Nitrogen-containing Disinfection By-products Research Articles

Using transcriptome analysis to reveal the effects of bromoacetamide at drinking water ambient concentrations on the transformation of eDNA carrying ARGs

Antibiotic resistance genes (ARGs) are frequently detected in drinking water. Transformation of extracellular antibiotic resistance genes (eARGs) is an important pathway for horizontal gene transfer, which facilitates the spread of ARGs among different species. Although most studies have pointed out that the presence of some common carbon-containing disinfection by-products, such as trihalomethanes, can increase the frequency of transformation by increasing the content of reactive oxygen species (ROS), nitrogen-containing disinfection by-products (N-DBPs), such as bromoacetamide (BAcAm), can also induce bacterial resistance to antibiotics by stimulating ROS. However, it is unclear whether such N-DBPs can similarly promote the transformation of ARGs in bacteria. In this study, the effect of BAcAm on the transformation of eDNA carrying ARGs was investigated, and found that DNA integration and repair (ruv, rec), efflux pumps (emr), and genes related to membrane proteins (bam, opm) were up-regulated in E. coli after addition of BAcAm. Furthermore, in addition to analyzing common functional genes, in terms of metabolic gene expression, which is usually overlooked, the genes related to amino acid biosynthesis (pot, arg, lys) were up-regulated while genes related to sulfur metabolism, which has a higher metabolic cost (thi, sssu) were down-regulated, which suggests that E. coli is able to effectively defend itself against the threat posed by BAcAm to its survival. In conclusion, the factors affecting the conversion of eDNA carrying ARGs into E. coli cells by BAcAm were suggested and elaborated that E. coli carrying ARGs can adapt to various unfavorable environments by regulating relevant metabolic mechanisms and survive in drinking water environment for a long period of time.

Enhanced degradation of nitrogen-containing disinfection by-products via radical attack in ZnAl particle electrode system: Mechanism and density functional theory calculations

Disinfection by-products (DBPs), in water receive attention because of their toxicity, mutagenicity and carcinogenicity. In this study, Nitrosopyrrolidine (NPYR) in water is electrocatalytically degraded by using ZnAl layered double hydroxide/activated carbon (ZnAl-LDH/AC) as a particle electrode in a three-dimensional electrode reactor (3DER). The results of SEM, TEM and XRD showed the successful synthesis of ZnAl-LDH, in which Zn2Al1-LDH had regular morphology and better crystallinity. The results of electrochemical characterization tests indirectly showed that Zn2Al1-LDH/AC had the largest OPE, the smallest mass transfer resistance, and higher mass transfer rate, and better electrocatalytic performance. The pollutant concentration had the greatest effect on the removal rate of NPYR in the one-way experiment, and the interaction effect between different influencing factors is determined by response surface optimization experiments. The optimal operating conditions showed a pollutant removal rate of 83.78%. A response surface prediction model is constructed. Hydroxyl radicals and superoxide radicals are demonstrated to be the main contributors to indirect oxidation by free radical quenching experiments and EPR. DFT calculations combined with GC-MS and LC-MS results deduced two possible degradation pathways. Toxicity prediction of NPYR and its intermediates is performed using software. Based on the above study, a mechanism for the degradation of NPYR by 3DER is proposed.

Removal of N-nitrosopyrrolidine from GAC by a three-dimensional electrochemical reactor: degradation mechanism and degradation path.

Nitrogen-containing disinfection by-products (N-DBPs) produced in the process of drinking water disinfection are widely concerning due to the high cytotoxicity and genotoxicity. It is due to the difficulty of natural degradation of N-DBPs in water and the fact that conventional treatment systems do not effectively treat N-DBPs in drinking water. In this study, N-nitrosopyrrolidine (NPYR) in water was electrocatalytically degraded by a three-dimensional electrode reactor (3DER). This system applied graphite plates as anode and cathode. The granular activated carbon (GAC) was used as third electrode. The degradation of NPYR using a continuous flow three-dimensional electrode reactor was investigated by examining the effects of flow rate, current density, electrolyte concentration, and pollutant concentration on the degradation efficiency, energy consumption, and reaction kinetics of GAC particle electrodes. The results showed that the optimal operating conditions were flow rate = 0.45mL/min, current density = 6mA/cm2, Na2SO4 concentration = 0.28mol/L, and NPYR concentration = 20mg/L. Under optimal conditions, the degradation of NPYR exceeded 58.84%. The main contributor of indirect oxidation was deduced from free radical quenching experiments. NPYR concentration was measured by GC-MS with DB-5 capillary column, operating in full scan monitoring mode for appropriate quantification of NPYR and intermediates. Based on the identification of reaction intermediates, a possible pathway for the electrochemical oxidation of NPYR on GAC particle electrodes was proposed.

Formation of nitrogen-containing disinfection by-products during the chloramination treatment of an emerging pollutant

Chloramination was commonly used as disinfectant for killing pathogens in water. However, in this process, nitrogen-containing disinfection by-products (N-DBPs) would accidently form and subsequently rise toxicity. Here, we investigated acute toxicity variation and by-products formation during chloramination treatment on UV filter 2-hydroxy-4-methoxy-5-sulfonic acid benzophenone (BP-4). Under alkaline conditions, the acute toxicity of this system had significant increase. A total of 17 transformation products were tentatively identified, and for them, plausible transformation pathways were proposed. Noticeably, numerous aniline and nitrosobenzene analogs were detected, and the dramatic increase of acute toxicity in this system might be primarily attributed to the formation of benzoquinone and aniline analogs. Besides, bromophenol, iodophenol and iodobenzoquinone analogs exhibiting high toxicity were generated in the presence of bromine and iodide ions. This study indicates that chloramination treatment may significantly increase potential health risk, further management on disinfection system is reasonable.

N-nitrosodimethylamine exposure to zebrafish embryos/larvae causes cardiac and spinal developmental toxicity

N-nitrosodimethylamine (NDMA), one of the new nitrogen-containing disinfection by-products, is potentially cytotoxic, genotoxic, and carcinogenic. Its potential toxicological effects have attracted a wide range of attention, but the mechanism is still not sufficiently understood. To better understand the toxicological mechanisms of NDMA, zebrafish embryos were exposed to NDMA from 3 h post-fertilization (hpf) to 120hpf. Mortality and malformation were significantly increased, and hatching rate, heart rate, and swimming behavior were decreased in the exposure groups. The result indicated that NDMA exposure causes cardiac and spinal developmental toxicity. mRNA levels of genes involved in the apoptotic pathway, including p53, bax, and bcl-2 were significantly affected by NDMA exposure. Moreover, the genes associated with spinal and cardiac development (myh6, myh7, nkx2.5, eph, bmp2b, bmp4, bmp9, run2a, and run2b) were significantly downregulated after treatment with NDMA. Wnt and TGF-β signaling pathways, crucial for the development of diverse tissues and organs in the embryo and the establishment of the larval spine, were also significantly disturbed by NDMA treatment. In summary, the disinfection by-product, NDMA, exhibits spinal and cardiac developmental toxicity in zebrafish embryos, providing helpful information for comprehensive analyses and a better understanding the mechanism of its toxicity.

Cocamidopropyl betaine - a potential source of nitrogen-containing disinfection by-products in pool water.

Water treatment for most public pools involves disinfection with active chlorine leading to the formation of disinfection by-products (DBPs). Among them, nitrogen-containing compounds (N-DBPs) having increased toxicity and adverse effects on human health are of the greatest concern. Being the major component of various body washers for swimmers, cocamidopropyl betaine (CAPB) represents a potential and still underestimated anthropogenic precursor of N-DBPs in pool water. The purpose of this study was to investigate CAPB transformation pathways and mechanisms under the aqueous chlorination conditions. High-performance liquid and two-dimensional gas chromatography hyphenated with high-resolution mass spectrometry were used for the search and tentative identification of the primary and final CAPB transformation products. A wide range of DBPs containing up to five chlorine atoms including these in combination with hydroxyl and additional carbonyl groups has been revealed in model chlorination experiments for the first time. The proposed mechanism of their formation involves nucleophilic substitution of the secondary amide hydrogen atom at the first stage with subsequent free radical and electrophilic addition reactions resulting in non-selective introduction of halogen atoms and hydroxyl groups in the alkyl chain. The deep transformation products include short-chain chlorinated hydrocarbons and their oxidation products as well as dimethylcarbamoyl chloride possessing high toxicity and carcinogenic properties. Targeted analysis of real swimming pool water samples confirmed the results of model experiments enabling semi-quantitative determination of CAPB (0.8µg L-1) and 18 primary DBPs, including 10 chlorine-containing compounds with the total concentration of 0.1µg L-1. Among them, monochloro (50%) and hydroxydichloro (25%) derivatives predominate. The toxicity and health of the main DBPs has been estimated using QSAR/QSTR approach. Thus, the possibility of formation of new classes of potentially toxic chlorine-containing DBPs associated with the widespread use of detergents and cosmetics was shown.

Kinetic-based model and pathways of chlorinated-halonitromethanes formation from tyrosine and tryptophan during UV/NH2Cl disinfection

Chlorinated-halonitromethanes (Cl-HNMs) are highly toxic nitrogen-containing disinfection by-products that are produced from amino acids (AAs) during UV/NH2Cl disinfection. This study aimed to establish a kinetic-based model to simulate Cl-HNMs formation from tyrosine (Tyr) and tryptophan (Trp) during UV/NH2Cl disinfection. Of note, once the degradation rates of AAs (kobs,AA) and Cl-HNMs (kd,HNM) and formation parameters (K) were obtained, the kinetic-based model could predict Cl-HNMs formation, which guided the selection of appropriate disinfection conditions. Firstly, the first-principles-based kinetic model of UV/NH2Cl system was established to describe kobs,AA in this study (sample deviation = 0.0776 for Tyr and 0.1240 for Trp), and that was also developed to obtain kd,HNM in our previous study. Then combined with kobs,AA and kd,HNM, the unknown values of K in the kinetic-based model of Cl-HNMs formation were estimated at different NH2Cl doses, pH, and alkalinity. The sample deviations of Cl-HNMs formation were 0.0257–0.3350. Compared with pH and alkalinity, increasing the NH2Cl dose significantly affected Cl-HNMs concentration and delayed the peak time of Cl-HNMs formation. Therefore, the correlations between K and the NH2Cl dose (K = f(NH2Cl)) were further explored to predict Cl-HNMs formation at different NH2Cl doses, and K = f(NH2Cl) was well described by elementary functions (R2 > 0.90). Combined with kobs,AA, kd,HNM and K = f(NH2Cl), the heatmaps for Cl-HNMs formation at different NH2Cl doses were determined and validated (R2 = 0.79 for Tyr and Trp) by the kinetic-based model of Cl-HNMs formation, which helped us choose appropriate UV and NH2Cl doses to control Cl-HNMs formation. Finally, the possible pathways of Cl-HNMs formation were proposed, including decarboxylation, (de)chlorination, hydroxylation, and nitration.

Characterization of young biofilm morphology, disinfection byproduct formation potential and toxicity of renewed water supply pipelines by phosphorus release from corroded pipes

The deterioration of drinking water quality due to corrosion of the water supply network has become inevitable and regular renewal of pipes has become a common means of doing so. Severely corroded pipes release certain nutrients (e.g., elemental phosphorus), however, little has been reported on the effect of old pipes on the young biofilm of new pipe sections and on ensuring water safety in the early stages of the water supply. The aim of our study was to model the effect of key phosphorus nutrients released from corroded old pipes on the morphological characteristics of young biofilms in new pipe sections, mediated disinfection byproducts (DBPs) production and their combined toxicity. Based on the experimental results, phosphorus showed significant differences in the morphological characteristics, spatial structure of extracellular polymers (EPS), functional abundance, disinfection byproduct formation potential (DBPsFP) and toxicity of young biofilms. Under residual chlorine (1.0 ± 0.2 mg/L) incubation, the functional abundance of young biofilm metabolism was dominant, particularly amino acid metabolism and carbohydrate metabolism. There is a dynamic balance between the trophic and shedding effects of phosphorus, where concentration changes affect young biofilm morphology and DBPFP. Relatively moderate phosphorus concentrations resulted in the highest density of PN/PS organic precursors in EPS and a clear advantage of DBPFP; relatively high phosphorus conditions had limited promotion of young biofilm, while membrane structure shedding was more pronounced, increasing young biofilm-mediated DBPs production. Nitrogen-containing disinfection byproducts (N-DBPs) in young biofilms had a clear toxicity advantage, with HANs and HNMs being key to controlling cytotoxicity and genotoxicity, respectively.

Non targeted screening of nitrogen containing disinfection by-products in formation potential tests of river water and subsequent monitoring in tap water samples.

The generation of disinfection by-products during water chlorination is a major concern in water treatment, given the potential health risks that these substances may pose. In particular, nitrogen-containing DBPs are believed to have greater toxicological significance than carbon-based DBPs. Hence, high performance liquid chromatography coupled to high-resolution mass spectrometry (HPLC-HRMS) in positive mode was employed to identify new non-volatile nitrogen containing disinfection by-products (DBPs) and to assess their presence in potable water. Nine water samples were taken in the Llobregat river, in the context of a water reuse trial, near the catchment of a drinking water treatment plant (DWTP) in 2019. River samples were disinfected with chlorine under controlled formation potential tests conditions and analysed with a non-target approach. The peak lists of raw and chlorinated samples were compared exhaustively, resulting in an extensive list of 495 DBPs that include bromine and/or chlorine atoms. 172 of these species were found frequently, in three or more chlorinated samples. The empirical formulae of these DBPs were unambiguously annotated on the basis of accurate m/z measurements, isotopic patterns and common heuristic rules. Most of the annotated species (310) contained bromide, which is consistent with the relatively high bromide content of the Llobregat basin (>0.3mg/l). Drinking water samples were taken at the outlet of the DWTP during the same sampling period. According to their analysis, a large portion of the DBPs detected after the formation potential tests do not reach real-life drinking water, which suggests that the treatment train successfully removes a significant fraction of DBP precursors. However, 131 DBPs could still be detected in the final product water. A larger sampling was carried in the Barcelona water distribution network, during six consecutive weeks, and it revealed the presence of 78 halogenated DBPs in end-consumer water, most of which were nitrogen-containing. MS/MS fragmentation and retention times were employed to tentatively suggest molecular structure for these recalcitrant DBPs.

Trace determination of fifteen free amino acids in drinking source water via solid-phase extraction coupled with liquid chromatography tandem mass spectrometry.

Amino acids (AAs) are important nitrogen-containing organics in water, and a large number of reports have proven that they were the precursors of many nitrogen-containing disinfection by-products, some of which have cytotoxicity and carcinogenicity. However, little has been done on their occurrence in drinking source water. Therefore, a trace determination method via solid-phase extraction coupled with ultra-high pressure liquid chromatography tandem mass spectrometry (UPLC-MS/MS) for 15 free AAs (FAAs) was developed, which was successfully applied for drinking source water samples. For sample preparation, strong cation-exchange stationary solid-phase extraction (SPE) cartridge showed better extraction performance to that of reverse phase stationary oasis HLB SPE cartridge. The optimal water pH was determined to be 2.8 before extraction. Strong matrix effects for most FAAs were observed in this work; thus, sample extraction with SPE was recommended to eliminate the matrix effects. The developed method showed excellent linearity (R2 > 0.991), low limits of detection (LODs, 0.01-0.27nmol/L), and good recoveries of 69.8-117.9% in drinking source water with low relative standard deviations (RSDs, 0.3-13.2%). The developed method was finally applied to eight drinking source water samples, and the top five FAAs were found to be serine, glycine, leucine, alanine, and isoleucine.

Disinfection byproducts in chlorinated or brominated swimming pools and spas: Role of brominated DBPs and association with mutagenicity

Although the health benefits of swimming are well-documented, health effects such as asthma and bladder cancer are linked to disinfection by-products (DBPs) in pool water. DBPs are formed from the reaction of disinfectants such as chlorine (Cl) or bromine (Br) with organics in the water. Our previous study (Daiber et al., Environ. Sci. Technol. 50, 6652; 2016) found correlations between the concentrations of classes of DBPs and the mutagenic potencies of waters from chlorinated or brominated swimming pools and spas. We extended this study by identifying significantly different concentrations of 21 individual DBPs in brominated or chlorinated pool and spa waters as well as identifying which DBPs and additional DBP classes were most associated with the mutagenicity of these waters. Using data from our previous study, we found that among 21 DBPs analyzed in 21 pool and spa waters, the concentration of bromoacetic acid was significantly higher in Br-waters versus Cl-waters, whereas the concentration of trichloroacetic acid was significantly higher in Cl-waters. Five Br-DBPs (tribromomethane, dibromochloroacetic acid, dibromoacetonitrile, bromoacetic acid, and tribromoacetic acid) had significantly higher concentrations in Br-spa versus Cl-spa waters. Cl-pools had significantly higher concentrations of Cl-DBPs (trichloroacetaldehyde, trichloromethane, dichloroacetic acid, and chloroacetic acid), whereas Br-pools had significantly higher concentrations of Br-DBPs (tribromomethane, dibromoacetic acid, dibromoacetonitrile, and tribromoacetic acid). The concentrations of the sum of all 4 trihalomethanes, all 11 Br-DBPs, and all 5 nitrogen-containing DBPs were each significantly higher in brominated than in chlorinated pools and spas. The 8 Br-DBPs were the only DBPs whose individual concentrations were significantly correlated with the mutagenic potencies of the pool and spa waters. These results, along with those from our earlier study, highlight the importance of Br-DBPs in the mutagenicity of these recreational waters.

Multivariate experimental design provides insights for the optimisation of rechloramination conditions and water age to control disinfectant decay and disinfection by-product formation in treated drinking water

The stability of drinking water disinfectant residuals is known to be influenced by multiple variables. To evaluate the effects of various influencing variables on disinfectant stability, a multivariate analysis of chloramine decay and associated disinfection by-products (DBPs) formation was investigated in a series of bench-scale experiments. Of nine water quality variables previously identified, monochloramine dose, pH, and bromide concentration were selected as key water quality variables based on previous investigations and modelling. Co-effects of these key variables on monochloramine decay and formation of 33 halogenated and nitrogen-containing DBPs were investigated using response surface experimental design.Rechloramination conditions, including monochloramine dose, pH and bromide concentration, were optimised via a 3-factorial multivariate analysis of monochloramine stability in post-treatment drinking water. Effects of influencing variables on disinfectant decay and DBP formation were assessed and graphically presented as response surfaces with minimal experiments using Doehlert matrix experimental design compared to other multivariate experimental designs. Concentrations of trihalomethanes (THMs), haloacetic acids (HAAs), and N-nitrosamines were found to increase with water age, whereas opposite phenomenon was observed in the net production of haloacetonitriles (HANs). Increasing pH was found to stabilise monochloramine but it could cause DBP speciation to shift. Furthermore, increasing bromide concentration elevated Br-DBP formation. In bromide-containing water, pH = 7.8–8.0 should be considered as higher pH increases Br-THMs formations and lower pH increases formations of Br-HAAs and Br-HANs. However, water age or pH has insignificant impacts on DBP formation after significant monochloramine decay or at low initial monochloramine dose.These findings indicate that effective combined control measures to maintain monochloramine stability should include the application of high monochloramine dose (>1.5 mg-Cl2.L−1) under conditions of moderate to high pH (pH = 7.8–8.0) and minimal bromide concentration. This study provides relevant insights to water utilities aiming to design effective disinfectant residual management strategies for controlling monochloramine decay and DBP formation.

Ultraviolet-Light-emitting-diode activated monochloramine for the degradation of carbamazepine: Kinetics, mechanisms, by-product formation, and toxicity

Monochloramine (NH2Cl) oxidant combined with a Ultraviolet (UV)-Light-emitting-diode (LED) light source forms a new advanced oxidation process (AOP), which can achieve high-efficiency degradation of carbamazepine (CBZ). The degradation of CBZ displayed pseudo-first-order reaction kinetics (R2 > 0.98, kCBZ = 0.0043 cm2 mJ−1 at pH 7). The degradation of CBZ was dependent on UV-LED wavelength, with maximum degradation efficiency observed at 265 nm since it was the lowest wavelength studied among UV-LEDs. Variation in pH across the range, which might be expected under normal environmental conditions (pH 6–8), and the presence of Cl− had no significant effect on the degradation efficiency of CBZ, while the presence of HCO3− and natural organic matter (NOM) inhibited degradation. Electron paramagnetic resonance (EPR) experiments detected OH in the system. Probe compounds were used to distinguish the contribution of reactive chlorine species (RCS). It was proved that OH and Cl played major roles and OH was responsible for around 50% of the observed degradation of CBZ. Eight transformative products (TPs) in the degradation process of CBZ were identified, with a generally decreasing toxicity. The concentration of disinfection by-products (DBPs) formed during CBZ degradation was all within limits of WHO and China standard for drinking water. Although the concentration of nitrogen-containing DBPs (N-DBPs) was the lowest, N-DBPs were the main contributors to toxicity, and these would require more attention in practical applications. UV-LED/NH2Cl AOP was identified as an effective way to degrade pharmaceutically active compounds.

Formation of nitrogenous disinfection by-products (N-DBPs) in drinking water: emerging concerns and current issue

Nitrogenous disinfection by-product (N-DBPs) has always been one of the most concerned disinfection by-products (DBPs) in recent years. The toxicity of regulated DBPs is generally less than that of N-DBPs, which have been widely detected in finished drinking water. Despite the fact that N-DBPs are highly toxic, there are currently no N-DBPS species officially regulated by governments around the world. This paper provides a review of the formation mechanism and precursors of nitrogen-containing disinfection by-products in drinking water treatment. Also, the spcieces and inducing factors of N-DBPs were summarized. The data were mainly collected from 2000-2002 and 2006-2007 US Survey in effluents of US WTPs. Because nitrogen source is a prerequisite for the formation of nitrogen-DBP in drinking water, the occurrence of N-DBPS may increase due to the influence of sewage and algae blooms on water sources. Chloramine disinfection are used in most of developed countries for preferred secondary disinfection to reduce the formation of chlorine-related by-products, but this increases the formation potential of N-DBPs. Furthermore, the safety control of N-DBPs and suggestions for the further exploration of for efficient drinking water are discussed. Coagulation and filtration are not very effective in removing precursors (such as amino acids) of N-DBPs and the precursors need to be removed before disinfection.

Trace Analysis of 61 Emerging Br-, Cl-, and I-DBPs: New Methods to Achieve Part-Per-Trillion Quantification in Drinking Water.

Disinfection byproducts (DBPs) are a ubiquitous source of chemical exposure in drinking water and have been associated with serious health impacts in human epidemiologic studies. While toxicology studies have pinpointed DBPs with the greatest toxic potency, analytical methods have been lacking for quantifying complete classes of most toxic DBPs at sufficiently low quantification limits (ng/L). This new method reports the parts-per-trillion quantification for 61 toxicologically significant DBPs from 7 different chemical classes, including unregulated iodinated haloacetic acids (HAAs) and trihalomethanes (THMs), haloacetaldehydes, haloketones, haloacetonitriles, halonitromethanes, and haloacetamides, in addition to regulated HAAs and THMs. The final optimized method uses salt-assisted liquid-liquid extraction in a single extraction method for a wide range of DBPs, producing the lowest method detection limits to-date for many compounds, including highly toxic iodinated, brominated, and nitrogen-containing DBPs. Extracts were divided for the analysis of the HAAs (including iodinated HAAs) by diazomethane derivatization and analysis using a GC-triple quadrupole mass spectrometer with multiple reaction monitoring, resulting in higher signal-to-noise ratios, greater selectivity, and improved detection of these compounds. The remaining DBPs were analyzed using a GC-single quadrupole mass spectrometer with selected ion monitoring, utilizing a multimode inlet allowed for lower injection temperatures to allow the analysis of thermally labile DBPs. Finally, the use of a specialty-phase GC column (Restek Rtx-200) significantly improved peak shapes, which improved separations and lowered detection limits. Method detection limits for most DBPs were between 15 and 100 ng/L, and relative standard deviations in tap water samples were mostly between 0.2 and 30%. DBP concentrations in real samples ranged from 40 to 17 760 ng/L for this study.

Effect of Ozonation on Microorganism in the Biological Activated Carbon and Disinfection By-Products in the Effluent

This study was carried out in the ozone (O3) and biological activated carbon (BAC) section of a drinking water plant to investigate the effects of O3 on microbial and effluent disinfection by-products (DBPs) in BAC during drinking water treatment. The water quality, dissolved organic matter (DOM) characteristics, microbial activity, and DBPs formation at different O3 concentrations were analyzed. Results showed that the effect of O3 on microorganisms is mainly that it increased the utilization efficiency of DOM. However, excessive O3 increased the amount of organic matter such as protein and microbial metabolites (SMPs) in the effluent. When the O3 concentration increased from 0 mg·L-1 to 2.0 mg·L-1, the survival rate of microorganisms in the BAC decreased from 95.10% to 62.60%. However, since O3 transforms organic matter into a biodegradable substance, we found that microbial activity increased by 62.52% and that the biofiltration of the BAC was enhanced. When the O3 concentration was further increased to 4.0 mg·L-1, the microbial survival rate decreased to 49.9% and the protein and SMPs produced by the microorganisms increased. This resulted in an increased formation of carbon-containing DBPs (C-DBPs) and nitrogen-containing DBPs (N-DBPs) by 41.93% and 7.18%, respectively. In summary, an appropriate dosage of O3 was beneficial for removing DOM by O3-BAC, but we found that an excessive O3 concentration caused the formation of new DBPs precursors.

Predominant N-Haloacetamide and Haloacetonitrile Formation in Drinking Water via the Aldehyde Reaction Pathway.

In drinking water disinfection, switching from free chlorine to alternative chemical disinfectants such as monochloramine may result in the formation of different classes of toxic disinfection byproducts (DBPs). Haloacetonitriles (HANs) and haloacetamides (HAMs) are two currently unregulated nitrogen-containing DBP (N-DBP) groups commonly found in water disinfected with monochloramine that have been shown to be more cyto- and genotoxic than regulated DBPs. For the first time, this study confirms the formation of HAN and HAM dominant species found in disinfected water, dichloroacetonitrile and dichloroacetamide, from the reaction between monochloramine and dichloroacetaldehyde via the aldehyde reaction pathway. Results from experiments with natural water treated with labeled 15 N-monochloramine confirmed the relevance of the aldehyde pathway. Monochloramine reacted quickly with dichloroacetaldehyde reaching equilibrium with the carbinolamine 2,2-dichloro-1-(chloroamino)ethanol ( K1 = 1.87 × 104 M-1 s-1). Then, 2,2-dichloro-1-(chloroamino)ethanol underwent two parallel reactions where, (1) it slowly dehydrated to 1,1-dichloro-2-(chloroimino)ethane ( k2 = 1.09 × 10-5 s-1) and further decomposed to dichloroacetonitrile, and (2) it was oxidized by monochloramine ( k3 = 4.87 × 10-2 M-1 s-1) to form a recently reported N-DBP, the N-haloacetamide N,2,2-trichloroacetamide. At high pH, dichloroacetonitrile hydrolyzed to dichloroacetamide ( k40 = 3.12 × 10-7 s-1, k4OH = 3.54 M-1 s-1). Additionally, trichloroacetaldehyde was also produced from the reaction of dichloracetaldehyde and monochloramine ( k5 = 2.12 × 10-2 M-1 s-1) under the presence of monochlorammonium ion, a product of monochloramine protonation. Within the N-haloacetamide family, N,2,2-trichloroacetamide (LC50 = 3.90 × 10-4 M) was found to be more cytotoxic than N-chloroacetamide but slightly less potent than N,2-dichloroacetamide.

Copper increases reductive dehalogenation of haloacetamides by zero-valent iron in drinking water: Reduction efficiency and integrated toxicity risk

The haloacetamides (HAcAms), an emerging class of nitrogen-containing disinfection byproducts (N-DBPs), are highly cytotoxic and genotoxic, and typically occur in treated drinking waters at low μg/L concentrations. Since many drinking distribution and storage systems contain unlined cast iron and copper pipes, reactions of HAcAms with zero-valent iron (ZVI) and metallic copper (Cu) may play a role in determining their fate. Moreover, ZVI and/or Cu are potentially effective HAcAm treatment technologies in drinking water supply and storage systems. This study reports that ZVI alone reduces trichloroacetamide (TCAcAm) to sequentially form dichloroacetamide (DCAcAm) and then monochloroacetamide (MCAcAm), whereas Cu alone does not impact HAcAm concentrations. The addition of Cu to ZVI significantly improved the removal of HAcAms, relative to ZVI alone. TCAcAm and their reduction products (DCAcAm and MCAcAm) were all decreased to below detection limits at a molar ratio of ZVI/Cu of 1:1 after 24 h reaction (ZVI/TCAcAm = 0.18 M/5.30 μM). TCAcAm reduction increased with the decreasing pH from 8.0 to 5.0, but values from an integrated toxic risk assessment were minimised at pH 7.0, due to limited removal MCAcAm under weak acid conditions (pH = 5.0 and 6.0). Higher temperatures (40 °C) promoted the reductive dehalogenation of HAcAms. Bromine was preferentially removed over chlorine, thus brominated HAcAms were more easily reduced than chlorinated HAcAms by ZVI/Cu. Although tribromoacetamide was more easily reduced than TCAcAm during ZVI/Cu reduction, treatment of tribromoacetamide resulted in a higher integrated toxicity risk than TCAcAm, due to the formation of monobromoacetamide (MBAcAm).

Granular Activated Carbon Treatment May Result in Higher Predicted Genotoxicity in the Presence of Bromide.

Certain unregulated disinfection byproducts (DBPs) are more of a health concern than regulated DBPs. Brominated species are typically more cytotoxic and genotoxic than their chlorinated analogs. The impact of granular activated carbon (GAC) on controlling the formation of regulated and selected unregulated DBPs following chlorine disinfection was evaluated. The predicted cyto- and genotoxicity of DBPs was calculated using published potencies based on the comet assay for Chinese hamster ovary cells (assesses the level of DNA strand breaks). Additionally, genotoxicity was measured using the SOS-Chromotest (detects DNA-damaging agents). The class sum concentrations of trihalomethanes, haloacetic acids, and unregulated DBPs, and the SOS genotoxicity followed the breakthrough of dissolved organic carbon (DOC), however the formation of brominated species did not. The bromide/DOC ratio was higher than the influent through much of the breakthrough curve (GAC does not remove bromide), which resulted in elevated brominated DBP concentrations in the effluent. Based on the potency of the haloacetonitriles and halonitromethanes, these nitrogen-containing DBPs were the driving agents of the predicted genotoxicity. GAC treatment of drinking or reclaimed waters with appreciable levels of bromide and dissolved organic nitrogen may not control the formation of unregulated DBPs with higher genotoxicity potencies.

Application of effect-directed analysis to identify mutagenic nitrogenous disinfection by-products of advanced oxidation drinking water treatment.

Advanced oxidation processes are important barriers for organic micropollutants in (drinking) water treatment. It is however known that medium pressure UV/H2O2 treatment may lead to mutagenicity in the Ames test, which is no longer present after granulated activated carbon (GAC) filtration. Many nitrogen-containing disinfection by-products (N-DBPs) result from the reaction of photolysis products of nitrate with (photolysis products of) natural organic material (NOM) during medium pressure UV treatment of water. Identification of the N-DBPs and the application of effect-directed analysis to combine chemical screening results with biological activity would provide more insight into the relation of specific N-DBPs with the observed mutagenicity and was the subject of this study. To this end, fractions of medium pressure UV-treated and untreated water extracts were prepared using preparative HPLC and tested using the Ames fluctuation test. In addition, high-resolution mass spectrometry was performed on all fractions to assess the presence of N-DBPs. Based on toxicity data and read across analysis, we could identify five N-DBPs that are potentially genotoxic and were present in relatively high concentrations in the fractions in which mutagenicity was observed. The results of this study offer opportunities to further evaluate the identity and potential health concern of N-DBPs formed during advanced oxidation UV drinking water treatment.