Search

Eutrophication is a globally concerned issue, which brings algal cells and algal organic matter (AOM) into drinking water treatment plants. AOM is an important branch of nitrogenous disinfection byproduct (N-DBP) precursors. The variation of AOM composition in UV-LEDs/chlorine process, and its relationship with N-DBP formation still remain much uncertainty. Herein, we used fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to investigate AOM transformation in UV-LEDs/chlorine process, with UV 285 and UV 365 as light source, and screen for typical precursors of N-DBPs. We found that more nitrogen-containing compounds were generated after UV-LEDs/chlorine process, leading to the larger formation of N-DBPs in postchlorination. Compounds such as lignin, proteins, and amino sugars tends to be oxidized by reactive species in UV-LEDs/chlorine process. Further, compounds with higher O/C and higher weighted average double bond equivalence (DBE w ) are easier to form N-DBPs, including dichloroacetonitrile and trichloronitromethane. Also, influence factors including pH, UV fluence, post-chlorination time and bromide concentration on N-DBP formation were evaluated. The results show that N-DBP formation generally followed the order of UV 285 /chlorine-postchlorination, UV 365 /chlorine-postchlorination, and direct chlorination. Our study provides comprehensive information on N-DBP formation from AOM in UV-LEDs/chlorine-postchlorination from molecular levels., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

In this study, the potential formation of trichloronitromethane (TCNM) from model organic compounds in ammonia-containing water treated by UV/chlorine process was evaluated. Monochloramine generated from the reaction of chlorine and ammonia can be photolyzed to produce NO 2 - and reactive nitrogen species (RNS), which play important roles in the formation of TCNM during the subsequent chlorination. The results showed that increase of nitrogen to chlorine molar ratio (from 0 to 1.0) and pH (from 6.5 to 8.0) enhanced the formation of TCNM, mainly due to the increased yield of NO 2 - and RNS from the photolyzed monochloramine. The formation of TCNM was interestingly found to be linearly correlated with Hammett constants of the model precursors, which is theoretically related to the rate constants of RNS with model compounds. Enhanced formation of TCNM was also observed during the treatment of natural organic matter by UV/chlorine process in ammonia-containing water. The toxicity assessment showed that TCNM significantly increased the genotoxicity of formed DBPs. Furthermore, the electrophilic substitution reaction of • NO 2 was proved to more likely occur on the ortho and para position of phenol according to the calculation of Gaussian program, and a possible reaction pathway of phenol and • NO 2 was proposed based on the calculated results., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

The UV/persulfate (PS) process is a promising water treatment technology, and it can not only effectively degrade contaminants of emerging concern, but also control formation of disinfection byproducts (DBPs). In this study, we investigated the potential and mechanisms of chloropicrin (i.e. trichloronitromethane, TCNM) formation during chlorination that followed UV/PS pretreatment in the presence of low concentrations of nitrite. We found that when nitrite was present in the UV/PS system, unexpected high concentrations of TCNM were formed. The formation potential of TCNM was impacted by operational conditions and water matrix components: (1) high pH enhanced TCNM formation; (2) high UV fluence inhibited TCNM formation; and (3) organic compounds containing phenolic groups enhanced TCNM formation. We discovered that electrophilic substitutions by reactive nitrogen species were favored for phenolic groups, and thus more nitrite-N was transformed to organic nitrogen. We also found that more TCNM was generated from natural organic matter than algal organic matter during chlorination following pretreatment using UV/PS. Accordingly, more attention needs to be paid to TCNM formation, if nitrite is present and the water is pretreated using UV/PS (when applied at upstream of chlorination). For example, we found that if monochloramine was used as a disinfectant downstream of the UV/PS process, the formation of TCNM was reduced., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Microcystin-LR (MC-LR) is the most widely distributed and harmful variant toxins released by cyanobacteria, which poses potential threaten to people and aquatic animals when entering natural water. In our research, solar/chlorine process was comprehensively investigated to degrade and detoxify MC-LR. Under the chlorine concentration of 1.0 mg L -1 , MC-LR (1.0 μM) was decreased by 96.7%, 26%, and 9% by solar/chlorine process, chlorination, and solar irradiation respectively. Quenching experiments confirmed that reactive chlorine species (RCS) and hydroxyl radical (HO) were the predominant reactive species in solar/chlorine process at neutral condition, and ozone was generated because of the participation of triplet-state oxygen (O( 3 P)). The respective contributions of each reactive species were calculated with the order as: RCS, HO, ozone, and solar irradiation. The presence of HCO 3 - and natural organic matter in water inhibited the degradation efficiency of MC-LR. Moreover, the transformation products of MC-LR generated during the solar/chlorine process were identified and a possible pathway was proposed. The hepatotoxicity of MC-LR and its transformation products was compared using protein phosphatase 2A. Our experimental results revealed that the concentration and hepatotoxicity of MC-LR both significantly decreased, and most products were not hepatoxic. Overall, the solar/chlorine process is a promising alternative technology to degrade MC-LR during eutrophication., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Recently, the UV/free chlorine process has gained attention as a promising technology for destroying refractory organic contaminants in the aqueous phase. We have developed a kinetic model based on first-principles to describe the kinetics and mechanisms of the oxidation of organic contaminants in the UV/free chlorine process. Substituted benzoic acid compounds (SBACs) were chosen as the target parent contaminants. We determined the second-order rate constants between SBACs and reactive chlorine species (RCS; including [Formula: see text], [Formula: see text] and [Formula: see text]) by fitting our model to the experimental results. We then predicted the concentration profiles of SBACs under various operational conditions. We analyzed the kinetic data and predicted concentration profiles of reactive radicals ([Formula: see text] and RCS), we found that [Formula: see text] was the dominant radicals for SBACs destruction. In addition, we established quantitative structure activity relationships (QSARs) that can help predict the second-order rate constants for SBACs destruction by each type of reactive radicals using SBACs Hammett constants. Our first-principles-based kinetic model has been verified using experimental data. Our model can facilitate a design for the most cost-effective application of the UV/free chlorine process. For example, our model can determine the optimum chlorine dosage and UV light intensity that result in the lowest energy consumption.

2,4-diaminobutyric acid (DAB), a newly identified algal toxins in water, pose a great threat to human health. DAB may react with chlorine or chloramine to produce CX 3 R-type disinfection by-products (DBPs) during water treatment processes. This study mainly investigated the formation and speciation of DBPs from chlor(am)ination of DAB. The results revealed that haloacetic acids (HAAs), trihalomethanes (THMs) and haloacetonitriles (HANs) were the main kinds of CX 3 R-type DBPs generated from DAB during chlor(am)ination, of which dichloroacetic acid yielded the highest. The formation and total toxicity of four CX 3 R-type DBPs from DAB during chloramination was significantly lower than that during chlorination at each Cl 2 :N molar ratio. However, more formation of Br-THMs and I-THMs were observed during chloramination in the presence of Br−/I−. Futhermore, the effects of chlor(am)ine dosage, solution pH, reaction time, and the concentration of Br− and I− on the formation and speciation of CX 3 R-type DBPs were also evaluated during chlor(am)ination. The plausible formation pathways of CX 3 R-type DBPs from DAB were proposed and verified by theoretical calculation. The quantum chemistry calculations indicate that 1N in DAB and 8N in 2,4-diaminochlorobutyric acid (C 4 H 9 O 2 N 2 Cl) were more likely to be attacked by electrophiles, supporting the proposed pathway schemes. Image 1 • CX 3 R-type DBPs formation from chlor(am)ination of DAB were investigated. • DCAA yielded the highest from both chlorination and chloramination of DAB. • The pathway schemes of CX 3 R-type DBPs from DAB were proposed and verified. [ABSTRACT FROM AUTHOR]