Fate of quaternary ammonium compounds upon the UV/monochloramine process: Kinetics, transformation pathways and the formation of N-nitroso-N-methyl-N-alkylamines.

Quaternary ammonium compounds (QACs) are widely detected in the aquatic environment due to their extensive use in a wide array of antibacterial products during the pandemic. In the current study, UV/monochloramine (UV/NH2Cl) was used to degrade three typical QACs, namely benzalkonium compounds (BACs), dialkyl dimethyl ammonium compounds (DADMACs), and alkyl trimethyl ammonium compounds (ATMACs). This process achieved high efficiency in removing BACs from water samples. The transformation products of QACs treated with UV/NH2Cl were identified and characterized using a high-resolution mass spectrometer, and transformation pathways were proposed. The formation of N-nitroso-N-methyl-N-alkylamines (NMAs) and N-nitrosodimethylamine (NDMA) were observed during QAC degradation. The molar formation yield of NDMA from C12-BAC was 0.04 %, while yields of NMAs reached 1.05 %. The ecotoxicity of NMAs derived from QACs was predicted using ECOSAR software. The increased toxicity could be attributed to the formation of NMAs with longer alkyl chains; these NMAs, exhibited a one order of magnitude increase in toxicity compared to their parent QACs. This study provides evidence that QACs are the specific and significant precursors of NMAs. Greater attention should be given to NMA formation and its potential threat to the ecosystem, including humans.

Statistical modeling for iodinated trihalomethanes: Preformed chloramination versus prechlorination followed by ammonia addition.

Developing predictive models for iodo-trihalomethane (I-THM) formation in water is needed and valuable to minimize extensive and costly analysis. The main objective of this study was to develop a statistical model for the formation of six types of I-THMs under uniform formation conditions. Prediction of I-THM formation in two different water sources (natural organic matter [NOM] and algal organic matter [AOM]) were comprehensively evaluated during both preformed chloramination and prechlorination followed by ammonia addition conditions. In addition, the prediction of THM10 (sum of six I-THM and THM4) formation was conducted during both oxidation strategies for NOM waters. In total, 460 experimental results were compiled from the literature and our own database. The results showed the coefficient of determination (R2) values for the six I-THM species ranged between 0.53-0.68 and 0.35-0.79 in the preformed NH2Cl and perchlorinated NOM waters, respectively. Among all independent variables, the I- exhibited the most significant influence on the formation of all I-THM species in the preformed NH2Cl, while SUVA254 was the most influential parameter for perchlorinated NOM water. When the preformed chloramination was compared with prechlorination followed by ammonia addition, the R2 value for I-THMs (0.93) was higher than for THM4 formation (0.79) in preformed chloramination. In the prechlorination followed by ammonia addition condition, the model prediction of I-THMs (R2= 0.45) formation was lower than THM4 (R2= 0.96). Overall, the pH, I-, SUVA254, and oxidant type are all played crucial roles in determining the I-THM formation, impacting the overall effectiveness and predictability of the models.

Probing nitro(so) and chloro byproducts and their precursors in natural organic matter during UV/NH2Cl treatment by FT-ICR MS with machine learning insights.

The UV/monochloramine (UV/NH2Cl) process, while efficiently eliminating micropollutants, produces toxic byproducts. This study utilized Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to investigate molecular-level changes in natural organic matter (NOM) and to disclose formation pathways of nitro(so) and chloro byproducts in the UV/NH2Cl process. The UV/NH2Cl process significantly increased the saturation and oxidation levels and altered the elemental composition of NOM. Using 15N labeling and a screening workflow, nitro(so) byproducts with nitrogen originating from inorganic sources (i.e., reactive nitrogen species (RNS) and/or NH2Cl) were found to exhibit total intensities comparable to those from NOM. RNS, rather than NH2Cl, played a significant role in incorporating nitrogen into NOM. Through linkage analysis, nitro(so) addition emerged as an important reaction type among the 25 reaction types applied. By using phenol as a representative model compound, the nitro byproducts were confirmed to be mainly generated through the oxidation of nitroso byproducts instead of nitration. Machine learning and SHAP analysis further identified the major molecular indices distinguishing nitro(so) and chloro precursors from non-precursors. This study enhances our fundamental understanding of the mechanisms driving the generation of nitro(so) and chloro byproducts from their precursors in complex NOM during the UV/NH2Cl process.

A new concern raised from algal bloom: Organic chloramines in chlorination.

Algal blooms have become a significant challenge in water treatment all over the world. In chlorination of drinking water, algal organic matter (AOM) leads to the formation of organic chloramines. The objectives of this review are to comprehensively summarize and discuss the up-to-date researches on AOM-derived organic chloramines and their chemical activities and toxicity, thereby drawing attention to the potentially chemical and hygienic risks of organic chloramines. The predominant algal species in water sources varied with location and season. AOM from cyanobacteria, green algae, and diatoms are composed of diverse composition. AOM-derived amino acids take a low portion of the precursors of organic chloramines. Both experimental kinetic data and quantum chemical calculation demonstrate the preferential formation of organic chloramines in the chlorination of model compounds (amino acids and peptides). Organic chloramines are persistent in water and can transform into dichloro- and trichloro-organic chloramines, unknown low-molecular-weight organic chloramines, and nitrogenous disinfection byproducts with the excess of free chlorine. The active chlorine (Cl+) in organic chloramines can lead to the formation of chlorinated phenolic compounds. Organic chloramines influence the generation and species of radicals and subsequent products in UV disinfection. Theoretical predictions and toxicological tests suggest that organic chloramines may cause oxidative or toxic pressure to bacteria or cells. Overall, organic chloramines, as one group of high-molecular-weight disinfection byproducts, have relatively long lifetimes, moderate chemical activities, and high hygienic risks to the public. Future perspectives of organic chloramines are suggested in terms of quantitative detection methods, the precursors from various predominant algal species, chemical activities of organic chloramines, and toxicity/impact.

Ultraviolet activation of monochloramine to treat contaminants of emerging concern: reactions, operating parameters, byproducts, and opportunities.

The presence of CECs in aquatic systems has raised significant concern since they are potentially harmful to the environment and human health. Eliminating CECs has led to the development of alternatives to treat wastewater, such as advanced oxidation processes (AOPs). The ultraviolet-mediated activation of monochloramine (UV/NH2Cl) is a novel and relatively unexplored AOPs for treating pollutants in wastewater systems. This process involves the production of amino radicals (•NH2) and chlorine radicals (Cl•) from the UV irradiation of NH2Cl. Studies have demonstrated its effectiveness in mitigating various CECs, exhibiting advantages, such as the potential to control the amount of toxic disinfection byproducts (TDBPs) formed, low costs of reagents, and low energy consumption. However, the strong influence of operating parameters in the degradation efficiency and existence of NH2Cl, the lack of studies of its use in real matrices and techno-economic assessments, low selectivity, and prolonged treatment periods must be overcome to make this technology more competitive with more mature AOPs. This review article revisits the state-of-the-art of the UV/NH2Cl technology to eliminate pharmaceutical and personal care products (PPCPs), micropollutants from the food industry, pesticides, and industrial products in aqueous media. The reactions involved in the production of radicals and the influence of operating parameters are covered to understand the formation of TDBPs and the main challenges and limitations of the UV/NH2Cl to degrade CECs. This review article generates critical knowledge about the UV/NH2Cl process, expanding the horizon for a better application of this technology in treating water contaminated with CECs.

Novel sunlight-induced monochloramine activation system for efficient microcontaminant abatement.

As an eco-friendly and sustainable energy, solar energy has great application potential in water treatment. Herein, simulated sunlight was for the first time utilized to activate monochloramine for the degradation of environmental organic microcontaminants. Various microcontaminants could be efficiently degraded in the simulated sunlight/monochloramine system. The average innate quantum yield of monochloramine over the wavelength range of simulated sunlight was determined to be 0.068 mol/Einstein. With the determined quantum yield, a kinetic model was established. Based on the good agreement between the simulated and measured photolysis and radical contributions to the degradation of ibuprofen and carbamazepine, the major mechanism of monochloramine activation by simulated sunlight was proposed. Chlorine radical (Cl∙) and hydroxyl radical (HO∙) were major radicals responsible for microcontaminant degradation in the system. Moreover, the model facilitated a deep investigation into the effects of different reaction conditions (pH, monochloramine concentration, and water matrix components) on the degradation of ibuprofen and carbamazepine, as well as the roles of the involved radicals. The differences between simulated and measured degradation data of each microcontaminant under all conditions were less than 10 %, indicating the strong reliability of the model. The model could also make good prediction for microcontaminant degradation in the natural sunlight/monochloramine system. Furthermore, the formation of disinfection byproducts (DBPs) was evaluated at different oxidation time in simulated sunlight/monochloramine with and without post-chloramination treatment. In real waters, organic components showed more pronounced suppression on microcontaminant degradation efficiency than inorganic ions. This study provided a systematic investigation into the novel sunlight-induced monochloramine activation system for efficient microcontaminant degradation, and demonstrated the potential of the system in practical applications.

Comparative analysis of chlorine-resistant bacteria after chlorination and chloramination in drinking water treatment plants.

Chlorine-resistant bacteria (CRB) in drinking water treatment plants (DWTPs) jeopardize water quality and pose a potential risk to human health. However, the specific response of CRB to chlorination and chloramination remains uncharacterized. Therefore, we analyzed 16 S rRNA sequencing data from water samples before and after chlorination and chloramination taken between January and December 2020. Proteobacteria and Firmicutes dominated all finished water samples. After chloramination, Acinetobacter, Pseudomonas, Methylobacterium, Ralstonia, and Sphingomonas were the dominant CRB, whereas Ralstonia, Bacillus, Acinetobacter, Pseudomonas, and Enterococcus were prevalent after chlorination. Over 75% of the CRB e.g. Acinetobacter, Pseudomonas, Bacillus, and Enterococcus were shared between the chlorination and chloramination, involving potentially pathogens, such as Acinetobacter baumannii and Pseudomonas aeruginosa. Notably, certain genera such as Faecalibacterium, Geobacter, and Megasphaera were enriched as strong CRB after chloramination, whereas Vogesella, Flavobacterium, Thalassolituus, Pseudoalteromonas, and others were enriched after chlorination according to LEfSe analysis. The shared CRB correlated with temperature, pH, and turbidity, displaying a seasonal pattern with varying sensitivity to chlorination and chloramination in cold and warm seasons. These findings enhance our knowledge of the drinking water microbiome and microbial health risks, thus enabling better infectious disease control through enhanced disinfection strategies in DWTPs.

Biofilm formation and antioxidation were responsible for the increased resistance of N. eutropha to chloramination for drinking water treatment.

Chloramination is an effective strategy for eliminating pathogens from drinking water and repressing their regrowth in water distribution systems. However, the inevitable release of NH4+ potentially promotes nitrification and associated ammonia-oxidizing bacteria (AOB) contamination. In this study, AOB (Nitrosomona eutropha) were isolated from environmental water and treated with two disinfection stages (chloramine disinfection and chloramine residues) to investigate the occurrence mechanisms of AOB in chloramination. The results showed that N. eutropha had considerable resistance to monochloramine compared to Escherichia coli, whose inactivation rate constant was 19.4-fold lower. The higher resistance was attributed to high levels of extracellular polymer substances (EPS) in AOB, which contribute to AOB surviving disinfection and entering the distribution system. In AOB response to the chloramine residues stage, the respiratory activity of N. eutropha remained at a high level after three days of continuous exposure to high chloramine residue concentrations (0.5-1.5 mg/L). Reverse transcription-quantitative polymerase chain reaction (RT-qPCR) suggested that the mechanism of N. eutropha tolerance involved a significantly high expression of the intracellular oxidative stress-regulating (sodB, txrA) and protein-related (NE1545, NE1546) genes. Additionally, this process enhanced EPS secretion and promoted biofilm formation. Adhesion predictions based on the XDLVO theory corroborated the trend of biofilm formation. Overall, the naturally higher resistance contributed to the survival of AOB in primary disinfection; the enhanced antioxidant response of surviving N. eutropha accompanied by biofilm formation was responsible for their increased resistance to the residual chloramines.

Closing Dichloramine Decomposition Nitrogen and Oxygen Mass Balances: Relative Importance of End-Products from the Reactive Nitrogen Species Pathway.

In drinking water chloramination, monochloramine autodecomposition occurs in the presence of excess free ammonia through dichloramine, the decay of which was implicated in N-nitrosodimethylamine (NDMA) formation by (i) dichloramine hydrolysis to nitroxyl which reacts with itself to nitrous oxide (N2O), (ii) nitroxyl reaction with dissolved oxygen (DO) to peroxynitrite or mono/dichloramine to nitrogen gas (N2), and (iii) peroxynitrite reaction with total dimethylamine (TOTDMA) to NDMA or decomposition to nitrite/nitrate. Here, the yields of nitrogen and oxygen-containing end-products were quantified at pH 9 from NHCl2 decomposition at 200, 400, or 800 µeq Cl2·L-1 with and without 10 µM-N TOTDMA under ambient DO (∼500 µM-O) and, to limit peroxynitrite formation, low DO (≤40 µM-O). Without TOTDMA, the sum of free ammonia, monochloramine, dichloramine, N2, N2O, nitrite, and nitrate indicated nitrogen recoveries ±95% confidence intervals were not significantly different under ambient (90 ± 6%) and low (93 ± 7%) DO. With TOTDMA, nitrogen recoveries were less under ambient (82 ± 5%) than low (97 ± 7%) DO. Oxygen recoveries under ambient DO were 88-97%, and the so-called unidentified product of dichloramine decomposition formed at about three-fold greater concentration under ambient compared to low DO, like NDMA, consistent with a DO limitation. Unidentified product formation stemmed from peroxynitrite decomposition products reacting with mono/dichloramine. For a 2:2:1 nitrogen/oxygen/chlorine atom ratio and its estimated molar absorptivity, unidentified product inclusion with uncertainty may close oxygen recoveries and increase nitrogen recoveries to 98% (ambient DO) and 100% (low DO).

Antiplatelet Action of Chloramine Derivatives of Adenosine Phosphates and Their Chemical Activity in Relation to Sulfur-Containing Compounds.

We studied the properties of N6-chloroadenosine phosphates (ATP, ADP, and AMP chloramines) as compounds with potentially increased antiplatelet efficacy determined by their binding to the plasma membrane of platelets. Chloramine derivatives of ATP, ADP, and AMP do not differ in their optical absorption characteristics: their absorption spectra are in the range of 220-340 nm with a maximum at 264 nm. Chloramines of adenosine phosphates are characterized by high reactivity with respect to thiol compounds. In particular, the rate constants of the reaction of N6-chloroadenosine-5'-diphosphate with N-acetylcysteine, reduced glutathione, dithiothreitol, and cysteine reach 59,000, 250,000, 340,000, and 1,250,000 M-1×sec-1, respectively, and only 1.10±0.02 M-1×sec-1 with methionine. It has been found that N6-chloradenosine-5'-triphosphate is a strong inhibitor of platelet functions: it effectively suppresses ADP-induced cell aggregation (IC50 in the whole blood is 5 µM) and inhibits aggregation of preactivated platelets and induces dissociation of their aggregates.

Pre-oxidation coupled with charged covalent organic framework membranes for highly efficient removal of organic chloramines precursors in algae-containing water treatment.

Organic chloramines in water would pose both chemical and microbiological risks. It is essential to remove the precursors of organic chloramine (amino acids and decomposed peptides/proteins) to limit its formation in disinfection. In our work, nanofiltration was chosen to remove organic chloramines precursors. To solve the "trade-off" effect and low rejection of small molecules in algae organic matter, we synthesized a thin film composite (TFC) nanofiltration (NF) membrane with a crumpled polyamide (PA) layer via interfacial polymerization on polyacrylonitrile (PAN) composite support loaded with covalent organic framework (COF) nanoparticles (TpPa-SO3H). The obtained NF membrane (PA-TpPa-SO3H/PAN) increased the permeance from 10.2 to 28.2 L m-2 h-1 bar-1 and the amino acid rejection from 24% to 69% compared to the control NF membrane. The addition of TpPa-SO3H nanoparticles decreased the thickness of PA layers, increased the hydrophilicity of the membrane, and increased the transition energy barrier for amino acids transferring through the membrane, which was identified by scanning electron microscope, contact angle test, and density functional theory computations, respectively. Finally, pre-oxidation coupled with PA-TpPa-SO3H/PAN membrane nanofiltration on the limitation of organic chloramines formation was evaluated. We found that the combined application of KMnO4 pre-oxidation and PA-TpPa-SO3H/PAN membranes nanofiltration in algae-containing water treatment could minimize the formation of organic chloramines in subsequent chlorination and maintain a high flux during filtration. Our work provides an effective way for algae-containing water treatment and organic chloramines control.

Bleach Emissions Interact Substantially with Surgical and KN95 Mask Surfaces.

Mask wearing and bleach disinfectants became commonplace during the COVID-19 pandemic. Bleach generates toxic species including hypochlorous acid (HOCl), chlorine (Cl2), and chloramines. Their reaction with organic species can generate additional toxic compounds. To understand interactions between masks and bleach disinfection, bleach was injected into a ventilated chamber containing a manikin with a breathing system and wearing a surgical or KN95 mask. Concentrations inside the chamber and behind the mask were measured by a chemical ionization mass spectrometer (CIMS) and a Vocus proton transfer reaction mass spectrometer (Vocus PTRMS). HOCl, Cl2, and chloramines were observed during disinfection and concentrations inside the chamber are 2-20 times greater than those behind the mask, driven by losses to the mask surface. After bleach injection, many species decay more slowly behind the mask by a factor of 0.5-0.7 as they desorb or form on the mask. Mass transfer modeling confirms the transition of the mask from a sink during disinfection to a source persisting >4 h after disinfection. Humidifying the mask increases reactive formation of chloramines, likely related to uptake of ammonia and HOCl. These experiments indicate that masks are a source of chemical exposure after cleaning events occur.

Formation characteristics and acute toxicity assessment of THMs and HAcAms from DOM and its different fractions in source water during chlorination and chloramination.

The formation characteristics of trihalomethanes (THMs) and haloacetamides (HAcAms) from dissolved organic matter and its fractions were investigated during chlorine-based disinfection processes. The relationships between water quality parameters, fluorescence parameters, and the formation levels of THMs and HAcAms were analyzed. The fractions contributing most to the acute toxicity were identified. The trichloromethane (TCM) generation level (72 h) generally followed the order of Cl2 > NH2Cl > NHCl2 process. The NHCl2 process was superior to the NH2Cl process in controlling TCM formation. Hydrophobic acidic substance (HOA), hydrophobic neutral substance (HON), and hydrophilic substance (HIS) were identified as primary precursors of 2,2-dichloroacetamide and trichloroacetamide during chlorination and chloramination. The formation of TCM mainly resulted from HOA, HON and HIS fractions relatively uniformly, while HOA and HIS fractions contributed more to the formation of bromodichloromethane and dibromomonochloromethane. UV254 could be used as an alternative indicator for the amount of ΣTHMs formed during chlorination and chloramination processes. Dissolved organic nitrogen was a potential precursor of 2,2-dichloroacetamide during chlorination process. The fractions with the highest potential acute toxicity after the chlorination were water-dependent.

Lysine and Arginine Reactivity and Transformation Products during Peptide Chlorination.

Chlorine reactions with peptide-bound amino acids form disinfection byproducts and contribute to pathogen inactivation by degrading protein structure and function. Peptide-bound lysine and arginine are two of the seven chlorine-reactive amino acids, but their reactions with chlorine are poorly characterized. Using N-acetylated lysine and arginine as models for peptide-bound amino acids and authentic small peptides, this study demonstrated conversion of the lysine side chain to mono- and dichloramines and the arginine side chain to mono-, di-, and trichloramines in ≤0.5 h. The lysine chloramines formed lysine nitrile and lysine aldehyde at ∼6% yield over ∼1 week. The arginine chloramines formed ornithine nitrile at ∼3% yield over ∼1 week but not the corresponding aldehyde. While researchers hypothesized that the protein aggregation observed during chlorination arises from covalent Schiff base cross-links between lysine aldehyde and lysine on different proteins, no evidence for Schiff base formation was observed. The rapid formation of chloramines and their slow decay indicate that they are more relevant than the aldehydes and nitriles to byproduct formation and pathogen inactivation over timescales relevant to drinking water distribution. Previous research has indicated that lysine chloramines are cytotoxic and genotoxic to human cells. The conversion of lysine and arginine cationic side chains to neutral chloramines should alter protein structure and function and enhance protein aggregation by hydrophobic interactions, contributing to pathogen inactivation.

Microbiological risks increased by ammonia-oxidizing bacteria under global warming: The neglected issue in chloraminated drinking water distribution system.

A rising outbreak of waterborne diseases caused by global warming requires higher microbial stability in the drinking water distribution system (DWDS). Chloramine disinfection is gaining popularity in this context due to its good persistent stability and fewer disinfection byproducts. However, the microbiological risks may be significantly magnified by ammonia-oxidizing bacteria (AOB) in distribution systems during global warming, which is rarely noticed. Hence, this work mainly focuses on AOB to explore its impact on water quality biosafety in the context of global warming. Research indicates that global warming-induced high temperatures can directly or indirectly promote the growth of AOB, thus leading to nitrification. Further, its metabolites or cellular residues can be used as substrates for the growth of heterotrophic bacteria (e.g., waterborne pathogens). Thus, biofilm may be more persistent in the pipelines due to the presence of AOB. Breakpoint chlorination is usually applied to control such situations. However, switching between this strategy and chloramine disinfection would result in even more severe nitrification and other adverse effects. Based on the elevated microbiological risks in DWDS, the following aspects should be paid attention to in future research: (1) to understand the response of nitrifying bacteria to high temperatures and the possible association between AOB and pathogenic growth, (2) to reveal the mechanisms of AOB-mediated biofilm formation under high-temperature stress, and (3) to develop new technologies to prevent and control the occurrence of nitrification in drinking water distribution system.

Elevated levels of chloramines and chlorine detected near an indoor sports complex.

Chloramines (NH2Cl, NHCl2, and NCl3) are toxic compounds that can be created during the use of bleach-based disinfectants that contain hypochlorous acid (HOCl) and the hypochlorite ion (OCl-) as their active ingredients. Chloramines can then readily transfer from the aqueous-phase to the gas-phase. Atmospheric chemical ionization mass spectrometry using iodide adduct chemistry (I-CIMS) made observations across two periods (2014 and 2016) at an urban background site on the University of Leicester campus (Leicester, UK). Both monochloramine (NH2Cl) and molecular chlorine (Cl2) were detected and positively identified from calibrated mass spectra during both sampling periods and to our knowledge, this is the first detection of NH2Cl outdoors. Mixing ratios of NH2Cl reached up to 2.2 and 4.0 parts per billion by volume (ppbv), with median mixing ratios of 30 and 120 parts per trillion by volume (pptv) during the 2014 and 2016 sampling periods, respectively. Levels of Cl2 were observed to reach up to 220 and 320 pptv. Analysis of the NH2Cl and Cl2 data pointed to the same local source, a nearby indoor sports complex with a swimming pool and a cleaning product storage shed. No appreciable levels of NHCl2 and NCl3 were observed outdoors, suggesting the indoor pool was not likely to be the primary source of the observed ambient chloramines, as prior measurements made in indoor pool atmospheres indicate that NCl3 would be expected to dominate. Instead, these observations point to indoor cleaning and/or cleaning product emissions as the probable source of NH2Cl and Cl2 where the measured levels provide indirect evidence for substantial amounts transported from indoors to outdoors. Our upper estimate for total NH2Cl emissions from the University of Leicester indoor sports complexes scaled for similar sports complexes across the UK is 3.4 × 105 ± 1.1 × 105 µg h-1 and 0.0017 ± 0.00034 Gg yr-1, respectively. The Cl-equivalent emissions in HCl are only an order of magnitude less to those from hazardous waste incineration and iron and steel sinter production in the UK National Atmospheric Emissions Inventory (NAEI).

Exploring Pathways and Mechanisms for Dichloroacetonitrile Formation from Typical Amino Compounds during UV/Chlorine Treatment.

The formation of disinfection byproducts (DBPs) during UV/chlorine treatment, especially nitrogenous DBPs, is not well understood. This study investigated the formation mechanisms for dichloroacetonitrile (DCAN) from typical amino compounds during UV/chlorine treatment. Compared to chlorination, the yields of DCAN increase by 88-240% during UV/chlorine treatment from real waters, while the yields of DCAN from amino compounds increase by 3.3-5724 times. Amino compounds with electron-withdrawing side chains show much higher DCAN formation than those with electron-donating side chains. Phenylethylamine, l- phenylalanine, and l-phenylalanyl-l-phenylalanine were selected to represent amines, amino acids, and peptides, respectively, to investigate the formation pathways for DCAN during UV/chlorine treatment. First, chlorination of amines, amino acids, and peptides rapidly forms N-chloramines via chlorine substitution. Then, UV photolysis but not radicals promotes the transformation from N-chloramines to N-chloroaldimines and then to phenylacetonitrile, with yields of 5.4, 51.0, and 19.8% from chlorinated phenylethylamine, l-phenylalanine, and l-phenylalanyl-l-phenylalanine to phenylacetonitrile, respectively. Finally, phenylacetonitrile is transformed to DCAN with conversion ratios of 14.2-25.6%, which is attributed to radical oxidation, as indicated by scavenging experiments and density functional theory calculations. This study elucidates the pathways and mechanisms for DCAN formation from typical amino compounds during UV/chlorine treatment.

Effects of different types of nitrogen sources in water on the formation potentials of nitrogenous disinfection by-products in chloramine disinfection process based on isotope labeling.

Nitrogenous disinfection by-products (N-DBPs) raise increasing concerns because of their high genotoxicity, cytotoxicity, and carcinogenicity compared to carbonaceous disinfection by-products (C-DBPs). Nitrogen-containing disinfectants, dissolved organic nitrogen (DON), and inorganic nitrogen may all promote the formation of N-DBPs. Therefore, it is urgent to explore the dominant nitrogen source of N-DBPs under the coexistence of multiple nitrogen sources. In this study, the effects of amino acids, nitrate, ammonia, and chloramine as different types of nitrogen sources on the formation of five N-DBPs were investigated systematically, including chloroacetonitrile (CAN), dichloroacetonitrile (DCAN), bromochloroacetonitrile (BCAN), dibromoacetonitrile (DBAN) and dichloroacetamide (DCAcAm). L-Aspartic acid (L-Asp) as the organic nitrogen source showed a high potential on the formation of N-DBPs by forming acetonitrile intermediates. Ammonia as the inorganic nitrogen source consumed oxidants and changed the existing form of chloramine, thus inhibiting the formation of N-DBPs. Instead of providing nitrogen to N-DBPs, nitrate as a salt promoted the volatilization of N-DBPs, thereby reducing the detected N-DBPs. Furthermore, an isotope labeling method was applied to clearly trace the nitrogen sources of N-DBPs via GC-MS with electron ionization. 15N-chloramine, 15N-amino acid, 15N-nitrate and 15N-ammonia were selected as the corresponding isotopic nitrogen sources. The results indicated that chloramine was the major nitrogen contributor to five N-DBPs during the chloramination of L-Asp under the coexistence of multiple nitrogen sources, ranging from 61 % to 79 %. The influence of environmental factors (reaction time, pH, and bromide) on the formation of N-DBPs during chloramination was also investigated. There was competition between brominated N-DBPs and chlorinated N-DBPs in chloramination. With the increase of reaction time or bromine, the formation potentials of chlorinated N-DBPs gradually decreased, while brominated N-DBPs gradually increased. Moreover, higher pH inhibited the generation of N-DBPs.

Organic chloramines attenuation and disinfection by-product formation during UV, chlorination and UV/chlorine processes.

Organic chloramines (OCs) have become one of the research focuses in the field of drinking water treatment due to its limited oxidation and sterilization ability as well as potential cytotoxicity and genetic toxicity to the public. Among widespread OCs, produced by chlorinating cytosine are a typical one exists during chlorine disinfection. OCs degradation during UV, chlorination and UV/chlorine processes were systematically investigated. UV irradiation at 254 nm could effectively degrade OCs by 96.6% after 60 min, mainly because N-Cl bond had significant UV absorption at 250-280 nm leading to the generation of Cl• and HO•. Direct chlorination had poor removal of OCs with the OCs concentration increased first and then decreased as time went by. On the other hand, the removal of OCs during UV/chlorination was much higher than that during chlorination, but was worse than that during UV alone. pH had a minor effect on OCs decomposition via UV irradiation, whereas the effect was pronounced in the chlorination and UV chlorine processes. UV wavelength can affect the degradation of OCs with efficiency decreased in the order of UV 254 > UV 265 > UV 275. The total yields of disinfection by-products (DBPs) during the degradation of OCs followed UV/chlorine > UV > chlorination. CH and DCAA were the two dominant types of DBPs among detected 7 DBPs. DBPs yield followed the order of UV254 > UV265 > UV275 at pH 6.0 and 7.0. After UV 265 irradiation, DBPs yield slightly decreased by 2.4%, 3.0% and 6.6% with the pH increased from 6.0 to 9.0. The results can provide theoretical basis for effective control of OCs in drinking water.

A Novel Reagent for Radioiodine Labeling of New Chemical Entities (NCEs) and Biomolecules.

Radioiodine labeling of peptides and proteins is routinely performed by using various oxidizing agents such as Chloramine T, Iodobeads, and Iodogen reagent and radioactive iodide (I-), although some other oxidizing agents were also investigated. The main objective of the present study was to develop and test a novel reagent, inorganic monochloramine (NH2Cl), for radioiodine labeling of new chemical entities and biomolecules which is cost-effective, easy to make and handle, and is selective to label amino acids, peptides, and proteins. The data presented in this report demonstrate that the yields of the non-radioactive iodine labeling reactions using monochloramine are >70% for an amino acid (tyrosine) and a cyclic peptide (cyclo Arg-Gly-Asp-d-Tyr-Lys, cRGDyK). No evidence of the formation of N-chloro derivatives in cRGDyK was observed, suggesting that the reagent is selective in iodinating the tyrosine residue in the biomolecules. The method was successfully translated into radioiodine labeling of amino acid, a peptide, and a protein, Bovine Serum Albumin (BSA).