Nitrogenous Disinfection By-products Research Articles

Study on the Control of Dichloroacetonitrile Generation by Two-Point Influent Activated Carbon-Quartz Sand Biofilter.

Aiming at the problem of highly toxic Nitrogenous disinfection by-products (N-DBPs) produced by disinfection in the process of drinking water, two-point influent activated carbon-quartz sand biofilter, activated carbon-quartz sand biofilter, and quartz sand biofilter are selected. This study takes typical N-DBPs Dichloroacetonitrile (DCAN) as the research object and aromatic amino acid Tyrosine (Tyr), an important precursor of DCAN, as the model precursor. By measuring the changes of conventional pollutants in different biofilters, and the changes of Tyr, the output DCAN formation potential of the biofilters, this article investigates the control of DCAN generation of the two-point influent activated carbon-quartz sand biofilter. The results show that the average Tyr removal rate of the three biofilters during steady operation is 73%, 50%, and 20%, respectively, while the average effluent DCAN generation potential removal rate is 78%, 52%, and 23%, respectively. The two-point influent activated carbon-sand biofilter features the highest removal rate. The two-point water intake improves the hypoxia problem of the lower filter material of the activated carbon-quartz sand biofilter, and at the same time, the soluble microbial products produced by microbial metabolism can be reduced by an appropriate carbon sand ratio, which is better than traditional quartz sand filters and activated carbon-quartz sand biofilters in the performance of controlling the precursors of N-DBPs.

Cytotoxicity of Nitrogenous Disinfection Byproducts: A Combined Experimental and Computational Study

Cytotoxicity of Nitrogenous Disinfection Byproducts: A Combined Experimental and Computational Study

Drivers of variability in disinfection by-product formation potential in a chain of thermally stratified drinking water reservoirs

Increasing hydraulic residence time (HRT) along a chain of interconnected reservoirs enhances the formation potential of carbonaceous disinfection by-products (DBPs) and reduces the formation potential of nitrogenous DBPs, particularly N-nitrosodimethylamine (NDMA).

Effects of pipe materials on the characteristic recognition, disinfection byproduct formation, and toxicity risk of pipe wall biofilms during chlorination in water supply pipelines

There are growing concerns over the contributions of biofilms to disinfection byproduct (DBP) formation in engineered water systems (EWSs). Three kinds of water supply pipes, ductile iron (DI), cement-lined stainless steel (SS) and polyethylene (PE) pipes, were selected for the experiment conducted in this study. Based on test results, the three pipe biofilms showed relatively obvious differences in growth, morphological characteristics, organic components and bacterial diversity. Secreted extracellular polymeric substance (EPS) accounted for more than 90% of the biofilm and had greater disinfection byproduct formation potential (DBPFP) than the cell phases. DI pipe wall biofilms had the highest DBPFP, which to a certain extent means that denser and richer organic matter can be produced as the precursor of different types of DBPs. UHPLC-Q Exactive was used to identify the types of DBPs generated from the chlorination of histidine (His), alanine (Ala) and tryptophan (Trp) shared by the three pipe materials and their formation pathways. Compared to carbonaceous disinfection by-products (C-DBPs), nitrogenous disinfection by-products (N-DBPs) had a significant advantage in toxicity generation potentials in the biofilms, especially dichloroacetonitrile (DCAN) and trichloronitromethane (TCNM). DCAN and haloacetic acids (HAAs) were the key to cytotoxicity in biofilms, while TCNM was dominant in biofilm genotoxicity.

Molecular insights into formation of nitrogenous disinfection byproducts from algal organic matter in UV-LEDs/chlorine process based on FT-ICR analysis

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 UV285 and UV365 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 (DBEw) 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 UV285/chlorine-postchlorination, UV365/chlorine-postchlorination, and direct chlorination. Our study provides comprehensive information on N-DBP formation from AOM in UV-LEDs/chlorine-postchlorination from molecular levels.

Effects of cast iron pipe corrosion on nitrogenous disinfection by-products formation in drinking water distribution systems via interaction among iron particles, biofilms, and chlorine

The effects of cast iron pipe corrosion on nitrogenous disinfection by-products formation (N-DBPs) in drinking water distribution systems (DWDSs) were investigated. The results verified that in the effluent of corroded DWDSs simulated by annular reactors with corroded cast iron coupons, typical N-DBPs, including haloacetamides, halonitromethanes, and haloacetonitriles, increased significantly compared with the influent of DWDSs. In addition, more dissolved organic carbon, adenosine triphosphate, and iron particles were simultaneously detected in the bulk water of corroded DWDSs, thereby indicating that abundant iron particles acted as a “protective umbrella” for microorganisms. Under the condition of corroded DWDSs, the extracellular polymeric substances gradually exhibited distinct characteristics, including a higher content and lower flocculation efficiency, thereby resulting in a large supply of N-DBPs precursors. Corroded cast iron pipes, equivalent to a unique microbial interface, induced completely distinct microbial community structures and metabolic functions in DWDSs, thereby enhancing the formation of N-DBPs. This is the first study to successfully reveal the interactions among iron particles, biofilms, and chlorine in DWDSs, which may help to fully understand the biofilm transformation and microbial community succession in DWDSs.

Nitriles as main products from the oxidation of primary amines by ferrate(VI): Kinetics, mechanisms and toxicological implications for nitrogenous disinfection byproduct control

Ferrate (Fe(VI)), a promising water treatment oxidant, can be used for micropollutant abatement or disinfection byproduct mitigation. However, knowledge gaps remain concerning the interaction between Fe(VI) and dissolved organic matter structures, notably primary amines. This study investigated degradation kinetics and products of several aliphatic primary amines by Fe(VI). Primary amines showed appreciable reactivity toward Fe(VI) (2.7–68 M−1s−1 at pH 7–9), ranking as follows: benzylamine > phenethylamine > phenylpropylamine > methylamine ≈ propylamine. Nitriles were the main oxidation products of the primary amines, with molar yields of 61–103%. Minor products included aldehydes, carboxylic acids, nitroalkanes, nitrite, nitrate, and ammonia. The buffering conditions were important. Compared to phosphate, borate enhanced the reactivity of the amines and shifted the products from nitriles to carbonyls. An evaluation of the effect potency of some cyano-compounds by an in vitro bioassay for oxidative stress response and cytotoxicity suggested that non-halogenated nitriles are unlikely to pose a significant threat because they were only toxic at high concentrations, acted as baseline toxicants and did not cause oxidative stress, unlike halonitroalkanes or halonitriles. The formation of non-halogenated nitriles is preferable to the formation of nitroalkanes arising from the ozonation of primary amines (other than amino acid N-terminals) because, during chlorination, nitriles remain unreactive while nitroalkanes lead to potent halonitroalkanes.

Cumulative impact of swimmers on pool water quality: A full-scale study revealing seasonal and daily variabilities of disinfection by-products

Swimming pool water is continuously disinfected to control microbial safety. However, the disinfection processes also generate disinfection by-products (DBPs) that are created by the reaction between a disinfectant and organic matter. In this study, the water quality of two indoor pools with different characteristics was monitored at full scale. To assess the cumulative impact of swimmers, pools water quality was monitored for long term (2 months), after complete water renewal in pools. The daily impact of swimmers on water quality was also estimated by intensively sampling water quality during one high attendance day. Samples were analyzed for DBPs (Trihalomethanes-THMs, Haloacetic acids-HAAs, chlorites and chlorates) and their precursors (total organic carbon-TOC, UV 254 nm, water temperature, pH, free and total chlorine). Results showed that swimmers had a clear impact on the levels of organic matter indicators (TOC and UV 254 nm) and total nitrogen, whose variabilities were associated with the swimmers attendance. The highest levels of DBPs (THMs and HAAs) were detected in the pools during periods of maximum attendance and when there was a higher ratio of swimmers to pool-water volume. THM levels were also found to be influenced by parameters associated with pool operations (water temperature, water renewal, disinfection). Most notably HAAs accumulated in both pools due to their low volatility. Further studies should include nitrogenous DBPs, given their important toxicity, and should assess the impact of water quality and ventilation on the presence of volatile DBPs in air.

Formation and transformation of halonitromethanes from dimethylamine in the presence of bromide during the UV/chlorine disinfection

Halonitromethanes (HNMs) is a typical class of nitrogenous disinfection byproducts with high toxicity. The effect of Br− on the formation and transformation of HNMs from dimethylamine (DMA) during the ultraviolet (UV)/chlorine disinfection has been investigated in current study. Results reveal that only chloronitromethane, dichloronitromethane and trichloronitromethane (TCNM) could be found during the UV/chlorine disinfection. Whereas in the presence of Br−, nine species of HNMs could be observed simultaneously. When Br− concentration increased from 0 to 15.0 mg L−1, the predominant species of HNMs were gradually changed from TCNM to dibromonitromethane and tribromonitromethane, which contributed to 23.37% and 31.07% of total HNMs concentration at 15 mg L−1 Br−, respectively. The presence of Br− not only shifted the chlorinated-HNMs (Cl-HNMs) towards brominated-HNMs (Br-HNMs) but also affected the dominant species and total concentration of HNMs. When Br− concentration was 4.0 mg L−1, the formation of HNMs decreased with the increase of pH from 6.0 to 8.0 and increased with the increase of free chlorine and DMA. When free chlorine concentration rose from 0.25 to 1.1 mmol L−1, Br-HNMs were shifted to Br(Cl)-HNMs and then to Cl-HNMs. According to the findings, possible formation and transformation pathways of HNMs from DMA were proposed in the presence of Br− during the UV/chlorine disinfection. Finally, it was proved that the effect of Br− on the trend of HNMs in real water was similar to that in deionized water, but higher HNMs concentrations and delayed peak time were observed in real water. This study can provide the scientific evidence and fundamental data for the applications of UV/chlorine disinfection in the treatment of water containing Br−.

Removal performance and mechanism of typical amino acids in water by the peroxymonosulfate/Fe3O4 nanoparticles

Abstract Dissolved organic nitrogen (DON) as precursors of nitrogenous disinfection byproducts (N-DBPs) has become a serious issue for drinking water treatment. Here, Fe3O4/peroxymonosulfate (PMS) system was used to examine the amino acid removal and formation of N-DBPs in the system and the corresponding mechanisms. Results showed a remarked variation in removal efficiency of three typical amino acids, i.e., glutamate (78%), histidine (53%) and phenylalanine (27%) in Fe3O4/PMS system at optimum conditions (0.1 g/L Fe3O4, 1.5 mM PMS, 1 h). Notably, Fe3O4/PMS treatment led to dichloroacetonitrile (DCAN) formation caused by the chlorination of glutamate, phenylalanine and histidine being reduced by 53.3%, 9.7% and 41.9%, respectively. The degradation and subsequent N-DBPs formation in the Fe3O4/PMS system mainly depended on the types and properties of the amino acids. The formation of dichloroacetamide (DCAcAm) exhibited different trends, which may be due to the different R group structure of the three amino acids and the special aromaticity of the imidazole ring in the histidine side chain that facilitates its quick electrophilic substitution and ring-opening reaction. This study highlights that the Fe3O4/PMS system is a promising strategy to remove DON and efficiently eliminate N-DBPs formation in the drinking water treatment process depending on the amino acid type.

CoFe-LDO nanoparticles as a novel catalyst of peroxymonosulfate (PMS) for histidine removal.

Dissolved organic nitrogen (DON) has been aresearch subject due to its potential to form nitrogenous disinfection byproducts (N-DBPs) in drinking water treatment. In our study, CoFe layered double oxide (CoFe-LDO) was selected as an effective catalyst for the removal of histidine by activation of peroxymonosulfate (PMS). The results investigated that the removal of DON and histidine within 1h in the CoFe-LDO/PMS system were up to 61% and 72%, respectively. The influences of CoFe-LDO dosage, PMS dosage, and pH value for DON removal were alsoelucidated. The optimum pH was 8, and the optimal dosage of CoFe-LDO and PMS were 0.04g/L and 0.5mmol/L. It was found that SO4•- and •OH induced by the transformation of Co2+-Co3+ and Fe2+-Fe3+ on the catalyst surface were responsible for the degradation by ESR detection, in which SO4•- played a more important role. The degradation pathway of histidine indicated that it was partly oxidized to NH4+-N in the 60min and no evident generation of N2 during the whole process. Furthermore, degradation products of histidine have also been revealed by the analysis of HPLC-MS. In addition, the generation potentials of two typical N-DBPs were also clarified. The formation potential of dichloroacetonitrile (DCAN) decreased, while that of dichloroacetamide (DCAcAm) increased firstly before declining.

Formation of nitrogenous disinfection byproducts in MP UV-based water treatments of natural organic matters: The role of nitrate

UV-based water treatment processes have been reported to induce genotoxicity during the treatments of surface water, drinking water and artificial water with natural organic matters (NOMs), causing genotoxicity concerns for the drinking water safety. Nitrogenous disinfection byproducts (N-DBPs) were generally reported to be much more genotoxic than their non-nitrogenous analogues, and might be responsible for the genotoxicity in UV processes. Although nitrate-rich water was getting attention for the possibility of genotoxicity and N-DBPs during UV treatments, the impact mechanism of nitrate on the degradation of NOMs, the formation of N-DBPs and genotoxicity has not been explicated. Here simulation experiments of NOM degradation under medium-pressure (MP) UV and MP UV/H2O2 treatments were conducted to explore the effect of nitrate on the molecular characteristics of NOM, the nitrate-derived N-DBPs and the potential genotoxicity through non-targeted analysis and CALUX® reporter gene assays. The results showed that nitrate can accelerate the degradation of NOMs in the MP UV process but inhibit the degradation of NOMs in the MP UV/H2O2 process. During the degradation of NOMs, the molecular compositions varied by the effect of nitrate on oxygen atoms, molecule analogs, and saturation. A total of 105 and 374 nitrate-derived N-DBPs were identified in the MP UV and MP UV/H2O2 treatment, respectively. Most of these N-DBPs contain one nitrogen atom, and the representative features are nitro-, methoxy- (or hydroxyl-) and ester- groups on benzene. No genotoxicity was observed without nitrate spiking, whereas genotoxicity was induced after both MP UV and MP UV/H2O2 treatments when nitrate was spiked, which is worthy of attention for the drinking water safety management.

Formation of N-nitrosodimethylamine (NDMA) from tetracycline antibiotics during the disinfection of ammonium-containing water: The role of antibiotics dissociation and active chlorine species

N-nitrosodimethylamine (NDMA), a nitrosamine, is a typical nitrogenous disinfection byproduct. In this study, NDMA formation potential and mechanism, from tetracycline and oxytetracycline (as model precursors) in an ammonium-contaminating water, were investigated. The results indicated that both monochloramine and dichloramine played a vital role in NDMA formation. Additionally, the determination of NDMA formation potential (NDMA FP) at a wide range of pH showed that the unprotonated tetracycline tended to have a higher NDMA conversion ratio. We also found that the dissociation of hydroxyl on the meta-position of dimethylamine group promoted on NDMA formation. The detection of significant intermediate products showed that N-chloro unsymmetrical dimethylhydrazine (UDMH-Cl) and sequences of chlorine substitution products were key intermediates, indicating that NDMA formation occurred via the UDMH mechanism pathway. These results improve the knowledge on NDMA formation mechanism and the control strategies during the disinfection of ammonium-containing water.

Nanoscale zero-valent iron particles supported on MIL-96: a novel material for adsorption-degradation of trichloronitromethane.

As an emerging class of nitrogenous disinfection by-products, halonitromethanes have caused public health concerns owing to their high toxicity. More and more attention has been paid to the new materials and technologies for the removal of halonitromethanes. In this study, a novel material, nanoscale zero-valent iron (nZVI) supported on MIL-96 (nZVI@MIL-96) with favorable stability and reusability, was synthesized and applied to the adsorption-degradation of trichloronitromethane (TCNM) in the water. The results revealed that almost all the TCNM could be removed under 20 mg/L nZVI@MIL-96 dosage with a wide temperature range. The optimum mass ratio of nZVI to MIL-96 was 1:2, and the TCNM adsorption-degradation followed a pseudo-first-order model. The coexisting ions, such as SO42-, PO43-, and NO3-, with high concentration brought adverse effects on the removal of TCNM; however, the effects of Cl- and CO32- were insignificant. The concentrations of aluminum and iron ions in water were all within the standard value after adsorption with the nZVI@MIL-96. The degradation mechanism of TCNM by nZVI@MIL-96 included two steps, namely, adsorption and degradation, and methylamine was the terminal dechlorination and denitration products. In a word, the as-prepared nZVI@MIL-96 nanoparticles demonstrated the capabilities as a material of adsorption-degradation of TCNM in the water.

Activation of permonosulfate by Co-Fe3O4 composite catalyst for amino acid removal: Performance and mechanism of Co-Fe3O4 nanoparticles

Dissolved organic nitrogen (DON) derived from amino acids has been a major concern in drinking water treatment because of its potential to form nitrogenous disinfection byproducts (N-DBPs). The degradation performance of amino acids by peroxymonosulfate (PMS) activated by Co-Fe3O4 composite catalyst in heterogeneous catalytic process was elucidated in our study. The sole and combined catalytic performance of PMS and Co-Fe3O4 were evaluated for two amino acid species (i.e., histidine and phenylalanine) separately and validated under varying levels of PMS dose, Co-Fe3O4 dose, initial pH. The removal of histidine (62%) and phenylalanine (33%) was achieved with 0.1 g/L Co-Fe3O4, 1.5 mM PMS in the PMS/Co-Fe3O4 system. In contrast, only 19% and 16% histidine removal were obtained under individual application of PMS and Co-Fe3O4, respectively, confirming the preferable performance in the Co-Fe3O4/PMS system. Moreover, the reusability of the Co-Fe3O4 was elucidated after four successive runs. Radical quenching experiments revealed •OH and SO4•− were active while SO4•− was the dominant radical species. Examination of degradation intermediates and N-DBPs in Co-Fe3O4/PMS system showed that the increase of DCAN in histidine was attributed to histamine formation which produced more DCAN. Finally, the mechanism by the Co-Fe3O4/PMS system for the degradation of amino acids was proposed. The catalyst Co-Fe3O4 exhibited a unique adsorption of amino acids and the electron donor ability of Fe2+ enhanced the Co3+/Co2+ cycle which promoted the generation of free radicals according to the conversion of Fe and Co valence states.

Removal Behavior of Protein-like Dissolved Organic Matter During Different Water Treatment Processes in Full-Scale Drinking Water Treatment Plants

Protein-like dissolved organic matter (pDOM), which is ubiquitous in natural waters, is a critical precursor of nitrogenous disinfection byproducts. Recently, the control and elimination of pDOM have been a growing concern during drinking water treatment processes. In this study, a high-performance size exclusion chromatography system coupled with photo-diode array, fluorescence detector, and online organic carbon detector (HPSEC-PDA/FLD/OCD) was used to determine the removal behaviors of different-sized pDOM from two full-scale drinking water treatment plants (DWTPs). Coagulation and activated carbon adsorption were selected for bench-scale experiments to further assess the removal behavior of pDOM during conventional water treatment processes. The results showed that different-sized pDOM fractions exhibited different removal characteristics. Pre-oxidation can effectively remove some tyrosine-like and tryptophan-like components with high MW, and as the oxidization effect was enhanced, more high MW fractions decomposed into low MW ones. Conversely, some aliphatic pDOM fractions in high MW (e.g., aliphatic proteins) were not subject to pre-oxidation removal. The coagulation-sedimentation unit was efficient in removing high MW fractions, specifically tryptophan-like fractions. Additionally, some pDOM components may be released during coagulation. pDOM with low MW and high hydrophobicity were easily removed during activated carbon filtration. However, long-term operation of the activated carbon filter may breed microorganisms, resulting in the partial release of pDOM fractions. Moreover, UV disinfection processes promoted the degradation of low MW pDOM components. Due to the complex water quality and uncontrollable microbial activities, the aforementioned water treatment units did not exhibit a synergistic effect on pDOM removal. In comparison with humic-like substances, pDOM was susceptible to water quality changes, and its removal was limited in the surveyed DWTPs. Therefore, DWTPs must strengthen pDOM monitoring in influent and effluent and adjust the operating parameters of different treatment units in a timely manner. Moreover, the combination of advanced water treatment processes, such as ozone-biological activated carbon process and nanofiltration, should also be considered to strictly control pDOM component removal.

Contribution of wastewater- versus non-wastewater-derived sources to haloacetonitriles formation potential in a wastewater-impacted river

Population growth and urbanization have led to the increasing presence of treated wastewater effluents in downstream drinking water sources. Drinking water sources influenced by organic matter from upstream wastewater treatment plant (WWTP) effluents are thought prone to the formation of haloacetonitriles (HANs), a group of nitrogenous disinfection by-products (DBPs) that can exhibit higher toxicity than currently regulated carbonaceous DBPs. We develop a framework for studying the HAN formation potential (HAN-FP) considering the WWTP and non-WWTP related sources of HAN precursors, and apply this framework to a representative WWTP-impacted river, the Illinois River, USA. A spatiotemporally-resolved river hydrodynamic and water quality model is developed using HEC-RAS to quantify the contribution of WWTP versus non-WWTP sources of HAN-FP precursors. Results show that non-WWTP sources of HAN-FP are considerable, accounting for up to 78% of HAN-FP concentration. Moreover, the contribution of the two sources varies due to streamflow discharge variability. During lower flows, the contribution of WWTPs drives the high concentration of HAN-FP and during higher flows, the contribution of non-WWTP sources becomes dominant. As a result, a high risk of HAN-FP may exist persistently (HAN-FP concentration is always larger than 9.7 μg/L in this study), not only during low flows but also during high flows due to both wastewater- and non-wastewater-derived HAN-FP sources.

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.

UV254 irradiation of N-chloro-α-amino acids: Kinetics, mechanisms, and N-DBP formation potentials

This study explores the degradation kinetics and mechanisms of N-chloro-α-amino acids and the changes in the formation potential of nitrogenous disinfection byproducts (N-DBPs) upon UV254 irradiation. UV254 irradiation significantly accelerated the degradation of all the tested N-chloro-α-amino acids compared to those in the dark. Both direct photolysis-induced cleavage of the N-Cl bonds and radical oxidation (e.g., Cl• and Cl2•−) involved reactions that contributed to their enhanced degradation. The fluence-based photolysis rate constants of the N-chloro-α-amino acids varied in the range of (1.06—5.47) × 10−3 cm2 mJ−1 at pH 6.0 and (0.74—2.79) × 10−3 cm2 mJ−1 at pH 8.0. The apparent quantum yields (Φapp) of the majority of the N-chloro-α-amino acids were in the range of 0.41−0.95 at pH 6.0 and 0.22−0.79 at pH 8.0, except N-chloroaspartic acid, N-chlorohistidine, and N-chloroalanine. UV254 irradiation significantly enhanced the formation of trichloronitromethane (TCNM) from the tested N-chloro-α-amino acids after post-chlorination, but exhibited various effects on the formation of dichloroacetonitrile (DCAN). A longer UV254 irradiation time generated more TCNM, and a lower pH produced more DCAN from the N-chloro-α-amino acids. The degradation pathways of N-chlorotyrosine, as a representative N-chloro-α-amino acid, are proposed, and the β-scission and 1,2-H shift pathways led to the formation of different precursors of TCNM and DCAN. The results of this study improve our understanding of the fate of N-chloro-α-amino acids under UV254 irradiation and post-chlorination.

A New Group of Heterocyclic Nitrogenous Disinfection Byproducts (DBPs) in Drinking Water: Role of Extraction pH in Unknown DBP Exploration.

pH adjustment prior to extraction is an important step in water sample pretreatment processes for exploration of new/unknown disinfection byproducts (DBPs) in drinking water. To achieve a better extraction efficiency, the pH of a water sample is usually adjusted to a low level (e.g., < 0.5) to ensure that target DBPs are in their neutral forms. However, such a practice may elude some amphoteric DBPs (especially those nitrogenous DBPs with multiple functional groups), which can accept protons at a low pH and lose protons at a high pH. In this study, with careful extraction pH selection and optimization, we first report the detection and identification of a new group of heterocyclic nitrogenous DBPs, halogenated pyridinols, in simulated drinking water using ultra performance liquid chromatography/electrospray ionization-triple quadrupole mass spectrometry and time-of-flight mass spectrometry, including 5-chloro-3-pyridinol, 2-bromo-3-pyridinol, 2,6-dichloro-4-pyridinol, 2,6-dibromo-3-pyridinol, 3-bromo-2-chloro-5-pyridinol, 5-bromo-2-chloro-3-pyridinol, 3,5,6-trichloro-2-pyridinol, and 2,4,6-tribromo-3-pyridinol. On the basis of the speciation of dissociated chemical species and recovery tests at different extraction pH values, it was found that, only at a pH of 3.0, all the eight new DBPs could achieve recoveries of >50%. With subsequent instrumental parameter optimization, the method detection and quantitation limits of the eight new DBPs were determined to be 0.04-1.58 and 0.15-4.11 ng/L, respectively. The optimized method enabled an accurate detection of the eight new DBPs in two real drinking water samples. Further aided with in vivo developmental and acute toxicity assays using zebrafish embryos, the developmental and acute toxicity of the new DBPs were found to be slightly lower than those of halogenated benzoquinones but dozens of times higher than those of commonly known DBPs such as tribromomethane and iodoacetic acid.