The illicit connection of sewage pipes to stormwater pipes commonly occurs in urban stormwater systems. This brings problems that sewage might be directly discharges into natural water and even drinking water sources without treatment, posing risks to ecological safety. Sewage contains various unknown dissolved organic matter (DOM), which could react with disinfectants and lead to the formation of carcinogenic disinfection byproducts (DBPs). Thus, understanding the impacts of illicit connections on downstream water quality is of significance. This study firstly investigated the characteristics of DOM using fluorescence spectroscopy and the formation of DBPs after chlorination in an urban stormwater drainage system in the case of illicit connections. The results found that the concentrations of dissolved organic carbon and dissolved organic nitrogen ranged from 2.6 to 14.9 mg/L and from 1.8 to 12.6 mg/L, respectively, with the highest levels occurring at the illicit connection points. Concerning DBP precursors, pipe illicit connections introduced considerable precursors of highly toxic haloacetaldehydes and haloacetonitriles into the stormwater pipes. Furthermore, illicit connections introduced more contents of tyrosine-like and tryptophan-like aromatic proteins, which may be related to foods, nutrients, personal care products, etc. in the untreated sewage. This indicated that the urban stormwater drainage system was a significant input source of DOM and DBP precursors to natural water. The results of this study are of great significance for protecting the security of water sources and promoting the sustainability of urban water environment.@en

In drinking water treatment plants (DWTPs), the widely used biological activated carbon filters (BACFs), as the last barrier before disinfection, can remove dissolved organic matter (DOM) known as precursors of disinfection by-products (DBPs). Whether phosphate addition can improve water purification and DBP control of BACFs is still controversial. This study investigated short-term and long-term effects of phosphate addition on controlling DBP formation potentials (FPs) by BACFs via column and batch experiments. The BAC columns presented good water purification performance: they removed around 50 % DOM, nearly all fulvic acid-likes and humic acid-likes as well as 5 %–70 % chlor(am)innated THM4, HAA9 and HAN4 FPs (except chloraminated THM4 FPs)， which was mainly contributed by aerobic bacteria not anoxic bacteria. Phosphate addition within 7–14 days further improved removals of DOM, aromatic organics, fluorescence fractions in DOM as well as HAA9 and HAN4 FPs (especially TCAA FP and TCAN FP) to different extent. However, this improvement did not last longer, and removals of DOM, aromatic organics, two fluorescence fractions (soluble microbial byproduct-likes and humic acid-likes) and DBP FPs decreased despite long-term phosphate addition. Oxic and anoxic batch experiments showed that the positive response of water purification to short-term phosphate addition was also mainly attributed to aerobic bacteria and not to anoxic bacteria. For example, the former decreased DOM and DBP FPs, while the latter increased protein- and tryptophan-like substances as well as chloraminated THM4 FPs. Phosphate addition resulted in EPS increase in anoxic reactors and decrease in oxic reactors. These results indicated that a high dissolved oxygen in BACFs may be helpful for water purification and DBP control. Overall, short-term phosphate addition into phosphorus-limited water is beneficial for BACFs to control DBPs while long-term addition has no effect. Therefore, an intermittent phosphate addition into BACFs is suggested to control DBPs in DWTPs.@en

Biological activated carbon (BAC) filtration is usually considered to be able to decrease formation potentials (FPs) of disinfection by-products (DBPs) in drinking water treatment plant (DWTP). However, BAC filters with long running time may release microbial metabolites to effluents and therefore increase FPs of nitrogenous DBPs with high toxicity. To verify this hypothesis, this study continuously tracked BAC filters in a DWTP for one year, and assessed effects of old (running time 8–9 years) and new (running time 0–13 months) BAC filters on FPs of 15 regulated and unregulated DBPs. Results revealed that dissolved organic carbon (DOC) removal was slightly higher in the new BAC than the old one. All fluorescent components of dissolved organic matter evidently declined after new BAC filtration, but fulvic acid-like and soluble microbial product-like substances increased after old BAC filtration, which could be caused by microbial leakage. Correspondingly, new BAC filter generally removed more DBP FPs than the old one. 46.5% HAA7 FPs from chlorination and 44.3% THM4 FPs from chloramination were removed by new BAC filter. However, some DBP FPs, especially HAN FPs, were poorly removed or even increased by the old BAC filter. Proteobacteria could be a main contributor for DBP precursor removal in BAC filters. Herminiimonas, most abundant genera in new BAC filter, may explain its better DOC and UV254 removal performance and lower DBP FPs, while Bradyrhizobium, most abundant genera in old BAC filter, might produce more extracellular polymeric substances and therefore increased N-DBP FPs in old BAC effluent. This study provided insight into variations of DBP FPs and microbial communities in the new and old BAC filters, and will be helpful for the optimization of DWTP design and operation for public health.@en

The high chlorine dosages in wastewater treatment plants during the COVID-19 pandemic may result in increased formation of disinfection by-products (DBPs), posing great threat to the aquatic ecosystem of the receiving water body and the public health in the downstream area. However, limited information is available on the effect of biological wastewater treatment processes on the formation of CX3R-type DBPs. This study investigated the effect of oxidation ditch (OD) and anaerobic-anoxic-oxic (AAO), two widely used biological wastewater treatment processes, on the formation of five classes of CX3R-type DBPs, including trihalomethanes (THMs), haloacetic acids (HAAs), haloacetaldehydes (HALs), haloacetonitriles (HANs) and halonitromethanes (HNMs), during chlorination. Experimental results showed that biological treatment effectively reduced the dissolved organic carbon (DOC) and UV254, while it increased the dissolved organic nitrogen (DON), and therefore the ratio of DON/DOC. In addition, increases in the contents of soluble microbial product- and humic acid-like matters, and the transformation of high molecular weight (MW) fractions in the dissolved organic matter into low MW fractions were observed after OD and AAO processes. Although biological treatment effectively decreased the formation of Cl-THMs, Cl-HAAs, Cl-HANs and Cl-HNMs, the formation of DBCM, DBAA, BDCAA, DBCAA, DCAL, TCAL and DBAN (where C = chloro, B = bromo, D = di, T = tri) all increased significantly, due to the increased formation reactivity. Moreover, biological treatment increased the ratio of bromide/DOC and bromine incorporation into THMs, HAAs and DHANs except for HALs and THANs. Different from previous studies, this study revealed that biological treatment increased the formation of some DBPs, especially brominated DBPs, despite the efficient removal of organic matters. It provides insights into the DBP risk control in wastewater treatment, particularly during the COVID-19 pandemic.@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 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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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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