Organic Chloramines Research Articles

Modelling the cost-effectiveness of a chloramine gel in treating infected, non-healing diabetic foot ulcers.

Organic chloramines have been developed as a topical wound bed preparation gel. This study aimed to estimate whether the addition of chloramine gel (Chlorasolv, RLS Global AB, Sweden) to standard care compared with standard care alone would afford a cost‑effective technology to the UK's health services for treating infected, non-healing diabetic foot ulcers (DFUs). A Markov model was developed to simulate the management of infected, non-healing DFUs. The model utilised data from a randomised controlled trial and was used to estimate the cost-effectiveness of chloramine plus standard care compared with standard care alone over a period of 24 weeks, expressed as the incremental cost per quality-adjusted life year (QALY) gained at 2021/22 prices. Using adjunctive chloramine to treat infected, non-healing DFUs was found to shorten the time to healing by 36% (from a mean of 17.1 weeks per ulcer to a mean of 11.0 weeks per ulcer). This translated into a 6% improvement in the probability of being healed by 24 weeks and a corresponding 3% improvement in health-related quality of life (HRQoL). Also, use of adjunctive chloramine was found to reduce the total cost of ulcer management by 13%. Sensitivity analysis found that adjunctive chloramine remained a cost-effective treatment, even when the value of the model inputs was varied by ±20%. Within the limitations of the study, treatment with adjunctive chloramine instead of standard care alone could potentially afford the UK's health services a cost-effective debridement strategy for infected, non-healing DFUs, due to its ability to accelerate the time to healing.

The formation and control of disinfection by-products by two-step chlorination for sewage effluent: Role of organic chloramine decomposition among molecular weight fractions

With the increasing discharge of wastewater effluent to natural waters, there is an urgent need to achieve both pathogenic microorganism inactivation and the mitigation of disinfection by-products (DBPs) during disinfection. Studies have shown that two-step chlorination, which injected chlorine disinfectant by splitting into two portions, was more effective in inactivating Escherichia coli than one-step chlorination under same total chlorine consumption and contact time. In this study, we observed a substantial reduction in the formation of five classes of CX3R-type DBPs, especially highly toxic haloacetonitriles (HANs), during two-step chlorination of secondary effluent when the mass ratio of chlorine-to-nitrogen exceeded 2. The shift of different chlorine species (free chlorine, monochloramine and organic chloramine) verified the decomposition of organic chloramines into monochloramine during second chlorination stage. Notably, the organic chloramines generated from the low molecular weight (< 1 kDa) fraction of dissolved organic nitrogen in effluent organic matter tended to decompose during the second step chlorination leading to the mitigation of HAN formation. Furthermore, the microbiological analysis showed that two-step chlorinated effluent had a slightly lower ecological impact on surface water compared to one-step chlorination. This work provided more information about the two-step chlorination for secondary effluent, especially in terms of organic chloramine transformation and HAN control.

Formation Mechanisms of Nitro Products from Transformation of Aliphatic Amines by UV/Chlorine Treatment.

Formation of nitrogenous disinfection byproducts from aliphatic amines is a widespread concern owing to the serious health risks associated with them. However, the mechanisms of transforming aliphatic amines and forming nitro products in the UV/chlorine process have rarely been discussed, which are investigated in this work. Initially, secondary amines (R1R2NH) are transformed into secondary organic chloramines (R1R2NCl) via chlorination. Subsequently, radicals, such as HO• and Cl•, are found to contribute predominantly to such transformations. The rate constants at which HO•, Cl•, and Cl2•- react with R1R2NCl are (2.4-5.1) × 109, (1.5-3.8) × 109, and (1.2-6.1) × 107 M-1 s-1, respectively. Consequently, R1R2NCl are transformed into primary amines (R1NH2/R2NH2) and chlorinated primary amines (R1NHCl/R2NHCl and R1NCl2/R2NCl2) by excess chlorine. Furthermore, primarily driven by UV photolysis, chlorinated primary amines can be transformed into nitroalkanes with conversion rates of ∼10%. Dissolved oxygen and free chlorine play crucial roles in forming nitroalkanes, and post-chlorination can further form chloronitroalkanes, such as trichloronitromethane (TCNM). Radicals are involved in forming TCNM in the UV/chlorine process. This study provides new insights into the mechanisms of transforming aliphatic amines and forming nitro products using the UV/chlorine process.

Degradation of atrazine by a UV-activated organic chloramines process: kinetics, degradation pathways, disinfection by-product formation, and toxicity changes

Pre-chlorination is a typical drinking water treatment process to control algae growth and degrade contaminants. However, abundant dissolved organic nitrogen in the water environment, forms organic chloramines after pre-chlorination, affecting the degradation of organic pollutants. Herein, UV radiation is used to activate organic chloramines to degrade atrazine (ATZ). Electron spin resonance (ESR) spectra showed that ATZ was effectively degraded after organic chloramines were activated to generate Cl• and HO• by UV irradiation. Combined with the analysis of Kintecus software, the reaction pH exhibited a significant effect on ATZ degradation in the UV-activated organic chloramines process. By integrating UPLC-MS/MS analysis and frontier molecular orbitals calculation, identified six major degradation intermediates of ATZ and conversion pathways were proposed. The disinfection by-products (DBPs) concentration decreased during the post-chlorination process, indicating the great potential of the UV-activated organic chloramines process in eliminating micropollutants and controlling the formation of DBPs. Acute toxic changes in zebrafish larvae during ATZ degradation and post-chlorination, combined with Toxicity Estimation Software Tool (T.E.S.T.) and Ecological Structure Activity Relationship (ECOSAR) software revealed that ATZ produced more toxic intermediates. Therefore, it is necessary to further optimize disinfection for the practical application of UV-activated organic chloramines.

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.

Insight into mixed chlorine/chloramines conversion and associated water quality variability in drinking water distribution systems

Mixed chlorine/chloramines are common in drinking water distribution systems (DWDSs); however, their transformation and impact on chemical and microbial characteristics are not well understood. We systematically investigated water quality parameters associated with mixed chlorine/chloramine species conversion in 192 samples (including raw, finished, and tap water) collected throughout the year in a city in East China. Various chlorine/chloramine species (free chlorine, monochloramine [NH2Cl], dichloramine [NHCl2], and organic chloramines [OC]) were detected in both chlorinated and chloraminated DWDSs. NHCl2 + OC increased with transport distance along the pipeline network. The maximum proportion of NHCl2 + OC in over total chlorine in tap water reached 66 % and 38 % from chlorinated and chloraminated DWDSs, respectively. Both free chlorine and NH2Cl showed a rapid decay in the water pipe systems, but NHCl2 and OC were more persistent. Correlations between chlorine/chloramine species and physicochemical parameters were established. Models for predicting the sum of chloroform/TCM, bromodichloromethane/BDCM, chlorodibromomethane/CBDM, and bromoform/TBM (THM4) (R2 = 0.56) and haloacetic acids (HAAs) (R2 = 0.65) exhibited greater accuracy based on machine learning tuned with chlorine/chloramine species, particularly NHCl2 + OC. The predominant bacterial communities in mixed chlorine/chloramine systems were those resistant to chlorine or chloramine such as proteobacteria. NH2Cl was the most significant explanatory factor (28.1 %) for the variation in microbial community assemblage in chloraminated DWDSs. Although residual free chlorine and NHCl2 + OC, accounted for a smaller proportion of chlorine species in chloraminated DWDSs, they played an essential role (12.4 % and 9.1 %, respectively) in the microbial community structure.

Transfer organic chloramines to monochloramine using two-step chlorination: A method to inhibit N-DBPs formation in algae-containing water treatment.

Organic chloramines formed in chlorination of algae-containing water are typical precursors of nitrogenous disinfection byproducts (N-DPBs). The objective to simultaneously enhance the removal efficiency of organic chloramines and control DBP formation remains a challenge. In this study, we report a two-step chlorination strategy for transferring organic chloramines to monochloramine based on the decomposition mechanisms of mono- and di-organic chloramines, which could limit organic chloramines formation and inhibit N-DBPs formation. We demonstrated that two-step chlorination could decrease the organic chloramines formation by nearly 50% than conventional one-step chlorination. Furthermore, two-step chlorination not only blocked the pathway that organic chloramines decomposed to nitriles, but also led to the conversion of organic chloramines to monochloramine. During two-step chlorination of algal organic matter, the organic chloramine transfer proportion decreased by 6.5% and the monochloramine transfer proportion increased by 17.0%. The N-DBP formation, especially haloacetonitriles (HANs), decreased significantly as organic nitrogen became inorganic nitrogen (monochloramine) in two-step chlorination. This work further clarified the process from algal organic matter to N-DBPs, which could expand our understanding of algae-derived organic chloramines removal and DBPs control.

Enhanced formation of haloacetonitriles during chlorination with bromide: Unveiling the important roles of organic bromamines

The formation of brominated disinfection byproducts (Br-DBPs) is an emerging issue in drinking water disinfection because its toxicity is tens to hundreds of times higher than that of chlorinated analogues and because of the widespread presence of bromide in source water. However, the mechanism and pathways of Br-DBPs formation remain unclear. In this study, we used glycine, alanine, and serine as model precursors and observed that brominated haloacetonitriles (Br-HANs) were more likely to be formed than brominated trihalomethanes. The results showed that there is not only one important way to HAN formation in the presence of bromide. We propose that organic bromamines, similar to organic chloramines, play a significant role in the formation of Br-HANs. Both the experimental and theoretical results confirmed that the decay of organic bromamines was faster than that of organic chloramines, which verified our assumption. The effect of the pH was investigated to further confirm the role of organic bromamines. In addition, we found that the formation of Br-HANs was significantly inhibited when monochloramine was used as a disinfectant, because the formation of organic bromamines was blocked. However, the formation of Br-HANs was promoted during the UV/chlorine process because of the faster decay of organic bromamines under UV photolysis. Overall, our study reveals the formation mechanism of Br-HANs and provides an alternative method to prevent Br-HAN formation.

Novel insights into formation mechanism of organic chloramines from pre-oxidized algae-laden water: Multiple roles of dissolved organic nitrogen.

Organic chloramines posed significant risks to drinking water safety. However, the formation mechanism of algae-derived organic chloramines remained unclear. In this study, it was observed that pre-oxidation of algal suspensions increased organic chloramine formation during chlorination. Compared to KMnO4 pre-oxidation, O3 significantly increased the organic chloramine formation potential of algal suspensions. Characterization was performed with size exclusion chromatography-multiple detectors (SEC-MDs) to better understand the organic chloramine formation mechanism. The results revealed that low molecular weight proteins (AMW ≤ 0.64 kDa) were the main precursors of organic chloramines after conventional water treatment processes. We then focused on 14 essential amino acids involved in protein formation. Their concentrations and organic chloramine formation potentials were determined, based on which the theoretical organic chloramine formation potentials of the studied samples were evaluated. However, dramatic gaps between theoretical and experimental organic chloramine formations were observed, which suggested that not all organic nitrogen could react with chlorine to form organic chloramine. The condensed dual descriptor (CDD) was calculated to predict the electrophilic substitution reaction sites on peptides. Furthermore, the activation barrier of each proposed reaction was computed to confirm that the reaction sites for chlorine were located on amino groups. This study clarified the formation mechanism of algal-derived organic chloramines, which could provide a powerful theoretical foundation for controlling organic chloramine formation in drinking water processes.

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 254nm could effectively degrade OCs by 96.6% after 60min, mainly because N-Cl bond had significant UV absorption at 250-280nm 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.

Enhanced trichloronitromethane formation during chlorine-UV treatment of nitrite-containing water by organic amines

This study explored the risk of trichloronitromethane (TCNM) formation during chlorination of the nitrite-containing water after pre-chlorination and subsequent UV irradiation (i.e., the chlorine-UV process). The competitive reaction between amino acid (AA) and NO2− for chlorine produced organic chloramine and reduced the oxidation from NO2− to NO3−, resulting in a significant enhancement of TCNM in the presence of AA (>5.52 μg L−1) as compared to the absence of AA (0.42 μg L−1). The generation of HO• during UV photolysis of organic chloramines was confirmed. Among the process parameters, pre-chlorination time (from 5 min to 30 min) had no significant effect on TCNM formation; the highest TCNM formation occurred at pH 7 (from pH 6 to pH 8); prolonged UV irradiation time (from 5 min to 30 min) and increased chlorine to AA ratio (Cl2:AA) (from 1 to 3) decreased the TCNM formation. The hydroxylated, chlorinated and nitrosated products were detected. The quantum chemical calculation results indicated the attack of NO2• was more likely to occur at the meta and para positions of benzoic acid (BZA), because of the steric hindrance of the carboxylic group in BZA to the ortho position. Based on the results of the toxicity assessment, pre-chlorination with a higher chlorine dosage could be an effective method of controlling both TCNM formation and acute toxicity. Overall, the results of this study contributed to the understanding of the TCNM formation mechanism as well as optimizing the parameters of the chlorine-UV process to reduce the risk of TCNM formation.

Presence of bromide and iodide promotes the horizontal transfer of antibiotic resistance genes during chlorination: A preliminary study

Chlorination was reported to have a great potential to increase horizontal gene transfer (HGT) of antibiotic resistance genes (ARGs), which poses a great threat to global human health. Bromide (Br−) and iodide (I−) ions are widely spread ions in water and wastewater. In chlorination, Br− and I− can be oxidized to active bromine and iodine species. The influence of the co-existing different halogen oxidants (chlorine + bromine or iodine species) on HGT of ARGs were rarely investigated. In this study, the conjugative transfer of ARGs between a donor strain E. coli K12 and a recipient strain E. coli HB101 was investigated in chlorination without/with the presence of Br− or I−. Immediately after the addition of sodium hypochlorite, 53–88 % of the dosed chlorine was rapidly consumed, 10 %–42 % fast transformed into organic combined chloramines, and only low levels of free chlorine (0.02–0.8 mg/L as Cl2) left in the diluted cultural medium. Conjugative transfer mediated by the RP4 plasmid was not significantly enhanced in chlorination without the presence of Br− or I−. With the presence of Br− (0.5–5.0 mg/L) or I− (0.05–0.5 mg/L) in chlorination, the co-existing free halogen oxidants and their organic combined ones up-regulated the mRNA expression of the oxidative stress-regulatory gene (rpoS), outer membrane protein gene (ompC), and conjugation-relevant genes (trbBp and trfAp), and caused more damage to cell entirety. As a result, the co-existing reactive halogen oxidants enhanced the HGT of ARGs probably via conjugative transfer and transformation. This study showed that the presence of Br− and I− of common levels in aquatic environment promoted HGT of ARGs in chlorination, thus accelerating the transmission and prevalence of ARGs.

Free chlorine formation in the process of the chlorine dioxide oxidation of aliphatic amines

Chlorine dioxide (ClO2) is commonly used as an alternative disinfectant to chlorine because it has a high bactericidal effect and may produce limited concentrations of halogenated disinfection byproducts (DBPs). However, previous studies have reported that free available chlorine (FAC) was produced when ClO2 reacted with some compounds, such as phenol, leading to the formation of halogenated DBPs. In this study aliphatic amines was found to react rapidly with ClO2 to form significant amount of FAC and its related DBPs. This study investigated the formation of FAC when ClO2 reacts with six model aliphatic amines (including primary amines, secondary amines and tertiary amines). FAC was formed immediately as ClO2 was added to the precursor solution. The maximum yield of FAC even reached 45% (based on consumed ClO2) when ClO2 reacted with 20 μM methylamine at a dose of 10 μM, which is close to a realistic maximum dose (about 0.8 mg/L) in the U.S.. The reactivity of amines to result FAC follows the sequence tertiary amines < secondary amines < primary amines. It was verified that the addition of aliphatic amines may enhance the formation of FAC during ClO2 oxidation in actual water samples. Organic chloramines and other chlorinated DBPs, such as cyanogen chloride, were detected when ClO2 was used as the sole oxidant of real water samples. This study demonstrated that chlorine-related byproducts may also be formed in the presence of organic amines during ClO2 treatment.

A new outlook in oxidative transformations and coupling reactions via in situ generation of organic chloramines

Owing to their various modes of coordinating and oxidizing reactivity, organic chloramines represent versatile building blocks for the synthesis of an ample range of multiatomic organic compounds. The present review focuses on synthetic methodologies using their dichotomous nature, which is the basis of their reactivity as oxidant and substrate. This is the first ever review covering the extensive applications of this large class of N–Cl compounds (organic chloramines) especially using one‐pot reaction strategies for various organic transformations, and construction of bonds such as chlorination (C–Cl, S–Cl), oxidation (C=O), cross‐coupling (C–N, CONR, S–N), cyclization, substitution, rearrangement, and catalysis, have been described, briefly to highlight important aspects of the organic chloramines in organic synthesis.

Comparison of iodinated disinfection by-product formation from the reaction of chlorine, monochloramine, and organic chloramine with seaweed salt during a simulated household cooking process

Here, the effects of key factors on I-DBP formation with seaweed salt during the household cooking process were ascertained. And its potential public health risk was confirmed by cytotoxicity tests.

Activation of organic chloramine by UV photolysis: A non-negligible oxidant for micro-pollutant abatement and disinfection by-product formation

Due to the wide-presence of organic amines in natural waters, organic chloramines are commonly formed during (pre-)chlorination. With the increasing application of UV disinfection in water treatment, both the activation mechanism of organic chloramine by UV photolysis and its subsequent impact on water quality are not clear. Using sarcosine (Sar) as an amine group-containing compound, it was found that organic chloramines (i.e., Cl-Sar) would be firstly formed during chlorination even in the presence of natural organic matter. Compared with self-decay of Cl-Sar, UV photolysis accelerated Cl-Sar decomposition and induced NCl bond cleavage. Using metoprolol (MTP) as a model micro-pollutant, UV-activated Cl-Sar (UV/Cl-Sar) can accelerate micro-pollutant degradation, attributed to reactive radicals formation. HO• and Cl• were important contributors, with a total contribution of 45%‒64%. Moreover, the degradation rate of MTP by UV/Cl-Sar was pH-dependent, which monotonically increased from 0.044 to 0.065 min‒1 under pHs 5.5‒8.5. Although the activation of organic chloramine by UV could accelerate micro-pollutant degradation, UV/Cl-Sar treatment could also enhance disinfection by-products formation. Trichloromethane (TCM) formation was observed during MTP degradation by UV/Cl-Sar. After post-chlorination, TCM, 1,1-dichloropropanone, 1,1,1-trichloropropanone, and dichloroacetonitrile were detected. Their individual and total concentrations were all positively proportional to UV/Cl-Sar treatment time. The total concentration with 30 min treatment (66.93 μg L‒1) was about 2.3 times that with 1 min treatment (28.76 μg L‒1). Finally, the accelerated effect was verified with Cl-glycine and Cl-alanine. It is expected to unravel the non-negligible role of organic chloramine on water quality during UV disinfection.

Organic chloramines formation from algal organic matters: Insights from Fourier transform-ion cyclotron resonance mass spectrometry

Release of algal organic matter (AOM) from algae poses great threats to drinking water safety. As organic nitrogen in AOM is relatively higher compared to natural organic matter (NOM), the organic chloramine formation during chlorination cause overestimation of effective chlorine, which may lead to a biological risk. This study compared the organic chloramine formation from AOM and NOM, and confirmed that AOM tend to form more organic chloramines during chlorination. Furthermore, it was found that hydrophilic fraction and high molecular weight (>100 kDa) fraction of AOM generated major organic chloramines due to a high content of protein. Based on the results of Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), Spearman's rank correlation was used to analyze the relationship between molecular composition of AOM and organic chloramine formation. Notably, molecules with high correlation to organic chloramine formation located in a triangle region of van Krevelen diagram, which is a typical area of peptides. Therefore, it indicates that the precursors of organic chloramine in AOM are mainly proteins/peptides, and appropriate treatment processes (e.g., biological treatment or membrane filtration) should be addressed to effectively remove the precursors before chlorination.

Formation of organic chloramines during chlorination of 18 compounds

Organic chloramines have attracted considerable attention because of their potential toxicity and reactivity. However, the lack of suitable and effective analytical methods has limited the study of organic chloramines due to their volatile and unstable properties. In this study, membrane introduction mass spectrometry (MIMS) combined with DPD/FAS titration was used to monitor the formation of organic chloramines. N-chlorodimethylamine [(CH3)2NCl] and N-chlorodiethylamine [(C2H5)2NCl] were detected and identified as the dominant volatile DBPs during chlorination of 18 organic compounds with dimethylamine or diethylamine functional groups, with yields ranging from 0.3% to 51.1% at a chlorine to precursor (Cl/P) molar ratio of 8.0. (CH3)2NBr was formed in the presence of bromide, while the formation of (CH3)2NCl was decreased. The reaction of phenol with (CH3)2NCl combined with theoretical calculations confirmed that the reactivity of (CH3)2NCl was similar to that of monochloramine. Moreover, (CH3)2NCl and (C2H5)2NCl were observed at the ppb level during chlorination of actual water samples collected from different areas. The results suggest that (CH3)2NCl and (C2H5)2NCl are important organic chloramines during chlorination, which may lead to the occurrence of further oxidation reactions and promote the formation of other disinfection byproducts simultaneously and should be of concern.

Formation and control of organic chloramines and disinfection by-products during the degradation of pyrimidines and purines by UV/chlorine process in water

Pyrimidine and purine bases (adenine, cytosine, guanine and thymine) are important precursors of organic chloramines (OC) and disinfection by-products (DBPs) during chlor(am)ination. In this study, OC and DBP formation derived from pyrimidine and purine bases during chlor(am)ination, post-chlor(am)ination after pretreated by UV alone and UV/chlorination were systematically investigated with ultraviolet light-emitting diodes (UV-LEDs, 265 and 275 nm) and low pressure mercury lamp (LPUV, 254 nm). The results revealed that higher OC formation was observed during chlorination than that during chloramination of pyrimidine and purine bases. The degradation of pyrimidine and purine bases followed the pseudo-first-order kinetics. Both solution pH and UV wavelength played vital influence on the degradation of pyrimidine and purine bases. In terms of fluence-based rate constants (kobs), the degradation rates of pyrimidine and purine bases decreased in the order of 275 nm > 265 nm > 254 nm in alkaline conditions. The synergistic effects of kobs, chlorine,kobs, •OH and kobs, RCS contributed to the differences of pyrimidine and purine bases degradation at different pH values and UV wavelengths. A vital suppression of OC formation was observed during post-chlorination after pretreated by 275 nm UV-LED/chlorination. In addition, compared with LPUV (254 nm), less DBP formation was observed at UV-LED (275 nm), especially during the UV/chlorine process. The phenomena obtained in this study indicated that 275 nm UV-LED combined with chlorine could be a preferred method to promote pyrimidine and purine bases degradation and control OC and DBP formation in practical water treatment.

UV-induced activation of organic chloramine: Radicals generation, transformation pathway and DBP formation

Organic chloramines of little disinfection efficacy commonly exist in disinfection process (chlor(am)ination) due to the wide presence of organic amines in water, of which N-chlorodimethylamine (CDMA) is a typical one. For the first time, UV photolysis for the activation of CDMA was investigated. UV photolysis caused the cleavage of N-Cl bond in CDMA to form Cl• and subsequently HO•, both of which are dominant contributors to the destruction of model contaminant bisphenol A (BPA). Typical spectra of HO• were detected by electron paramagnetic resonance (EPR) experiments, while spectra of reactive nitrogen species (RNS) were not detected during UV photolysis of CDMA. The increase of pH (6.0–8.0), HCO3−/CO32−, Cl− and nature organic matter inhibited the degradation of BPA. We proposed pathways of CDMA and BPA degradation based on the identified transformation products. UV photolysis of CDMA and BPA reduced the formation of N-nitrosodimethylamine (NDMA) at pH 8.0, but increased the formation of trichloronitromethane (TCNM) at pH 7.0 and 8.0. The increasing toxicity and the formation of TCNM and NDMA gave us a hint that formation of organic chloramines should be concerned.