HOCl forms lipid N-chloramines in cell membranes of bacteria and immune cells.

Neutrophils orchestrate a coordinated attack on bacteria, combining phagocytosis with a potent cocktail of oxidants, including the highly toxic hypochlorous acid (HOCl), renowned for its deleterious effects on proteins. Here, we examined the occurrence of lipid N-chloramines in vivo, their biological activity, and their neutralization. Using a chemical probe for N-chloramines, we demonstrate their formation in the membranes of bacteria and monocytic cells exposed to physiologically relevant concentrations of HOCl. N-chlorinated model membranes composed of phosphatidylethanolamine, the major membrane lipid in Escherichia coli and an important component of eukaryotic membranes, exhibited oxidative activity towards the redox-sensitive protein roGFP2, suggesting a role for lipid N-chloramines in protein oxidation. Conversely, glutathione a cellular antioxidant neutralized lipid N-chloramines by removing the chlorine moiety. In line with that, N-chloramine stability was drastically decreased in bacterial cells compared to model membranes. We propose that lipid N-chloramines, like protein N-chloramines, are involved in inflammation and accelerate the host immune response.

N-Chlorotaurine Solutions as Agents for Infusion Detoxification Therapy: Preclinical Studies.

N-chlorotaurine (NCT) is a broad-spectrum antimicrobial agent with outstanding tolerability, effective for topical and inhalation use. This paper presents the results of studies of single and repeated intravenous infusions of NCT to laboratory animals. The studies were conducted on female Wistar Han rats. The effect of NCT infusions on the general condition, behavioral reactions, main biochemical and hematological parameters, hemocoagulation system, cardiovascular system, and on the condition of the internal organs was studied. It was found that NCT infusions do not reveal deviations in the studied parameters that could indicate a toxic effect. The estimated LD50 is more than 80 mg/kg. In a subchronic experiment, a statistically significant decrease in cholesterol (by up to 11%), glucose (by up to 15%) and excess bases (up to four times) in the blood, and an increase in heart rate (by up to 31%) and frequency of defecations (by up to 35%), as well as pronounced antiplatelet effect, were found. In animals with simulated endotoxicosis, a decrease in the cytolysis and oxidative stress markers was observed. Such effects are caused by both chlorine-active compounds and taurine.The results obtained indicate broad prospects for the use of NCT solutions as an infusion detoxifying agent.

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.

UV-chlorine advanced oxidation for potable water reuse: A review of the current state of the art and research needs.

This paper reports conclusions from a recent study completed for the Water Research Foundation and the State of California to offer guidance on UV-chlorine advanced oxidation for potable water reuse. The fundamentals of UV-chlorine advanced oxidation are discussed, and lessons learned from some of the early adopters of this technology are presented. Important highlights include the significant impact of ammonia and chloramines on UV-chlorine treatment, challenges associated with predicting UV-chlorine performance due to complex photochemistry, and an ongoing need to monitor potential byproducts and transformation products when employing any form of advanced oxidation for potable reuse.

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.

Toxicological aspect of water treated by chlorine-based advanced oxidation processes: A review.

As well established in the literature, residual toxicity is an important parameter for evaluating the sanitary and environmental safety of water treatment processes, and this parameter becomes even more crucial when chlorine-based processes are applied for water treatment. Eliminating initial toxicity or preventing its increase after water treatment remains a huge challenge mainly due to the formation of highly toxic disinfection by-products (DBPs) that stem from the degradation of organic contaminants or the interaction of the chlorine-based oxidants with different matrix components. In this review, we present a comprehensive discussion regarding the toxicological aspects of water treated using chlorine-based advanced oxidation processes (AOPs) and the recent findings related to the factors influencing toxicity, and provide directions for future research in the area. The review begins by shedding light on the advances made in the application of free chlorine AOPs and the findings from studies conducted using electrochemical technologies based on free chlorine generation. We then delve into the insights and contributions brought to the fore regarding the application of NH2Cl- and ClO2-based treatment processes. Finally, we broaden our discussion by evaluating the toxicological assays and predictive models employed in the study of residual toxicity and provide an overview of the findings reported to date on this subject matter, while giving useful insights and directions for future research on the topic.

Hypochlorous Acid and Chloramines Induce Specific Fragmentation and Cross-Linking of the G1-IGD-G2 Domains of Recombinant Human Aggrecan, and Inhibit ADAMTS1 Activity.

Atherosclerosis is a chronic inflammatory disease and a leading cause of mortality. It is characterized by arterial wall plaques that contain high levels of cholesterol and other lipids and activated leukocytes covered by a fibrous cap of extracellular matrix (ECM). The ECM undergoes remodelling during atherogenesis, with increased expression of aggrecan, a proteoglycan that binds low-density-lipoproteins (LDL). Aggrecan levels are regulated by proteases, including a disintegrin and metalloproteinase with thrombospondin motifs 1 (ADAMTS1). Activated leukocytes release myeloperoxidase (MPO) extracellularly, where it binds to proteins and proteoglycans. Aggrecan may therefore mediate colocalization of MPO and LDL. MPO generates hypochlorous acid (HOCl) and chloramines (RNHCl species, from reaction of HOCl with amines on amino acids and proteins) that damage LDL and proteins, but effects on aggrecan have not been examined. The present study demonstrates that HOCl cleaves truncated (G1-IGD-G2) recombinant human aggrecan at specific sites within the IGD domain, with these being different from those induced by ADAMTS1 which also cleaves within this region. Irreversible protein cross-links are also formed dose-dependently. These effects are limited by the HOCl scavenger methionine. Chloramines including those formed on amino acids, proteins, and ECM materials induce similar damage. HOCl and taurine chloramines inactivate ADAMTS1 consistent with a switch from proteolytic to oxidative aggrecan fragmentation. Evidence is also presented for colocalization of aggrecan and HOCl-generated epitopes in advanced human atherosclerotic plaques. Overall, these data show that HOCl and chloramines can induce specific modifications on aggrecan, and that these effects are distinct from those of ADAMTS1.

Electrochemical Dechlorination of Municipal Wastewater Effluent.

The use of sodium bisulfite as an electron donor to quench chloramine disinfectant residuals in municipal wastewater effluents prior to discharge incurs the cost of purchasing and transporting bisulfite to the utility and increases the loading of salts to the receiving water. In this study, degradation of chloramine residuals within authentic municipal wastewater effluents was achieved within a 30 min timescale using a reductive electrochemical reactor, which supplied electrons via a stainless-steel cathode under galvanostatic conditions without an ion exchange membrane separating the cathode and anode. Application of a 0.26 mA/cm2 cathodic current density reduced chloramines to ammonia and avoided oxidation at the IrO2-coated titanium anode of chloride to chlorine or chlorate and of ammonia to nitrite or nitrate. Net chloramine production was observed at a higher current density (2 mA/cm2). Chloramine degradation rates and Coulombic efficiencies were highest and electrical energy per order (EEO) values were lowest for the 304-grade stainless-steel cathode, which contains the highest nickel content, and for a stainless-steel cathode with a high surface area. Differences in ionic strength and pH were less important. For chloraminated municipal wastewater samples, the highest Coulombic efficiency was 4.1% and the lowest EEO value was 0.08 kWh/m3. An initial comparison indicated that the electricity cost associated with this EEO value would be comparable to the cost of sodium bisulfite for areas with low electricity costs.

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.

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.

Activation and Inhibition of Human Matrix Metalloproteinase-9 (MMP9) by HOCl, Myeloperoxidase and Chloramines.

Matrix metalloproteinase-9 (MMP9, gelatinase B) plays a key role in the degradation of extracellular-matrix (ECM) proteins in both normal physiology and multiple pathologies, including those linked with inflammation. MMP9 is excreted as an inactive proform (proMMP9) by multiple cells, and particularly neutrophils. The proenzyme undergoes subsequent processing to active forms, either enzymatically (e.g., via plasmin and stromelysin-1/MMP3), or via the oxidation of a cysteine residue in the prodomain (the "cysteine-switch"). Activated leukocytes, including neutrophils, generate O2- and H2O2 and release myeloperoxidase (MPO), which catalyzes hypochlorous acid (HOCl) formation. Here, we examine the reactivity of HOCl and a range of low-molecular-mass and protein chloramines with the pro- and activated forms of MMP9. HOCl and an enzymatic MPO/H2O2/Cl- system were able to generate active MMP9, as determined by fluorescence-activity assays and gel zymography. The inactivation of active MMP9 also occurred at high HOCl concentrations. Low (nM-low µM) concentrations of chloramines formed by the reaction of HOCl with amino acids (taurine, lysine, histidine), serum albumin, ECM proteins (laminin and fibronectin) and basement membrane extracts (but not HEPES chloramines) also activate proMMP9. This activation is diminished by the competitive HOCl-reactive species, methionine. These data indicate that HOCl-mediated oxidation and MMP-mediated ECM degradation are synergistic and interdependent. As previous studies have shown that modified ECM proteins can also stimulate the cellular expression of MMP proteins, these processes may contribute to a vicious cycle of increasing ECM degradation during disease development.

Electrochemical oxidation of pretreated landfill leachate nanofiltration concentrate in terms of pollutants removal and formation of by-products.

This study compares the efficiencies of active (Ti/TiO2-RuO2-IrO2 (TIR)) and inactive (Ni/Boron Doped Diamond (BDD)) anodes in terms of pollutant treatment and by-product formation in pretreated (chemical coagulation) landfill leachate nanofiltration membrane concentrate (PLNC). PLNC has high chemical oxygen demand (COD:4900 mg/L), total organic carbon (TOC: 1874 mg/L), total Kjeldahl nitrogen (TKN: 520 mg/L), ammonium nitrogen (NH3-N: 21.35 mg/L), chloride (5700 mg/L) and sulfate (9000 mg/L - due to coagulant type). The parameters of COD, TOC, NH3-N, TKN, free and combined chlorine species, halogenated organic compounds (HOCs), adsorbable organic halogens (AOX), and nitrate at different current density (J: 111-555 A/m2) and initial pH (pHi:3.5-7) were compared for both anodes. The removal efficiencies at the optimum conditions (pHi 5.5, 333 A/m2 and 8 h) were obtained as 86.4% COD, 77.4% TOC, 93.4% TKN, 94.4% NH3-N with BDD and 34.3% COD, 27.3% TOC, 93.7% TKN, 97.4% NH3-N with TIR. According to gas chromatography-mass spectrometry (GC-MS) results obtained under optimum conditions, haloalkane/alkene, halonitroalkane, halonitrile, haloketone, haloalcohols, haloacids, haloaldehydes, haloamines/amides on both electrodes were detected as species of HOCs. In addition, the highest nitrate concentration was observed at the TIR anode, while the highest AOX concentration was observed at the BDD anode.

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.

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.

Reactive Chlorine Species Reversibly Inhibit DnaB Protein Splicing in Mycobacteria.

Intervening proteins, or inteins, are mobile genetic elements that are translated within host polypeptides and removed at the protein level by splicing. In protein splicing, a self-mediated reaction removes the intein, leaving a peptide bond in place. While protein splicing can proceed in the absence of external cofactors, several examples of conditional protein splicing (CPS) have emerged. In CPS, the rate and accuracy of splicing are highly dependent on environmental conditions. Because the activity of the intein-containing host protein is compromised prior to splicing and inteins are highly abundant in the microbial world, CPS represents an emerging form of posttranslational regulation that is potentially widespread in microbes. Reactive chlorine species (RCS) are highly potent oxidants encountered by bacteria in a variety of natural environments, including within cells of the mammalian innate immune system. Here, we demonstrate that two naturally occurring RCS, namely, hypochlorous acid (the active compound in bleach) and N-chlorotaurine, can reversibly block splicing of DnaB inteins from Mycobacterium leprae and Mycobacterium smegmatis in vitro. Further, using a reporter that monitors DnaB intein activity within M. smegmatis, we show that DnaB protein splicing is inhibited by RCS in the native host. DnaB, an essential replicative helicase, is the most common intein-housing protein in bacteria. These results add to the growing list of environmental conditions that are relevant to the survival of the intein-containing host and influence protein splicing, as well as suggesting a novel mycobacterial response to RCS. We propose a model in which DnaB splicing, and therefore replication, is paused when these mycobacteria encounter RCS. IMPORTANCE Inteins are both widespread and abundant in microbes, including within several bacterial and fungal pathogens. Inteins are domains translated within host proteins and removed at the protein level by splicing. Traditionally considered molecular parasites, some inteins have emerged in recent years as adaptive posttranslational regulatory elements. Several studies have demonstrated CPS, in which the rate and accuracy of protein splicing, and thus host protein functions, are responsive to environmental conditions relevant to the intein-containing organism. In this work, we demonstrate that two naturally occurring RCS, including the active compound in household bleach, reversibly inhibit protein splicing of Mycobacterium leprae and Mycobacterium smegmatis DnaB inteins. In addition to describing a new physiologically relevant condition that can temporarily inhibit protein splicing, this study suggests a novel stress response in Mycobacterium, a bacterial genus of tremendous importance to humans.

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.

N-chlorotaurine, a potent weapon against multiresistant bacteria.

AIMS: N-chlorotaurine (NCT) is a body-own mild oxidizing antiseptic that can be applied topically as a well-tolerated anti-infective at many body sites. The objective of this study was to demonstrate its activity against representative nosocomial multidrug-resistant bacteria. METHODS AND RESULTS: The bactericidal activity of NCT was tested in quantitative killing assays against a panel of multiresistant Gram-positive and Gram-negative clinical isolates. N-chlorotaurine (1%, 55 mmol l-1 ) reduced the number of CFU of strains of methicillin-resistant Staphylococcus aureus, linezolid-resistant Staphylococcus epidermidis, vancomycin-resistant, and linezolid- and vancomycin-resistant Enterococcus faecium, 3MRGN and 4MRGN Escherichia coli, Pseudomonas aeruginosa, Acinetobacter baumannii and Klebsiella pneumoniae by at least 2 log10 steps after 15 min and completely or nearly to the detection limit after 30 min at pH 7·1 and 37°C. CONCLUSION: The activity of NCT against these clinical isolates is similar to that against non-resistant ATCC strains and therefore not influenced by antibiotic resistance. This can be explained by the oxidizing and chlorinating mechanism of action of NCT, which leads to an attack of multiple targets in the microorganisms. SIGNIFICANCE AND IMPACT OF THE STUDY: The bactericidal spectrum of NCT is not restricted by resistance against antibiotics. Therefore, it can be used against resistant strains, too.

N-Nitrosodimethylamine Formation during UV/Hydrogen Peroxide and UV/Chlorine Advanced Oxidation Process Treatment Following Reverse Osmosis for Potable Reuse.

Chloramines applied to control microfiltration and reverse osmosis (RO) membrane biofouling in potable reuse trains form the potent carcinogen, N-nitrosodimethylamine (NDMA). In addition to degrading other contaminants, UV-based advanced oxidation processes (AOPs) strive to degrade NDMA by direct photolysis. The UV/chlorine AOP is gaining attention because of its potential to degrade other contaminants at lower UV fluence than the UV/hydrogen peroxide AOP, although previous pilot studies have observed that the UV/chlorine AOP was less effective for NDMA control. Using dimethylamine (DMA) as a model precursor and secondary municipal wastewater effluent, this study evaluated NDMA formation during the AOP treatment via two pathways. First, NDMA formation by UV treatment of monochloramine (NH2Cl) and chlorinated DMA (Cl-DMA) passing through RO membranes was maximized at 350 mJ/cm2 UV fluence, declining at higher fluence, where NDMA photolysis outweighed NDMA formation. Second, this study demonstrated that chlorine addition to the chloramine-containing RO permeate during the UV/chlorine AOP treatment initiated rapid NDMA formation by dark breakpoint reactions associated with reactive intermediates from the hydrolysis of dichloramine. At pH 5.7, this formation was maximized at a chlorine/ammonia molar ratio of 3 (out of 0-10), conditions typical for UV/chlorine AOPs. At 700 mJ/cm2 UV fluence, which is applicable to current practice, NDMA photolysis degraded a portion of the NDMA formed by breakpoint reactions. Lowering UV fluence to ∼350 mJ/cm2 when switching to the UV/chlorine AOP exacerbates effluent NDMA concentrations because of concurrent NDMA formation via the UV/NH2Cl/Cl-DMA and breakpoint chlorination pathways. Fluence >700 mJ/cm2 or chlorine doses greater than the 3:1 chlorine/ammonia molar ratios under consideration for the UV/HOCl AOP treatment are needed to achieve NDMA control.

The influence of chlorine in indoor swimming pools on the composition of breathing phase of professional swimmers.

OBJECTIVES: Swimming is one of the most popular forms of physical activity. Pool water is cleaned with chlorine, which - in combination with compounds contained in water - could form chloramines and trichloromethane in the swimmer's lungs. The aim of the present study was to examine the effect of swimming training in an indoor pool on the composition of swimmers' respiratory phase metabolomics, and develop a system to provide basic information about its impact on the swimmer's airway mucosa metabolism, which could help to assess the risk of secondary respiratory tract diseases i.e. sport results, condition, and health including lung acute and chronic diseases). DESIGN: A group of competitive swimmers participated in the study and samples of their respiratory phase before training, immediately after training, and 2 h after training were assessed. METHODS: Sixteen male national and international-level competitive swimmers participated in this study. Respiratory phase analysis of the indoor swimming pool swimmers was performed. Gas chromatography combined with mass spectrometry (GCMS) was used in the measurements. All collected data were transferred to numerical analysis for trends of tracking and mapping. The breathing phase was collected on special porous material and analyzed using GCMS headspace. RESULTS: The obtained samples of exhaled air were composed of significantly different metabolomics when compared before, during and after exercise training. This suggests that exposition to indoor chlorine causes changes in the airway mucosa. CONCLUSION: This phenomenon may be explained by occurrence of a chlorine-initiated bio-reaction in the swimmers' lungs. The obtained results indicate that chromatographic exhaled gas analysis is a sensitive method of pulmonary metabolomic changes assessment. Presented analysis of swimmers exhaled air indicates, that indoor swimming may be responsible for airway irritation caused by volatile chlorine compounds and their influence on lung metabolism.

Development of an automated system for the analysis of inorganic chloramines in swimming pools via multi-syringe chromatography and photometric detection with ABTS.

Inorganic chloramines are disinfection by-products resulting from the unwanted reaction between chlorine used as disinfectant in swimming pools and nitrogenous compounds brought by bathers. This parameter (total chloramines or combined chlorine) is currently measured on site by a colorimetric method that does not allow to measure only inorganic chloramines. In this paper, a multi-syringe chromatography system combined with a post column derivatization is applied for the first time for the specific detection of the three individual inorganic chloramines (monochloramine, dichloramine and trichloramine). These latter ones are separated using a low-pressure monolithic C18 column, and separately detected after a post-column reaction with the chromogenic reagent ABTS (2,2'-azino-bis-(3-ethyl-benzothiazoline)-6-sulfonic acid-diammonium salt). Development of two ABTS reagents provides discrimination of chlorine and monochloramine that are not separated on the column. Optimization of the experimental conditions enables determination of inorganic chloramines with very good detection limits (around 10 µg eq.Cl2 L-1) without interferences from other chlorinated compounds such as organic chloramines or free available chlorine. The validation of the whole procedure has been successfully applied to real swimming pools samples.