Nitrogenous Disinfection By-products Research Articles

A group of emerging heterocyclic nitrogenous disinfection byproducts: Formation and cytotoxicity of halopyridinols in drinking water

Recently, a new group of halopyridinol disinfection byproducts (DBPs) was reported in drinking water. The in vivo developmental and acute toxicity assays have shown that they were more toxic than a few commonly known aliphatic DBPs such as bromoform and iodoacetic acid. However, many pyridinol DBPs with the same main structures but different halogen substitutions were still unknown due to complicated water quality conditions and various disinfection methods applied in drinking water treatment plants. Studies on their transformation mechanisms in drinking water disinfection were quite limited. In this study, comprehensive detection and identification of halopyridinols were conducted, and five new halopyridinols were first reported, including 2-chloro-3-pyridinol, 2,6-dichloro-3-pyridinol, 2-bromo-5-chloro-3-pyridinol, 2,4,6-trichloro-3-pyridinol and 2,5,6-trichloro-3-pyridinol. Formation conditions and mechanisms of the halopyridinols were explored, and results showed that chlorination promoted their formation compared with chloramination. Halopyridinols were intermediate DBPs that could undergo further transformation/degradation with increasing contact time, disinfectant dose, bromide concentration, and pH. The in vitro cytotoxicity of the halopyridinols was evaluated using human hepatocellular carcinoma cells. Results showed that the cytotoxicity of 3,5,6-trichloro-2-pyridinol was the highest (EC50 = 474.3 μM), which was 13.0 and 1.6 times higher than that of 2-bromo-3-pyridinol (EC50 = 6214.5 μM) and tribromomethane (EC50 = 753.6 μM), respectively.

The ideal model for determination the formation potential of priority DBPs during chlorination of free amino acids

Amino acids (AAs) account for about 15-35% of dissolved organic nitrogen (DON), and are known as the important precursors of nitrogenous disinfection by-products (N-DBPs). Determining the formation potential (FP) of AAs to DBPs is used to reveal the key precursors of DBPs for further control, while the ideal method for N-DBPs FP of AAs during chlorination is not revealed. In this study, the ideal FP test models for five classes of priority DBPs during chlorination of four representative AAs (accounted for about 35% of total AAs) were analyzed. For haloaldehydes (HALs), haloketones (HKs), haloacetonitriles (HANs), haloacetamides (HAMs), and halonitromethanes (HNMs), their FPs during chlorination of four AAs were 0.1-13.0, 0.01-1.1, 0.1-104, not detectable (nd)-173, and nd-0.4 μg/mg, respectively. The FPs of priority DBPs had significant deviations between different FP test models and different tested AAs. For HALs, the model, whose chlorine dosage was determined by 15× molar concentration of AAs [Cl (mM) = 15×M](named: model II), was the ideal model. For HKs, model II was also the ideal FP test model for AAs with ≤ 3 carbons, while for AAs with 4 carbons, the model, whose chlorine dosage was determined by keeping the residual chlorine at 1±0.2 mg/L after 24 h of reaction (named: model 4), was the ideal model. For HANs and HNMs, model 4 was the ideal FP test model for most of the studied AAs. The performance of HAMs during chlorination of amino acids is totally different from other P-DBPs, and model 3 is recommended to be the ideal model, in which chlorine dosage was determined by 3× mass concentration of AAs [Cl (mg/L) = X×DOC]. This study is a reference that helps researchers select an ideal model for N-DBPs FP study of AAs.

Disinfection byproducts and their cytotoxicity contribution from dissolved black carbon in source water during chlor(am)ination

Dissolved black carbon (DBC), the soluble component of black carbon, which mainly comes from the incomplete combustion of fossil fuels or biomass, is widely spread in source water and significantly contributes to the formation of dissolved organic matter (DOM). However, the origin of DBC in different types of source water in China has not been well studied, as well as its subsequent transformation and toxicity contribution during disinfection of source water DOM by chlor(am)ine. In this study, DBC from 17 different source water in East China at different seasons was collected. The δ13C compositions indicated that straw burning was the main origin of DBC in source water. After simulated chlor(am)ination of DBC, 5 categories of aliphatic disinfection byproducts (DBPs) including trihalomethanes, haloacetic acids, haloacetonitriles, haloketones, halonitromethanes and 6 categories of aromatic DBPs including halophenols, halonitrophenols, halohydroxybenzaldehyde, halohydroxybenzoic acid, halobenzoquinones and haloaniline were detected. Compared with chlorination of DBC, higher levels of nitrogenous DBPs and aromatic DBPs were generated during chloramination. Detected DBPs accounted for 42 % of total organic halogen. What's more, Chinese hamster ovary cells cytotoxicity tests showed that the cytotoxicity of DBPs formed by chlor(am)ination of DBC was 4 times higher than that by chlor(am)ination of DOM. Haloacetonitriles contributed to the highest cytotoxicity in the chloramination of DBC, and haloacetic acids contributed to the highest cytotoxicity in chlorination. 67 % of the total cytotoxicity attributed to the undetected DBPs. As a result, DBPs generated from DBC contributed to 11.7 % of the total cytotoxicity in the chlor(am)ination of the source water DOM although DBC only took up 2 % of DOC in the source water. Results obtained from this study systematically revealed the DBPs formation from DBC and their potential cytotoxicity contribution in the chlor(am)ination of source water DOM, which should not be ignored in drinking water treatment.

Impact of climate change on formation of nitrogenous disinfection by-products. Part II: water blooming and enrichment by humic substances.

Climate change affects the concentration and characteristics of dissolved organic matter (DOM) in surface water. The changes in composition of DOM have many implications to drinking water quality, especially in the case of formation of disinfection by-products (DBPs). The aim of this study was to investigate the formation of nitrogenous DBPs (N-DBPs) during chlorination and chloramination, caused by the alternation of surface water's DOM driven by climate change. For this reason, two different cases were examined: (a) rise of algal organic matter (AOM) due to water blooming and (b) water enrichment by humic substances. The target compounds were haloacetonitriles (HANs), haloacetamides (HAcAms), and halonitromethane (TCNM). The results showed that Anabaena appears to be a major precursor for HAcAms and TCNM, while humic acids are precursors for HANs. The results of the mixtures presented the same pattern. During the water blooming case, HAcAms and TCNM formation are in favor, while during water enrichment by humic substances case, HANs is the N-DBP group with higher formation yield. Cloraminated samples presented higher values of cytotoxicity and genotoxicity compared to the chlorinated.

Far-UVC Photolysis of Peroxydisulfate for Micropollutant Degradation in Water.

Increasing radical yields to reduce UV fluence requirement for achieving targeted removal of micropollutants in water would make UV-based advanced oxidation processes (AOPs) less energy demanding in the context of United Nations' Sustainable Development Goals and carbon neutrality. We herein demonstrate that, by switching the UV radiation source from conventional low-pressure UV at 254 nm (UV254) to emerging Far-UVC at 222 nm (UV222), the fluence-based concentration of HO• in the UV/peroxydisulfate (UV/PDS) AOP increases by 6.40, 2.89, and 6.00 times in deionized water, tap water, and surface water, respectively, with increases in the fluence-based concentration of SO4•- also by 5.06, 5.81, and 55.47 times, respectively. The enhancement to radical generation is confirmed using a kinetic model. The pseudo-first-order degradation rate constants of 16 micropollutants by the UV222/PDS AOP in surface water are predicted to be 1.94-13.71 times higher than those by the UV254/PDS AOP. Among the tested water matrix components, chloride and nitrate decrease SO4•- but increase HO• concentration in the UV222/PDS AOP. Compared to the UV254/PDS AOP, the UV222/PDS AOP decreases the formation potentials of carbonaceous disinfection byproducts (DBPs) but increases the formation potentials of nitrogenous DBPs.

Regression model and pathways of halonitromethane formation from amino acids in the presence of bromide ion under UV/monochloramine disinfection

Halonitromethanes (HNMs) including chlorinated and brominated HNMs, a category of nitrogenous disinfection by-products with high toxicity, were formed from amino acids (AAs) in the presence of bromide ion (Br-) under UV/monochloramine (UV/NH2Cl) disinfection. This study developed a regression model using water characteristics (pH, HCO3– and Br-) and disinfection conditions (disinfection time and NH2Cl doses) to predict HNM formation from AAs (tyrosine (Tyr), tryptophan (Trp) and aspartic acid (Asp)) in the presence of Br- under UV/NH2Cl disinfection. Main contributors to the abatement of Tyr and Trp were UV (6.1%-18.7%), HO (18.5%-62.3%), Cl2− (0.3%-17.9%), Br (2.4%-41.3%, kBr•,AA=∼109-1010 M−1·s−1), Br2− (1.3%-11.0%, kBr2•-,AA=∼108-109 M−1·s−1), NO (2.6%-43.0%) and CO3− (0%-43.2%) based on the first-principle kinetic model of UV/NH2Cl/Br- process, while the removal ratio of Asp was low. It was responsible for higher HNM concentrations from Tyr and Trp than those from Asp. Due to the decline in HNM concentrations with prolongation of reaction time, HNM concentrations were considered as the quadratic function of disinfection time with coefficients related to water characteristics and NH2Cl doses. The regression model with backward stepwise regression described HNM formation well. After introducing specific UV absorbance at 254 nm (SUVA254) and interaction terms associated with SUVA254, HNM formation from three AAs was successfully predicted by one regression equation (R2 = 0.91, mean absolute error = 0.46, mean relative error = 37%, root-mean-square error = 0.81). Using the optimal regression model, increasing NH2Cl doses was found to advance the peak time for HNM formation. Besides, obtained heatmaps of HNM formation revealed that a high NH2Cl dose with a high UV dose or low NH2Cl dose helped to limit HNM formation. Lastly, the possible formation pathways of HNMs were presented.

Impact of changes in biofilm composition response following chlorine and chloramine disinfection on nitrogenous disinfection byproduct formation and toxicity risk in drinking water distribution systems

In practical drinking water treatment, chlorine and chloramine disinfection exhibit different mechanisms that affect biofilm growth. This study focused on the influence of biofilm composition changes, especially extracellular polymeric substance (EPS) fractions, on the potential formation and toxicity of nitrogenous disinfection by-products (N-DBP). Significant differences in microbial diversity and community structure were observed between the chlorine and chloramine treatments. Notably, the biofilms from the chloramine-treated group had higher microbial dominance and greater accumulation of organic precursors, as evidenced by the semi-quantitative confocal laser-scanning microscopy assay of more concentrated microbial aggregates and polysaccharide proteins in the samples. Additionally, the chloramine-treated group compared with chlorine had a higher EPS matrix content, with a 13.5 % increase in protein. Furthermore, the protein distribution within the biofilm differed; in the chlorine group, proteins were concentrated in the central region, whereas in the chloramine group, proteins were primarily located at the water–biofilm interface. Notably, functional prediction analyses of protein fractions in biofilms revealed specific functional regulation patterns and increased metabolism-related abundance of proteins in the chlorine-treated group. This increase was particularly pronounced for proteins such as dehydrogenases, reductases, transcription factors, and acyl-CoA dehydrogenases. By combining the Fukui function and density functional calculations to further analyse the effect of biofilm component changes on N-DBP production under chlorine/chloramine and by assessing the toxicity risk potential of N-DBP, it was determined that chloramine disinfection is detrimental to biofilm control and the accumulation of protein precursors has a higher formation potential of N-DBPs and toxicity risk, increasing the health risk of drinking water.

Is monochloramine pre-oxidation a viable strategy for enhancing the treatment efficiency of algae-laden water with conventional drinking water treatment process?

Algal blooms worldwide pose many challenges to drinking water production. Pre-oxidation with NaClO, KMnO4, or ozone is commonly used to enhance algal removal in conventional drinking water treatment processes. However, these currently utilized oxidation methods often result in significant algal cell lysis or impede the operation of the subsequent units. Higher algal removal with pre-chlorination in algal solutions prepared with natural water, compared to those prepared with ultrapure water, has been observed. In the present studies, preliminary findings indicate that ammonium in natural water alters chlorine species to NH2Cl, leading to improved treatment efficiency. NH2Cl with 1.5–3.0 mg∙L−1 as Cl2 with an oxidation time of 3–7 h significantly enhancing algal removal by coagulation. The selective oxidation of surface-absorbed organic matter (S-AOM) by NH2Cl, followed by the subsequent peeling off of this material from the algal surface, leading to an increase in zeta potential from −20.2 mV to −3.8 mV, constitutes the primary mechanism of enhanced algal removal through coagulation. These peeled S-AOM retained their large molecular weight and acted as polymer aids. Compared with NaClO and KMnO4, NH2Cl displays the best performance in improving algal removal, avoiding cell lysis, and decreasing the potential for nitrogenous disinfection byproducts formation under the reaction conditions used in this study. Notably, in major Chinese cities, water purification plants commonly rely on suburban lakes or reservoirs as water sources, necessitating the transportation of raw water over long distances for times up to several hours. These conditions favor the implementation of NH2Cl pre-oxidation. The collective results indicate the potential of NH2Cl oxidation as a viable pretreatment strategy for algal contamination during water treatment processes.

Disinfection byproduct formation from chlorination of agricultural reuse water sources

Treatment of reuse water sources is critical for achieving proper water quality for the desired end-use. Disinfection is often achieved through chlorination, but this leads to the formation of toxic disinfection byproducts (DBPs). During reuse for agricultural purposes, it is important to reduce the potential for contamination of food crops and thereby minimize DBP production from treatment processes. This study evaluates the DBP formation potential from various reuse water sources under different reaction conditions to determine the implications of chlorination-derived DBPs for agricultural water reuse. Chlorination experiments were conducted on wastewater, stormwater, and farm lagoon water at pH 5, 6, 7, and with Br− addition. DBP concentrations were then evaluated in conjunction with initial concentrations of dissolved organic carbon (DOC), total nitrogen (TN), initial bromide, and specific UV-absorbance (SUVA). The most abundantly formed DBP class for nearly all sources was trihalomethanes (THMs), followed by nitrogenous DBPs (N-DBPs). Despite a high DOC concentration of 37.8 mg/L, lagoon source 2 only formed a total of 4.15 µg/L DBPs, likely due to oxidation of the inorganic nitrogen (54.8 mg/L TN) inhibiting DBP formation. Stormwater sources (DOC range 3.0-15.3 mg/L) had the highest DBP formation potential, with chloroform concentrations reaching up to 92 µg/L. Waters with lower DOC, TN and bromide and at lower pH ranges had less DBP formation potential for the compounds evaluated in this study. While SUVA did not prove to be a strong indicator of DBP formation, with increasing Br/UVA, there was an exponential increase in bromine substitution factor for THMs (R2=0.927, p < 0.0001) across all reuse sources. Toxicity-weighted DBP concentrations were also evaluated for all sources. Waters with higher TN and bromide content produced more toxic N-DBPs, mainly dichloroacetonitrile and dibromoacetonitrile.

Functional UiO-66 for highly selective adsorption of N-nitrosodipropylamine: adsorption performance and mechanisms.

N-Nitrosodipropylamine (NDPA) is a class of nitrogenous disinfection by-products (N-DBPs) with high toxicity. Although NDPA present in water bodies is at relatively low concentrations, the potential risk is high due to its high toxicity and bioaccumulation. Metal-organic frameworks (MOFs), a new type of porous material with remarkable functionality, have shown great performance in a wide variety of applications in adsorption. This is the first study investigating the adsorption of MOFs on NDPA. Herein, UiO-66 with -NH2 and imidazolium functional groups were synthesized by modifying UiO-66 after amination. Adsorption kinetics and isotherm models were used to compare the adsorption properties of the two materials for low-concentration NDPA in water. The results showed that the behavior of all the adsorbents was consistent with the Langmuir model and the pseudo-second-order model and that the adsorption was homogeneous chemisorption. The structures of the nanoparticles were characterized by FTIR, zeta potential, XRD, SEM and BET measurements. Based on the characteristics, four adsorption mechanisms, namely electron conjugation, coordination reaction, anion-π interaction, and van der Waals forces, were simultaneously involved in the adsorption. The influencing factor experiment revealed that the adsorption of UiO-66-NH2 and (I-)Meim-UiO-66 involved hydrogen bonding and electrostatic interactions, respectively.

N-nitrosamines induced gender-dimorphic effects on infant rats at environmental levels

The safety of drinking water has always been a concern for people all over the world. N-nitrosamines (NAs), a kind of nitrogenous disinfection by-products (N-DBPs), are generally detected as a mixture in drinking water at home and abroad. Studies have shown that individual NAs posed strong carcinogenicity at high concentrations. However, health risks of NAs at environmental levels (concentrations in drinking water) are still unclear. Therefore, the potential health risks of environmentally relevant NAs exposure in drinking water needs to be conducted. In this study, blood biochemical analysis and metabolomics based on nuclear magnetic resonance (NMR) were performed to comprehensively investigate NAs induced metabolic disturbance in infant rats at environmental levels. Results of blood biochemical indices analysis indicated that AST in the serum of male rats in NAs-treated group exhibited a significant gender-specific difference. Multivariate statistics showed that two and eight significantly disturbed metabolic pathways were identified in the serum samples of NAs-treated male and female rats, respectively. In the urine samples of NAs-treated female rats, glycine, serine, and threonine metabolism pathway was significantly disturbed; while three significantly disturbed metabolic pathways were found in the urine of NAs-treated male rats. Finally, results of spearman correlation coefficients suggested that the disturbances of metabolism profile in serum and urine were correlated with changes in the gut microbiota (data derived from our published paper). Data presented here aimed to generate new health risk data of NAs mixture exposure at environmental levels and provide theoretical support for drinking water safety management. Environmental implicationN-nitrosamines (NAs) are a kind of nitrogenous disinfection by-products (N-DBPs) generated during drinking water disinfection processes. Herein, health risks of NAs at environmental levels (concentrations in drinking water) are investigated using blood biochemical analysis and nuclear magnetic resonance (NMR)-based metabolomics. Results confirmed NAs induced gender-specific on the metabolism in rat and the disturbances of metabolism profile in serum and urine were correlated with changes in the gut microbiota. Data presented here aimed to generate new health risk data of NAs mixture exposure at environmental levels and provide theoretical support for drinking water safety management.

New mechanistic insights into halogen-dependent cytotoxic pattern of monohaloacetamide disinfection byproducts

As highly toxic nitrogenous disinfection byproducts (DBPs), monohaloacetamides (monoHAcAms) generally exhibited a cytotoxic rank order of iodoacetamide ˃ bromoacetamide ˃ chloroacetamide. However, the mechanisms underlying the halogen-dependent cytotoxic pattern remain largely veiled as yet. In this work, oxidative stress/damage levels in monoHAcAm-treated Chinese hamster ovary cells were thoroughly analyzed, and binding interactions between monoHAcAms and antioxidative enzyme Cu/Zn-superoxide dismutase (Cu/Zn-SOD) were investigated by multiple spectroscopic techniques and molecular docking. Upon exposure to monoHAcAms, the intracellular levels of key biomarkers associated with oxidative stress/damage, including reactive oxygen species, malondialdehyde, lactate dehydrogenase, 8-hydroxy-2-deoxyguanosine, cell apoptosis, and G1 cell cycle arrest, were all significantly increased in a dose-response manner with the same halogen-dependent rank order as their cytotoxicity. Moreover, this rank order was also determined to be applicable to the monoHAcAm-induced alterations in the conformation, secondary structure, and activity of Cu/Zn-SOD, the microenvironment surrounding aromatic amino acid residues in Cu/Zn-SOD, as well as the predicted binding energy of SOD-monoHAcAm interactions. Our results revealed that the halogen-dependent cytotoxic pattern of monoHAcAms was attributed to their differential capacity to induce oxidative stress/damage and their interaction with antioxidative enzyme, which contribute to a better understanding of the halogenated DBP-induced toxicological mechanisms.

Effect of UV/peroxymonosulfate pretreatment on disinfection byproduct (DBP) formation during post-chlorination of humic acid.

UV/peroxymonosulfate (UV/PMS) is a promising advanced oxidation technology in water treatment. This study aimed to investigate the impact of UV/PMS on humic acid (HA) and the influence of PMS dosage, pretreatment time, pH pretreatment, nitrate, nitrite, ammonium, and bicarbonate influencing factors on disinfection byproduct (DBP) formation during post-chlorination. With increased PMS dosage or pretreatment time, the UV/PMS treatment significantly reduced ultraviolet absorbance and increased mineralization. It altered the fractional constituent as humic substances were gradually transformed into building blocks and low-molecular-weight acids. However, most DBP formation increased initially and then decreased after subsequent chlorination. Rising nitrate or nitrite concentrations markedly promoted halonitromethane (HNM) formation. The presence of ammonia had a more significant impact on dichloroacetonitrile (DCAN) formation. Bicarbonate in UV/PMS pretreatment increased carbonated disinfection byproduct (C-DBP) formation, whereas it had a negligible impact on nitrogenous disinfection byproduct (N-DBP) formation. The present study revealed the impact of a series of influencing factors on DBP formation in UV/PMS reaction systems, providing comprehensive insights on applying UV/PMS in actual practice.

Effective control of DBPs formation and membrane fouling in catalytic ozonation membrane reactor for municipal wastewater reclamation

This study aimed to evaluate the performance of different ceramic membranes, namely CuMn2O4 (CMO), g-C3N4 (CN), and CuMn2O4/g-C3N4 (CMO/CN) ceramic membrane (CM), in a catalytic ozonation membrane reactor (COMR) for municipal wastewater reclamation. The results demonstrated that CMO/CM and CMO/CN/CM used in the COMR exhibited high performance in terms of flux, removal efficiency of effluent organic matter (EfOM), control of disinfection by-products formation potential (DBPs-FP), and mitigation of membrane fouling. Notably, catalytic ozonation by CMO/CM showed superior reduction in DBPs formation (40.6 % of nitrogenous DBPs, 83.4 % of halogenated hydrocarbons, 36.6 % of haloacetic acids). Furthermore, significant inhibition of both organic fouling and biofouling was observed in the COMR. The addition of O3 altered the membrane fouling mechanism from gel layer formation to intermediate blocking. Ozonation primarily reduced the physically reversible fouling while catalytic ozonation additionally mitigated physically irreversible fouling. In addition to the almost complete removal of total cells and proteins, catalytic ozonation by CMO/CM further cleaned the α-polysaccharides and β-polysaccharides on the membrane surface, resulting in a 55.3 % reduction in biofilm thickness and demonstrating strong self-cleaning properties. These findings have important implications for enhancing the overall performance and durability of COMR systems in municipal wastewater reclamation.

Reductive Degradation of N-Nitrosodimethylamine via UV/Sulfite Advanced Reduction Process: Efficiency, Influencing Factors and Mechanism

N-nitrosodimethylamine (NDMA), as an emerging nitrogenous disinfection byproduct, is strictly controlled by multiple countries due to its high toxicity in drinking water. Advanced reduction processes (ARPs) are a new type of water treatment technology that can generate highly reactive reducing radicals and make environmental contaminants degrade rapidly and innocuously. In this study, a systematic investigation on the kinetics of the NDMA degradation via the chosen UV/sulfite ARP and the impacts of some key parameters of reaction system was conducted. The results indicated that the UV/sulfite ARP was an efficient and energy saving method for the reductive degradation of NDMA. A total of 94.40% of NDMA was removed using the UV/sulfite ARP, while only 45.48% of NDMA was removed via direct UV photolysis under the same reaction conditions. The degradation of NDMA via the UV/sulfite ARP followed pseudo-first-order kinetics. Increasing both the UV light intensity and sulfite dosage led to a proportional increase in the NDMA removal efficiency. The alkaline condition favored the degradation of NDMA, with the removal efficiency increasing from 21.57% to 66.79% within the initial 5 min of the reaction when the pH increased from 3 to 11. The presence of dissolved oxygen substantially decreased the removal efficiency of NDMA due to the formation of oxidizing superoxide radicals, which competed with NDMA by capturing the reducing active radicals during the reaction. An analysis of the degradation products indicated that several refractory intermediates such as dimethylamine, methylamine and nitrite were completely decomposed via the UV/sulfite ARP, and the final degradation products were formate, ammonia and nitrogen.

Response mechanisms of pipe wall biofilms in water supply networks under different disinfection strategy pressures and the effect of mediating halogenated acetonitrile formation

Residual chlorine and biofilm coexistence is inevitable in drinking water transmission and distribution networks. Understanding the microbial response and its mediated effects on disinfection byproducts under different categories of residual chlorine stress is essential to ensure water safety. The aim of our study was to determine the response of pipe wall biofilms to residual chlorine pressure in chlorine and chloramine systems and to understand the microbially mediated effects on the formation and migration of haloacetonitriles (HANs), typical nitrogenous disinfection byproducts. According to the experimental results, the biofilm response changes under pressure, with significant differences noted in morphological characteristics, the extracellular polymeric substances (EPS) spatial structure, bacterial diversity, and functional abundance potential. Upon incubation with residual chlorine (1.0 ± 0.2 mg/L), the biofilm biomass per unit area, EPS, community abundance, and diversity increased in the chloramine group, and the percentage of viable bacteria increased, potentially indicating that the chloramine group provides a richer variety of organic matter precursors. Compared with the chloramine group, the chlorination group exhibited increased haloacetonitrile formation potential (HANFP), with Rhodococcus (43.2%) dominating the system, whereas the prediction abundance of metabolic functions was advantageous, especially with regard to amino acid metabolism, carbohydrate metabolism, and the biodegradation and metabolism of foreign chemicals. Under chlorine stress, pipe wall biofilms play a stronger role in mediating HAN production. It is inferred that chlorine may stimulates microbial interactions, and more metabolites (e.g., EPS) consume chlorine to protect microbial survival. EPS dominates in biofilms, in which proteins exhibit greater HANFP than polysaccharides.

Bibliometric analysis of disinfection by-product research trends in Türkiye

The goal of this study is to reveal the time dynamics of studies systematically and comprehensively on drinking water treatment and disinfection, as well as the situation in the literature, by using the bibliometric analysis method to examine scientific publications in the field of "Disinfection By-Products" between 2001 and 2022. The data gathered from the investigated articles is shown using the visual mapping approach. In this regard, the research provides for an evaluation of the disinfection by-products literature. The study's database contained 115 scientific papers retrieved from Web of Science. Istanbul Technical University is the most productive university with 23 published articles on Disinfection By-products, followed by Suleyman Demirel University with 18 published articles. Trihalomethanes, haloacetic acids are the most studied types of carbonaceous disinfection by-products in published articles, and N-nitrosodimethylamine is one of the most widely published nitrogenous disinfection by-products. The precursors of disinfection by-products or the removal of disinfection by-products are the two main focuses of the purpose of all studies. Coagulation, advanced oxidation processes and membrane processes constitute the methods used in the control of disinfection by-products. Brominated, and nitrogenous DBPs have attracted much attention due to their high toxicity. Future studies on disinfection by-products should focus on water quality standards, precursor controls, toxicity, and health effects. The necessity of bibliometric analysis of disinfection by-products is a necessity to fill the existing knowledge gaps in global and regional studies.

Removal performance of dissolved organic matter from municipal secondary effluent by different advanced treatment processes and preventing the formation of disinfection by-products.

Various advanced treatment processes including ultrafiltration (UF), ozonation, enhanced coagulation, and biological aerated filter (BAF) have been applied to reduce dissolved organic matter (DOM) from the secondary effluent of municipal wastewater treatment plants (MWTPs). In this study, DOM were characterized and the relationship between DOM characteristics and disinfection by-products (DBPs) generation was investigated systematically. Results showed that BAF and ozonation processes could significantly affect DOM characteristics in the treated effluents and the following DBP generation. UF and enhanced coagulation reduced the production of DBPs by removing large molecular hydrophobic organics. The removal of low molecule DOM by BAF resulted in a 67.6% reduction in trihalomethanes (THMs) production. Ozonation could oxidize large hydrophobic DOM into small hydrophilic molecules containing aldehyde and ketone groups, leading to 54% increase of halogenated aldehydes (HALs) and halogenated ketones (HKs). Humic acid (HA) was the main organic type in DOM and important precursor for THMs and dichloroacetonitrile (DCAN) formation. The generation of trichloromethane (TCM) showed a significant positive correlation (R2 = 0.987) with the specific ultraviolet absorbance at 254nm (SUVA). Large molecule hydrophobic DOM devoted the most to the formation of carbonaceous disinfection by-products and [Formula: see text]-N content was an important factor affecting the generation of nitrogenous disinfection by-products. These results are important for the optimization of advanced treatment process in MWTPs, and controlling DBPs should consider the removal of low MW hydrophobic DOM and the reduction of SUVA.

Occurrence, stability and cytotoxicity of halobenzamides: A new group of nitrogenous disinfection byproducts in drinking water

Exploring disinfection byproducts (DBPs) with adverse health effects in drinking water is a constant challenge. Halobenzamides (HBZAMs) are suspected to be a new group of nitrogenous DBPs but have not been reported in drinking water to date. In this study, by coupling SPE and UPLC‒MS/MS, a sensitive method was established to detect eight HBZAMs in drinking water with recoveries and limits of detection of 80–103% and 0.01–0.04 ng/L, respectively. Subsequently, distinct fragments of HBZAMs were extended to the development of a pseudotargeted method for the analysis of the fourteen HBZAMs that were speculated and lack chemical standards. Using the developed method, eight HBZAMs were quantified in ten drinking water samples with concentrations ranging from 2.4 to 7.2 ng/L and a detection frequency of 100%, among which five HBZAMs were stable with half-lives over 72 h under real chlorine levels. Twelve HBZAMs without standards were identified in three to ten drinking water samples with comparable levels. The cytotoxicity of eight quantified HBZAMs in CHO-K1 cells varied with disparity, in which the cytotoxicity of 3,5-DBBZAM was over 10-fold higher than that of aliphatic dichloroacetamide. Considering their diversity, toxicity and stability, the occurrence of HBZAMs in drinking water deserves attention.

Evolutions of dissolved organic matter and disinfection by-products formation in source water during UV-LED (275 nm)/chlorine process.

Ultraviolet light-emitting diode (UV-LED) is a promising option for the traditional low-pressure UV lamp, but the evolutions of DOM composition, the formation of disinfection by-products (DBPs) and their toxicity need further study in raw water during UV-LED/chlorine process. In UV-LED (275nm)/chlorine process, two-dimensional correlation spectroscopy (2DCOS) analysis on synchronous fluorescence and UV-vis spectra indicated the protein-like fractions responded faster than the humic-like components, the reactive sequence of peaks for DOM followed the order: 340 nm→240 nm→410 nm→205 nm→290nm. Compared to chlorination for 30 mins, the UV-LED/chlorine process enhanced the degradation efficiency of three fluorescent components (humic-like, tryptophan-like, tyrosine-like) by 5.1%-46.1%, and the formation of carbonaceous DBPs (C-DBPs) significantly reduced by 43.8% while the formation of nitrogenous DBPs (N-DBPs) increased by 27.3%. The concentrations of C-DBPs increased by 17.8% whereas that of N-DBPs reduced by 30.4% in 24h post-chlorination. The concentrations of brominated DBPs increased by 17.2% during UV-LED/chlorine process, and further increased by 18.5% in 24h post-chlorination. According to the results of principal component analysis, the non-fluorescent components of DOM might be important precursors in the formation of haloketones, haloacetonitriles and halonitromethanes during UV-LED/chlorine process. Unlike chlorine treatment, the reaction of DOM in UV-LED/chlorine treatment generated fewer unknown DBPs. Compared with chlorination, the cytotoxicity of C-DBPs reduced but the cytotoxicity of both N-DBPs and Br-DBPs increased during UV-LED/chlorine process. Dichloroacetonitrile had the highest cytotoxicity, followed by monobromoacetic acid, bromochloroacetonitrile and trichloroacetic acid during 30 mins of UV-LED/chlorine process. Therefore, besides N-DBPs, the more toxic Br-DBPs formation in bromide-containing water is also not negligible in the practical applications of UV-LED (275nm)/chlorine process.