activity (as measured by ATP) while high H2O2 dosages, 1, 3 and 5 mg/L, resulted in reduced microbial activity of 23%, 37% and 37% respectively. Therefore, DOC removal was promoted by the increase of H2O2 dosage while microbial activity was reduced. The pyrosequencing results illustrated that bacterial communities were dominated by Proteobacteria. The presence of H2O2 showed clear influence on the diversity and composition of bacterial communities, which became more diverse under 0.25 mg/L H2O2 but conversely less diverse when the dosage increased to 5 mg/L H2O2. Anaerobic bacteria were found to be most sensitive to H2O2 as their growth in batch reactors was limited by both 0.25 and 5 mg/L H2O2 (17–88% reduction). In conclusion, special attention should be given to effects of AOPs residuals on microbial ecology before introducing AOPs as a pre-treatment to biological (sand) processes. Additionally, the guideline on the maximum allowable H2O2 concentration should be properly evaluated.@en

The removal of bromate (BrO3−) as a by-product of ozonation in subsequent managed aquifer recharge (MAR) systems, specifically in anoxic nitrate (NO3−)-reducing zones, has so far gained little attention. In this study, batch reactors and columns were used to explore the influence of NO3− and increased assimilable organic carbon (AOC) due to ozonation pre-treatment on BrO3− removal in MAR systems. 8 m column experiments were carried out for 10 months to investigate BrO3− behavior in anoxic NO3−-reducing zones of MAR systems. Anoxic batch experiments showed that an increase of AOC promoted microbial activity and corresponding BrO3− removal. A drastic increase of BrO3− biodegradation was observed in the sudden absence of NO3− in both batch reactors and columns, indicating that BrO3− and NO3− competed for biodegradation by denitrifying bacteria and NO3− was preferred as an electron acceptor under the simultaneous presence of NO3− and BrO3−. However, within 75 days’ absence of NO3− in the anoxic column, BrO3− removal gradually decreased, indicating that the presence of NO3− is a precondition for denitrifying bacteria to reduce BrO3− in NO3−-reducing anoxic zones. In the 8 m anoxic column set-up (retention time 6 days), the BrO3− removal achieved levels as low as 1.3 μg/L, starting at 60 μg/L (98% removal). Taken together, BrO3− removal is likely to occur in vicinity of NO3−-reducing anoxic zones, so MAR systems following ozonation are potentially effective to remove BrO3−.@en