Mechanistic Insight for Disinfection Byproduct Formation Potential of Peracetic Acid and Performic Acid in Halide-Containing Water.

Peracetic acid (PAA) and performic acid (PFA) are two major peroxyacid (POA) oxidants of growing usage. This study reports the first systematic evaluation of PAA, PFA, and chlorine for their disinfection byproduct (DBP) formation potential in wastewater with or without high halide (i.e., bromide or iodide) concentrations. Compared with chlorine, DBP formation by PAA and PFA was minimal in regular wastewater. However, during 24 h disinfection of saline wastewater, PAA surprisingly produced more brominated and iodinated DBPs than chlorine, while PFA effectively kept all tested DBPs at bay. To understand these phenomena, a kinetic model was developed based on the literature and an additional kinetic investigation of POA decay and DBP (e.g., bromate, iodate, and iodophenol) generation in the POA/halide systems. The results show that PFA not only oxidizes halides 4-5 times faster than PAA to the corresponding HOBr or HOI but also efficiently oxidizes HOI/IO- to IO3-, thereby mitigating iodinated DBP formation. Additionally, PFA's rapid self-decay and slow release of H2O2 limit the HOBr level over the long-term oxidation in bromide-containing water. For saline water, this paper reveals the DBP formation potential of PAA and identifies PFA as an alternative to minimize DBPs. The new kinetic model is useful to optimize oxidant selection and elucidate involved DBP chemistry.

Characteristics of extracellular organic matters and the formation potential of disinfection by-products during the growth phases of M. aeruginosa and Synedra sp.

Extracellular organic matter (EOM) is an important precursor of disinfection by-products (DBPs). Nowadays, little is known about changes in molecular weight (MW) and hydrophilic (HPI)/hydrophobic (HPO) fractions of EOM during the entire algal growth phase. In this study, a combined approach of fractionation procedure and parallel factor (PARAFAC) analysis was applied to characterize the EOM during the entire growth phase of two algal species (M. aeruginosa and Synedra sp.), and investigated the relationships between fluorescent component and the DBP formation potential (FP) in MW and HPI/HPO fractions. Thereinto, three components (including one protein-like component (C1), one humic-like component (C2), and one fulvic acid-like component (C3)) were identified by the PARAFAC model. For two algae, the HPI and high MW (> 100 kDa) fractions were both the main components of algal EOM in the three growth phases in terms of the dissolved organic carbon. The high MW fraction had more C1 compared with other MW fractions, especially for M. aeruginosa. Besides, the formation risk of EOM-derived DBPs from M. aeruginosa was lower than that from Synedra sp. The result of this study showed the FP of DBPs varied with fluorescent components of algal EOM fractions and also indicated that the humic-like substances were tended to form trichloromethane and the tryptophan-like substances were associated with dichloroacetic acid by canonical correspondence analysis for both two algae.

Comparison of fleroxacin oxidation by chlorine and chlorine dioxide: Kinetics, mechanism and halogenated DBPs formation.

Fleroxacin (FLE) is a widely used fluoroquinolones to cure urinary tract infections and respiratory disease, which has been frequently detected in the aquatic environment. The reactivity kinetics of FLE by chlorine and chlorine dioxide (ClO2) and transformation mechanism were investigated in this study. The results showed that FLE was degraded efficiently by chlorine and ClO2, and both reactions followed second-order kinetics overall. The increase of disinfectant dosage and temperature would enhance the degradation of FLE. The highest removal of FLE by chlorine was achieved at a neutral condition (pH 7.4), whereas ClO2 reaction rates increased dramatically with the increasing pH in this study condition. The number of intermediates identified in FLE chlorination and ClO2 oxidation was seven and ten, respectively. The piperazine ring cleavage was the principal and initial reaction in both above reactions. Then, the removal of the piperazine group was predominantly in FLE removal by chlorine, while the decarboxylation mainly occurred in FLE removal by ClO2. The intermediates increased first and then decreased with time, while three kinds of halogenated DBPs increased with time, indicating the above-identified intermediates were further transformed to the halogenated DBPs. Additionally, compared to chlorine reaction, the reaction of ClO2 with FLE reduced the formation of halogenated DBPs, but it also induced the formation of chlorite. The analysis of toxicity showed that compared with chlorination, the oxidation of ClO2 was more suitable for FLE removal.

Polymer brush-grafted cotton fiber for the efficient removal of aromatic halogenated disinfection by-products in drinking water.

Apart from the activated carbon, other functional adsorbents are usually not frequently reported for the removal of disinfection by-products (DBPs) in drinking water. In this study, a novel polymer brush-grafted cotton fiber was prepared and for the first time used as adsorbents for the efficient removal of aromatic halogenated DBPs in drinking water in the column adsorption mode. Poly (glycidyl methacrylate) (PGMA) was grafted onto the surface of cotton fibers via UV irradiation, and then diethylenetriamine was immobilized on the PGMA polymer brush through amination reaction to obtain the aminated cotton fibers (ACFs). The adsorption performance of the prepared ACF was investigated with eight aromatic halogenated DBPs via dynamic adsorption experiments. The results revealed that ACF showed significantly longer breakthrough point (38,500-225,500 BV) for aromatic halogenated DBPs compared with the granular activated carbon (150-500 BV). Thomas model was used to fit the breakthrough curves, and the theoretical value of the maximum adsorption capacity ranged from 14.76 to 89.47 mg/g. The enhanced adsorption performance of the ACF for aromatic halogenated DBPs was mainly due to the formation of hydrogen bonds. Additionally, the partially protonated amine groups also improved the adsorption performance. Furthermore, the ACF also showed remarkable stability and reusability.

Occurrence and risk assessment of volatile halogenated disinfection by-products in an urban river supplied by reclaimed wastewater.

The reuse of the sewage is an effective way to solve the shortage of water resources, but disinfection by-products (DBPs) caused by chlorination may bring potential ecological and health risks to the supplied water. In this study, the occurrence and potential ecological risk of DBPs in SH River in Beijing were evaluated. Four kinds of DBPs were detected in 84 samples by GC-MS, including THM, CH, CTC and TCAN, whose detection rates were 100%, 100%, 100% and 2.38%, respectively. Combining with the relevant standard limitation and corresponding threshold values in China, and the reported concentration in domestic and foreign literatures, the results showed that the number of samples which [THM], [CTC] and [CH] exceeded the threshold values in relevant standard for 23.81%, 100.00% and 89.29%, respectively. CTC showed the highest excess times than the threshold value with [CTC]max was 356.46 µg/L. In addition, the temporal and spatial characteristics of identified DBPs were studied. [THM], [CTC] and [CH] all exhibited the highest concentration in Aug., which was as the same as the variation trend of air and water temperature. With the increase of sampling distance, [THM] and [CTC] fluctuated greatly, and the background values in SH River were higher due to the supplement of the reclaimed water. [CH] and [TCAN] gradually decreased, which may be due to that they were more prone to volatilize in the channel and be degraded by aquatic microorganisms. In addition, the occurrence situation in S2 and S7, were in the order of CTC > CH > THM. Hence, the rank of the occurrence situation of identified DBPs was CTC > CH > THM > TCAN. Multivariate analysis showed that THM was significantly positively correlated with CTC and their sources were similar. Moreover, they were all affected by solution pH and DO. Potential ecological risk assessment indicated that the rank of identified DBPs ecological risk was CTC > THM > CH > TCAN. Among them, the risk level of CTC and THM were high in both daily and extreme situations. Therefore, the potential ecological risk caused by DBPs should be fully considered in the process of reclaimed water supplying landscape water, such as urban river. If a higher level of the ecological risk management is needed, THM, CTC and CH, especially CTC, should be considered firstly.

The identification of halogenated disinfection by-products in tap water using liquid chromatography-high resolution mass spectrometry.

In this paper, a comprehensive method for the identification of the unknown halogenated DBPs (X-DBPs, X = Cl, Br, and I) in the tap water of Wuhan, China via liquid chromatography-high resolution mass spectrometry (LC-HRMS) was developed. 123 X-DBPs were identified through the stepwise procedure, 94 of them were newly identified, and 3 of them were confirmed by standards. Most X-DBPs were aliphatic compounds and highly unsaturated and phenolic compounds, some X-DBPs contained multiple halogen atoms and rich in carboxyl groups, such as C2H2O2BrCl, C2H2O2Br2, and C2H2O2ClI. It was worth noting that the concentration of some X-DBPs had the same trend with time. Most Cl-DBPs remained stable and I-DBPs were detected occasionally by monitoring the change of concentration of these X-DPBs with the time during three consecutive months. The results demonstrate that the proposed method could provide valuable molecular formula and structure information on unknown multiple halogenated DBPs, or be used for the identification of other multiple halogenated organic compounds in different media.

Bench-scale column evaluation of factors associated with changes in N-nitrosodimethylamine (NDMA) precursor concentrations during drinking water biofiltration.

Biofiltration has been observed to increase or decrease the concentrations of N-nitrosodimethylamine (NDMA) precursors in the effluents of full-scale drinking water facilities, but these changes have been inconsistent over time. Bench-scale tests comparing biofiltration columns side-by-side exposed to different conditions were employed to characterize factors associated with changes in NDMA precursor concentrations, as measured by application of chloramines under uniform formation conditions (UFC). Side-by-side comparisons of biofiltration media from different facilities fed with water from each of these facilities demonstrated that differences in source water quality were far more important than any original differences in the microbial communities on the biofiltration media for determining whether NDMA precursor concentrations increased, decreased or remained constant across biofilters. Additional tests involving spiking of specific constituents hypothesized to promote increases in NDMA precursor concentrations demonstrated that inorganic nitrogen species associated with nitrification, including ammonia, hydroxylamine and chloramines, and biotransformation of known precursors (i.e., municipal wastewater and the cationic polymer, polyDADMAC) to more potent forms were not important. Biotransformation of uncharacterized components of source waters determined whether NDMA precursor concentrations increased or decreased across biofilters. These uncharacterized source water component concentrations varied temporally and across locations. Where biotransformation of source water precursors increased NDMA precursor concentrations, ∼30-60% of the levels observed in column effluents fed with biofiltration influent water remained associated with the media and could be rinsed therefrom in either the dissolved or particulate form. Ozone pre-treatment significantly reduced NDMA precursor concentrations at one facility, suggesting that pre-oxidation could be an effective technique to mitigate the increase in NDMA precursor concentrations during biofiltration. Biofiltration decreased the concentrations of halogenated disinfection byproduct precursors.

A comparative evaluation of the immunotoxicity and immunomodulatory effects on macrophages exposed to aromatic trihalogenated DBPs.

Objective: 2,4,6-trichlorophenol (TCP), 2,4,6-tribromophenol (TBP), and 2,4,6-triiodophenol (TIP) are three aromatic halogenated disinfection byproducts (DBPs) identified in chlorinated saline effluents. This study aimed to evaluate and compare their immunotoxicity and immunomodulatory effects on macrophages. Materials and methods: CCK-8 assay was used to evaluate cytotoxicity of TCP, TBP, and TIP in mouse macrophage RAW264.7 cells. A light microscope and digital camera were used to record the morphological changes of RAW264.7 cells. qRT-PCR was used to measure the mRNA levels of polarization markers and secreted cytokines. Cytokine production was also detected by ELISA. Flow cytometry was performed to analyze the expression of M1 and M2 markers on macrophages. Results: TCP, TBP, and TIP had different cytotoxic effects on macrophages. The rank order of cytotoxicity was TIP > TBP > TCP. Furthermore, the three halogenated DBPs displayed different preferences for macrophage polarization. Intriguingly, 200 µM TIP remarkably induced the M2-dominant polarization of macrophages, while 200 µM TCP induced an M1-dominant polarization of macrophages. TBP has a moderate ability in inducing M1 and M2 polarization compared with TCP and TIP. Conclusions: TIP displayed higher cytotoxicity against macrophages than TBP and TCP, its brominated and chlorinated analogs. Since M1 and M2 macrophages facilitate the inflammatory and anti-inflammatory responses, respectively, the discrepancy of TCP, TBP, and TIP in inducing macrophage polarization may lead to distinct immunomodulatory and toxicological outcomes, thus giving rise to different types of diseases. This finding may provide novel insights into evaluating the toxicity of environmental pollutants on the immune system.

New phenolic halogenated disinfection byproducts in simulated chlorinated drinking water: Identification, decomposition, and control by ozone-activated carbon treatment.

Recently, 13 new phenolic halogenated disinfection byproducts (DBPs) were discovered and confirmed in chlorinated drinking water using ultra performance liquid chromatography/electrospray ionization-triple quadrupole mass spectrometry (UPLC/ESI-tqMS), which have been attracting a growing concern due to their higher chronic cytotoxicity, developmental toxicity, and growth inhibition compared with commonly known aliphatic DBPs. In this study, another 12 new phenolic halogenated DBPs were detected and identified in simulated chlorinated drinking water samples, including two monohalo-4-hydroxybenzaldehydes, two monohalo-4-hydroxybenzoic acids, three monohalo-salicylic acids, and five mono/di/trihalo-phenols. Decomposition mechanisms of these new phenolic halogenated DBPs during chlorination were speculated and partially verified by identifying intermediate products. These new DBPs could undergo hydrolysis, halogenation, substitution, addition, decarboxylation, and rearrangement reactions to form a series of decomposition products, including dihaloacetic acids, 2-halomaleic acids, and a group of new heterocyclic DBPs (trihalo-hydroxy-cyclopentene-diones). A bench-scale ozone-granular activated carbon (GAC) treatment unit was designed and set up in the lab. It was found that ozonation and GAC filtration were effective in reducing dissolved organic carbon levels and aromaticity (DBP precursors) of simulated raw water samples, and thus were effective in decreasing the concentrations of these new phenolic DBPs by 82.5% and 88.6%, respectively. Furthermore, four different treatment scenarios (i.e., ozonation, GAC filtration, ozonation followed by GAC filtration, and GAC filtration followed by ozonation) were evaluated and compared. Results showed that ozonation followed by GAC filtration was most effective in precursor removal and could decrease the level of these new phenolic DBPs by up to 97.3%.

N-Nitrosamines and halogenated disinfection byproducts in U.S. Full Advanced Treatment trains for potable reuse.

Water utilities are increasingly considering indirect and direct potable reuse of municipal wastewater effluents. Disinfection byproducts (DBPs), particularly N-nitrosamines, are key contaminants of potential health concern for potable reuse. This study quantified the concentrations of N-nitrosamines and a suite of regulated and unregulated halogenated DBPs across five U.S. potable reuse Full Advanced Treatment trains incorporating microfiltration, reverse osmosis, and UV-based advanced oxidation. Low µg/L concentrations of trihalomethanes, haloacetic acids, dichloroacetonitrile, and dichloroacetamide were detected in the secondary or tertiary wastewater effluents serving as influents to potable reuse treatment trains, while the concentrations of N-nitrosamines were more variable (e.g., <2-320 ng/L for N-nitrosodimethylamine). Ozonation promoted the formation of N-nitrosamines, haloacetaldehydes, and haloacetamides, but biological activated carbon effectively reduced concentrations of these DBPs. Application of chloramines upstream of microfiltration for biofouling control increased DBP concentrations to their highest levels observed along the treatment trains. Reverse osmosis rejected DBPs to varying degrees, ranging from low for some (e.g., N-nitrosamines, trihalomethanes, and haloacetonitriles) to high for other DBPs. UV-based advanced oxidation eliminated N-nitrosamines, but only partially removed halogenated DBPs. Chloramination of the treatment train product waters under simulated distribution system conditions formed additional DBPs, with concentrations often equaling or exceeding those in the treatment train influents. Overall, the concentration profiles of DBPs were fairly consistent within individual treatment trains for sampling campaigns separated by months and across different treatment trains for the same sampling time window. Weighting DBP concentrations by their toxic potencies highlighted the potential significance of haloacetonitriles, which were not effectively removed by reverse osmosis and advanced oxidation, to the DBP-associated toxicity in potable reuse waters.

Halogenated methanesulfonic acids: A new class of organic micropollutants in the water cycle.

Mobile and persistent organic micropollutants may impact raw and drinking waters and are thus of concern for human health. To identify such possible substances of concern nineteen water samples from five European countries (France, Switzerland, The Netherlands, Spain and Germany) and different compartments of the water cycle (urban effluent, surface water, ground water and drinking water) were enriched with mixed-mode solid phase extraction. Hydrophilic interaction liquid chromatography - high resolution mass spectrometry non-target screening of these samples led to the detection and structural elucidation of seven novel organic micropollutants. One structure could already be confirmed by a reference standard (trifluoromethanesulfonic acid) and six were tentatively identified based on experimental evidence (chloromethanesulfonic acid, dichloromethanesulfonic acid, trichloromethanesulfonic acid, bromomethanesulfonic acid, dibromomethanesulfonic acid and bromochloromethanesulfonic acid). Approximated concentrations for these substances show that trifluoromethanesulfonic acid, a chemical registered under the European Union regulation REACH with a production volume of more than 100 t/a, is able to spread along the water cycle and may be present in concentrations up to the µg/L range. Chlorinated and brominated methanesulfonic acids were predominantly detected together which indicates a common source and first experimental evidence points towards water disinfection as a potential origin. Halogenated methanesulfonic acids were detected in drinking waters and thus may be new substances of concern.

Formation of chlorinated breakdown products during degradation of sunscreen agent, 2-ethylhexyl-4-methoxycinnamate in the presence of sodium hypochlorite.

In this study, a new degradation path of sunscreen active ingredient, 2-ethylhexyl-4-methoxycinnamate (EHMC) and 4-methoxycinnamic acid (MCA) in the presence of sodium hypochlorite (NaOCl), was discussed. The reaction products were detected using gas chromatography-mass spectrometry (GC-MS). Since HOCl treatment leads to more polar products than EHMC, application of polar extracting agents, dichloromethane and ethyl acetate/n-hexane mixture, gave better results in terms of chlorinated breakdown products identification than n-hexane. Reaction of EHMC with HOCl lead to the formation of C=C bridge cleavage products such as 2-ethylhexyl chloroacetate, 1-chloro-4-methoxybenzene, 1,3-dichloro-2-methoxybenzene, and 3-chloro-4-methoxybenzaldehyde. High reactivity of C=C bond attached to benzene ring is also characteristic for MCA, since it can be converted in the presence of HOCl to 2,4-dichlorophenole, 2,6-dichloro-1,4-benzoquinone, 1,3-dichloro-2-methoxybenzene, 1,2,4-trichloro-3-methoxybenzene, 2,4,6-trichlorophenole, and 3,5-dichloro-2-hydroxyacetophenone. Surprisingly, in case of EHMC/HOCl/UV, much less breakdown products were formed compared to non-UV radiation treatment. In order to describe the nature of EHMC and MCA degradation, local reactivity analysis based on the density functional theory (DFT) was performed. Fukui function values showed that electrophilic attack of HOCl to the C=C bridge in EHMC and MCA is highly favorable (even more preferable than phenyl ring chlorination). This suggests that HOCl electrophilic addition is probably the initial step of EHMC degradation.

Speciation of common volatile halogenated disinfection by-products in tap water under different oxidising agents.

A simple and efficient method has been developed for the extraction and determination of sixteen common volatile halogenated disinfection by-products (DBPs) using the static headspace (HS) technique coupled with gas chromatography-mass spectrometry (GC-MS). The DBPs determined included trihalomethanes (THMs), halonitromethanes (HNMs) and haloacetonitriles (HANs). The extraction parameters (HS conditions, ionic strength and organic modifier) were studied in order to obtain the highest sensitivity. Under optimum conditions (water containing 250 µL of methyl tert-butyl ether and 6g of anhydrous sodium sulphate was heated 20 min at 80°C), the HS-GC-MS method provides limits of detection between 10 and 200 ng/L and a relative standard deviation of ∼5.6%. Samples collected from genuine tap water treated with different oxidising agents (ClO2/Cl2, Cl2/NH2Cl and O3/Cl2) in several disinfection treatment plants were successfully analysed in order to establish their effect on the occurrence of DBPs. In parallel, the influence of the main parameters of the water (pH, conductivity, nitrite, nitrate, free residual chlorine, permanganate oxidability and bromide) was also studied. The results suggest that the permanganate oxidability (related to organic matter) and the bromide concentration as well as disinfection conditions are directly related to the occurrence of THMs, HNMs and HANs, both in their concentrations and speciation. The method developed was compared to the reference EPA Method 551.1 for the analysis of tap water.