Reaction of Amino Acids with Ferrate(VI): Impact of the Carboxylic Group on the Primary Amine Oxidation Kinetics and Mechanism.

Ferrate (Fe(VI)) is a novel oxidant that can be used to mitigate disinfection byproduct (DBP) precursors. However, the reaction of Fe(VI) with organic nitrogen, which is a potential precursor of potent nitrogenous DBPs, remains largely unexplored. The present work aimed to identify the kinetics and products for the reaction of Fe(VI) with primary amines, notably amino acids. A new kinetic model involving ionizable intermediates was proposed and can describe the unusual pH effect on the Fe(VI) reactivity toward primary amines and amino acids. The Fe(VI) oxidation of phenylalanine produced a mixture of nitrile, nitrite/nitrate, amide, and ammonia, while nitroalkane was an additional product in the case of glycine. The product distribution for amino acids significantly differed from that of uncarboxylated primary amines that mainly generate nitriles. A general reaction pathway for primary amines and amino acids was proposed and notably involved the formation of imines, the degradation of which was affected by the presence of a carboxylic group. In comparison, ozonation led to higher yields of nitroalkanes that could be readily converted to potent halonitroalkanes during chlor(am)ination. Based on this study, Fe(VI) can effectively mitigate primary amine-based, nitrogenous DBP precursors with little formation of toxic halonitroalkanes.

Chemical analysis of fresh and aged Australian e-cigarette liquids.

OBJECTIVES: To assess the chemical composition of electronic cigarette liquids (e-liquids) sold in Australia, in both their fresh and aged forms. DESIGN, SETTING: Gas chromatography-mass spectrometry analysis of commercial e-liquids sold in Australia (online and physical stores). MAIN OUTCOME MEASURES: Chemical composition of 65 Australian e-liquids - excipients/solvents, flavouring chemicals, other known e-liquid constituents (including nicotine), and polycyclic aromatic hydrocarbons - before and after an accelerated ageing process that simulated the effects of vaping. RESULTS: The measured levels of propylene glycol and glycerol often diverged from those recorded on the e-liquid label. All e-liquids contained one or more potentially harmful chemicals, including benzaldehyde, menthol, trans-cinnamaldehyde, and polycyclic aromatic hydrocarbons. Nicotine or nicotyrine were detected in a small proportion of e-liquids at extremely low concentrations. CONCLUSIONS: Australian e-liquids contain a wide variety of chemicals for which information on inhalation toxicity is not available. Further analyses are required to assess the potential long term effects of e-cigarette use on health.

Mechanistic and Kinetic Understanding of the UV254 Photolysis of Chlorine and Bromine Species in Water and Formation of Oxyhalides.

This study investigated the UV254 photolysis of free available chlorine and bromine species in water. The intrinsic quantum yields for •OH and X• (X = Cl or Br) generation were determined by model fitting of formaldehyde formation using a tert-butanol assay to be 0.61/0.45 for HOCl/OCl- and 0.32/0.43 for HOBr/OBr-. The steady-state •OH concentration in UV/HOX was higher than that in UV/OX- by a factor of 23.3 and 7.8 for Cl and Br, respectively. This was attributed to the different •OH consumption rate by HOCl versus OCl-, while for HOBr/OBr-, both the •OH formation and consumption rates were implied. This was supported by a k of 1.4 × 108 M-1 s-1 for the •OH reaction with HOCl, which was >14 times less than the k for •OH reactions with OCl-, HOBr, and OBr-. Formation of ClO3- and BrO3- was found to be significant with apparent quantum yields of 0.12-0.23. A detailed mechanistic study on the formation of XO3- including a new pathway involving XO• is presented, which has important implications as the level of XO3- can exceed the regulation (BrO3-) or guideline (ClO3-) values during UV/halogen oxidant water treatment. Our new kinetic models well simulate the experimental results for the halogen oxidant decomposition, probe compound degradation, and formation of ClO3- and BrO3-.

Ozone combined with ceramic membranes for water treatment: Impact on HO radical formation and mitigation of bromate.

The beneficial effect of combining ozone with ceramic membrane filtration (CMF) to enhance membrane flux performances during water treatment (e.g., wastewater and drinking water) could be related to the formation of hydroxyl (HO) radicals from the interaction of ozone with ceramic membrane. To explore this effect, para-chlorobenzoic acid was used to probe HO radical activity during a combined ozone/CMF process using a 0.1 µm pore size membrane supplied by Metawater, Japan. Tests were then extended to explore the impact on bromate formation downstream CMF, a well-known undesirable by-product from ozone use in water treatment. Ozone reduction by the membrane and its module appeared to be more associated with physical degassing, but a noticeable formation of HO radicals was observed during the interaction of ozone with the ceramic membrane. CMF treatment of ozonated potable water containing bromide showed a reduced bromate formation of 50% when the water was recirculated to the filtration module containing the ceramic membrane, compared to the experiment performed with an empty module. Single pass experiments showed bromate mitigation of around 10%. The mitigation of bromate formation was attributed to reduced overall ozone exposure by deagassing effect, but also potentially from suppression of the oxidation of Br- and HOBr/BrO- to BrO3- due to the catalytic degradation of ozone via a HO radical pathway.

In Situ Formation of Free Chlorine During ClO2 Treatment: Implications on the Formation of Disinfection Byproducts.

Chlorine dioxide (ClO2) is commonly used as an alternative disinfectant to chlorine in drinking water treatment because it produces limited concentrations of halogenated organic disinfection byproducts. During drinking water treatment, the primary ClO2 byproducts are the chlorite (50-70%) and the chlorate ions (0-30%). However, a significant portion of the ClO2 remains unaccounted for. This study demonstrates that when ClO2 was reacting with phenol, one mole of free available chlorine (FAC) was produced per two moles of consumed ClO2. The in situ formed FAC completed the mass balance on Cl for inorganic ClO2 byproducts (FAC + ClO2- + ClO3-). When reacting with organic matter extracts at near neutral conditions (pH 6.5-8.1), ClO2 also yielded a significant amount of FAC (up to 25%). Up to 27% of this in situ formed FAC was incorporated in organic matter forming adsorbable organic chlorine, which accounted for up to 7% of the initial ClO2 dose. Only low concentrations of regulated trihalomethanes were produced because of an efficient mitigation of their precursors by ClO2 oxidation. Conversely, dichloroacetonitrile formation from ClO2-induced generation of FAC was higher than from addition of FAC in absence of ClO2. Overall, these findings provide important information on the formation of FAC and disinfection byproducts during drinking water treatment with ClO2.

Method Development for Quantification of Bromochloramine Using Membrane Introduction Mass Spectrometry.

During chloramination of bromide-containing waters, the main brominated amine formed is bromochloramine (NHBrCl). To date, there is no analytical method, free of interference, allowing its accurate quantification. The major reason is that it is not possible to produce a pure NHBrCl solution. In this study, we report a method allowing the accurate quantification of NHBrCl with membrane introduction mass spectrometry (MIMS). First, the molar absorption coefficient for NHBrCl was determined by quantifying NHBrCl as 2,4,6-tribromophenol by HPLC-UV and comparing the results with the direct UV response at 320 nm. A molar absorption coefficient of 304 M-1cm-1 was obtained. The results obtained by direct UV measurements were compared to the MIMS signal recorded at m/ z 131 corresponding to the mass of the molecular ion and used to establish a calibration curve. A limit of detection of 2.9 µM (378 µg/L) was determined. MIMS is the only method enabling the unambiguous quantification of NHBrCl, as it is based on m/ z 131, while with other analytical techniques, other halamines can interfere, i.e., overlapping peaks with direct UV measurements and reaction of several halamines with colorimetric reagents or phenols. While the detection limit is not quite low enough to measure NHBrCl in actual drinking water, this analytical method will benefit the scientific community by allowing further mechanistic studies on the contribution of NHBrCl to the formation of toxic disinfection by-products.

Reactions of Ferrate(VI) with Iodide and Hypoiodous Acid: Kinetics, Pathways, and Implications for the Fate of Iodine during Water Treatment.

Oxidative treatment of iodide-containing waters can form toxic iodinated disinfection byproducts (I-DBPs). To better understand the fate of iodine, kinetics, products, and stoichiometries for the reactions of ferrate(VI) with iodide (I-) and hypoiodous acid (HOI) were determined. Ferrate(VI) showed considerable reactivities to both I- and HOI with higher reactivities at lower pH. Interestingly, the reaction of ferrate(VI) with HOI ( k = 6.0 × 103 M-1 s-1 at pH 9) was much faster than with I- ( k = 5.6 × 102 M-1 s-1 at pH 9). The main reaction pathway during treatment of I--containing waters was the oxidation of I- to HOI and its further oxidation to IO3- by ferrate(VI). However, for pH > 9, the HOI disproportionation catalyzed by ferrate(VI) became an additional transformation pathway forming I- and IO3-. The reduction of HOI by hydrogen peroxide, the latter being produced from ferrate(VI) decomposition, also contributes to the I- regeneration in the pH range 9-11. A kinetic model was developed that could well simulate the fate of iodine in the ferrate(VI)-I- system. Overall, due to a rapid oxidation of I- to IO3- with short-lifetimes of HOI, ferrate(VI) oxidation appears to be a promising option for I-DBP mitigation during treatment of I--containing waters.

Mechanistic Aspects of the Formation of Adsorbable Organic Bromine during Chlorination of Bromide-containing Synthetic Waters.

During chlorination of bromide-containing waters, a significant formation of brominated disinfection byproducts is expected. This is of concern because Br-DBPs are generally more toxic than their chlorinated analogues. In this study, synthetic water samples containing dissolved organic matter (DOM) extracts and bromide were treated under various disinfection scenarios to elucidate the mechanisms of Br-DBP formation. The total concentration of Br-DBPs was measured as adsorbable organic bromine (AOBr). A portion of the bromine (HOBr) was found to react with DOM via electrophilic substitution (≤40%), forming AOBr, and the remaining HOBr reacted with DOM via electron transfer with a reduction of HOBr to bromide (≥60%). During chlorination, the released bromide is reoxidized (recycled) by chlorine to HOBr, leading to further electrophilic substitution of unaltered DOM sites and chlorinated DOM moieties. This leads to an almost complete bromine incorporation to DOM (≥87%). The type of DOM (3.06 ≤ SUVA254 ≤ 4.85) is not affecting this process, as long as the bromine-reactive DOM sites are in excess and a sufficient chlorine exposure is achieved. When most reactive sites were consumed by chlorine, Cl-substituted functional groups (Cl-DOM) are reacting with HOBr by direct bromination leading to Br-Cl-DOM and by bromine substitution of chlorine leading to Br-DOM. The latter finding was supported by hexachlorobenzene as a model compound from which bromoform was formed during HOBr treatment. To better understand the experimental findings, a conceptual kinetic model allowing to assess the contribution of each AOBr pathway was developed. A simulation of distribution system conditions with a disinfectant residual of 1 mgC2 L-1 showed complete conversion of Br- to AOBr, with about 10% of the AOBr formed through chlorine substitution by bromine.

Halogen-specific total organic halogen analysis: Assessment by recovery of total bromine.

Determination of halogen-specific total organic halogen (TOX) is vital for studies of disinfection of waters containing bromide, since total organic bromine (TOBr) is likely to be more problematic than total organic chlorine. Here, we present further halogen-specific TOX method optimisation and validation, focusing on measurement of TOBr. The optimised halogen-specific TOX method was validated based on the recovery of model compounds covering different classes of disinfection by-products (haloacetic acids, haloacetonitriles, halophenols and halogenated benzenes) and the recovery of total bromine (mass balance of TOBr and bromide concentrations) during disinfection of waters containing dissolved organic matter and bromide. The validation of a halogen-specific TOX method based on the mass balance of total bromine has not previously been reported. Very good recoveries of organic halogen from all model compounds were obtained, indicating high or complete conversion of all organic halogen in the model compound solution through to halide in the absorber solution for ion chromatography analysis. The method was also successfully applied to monitor conversion of bromide to TOBr in a groundwater treatment plant. An excellent recovery (101%) of total bromine was observed from the raw water to the post-chlorination stage. Excellent recoveries of total bromine (92%-95%) were also obtained from chlorination of a synthetic water containing dissolved organic matter and bromide, demonstrating the validity of the halogen-specific TOX method for TOBr measurement. The halogen-specific TOX method is an important tool to monitor and better understand the formation of halogenated organic compounds, in particular brominated organic compounds, in drinking water systems.

Mechanistic Study on the Formation of Cl-/Br-/I-Trihalomethanes during Chlorination/Chloramination Combined with a Theoretical Cytotoxicity Evaluation.

Chlorination followed by chloramination can be used to mitigate the formation of potentially toxic iodinated disinfection byproducts (I-DBPs) while controlling the formation of regulated chloro-bromo-DBPs (Cl-/Br-DBPs). Water samples containing dissolved organic matter (DOM) isolates were subjected to 3 disinfection scenarios: NH2Cl, prechlorination followed by ammonia addition, and HOCl alone. A theoretical cytotoxicity evaluation was carried out based on the trihalomethanes (THMs) formed. This study demonstrates that the presence of bromide not only enhances the yield and rate of iodate formation, it also increases the formation of brominated I-THM precursors. A shift in the speciation from CHCl2I to the more toxic CHBr2I, as well as increased iodine incorporation in THMs, was observed in the presence of bromide. For low bromide concentrations, a decrease in I-THM formation and theoretical cytotoxicity was achieved only for high prechlorination times, while for high bromide concentrations, a short prechlorination time enabled the full conversion of iodide to iodate. For low DOM concentrations or DOM with low reactivity, Br-/I-THMs were preferentially formed for short prechlorination times, inducing high cytotoxicity. However, for high chlorine exposures, the cytotoxicity induced by the formation of regulated THMs might outweigh the benefit of I-THM mitigation. For high DOM concentrations or DOM with higher reactivity, mixed I-THMs were formed together with high concentrations of regulated THMs. In this case, based on the cytotoxicity of the THMs formed, the use of NH2Cl is recommended.

Iodate and iodo-trihalomethane formation during chlorination of iodide-containing waters: role of bromide.

The kinetics of iodate formation is a critical factor in mitigation of the formation of potentially toxic and off flavor causing iodoorganic compounds during chlorination. This study demonstrates that the formation of bromine through the oxidation of bromide by chlorine significantly enhances the oxidation of iodide to iodate in a bromide-catalyzed process. The pH-dependent kinetics revealed species specific rate constants of k(HOBr + IO(-)) = 1.9 × 10(6) M(-1) s(-1), k(BrO(-) + IO(-)) = 1.8 × 10(3) M(-1) s(-1), and k(HOBr + HOI) < 1 M(-1) s(-1). The kinetics and the yield of iodate formation in natural waters depend mainly on the naturally occurring bromide and the type and concentration of dissolved organic matter (DOM). The process of free chlorine exposure followed by ammonia addition revealed that the formation of iodo-trihalomethanes (I-THMs), especially iodoform, was greatly reduced by an increase of free chlorine exposure and an increase of the Br(-)/I(-) ratio. In water from the Great Southern River (with a bromide concentration of 200 µg/L), the relative I-incorporation in I-THMs decreased from 18 to 2% when the free chlorine contact time was increased from 2 to 20 min (chlorine dose of 1 mg Cl(2)/L). This observation is inversely correlated with the conversion of iodide to iodate, which increased from 10 to nearly 90%. Increasing bromide concentration also increased the conversion of iodide to iodate: from 45 to nearly 90% with a bromide concentration of 40 and 200 µg/L, respectively, and a prechlorination time of 20 min, while the I-incorporation in I-THMs decreased from 10 to 2%.

Kinetic and mechanistic understanding of chlorite oxidation during chlorination: Optimization of ClO2 pre-oxidation for disinfection byproduct control.

Chlorine dioxide (ClO2) applications to drinking water are limited by the formation of chlorite (ClO2-) which is regulated in many countries. However, when ClO2 is used as a pre-oxidant, ClO2- can be oxidized by chlorine during subsequent disinfection. In this study, a kinetic model for the reaction of chlorine with ClO2- was developed to predict the fate of ClO2- during chlorine disinfection. The reaction of ClO2- with chlorine was found to be highly pH-dependent with formation of ClO3- and ClO2 in ultrapure water. In presence of dissolved organic matter (DOM), 60-70% of the ClO2- was transformed to ClO3- during chlorination, while the in situ regenerated ClO2 was quickly consumed by reaction with DOM. The remaining 30-40% of the ClO2- first reacted to ClO2 which then formed chlorine from the DOM-ClO2 reaction. Since only part of the ClO2- was transformed to ClO3-, the sum of the molar concentrations of oxychlorine species (ClO2- + ClO3-) decreased during chlorination. By kinetic modelling, the ClO2- concentration after 24 h of chlorination was accurately predicted in synthetic waters but was largely overestimated in natural waters, possibly due to a ClO2- decay enhanced by high concentrations of chloride and in situ formed bromine from bromide. Understanding the chlorine-ClO2- reaction mechanism and the corresponding kinetics allows to potentially apply higher ClO2 doses during the pre-oxidation step, thus improving disinfection byproduct mitigation while keeping ClO2-, and if required, ClO3- below the regulatory limits. In addition, ClO2 was demonstrated to efficiently degrade haloacetonitrile precursors, either when used as pre-oxidant or when regenerated in situ during chlorination.

Kinetic modelling of the bromine-ammonia system: Formation and decomposition of bromamines.

Bromamines i.e. monobromamine (NH2Br), dibromamine (NHBr2), and tribromamine (NBr3) can be formed during oxidative treatment of waters containing bromide and ammonia. The formation and decomposition of bromamines in aqueous solution was investigated and a comprehensive kinetic model of the bromine-ammonia system was developed at 23 ± 1 °C. Determination of rate constants and model validation were primarily performed at pH 8.0 - 8.3 for subsequent application to seawater disinfection. The rate constant of NHBr2 self-decomposition was determined by second-order rate law linearization with k9 = 5.5 (± 0.8) M-1s-1 at pH 8.10. The rate constant of NBr3 self-decomposition increased proportionately to the concentration of hydroxide ions (OH-) according to the equation k10 = 4.4 (± 0.1) × 107. [OH-] over the pH range 6.0 - 8.5, which gave k10 = 56 (± 1) M-1s-1 at pH 8.10. The rate constants of NHBr2 and NBr3 formation were obtained by fitting model-predicted data to the experimental results and were found to be k3 = 2.3 (± 0.2) × 104M-1s-1 and k5 = 4.0 (± 0.6) × 103M-1s-1, respectively at pH 8.10. NBr3 was also found to react with NHBr2 with k11 = 3.4 (± 0.2) × 103M-1s-1 at pH 8.10. A kinetic model was proposed based on these experimental rate constants and literature values, which provided a good prediction of bromamines formation and decomposition for various initial bromine and ammonia concentrations. The kinetic model was also used to accurately predict the total oxidant concentration and the speciation of bromamines during breakpoint bromination. This study provides kinetic data to model more complex oxidative systems such as seawater chlorination in the presence of ammonia.

Brominated trihalamines in chlorinated seawaters: Quantification of tribromamine and identification of bromochloramines by Membrane Introduction Mass Spectrometry.

During chlorination of seawater, the presence of bromide and ammonia alters the speciation of the oxidant and lead to the formation of chlorinated and brominated amines. This can affect the effectiveness of the disinfection treatment and the formation of disinfection by-products released to the environment. In this study, a Membrane Introduction Mass Spectrometry (MIMS) analytical method was developed to differentiate brominated trihalamines (i.e. tribromamine NBr3, dibromochloramine NBr2Cl and bromodichloramine NBrCl2) in synthetic and natural chlorinated seawater. A mass-to-charge ratio of m/z = 253 corresponding to the parent ion was used for the quantification of NBr3 in absence of organic matter and the signal of the fragment at m/z = 177 was chosen in presence of high concentration of organic matter. Limits of detection were 0.23 µM (49 µg Cl2/L) and 0.18 µM (38 µg Cl2/L) for m/z 253 and m/z 177, respectively. Both NBr2Cl and NBrCl2 were monitored in chlorinated seawaters with their respective parent ion at m/z = 207 and m/z = 163 but were not quantified. MIMS results also showed that reaction of brominated trihalamines with natural organic matter (NOM) was a minor pathway for 1-2 mg C/L compared to their auto-decomposition in natural or synthetic seawater. Overall, MIMS was able to unambiguously differentiate and monitor brominated trihalamines for the first time in chlorinated seawater, which was not possible by using UV measurement, titration and colorimetric methods.

Kinetic and mechanistic investigations of the decomposition of bromamines in the presence of Cu(II).

This study demonstrates that Cu(II) can significantly enhance the decomposition rate of bromamines. Apparent second order rate constants of 2.31 ± 0.01 M-1s-1 and 0.36 ± 0.01 M-1s-1 at pH 7.5 were determined for the reaction of Cu(II) with bromamines and the self-decomposition of bromamines, respectively. Increasing the pH from 6.0 to 8.5, the rate of bromamines self-decomposition decreased while the rate of Cu(II)-catalysed decomposition of bromamines increased. Species-specific rate constants indicated that Cu(OH)2 was the most reactive copper species towards NH2Br and NHBr2. Experiments were carried out with 15N-labelled bromamines to analyse the nitrogenous degradation products of bromamines in the presence and absence of Cu(II). Nitrogen gas (N2) was found to be the major product from the self-decomposition of bromamines, with N2O, NO2-, and NO3- as additional minor products. When Cu(II) was present, the product distribution changed and NO2- and N2O became significant, while N2 and NO3- were produced at low levels. Increasing the Cu(II) concentration from 1.0 to 5.0 mg/L increased the N2O production while decreased the NO2- formation. Based on these results, a mechanism for Cu(II)-catalysed decomposition of bromamines is proposed. This work provides new insights related to the chemistry of bromamines in chloraminated drinking water distribution systems where copper is present.

Effect of copper oxide on monochloramine decomposition in bromide-containing waters.

Copper oxide (CuO), a common corrosion product found in copper pipes, has been shown to catalyse the decay of different oxidants in drinking water, including chlorine, bromine, iodine, and chlorine dioxide. However, its impact on monochloramine (NH2Cl), a disinfectant commonly used in long distribution system worldwide is still unknown. In this study, the effect of CuO on NH2Cl decay in the absence or presence of bromide was investigated. Results showed that in the presence of CuO and the absence of bromide, NH2Cl slightly decayed under acidic conditions. When bromide was present in NH2Cl solutions, the total oxidant concentration (sum of the different bromo-chloro-amines) was significantly decreased by CuO. This was primarily due to the degradation of bromochloramine (NHBrCl) by CuO which was evidenced by membrane inlet mass spectrometry. The decomposition rate of the total oxidant was similar for different CuO dosages (0.02-0.2 g/L) but increased with increasing bromide concentration (0-80 µM) and decreasing pH (6.5-8). An apparent second-order rate constant of 0.73 M-1 s-1 was determined with respect to NH2Cl and bromide concentrations for a CuO concentration of 0.05 g/L. Our findings suggest that, during water transportation in copper pipes or in distribution systems where copper oxide is present, special attention should be given to the stability of chloramines when bromide-containing waters are chloraminated.

Identification and quantification of chloramines, bromamines and bromochloramine by Membrane Introduction Mass Spectrometry (MIMS).

A Membrane Introduction Mass Spectrometry (MIMS) method was developed to differentiate and quantify the different chlorinated and brominated-amines, present in drinking water during chloramination. The representative mass to charge ratios (m/z) of 53, 85, 97, 175 and 131 corresponding to the mass of the parent compounds were selected to monitor NH2Cl, NHCl2, NH2Br, NHBr2 and NHBrCl and the detection limits were found to be 0.034, 0.034, 0.10, 0.12 and 0.36 mg/L as Cl2, respectively. NHCl2, NHBr2 and NHBrCl fragments interfere with the analysis/quantification of NH2Cl and NH2Br via protonation reactions at hot metal surfaces inside the mass spectrometer. To accurately quantify NH2Cl or NH2Br in mixtures of NH2Cl/NHCl2 or NH2Br/NHBr2, the interference from NHCl2 or NHBr2 was subtracted to the signal of the parent compound. If NHBrCl is present, NH2Br and NH2Cl cannot be accurately quantified since the interference from the NHBrCl fragment cannot be distinguished from the signal of the parent compound. Under drinking water conditions, the interference from NHBrCl on NH2Cl was negligible. The different halamines were monitored and quantified for the first time in two surface waters and one seawater that were chloraminated to mimic a realistic disinfection scenario.

Efficiency of pre-oxidation of natural organic matter for the mitigation of disinfection byproducts: Electron donating capacity and UV absorbance as surrogate parameters.

Pre-oxidation is often used before disinfection with chlorine to decrease the reactivity of the water matrix and mitigate the formation of regulated disinfection byproducts (DBPs). This study provides insights on the impact of oxidative pre-treatment with chlorine dioxide (ClO2), ozone (O3), ferrate (Fe(VI)) and permanganate (Mn(VII)) on Suwannee River Natural Organic Matter (SRNOM) properties characterized by the UV absorbance at 254 nm (UV254) and the electron donating capacity (EDC). Changes in NOM reactivity and abatement of DBP precursors are also assessed. The impact of pre-oxidants (based on molar concentration) on UV254 abatement ranked in the order O3 > Mn(VII) > Fe(VI)/ClO2, while the efficiency of pre-oxidation on EDC abatement followed the order Mn(VII) > ClO2 > Fe(VI) > O3 and two phases were observed. At low specific ClO2, Fe(VI) and Mn(VII) doses corresponding to < 50% EDC abatement, a limited relative abatement of UV254 compared to the EDC was observed (~ 8% EDC abatement per 1% UV254 abatement). This suggests the oxidation of phenolic-type moieties to quinone-type moieties which absorb UV254 and don't contribute to EDC. At higher oxidant doses (> 50% EDC abatement), a similar abatement of EDC and UV254 (~ 0.9-1.2% EDC abatement per 1% UV254 abatement) suggested aromatic ring cleavage. In comparison to the other oxidants, O3 abated the relative UV254 more effectively, due to a more efficient cleavage of aromatic rings. For a pre-oxidation with Mn(VII), ClO2 and Fe(VI), similar correlations between the EDC abatement and the chlorine demand or the adsorbable organic halide (AOX) formation were obtained. In contrast, O3 pre-treatment led to a lower chlorine demand and AOX formation for equivalent EDC abatement. For all oxidants, trihalomethane formation was poorly correlated with both EDC and UV254. The EDC abatement was found to be a pre-oxidant-independent surrogate for haloacetonitrile formation. These results emphasize the benefits of combining EDC and UV254 measurement to understand and monitor oxidant-induced changes of NOM and assessing DBP formation.